JP2018035277A - Resin composition and resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of giving a resin molding having excellent impact resistance and a high flexural modulus.SOLUTION: The resin composition contains: a cellulose acylate having a weight-average molecular weight of 30,000 or more and 90,000 or less; and an olefin-(meth)acrylate-glycidyl methacrylate copolymer in which the mass ratio Ma/Mb of the content Ma of a constituent unit represented by formula (a) to the content Mb of a constituent unit represented by formula (b) is 4 or more and 10 or less. In the formula, Rrepresents a hydrogen atom or a methyl group, and Rrepresents a C1-10 alkyl group.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a resin molded body.

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 Literature 1 includes, as a main component, “a cellulose ester resin, a non-reactive plasticizer having no functional group capable of reacting with the cellulose ester resin, and a polyolefin obtained by polymerizing an olefin having 2 to 4 carbon atoms. And a resin composition having at least a polyolefin-containing polyfunctional elastomer having a plurality of functional groups capable of reacting with the cellulose ester resin.

  Patent Document 2 discloses that “(A) thermoplasticity of a core-shell structure containing 2 to 100 parts by weight of a plasticizer and (C) a (meth) acrylic acid alkyl ester unit with respect to 100 parts by weight of a cellulose ester. "A cellulose ester composition containing 1 to 50 parts by weight of an elastomer."

JP 2006-069397 A JP 2014-084343 A

  The problem to be solved by the present invention is a resin composition comprising a cellulose acylate having a weight average molecular weight of 30,000 to 90,000 and an olefin- (meth) acrylate-glycidyl methacrylate copolymer. The mass ratio Ma / Mb between the amount Ma of the structural unit represented by the following formula (a) and the amount Mb of the structural unit represented by the following formula (b) is less than 4, or 10 Compared with the case where it exceeds, it is providing the resin composition which is excellent in impact resistance and from which a resin molding with a high bending elastic modulus is obtained.

  The above problem is solved by the following means.

The invention according to claim 1
The cellulose acylate having a weight average molecular weight of 30,000 to 90,000, and the content Ma of the structural unit represented by the following formula (a) contained in the copolymer and the structural unit represented by the following formula (b) It is a resin composition containing the olefin- (meth) acrylate-glycidyl methacrylate copolymer whose mass ratio Ma / Mb with content Mb is 4-10.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms.

The invention according to claim 2
The resin composition according to claim 1, wherein the olefin- (meth) acrylate-glycidyl methacrylate copolymer is an ethylene- (meth) acrylate-glycidyl methacrylate copolymer.

The invention according to claim 3
The resin composition according to claim 1 or 2, wherein a substitution degree of the cellulose acylate is 2.0 or more and 2.5 or less.

The invention according to claim 4
The resin composition according to any one of claims 1 to 3, wherein the cellulose acylate has at least an acetyl group.

The invention according to claim 5
The resin composition according to any one of claims 1 to 4, wherein a content of the copolymer is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the cellulose acylate. is there.

The invention according to claim 6
The resin composition according to any one of claims 1 to 5, further comprising an adipic acid ester-containing compound.

The invention according to claim 7 provides:
It is a resin molding formed by shape | molding the resin composition of any one of Claim 1 thru | or 6.

The invention according to claim 8 provides:
The cellulose acylate having a weight average molecular weight of 30,000 to 90,000, and the content Ma of the structural unit represented by the following formula (a) contained in the copolymer and the structural unit represented by the following formula (b) It is a resin molding containing a resin formed by reaction of an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 to 10 with respect to the content Mb.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms.

The invention according to claim 9 is:
The resin molded product according to claim 8, wherein the olefin- (meth) acrylate-glycidyl methacrylate copolymer is an ethylene- (meth) acrylate-glycidyl methacrylate copolymer.

According to the invention of claim 1, in the resin composition containing a cellulose acylate having a weight average molecular weight of 30,000 to 90,000 and an olefin- (meth) acrylate-glycidyl methacrylate copolymer, the copolymer The mass ratio Ma / Mb between the amount Ma of the structural unit represented by the formula (a) and the amount Mb of the structural unit represented by the formula (b) contained in the formula is less than 4, or 10 Compared with the case where it exceeds, the resin composition which is excellent in impact resistance and can obtain the resin molding with a high bending elastic modulus is provided.
According to the invention which concerns on Claim 2, compared with the case where the said copolymer is an olefin- (meth) acrylate-glycidyl methacrylate copolymer other than ethylene, it is excellent in impact resistance, and resin with a higher bending elastic modulus. A resin composition from which a molded body can be obtained is provided.
According to the invention of claim 3, the resin composition is obtained in which the degree of substitution of the cellulose acylate is less than 2.0 or more than 2.5 when the resin molded article is superior in impact resistance. Is provided.
According to the invention of claim 4, the mass ratio Ma / Mb in the copolymer is less than 4, or contains cellulose acetate as the cellulose acylate as compared with the case where it exceeds 10, and has impact resistance. Thus, a resin composition is obtained that is superior and can provide a resin molded product having a higher flexural modulus.
According to the invention which concerns on Claim 5, content of the said copolymer is less than 0.5 mass part with respect to 100 mass parts of the said cellulose acylate, or compared with the case where it exceeds 10 mass parts, There is provided a resin molded body from which a resin molded body excellent in impact resistance can be obtained.
According to the invention which concerns on Claim 6, the said mass ratio Ma / Mb in the said copolymer is less than 4, or contains the adipate ester containing compound compared with the case where it exceeds 10, and the shaping | molding at the time of resin molding There is provided a resin composition that provides a resin molded article that is superior in impact properties and superior in impact resistance.

  According to the invention of claim 7, in the resin composition containing a cellulose acylate having a weight average molecular weight of 30,000 to 90,000 and an olefin- (meth) acrylate-glycidyl methacrylate copolymer, the copolymer The mass ratio Ma / Mb between the amount Ma of the structural unit represented by the formula (a) and the amount Mb of the structural unit represented by the formula (b) contained in the formula is less than 4, or 10 Compared with the case where the resin composition exceeding is used, the resin molded object which is excellent in impact resistance and has a high bending elastic modulus is provided.

According to the invention concerning Claim 8, in the resin molding containing the resin formed by the reaction of cellulose acylate having a weight average molecular weight of 30,000 to 90,000 and an olefin- (meth) acrylate-glycidyl methacrylate copolymer Whether the mass ratio Ma / Mb between the amount Ma of the structural unit represented by the formula (a) and the amount Mb of the structural unit represented by the formula (b) contained in the copolymer is less than 4. Or compared with the case where it exceeds 10, the resin molded object which is excellent in impact resistance and has a high bending elastic modulus is provided.
According to the invention of claim 9, the resin is superior in impact resistance and has a higher flexural modulus than the case where the copolymer is an olefin- (meth) acrylate-glycidyl methacrylate copolymer other than ethylene. A shaped body is provided.

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

[Resin composition]
The resin composition according to the present embodiment includes cellulose acylate having a weight average molecular weight of 30,000 to 90,000, and the content Ma of the structural unit represented by the following formula (a) contained in the copolymer and the following formula The olefin- (meth) acrylate-glycidyl methacrylate copolymer whose mass ratio Ma / Mb with respect to content Mb of the structural unit represented by (b) is 4-10 is included.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms.

  The resin composition which concerns on this embodiment is excellent in impact resistance by the said structure, and a resin molding with a high bending elastic modulus is obtained. The reason is estimated as follows.

Cellulose has a rigid chemical structure and a strong intramolecular and intermolecular hydrogen bonding force, so it has extremely high elastic modulus and heat resistance, but has almost no thermal fluidity, so it is rarely used as plastic.
Therefore, by adding a substituent (particularly an acyl group) to cellulose, the plasticity is imparted, and the thermal fluidity is improved by lowering the melting temperature, making it usable as a plastic.

Cellulose acylate has essentially low CO ₂ emissions and exhibits excellent environmental performance. However, when used for casing applications such as copying machines and home appliance parts, the intramolecular and intermolecular hydrogen bonds in cellulose acylate are strong, the rigidity is high, and the impact strength is low.
Moreover, in patent document 1, with respect to 100 mass parts of cellulose esters, such as a cellulose acylate, 2-100 mass parts of plasticizers, and the thermoplastic elastomer 1-50 of the core-shell structure containing a (meth) acrylic-acid alkylester unit. By including the mass part, the impact strength is improved, but the rigidity, which is the original strength, specifically, the bending elastic modulus is lowered.

In the present embodiment, even when cellulose acylate is used, the impact strength is improved and the high bending elastic modulus, which is the original characteristic, has been successfully achieved. Specifically, the cellulose acylate having a weight average molecular weight of 30,000 to 90,000, and the content Ma of the structural unit represented by the formula (a) contained in the copolymer and the formula (b) The resin composition containing an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 to 10 with respect to the content Mb of the structural unit is excellent in impact resistance and flexural modulus. High resin molding is obtained.
By reacting and bonding the hydroxyl group or ester group of the cellulose acylate and the glycidyl group in the copolymer, the side chain becomes a bulky structure containing the structural unit represented by the formula (a), Reduces hydrogen bonding strength and improves impact strength.
However, when the side chain becomes bulky, the bending elastic modulus, which is usually a characteristic of cellulose acylate, decreases.
Therefore, a cellulose acylate having a weight average molecular weight of 30,000 to 90,000 and a olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 to 10 is used. As a result, the hydroxyl group at the end of the molecule also reacts with the glycidyl group, and the molecular chain extension, the bulkiness of the side chain, and the amount of hydrogen bonds are in an appropriate balance. A resin molded body is obtained.
In addition, when the weight average molecular weight of cellulose acylate is less than 30,000, the molecular chain extension becomes insufficient and the flexural modulus decreases. On the other hand, when the weight average molecular weight of cellulose acylate exceeds 90,000, the reaction probability between the molecular terminal and the glycidyl group is lowered, and the flexural modulus is lowered.
Furthermore, when the mass ratio Ma / Mb of the copolymer is less than 4, the reaction between the cellulose acylate and the copolymer proceeds excessively, resulting in a decrease in hydrogen bonding properties. Decreases. On the other hand, when the mass ratio Ma / Mb of the copolymer exceeds 10, the copolymer to be reacted is decreased and the impact strength is insufficient.

  Hereinafter, the detail of the resin composition which concerns on this embodiment is demonstrated.

<Cellulose acylate>
The resin composition according to this embodiment includes cellulose acylate having a weight average molecular weight of 30,000 to 90,000.

The cellulose acylate used in the present embodiment is preferably a cellulose acylate having a weight average molecular weight of 30,000 to 90,000 and a substitution degree of 2.0 to 2.5. Cellulose acylate having this characteristic has a low melting temperature and high transparency. When a cellulose acylate having the above characteristics is used for a resin molded body, a resin molded body having high moldability (for example, high injection moldability) and excellent impact resistance can be obtained.
However, the properties of the cellulose acylate used in the present embodiment are not limited to the above properties except that the weight average molecular weight is 30,000 or more and 90,000 or less, and are selected according to the intended use of the cellulose acylate.

  The cellulose acylate used in the present embodiment has a weight average molecular weight of 30,000 to 90,000, preferably 40,000 to 90,000, and preferably 60,000 to 90,000 from the viewpoint of impact resistance of the resulting resin molded product. The following is more preferable.

The weight average molecular weight of the cellulose acylate in this embodiment is measured by the following method.
A dimethylacetamide / lithium chloride = 90/10 solution is used and measured in terms of polystyrene using a gel permeation chromatography apparatus (GPC apparatus: manufactured by Tosoh Corporation, HLC-8320GPC, column: TSKgelα-M).

  The degree of polymerization of the cellulose acylate according to this embodiment is preferably 100 or more and 350 or less, more preferably 150 or more and 350 or less, from the viewpoint of reduction of the melting temperature (improvement of moldability) and impact resistance of the obtained resin molding. Preferably, it is 200 or more and 350 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 measured by the above method.
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 284 when the degree of substitution is 2.9.

  The degree of substitution of the cellulose acylate according to this embodiment is 2.0 or more and 2.5 or less from the viewpoint of reduction of melting temperature (improvement of moldability), impact resistance and bending elastic modulus of the obtained resin molded body. Preferably, 2.1 or more and 2.5 or less are more preferable, and 2.2 or more and 2.5 or less are especially 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.
The degree of substitution is measured from the integral ratio of the cellulose-derived hydrogen and the acyl group-derived peak by ¹ H-NMR (manufactured by JMN-ECA / JEOL RESONANCE).

The acyl group possessed by the cellulose acylate used in the present embodiment is not particularly limited, but from the viewpoint of impact resistance and bending elastic modulus of the obtained molded product, linear or branched carbon number of 1 or more. The acyl group is preferably 6 or less, and is at least one acyl group selected from the group consisting of formyl group, acetyl group, propionyl group, butyroyl group, 2-methylpropionyl group, and pentanoyl group. More preferably, it is more preferably at least one acyl group selected from the group consisting of an acetyl group and a propionyl group, and particularly preferably an acetyl group.
Moreover, the cellulose acylate used in the embodiment may have one acyl group alone or two or more acyl groups.

  Specific examples of the cellulose acylate used in the present embodiment include cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.

The cellulose acylate used in this embodiment may be used alone or in combination of two or more.
The content of cellulose acylate in the resin composition according to the present embodiment is 50% by mass or more and 99.9% with respect to the total mass of the resin composition from the viewpoint of impact resistance and bending elastic modulus of the obtained resin molded body. It is preferably at most mass%, more preferably at least 65 mass% and at most 99.8 mass%, particularly preferably at least 75 mass% and at most 99.5 mass%.

In addition, although the resin composition which concerns on this embodiment is not the whole quantity, it is estimated that the said cellulose acylate and the said copolymer have partially reacted.
The cellulose acylate content includes not only the amount of unreacted cellulose acylate but also the amount of cellulose acylate component in the reacted resin.
Moreover, it is preferable that the resin composition which concerns on this embodiment contains resin formed by the said cellulose acylate and the said copolymer reacting.

  There is no restriction | limiting in particular in the manufacturing method of the cellulose acylate used for this embodiment, For example, acylation, low molecular weight (depolymerization), and deacylation are performed with respect to a cellulose as needed. It is suitably manufactured by the method. Moreover, you may manufacture a cellulose acylate of a commercial item by performing low molecular weight (depolymerization) etc. so that it may become the said weight average molecular weight.

<Olefin- (meth) acrylate-glycidyl methacrylate copolymer>
The resin composition according to the present embodiment includes an olefin- (meth) acrylate-glycidyl methacrylate copolymer, and the copolymer is represented by a structural unit represented by the following formula (a) and a formula (b) below. The mass ratio Ma / of the content Ma of the structural unit represented by the following formula (a) in the copolymer and the content Mb of the structural unit represented by the following formula (b) in the copolymer Mb is 4 or more and 10 or less.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms.

The structural unit represented by the formula (a) is preferably a structural unit derived from (meth) acrylate.
R ¹ in formula (a) is preferably a hydrogen atom.
R ² in the formula (a) is preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms from the viewpoint of impact resistance and bending elastic modulus of the obtained resin molded body. Is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
Further, the alkyl group in R ² may be a linear alkyl group or a branched alkyl group.

In the copolymer, the structural unit represented by the formula (a) may be used alone or in combination of two or more.
The content of the structural unit represented by the formula (a) in the copolymer is 10% by mass or more and 40% by mass with respect to the total mass of the copolymer from the viewpoint of impact resistance of the obtained resin molding. Or less, more preferably 12% by mass or more and 35% by mass or less, and particularly preferably 15% by mass or more and 30% by mass or less.

The structural unit represented by the formula (b) is preferably a structural unit derived from glycidyl methacrylate.
The content of the structural unit represented by the formula (b) in the copolymer is 0.5% by mass or more and 15% by mass or more based on the total mass of the copolymer from the viewpoint of impact resistance of the obtained resin molded body. It is preferably at most mass%, more preferably at least 1 mass% and at most 12 mass%, particularly preferably at least 2 mass% and at most 10 mass%.

  The mass ratio Ma / Mb between the content Ma of the structural unit represented by the formula (a) and the content Mb of the structural unit represented by the formula (b) in the copolymer is 4 or more and 10 or less. In view of the impact resistance and the flexural modulus of the resin molded product obtained, it is preferably 5 or more and 9 or less, and more preferably 6 or more and 8.5 or less.

The copolymer has structural units derived from olefins.
The olefin copolymerized with the copolymer is preferably an aliphatic hydrocarbon compound having an ethylenically unsaturated group, and is at least one compound selected from the group consisting of ethylene and α-olefins. It is more preferable that it is at least one compound selected from the group consisting of ethylene and propylene, and ethylene is particularly preferable.
Moreover, it is preferable that the said copolymer has a structural unit represented by following formula (c) as a structural unit derived from the said olefin.

In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ³ in the formula (c) is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms from the viewpoint of impact resistance and bending elastic modulus of the obtained resin molded body, and is preferably a hydrogen atom or a methyl group. More preferably, it is particularly preferably a hydrogen atom.
The alkyl group in R ³ may be a linear alkyl group or a branched alkyl group, but is preferably a linear alkyl group.

In the copolymer, the structural unit represented by the formula (c) may be used alone or in combination of two or more.
The content of the structural unit represented by the formula (c) in the copolymer is 50% by mass or more and 89.5% by mass with respect to the total mass of the copolymer from the viewpoint of impact resistance of the obtained resin molded body. It is preferably at most mass%, more preferably at least 60 mass% and at most 85 mass%, particularly preferably at least 65 mass% and at most 80 mass%.

Although the said copolymer may have other structural units other than the structural unit represented by Formula (a) thru | or Formula (c), it is preferable not to have.
There is no restriction | limiting in particular as a monomer which forms another structural unit, Well-known ethylenically unsaturated compounds other than having mentioned above are mentioned.
Specific examples of monomers that form other structural units include styrene compounds, vinyl ether compounds, vinyl ester compounds, and (meth) acrylate compounds other than those described above.

The said copolymer may have another structural unit individually by 1 type, or may have 2 or more types.
The content of other structural units in the copolymer is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass or less with respect to the total mass of the copolymer. More preferably, it is particularly preferable that there is no other structural unit.

The copolymer is preferably an olefin- (meth) acrylate-glycidyl methacrylate ternary copolymer.
The copolymer is a copolymer composed of a structural unit represented by the formula (a), a structural unit represented by the formula (b), and a structural unit represented by the formula (c). Is preferred.

  The terminal structure of the copolymer is not particularly limited and may form various groups depending on the reaction conditions and the type of reaction terminator. However, a hydrogen atom, a hydroxy group, an ethylenically unsaturated group, an alkoxy group may be formed. And an alkylthio group.

  The weight average molecular weight Mw of the copolymer is preferably 5,000 or more and 200,000 or less, preferably 10,000 or more and 100,000 or less, from the viewpoint of impact resistance and bending elastic modulus of the obtained resin molding. Is more preferable.

The said copolymer used for this embodiment may be used individually by 1 type, or may use 2 or more types together.
The content of the copolymer in the resin composition according to the present embodiment is 0.1 part by mass with respect to 100 parts by mass of the cellulose acylate from the viewpoint of impact resistance and bending elastic modulus of the obtained resin molding. It is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less.

  The resin composition according to the present embodiment may include a plasticizer, other components, and the like as necessary.

<Plasticizer>
The resin composition according to the present embodiment preferably contains a plasticizer from the viewpoints of moldability and impact resistance of the obtained resin molded body.
Moreover, it is preferable that the resin composition which concerns on this embodiment does not contain a plasticizer from a viewpoint of the bending elastic modulus of the resin molding obtained.
Examples of plasticizers 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), ^REE1 and ^REE2 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 uses Tosoh Co., Ltd. product and HPLC1100 as a measuring apparatus, and uses Tosoh Co., Ltd. column and TSKgel GMHHR-M + TSKgel GMHHR-M (7.8 mm ID30cm). Perform with chloroform solvent. 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.

  The content of the plasticizer in the resin composition according to this embodiment is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less with respect to the total mass of the resin composition. 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.

<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 and the copolymer. However, it is preferable that other resin is 5 mass% or less with respect to the total mass of a resin composition, It is more preferable that it is 1 mass%, It is especially preferable not to contain other resin.
Examples of the other resin include conventionally known thermoplastic resins. Specifically, polycarbonate resin; polypropylene resin; polyester resin; polyolefin resin; polyester carbonate resin; polyphenylene ether resin; 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.

[Method for Producing Resin Composition]
The manufacturing method of the resin composition of this embodiment has the process of preparing the resin composition containing the said cellulose acylate and the said copolymer.
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. From the viewpoint of thermal decomposition and fluidity, for example, 140 ° C. or higher and 240 ° C. or lower is preferable, and 160 ° C. or higher and 210 ° C. or lower. More preferably, it is not higher than ° C.

[Resin molding and its production method]
The resin molded body according to the present embodiment includes a cellulose acylate having a weight average molecular weight of 30,000 to 90,000, and a content Ma of the structural unit represented by the following formula (a) contained in the copolymer and the following formula: It includes a resin formed by reaction of an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 to 10 with respect to the content Mb of the structural unit represented by (b).

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms.

  The preferable aspect in the said cellulose acylate and the said copolymer in the resin molding which concerns on this embodiment is the same as the preferable aspect in the said cellulose acylate and the said copolymer in the resin composition which concerns on this embodiment mentioned above, respectively. is there.

The resin molded body according to the present embodiment is preferably formed by molding the resin composition according to the present embodiment. At least a part of the cellulose acylate and the copolymer contained in the resin composition according to the present embodiment reacts at the time of molding to form a resin formed by the reaction of the cellulose acylate and the copolymer.
Moreover, it is preferable that the manufacturing method of the resin molding which concerns on this embodiment has the process of shape | molding the resin composition which concerns on this 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 method for producing a resin molded body according to the present embodiment is preferably performed by injection molding in terms of 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 preferably 140 ° C. or higher and 240 ° C. or lower, more preferably 150 ° C. or higher and 220 ° C. or lower, and further preferably 160 ° C. or higher and 220 ° C. or lower. The mold temperature for injection molding is preferably 30 ° C. or higher and 120 ° C. or lower, and more preferably 40 ° C. or higher and 80 ° C. or lower. The injection molding is performed using, for example, a commercially available apparatus such as NEX500 manufactured by Nissei Plastic Industry Co., Ltd., NEX150 manufactured by Nissei Plastic Industry Co., Ltd., NEX70000 manufactured by Nissei Plastic Industry Co., Ltd., SE50D manufactured by Toshiba Machine Co., Ltd. Also good.

  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 more 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)
Acetylation: 3 parts of cellulose powder (manufactured by Nippon Paper Chemicals Co., Ltd., KC Flock W50), 0.15 part of sulfuric acid, 30 parts of acetic acid and 6 parts of acetic anhydride are placed in a reaction vessel and stirred at 20 ° C. for 4 hours. Cellulose was acetylated.
Deacetylation and molecular weight reduction: 3 parts of acetic acid and 1.2 parts of pure water were immediately added to the acetylated solution after stirring, and the mixture was stirred at 20 ° C. for 30 minutes. Part was added, heated to 75 ° C. and stirred for 5 hours. This solution was dropped into 200 parts 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 parts of white powder.
Washing: The obtained white powder was washed with pure water using a filter press (manufactured by Kurita Machinery Co., Ltd., SF (PP)) until the conductivity was 50 μS or less, and then dried.
Post-treatment: Add 3 parts of calcium acetate and 30 parts of pure water to 3 parts of the dried white powder, stir at 25 ° C. for 2 hours, filter, and obtain the resulting powder at 60 ° C. for 72 hours. It dried and obtained about 2.5 parts of cellulose acetate CA1.

(Synthesis of cellulose acetate CA2)
Cellulose acetate CA2 was obtained in the same manner as CA1, except that the amount of sulfuric acid used for acetylation was changed to 0.10 part.

(Synthesis of cellulose acetate CA3)
Cellulose acetate CA3 was obtained in the same manner as CA1, except that the amount of sulfuric acid used for acetylation was changed to 0.03 part.

(Synthesis of cellulose acetate CA4)
In deacetylation and molecular weight reduction, cellulose acetate CA4 was obtained in the same manner as CA1, except that the place of stirring for 5 hours was changed to 7 hours.

(Synthesis of cellulose acetate CA5)
In deacetylation and molecular weight reduction, cellulose acetate CA5 was obtained in the same manner as CA1, except that stirring at 75 ° C. for 5 hours was performed at 65 ° C. for 7 hours.

(Synthesis of cellulose acetate CA6)
In deacetylation and molecular weight reduction, cellulose acetate CA6 was obtained in the same manner as CA1, except that stirring at 75 ° C. for 5 hours was performed at 80 ° C. for 4 hours.

(Synthesis of cellulose propionate CP1)
In the acetylation, cellulose pro-acetate was used in the same manner as CA1, except that 2 parts of acetic anhydride was used, 2.5 parts of propionic anhydride was used, and the reaction time in deacetylation and molecular weight reduction was changed to 7 hours. Pionate CP1 was obtained.

(Preparation of cellulose acetate CA7-1 to 3)
Commercially available cellulose acetate (manufactured by Daicel Corporation, L50) is cellulose acetate CA7-1, (manufactured by Daicel Corporation, L20) is cellulose acetate CA7-2, (Eastman Chemical Corporation, CA398-3) is CA7. -3.

(Synthesis of cellulose acetate CA8)
In deacetylation and low molecular weight reduction, cellulose acetate CA8 was obtained in the same manner as CA1, except that the place where stirring was performed for 5 hours was changed to 4 hours 30 minutes.

(Synthesis of cellulose acetate CA9)
Cellulose acetate CA9 was obtained in the same manner as CA1, except that the solution obtained by acetylation was allowed to stand at room temperature (20 ° C., hereinafter the same) for 10 hours and then deacetylated and reduced in molecular weight.

<Measurement of weight average molecular weight, degree of polymerization, degree of substitution>
The degree of polymerization of cellulose acylate is determined from the weight average molecular weight by the following procedure.
First, the weight average molecular weight of cellulose acylate is measured in terms of polystyrene using a dimethylacetamide / lithium chloride = 90/10 solution with a GPC apparatus (manufactured by Tosoh Corporation, HLC-8320GPC, column: TSKgelα-M). .
Next, the degree of polymerization of cellulose acylate is determined by dividing by the molecular weight of the structural unit of cellulose acylate. The molecular weight of the structural unit is, for example, 263 when the substitution degree is 2.4 with an acetyl group and 287 when the substitution degree is 2.9. The results of evaluating the degree of polymerization and the degree of substitution of cellulose acylate synthesized by this method are summarized in Table 1.

<Synthesis of ethylene- (meth) acrylate-glycidyl methacrylate copolymer>
(Preparation of EAG1 to 3)
Commercially available ethylene- (meth) acrylate-glycidyl methacrylate copolymer, LAKEDER AX8930 manufactured by Arkema (EAG1), BondFirst BF-7M manufactured by Sumitomo Chemical Co., Ltd. (EGA2), LOTDER AX8900 manufactured by Arkema ( EGA3).

(Synthesis of EAG4)
A solution obtained by dissolving 72 parts by mass of ethylene monomer, 20 parts by mass of methyl acrylate, and 8 parts by mass of glycidyl methacrylic acid monomer in tetrahydrofuran, adding 0.05 part by mass of azobisisobutyronitrile, and stirring for 24 hours at 40 ° C. The resultant precipitate was dropped into water, and the resulting precipitate was filtered and dried to obtain an ethylene-methyl methacrylate-glycidyl methacrylate copolymer (EAG4).

(Synthesis of EAG5 to 9)
(EAG5) to (EAG5) in the same manner as in the synthesis of (EAG4) except that ethylene monomers, propylene (1-methylethylene) monomers, (meth) acrylate monomers, or glycidyl methacrylate monomers were used at the composition ratios shown in Table 2. (EAG8) was obtained respectively.

  In Table 2, MA represents methyl acrylate, EA represents ethyl acrylate, and BA represents n-butyl acrylate.

<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.

<Evaluation of impact strength and flexural modulus>
Kneading was carried out with a biaxial kneading apparatus (Toshiki Machine Co., Ltd., TEX41SS) at a charging composition ratio shown in Table 3 to obtain a resin composition (pellet).
In addition, about the comparative examples 7 and 8, it knead | mixed with the composition of Example 1 or 3 as described in Unexamined-Japanese-Patent No. 2014-084343, and obtained the pellet.
Specifically, in Comparative Example 7, 25 parts by mass of adipic acid ester-containing compound (Daifaty 101, manufactured by Daihachi Chemical Industry Co., Ltd.) with respect to 100 parts by mass of cellulose acetate CA7-1 (manufactured by Daicel Corporation, L50). 14 parts by mass and Rohm and Haas Paraloid (registered trademark) EXL-2602 (core / shell type graft copolymer made of butadiene-methyl methacrylate copolymer) were used.
In Comparative Example 8, 25 parts by mass of triphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.) and Rohm and Haas for 100 parts by mass of cellulose acetate CA7-1 (manufactured by Daicel Corporation, L50) 14 parts by mass of Paraloid (registered trademark) EXL-2602 (a core / shell type graft copolymer made of a butadiene-methyl methacrylate copolymer) was used.

For the obtained pellets, an ISO multipurpose dumbbell (measurement part dimensions: width 100 mm × thickness 40 mm) is used with an injection molding machine (Nex140III, manufactured by Nissei Plastic Industry Co., Ltd.) at a cylinder temperature B where the injection peak pressure does not exceed 180 MPa. ).
The cylinder temperatures A and B are shown in Table 3.
Using the obtained ISO multipurpose dumbbell test piece, it was processed into a notched impact test piece by a method in accordance with ISO 179, and an impact strength measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd., Charpy Auto Impact Tester CHN3 type) The impact strength with a notch at 23 ° C. was measured. The results are shown in Table 3.
Moreover, it measured by the bending elastic modulus by the method based on ISO-178 using the universal testing apparatus (Corporation | KK Shimadzu Corp. make, autograph AG-Xplus). The results are shown in Table 3.

  From the said result, it turns out that the resin composition of a present Example is excellent in impact resistance compared with the resin composition of a comparative example, and the resin molding which has a high bending elastic modulus is obtained.

Claims (9)

Cellulose acylate having a weight average molecular weight of 30,000 to 90,000, and
The mass ratio Ma / Mb between the content Ma of the structural unit represented by the following formula (a) contained in the copolymer and the content Mb of the structural unit represented by the following formula (b) is 4 or more and 10 or less. A resin composition comprising an olefin- (meth) acrylate-glycidyl methacrylate copolymer.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms.   The resin composition according to claim 1, wherein the olefin- (meth) acrylate-glycidyl methacrylate copolymer is an ethylene- (meth) acrylate-glycidyl methacrylate copolymer.   The resin composition according to claim 1 or 2, wherein a substitution degree of the cellulose acylate is 2.0 or more and 2.5 or less.   The resin composition according to claim 1, wherein the cellulose acylate has at least an acetyl group.   The resin composition according to any one of claims 1 to 4, wherein a content of the copolymer is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the cellulose acylate.   The resin composition according to any one of claims 1 to 5, further comprising an adipic acid ester-containing compound.   The resin molding formed by shape | molding the resin composition of any one of Claims 1 thru | or 6. The cellulose acylate having a weight average molecular weight of 30,000 to 90,000, and the content Ma of the structural unit represented by the following formula (a) contained in the copolymer and the structural unit represented by the following formula (b) A resin molded body comprising a resin formed by a reaction of an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 to 10 with respect to the content Mb.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 10 carbon atoms.   The resin molded product according to claim 8, wherein the olefin- (meth) acrylate-glycidyl methacrylate copolymer is an ethylene- (meth) acrylate-glycidyl methacrylate copolymer.