JP6805647B2 - Resin composition and resin molded product - Google Patents

Description

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

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

For example, Patent Document 1 describes "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 or more and 4 or less carbon atoms as a main component. 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. "

Further, Patent Document 2 states, "The thermoplasticity of the core-shell structure containing (A) 100 parts by mass of cellulose ester, (B) 2 to 100 parts by mass of plasticizer, and (C) (meth) acrylic acid alkyl ester unit. A cellulose ester composition containing 1 to 50 parts by mass of an elastomer. "

Japanese Unexamined Patent Publication No. 2016-06937 Japanese Unexamined Patent Publication No. 2014-084343

The problem to be solved by the present invention is in a resin composition containing 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. The mass ratio Ma / Mb of the amount Ma of the constituent unit represented by the following formula (a) and the amount Mb of the constituent unit represented by the following formula (b) contained in is less than 4, or 10. It is an object of the present invention to provide a resin composition capable of obtaining a resin molded product having excellent impact resistance and a high bending elasticity as compared with the case where the amount exceeds the limit.

The above problem is solved by the following means.

<1> is
Cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less, and the content Ma of the constituent unit represented by the following formula (a) and the constituent unit represented by the following formula (b) contained in the copolymer. It is a resin composition containing an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb with a content Mb of 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.

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

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

<4> is
The cellulose acylate is a resin composition according to any one of <1> to <3> has at least an acetyl group.

<5> is
The content of the copolymer, relative to the cellulose acylate 100 parts by mass, 10 parts by mass or less than 0.5 part by weight <1> to the resin composition according to any one of <4> is there.

<6> is
Further comprising adipic acid ester-containing compound <1> to a resin composition according to any one of <5>.

<7> is
<1> to a resin molded article obtained by molding the resin composition according to any one of <6>.

<8> is
Cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less, and the content Ma of the constituent unit represented by the following formula (a) and the constituent unit represented by the following formula (b) contained in the copolymer. It is a resin molded product containing a resin obtained by reacting an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 or more and 10 or less with 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.

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

According to <1>, the resin composition containing 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 is contained in the copolymer. When the mass ratio Ma / Mb of 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) is less than 4 or more than 10. In comparison, there is provided a resin composition capable of obtaining a resin molded body having excellent impact resistance and a high bending elasticity.
According to <2> , a resin molded product having better impact resistance and a higher flexural modulus than the case where the copolymer is an olefin- (meth) acrylate-glycidyl methacrylate copolymer other than ethylene is produced. The resulting resin composition is provided.
According to <3> , there is provided a resin composition capable of obtaining a resin molded product having better impact resistance than when the degree of substitution of cellulose acylate is less than 2.0 or more than 2.5. To.
According to <4> , as compared with the case where the mass ratio Ma / Mb in the copolymer is less than 4 or more than 10, cellulose acetate is contained as the cellulose acylate, and the impact resistance is superior. Provided is a resin composition capable of obtaining a resin molded product having a higher flexural modulus.
According to <5> , the content of the copolymer is less than 0.5 parts by mass or more than 10 parts by mass with respect to 100 parts by mass of the cellulose acylate. Provided is a resin molded product which can obtain a more excellent resin molded product.
According to <6> , as compared with the case where the mass ratio Ma / Mb in the copolymer is less than 4 or more than 10, it contains an adipate-containing compound and is excellent in moldability at the time of resin molding. Provided is a resin composition capable of obtaining a resin molded product having more excellent impact resistance.

According to <7> , the resin composition containing 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 is contained in the copolymer. The mass ratio Ma / Mb of 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) is less than 4 or more than 10. A resin molded body having excellent impact resistance and a high bending elasticity as compared with the case of using an object is provided.

According to <8> , in a resin molded product containing a cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less and a resin obtained by reacting an olefin- (meth) acrylate-glycidyl methacrylate copolymer, the same. The mass ratio Ma / Mb of 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 polymer is less than 4, or A resin molded body having excellent impact resistance and a high bending elasticity as compared with the case of exceeding 10 is provided.
According to <9> , a resin molded body having better impact resistance and a higher flexural modulus than the case where the copolymer is an olefin- (meth) acrylate-glycidyl methacrylate copolymer other than ethylene is produced. Provided.

Hereinafter, embodiments that are an example of the present invention will be described.

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

With the above configuration, the resin composition according to the present embodiment can obtain a resin molded product having excellent impact resistance and a high flexural modulus. The reason is presumed as follows.

Cellulose has a rigid chemical structure and has extremely high elastic modulus and heat resistance due to its strong intramolecular and intermolecular hydrogen bonding forces, but has almost no thermal fluidity, so it is not often used as a plastic.
Therefore, by attaching a substituent (particularly an acyl group) to cellulose, plasticity is imparted and the melting temperature is lowered to improve heat fluidity, and the cellulose can be used as a plastic.

Cellulose acylate has essentially low CO ₂ emissions and exhibits excellent environmental performance. However, when used for housing applications such as copiers and home appliance parts, the intramolecular and intermolecular hydrogen bonds in cellulose acylate are strong, and while the rigidity is high, the impact resistance is low.
Further, in Patent Document 1, 1 to 50 thermoplastic elastomers having a core-shell structure containing 2 to 100 parts by mass of a plasticizer and (meth) acrylic acid alkyl ester units with respect to 100 parts by mass of a cellulose ester such as cellulose acylate. By including a mass part, the impact resistance is improved, but the rigidity, which is the original strength, specifically, the flexural modulus is lowered.

In the present embodiment, even when cellulose acylate is used, it has succeeded in improving the impact resistance and ensuring the high flexural modulus, which is the original characteristic. Specifically, the content Ma of the cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less and the structural unit represented by the above formula (a) contained in the copolymer and the above formula (b) are shown. The resin composition containing an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 or more and 10 or less with the content Mb of the constituent unit is excellent in impact resistance and bending elasticity. High resin molded body can be obtained.
The hydroxyl group or ester group of the cellulose acylate reacts with the glycidyl group in the copolymer to form a bulky structure in which the side chain contains the structural unit represented by the formula (a). It relaxes the hydrogen bonding force and improves the impact resistance.
However, when the side chain becomes bulky, the flexural modulus, which is usually a characteristic of cellulose acylate, decreases.
Therefore, a cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less, which is lower than the conventional one, and an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio of Ma / Mb of 4 or more and 10 or less are used. As a result, the hydroxyl group at the end of the molecule also reacts with the glycidyl group, and the extension of the molecular chain, the bulkiness of the side chain, and the amount of hydrogen bonds are in an appropriate balance, resulting in excellent impact resistance while maintaining a high bending elasticity. A resin molded body is obtained.
If 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 end and the glycidyl group becomes low, and the flexural modulus decreases.
Further, when the mass ratio Ma / Mb of the copolymer is less than 4, the reaction between the cellulose acylate and the copolymer proceeds too much, and the hydrogen bondability is lowered, so that the flexural modulus Decreases. Further, when the mass ratio Ma / Mb of the copolymer exceeds 10, the number of reacting copolymers decreases and the impact resistance becomes insufficient.

Hereinafter, the details of the resin composition according to the present embodiment will be described.

<Cellulose acylate>
The resin composition according to the present embodiment contains cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less.

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

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

The weight average molecular weight of cellulose acylate in this embodiment is measured by the following method.
Using a dimethylacetamide / lithium chloride = 90/10 solution, measurement is performed in terms of polystyrene with a gel permeation chromatography device (GPC device: manufactured by Toso Co., Ltd., HLC-8320GPC, column: TSKgelα-M).

The degree of polymerization of the cellulose acylate according to the present embodiment is preferably 100 or more and 350 or less, more preferably 150 or more and 350 or less, from the viewpoint of reducing the melting temperature (improving moldability) and impact resistance of the obtained resin molded product. It is preferable, and 200 or more and 350 or less are particularly preferable.

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 molecular weight of the structural unit 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 cellulose acylate according to the present 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 flexural modulus of the obtained resin molded product. Preferably, 2.1 or more and 2.5 or less is more preferable, and 2.2 or more and 2.5 or less is particularly preferable.

Here, the degree of substitution is an index indicating the degree to which the hydroxyl group of cellulose is replaced by 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 the 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 measured by ¹ H-NMR (manufactured by JMN-ECA / JEOL RESONANCE) from the integral ratio of the cellulose-derived hydrogen and the acyl group-derived peak.

The acyl group of the cellulose acylate used in the present embodiment is not particularly limited, but from the viewpoint of impact resistance and bending elasticity of the obtained molded product, it has a linear or branched carbon number of 1 or more. It is preferably an acyl group of 6 or less, and is at least one acyl group selected from the group consisting of a formyl group, an acetyl group, a propionyl group, a butyroyl group, a 2-methylpropionyl group, and a 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.
In addition, the cellulose acylate used in the embodiment may have one type of acyl group alone or two or more types.

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% by mass with respect to the total mass of the resin composition from the viewpoint of impact resistance and bending elasticity of the obtained resin molded body. It is preferably 65% by mass or more, more preferably 99.8% by mass or less, and particularly preferably 75% by mass or more and 99.5% by mass or less.

In the resin composition according to the present embodiment, it is presumed that the cellulose acylate and the copolymer are partially reacted, though not in the total amount.
The content of the cellulose acylate shall include not only the amount of unreacted cellulose acylate but also the amount of the cellulose acylate component in the reacted resin.
Further, the resin composition according to the present embodiment preferably contains a resin formed by reacting the cellulose acylate with the copolymer.

The method for producing cellulose acylate used in the present embodiment is not particularly limited, and for example, cellulose is acylated, reduced in molecular weight (depolymerization), and deacylated, if necessary. It is preferably produced by the method. Further, a commercially available cellulose acylate may be produced by reducing the molecular weight (depolymerization) or the like so as to have the weight average molecular weight.

<Olefin- (meth) acrylate-glycidyl methacrylate copolymer>
The resin composition according to the present embodiment contains an olefin- (meth) acrylate-glycidyl methacrylate copolymer, and the copolymer is represented by a structural unit represented by the following formula (a) and a following formula (b). The mass ratio Ma / of the content Ma of the structural unit represented by the following formula (a) 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 the formula (a) is preferably a hydrogen atom.
From the viewpoint of impact resistance and flexural modulus of the obtained resin molded product, R ² in the formula (a) is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and an alkyl group having 1 or more and 4 or less carbon atoms. It is more preferable that it is a methyl group or an ethyl group, and it is particularly preferable that it is a methyl group.
Further, the alkyl group in R ² may be a linear alkyl group or a branched alkyl group.

The copolymer may have one type of structural unit represented by the formula (a) alone, or may have two or more types.
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 molded product. It is preferably 12% by mass or more, more preferably 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 15% by mass with respect to the total mass of the copolymer from the viewpoint of impact resistance of the obtained resin molded product. It is preferably 1% by mass or less, more preferably 1% by mass or more and 12% by mass or less, and particularly preferably 2% by mass or more and 10% by mass or less.

The mass ratio Ma / Mb of 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. From the viewpoint of impact resistance and flexural modulus of the obtained resin molded product, it is preferably 5 or more and 9 or less, and more preferably 6 or more and 8.5 or less.

The copolymer has a structural unit derived from an olefin.
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-olefin. Is more preferable, and at least one compound selected from the group consisting of ethylene and propylene is more preferable, and ethylene is particularly preferable.
Further, the copolymer preferably has a structural unit represented by the following formula (c) as a structural unit derived from the olefin.

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

From the viewpoint of impact resistance and bending elasticity of the obtained resin molded product, R ³ in the formula (c) is preferably a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and is preferably a hydrogen atom or a methyl group. It is more preferable to have a hydrogen atom, and it is particularly preferable to have 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.

The copolymer may have one type of structural unit represented by the formula (c) alone, or may have two or more types.
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 or more with respect to the total mass of the copolymer from the viewpoint of impact resistance of the obtained resin molded product. It is preferably 60% by mass or more, more preferably 85% by mass or less, and particularly preferably 65% by mass or more and 80% by mass or less.

The copolymer may have other structural units other than the structural units represented by the formulas (a) to (c), but it is preferable not to have them.
The monomer forming another structural unit is not particularly limited, and examples thereof include known ethylenically unsaturated compounds other than those described above.
Specific examples of the monomer forming another structural unit include styrene compounds, vinyl ether compounds, vinyl ester compounds, and (meth) acrylate compounds other than those described above.

The copolymer may have one type of other structural unit alone or two or more types.
The content of the other structural units in the copolymer is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less, based on the total mass of the copolymer. It is more preferable to have it, and it is particularly preferable to have no other structural unit.

The copolymer is preferably a ternary copolymer of olefin- (meth) acrylate-glycidyl methacrylate.
Further, 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 preferable.

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

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

The copolymer used in the present embodiment may be used alone or in combination of two or more.
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 elasticity of the obtained resin molded product. 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 contain a plasticizer, other components, and the like, if necessary.

<Plasticizer>
The resin composition according to the present embodiment preferably contains a plasticizer from the viewpoint of moldability and impact resistance of the obtained resin molded product.
Further, the resin composition according to the present embodiment preferably does not contain a plasticizer from the viewpoint of the flexural modulus of the obtained resin molded product.
Examples of the plasticizer include adipic acid ester-containing compounds, polyether ester compounds, sebacic acid ester compounds, glycol ester compounds, acetic acid esters, dibasic acid ester compounds, phosphoric acid ester compounds, phthalic acid ester compounds, cypress, and citric acid. Examples thereof include esters, stearic acid esters, metal soaps, polyols, polyalkylene oxides and the like.
Among these, adipate ester-containing compounds and polyether ester compounds are preferable, and adipate ester-containing compounds are more preferable.

-Adipate-containing compound-
The adipate-containing compound (compound containing adipate) is a compound of adipate alone or a mixture of adipate and a component other than adipate (a compound different from adipate). Is shown. However, the adipate-containing compound may contain the adipate ester in an amount of 50% by mass or more based on all the components.

Examples of the adipic acid ester include adipic acid diester and adipic acid polyester. Specific examples thereof include adipic acid diester represented by the following general formula (AE-1), polyester adipate represented by the following general formula (AE-2), and the like.

In the general formula (AE1) and ^{(AE2), R AE1} and ^{R AE2} are each independently an alkyl group, or polyoxyethylene group _{[- (C x H 2X -O} ) y -R A1] ( However, ^RA1 represents an alkyl group, x represents an integer of 1 or more and 10 or less, and y represents an integer of 1 or more and 10 or less).
^RAE3 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 the general formulas (AE-1) and (AE-2), the alkyl group represented by ^RAE1 and ^RAE2 is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 4 or less carbon atoms. .. The alkyl group represented by R ^AE1 and R ^AE2 may be linear, branched or cyclic, but linear or branched is preferable.
In the general formula (AE1) and ^(AE2), polyoxyethylene alkyl ^{group R AE1} and ^{R AE2} represents - in _{[(C x H 2X -O)} y -R A1], the alkyl group represented by ^{R A1} is , An alkyl group having 1 or more and 6 or less carbon atoms is preferable, and an alkyl group having 1 or more and 4 or less carbon atoms is more preferable. Alkyl group R ^A1 represents a straight chain, branched, may be any of circular, linear, branched is preferred.

In the general formula (AE-2), the alkylene group represented by ^RAE3 is preferably an alkylene group having 1 or more and 6 or less carbon atoms, and more preferably an alkylene group having 1 or more and 4 or less carbon atoms. The alkylene group may be linear, branched or cyclic, but linear or branched is preferable.

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

The molecular weight (or weight average molecular weight) of the adipate 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-mentioned method for measuring the weight average molecular weight of cellulose acylate.

Hereinafter, specific examples of the adipate-containing compound will be shown, but the present invention is not limited to this.

-Polyester ester compound-
Specific examples of the polyether ester compound include a polyether ester compound represented by the general formula (EE).

In the general formula (EE), ^REE1 and ^REE2 each independently represent an alkylene group having 2 to 10 carbon atoms. A ^EE1 and ^AEE2 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 the general formula (EE), the alkylene group represented by ^REE1 is preferably an alkylene group having 3 or more and 10 or less carbon atoms, and more preferably an alkylene group having 3 or more and 6 or less carbon atoms. The alkylene group represented by ^REE1 may be linear, branched, or cyclic, but linear is preferable.
When the carbon number of the alkylene group represented by ^REE1 is 3 or more, the decrease in the fluidity of the resin composition is suppressed, and the thermoplasticity is easily exhibited. When the carbon number of the alkylene group represented by ^REE1 is 10 or less or the alkylene group represented by ^REE1 is linear, the affinity with cellulose acylate tends to increase. Therefore, if the alkylene group represented by ^REE1 is linear and the number of carbon atoms is within the above range, the moldability of the resin composition is improved.
From these viewpoints, the alkylene group represented by ^REE1 is 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 ^REE1 .

In the general formula (EE), as the alkylene group represented by ^REE2 , an alkylene group having 3 or more and 10 or less carbon atoms is preferable, and an alkylene group having 3 or more and 6 or less carbon atoms is more preferable. The alkylene group represented by ^REE2 may be linear, branched, or cyclic, but linear is preferable.
When the number of carbon atoms of the alkylene group represented by ^REE2 is 3 or more, the decrease in fluidity of the resin composition is suppressed, and thermoplasticity is easily exhibited. When the carbon number of the alkylene group represented by ^REE2 is 10 or less or the alkylene group represented by ^REE2 is linear, the affinity with cellulose acylate tends to increase. Therefore, if the alkylene group represented by ^REE2 is linear and the number of carbon atoms is within the above range, the moldability of the resin composition is improved.
From these viewpoints, in ^particular, alkylene ^{group R EE2} represent may, n- butylene _{(- (CH 2) 4 -} ) is preferred. In other words, a polyether ester ^compound, as ^{R EE2} n-butylene _{(- (CH 2) 4 -} ) is preferably a compound represented the.

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. The alkyl group represented by A ^EE1 and ^AEE2 may be linear, branched, or cyclic, but branched is preferable.
The aryl group represented by A ^EE1 and ^AEE2 is an aryl group having 6 to 12 carbon atoms, and is an unsubstituted aryl group such as a phenyl group or a naphthyl group, or a substituted phenyl such as a t-butylphenyl group or a hydroxyphenyl group. The group is mentioned.
A ^EE1, and aralkyl group represented by ^{A EE2,} a group represented by -R A -Ph. ^RA represents a linear or branched alkylene group having 1 or more and 6 or less carbon atoms (preferably 2 or more and 4 or less carbon atoms). Ph represents an unsubstituted phenyl group or a substituted phenyl group substituted with a linear or branched alkyl group having 1 or more and 6 or less carbon atoms (preferably 2 or more and 6 or less carbon atoms). Specifically, as the aralkyl group, for example, an unsubstituted aralkyl group such as a benzyl group, a phenylmethyl group (phenethyl group), a phenylpropyl group or a phenylbutyl group, or a substitution of a methylbenzyl group, a dimethylbenzyl group, a methylphenethyl group or the like. Aralkill group can be mentioned.

At least one of A ^EE1 and A ^EE2 preferably represents 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} ( It is preferably a compound representing a phenyl group) or an arylyl group.

Next, the characteristics of the polyether ester compound will be described.

The weight average molecular weight (Mw) of the polyether ester compound is preferably 450 or more and 650 or less, and more preferably 500 or more and 600 or less.
When the weight average molecular weight (Mw) is 450 or more, bleeding (precipitation phenomenon) becomes difficult. When the weight average molecular weight (Mw) is 650 or less, the affinity with cellulose acylate tends to increase. Therefore, when the weight average molecular weight (Mw) is set in the above range, the moldability of the resin composition is improved.
The weight average molecular weight (Mw) of the polyether ester compound is a value measured by gel permeation chromatography (GPC). Specifically, for the molecular weight measurement by GPC, an HPLC1100 manufactured by Tosoh Corporation was used as a measuring device, and a column TSKgel GMHHR-M + TSKgel GMHR-M (7.8 mm ID 30 cm) manufactured by Tosoh Corporation was used. , Chloroform solvent. Then, the weight average molecular weight is calculated from this measurement result using a molecular weight calibration curve prepared from 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, the dispersibility in cellulose acylate is likely to be improved. When the viscosity is 50 mPa · s or less, the anisotropy of the dispersion of the polyether ester compound is less likely to appear. Therefore, when the viscosity is set in the above range, the moldability of the resin composition is improved.
The viscosity is a value measured by an E-type viscometer.

The solubility parameter (SP value) of the polyether ester compound is preferably 9.5 or more and 9.9 or less, and more preferably 9.6 or more and 9.8 or less.
When the solubility parameter (SP value) is 9.5 or more and 9.9 or less, the dispersibility in cellulose acylate is likely to be improved.
The solubility parameter (SP value) is a value calculated by Fedor's method. Specifically, the solubility parameter (SP value) is, for example, Polym. Eng. Sci. , Vol. 14, p. Based on the description of 147 (1974), the SP value is calculated by the following formula.
Formula: SP value = √ (Ev / v) = √ (ΣΔei / ΣΔvi)
(In the formula, 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)
As the solubility parameter (SP value), (cal / cm ³ ) ^1/2 is adopted as the unit, but the unit is omitted according to the practice and is expressed dimensionlessly.

Hereinafter, specific examples of the polyether ester compound will be shown, but the present invention is not limited to this.

The content of the plasticizer in the resin composition according to the present embodiment is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, based on the total mass of the resin composition. When the ratio of the plasticizer is in the above range, the elasticity becomes higher and the heat resistance becomes higher. Bleed of the plasticizer is also suppressed.

<Other ingredients>
Other components include, for example, flame retardants, compatibilizers, antioxidants, mold release agents, lightfasteners, weatherproofing agents, colorants, pigments, modifiers, drip inhibitors, antistatic agents, antioxidants. , Fillers, reinforcing agents (glass fiber, carbon fiber, talc, clay, mica, glass flakes, milled glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, etc.) and the like. The content of these components is preferably 0% by mass or more and 5% by mass or less with respect to the entire resin composition. Here, "0% by mass" means that it does not contain other components.

(Other resins)
The resin composition according to the present embodiment may contain a resin other than the cellulose acylate and the copolymer. However, the other resin is preferably 5% by mass or less, more preferably 1% by mass, and particularly preferably not containing other resin with respect to the total mass of the resin composition.
Examples of other resins include conventionally known thermoplastic resins, and specifically, polycarbonate resin; polypropylene resin; polyester resin; polyolefin resin; polyester carbonate resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; Polyether sulfone resin; Polyarylene resin; Polyetherimide resin; Polyacetal resin; Polypolyacetal resin; Polyketone resin; Polyetherketone resin; Polyetheretherketone resin; Polyarylketone resin; Polyethernitrile resin; Liquid crystal resin; Polybenz Imidazole resin; polyparavanic acid resin; vinyl obtained by polymerizing or copolymerizing one or more vinyl monomers selected from the group consisting of aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters, and vinyl cyanide compounds. System polymer or copolymer resin; Diene-aromatic alkenyl compound copolymer resin; Vinyl cyanide-diene-aromatic alkenyl compound copolymer resin; Aromatic alkenyl compound-diene-vinyl cyanide-N-phenylmaleimide Copolymer resins; vinyl cyanide- (ethylene-diene-propylene (EPDM)) -aromatic alkenyl compound copolymer resins; vinyl chloride resins; chlorinated vinyl chloride resins; and the like. These resins may be used alone or in combination of two or more.

[Manufacturing method of resin composition]
The method for producing a resin composition of the present embodiment includes a step of preparing a resin composition containing the cellulose acylate and the copolymer.
The resin composition according to the present embodiment is produced by melt-kneading a mixture containing, for example, cellulose acylate and, if necessary, a plasticizer, other components, and the like. In addition, the resin composition according to the present embodiment can also be produced, for example, by dissolving the above components in a solvent.
Examples of the means for melt-kneading include known means, and specific examples thereof include a twin-screw extruder, a Henschel mixer, a Banbury mixer, a single-screw screw extruder, a multi-screw screw extruder, and a conider.
The temperature at the time of kneading may be determined according to the melting temperature of the cellulose acylate used, but 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 higher. More preferably, it is below ° C.

[Resin molded product and its manufacturing method]
The resin molded product according to the present embodiment contains a cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less, and a content Ma of a structural unit represented by the following formula (a) contained in the copolymer and the following formula. It contains a resin obtained by reacting an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 4 or more and 10 or less with 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 preferred embodiments of the cellulose acylate and the copolymer in the resin molded product according to the present embodiment are the same as the preferred embodiments of the cellulose acylate and the copolymer in the resin composition according to the present embodiment. 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, and the cellulose acylate and the copolymer react to form a resin.
Moreover, it is preferable that the method for producing a resin molded product according to the present embodiment includes a step of molding the resin composition according to the present embodiment.
As the molding method, for example, injection molding, extrusion molding, blow molding, hot press molding, calender molding, coating molding, cast molding, dipping molding, vacuum molding, transfer molding and the like may be applied.

The method for producing a resin molded product according to the present embodiment preferably performs injection molding because it has a high degree of freedom in shape. For injection molding, a molded product is obtained by heating and melting the resin composition, pouring it into a mold, and solidifying it. It may be molded 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. Injection molding is performed using commercially available equipment such as NEX500 manufactured by Nissei Resin Industry Co., Ltd., NEX150 manufactured by Nissei Resin Industry Co., Ltd., NEX70000 manufactured by Nissei Resin Industry Co., Ltd., SE50D manufactured by Toshiba Machine Co., Ltd. May be good.

The resin molded product 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, housings for electronic / electrical equipment and home appliances; various parts for electronic / electrical equipment and home appliances; interior parts for automobiles; storage cases for CD-ROMs and DVDs; tableware; beverage bottles; food trays Wrap material; film; sheet; etc.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by mass".

<Synthesis of cellulose acylate>
(Synthesis of Cellulose Acetate CA1)
Acetylation: 3 parts of cellulose powder (manufactured by Nippon Paper Chemical Co., Ltd., KC Flock W50), 0.15 parts 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.
Deacetylase and low molecular weight: Immediately after stirring is completed, 3 parts of acetic acid and 1.2 parts of pure water are added to the acetylated solution, and after stirring at 20 ° C. for 30 minutes, a 0.2 M hydrochloric acid aqueous solution 4.5 The portion was added, and the mixture was heated to 75 ° C. and stirred for 5 hours. This solution was added dropwise to 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.
Cleaning: The obtained white powder was washed with pure water using a filter press (manufactured by Kurita Kikai Seisakusho Co., Ltd., SF (PP)) until the conductivity became 50 μS or less, and then dried.
Post-treatment: 0.2 parts of calcium acetate and 30 parts of pure water are added to 3 parts of the dried white powder, stirred at 25 ° C. for 2 hours, filtered, and the obtained powder is filtered at 60 ° C. for 72 hours. It was dried to obtain 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 0.15 and 0.30.

(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 0.15 parts to 0.03 parts.

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

(Synthesis of Cellulose Acetate CA5)
Cellulose acetate CA5 was obtained in the same manner as CA1 except that the mixture was stirred at 75 ° C. for 5 hours in deacetylation and reduced molecular weight, except that the mixture was stirred at 65 ° C. for 7 hours.

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

(Synthesis of Cellulose Propionate CP1)
Cellulose pro in the same manner as CA1 except that 2 parts of acetic anhydride was used for acetylation, and 2.5 parts of propionic anhydride was used, and the reaction time for deacetylation and low molecular weight reduction was changed from 5 hours to 7 hours. Obtained Pionate CP1.

(Preparation of Cellulose Acetate CA7-1 to 3)
Commercially available cellulose acetate (manufactured by Daicel Co., Ltd., L50) is cellulose acetate CA7-1, (manufactured by Daicel Co., Ltd., L20) is cellulose acetate CA7-2, (Eastman Chemical Co., Ltd., CA398-3) is CA7. Prepared as -3.

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

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

<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 polystyrene conversion using a GPC device (manufactured by Tosoh Corporation, HLC-8320GPC, column: TSKgelα-M) using a dimethylacetamide / lithium chloride = 90/10 solution. ..
Next, the degree of polymerization of cellulose acylate can be 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 degree of substitution is 2.4 with an acetyl group, and 287 when the degree of substitution is 2.9. Table 1 summarizes the results of evaluating the degree of polymerization and the degree of substitution of the cellulose acylate synthesized by this method.

<Synthesis of ethylene- (meth) acrylate-glycidyl methacrylate copolymer>
(Preparation of EAG1 to 3)
Arkema's LOTADER AX8930 (EAG1), Sumitomo Chemical's Bond First BF-7M (EGA2), and Arkema's LOTDER AX8900, which are commercially available ethylene- (meth) acrylate-glycidyl methacrylate copolymers It was designated as EGA3).

(Synthesis of EAG4)
72 parts by mass of ethylene monomer, 20 parts by mass of methyl acrylate, and 8 parts by mass of glycidyl methacrylate monomer were dissolved in tetrahydrofuran, 0.05 part by mass of azobisisobutyronitrile was added, and the mixture was stirred at 40 ° C. for 24 hours and obtained as pure. The mixture was added dropwise to water, and the resulting precipitate was filtered and dried to obtain an ethylene-methylmethacrylate-glycidylmethacrylate copolymer (EAG4).

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

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

<Preparation of adipate-containing compound>
A commercially available adipate-containing compound (Daifatity101, manufactured by Daihachi Chemical Industry Co., Ltd.) was prepared as compound AE1.

<Evaluation of impact resistance and flexural modulus>
A resin composition (pellets) was obtained by kneading with a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., TEX41SS) at a cylinder temperature A at the charged composition ratio shown in Table 3.
Comparative Examples 7 and 8 were kneaded with the composition of Example 1 or 3 described in JP-A-2014-084343 to obtain pellets.
Specifically, in Comparative Example 7, 25 parts by mass of an adipate ester-containing compound (Daifacy101 manufactured by Daihachi Chemical Industry Co., Ltd.) was added to 100 parts by mass of cellulose acetate CA7-1 (manufactured by Daicel Corporation, L50). 14 parts by mass of Paraloid (registered trademark) EXL-2602 (core / shell type graft copolymer composed of butadiene-methylmethacrylate copolymer) manufactured by Roam & Haas Co., Ltd. was used.
In Comparative Example 8, 25 parts by mass of triphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.) and Rohm and Haas were added to 100 parts by mass of cellulose acetate CA7-1 (manufactured by Daicel Co., Ltd., L50). 14 parts by mass of Paraloid (registered trademark) EXL-2602 (core / shell type graft copolymer composed of butadiene-methylmethacrylate copolymer) was used.

For the obtained pellets, use an injection molding machine (NEX140III manufactured by Nissei Resin Industry Co., Ltd.) at a cylinder temperature B where the injection peak pressure does not exceed 180 MPa, and an ISO multipurpose dumbbell (measurement part dimensions: width 100 mm x thickness 40 mm). ) Was molded.
The cylinder temperatures A and B are shown in Table 3.
Using the obtained ISO multipurpose dumbbell test piece, it is processed into a notched impact test piece by a method conforming to ISO179, and it is processed by an impact strength measuring device (Charpy Auto Impact Tester CHN3 type manufactured by Toyo Seiki Seisakusho Co., Ltd.). , Notched impact strength at 23 ° C. was measured. The results are shown in Table 3.
In addition, a universal test device (manufactured by Shimadzu Corporation, Autograph AG-Xplus) was used to measure the flexural modulus by a method conforming to ISO-178. The results are shown in Table 3.

From the above results, it can be seen that the resin composition of this example can obtain a resin molded product having excellent impact resistance and a high flexural modulus as compared with the resin composition of the comparative example.

Claims (11)

Cellulose acylate with a weight average molecular weight of 30,000 or more and 90,000 or less, and
When the mass ratio Ma / Mb of the content Ma of the structural unit represented by the following formula (a) and the content Mb of the structural unit represented by the following formula (b) contained in the copolymer is 5 or more and 10 or less. A resin composition comprising a 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 the degree of substitution of the cellulose acylate is 2.0 or more and 2.5 or less. The resin composition according to any one of claims 1 to 3, wherein the cellulose acylate has at least an acetyl group. The resin composition according to any one of claims 1 to 4, wherein the 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 adipate-containing compound. A resin molded product obtained by molding the resin composition according to any one of claims 1 to 6. The resin molded product according to claim 7, wherein the resin molded product is an injection molded product obtained by injection molding the resin composition. Cellulose acylate having a weight average molecular weight of 30,000 or more and 90,000 or less, and the content Ma of the constituent unit represented by the following formula (a) and the constituent unit represented by the following formula (b) contained in the copolymer. A resin molded product containing a resin obtained by reacting an olefin- (meth) acrylate-glycidyl methacrylate copolymer having a mass ratio Ma / Mb of 5 or more and 10 or less with 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 9 , wherein the olefin- (meth) acrylate-glycidyl methacrylate copolymer is an ethylene- (meth) acrylate-glycidyl methacrylate copolymer. The resin molded product according to claim 9 or 10, wherein the resin molded product is an injection molded product.