JP2011162695A - Resin composition, molded article, manufacturing method therefor, and box body for electric/electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having molding processability, rigidity, heat-resistance, impact-resistance and excellent repeating impact characteristic of flexural strength. <P>SOLUTION: The resin composition contains an imide based compound represented by formula (I) and a cellulose ester based resin. Wherein R<SP>1</SP>and R<SP>2</SP>each independently represents a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R<SP>1</SP>and R<SP>2</SP>may have a substituent and may further contain one or more of divalent groups selected from -O-, -S-, -NR<SP>4</SP>-, -CO-, -SO<SB>2</SB>- and a divalent group obtained by combining these (R<SP>4</SP>represents a hydrogen atom or a hydrocarbon group which may have a substituent, and when a plurality of R<SP>4</SP>s are present, they may be same or different). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition, a molded body, a method for producing the same, and a casing for electrical and electronic equipment.

Various materials are used for members constituting electric and electronic devices such as copiers and printers in consideration of characteristics and functions required for the members. For example, PC (Polycarbonate), ABS (Acrylonitrile-butadiene-styrene) resin, PC / ABS, etc. are generally used as a member (housing) that stores a drive machine for electrical and electronic equipment and protects the drive machine. In large amounts (Patent Document 1). These resins are produced by reacting compounds obtained from petroleum as a raw material.
By the way, fossil resources such as oil, coal, and natural gas are mainly composed of carbon that has been fixed in the ground for many years. When such fossil resources or products made from fossil resources are burned and carbon dioxide is released into the atmosphere, carbon that was originally not deep in the atmosphere but fixed deep in the ground Is rapidly released as carbon dioxide, and carbon dioxide in the atmosphere greatly increases, which causes global warming. Therefore, polymers such as ABS and PC made from petroleum, which is a fossil resource, have excellent characteristics as materials for electrical and electronic equipment, but are made from petroleum, which is a fossil resource. Therefore, it is desirable to reduce the amount used from the viewpoint of preventing global warming.
On the other hand, a plant-derived resin is originally produced by a photosynthesis reaction using carbon dioxide and water in the atmosphere as raw materials. Therefore, even if plant-derived resin is incinerated to generate carbon dioxide, the carbon dioxide is equivalent to carbon dioxide originally in the atmosphere, so the balance of carbon dioxide in the atmosphere is plus or minus zero After all, there is an idea that the total amount of CO _{2 in} the atmosphere is not increased. Based on this idea, plant-derived resins are referred to as so-called “carbon neutral” materials. The use of carbon-neutral materials in place of petroleum-derived resins is an urgent need to prevent global warming in recent years.
For this reason, in PC polymer, the method of reducing petroleum origin resources is proposed by using plant origin resources, such as starch, as some raw materials derived from petroleum (patent documents 2).
However, further improvements are required from the perspective of aiming for a more complete carbon neutral material.

  Cellulose is currently attracting a great deal of attention as a biomass material reproducible on the earth obtained from plants and as a biodegradable material in the environment. Cellulose is not only used for paper, but also cellulose derivatives, for example, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, etc. are used as film materials and the like.

JP-A-56-55425 JP 2008-24919 A

The inventors of the present invention focused on using cellulose as a carbon neutral resin. However, since cellulose generally does not have thermoplasticity, it is difficult to mold by heating or the like, and thus is not suitable for molding. Further, even if thermoplasticity can be imparted, there is a problem that strength such as impact resistance is greatly reduced.
In addition, since the cellulose ester-based resin has high water absorption, when it is made into a film, the moisture permeability of the film becomes high, and improvement is necessary from the viewpoint of dimensional stability. A film having a low Rth (retardation in the film thickness direction) is also required from the viewpoint that the optical properties do not change.

  The objective of this invention is providing the novel resin composition which can be used for various uses. In particular, to provide a resin composition excellent in moldability (flow characteristics) and excellent in terms of rigidity (flexural modulus), heat resistance (deflection temperature under load), and impact resistance (Charpy impact strength). It is. Another object of the present invention is to provide a molded body obtained by molding the resin composition, a method for producing the molded body, and a casing for electric and electronic equipment composed of the molded body. .

The present inventors have found that the above problems can be solved by a resin composition containing a cellulose ester resin and a specific imide compound, and have completed the present invention.
That is, the said subject can be achieved by the following means.

1.
The resin composition containing the imide type compound represented by the following general formula (I), and a cellulose-ester type resin.

(In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. R ¹ and R ² further have a substituent. Or a divalent group obtained by combining —O—, —S—, —NR ⁴ —, —CO—, —SO ₂ —, and a combination thereof (R ⁴ represents a hydrogen atom or a substituent). Represents a hydrocarbon group that may be present, provided that when a plurality of R ⁴ are present, they may be the same or different. One or more groups may be included.)
2.
2. The resin composition according to 1 above, wherein the content of the imide compound represented by the general formula (I) is 40% by mass or less based on the total solid content of the resin composition.
3.
The cellulose ester-based resin is at least one selected from the group consisting of cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose propionate butyrate, 3. The resin composition according to 1 or 2.
4).
4. The resin composition according to any one of 1 to 3 above, wherein the cellulose ester resin is cellulose acetate.
5.
5. The resin composition according to any one of 1 to 4, wherein the cellulose ester resin has an acyl substitution degree of 2.7 or less.
6).
The molded object obtained by heat-molding the resin composition in any one of said 1-5.
7).
The manufacturing method of a molded object including the process of heating and molding the resin composition in any one of said 1-5.
8).
A housing for electrical and electronic equipment, comprising the molded article according to 6 above.

  Since the resin composition of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Moreover, the film obtained using the resin composition of this invention is excellent in terms of optical characteristics and moisture permeability. In addition, the resin composition of the present invention is excellent in terms of moldability, rigidity, heat resistance, impact resistance, and in addition to the film, for example, components such as automobiles, home appliances, electrical and electronic devices, mechanical parts, It can be suitably used as a house / building material. Moreover, since the resin composition of this invention uses the cellulose ester-type resin obtained from the cellulose which is resin derived from a plant, it can substitute for conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.

  The resin composition of the present invention contains an imide compound represented by the following general formula (I) and a cellulose ester resin.

(In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. R ¹ and R ² further have a substituent. Or a divalent group obtained by combining —O—, —S—, —NR ⁴ —, —CO—, —SO ₂ —, and a combination thereof (R ⁴ represents a hydrogen atom or a substituent). Represents a hydrocarbon group that may be present, provided that when a plurality of R ⁴ are present, they may be the same or different. One or more groups may be included.)

1. Imide compound represented by general formula (I) The resin composition of the present invention contains an imide compound represented by the following general formula (I).

(In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. R ¹ and R ² further have a substituent. Or a divalent group obtained by combining —O—, —S—, —NR ⁴ —, —CO—, —SO ₂ —, and a combination thereof (R ⁴ represents a hydrogen atom or a substituent). Represents a hydrocarbon group that may be present, provided that when a plurality of R ⁴ are present, they may be the same or different. One or more groups may be included.)

Since the imide compound represented by the general formula (I) has an imide moiety and the imide moiety and the cellulose ester resin can interact with each other, the effects of improving heat resistance and impact resistance are achieved. I think that.
As represented by the above general formula (I), the imide moiety at both ends of the rigid structure imide compound directly bonded by a benzene ring interacts with the carbonyl group or hydroxyl group of the cellulose ester, resulting in heat resistance. It is considered that an extremely high effect can be obtained with respect to the impact resistance.

When at least one of R ¹ and R ² represents an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have an unsaturated bond. . Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. The aliphatic hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and still more preferably an alkyl group having 2 to 20 carbon atoms, for the purpose of improving impact resistance. Particularly preferred is an alkyl group having 2 to 15 carbon atoms, and most preferred is an alkyl group having 2 to 12 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group, octyl group, nonyl group Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, stearyl group and the like, and ethyl group, 2-ethylhexyl group, octyl group and dodecyl group are particularly preferable.

When at least one of R ¹ and R ² represents an aromatic hydrocarbon group, the aromatic hydrocarbon group may be either a single ring or a condensed ring. As an aromatic hydrocarbon group, Preferably it is a C6-C18 aromatic hydrocarbon group, More preferably, it is a C6-C14 aromatic hydrocarbon group, More preferably, it is C6-C10. It is an aromatic hydrocarbon group. Specific examples include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, and the like. A phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

When R ¹ and R ² represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, each of the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. Substituents include halogen atoms (eg, chlorine, bromine, fluorine and iodine), alkyl groups, halogenated alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and acyloxy groups. Sulfonylamino group, hydroxy group, cyano group, amino group, acylamino group and the like. The substituent is preferably an alkyl group, an aryl group, an alkoxy group, or a morpholyl group. 1-30 are preferable and, as for carbon number of this substituent, 1-20 are more preferable.

Further, when R ¹ and R ² represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, —O—, —S—, —NR ⁴ —, —CO—, —SO ₂ — is included in the chain. , and divalent groups obtained by combining these ^{(e.g., -COO -, - NR 4 CO} -, - NR 4 COO -, - NR 4 CONR 4 -, - SO 2 NR 4 -) (R 4 is hydrogen Represents a hydrocarbon group optionally having an atom or a substituent, provided that when a plurality of R ⁴ are present, they may be the same or different. One or more divalent groups selected from the group may be contained.
R ⁴ preferably represents a linear, branched or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the linear, branched substituted or unsubstituted aliphatic hydrocarbon group has 1 to Thirty alkyl groups are preferred. For example, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, trifluoromethyl group, 2-methoxyethyl group, A 2-hydroxyethyl group, a 3-dimethylaminopropyl group, and a 2-ethylhexyl group can be exemplified, and an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable.
As the cyclic aliphatic hydrocarbon group, a cycloalkyl group having 3 to 30 carbon atoms is preferable. Examples thereof include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group, and more preferably a cycloalkyl group having 6 to 8 carbon atoms.
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. More preferably, they are a phenyl group and a p-tolyl group.

  Although the preferable specific example of the imide type compound represented by general formula (I) in this invention is shown below, it is not limited to these.

  The imide compound represented by the general formula (I) in the present invention can be produced by a known method. For example, dehydration condensation reaction between carboxylic acids and amines using a condensing agent (such as dicyclohexylcarbodiimide (DCC)), substitution reaction between carboxylic acid chloride derivatives and amine derivatives, reaction between carboxylic acid anhydrides and amine derivatives Etc.

  200-1000 are preferable and, as for the molecular weight of the imide type compound represented by general formula (I) in this invention, 300-800 are more preferable.

  The content of the imide compound represented by the general formula (I) in the resin composition of the present invention is preferably 40% by mass or less, more preferably 1 to 40% by mass, based on the total solid content. -35 mass% is still more preferable, and 10-30 mass% is especially preferable. Within the above range, more excellent moldability, bending elastic modulus, heat resistance, and impact resistance can be obtained.

  When the resin composition of the present invention is formed into a film and used as a film, the content of the imide compound represented by the general formula (I) in the resin composition of the present invention is the total solid content of the resin composition. Is preferably 30% by mass or less, more preferably 1 to 25% by mass, still more preferably 2 to 22% by mass, and particularly preferably 3 to 20% by mass. Within the above range, more excellent optical characteristics and moisture permeability can be obtained.

2. Cellulose ester resin The resin composition of the present invention contains a cellulose ester resin.
The cellulose ester resin in the present invention is not particularly limited. Cellulose esters are usually produced by esterifying cellulose such as wood pulp (conifer pulp, hardwood pulp) and cotton linter pulp.

  The cellulose ester-based resin can be produced by a conventional esterification method in which cellulose is reacted with an acylating agent, and can be produced through a saponification or aging step as necessary. Cellulose ester resins are generally prepared by activating pulp (cellulose) with an activating agent (activation step), and then preparing an ester (such as a triester) with an acylating agent using a catalyst such as sulfuric acid (acyl). Saponification step), saponification (hydrolysis) and aging to adjust the degree of esterification (saponification and aging step). In the case of cellulose acetate, it can be produced by a conventional method such as a sulfuric acid catalyst method, an acetic acid method, or a methylene chloride method.

  The ratio of the acylating agent in the acylation step can be selected within a range where the desired degree of acylation (eg, degree of acetylation) can be selected. For example, 230 to 300 parts by weight, preferably 240 parts per 100 parts by weight of pulp (cellulose). It is about 290 mass parts, More preferably, it is about 250-280 mass parts. In the case of cellulose acetate, for example, acetic anhydride can be used as the acylating agent.

As the acylation or aging catalyst, sulfuric acid is usually used. The usage-amount of a sulfuric acid is 0.5-15 mass parts normally with respect to 100 mass parts of cellulose, Preferably it is 5-15 mass parts, More preferably, it is about 5-10 mass parts. The saponification / ripening temperature can be selected from the range of 40 to 160 ° C, and is, for example, about 50 to 70 ° C.
Furthermore, in order to neutralize the remaining sulfuric acid, it may be treated with an alkali.

Examples of the cellulose ester resin include organic acid esters [cellulose acetate (cellulose acetate), cellulose propionate, cellulose C _2-6 carboxylates such as cellulose butyrate, etc.], mixed esters (cellulose acetate propionate, Cellulose di-C _2-6 carboxylic acid ester such as cellulose acetate butyrate), grafted body (polycaprolactone grafted cellulose acetate etc.), inorganic acid ester (cellulose nitrate, cellulose sulfate, cellulose phosphate etc.), organic acid / inorganic Examples include acid mixed esters (such as cellulose nitrate acetate).
In the present invention, among these cellulose esters, a cellulose organic acid ester modified with an organic acid is preferable, and a cellulose organic acid ester modified with an organic acid having 2 to 12 carbon atoms is more preferable. Specifically, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, cellulose propionate butyrate and the like are preferable, cellulose acetate, cellulose propionate, Cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose propionate butyrate are more preferable, cellulose acetate is more preferable, and cellulose diacetate and cellulose triacetate are particularly preferable.

The acyl substitution degree of the cellulose ester is preferably 2.7 or less, more preferably 2.65 or less, and even more preferably 2.6 or less from the viewpoint of impact resistance. The acyl substitution degree is preferably 1 to 2.7, more preferably 1.3 to 2.65, and still more preferably 1.5 to 2.6.
In the case of cellulose acetate, it can be selected from the range of an average degree of acetylation of about 30 to 62.5%, and usually an average degree of acetylation of 43.7 to 62.5% (average substitution degree of acetyl group of 1.7 to 3), Preferably it is 45-62.5% (average substitution degree 1.8-3), More preferably, it is about 48-62.5% (average substitution degree 2-3).

  The polymerization degree of the cellulose ester is not particularly limited, and is a viscosity average polymerization degree of 200 to 400, preferably 250 to 400, and more preferably about 270 to 350.

  The cellulose ester resin in the present invention can be produced by a known method. Moreover, a commercial item can also be used. For example, as cellulose acetate propionate, “482-20 (acetyl substitution degree: 0.1, propionyl substitution degree: 2.5, Mn: 73000, Mw: 234000)” manufactured by Eastman Chemical Co., Ltd. is cellulose diacetate. As a product made by Daicel Chemical Industries, Ltd., “L-70 (acetyl substitution degree: 2.45, Mn: 65000, Mw: 200000)” and cellulose triacetate, Daicel Chemical Industries, “FRM (acetyl substitution degree: 2.79, Mn: 66000, Mw: 186000) ".

  The content of the cellulose ester resin contained in the resin composition of the present invention is not particularly limited. Preferably, the cellulose ester-based resin is contained in an amount of 50 to 95% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 85% by mass with respect to the total solid content of the resin composition.

  In addition, when the resin composition of the present invention is used as a film after forming a film, the content of the cellulose ester resin contained in the resin composition is preferably 50 to 95% by mass with respect to the total solid content. More preferably, it contains 55-95 mass%, More preferably, it contains 60-90 mass%.

3. Flame retardant The resin composition of the present invention may contain a flame retardant. By containing a flame retardant, a flame retardant effect such as reduction or suppression of the combustion rate can be improved.
The flame retardant is not particularly limited, and a conventional flame retardant can be used. For example, nitrogen compound flame retardants, inorganic flame retardants, halogen flame retardants, phosphorus flame retardants, silicon flame retardants and the like can be mentioned. In the present invention, a flame retardant containing at least one selected from the group consisting of halogen, phosphorus, and silicon is preferable because it prevents the impact resistance from decreasing.
As the flame retardant containing halogen, a brominated flame retardant and a chlorine based flame retardant are particularly preferable.
The halogen-based flame retardant preferably has a halogen content in the compound of 20% or more of the molecular weight of the compound. Such a specific halogen compound can improve the flame retardancy. Furthermore, since the halogen content in the compound is 20% or more of the molecular weight of the compound, hydrogen halide is generated during the mixing with the cellulose ester resin or in the molding process to generate hydrogen halide, which corrodes the processing machine or the mold. Or worsen the work environment.
The halogen content in the halogen-based flame retardant is preferably 20% or more of the molecular weight of the compound, but more preferably 95% or less from the viewpoint of solvent resistance in addition to suppression of volatility. More preferably, it is 30 to 90%, Especially preferably, it is 40 to 85%, Most preferably, it is 50 to 85%.

  Examples of the halogen-based flame retardant include a fluorine-containing compound, a chlorine-containing compound, a bromine-containing compound, and the like. From the viewpoint of flame retardancy, a chlorine-containing compound and a bromine-containing compound are preferable, and a bromine-containing compound is particularly preferable.

Examples of the fluorine-containing compound include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / fluoropropylene copolymer. Moreover, the copolymer of a fluorine-containing monomer and the various monomer copolymerizable with this monomer can also be used.
Examples of the chlorine-containing compound include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, tetrachlorophthalic anhydride, and chlorine-containing phosphate.

  Examples of bromine-containing compounds include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, tetrabromophthalate ester, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, Ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris (2, 3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobi Phenol-A, tetrabromobisphenol A or a derivative thereof, tetrabromobisphenol A epoxy oligomer or polymer, brominated epoxy oligomer or polymer such as brominated phenol novolac epoxy, tetrabromobisphenol A carbonate oligomer or polymer, tetrabromobisphenol-A- Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (Tribromoneopentyl) phosphate, poly (pentabromobenzyl) acrylate, octabromotrimethylphenylindane, dibromo Opentyl glycol, pentabromobenzyl polyacrylate and its reactant, dibromocresyl glycidyl ether, N, N′-ethylene-bis-tetrabromoterephthalimide, brominated triazine, tribromostyrene and its reactant, tribromophenylmaleimide And reactants thereof.

  Among the above halogen flame retardants, preferred are tetrabromobisphenol A, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A carbonate oligomer, tribromophenyl allyl ether, hexabromocyclododecane, ethylenebistetrabromophthalimide, bromine. Polystyrene, decabromodiphenyl oxide, octabromodiphenyl oxide, brominated triazine, ethylenebispentabromodiphenyl, tetrabromophthalate ester, poly (pentabromobenzyl) acrylate, polydibromophenylene oxide, brominated epoxy oligomer, tribromostyrene and Its reactant, tribromophenylmaleimide and its reactant, pentabromobenzyl acrylate and Reactants, chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane and chlorendic acid and chlorine-containing phosphoric acid esters. More preferable examples include tetrabromobisphenol A, decabromodiphenyl ether, tetrabromobisphenol A oligomer, hexabromocyclododecane, tetrabromobisphenol A carbonate oligomer, chlorinated paraffin, perchlorocyclopentadecane, and chlorendic acid.

  In the present invention, hydrogen halide is not generated by thermal decomposition at the time of compounding or molding with a cellulose ester resin, and does not corrode processing machines or molds, and does not deteriorate the working environment. Phosphorus-containing flame retardants and silicon-containing flame retardants are preferred because halogens are scattered during incineration and are less likely to cause adverse effects on the environment due to the generation of harmful substances such as dioxins. A flame retardant containing phosphorus is more preferable because it prevents a decrease in rate and impact resistance.

  The phosphorus-containing flame retardant is not particularly limited, and a commonly used one can be used. Examples thereof include organic phosphorus compounds such as phosphate esters, phosphate condensation esters, and polyphosphates.

  Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) Phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl Acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl Examples include 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate be able to.

  Examples of phosphoric acid condensed esters include resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. Aromatic phosphoric acid condensed ester and the like.

  Moreover, the polyphosphate which consists of a salt of phosphoric acid, polyphosphoric acid, a periodic table group 1-14 group metal, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.

In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and structures in which a phosphorus atom and a nitrogen atom are connected by a double bond Phosphazene compounds having phosphoric acid and phosphoric ester amides.
These phosphorus-containing flame retardants may be used singly or in combination of two or more.

  Examples of the silicon-containing flame retardant include an organic silicon compound having a two-dimensional or three-dimensional structure, polydimethylsiloxane, or a methyl group at a side chain or a terminal of polydimethylsiloxane, a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, Examples thereof include those substituted or modified with an aromatic hydrocarbon group, so-called silicone oils, or modified silicone oils.

Examples of the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group include an alkyl group, a cycloalkyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, a polyether group, a carboxyl group, a mercapto group, Examples include a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group.
These silicon-containing flame retardants may be used alone or in combination of two or more.

  Examples of the flame retardant other than the phosphorus-containing flame retardant or the silicon-containing flame retardant include, for example, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, Metastannic acid, tin oxide, tin oxide salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, tungsten Inorganic flame retardants such as acid metal salts, complex oxides of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, and swellable graphite can be used. . These other flame retardants may be used alone or in combination of two or more.

  The flame retardant in the present invention can be produced by a known method. Moreover, a commercial item can also be used. For example, “X-22-343, reactive silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)” as a silicon-containing flame retardant, and “PX-200, 1,3-phenylenebis (di-2,6) as a phosphorus-containing flame retardant. -Xylenyl phosphate) (manufactured by Daihachi Chemical).

  When the resin composition of the present invention contains a flame retardant, the content is not limited, but is preferably 30% by mass or less, more preferably 2 to 10% by mass, based on the total solid content of the resin composition. By setting it as this range, impact resistance, brittleness, etc. can be improved, or generation | occurrence | production of pellet blocking can be suppressed.

4). Plasticizer The resin composition of the present invention may contain a plasticizer. Thereby, a moldability can be improved further. As the plasticizer, those commonly used for polymer molding can be used. For example, phosphate esters such as triphenyl phosphate (TPP) and tricresyl phosphate (TCP), dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), di-2- Phthalic acid esters such as ethylhexyl phthalate (DEHP), fatty acid esters such as butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, citrate esters such as acetyl tributyl citrate (OACTB), trimellitic acid esters, polyester plasticizers Glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers and epoxy plasticizers.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 -Polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Tributyl ester such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid Adipic acid esters such as benzylbutyl diglycol, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacin Dibutyl, and include di-2-ethylhexyl sebacate and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and bisphenols. And a polyalkylene glycol such as a propylene oxide addition polymer, a tetrahydrofuran addition polymer of bisphenol, or a terminal epoxy-modified compound thereof, a terminal ester-modified compound, a terminal ether-modified compound, and the like.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxy acid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, and various sorbitols.

  When the resin composition of this invention contains a plasticizer, 1 type or 2 types or more may be sufficient, and the content is 30 mass% or less with respect to the total solid of a resin composition, 0.005- 20 mass% is more preferable, More preferably, it is 0.01-10 mass%.

5. Compatibilizer The resin composition of the present invention preferably further contains a compatibilizer. The compatibilizing agent is used to compatibilize the cellulose ester resin in the present invention and the imide compound represented by the general formula (I). When a compatibilizing agent is added to the resin composition of the present invention, the dispersibility of the imide compound represented by the general formula (I) with respect to the cellulose ester resin is further improved, and the fluidity (molding processability) of the resin composition. Further, performance such as impact resistance is further improved.

In the present invention, the compatibilizing agent preferably has a reactive group, and more preferably a carboxylic acid anhydride or a compound having at least one selected from an epoxy group, an isocyanate group, and an oxazoline group.
Preferred compatibilizers include polymers modified with carboxylic acid anhydrides, epoxy groups, isocyanate groups, and oxazoline groups, block copolymers, graft polymers, random copolymers, and various nonionic surfactants. Agents, coupling agents, and crosslinking agents.
The compatibilizing agent is not particularly limited as long as it satisfies the above conditions, and specifically, Nippon Oil & Fats Modiper Series, Sumitomo Chemical Co., Ltd., Bond First, Bondine Series, Nippon Oil Commercially available such as Lexpearl series manufactured by Co., Ltd., Reseda series manufactured by Toagosei Co., Ltd., Alfon series, Epocross series manufactured by Nippon Shokubai Co., Ltd., Duranate series manufactured by Asahi Kasei Chemicals Co., Ltd. The product is preferably used. In addition, the compatibilizer is not limited to these, and the compatibilizer described in “Plastic compatibilizer development / evaluation / recycling” (CMC Publishing Co., Ltd.) can also be suitably used.

  The content of the compatibilizing agent in the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total solid content of the resin composition.

6). Antioxidant It is preferable that the resin composition of the present invention further contains an antioxidant. Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like, and phenol-based antioxidants are preferable. As the phenolic antioxidant, Irganox 1010, Irganox 1076, Irganox 3114 manufactured by Ciba Specialty Chemicals Co., Ltd. can be suitably used.
When the resin composition of the present invention contains an antioxidant, the content is not limited, but is preferably 30% by mass or less, more preferably 0.01 to 10%, based on the total solid content of the resin composition. % By mass. By setting it within this range, the resin can obtain a sufficient stability improving effect against heating in the kneading or molding process, which is preferable.

7). Resin composition and molded body The resin composition of the present invention contains a cellulose ester resin and an imide compound represented by the general formula (I), and, if necessary, a flame retardant, a plasticizer, Compatibilizers, antioxidants, and other additives can be included.

  The resin composition of the present invention may contain various additives such as a filler (reinforcing material) as necessary in addition to the above-described components.

The resin composition of the present invention may contain a filler (reinforcing material). By containing the filler, the mechanical properties of the molded body formed from the resin composition can be enhanced.
A well-known thing can be used as a filler. The shape of the filler may be any of fibrous, plate-like, granular, powdery and the like. Further, it may be inorganic or organic.
Specifically, as the inorganic filler, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, and other inorganic fillers; glass flakes, non-swellable mica, carbon black, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicate, feldspar, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide Beam, aluminum oxide, titanium oxide, magnesium oxide, aluminum silicate, silicon oxide, aluminum hydroxide, magnesium hydroxide, gypsum, novaculite, dawsonite, and a plate-like or granular inorganic fillers of clay or the like.

  Organic fillers include synthetic fibers such as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, and acetate fiber, and natural fibers such as kenaf, ramie, cotton, jute, hemp, sisal, Manila hemp, flax, linen, silk, and wool. Examples thereof include fibrous organic fillers obtained from microcrystalline cellulose, sugar cane, wood pulp, paper waste, waste paper and the like, and granular organic fillers such as organic pigments.

  When the resin composition contains a filler, the content is not limited, but is preferably 30% by mass or less, and more preferably 5 to 10% by mass with respect to the total solid content of the resin composition.

In addition to those described above, the resin composition of the present invention may contain other components for the purpose of further improving various properties such as moldability and flame retardancy, as long as the object of the present invention is not impaired. Good.
Examples of other components include polymers other than the cellulose ester resins, stabilizers (such as ultraviolet absorbers), mold release agents (fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, aliphatic partially saponified esters, paraffins, Low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone), antistatic agent, flame retardant aid, processing aid, drip Examples thereof include an inhibitor, an antibacterial agent and an antifungal agent. Further, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose ester-based resin, any of a thermoplastic polymer and a thermosetting polymer can be used, but a thermoplastic polymer is preferable from the viewpoint of moldability. Specific examples of polymers other than cellulose ester resins include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene- Butene-1 copolymers, polypropylene homopolymers, polypropylene copolymers (such as ethylene-propylene block copolymers), polyolefins such as polybutene-1 and poly-4-methylpentene-1, polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters Polyester such as nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 12, etc., polystyrene, high impact polystyrene, Reacetal (including homopolymers and copolymers), polyurethane, aromatic and aliphatic polyketones, polyphenylene sulfide, polyetheretherketone, thermoplastic starch resin, polymethyl methacrylate and methacrylate-acrylate copolymers Acrylic resin, AS resin (acrylonitrile-styrene copolymer), ABS resin, AES resin (ethylene rubber reinforced AS resin), ACS resin (chlorinated polyethylene reinforced AS resin), ASA resin (acrylic rubber reinforced AS resin) ), Polyvinyl chloride, polyvinylidene chloride, vinyl ester resin, maleic anhydride-styrene copolymer, MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone, polyethersulfone, pheno Thermoplastic polyimide such as silicone resin, polyphenylene ether, modified polyphenylene ether, polyetherimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoro Fluoropolymers such as alkyl vinyl ether copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, polyvinyl alcohol, unsaturated polyester, melamine resin, phenol resin, A urea resin, a polyimide, etc. can be mentioned.
In addition, various acrylic rubbers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymer) Copolymer, ethylene-butyl acrylate copolymer), diene rubber (for example, 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, Styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer Polymer, polybutadiene Styrene-grafted styrene, butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, butyl rubber, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, nitrile rubber, poly Examples include ether rubber, epichlorohydrin rubber, fluoro rubber, silicone rubber, and other thermoplastic elastomers such as polyurethane, polyester, and polyamide.

Furthermore, those having various degrees of crosslinking, those having various microstructures such as cis structure and trans structure, those having vinyl groups, those having various average particle diameters, core layers and the like A multi-layer structure polymer called a so-called core-shell rubber, which is composed of one or more shell layers to be covered and whose adjacent layers are composed of different types of polymers, can also be used, and further a core-shell rubber containing a silicone compound Can also be used.
These polymers may be used alone or in combination of two or more.

  When the resin composition of this invention contains polymers other than a cellulose ester-type resin, 30 mass% or less is preferable with respect to the total solid of a resin composition, and 2-10 mass% is more preferable.

The resin composition of the present invention can be used for various applications. For example, it is good also as a film by melt | dissolving in a solvent and the apply | coating method. Moreover, it is good also as a film by the melt extrusion method.
A film obtained using the resin composition of the present invention is excellent in terms of optical properties (Rth and the like) and moisture permeability.

The molded article of the present invention is obtained by molding a resin composition containing the cellulose ester resin and the imide compound represented by the general formula (I). More specifically, a step of heating a resin composition containing a cellulose ester resin, an imide compound represented by the general formula (I), and various additives as necessary, and molding them by various molding methods. It is obtained by the manufacturing method containing.
The manufacturing method of the molded object of this invention includes the process of heating and molding the said resin composition.
Examples of the molding method include injection molding, extrusion molding, blow molding and the like.
The heating temperature is usually 160 to 300 ° C, preferably 180 to 260 ° C.

  The use of the molded product of the present invention is not particularly limited. For example, interior or exterior parts of electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.), automobiles, mechanical parts, etc. And materials for housing and construction. Among these, from the viewpoint of having excellent heat resistance and impact resistance and low environmental impact, for example, exterior parts (especially casings) for electrical and electronic equipment such as copiers, printers, personal computers, and televisions. ) Can be suitably used.

  Moreover, the resin composition of the present invention can be formed into a film excellent in terms of moisture permeability and Rth by forming a film, and can be used as, for example, an optical film.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the scope of the present invention is not limited to the examples shown below.

  The exemplary compound which is an imide type compound represented by general formula (I) was synthesize | combined as follows.

<Synthesis Example 1 (Synthesis of Exemplified Compound 1)>

  To a 500 mL three-necked flask, 30 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and cooled to 0 ° C. 36 g of 2-ethylhexylamine (manufactured by Kanto Kagaku) was slowly added, and the mixture was heated and stirred at 100 ° C. for 4 hours. Thereafter, the solution was added to 700 mL of water, suction filtered, and washed with 300 mL of water and methanol to obtain 38 g of a colorless solid.

<Synthesis Example 2 (Synthesis of Exemplified Compound 2)>

  To a 500 mL three-necked flask, 30 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and cooled to 0 ° C. 29.5 g (manufactured by Tokyo Chemical Industry Co., Ltd.) of benzylamine was slowly added, and the mixture was heated and stirred at 120 ° C. for 4 hours. Thereafter, the solution was added to 700 mL of water and subjected to suction filtration, and washed with 300 mL of water and methanol to obtain 34 g of a colorless solid.

<Synthesis Example 3 (Synthesis of Exemplary Compound 4)>

  To a 500 mL three-necked flask, 30 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and cooled to 0 ° C. 24 g of amylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added and stirred at 100 ° C. for 3 hours. Thereafter, the solution was added to 700 mL of water and subjected to suction filtration, and washed with 300 mL of water and methanol to obtain 29 g of a colorless solid.

<Synthesis Example 4 (Synthesis of Exemplified Compound 6)>

  To a 500 mL three-necked flask, 30 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and heated to 50 ° C. 2-ethylhexylamine 17.8g (product made from Tokyo Chemical Industry) was added slowly, and it heat-stirred at 100 degreeC for 3 hours. Next, the temperature was again adjusted to 50 ° C., 14.8 g of benzylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added, and the mixture was heated and stirred at 120 ° C. for 4 hours. Thereafter, the solution was added to 700 mL of water, suction filtered, washed with 300 mL of water and methanol, and the obtained solid was isolated and purified by silica gel column chromatography to obtain 11 g of a solid.

<Synthesis Example 5 (Synthesis of Exemplified Compound 7)>

  To a 500 mL three-necked flask, 30 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) were added and cooled to 0 ° C. 38 g of 4- (2-aminoethyl) morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added, and the mixture was heated and stirred at 100 ° C. for 3 hours. Thereafter, the solution was added to 700 mL of water, suction filtered, and washed with 300 mL of water and methanol to obtain 37 g of a colorless solid.

  For other imide compounds used in the examples, the same method and Journal of Heterocyclic Chemistry, 1972, vol. 9, p. Synthesis was performed by the method described in 319,322,323.

<Examples 1 to 12, Comparative Examples 1 and 2>
[Production of molded body]
A cellulose ester resin, an imide compound, and other components were mixed at a blending ratio (mass%) shown in Table 1 to prepare a resin composition. This resin composition was supplied to a twin-screw kneading extruder (manufactured by Technobel, Ultranano) to produce pellets, and the resulting pellets were then injected into an injection molding machine (FANUC ROBOSHOT S-2000i, automatic injection molding). Machine), 4 × 10 × 80 mm multi-purpose test pieces were molded.

In Table 1, each component indicates the following.
Ethyl cellulose: manufactured by Dow Chemical Japan Co., Ltd., trade name: etosel 100 cp (ethyl substitution degree: 2.55, Mw: 185000, Mn: 76000)
Cellulose acetate propionate: Eastman Chemical Co., Ltd., 482-20 (acetyl substitution degree: 0.1, propionyl substitution degree: 2.5, Mn: 73000, Mw: 234000)
Cellulose diacetate: manufactured by Daicel Chemical Industries, L-70 (acetyl substitution degree: 2.45, Mn: 65000, Mw: 200000)
Di (2-ethylhexyl) phthalate: Irganox 1010 manufactured by Tokyo Chemical Industry: Phenolic antioxidant “Irganox 1010”, Ciba Specialty Chemicals Co., Ltd.
The imide compound has the following structure.

[Evaluation]
Using the obtained resin composition for injection molding and the multipurpose test piece, the following items were evaluated. The evaluation results are shown in Table 1.

(Flow characteristics)
Using a flow tester (CFT-100D manufactured by Shimadzu Corp., using a die with L = 10 mm and D = 1.0 mm), the above injection molding resin composition was put into the apparatus at a temperature not higher than the glass transition temperature. The temperature rise was measured at a shear rate of 100 S ⁻¹ and a rate of temperature rise of 2 ° C./min. In general, the temperature at which the apparent viscosity in this measurement is 100 Pa · S, at which injection molding can be easily performed, was defined as the flow characteristic temperature. A lower flow characteristic temperature is preferable because molding becomes easier.

(Flexural modulus)
In accordance with ISO178, after adjusting the test piece molded by injection molding for 48 hours or more at 23 ° C ± 2 ° C, 50% ± 5% RH, the distance between fulcrums by Instron (Toyo Seiki, Strograph V50) The flexural modulus was measured at 64 mm and a test speed of 2 mm / min. The measurement is an average of three measurements.

(Heat deformation temperature (HDT))
In accordance with ISO75, a constant bending load (1.8 MPa) is applied to the center of the test piece (in the flatwise direction), the temperature is increased at a constant speed, and the temperature when the strain at the center reaches 0.34 mm ( ° C). As a heat distortion temperature measuring device, HDT tester 6M-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The measurement is an average of three measurements. Higher HDT is preferable because it is less likely to be thermally deformed.

(Charpy impact strength)
In accordance with ISO 179, a notch having an incident angle of 45 ± 0.5 ° and a tip of 0.25 ± 0.05 mm is formed on a test piece molded by injection molding, 23 ° C. ± 2 ° C., 50% ± 5% RH Then, the impact strength was measured edgewise with a Charpy impact tester (manufactured by Toyo Seiki Seisakusho). The measurement is an average of three measurements.

  The test pieces of Examples 1 to 12 were excellent in terms of flexural modulus, flow characteristics, deflection temperature under load, and Charpy impact strength. Comparative Example 1 not containing a cellulose ester resin and Comparative Example 2 not containing an imide compound represented by the general formula (I) are more effective than the examples in terms of flexural modulus, deflection temperature under load, and Charpy impact strength. It was inferior.

<Examples 13 to 20, Comparative Examples 3 and 4>
(Preparation of cellulose ester solution)
Cellulose triacetate (cellulose acylate flakes having a substitution degree of acetyl group of 2.78, a viscosity average polymerization degree of 303, and a water content of 1% by mass or less. The imide compound represented by the general formula (I) and TPP / BDP (mass ratio 2/1) were used in the ratio (mass%) shown in Table 2 below, and 300 g of methylene chloride and 45 g of methanol were added. Thus, a resin composition was prepared. In addition, the content rate of each component in Table 2 is a value with respect to the total solid content of the resin composition.
In preparation of the cellulose ester solution, the following operation was performed in more detail.
Cellulose triacetate powder (flakes) and an imide compound represented by the general formula (I), TPP / BDP while being well stirred and dispersed in a solvent mixture of methylene chloride and methanol in a 5 L glass container having a stirring blade Was gradually added at a rate shown in Table 2 below, and the whole was charged to 2 kg. In addition, as for the methylene chloride and methanol which are solvents, the thing whose water content is 0.2 mass% or less was utilized. First, a mixture of cellulose triacetate powder, an imide compound represented by the general formula (I), and TPP / BDP at a ratio shown in Table 2 below, is charged with powder in a dispersion tank and filled with nitrogen gas. Dissolver type eccentric stirring shaft and anchor blade on the central shaft were dispersed for 30 minutes. The starting temperature of dispersion was 30 ° C. After completion of the dispersion, the high-speed stirring was stopped, and the peripheral speed of the anchor blade was set to 0.5 m / sec and further stirred for 100 minutes to swell cellulose triacetate flakes. Until the end of swelling, the inside of the tank was pressurized to 0.12 MPa with nitrogen gas. At this time, the oxygen concentration in the tank was less than 2 vol%, and the state of no problem was maintained in terms of explosion protection. Further, it was confirmed that the water content in the dope was 0.2% by mass or less.

  The obtained non-uniform gel solution was fed with a screw pump, and allowed to pass through the cooling part at −70 ° C. for 3 minutes. Cooling was performed using a -80 ° C refrigerant cooled by a refrigerator. The solution obtained by cooling is transferred to a stainless steel container, stirred at 50 ° C. for 2 hours to obtain a uniform solution, and then filtered with a filter paper with absolute filtration accuracy of 0.01 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63). The solution was filtered, and further filtered through a filter paper having an absolute filtration accuracy of 2.5 μm (manufactured by Pall, FH025).

(Production of cellulose triacetate film)
The filtered cellulose triacetate solution at 50 ° C. was cast on a mirror surface stainless steel support through a casting Giuser. The temperature of the support was 5 ° C., the casting speed was 3 m / min, and the coating width was 30 cm. The mixture was left at room temperature for 1 minute, and then a drying air of 55 ° C. was blown for drying. After 5 minutes, it was peeled off from the mirror surface stainless steel support, and then dried at 133 ° C. for 27 minutes to obtain a cellulose triacetate film having a thickness of 60 μm.

[Evaluation]
About the obtained film, the following items were evaluated. The evaluation results are shown in Table 2.

(Moisture permeability)
The moisture permeability of the obtained cellulose triacetate film was determined by leaving the cup containing calcium chloride covered with each film sample and sealing the sample for 24 hours at 60 ° C. and 95% RH. . The moisture permeability of the cellulose triacetate film based on the hygroscopicity of calcium chloride was calculated from the mass change (g / (m ² · day)) before and after standing for 24 hours.

(Rth)
Using an ellipsometer (AEP-100, manufactured by Shimadzu Corporation), the value obtained by multiplying the film thickness by the vertical and horizontal refractive index difference in the film plane measured at a wavelength of 632.8 nm was obtained according to the following formula.
Rth = {(nx + ny) / 2−nz} × d
nx: refractive index in the slow axis direction (direction in which the refractive index is maximum) ny: refractive index in the direction orthogonal to the slow axis nz: refractive index in the thickness direction d: film thickness (unit: nm) )

  In Table 2, TPP and BDP represent the following compounds.

  The films of Examples 13 to 20 have a relatively low Rth of 31 to 38 and a low moisture permeability. The films of Comparative Examples 3 and 4 not containing the imide compound represented by the general formula (I) had high Rth and high moisture permeability.

Claims (8)

The resin composition containing the imide type compound represented by the following general formula (I), and a cellulose-ester type resin.

(In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. R ¹ and R ² further have a substituent. Or a divalent group obtained by combining —O—, —S—, —NR ⁴ —, —CO—, —SO ₂ —, and a combination thereof (R ⁴ represents a hydrogen atom or a substituent). Represents a hydrocarbon group that may be present, provided that when a plurality of R ⁴ are present, they may be the same or different. One or more groups may be included.)   2. The resin composition according to claim 1, wherein the content of the imide compound represented by the general formula (I) is 40% by mass or less based on the total solid content of the resin composition.   The cellulose ester-based resin is at least one selected from the group consisting of cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose propionate butyrate. Item 3. The resin composition according to Item 1 or 2.   The resin composition according to claim 1, wherein the cellulose ester resin is cellulose acetate.   The resin composition according to claim 1, wherein the cellulose ester resin has an acyl substitution degree of 2.7 or less.   The molded object obtained by heat-molding the resin composition in any one of Claims 1-5.   The manufacturing method of a molded object including the process of heating and shape | molding the resin composition in any one of Claims 1-5.   A housing for electrical and electronic equipment comprising the molded body according to claim 6.