JP6229773B1 - Cellulose acylate, resin composition, resin molded product, and method for producing cellulose acylate - Google Patents

Abstract

The present invention provides a cellulose acylate that suppresses coloring of a resin molded product, which is generated when a resin composition containing cellulose acylate is molded at a high temperature. A cellulose acylate having a mass ratio (A / B) of a sulfate ion content A and a chloride ion content B of 1 or more and 4 or less. [Selection figure] None

Description

  The present invention relates to a cellulose acylate, a resin composition, a resin molded body, and a method for producing cellulose acylate.

Conventionally, various thermoplastic resins have been provided and used for various applications. For example, thermoplastic resins are used in various parts of home appliances, automobiles, office equipment, electronic electrical equipment, and the like.
In recent years, plant-derived resins have been used as thermoplastic resins, and cellulose acylate is one of conventionally known plant-derived resins.

  For example, Patent Document 1 states that “components having different molecular weights are obtained by derivatizing cellulose that has been reduced in molecular weight by heating in an acidic aqueous solution under mild conditions that do not change the molecular weight, and then reprecipitating in a hydrous or anhydrous organic solvent. Is a method for producing a low molecular weight cellulose having a narrow molecular weight distribution having a degree of polymerization of 5 to 400 and a number average molecular weight / weight average molecular weight ratio of 3 or less.

  In Patent Document 2, “1) the total sulfuric acid remaining in the cellulose ester is 10 ppm or more and 160 ppm or less as an amount with respect to the cellulose ester as an amount converted to sulfuric acid, and 2) calcium is not contained or contained. Even if it is a case, it is 10 ppm or less as a quantity with respect to a cellulose ester, and 3) The cellulose ester which contains magnesium and the amount of magnesium is 10-60 ppm as a quantity with respect to a cellulose ester.

Japanese Patent Laid-Open No. 62-195395 JP 2009-161701 A

  Resin produced when a resin composition containing cellulose acylate is molded at a high temperature as compared with the case where the mass ratio (A / B) of the sulfate ion content A and the chloride ion content B is less than 1 or more than 4. It is to provide a cellulose acylate that suppresses coloring of a molded product.

  The above problem is solved by the following means.

The invention according to claim 1
The mass ratio (A / B) between the content A of sulfate ions and the content B of chloride ions is 1 or more and 4 or less,
The sulfate ion content is 0.0044% by mass or more and 0.2% by mass or less,
The content of hydrochloric acid ions is 0.002% by mass or more and 0.12% by mass or less,
The degree of polymerization is 100 or more and 350 or less,
Cellulose acylate having a substitution degree of 2.05 or more and 2.65 or less.

The invention according to claim 2
The cellulose acylate according to claim 1, wherein the substitution degree is 2.1 or more and 2.6 or less.

The invention according to claim 3
The cellulose acylate according to claim 1 or 2 , which has an acetyl group.

The invention according to claim 4
The resin composition containing the cellulose acylate of any one of Claims 1-3 .

The invention according to claim 5
The resin molding containing the resin composition of Claim 4 .

The invention according to claim 6
The resin molded body according to claim 5 , wherein the resin molded body is an injection molded body.

The invention according to claim 7 provides:
A first step of acylating cellulose in the presence of sulfuric acid having a mass ratio of 2% by mass to 20% by mass with respect to cellulose;
A second step of deacylating and depolymerizing the acylated cellulose in the presence of hydrochloric acid having a mass ratio of 0.1% by mass to 5% by mass with respect to the acylated cellulose;
The manufacturing method of the cellulose acylate of any one of Claims 1-3 which has these .

The invention according to claim 8 provides:
The manufacturing method of the cellulose acylate of Claim 7 which implements said 1st process and said 2nd process continuously in the same container.

According to the invention of claim 1, the resin composition containing cellulose acylate as compared with the case where the mass ratio (A / B) of the sulfate ion content A and the chloride ion content B is less than 1 or more than 4. There is provided a cellulose acylate that suppresses the coloring of a resin molded product, which is produced when the is molded at a high temperature.
According to the first aspect of the present invention, there is provided a cellulose acylate that suppresses coloring of a resin molded product, which occurs when a resin composition containing cellulose acylate is molded at a high temperature as compared with a case where the degree of polymerization exceeds 350. The
According to the invention of claim 2 , compared with the case where the degree of substitution is less than 2.1 or more than 2.6, coloring of the resin molded product, which occurs when a resin composition containing cellulose acylate is molded at a high temperature, is suppressed. Cellulose acylate is provided.
According to the invention which concerns on Claim 3 , compared with the case where mass ratio (A / B) of the content A of sulfate ion and the content B of chloride ion is less than 1 or exceeds 4, cellulose acetate is included as a cellulose acylate. There is provided a cellulose acylate that suppresses coloring of a resin molded product, which is generated when a resin composition is molded at a high temperature.

According to the invention which concerns on Claim 4 , compared with the case where the mass ratio (A / B) of the content A of sulfate ions and the content B of chloride ions (A / B) is less than 1 or more than 4, the cellulose acylate is applied. Provided is a resin composition that suppresses coloring of a resin molded product, which occurs when a resin composition containing a rate is molded at a high temperature.

According to the invention which concerns on Claim 5 , compared with the case where the cellulose acylate whose mass ratio (A / B) of content A of sulfate ion and content B of chloride ion is less than 1 or more than 4, is applied. There is provided a resin molded product in which coloring generated when a resin composition containing a rate is molded at a high temperature is suppressed.
According to the invention which concerns on Claim 6 , compared with the case where the mass ratio (A / B) of the sulfate ion content A and the chlorine ion content B is less than 1 or more than 4, the cellulose acylate is applied. Provided is a resin molded body in which coloring that occurs when a resin composition containing a rate is molded by injection molding is suppressed.

According to the invention according to claim 7 or 8 , the first step of acylating cellulose in the presence of sulfuric acid having a mass ratio of less than 2% by mass or more than 20% by mass to cellulose, and the mass to acylated cellulose Resin composition containing cellulose acylate as compared with the case of having a second step of deacylating and depolymerizing acylated cellulose in the presence of hydrochloric acid having a ratio of less than 0.1% by mass or exceeding 5% by mass There is provided a method for producing a cellulose acylate that suppresses the coloring of a resin molded product, which is produced when the is molded at a high temperature.

  Embodiments that are examples of the present invention will be described below.

[Cellulose acylate]
In the cellulose acylate according to this embodiment, the mass ratio (A / B) of the sulfate ion content A and the chloride ion content B is 1 or more and 4 or less. “Ppm” is based on mass.

Here, since the cellulose acylate has a melting temperature and a decomposition temperature close to each other, the cellulose acylate may be decomposed simultaneously with heating to the melting temperature (melting point). Therefore, when a resin composition containing cellulose acylate is molded by molding (for example, injection molding or the like) that is heated to a temperature close to the melting temperature (melting point) of cellulose acylate, cellulose acylate is decomposed and obtained. The resin molding may be colored. The colored resin molded product tends to impair the transmittance in applications that require transparency. Even in applications that do not require transparency, the color difference changes due to the difference in time held at a temperature close to the melting temperature (melting point) of cellulose acylate, and the product color is difficult to stabilize. For this reason, cellulose acylate is difficult to use in molding applications (for example, injection molding, etc.) that are heated to a temperature close to the melting temperature (melting point) of cellulose acylate, and is limited to molding applications that do not require high temperatures such as casting. This is the current situation.
Thus, even when the resin composition containing cellulose acylate is molded (for example, injection molding or the like) at a high temperature (above the temperature close to the melting temperature (melting point) of cellulose acylate), the coloring of the resin molded product is suppressed. Is desired.

  On the other hand, in the cellulose acylate according to the present embodiment, the mass ratio (A / B) of the sulfate ion content A and the chloride ion content B is 1 or more and 4 or less. This suppresses coloring of the resin molded body that occurs when the resin composition containing cellulose acylate is molded (for example, injection molding or the like) at a high temperature (above the temperature close to the melting temperature (melting point) of cellulose acylate). . The reason is presumed as follows.

Although the coloration factor of cellulose acylate was thought to be the degradation of the main chain of cellulose acylate or the influence of impurities, it was not caused by the degradation of the main chain or impurities, but may be caused by the decomposition of sulfate. Conceivable.
Usually, sulfuric acid is used as a catalyst for acylation of cellulose. In this case, it is reported that a part of sulfuric acid undergoes an exchange reaction with a hydroxyl group or acyl group of cellulose acylate to form a sulfate ester. Sulfuric acid esters are difficult to remove even after washing, and when the amount of sulfuric acid ester increases, decomposition is faster than normal acyl groups, and as a result of the temperature rise during high temperature molding (such as injection molding), It is considered that coloring of the resin molded body by decomposition is promoted.
On the other hand, when a sulfuric acid (that is, a chlorine ion (Cl ⁻ )) is present in the cellulose acylate together with sulfuric acid (ie, sulfate ion (SO ₄ ²⁻ )), it is considered that the chlorine ion is coordinated to the acyl group. And when a chlorine ion coordinates to an acyl group, it is thought that formation of a sulfate ester by manufacture and washing | cleaning of a cellulose acylate may be suppressed. Therefore, the formation of sulfate ester that causes coloring of the resin molded body by chlorine ions is reduced, so that the resin composition containing cellulose acylate is heated at a high temperature (above the temperature close to the melting temperature (melting point) of cellulose acylate). Even when molding (for example, injection molding or the like), it is considered that coloring of the resin molded body is suppressed.

  In the cellulose acylate according to the present embodiment, the mass ratio (A / B) of the sulfate ion content A and the chloride ion content B is 1 or more and 4 or less, but from the viewpoint of suppressing the coloring of the resin molded product. 1.2 to 3.5 is preferable, and 1.5 to 3 is more preferable.

The content A of sulfate ions is preferably 0.08% by mass or more and 0.2% by mass or less, and preferably 0.08 to 0.15 in terms of mass ratio with respect to cellulose acylate from the viewpoint of reaction rate and suppression of coloring during heating. More preferred.
The content A of chloride ions is preferably 0.002% by mass or more and 0.01% by mass or less, and preferably 0.003% by mass or more and 0.007% by mass with respect to cellulose acylate from the viewpoint of reaction rate and suppression of coloring during heating. The mass% or less is more preferable.
In addition, content of a sulfate ion and a chlorine ion is a mass ratio with respect to the whole cellulose acylate containing a sulfate ion, a chlorine ion, another impurity, etc.

  Here, the supply source of sulfate ions is sulfuric acid used as an acylation catalyst when producing cellulose acylate. On the other hand, the supply source of chloride ions is preferably hydrochloric acid which is a deacylation catalyst (or a depolymerization catalyst) when producing cellulose acylate.

The content of sulfate ion and chloride ion is a value measured by a combustion ion chromatograph (Thermo Scientific SCIENTIFIC, Thermo Scientific Interaction).
Specific measurement conditions are as follows: Absorbing liquid: 25 mg / l as an internal standard, 1.0 mg / l H ₂ O ₂ aqueous solution containing PO ₄ ³⁻ , heating range: 25 ° C. to 600 ° C., heating rate: 10 ° C / min.

  Hereinafter, the details of the cellulose acylate according to the present embodiment will be described.

  The cellulose acylate according to the present embodiment is a cellulose derivative in which at least a part of hydroxyl groups in cellulose is substituted (acylated) with an acyl group. Specifically, for example, the cellulose acylate is represented by the general formula (1). It is a cellulose derivative.

In General Formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or an acyl group. n represents an integer of 2 or more. However, at least a part of n R ¹ , n R ² , and n R ³ represents an acyl group.
The acyl group represented by R ¹ , R ² and R ³ is preferably an acyl group having 1 to 6 carbon atoms.

In general formula (1), the range of n is not particularly limited, but is preferably 100 or more and 350 or less, and more preferably 100 or more and 200 or less.
When n is 40 or more, the strength of the resin molded body is likely to increase. When n is set to 300 or less, a decrease in flexibility of the resin molded body is easily suppressed.

In the cellulose acylate according to this embodiment, a part of the hydroxyl group may be substituted with an acyl group (more preferably, an acyl group having 1 to 6 carbon atoms). That is, in the case of the cellulose derivative having the structure represented by the general formula (1), at least a part of n R ¹ , n R ² , and n R ³ represents an acyl group.
Thus, R ¹ and n times in the cellulose acylate of the general formula (1) may be different from each other in the same part in all the same. Similarly, n R ^{2 s} and n R ^{3 s} may all be the same, partially the same, or different from each other. And at least one of these represents an acyl group.

  Cellulose acylate has an acyl group having 1 to 6 carbon atoms as an acyl group, so that the elastic modulus and heat resistance are improved as compared with the case of having an acyl group having 7 or more carbon atoms.

The acyl group is represented by a structure of “—CO—R _AC ”, and R _AC represents a hydrogen atom or a hydrocarbon group (more preferably a hydrocarbon group having 1 to 5 carbon atoms).
The hydrocarbon group represented by R _AC is a linear, branched, and may be any of circular, but more preferably is linear.
The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group.
Further, the hydrocarbon group may have other atoms (for example, oxygen, nitrogen, etc.) other than carbon and hydrogen, but is more preferably a hydrocarbon group consisting of only carbon and hydrogen.
Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group (butanoyl group), propenoyl group, hexanoyl group and the like.
Among these, as the acyl group, from the viewpoint of improving moldability of the resin composition, an acyl group having 2 to 4 carbon atoms is more preferable, an acyl group having 2 to 3 carbon atoms is more preferable, and an acyl group having 2 carbon atoms is more preferable. An acyl group (acetyl group) is particularly preferred. That is, the cellulose acylate preferably has an acetyl group.

  The degree of polymerization of the cellulose acylate according to this embodiment is preferably from 100 to 350, preferably from 120 to 330, from the viewpoint of reducing the melting temperature (improving moldability) and improving the strength of the resulting resin composition. More preferably, it is 150 or more and 320 or less.

Here, the degree of polymerization is determined from the weight average molecular weight by the following procedure.
First, the weight average molecular weight of cellulose acylate is polystyrene in a gel permeation chromatography apparatus (GPC apparatus: HLC-8320GPC, column: TSKgel α-M, manufactured by Tosoh Corporation) using a dimethylacetamide / lithium chloride = 90/10 solution. Measure in conversion.
Next, the degree of polymerization of cellulose acylate is determined by dividing by the molecular weight of the structural unit of cellulose acylate. For example, when the substituent of cellulose acylate is an acetyl group, the structural unit molecular weight is 263 when the degree of substitution is 2.4, and 287 when the degree of substitution is 2.9.

  The substitution degree of the cellulose acylate according to this embodiment is preferably a substitution degree of 2.1 or more and 2.6 or less from the viewpoint of reducing the melting temperature (improving moldability) and improving the strength of the resulting resin composition. 2 or more and 2.5 or less is more preferable, and 2.2 or more and 2.45 or less is more preferable.

Here, the degree of substitution is an index indicating the degree to which the hydroxyl group of cellulose is substituted with an acyl group. That is, the degree of substitution is an index indicating the degree of acylation of cellulose acylate. Specifically, the degree of substitution means an intramolecular average of the number of substitutions in which three hydroxyl groups in the D-glucopyranose unit of cellulose acylate are substituted with acyl groups.
Then, the degree of substitution is ^at H 1 -NMR (manufactured by JMN-ECA / JEOL RESONANCE Co.), measured from the area ratio of the cellulose-derived hydrogen and an acyl group derived peak.

[Method for producing cellulose acylate]
The method for producing cellulose acylate according to the present embodiment is not particularly limited, but the first step of acylating cellulose in the presence of sulfuric acid having a mass ratio of 2% by mass to 20% by mass with respect to cellulose (hereinafter referred to as “ The second step of deacylating and depolymerizing the acylated cellulose in the presence of hydrochloric acid having a mass ratio of 0.1% by mass to 5% by mass with respect to the acylated cellulose (also referred to as “acylation step”) (Hereinafter also referred to as “deacylation step”).

Here, in the method for producing cellulose acylate according to the present embodiment, after acylating cellulose in the presence of sulfuric acid as an acylation catalyst, deacylation and depolymerization are performed by deacylating hydrochloric acid instead of sulfuric acid. The catalyst is used as a crystallization catalyst and depolymerization catalyst. In this operation, by adjusting the amount of sulfuric acid and the amount of hydrochloric acid within the above ranges, chlorine ions are effectively introduced into the cellulose acylate, and “mass ratio of sulfate ion content A to chloride ion content B ( A / B) "is easily controlled within the above range.
Moreover, after adjusting the amount of sulfuric acid and the amount of hydrochloric acid to the above ranges, the deacylation and the depolymerization proceed with hydrochloric acid as a deacylation catalyst and a depolymerization catalyst. It is considered that the coordination of chlorine ions to the group is promoted.
Therefore, in the method for producing cellulose acylate according to the present embodiment, coloring of the resin molded body, which occurs when a resin composition containing cellulose acylate is molded at a high temperature, is further suppressed.

(Acylation step)
In the acylation step, cellulose is acylated in the presence of an acylation catalyst (sulfuric acid).
Specifically, in the acylation step, for example, cellulose is acylated while stirring in a state where cellulose is immersed or dispersed in a solution containing an acylation catalyst, an acylating agent, and an acylating solvent. In addition, cellulose may be immersed or dispersed in a solution containing an acylation catalyst (or an acylation catalyst aqueous solution), an acylating agent, and an acylating solvent, or in a solution in which cellulose is immersed or dispersed in an acylating solvent, An acylation catalyst (or an acylation catalyst aqueous solution) and an acylating agent may be added.

The cellulose to be acylated is high molecular weight cellulose (for example, cellulose having a polymerization degree of 1000 or more and 10,000 or less). As the high molecular weight cellulose, for example, various raw material celluloses such as wood pulp (coniferous pulp, hardwood pulp) and cotton linter pulp are used. Commercially available cellulose may be used as the high molecular weight cellulose. Examples of commercially available high molecular weight cellulose include KC Flock W50, W100, W200, W300G, W400G, W-100F, W60MG, W-50GK, W-100GK, NDPT, NDPS, LNDP, NSPP manufactured by Nippon Paper Industries Co., Ltd. -HR etc. are mentioned.
In addition, the cellulose used as the object of acylation may also contain different components such as hemicellulose derived from the raw material (pulp). For this reason, in this specification, the term "cellulose" also means containing different components, such as hemicellulose.

  The cellulose to be acylated may be subjected to an activation treatment. The activation treatment is, for example, a method of treating cellulose using an activator containing water (a method of spraying an activator on cellulose, a method of immersing cellulose in an activator, or the like). The activator may use an acylating solvent. Specifically, as the activation treatment, 1) a method of mixing cellulose and water, filtering the cellulose, mixing cellulose and an acylating solvent, and filtering the cellulose, and 2) mixing water and cellulose Examples thereof include a method of mixing a liquid (for example, a mixed liquid having a water content of 0 to 50% by mass) and cellulose and filtering the cellulose.

In addition, the temperature of an activation process is 0 degreeC-100 degreeC (preferably 10 degreeC-40 degreeC), for example.
The time for the activation treatment (the total time when the treatment is performed twice) is, for example, 0.1 hours to 20 hours (preferably 1 hour to 15 hours).

  Sulfuric acid is applied as the acylation catalyst. As the acylation catalyst, formic acid, acetic acid, hydrochloric acid, nitric acid and the like may be used in combination.

  The amount of sulfuric acid as an acylation catalyst is 2% by mass or more and 20% by mass or less in terms of mass ratio to cellulose. It is more preferably 9% by mass or less.

Examples of the acylating agent include compounds having an acyl group. Specifically, as the acylating agent, an alkylcarboxylic acid anhydride (for example, an alkyl having 2 to 6 carbon atoms in a straight or branched chain such as acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, etc. Suitable examples include carboxylic acid anhydrides) and organic acid halides (eg, acetic acid chloride, propionic acid chloride, butyric acid chloride, etc.). However, alkylcarboxylic acid anhydride is usually used as the acylating agent.
The acylating agent is selected according to the type of cellulose acylate desired to be obtained by acylation. For example, when cellulose acetate is obtained, acetic anhydride is applied as an acylating agent. Further, when cellulose acetate propionate is obtained, two kinds of acetic anhydride and propionic anhydride are applied as acylating agents.
In addition, an acylating agent may be used individually by 1 type, and may be used together 2 or more types.

  The amount of acylating agent is selected according to the degree of substitution of cellulose acylate desired to be obtained by acylation. Usually, in the acylation step, cellulose acylate having a substitution degree of 3 (cellulose triacylate) is often obtained. In this case, the amount of acylating agent is preferably from 1 to 5 times, more preferably from 1.1 to 3 times, as the molar ratio of cellulose to hydroxyl groups.

As the acylating solvent, an alkyl carboxylic acid (for example, a linear or branched alkyl carboxylic acid having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and valeric acid) is preferably used. Can be mentioned.
Among these, formic acid and acetic acid are preferable as the acylating solvent, and acetic acid is particularly preferable from the viewpoint of suppressing coloring of the resin molded body.
In addition, an acylating agent may be used individually by 1 type, and may be used together 2 or more types.

  The amount of acylating solvent is preferably 3 times or more and 20 times or less, more preferably 5 times or more and 15 times or less, in terms of mass ratio to cellulose from the viewpoint of increasing reactivity and simplifying the subsequent solvent removal step.

  As the acylating solvent, water may be used in combination with the alkylcarboxylic acid. However, the amount of water is 50% by mass or less based on the alkylcarboxylic acid.

Suitable conditions for the acylation step are, for example, as follows.
Temperature: For example, 10 ° C to 80 ° C (preferably 15 ° C to 40 ° C)
Time: For example, 1 hour to 12 hours (preferably 2 hours to 8 hours).

(Deacylation step)
In the deacylation step, acylated cellulose (hereinafter also referred to as “primary cellulose acylate”) is deacylated and depolymerized in the presence of hydrochloric acid. In the deacylation step, the degree of substitution of the primary cellulose acylate is adjusted by deacylation (hydrolysis or saponification), and the molecular weight of the primary cellulose acylate is reduced by depolymerization. This is a step of obtaining cellulose acylate having a degree of polymerization (hereinafter also referred to as “secondary cellulose acylate”).

  Specifically, in the deacylation step, for example, after adding an aqueous hydrochloric acid solution to the solution that has undergone the acylation step (a solution containing a primary cellulose acylate, an acylation catalyst, an acylating agent, and an acylating solvent), Stir. That is, from the viewpoint of productivity, the acylation step and the deacylation step are preferably performed continuously in the same container.

In addition, in order to deactivate the remaining acylating agent before adding the hydrochloric acid aqueous solution, water or a mixed solution containing water and at least one selected from an acylating solvent (alkylcarboxylic acid) and a neutralizing agent, etc. It is better to add a quencher to the solution.
Neutralizing agents are alkali metal compounds (hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate and potassium carbonate; organic acid salts such as sodium acetate and potassium acetate), alkaline earth metal compounds Bases such as (hydroxides such as calcium hydroxide; carbonates such as calcium carbonate; organic acid salts such as calcium acetate).

In the deacylation step, the amount of hydrochloric acid is 0.1% by mass or more and 5% by mass or less in terms of mass ratio to primary cellulose acylate (cellulose acylated in the acylation step). From 0.5 mass% to 5 mass% is preferable, and from 1 mass% to 3 mass% is more preferable.
When the acylation step and the deacylation step are carried out continuously in the same container, the mass of the primary cellulose acylate is calculated on the assumption that all of the charged cellulose is triacylate with a substitution degree of 3. To do.

Suitable conditions for the deacylation step are selected according to the degree of substitution and the degree of polymerization of the secondary cellulose acylate to be obtained, and are as follows, for example.
Temperature: For example, 40 ° C. or higher and 100 ° C. or lower (preferably 50 ° C. or higher and 90 ° C. or lower)
Time: For example, 1 hour to 15 hours (preferably 2 hours to 12 hours).

The deacylation step was obtained by, for example, precipitating and filtering primary cellulose acylate after the acylation step (obtained by washing, drying, etc., if necessary). An acylate may be used. Here, the precipitation of the primary cellulose acylate is carried out, for example, by mixing a solution containing the primary cellulose acylate and a large amount of water.
In this case, in the deacylation step, a solution containing hydrochloric acid and a deacylation solvent (the same solvent as the acylation solvent, specifically, an alkylcarboxylic acid or a mixed solvent of an alkylcarboxylic acid and water) is powdered. The primary cellulose acylate is deacylated and depolymerized with the primary cellulose acylate dissolved. Note that powdery primary cellulose acylate may be dissolved in a solution containing hydrochloric acid and a solvent, or an aqueous hydrochloric acid solution may be added to a solution in which powdered primary cellulose acylate is dissolved in a solvent.

  After the deacylation step, water is added to the solution containing the secondary cellulose acylate, the secondary cellulose acylate is precipitated, filtered, and dried to obtain the desired powdery cellulose acylate.

In addition, after carrying out the step of neutralizing the filtered secondary cellulose acylate, the step of washing the neutralized secondary cellulose acylate with water, etc., it is dried to obtain the desired powdery cellulose acylate. It is good to get a rate.
Here, the neutralization treatment is, for example, alkyl carboxylic acid (for example, linear or branched alkyl carboxylic acid having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, etc. ) Metal salts (metal salts such as periodic table group elements such as Na and periodic table group 2 elements such as Ca).

  In the method for producing cellulose acylate according to the present embodiment described above, depending on the type of acylating agent, various methods such as cellulose monoacetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, etc. Cellulose acylate is obtained.

[Resin composition]
The resin composition according to the present embodiment includes the cellulose acylate according to the present embodiment. The resin composition according to the present embodiment may include a plasticizer, other components, and the like as necessary.

  In addition, it is preferable that content of a plasticizer shall be the quantity from which the ratio of the cellulose acylate to the whole resin composition becomes the above-mentioned range. More specifically, the proportion of the plasticizer in the entire resin composition is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. When the ratio of the plasticizer is within the above range, the elastic modulus becomes higher and the heat resistance becomes higher. In addition, bleeding of the plasticizer is also suppressed.

(Plasticizer)
Examples of the plasticizer include adipic acid ester-containing compounds, polyether ester compounds, sebacic acid ester compounds, glycol ester compounds, acetate esters, dibasic acid ester compounds, phosphate ester compounds, phthalate ester compounds, camphor, citric acid. Examples include esters, stearates, metal soaps, polyols, polyalkylene oxides, and the like.
Among these, adipic acid ester-containing compounds and polyether ester compounds are preferable, and adipic acid ester-containing compounds are more preferable.

-Adipate-containing compound-
The adipic acid ester-containing compound (compound containing adipic acid ester) is a compound of adipic acid ester alone or a mixture of adipic acid ester and a component other than adipic acid ester (a compound different from adipic acid ester) Indicates. However, the adipic acid ester-containing compound may contain 50% by mass or more of the adipic acid ester with respect to all components.

  Examples of the adipic acid ester include adipic acid diester and adipic acid polyester. Specifically, an adipic acid diester represented by the following general formula (AE-1), an adipic acid polyester represented by the following general formula (AE-2), and the like can be given.

In General Formulas (AE-1) and (AE-2), R ^AE1 and R ^AE2 are each independently an alkyl group or a polyoxyalkyl group [— (C _x H _2X —O) _y —R ^A1 ] ( However, R ^A1 represents an alkyl group, x represents an integer of 1 to 10, and y represents an integer of 1 to 10.
R ^AE3 represents an alkylene group.
m1 represents an integer of 1 or more and 20 or less.
m2 represents an integer of 1 or more and 10 or less.

In general formulas (AE-1) and (AE-2), the alkyl group represented by R ^AE1 and R ^AE2 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. . The alkyl group represented by R ^AE1 and R ^AE2 may be linear, branched or cyclic, but is preferably linear or branched.
In the general formulas (AE-1) and (AE-2), in the polyoxyalkyl group [— (C _x H _2X —O) _y —R ^A1 ] represented by R ^AE1 and R ^AE2 , the alkyl group represented by R ^A1 is An alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group represented by R ^A1 may be linear, branched or cyclic, but is preferably linear or branched.

In general formula (AE-2), the alkylene group represented by R ^AE3 is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched.

  In general formulas (AE-1) and (AE-2), the group represented by each symbol may be substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group, and a hydroxyl group.

  The molecular weight (or weight average molecular weight) of the adipic acid ester is preferably 200 or more and 5000 or less, and more preferably 300 or more and 2000 or less. The weight average molecular weight is a value measured according to the above-described method for measuring the weight average molecular weight of cellulose acylate.

  Hereinafter, although the specific example of an adipic acid ester containing compound is shown, it is not necessarily restricted to this.

-Polyetherester compound-
Specific examples of the polyetherester compound include a polyetherester compound represented by the general formula (EE).

In General Formula (EE), R ^EE1 and R ^EE2 each independently represent an alkylene group having 2 to 10 carbon atoms. ^AEE1 and ^AEE2 each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. m represents an integer of 1 or more.

In general formula (EE), as an alkylene group which ^REE1 represents, a ^C3-C10 alkylene group is preferable and a C3-C6 alkylene group is more preferable. The alkylene group represented by ^REE1 may be linear, branched, or cyclic, but is preferably linear.
When the number of carbon atoms of the alkylene group represented by ^REE1 is 3 or more, a decrease in fluidity of the resin composition is suppressed, and thermoplasticity is easily exhibited. When the alkylene group represented by ^REE1 has 10 or less carbon atoms or the alkylene group represented by ^REE1 is linear, the affinity with cellulose acylate is likely to increase. For this reason, when the alkylene group represented by ^REE1 is linear, and the carbon number is in the above range, the moldability of the resin composition is improved.
From these viewpoints, the alkylene group represented by ^REE1 is particularly preferably an n-hexylene group (— (CH ₂ ) ₆ —). That is, the polyether ester compound is preferably a compound representing an n-hexylene group (— (CH ₂ ) ₆ —) as R ^EE1 .

In general formula (EE), as an alkylene group which ^REE2 represents, a ^C3-C10 alkylene group is preferable and a C3-C6 alkylene group is more preferable. The alkylene group represented by ^REE2 may be linear, branched or cyclic, but is preferably linear.
When the number of carbon atoms of the alkylene group represented by ^REE2 is 3 or more, a decrease in fluidity of the resin composition is suppressed and thermoplasticity is easily exhibited. When the alkylene group represented by ^REE2 has a carbon number of 10 or less or the alkylene group represented by ^REE2 is linear, the affinity with cellulose acylate is likely to increase. For this reason, when the alkylene group represented by ^REE2 is linear and the carbon number is in the above range, the moldability of the resin composition is improved.
From these viewpoints, the alkylene group represented by ^REE2 is particularly preferably an n-butylene group (— (CH ₂ ) ₄ —). That is, the polyether ester compound is preferably a compound representing an n-butylene group (— (CH ₂ ) ₄ —) as ^REE2 .

In the general formula ^(EE), the alkyl group represented by ^{A EE1,} and ^{A EE2} is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms. A ^EE1, and alkyl group represented by A ^EE2 are linear, branched, and may be either cyclic, branched is preferred.
Aryl groups A ^EE1, and represented by A ^EE2 is an aryl group having 6 to 12 carbon atoms, a phenyl group, an unsubstituted aryl group such as a naphthyl group, or t- butyl phenyl, substituted phenyl such as hydroxyphenyl group Groups.
A ^EE1, and aralkyl group represented by ^{A EE2,} a group represented by -R A -Ph. R ^A represents a linear or branched alkylene group having 1 to 6 carbon atoms (preferably 2 to 4 carbon atoms). Ph represents an unsubstituted phenyl group or a substituted phenyl group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms (preferably 2 to 6 carbon atoms). Specific examples of the aralkyl group include unsubstituted aralkyl groups such as benzyl group, phenylmethyl group (phenethyl group), phenylpropyl group, and phenylbutyl group, or substituted groups such as methylbenzyl group, dimethylbenzyl group, and methylphenethyl group. An aralkyl group is mentioned.

At least one of A ^EE1, and ^{A EE2} is preferably an aryl group or an aralkyl group. In other words, a polyether ester ^{compound, A EE1,} and preferably (preferably a phenyl group) an aryl group as at least one of ^{A EE2} is a compound represented or aralkyl ^{group, A EE1,} and aryl groups as both ^{A EE2} ( A compound that preferably represents a phenyl group) or an aralkyl group is preferred.

  Next, the characteristics of the polyetherester compound will be described.

The weight average molecular weight (Mw) of the polyetherester compound is preferably from 450 to 650, more preferably from 500 to 600.
When the weight average molecular weight (Mw) is 450 or more, bleeding (a phenomenon of precipitation) becomes difficult. When the weight average molecular weight (Mw) is 650 or less, the affinity with cellulose acylate is likely to increase. For this reason, when a weight average molecular weight (Mw) is made into the said range, the moldability of a resin composition will improve.
In addition, the weight average molecular weight (Mw) of a polyetherester compound is a value measured by a gel permeation chromatograph (GPC). Specifically, the molecular weight measurement by GPC is carried out with a chloroform solvent using a Tosoh Corporation HPLC1100 as a measuring apparatus, using a Tosoh column TSKgel GMHHR-M + TSKgel GMHHR-M (7.8 mm ID 30 cm). . The weight average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

The viscosity of the polyether ester compound at 25 ° C. is preferably 35 mPa · s or more and 50 mPa · s or less, and more preferably 40 mPa · s or more and 45 mPa · s or less.
When the viscosity is 35 mPa · s or more, dispersibility in cellulose acylate is easily improved. When the viscosity is 50 mPa · s or less, the anisotropy of the dispersion of the polyetherester compound hardly appears. For this reason, when a viscosity is made into the said range, the moldability of a resin composition will improve.
The viscosity is a value measured with an E-type viscometer.

The solubility parameter (SP value) of the polyether ester compound is preferably from 9.5 to 9.9, and more preferably from 9.6 to 9.8.
When the solubility parameter (SP value) is 9.5 or more and 9.9 or less, the dispersibility in cellulose acylate is easily improved.
The solubility parameter (SP value) is a value calculated by the method of Fedor. Specifically, the solubility parameter (SP value) is, for example, Polym. Eng. Sci. , Vol. 14, p. 147 (1974), the SP value is calculated by the following formula.
Formula: SP value = √ (Ev / v) = √ (ΣΔei / ΣΔvi)
(Wherein Ev: evaporation energy (cal / mol), v: molar volume (cm ³ / mol), Δei: evaporation energy of each atom or atomic group, Δvi: molar volume of each atom or atomic group)
The solubility parameter (SP value) employs (cal / cm ³ ) ^1/2 as a unit, but the unit is omitted in accordance with common practice and expressed in a dimensionless manner.

  Hereinafter, although the specific example of a polyetherester compound is shown, it is not necessarily restricted to this.

(Other ingredients)
Examples of other components include flame retardants, compatibilizers, antioxidants, mold release agents, light proofing agents, weathering agents, colorants, pigments, modifiers, anti-drip agents, antistatic agents, and hydrolysis inhibitors. , Fillers, reinforcing agents (glass fiber, carbon fiber, talc, clay, mica, glass flake, milled glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, etc.). The content of these components is preferably 0% by mass to 5% by mass with respect to the entire resin composition. Here, “0 mass%” means that other components are not included.

(Other resins)
The resin composition according to the present embodiment may contain a resin other than the cellulose acylate. However, it is preferable that other resins have an amount such that the ratio of cellulose acylate in the entire resin composition falls within the above-described range.
Examples of other resins include conventionally known thermoplastic resins, and specifically, polycarbonate resins; polypropylene resins; polyester resins; polyolefin resins; polyester carbonate resins; polyphenylene ether resins; Polyethersulfone resin; Polyarylene resin; Polyetherimide resin; Polyacetal resin; Polyvinyl acetal resin; Polyketone resin; Polyetherketone resin; Polyetheretherketone resin; Polyarylketone resin; Polyethernitrile resin; Imidazole resin; polyparabanic acid resin; selected from the group consisting of aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters, and vinyl cyanide compounds Vinyl-based polymer or copolymer resin obtained by polymerizing or copolymerizing two or more kinds of vinyl monomers; diene-aromatic alkenyl compound copolymer resin; vinyl cyanide-diene-aromatic alkenyl compound copolymer Polymer resin; aromatic alkenyl compound-diene-vinyl cyanide-N-phenylmaleimide copolymer resin; vinyl cyanide- (ethylene-diene-propylene (EPDM))-aromatic alkenyl compound copolymer resin; vinyl chloride resin Chlorinated vinyl chloride resin; and the like. These resins may be used alone or in combination of two or more.

(Production method of resin composition)
The resin composition according to the present embodiment is produced, for example, by melt-kneading a mixture containing at least cellulose acylate and, if necessary, a plasticizer and other components. In addition, the resin composition according to the present embodiment is produced, for example, by dissolving the above components in a solvent.
Examples of the melt-kneading means include known means, and specific examples include a twin screw extruder, a Henschel mixer, a Banbury mixer, a single screw extruder, a multi-screw extruder, and a kneader.
The temperature at the time of kneading may be determined according to the melting temperature of the cellulose acylate to be used, but is preferably 140 ° C. or higher and 240 ° C. or lower, and preferably 160 ° C. or higher and 200 ° C. or higher from the viewpoint of thermal decomposition and fluidity. More preferably, it is not more than

[Resin molding]
Hereinafter, a resin molded body using the resin composition according to the present embodiment (hereinafter also referred to as “resin molded body according to the present embodiment”) will be described.

The resin molded body according to the present embodiment includes the resin composition according to the present embodiment. That is, the resin molded body according to the present embodiment is configured with the same composition as the resin composition according to the present embodiment.
Specifically, the resin molded body according to the present embodiment is obtained by molding the resin composition according to the present embodiment. As the molding method, for example, injection molding, extrusion molding, blow molding, hot press molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding, transfer molding, or the like may be applied.

The molding method of the resin molded body according to the present embodiment is preferably injection molding because it has a high degree of freedom in shape. About injection molding, a resin composition is heated and melted, poured into a mold, and solidified to obtain a molded body. You may shape | mold by injection compression molding.
The cylinder temperature for injection molding is, for example, 140 ° C. or higher and 240 ° C. or lower, preferably 150 ° C. or higher and 220 ° C. or lower, more preferably 160 ° C. or higher and 200 ° C. or lower. The mold temperature for injection molding is, for example, 30 ° C. or more and 120 ° C. or less, and more preferably 40 ° C. or more and 80 ° C. or less. The injection molding may be performed using a commercially available device such as NEX500 manufactured by Nissei Plastic Industry, NEX150 manufactured by Nissei Plastic Industry, NEX70000 manufactured by Nissei Plastic Industry, SE50D manufactured by Toshiba Machine.

  The resin molded body according to the present embodiment is suitably used for applications such as electronic / electrical equipment, office equipment, home appliances, automobile interior materials, engine covers, vehicle bodies, and containers. More specifically, casings for electronic / electrical equipment and home appliances; various parts of electronic / electrical equipment and home appliances; interior parts for automobiles; storage cases such as CD-ROM and DVD; tableware; beverage bottles; Wrap material; film; sheet;

  EXAMPLES The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. Note that “part” means “part by mass” unless otherwise specified.

<Synthesis of cellulose acylate>
(Synthesis of cellulose acetate (CA1))
-Acylation step-
Cellulose powder (manufactured by Nippon Paper Chemical Co., Ltd., KC Flock W50, polymerization degree = 1020), 3 kg of concentrated sulfuric acid, 156 g of concentrated sulfuric acid (sulfuric acid amount = 150 g), 30 kg of acetic acid and 6 kg of acetic anhydride were placed in a 50 L reaction vessel and stirred at 20 ° C. for 4 hours. . This produced cellulose triacetate.

-Deacylation step-
Immediately after stirring, 3 kg of acetic acid and 1.2 L of pure water were added to the resulting solution containing cellulose triacetate. After stirring at 20 ° C. for 30 minutes, 0.2 M hydrochloric acid aqueous solution 20 L (hydrochloric acid amount = 0.3 kg) was added. In addition, the mixture was heated to 75 ° C. and stirred for 5 hours. Thereby, depolymerization proceeded with deacylation of cellulose triacetate.
Next, the stirred solution was dropped into 200 L of pure water over 2 hours, allowed to stand for 20 hours, and then filtered through a filter having a pore size of 6 μm to obtain 4 kg of white powder (cellulose diacetate).

-Washing process-
The obtained white powder (cellulose diacetate) was washed with pure water using a filter press (manufactured by Kurita Kikai Co., Ltd., SF (PP)) until the conductivity became 50 μS or less, and then dried.

-Post-treatment process-
200 g of calcium acetate and 30 L of pure water were added to 3 kg of dried white powder, stirred for 2 hours at 25 ° C., filtered, and the resulting powder was dried at 60 ° C. for 72 hours to obtain cellulose acetate (CA1). 2.5 kg was obtained.

(Synthesis of cellulose acetate (CA2))
Cellulose acetate (CA2) was obtained in the same manner as cellulose acetate (CA1) except that 150 g of sulfuric acid used in the acylation step was changed to 290 g.

(Synthesis of cellulose acetate CA3)
Cellulose acetate (CA3) was obtained in the same manner as cellulose acetate (CA1) except that the amount of sulfuric acid used in the acylation step was changed to 150 g.

(Synthesis of cellulose acetate CA4)
Cellulose acetate (CA4) was obtained in the same manner as cellulose acetate (CA1) except that the place of stirring for 5 hours in the deacylation step was changed to 7 hours.

(Synthesis of cellulose acetate CA5)
Cellulose acetate (CA5) was obtained in the same manner as cellulose acetate (CA1) except that the place where stirring was carried out for 5 hours in the deacylation step was changed to 4 hours 30 minutes.

(Synthesis of cellulose acetate CA6)
Cellulose acetate (CA6) was obtained in the same manner as cellulose acetate (CA1) except that the solution obtained in the acylation step was allowed to stand at room temperature for 10 hours and then deacylated.

(Synthesis of cellulose acetate CA7)
In the deacylation step, cellulose acetate (CA7) was obtained in the same manner as cellulose acetate (CA1) except that stirring at 75 ° C. for 5 hours was performed at 65 ° C. for 7 hours.

(Synthesis of cellulose acetate CA8)
In the deacylation step, cellulose acetate (CA8) was obtained in the same manner as cellulose acetate (CA1) except that stirring at 75 ° C. for 5 hours was performed at 80 ° C. for 4 hours.

(Synthesis of cellulose propionate CP1)
Cellulose propionate (CP1) was obtained in the same manner as cellulose acetate (CA1) except that 6 kg of acetic anhydride was used in the acylation step except that 12.5 kg of propionic anhydride was used.

(Synthesis of cellulose acetate CA9)
Cellulose acetate (CA9) was obtained in the same manner as cellulose acetate (CA1) except that the amount of sulfuric acid used in the acylation step was changed to 621 g.

(Synthesis of cellulose acetate CA10)
Cellulose acetate (CA10) was obtained in the same manner as cellulose acetate (CA1) except that the amount of sulfuric acid used in the acylation step was changed to 150 g.

(Preparation of cellulose acetate CA11)
Commercially available cellulose acetate (manufactured by Daicel, L50) was prepared as cellulose acetate (CA11).

(Synthesis of cellulose acetate (CA12) to (CA13))
Cellulose acetates (CA12) to (CA13) were synthesized by the synthesis methods described in Example 1 and Example 7 of JP2009-161701, respectively.

(Synthesis of cellulose acylate (CA14) to (CA17))
Cellulose acetate (CA14) to (CA17) in the same manner as cellulose acetate (CA1) except that 20 L of 0.2M hydrochloric acid aqueous solution added in the deacylation step was changed to 0.8 L, 34 L, 0.6 L, and 40 L, respectively. Got

(Physical properties of cellulose acylate)
The physical properties (degree of polymerization, degree of substitution, sulfate ion content, hydrochloric acid ion content) of each cellulose acylate obtained were measured according to the method described above. The results are shown in Table 1.

<Preparation of adipic acid ester-containing compound>
A commercially available adipic acid ester-containing compound (Daifatty 101, manufactured by Daihachi Chemical Industry Co., Ltd.) was prepared as Compound AE1.

<Examples and comparative examples>
The cylinder temperature was adjusted at the charged composition ratio shown in Table 2, and kneading was performed with a biaxial kneader (TEX41SS, manufactured by Toshiba Machine Co., Ltd.) to obtain a resin composition (pellet).
About the obtained pellet, D1 and D2 test piece (measurement part dimension: width 60x60mm / thickness) using an injection molding machine (Nex140III made by Nissei Plastic Industry Co., Ltd.) and a cylinder temperature at which an injection peak pressure does not exceed 180 MPa. A 1 mm D1 test piece and a D2 test piece having a width of 60 × 60 mm and a thickness of 2 mm were molded. The cylinder temperature is shown in Table 2.

(Evaluation of coloring after injection molding)
The total light transmittance of the obtained D1 and D2 test pieces was measured with a spectroscopic haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., SH7000), and the coloration was quantitatively evaluated. The results are shown in Table 2.

The details of the examples and comparative examples are listed in Tables 1 and 2 below.
In Table 1, the amount of sulfuric acid in the column of acylation step indicates “mass ratio of sulfuric acid to cellulose (mass%)”, and the amount of sulfuric acid charged is divided by the amount of cellulose. The amount of hydrochloric acid in the column of the deacylation step indicates “mass ratio (mass%) of hydrochloric acid to acylated cellulose (cellulose acylate)”. The amount of acylated cellulose was calculated according to the method described above.

  From the above results, it can be seen that in this example, even when high temperature injection molding is performed, the total light transmittance of the test piece is high and coloring is suppressed.

Claims (8)

The mass ratio (A / B) between the content A of sulfate ions and the content B of chloride ions is 1 or more and 4 or less,
The sulfate ion content is 0.0044% by mass or more and 0.2% by mass or less,
The content of hydrochloric acid ions is 0.002% by mass or more and 0.12% by mass or less,
The degree of polymerization is 100 or more and 350 or less,
Cellulose acylate having a substitution degree of 2.05 or more and 2.65 or less.   The cellulose acylate according to claim 1, wherein the substitution degree is 2.1 or more and 2.6 or less.   The cellulose acylate according to claim 1 or 2, which has an acetyl group.   The resin composition containing the cellulose acylate of any one of Claims 1-3.   The resin molding containing the resin composition of Claim 4.   The resin molded body according to claim 5, wherein the resin molded body is an injection molded body. A first step of acylating cellulose in the presence of sulfuric acid having a mass ratio of 2% by mass to 20% by mass with respect to cellulose;
A second step of deacylating and depolymerizing the acylated cellulose in the presence of hydrochloric acid having a mass ratio of 0.1% by mass to 5% by mass with respect to the acylated cellulose;
The manufacturing method of the cellulose acylate of any one of Claims 1-3 which has these.   The manufacturing method of the cellulose acylate of Claim 7 which implements said 1st process and said 2nd process continuously in the same container.