JP2011225841A - Resin composition, resin composition for injection molding, molded article, and housing for electric/electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that has superior moldability, resistance to bleedout, resistance to sublimation, and flame resistance, and provides a molded article having flame resistance as well as high levels of both impact strength and bending strength.SOLUTION: The resin composition contains (A) a cellulose ester, (B) a thermoplastic resin having an aromatic ring on the main chain, (C) a plasticizer containing a polymer having repeated structural units and a number average molecular weight of 500-5,000, and (D) a phosphorus-containing flame retardant with a molecular weight of 400-1,500.

Description

  The present invention relates to a resin composition, a resin composition for injection molding, a molded body, 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.

In Patent Document 3, a cellulose ester, a polylactic acid resin, an aromatic polycarbonate resin, a resin composition containing a condensed phosphate ester as a flame retardant, ethylene bislauric acid amide (molecular weight 425), or polyethylene / propylene as a plasticizer It describes that a molded body is formed using glycol (average molecular weight of about 8400).
In Patent Document 4, a cellulose acetate solution, a polystyrene resin as an additive having negative intrinsic refraction, triphenyl phosphate (molecular weight 326) as a plasticizer, and ethylphthalyl glycolate (molecular weight 280 as another plasticizer) are disclosed. To form a film from a coating solution containing

JP-A-56-55425 JP 2008-24919 A JP 2006-111858 A JP 2006-291192 A

However, the plasticizer used in the resin composition described in Patent Document 3 has been studied by the present inventors when the content of the thermoplastic resin having a cellulose ester or aromatic ring in the main chain is changed. It has been found that the flame retardancy of the molded body is reduced. On the other hand, in the resin composition, it was found that when the amount of the flame retardant added is increased, the impact resistance of the molded article is lowered.
Moreover, it turned out that the plasticizer used for the composition of patent document 4 also reduces the flame retardance of a molded object similarly to the plasticizer of patent document 3, and bleed-out is remarkable.
As described above, in a molded body using cellulose ester as a carbon neutral material, it is difficult to balance flame retardancy and impact strength. In addition, the addition of a plasticizer and a flame retardant also has a problem that volatilization or bleed out occurs in the molding process.

  The present invention has been made by paying attention to the above-mentioned problems in a resin composition containing a cellulose ester, and the object thereof is a novel resin composition that can be used for various applications, such as moldability and bleed-out resistance. It is providing the resin composition from which the molded object which is excellent in property, volatilization resistance, impact strength, bending strength, and a flame retardance is obtained. Another object of the present invention is to provide a molded body obtained by molding the resin composition, and a housing for electric and electronic equipment composed of the molded body.

As a result of intensive investigations to achieve the above object, the present inventors have found that a cellulose ester, a thermoplastic resin having a specific structure, a plasticizer having a specific structure and molecular weight, and a specific type of flame retardant The present inventors have found that the above problems can be solved by a resin composition containing
That is, the said subject can be achieved by the following means.

1.
(A) a cellulose ester, (B) a thermoplastic resin having an aromatic ring in the main chain, (C) a plasticizer comprising a polymer having a repeating structural unit and a number average molecular weight of 500 to 5000, and (D) a molecular weight. The resin composition containing the phosphorus containing flame retardant which is 400-1500.
2.
2. The resin composition as described in 1 above, wherein the cellulose ester (A) is cellulose acetate or cellulose acetate propionate.
3.
3. The resin composition as described in 1 or 2 above, wherein the cellulose ester (A) has an acyl substitution degree of 1.3 to 2.65.
4).
4. The resin composition according to any one of 1 to 3 above, wherein the content of the (A) cellulose ester is 30 to 70% by mass.
5).
5. The resin composition according to any one of the above 1 to 4, wherein the (B) thermoplastic resin is a polycarbonate resin.
6).
6. The resin composition according to any one of 1 to 5 above, wherein the number average molecular weight of the (B) thermoplastic resin is 15000 to 30000.
7).
7. The resin composition according to any one of 1 to 6, wherein the repeating units in the (C) plasticizer are linked to each other by an ester bond.
8).
8. The resin composition according to any one of 1 to 7 above, wherein the polymer in the (C) plasticizer does not contain a hydroxyl group and a carboxyl group.
9.
9. The resin composition according to any one of 1 to 8 above, wherein the (D) phosphorus-containing flame retardant is a phosphate ester.
10.
10. The resin composition according to 9 above, wherein the phosphate ester is a condensed phosphate ester.
11.
11. The resin composition according to any one of 1 to 10 above, wherein the total content of the (C) plasticizer and the (D) phosphorus-containing flame retardant is 10 to 40% by mass.
12
The content of the (C) plasticizer with respect to the total content of the (C) plasticizer and the (D) phosphorus-containing flame retardant is 15 to 75% by mass, according to any one of 1 to 11 above. Resin composition.
13.
Furthermore (E) The resin composition of any one of said 1-12 containing a compatibilizing agent.
14
The resin composition according to any one of 1 to 13, further comprising (F) a stabilizer.
15.
Furthermore (G) The resin composition of any one of said 1-14 containing a fluorine resin.
16.
16. A resin composition for injection molding comprising the resin composition according to any one of 1 to 15 above.
17.
16. A molded product obtained by molding the resin composition according to any one of 1 to 15 or the resin composition for injection molding according to 16 above.
18.
18. A housing for electrical and electronic equipment, comprising the molded body as described in 17 above.

  The resin composition of the present invention is a resin composition from which a molded article having excellent moldability, bleed-out resistance, volatilization resistance, flame retardancy, impact strength and bending strength can be obtained. It can be suitably used as a component part such as equipment, a machine part, a house / building material, or the like. 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 is a plastic comprising (A) a cellulose ester, (B) a thermoplastic resin having an aromatic ring in the main chain, and (C) a polymer having a repeating structural unit and having a number average molecular weight of 500 to 5,000. And (D) a phosphorus-containing flame retardant having a molecular weight of 400 to 1500.

1. Cellulose ester The resin composition of the present invention contains a cellulose ester.
There is no limitation in particular as a cellulose ester in this invention. Cellulose esters are usually produced by esterifying cellulose such as wood pulp (conifer pulp, hardwood pulp) and cotton linter pulp.

  The cellulose ester 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 esters are usually 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 (acylation 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 include organic acid esters [cellulose acetate (cellulose acetate), cellulose propionate, cellulose butyrate, etc., cellulose and carboxylic acid ester having 2 to 6 carbon atoms, etc.], mixed esters (cellulose acetate propionate). , Cellulose such as cellulose acetate butyrate and dicarboxylic acid esters having 2 to 6 carbon atoms), grafts (polycaprolactone-grafted cellulose acetate, etc.), inorganic acid esters (cellulose nitrate, cellulose sulfate, cellulose phosphate, etc.), organic Examples include acid / inorganic 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 acetate, 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, and cellulose acetate and cellulose acetate propionate are still more 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 viscosity average degree of polymerization can be measured by the method described in JP-A-9-77801, [0018] to [0019].

  The cellulose ester 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 Daicel Chemical, “L-70 (acetyl substitution degree: 2.45, Mn: 65000, Mw: 200000)”, “L-40 (acetyl substitution degree: 2.45)”, cellulose triacetate, Daicel Chemical “FRM (acetyl substitution degree: 2.79, Mn: 66000, Mw: 186000)”, etc.

  Content of the cellulose ester contained in the resin composition of this invention is not specifically limited. Preferably, the cellulose ester is contained in an amount of 30 to 70% by mass, more preferably 35 to 65% by mass, and still more preferably 40 to 60% by mass with respect to the total solid content of the resin composition. By setting it as this range, a resin composition excellent in strength, flame retardancy, and moldability of a molded product can be obtained while having significance as a carbon neutral material.

2. Thermoplastic resin having an aromatic ring in the main chain The resin composition of the present invention contains a thermoplastic resin having an aromatic ring in the main chain.
The thermoplastic resin having an aromatic ring in the main chain in the present invention is not particularly limited, and examples thereof include polycarbonate resin, aromatic polyester, polyphenylene ether, polyetherimide, polyphenylene sulfide, and the like. When the resin is used together with cellulose ester, it is preferable because it has a good balance of rigidity, impact resistance, heat resistance and moldability.
Moreover, it is preferable that the thermoplastic number average molecular weight which has an aromatic ring is 15000-30000. This is because when the number average molecular weight is 15000 or more, the mechanical strength is further improved, and when the number average molecular weight is 30000 or less, the moldability is further improved. The value of the number average molecular weight is obtained, for example, using a converted molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene using N-methylpyrrolidone as a solvent and using a polystyrene gel. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.
In the present invention, a thermoplastic resin having an aromatic ring only in the side chain, such as polystyrene, is not preferable from the viewpoint of impact strength and flame retardancy.

(Polycarbonate resin)
In the present invention, examples of the polycarbonate resin include an aromatic polycarbonate resin and an aromatic-aliphatic polycarbonate resin.
Examples of the aromatic polycarbonate resin include thermoplastic aromatic polycarbonate polymers or copolymers obtained by reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester.
Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4, 4-dihydroxybiphenyl, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2- Bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxy) Rokishifeniru) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane. These can be used alone or as a mixture. Bisphenol A is preferable. Furthermore, for the purpose of further enhancing the flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a polymer or oligomer having a siloxane structure and containing both terminal phenolic OH groups is used. Can do.

  The aromatic polycarbonate resin that can be used in the present invention is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane. Examples thereof include polycarbonate copolymers derived from other aromatic dihydroxy compounds. Further, two or more kinds of polycarbonate resins may be used in combination.

Examples of the aromatic-aliphatic polycarbonate resin that can be used in the present invention include copolymers of the aromatic polycarbonate resin described above and the aliphatic polycarbonate resin described below. For the reason of increasing the compatibility with the cellulose derivative, the copolymerization ratio of the aromatic component and the aliphatic component is preferably 95/5 to 30/70, more preferably 90/10 to 50/50.
The aliphatic polycarbonate resin that can be used for the copolymerization of the aromatic-aliphatic polycarbonate resin is preferably an aliphatic diol residue having 2 to 12 carbon atoms. Examples of these aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2, 2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8- 5-membered ring diols such as octanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, bis (hydroxymethyl) tricyclo- [5.2.1.0] decane, erythritan, isosorbide, etc. -Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane Sandimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) -propane, 1,3-adamantanediol, 1,3-adamantanedimethanol, 4, 9: 5,8-dimethano-1 (2), 6 (7) -hydroxymethyl-3a, 4,4a, 5,8,8,9,9a-octahydro-1H-pentoindene, 2,3-norbornanediol, Examples thereof include 6-membered ring diols such as 2,3-norbornane dimethanol, 2,5-norbornane diol and 2,5-norbornane dimethanol, and spiro ring diols such as spiroglycol. In particular, alicyclic aliphatic diols are preferable from the viewpoint of rigidity and heat resistance of the molding material to be obtained. These components may be used independently and may use 2 or more types together as needed.

  The production method of the polycarbonate resin in the present invention is not limited, and it is produced by a phosgene method (interfacial polymerization method), a melting method (transesterification method), or a non-phosgene method using carbon dioxide as a raw material. Can do. Furthermore, the aromatic polycarbonate resin which adjusted the amount of OH groups of the terminal group manufactured by the melting method can be used.

  Furthermore, as the aromatic polycarbonate resin, not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product, that is, a so-called material recycled aromatic polycarbonate resin can be used. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. In addition, as the recycled aromatic polycarbonate resin, non-conforming product, pulverized product obtained from sprue or runner or pellets obtained by melting them can be used.

  In the present invention, a commercially available product can also be used as the carbonate resin. For example, Panlite L1225Y: Polycarbonate resin having a bisphenol A skeleton (Mn = 25000) (manufactured by Teijin Chemicals Ltd.), Panlite L1225L: having a bisphenol A skeleton Polycarbonate resin (Mn = 21000) (manufactured by Teijin Chemicals Ltd.), Panlite L-1250Y: Polycarbonate resin having a bisphenol A skeleton (Mn = 26000) (manufactured by Teijin Chemicals Ltd.), Panlite L-1300Y: And polycarbonate resin having a bisphenol A skeleton (Mn = 33000) (manufactured by Teijin Chemicals Ltd.). An alloy resin containing polycarbonate, for example, a polycarbonate / ABS alloy resin can also be preferably used. Examples of commercially available products include “Multilon TN-7500”: polycarbonate / ABS alloy resin, manufactured by Teijin Chemicals Limited.

(Aromatic polyester)
The aromatic polyester referred to in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid and a diol or an ester derivative thereof.
As the aromatic dicarboxylic acid that is a raw material of the aromatic polyester in the present invention, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane Aromatic dicarboxylic such as -4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p-terphenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid Acids are preferably used, particularly terephthalic acid and 2,6-naphthalenedicarboxylic acid. Can be used properly.

  Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. together with the dicarboxylic acid. .

  Examples of the diol that is a raw material constituting the aromatic polyester of the present invention include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol. , Alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof.

  Specific aromatic polyesters include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2 In addition to -bis (phenoxy) ethane-4,4'-dicarboxylate, etc., there may be mentioned copolyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate having a good balance of mechanical properties and the like can be preferably used, and polyethylene terephthalate and polybutylene terephthalate can be more preferably used. In the present invention, these may be used alone or in combination of two or more.

  As the aromatic polyester, a commercially available product may be used, and examples thereof include polyethylene terephthalate resin (Mitsui PET J005, manufactured by Mitsui PET Resin Co., Ltd.), polybutylene terephthalate resin (Juranex 2002, manufactured by Nippon Polyplastics Co., Ltd.), and the like. .

  With respect to the method for producing such an aromatic polyester, according to a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., the dicarboxylic acid component and the diol component are polymerized while heating, and water produced as a by-product Alternatively, the lower alcohol is discharged out of the system.

(Polyphenylene ether)
The polyphenylene ether used in the present invention refers to a homopolymer having the following general formula () as a repeating unit, a copolymer containing a repeating unit of the following general formula (a), or a modified polymer thereof.

In the formula, R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a primary or secondary lower alkyl group, or a phenyl group. R ₂ , R ₃ , R ₄ and R ₅ are particularly preferably a hydrogen atom or a primary alkyl group having 1 to 3 carbon atoms. n represents the number of repeating units.

  A polymer having a wide molecular weight can be used as the polyphenylene ether, but the reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.15 to 1.0 dl / g. Homopolymers and / or copolymers are used, and more preferred reduced viscosities are in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60. As the polyphenylene ether, a wide range of melt fluidity resins can be used depending on the purpose, and there is no particular limitation on melt fluidity. However, for example, when used as a structural material that requires particularly high strength, high heat resistance and various mechanical properties, the melt index value measured in accordance with JIS K6730 and at 280 ° C. and a load of 10 kg is used. A resin having a value of 6 (g / 10 min) or less, more preferably 5 (g / 10 min) or less, particularly preferably 4 (g / 10 min) or less is used.

  Typical examples of polyphenylene ether homopolymers include poly (1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4- Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) Phenylene) ether, poly (2,3,6-trimethyl-1,4-phenylene) ether, and the like. Of these, poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred. Examples of the polyphenylene ether copolymer include 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol, 2,6-diphenylphenol, or 2-methylphenol (o-cresol)). And a copolymer thereof. Among the various polyphenylene ether resins as described above, poly (2,6-dimethyl-1,4-phenylene) ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable. Is particularly preferably poly (2,6-dimethyl-1,4-phenylene) ether.

  An example of a method for producing polyphenylene ether used in the present invention is a method in which 2,6-xylenol is oxidatively polymerized using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst.

  The methods described in U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, Japanese Patent Publication Nos. 52-17880, and JP-A-50-51197, and 63-152628 are also polyphenylene. This is preferred as a method for producing ether.

  The polyphenylene ether of the present invention may be used as a powder after the polymerization step, or melt-kneaded in a nitrogen gas atmosphere or a non-nitrogen gas atmosphere, devolatilization or non-devolatilization using an extruder or the like. By doing so, it may be used as a pellet.

  The polyphenylene ether of the present invention includes polyphenylene ether modified with a dienophile compound. For this modification treatment, various dienophile compounds are used. Examples of dienophile compounds include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl allylate, methyl Examples of the compound include methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, and styrene. Furthermore, as a method of modifying with these dienophile compounds, an extruder or the like may be used in the presence or absence of a radical generator, and functionalization may be performed in a molten state under devolatilization or non-devolatilization. Alternatively, it may be functionalized in the non-molten state, that is, in the temperature range from room temperature to the melting point in the presence or absence of a radical generator. In this case, the melting point of polyphenylene ether is defined by the peak top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is raised at 20 ° C./min in the differential thermal scanning calorimeter (DSC) measurement. If there are a plurality of peak top temperatures, the peak top temperature is defined as the highest temperature.

  As the polyphenylene ether, commercially available ones can be used. For example, Asylon Chemicals Co., Ltd. Zylon (polymer alloy of thermoplastic polyphenylene ether and polystyrene resin), GE Plastics Noryl PX9701 (Poly (2,6-dimethyl) -1,4-phenylene) ether).

(Polyetherimide)
Polyetherimide is a well-known resin, for example, what is marketed by GE Plastics under the trade name ULTEM.

(Polyphenylene sulfide)
Polyphenylene sulfide (PPS) is a known resin having a substituted or unsubstituted phenylene sulfide repeating unit. Examples thereof include those commercially available from Phillips Petroleum Co., Ltd., Tosoh Sustiel Co., Ltd., Toprene Co., Ltd., and Kureha Chemical Co., Ltd.

  The content of the thermoplastic resin having an aromatic ring in the main chain contained in the resin composition of the present invention is not particularly limited. Preferably, the thermoplastic resin is contained in an amount of 30 to 70% by mass, more preferably 35 to 65% by mass, and still more preferably 40 to 60% by mass with respect to the total solid content of the resin composition. By setting it as this range, the strength of the molded body, in particular, the impact strength and flame retardancy will be more excellent.

3. Plasticizer The resin composition of the present invention contains a plasticizer.
The plasticizer in the present invention is not particularly limited as long as it contains a polymer having a repeating structural unit and a number average molecular weight of 500 to 5,000.
Usually, a plasticizer reduces the flame retardancy of a resin molded article. However, in the present invention, since a polymer having a repeating structural unit is used as a plasticizer, it is difficult to suppress volatilization of combustible components. A decrease in flammability can be suppressed. Moreover, volatilization at the time of shaping | molding and the bleeding out of a resin molding can be suppressed, maintaining a moldability by making molecular weight into said range, without changing the polarity of a molecule | numerator largely.

  As the plasticizer containing such a repeating structural unit, for example, polyvinyl oligomers ((meth) acrylic oligomers, styrene oligomers, etc.), polyether oligomers, polyurethane oligomers, polyester oligomers, polycarbonate oligomers and the like are preferably used. be able to. Among these, a polyester oligomer in which repeating units are connected to each other through an ester bond is preferable because it has an excellent balance of moldability, strength, and flame retardancy.

  A specific example of the polyester oligomer is not particularly limited as long as it has a repeating structural unit and the number average molecular weight is 500 to 5,000. A divalent carboxylic acid, a divalent alcohol, and a hydroxy group-containing carboxylic acid are used. What is contained as a constituent component is preferable. Examples of the divalent carboxylic acid include adipic acid, succinic acid, decanedicarboxylic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and the like. It is more preferable that the compatibility with the cellulose ester is high. Specifically, adipic acid, succinic acid, phthalic acid, terephthalic acid, and isophthalic acid are preferable.

  Examples of divalent alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene And glycols. It is more preferable that the compatibility with the cellulose ester is high as in the case of the divalent carboxylic acid, and specific examples include ethylene glycol, propylene glycol, 1,3-propanediol, and 1,4-butanediol. .

  Preferred examples of the hydroxy group-containing carboxylic acid include glycolic acid, lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, and 3-hydroxyhexanoic acid. It is more preferable that the compatibility with the cellulose ester is high as in the case of the divalent carboxylic acid, and specific examples include glycolic acid, lactic acid, 3-hydroxybutyric acid, and 4-hydroxybutyric acid.

  Furthermore, preferred examples include polyester oligomers using hydroxycarboxylic acids such as polycaprolactone and polylactic acid or cyclic lactones as raw materials.

As a plasticizer in this invention, a number average molecular weight is 500-5000, 600-3500 are preferable and 700-2000 are more preferable.
The number average molecular weight of the plasticizer can be measured using gel permeation chromatography (GPC). Specifically, N-methylpyrrolidone can be used as a solvent, a polystyrene gel can be used, and the molecular weight can be obtained using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.

The ends of these polyester oligomers may remain COOH residues or OH residues without being sealed, but from the viewpoint of the stability and hygroscopicity of the resin composition, they have OH residues or the ends are It is preferable that it is sealed, and it is more preferable that the terminal is sealed and does not contain a hydroxyl group and a carboxyl group.
Sealing can be carried out by any method. Preferred examples include ester sealing in the case of a carboxyl group, and ester sealing and ether sealing in the case of a hydroxyl group. As a sealing method, after synthesizing a compound having a hydroxyl group and / or a carboxyl group, the compound may be reacted with a sealant, or the sealant may be allowed to coexist in a polymerization reaction. In the case of ester sealing, examples of monocarboxylic acids used for sealing include acetic acid, propionic acid, butanoic acid, 2-ethylhexanoic acid, benzoic acid, toluic acid, p-tert-butylbenzoic acid, and naphthoic acid. it can. Examples of monoalcohols used for sealing include methanol, ethanol, propanol, isopropanol, butanol, and isobutanol.

The polyester oligomer can be produced by a known method described in, for example, JP-A-61-276836, JP-A-2006-64803, and JP-A-2007-269850.
These plasticizers may be used alone or in combination of two or more.

  In an oligomer obtained by radical polymerization such as a polyvinyl oligomer ((meth) acrylic oligomer, styrene oligomer, etc.), it is not necessary to seal the end of the main chain. On the other hand, a compound having a hydroxyl group at the end, which is a polyether oligomer or polyurethane oligomer, is preferable even if it is ester-sealed or ether-sealed.

4). Phosphorus-containing flame retardant having a molecular weight of 400-1500 The resin composition of the present invention contains a phosphorus-containing flame retardant having a molecular weight of 400-1500. Thereby, the flame-retardant effect, such as a reduction or suppression of a combustion rate, can be improved.
Phosphorus-containing flame retardants are thermally decomposed when combined with resin or during molding, compared with other flame retardants such as brominated flame retardants and chlorinated flame retardants. It does not corrode processing machines or molds and does not deteriorate the working environment, and halogens are volatilized at the time of incineration, or it decomposes and generates harmful substances such as dioxins. There is an advantage that there is little possibility of giving. Furthermore, compared with flame retardants such as silicon-containing flame retardants, nitrogen compound flame retardants, and inorganic flame retardants that are commonly used, the flame retardant effect is large, and the decrease in flexural modulus and impact resistance is suppressed. There are advantages.

  The phosphorus-containing flame retardant in the present invention is not particularly limited, and a commonly used one can be used. For example, organic phosphorus compounds such as phosphate esters, condensed phosphate esters, and polyphosphates may be mentioned. From the viewpoint of improving the thermal stability of the resin material, phosphate esters are preferable, and volatilization prevention and bleeding out during molding processing From the viewpoint of suppression, condensed phosphate esters (compounds having two or more phosphate ester units in the molecule) are more preferred.

  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 the condensed phosphate ester include resorcinol polyphenyl phosphate, 1,3-phenylenebis (2,6-dimethylphenyl phosphate), resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, Examples thereof include bisphenol A polyphenyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and aromatic condensed phosphate esters such as condensates thereof.

  These phosphorus-containing flame retardants have a molecular weight of 400-1500, preferably 500-1000. By making molecular weight into this range, it becomes easy to suppress volatilization at the time of shaping | molding and bleed-out of a molded object. If the molecular weight of the phosphorus-containing flame retardant is less than 400, it is not preferable from the viewpoints of volatility and bleed out. If the molecular weight of the phosphorus-containing flame retardant is larger than 1500, it is not preferable from the viewpoint of compatibility with the resin.

  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.

  These phosphorus-containing flame retardants can be produced by a known method. Moreover, a commercial item can also be used, for example, "CR-733S, CR-741, PX-200 (manufactured by Daihachi Chemical Co., Ltd.)" or "FP-600, FP-700 (and above Co., Ltd.). Adeka) ”.

The content of the plasticizer and phosphorus-containing flame retardant contained in the resin composition of the present invention is not particularly limited, but the addition amount of the plasticizer is preferably 3 to 20% by mass with respect to the total solid content of the resin composition. -15 mass% is more preferable. Moreover, it is preferable that the addition amount of a phosphorus containing flame retardant is 3-25 mass% with respect to the total solid of a resin composition, and it is more preferable that it is 5-20 mass%. In addition, Preferably the sum total of content of a plasticizer and a phosphorus containing flame retardant contains 10-40 mass% with respect to the total solid of a resin composition, More preferably, 15-30 mass% contains. By setting it within this range, it becomes easy to balance the moldability and the strength of the molded body, the impact resistance, and the flame retardancy.
Further, the content of the plasticizer relative to the total content of the plasticizer and the phosphorus-containing flame retardant is preferably 15 to 75% by mass from the viewpoint of improving the flame retardant level, and is preferably 20 to 60% by mass. More preferred.

5). Compatibilizer The resin composition of the present invention preferably further contains a compatibilizer. The compatibilizing agent is used to compatibilize the cellulose ester and the thermoplastic resin in the present invention. The compatibilizing agent includes a compound having a part having affinity for the cellulose ester and a part having affinity for the thermoplastic resin, and the two kinds described above. A compound having a functional group that reacts with any of these resins is preferred. As the former example, a block polymer or a graft polymer having portions having different polarities can be preferably used. As an example of the latter, a carboxylic acid anhydride as a reactive group, or an oligomer or polymer having at least one selected from an epoxy group, an isocyanate group, and an oxazoline group is preferable. When a compatibilizing agent is added to the resin composition of the present invention, the dispersibility of the cellulose ester with respect to the thermoplastic resin is further improved, and the properties such as the fluidity (molding processability) of the resin composition and the impact resistance of the molded product. Will be improved.

  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 products such as Lexpearl series manufactured by Co., Ltd., Reseda series manufactured by Toagosei Co., Ltd., Alfon series, and Epochros series manufactured by Nippon Shokubai Co., Ltd. (all trade names) are 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 20% by mass, more preferably 0.3 to 10% by mass, based on the total solid content of the resin composition.

6). Stabilizer It is preferable that the resin composition of the present invention further contains a stabilizer. Although it does not specifically limit as a stabilizer, hindered phenolic antioxidant, phosphorus antioxidant, amine antioxidant, sulfur antioxidant, light resistance agent, ultraviolet absorber, copper damage inhibitor, etc. Can be mentioned. Stabilizers particularly effective for cellulose esters are disclosed in JP-A-10-306175 and the like, and they can be preferably used in the present invention. As commercially available products, Irganox 1010: phenolic antioxidant “Irganox 1010”, Ciba Specialty Chemicals Co., Ltd. can be preferably used.
As for content of the stabilizer in the resin composition of this invention, 0.01-5 mass% is preferable with respect to the total solid of a resin composition, More preferably, it is 0.1-3 mass%.

7). Fluorine-based resin The resin composition of the present invention preferably further contains a fluorine-based resin. This is to prevent drip when the molded body burns and to obtain higher flame retardancy.
The fluororesin in the present invention is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene. / Perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, etc., among which polytetrafluoro Ethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride In particular, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymers are preferred, and polytetrafluoroethylene is more preferred, and polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer. The body is also preferably used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if they are mechanically strongly mixed with other resin compositions using a Henschel mixer or the like, agglomeration may occur due to aggregation. There are problems in handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Examples thereof include polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer. Examples of the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide. An organic polymer containing 10% by weight or more of a monomer, and a mixture thereof may be used. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is from 0.1% by weight to 90%. It is preferable that it is weight%.

  The blending amount of the fluororesin in the resin composition of the present invention is preferably 1 to 0.01% by mass, more preferably 0.8 to 0.02% by mass, and still more preferably 0.5 to 0.03. Parts by weight. By setting it as this range, a flame retardance can be improved more, suppressing the influence on a moldability.

8). Resin Composition and Molded Body 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.
Other components include, for example, the cellulose ester, a thermoplastic resin having an aromatic ring in the main chain, and a polymer other than a plasticizer, a release agent (fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, aliphatic moiety. Saponified ester, paraffin, 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 aids, antibacterial agents, antifungal agents and the like can be mentioned. Further, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose ester, the thermoplastic resin having an aromatic ring in the main chain, and the plasticizer, 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 esters include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene- 1 copolymer, polypropylene homopolymer, polypropylene copolymer (such as ethylene-propylene block copolymer), polyolefin such as polybutene-1 and poly-4-methylpentene-1, polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters, etc. Polyamide such as polyester, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 12, etc., polystyrene, high impact polystyrene, poly Tar (including homopolymer and copolymer), polyurethane, aromatic and aliphatic polyketone, polyphenylene sulfide, polyether ether ketone, thermoplastic starch resin, polymethyl methacrylate, methacrylate ester-acrylate copolymer, etc. 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, phenoxy tree , Polyphenylene ether, modified polyphenylene ether, thermoplastic polyimide such as polyetherimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether Fluoropolymers such as copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, polyvinyl alcohol, unsaturated polyester, melamine resin, phenol resin, urea resin And polyimide.
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 the present invention contains the cellulose ester, a thermoplastic resin having an aromatic ring in the main chain, and a polymer other than the plasticizer, the content is 30 with respect to the total solid content of the resin composition. The mass% or less is preferable, and 2 to 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.
The resin composition of the present invention is preferably an injection molding resin composition.

The molded product of the present invention can be obtained by molding the resin composition of the present invention.
The manufacturing method of the molded object of this invention includes the process of heating and shape | molding the resin composition of this invention.
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.

  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.

<Examples 1 to 65, Comparative Examples 1 to 18>
[Production of molded body]
Cellulose ester, thermoplastic resin, plasticizer, flame retardant, and other components were mixed at a blending ratio (mass%) shown in Tables 2 to 7 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 Tables 2 to 7, the abbreviations for each component are as follows.
CA (1): Cellulose acetate “L-70” (acetyl substitution degree: 2.45, Mn: 65000, Mw: 200000), Daicel Chemical Industries, Ltd. CA (2): Cellulose acetate “L-40” ( Degree of acetyl substitution: 2,45, Mn: 54000, Mw: 170000), manufactured by Daicel Chemical Industries, Ltd. CAP: cellulose acetate propionate “CAP482-20” (acetyl substitution degree: 0.1, propionyl substitution degree: 2) .5, Mn: 73000, Mw: 234000), Eastman Chemical Company PC (1): Polycarbonate resin “Panlite L-1225Y” (polycarbonate resin having a bisphenol A skeleton (Mn = 25000)), Teijin Chemicals Ltd. PC (2): Polycarbonate resin “Panlite L-1225L” (bisphenol A skeleton Polycarbonate resin (Mn = 21000)), PC (3) manufactured by Teijin Chemicals Limited: Polycarbonate resin “Panlite L-1250Y” (polycarbonate resin having a bisphenol A skeleton (Mn = 26000)), Teijin Chemicals Limited PC (4): Polycarbonate resin “Panlite L-1300Y” (polycarbonate resin having bisphenol A skeleton (Mn = 33000)), PC / ABS: Polycarbonate / ABS alloy resin “Multilon TN-7500 manufactured by Teijin Chemicals Ltd. "
(Mn = 130,000), TPE Chemicals Co., Ltd. PPE: Polyphenylene ether resin “Noryl PX9701” (Mn = 14000), GE Plastics PBT: Polybutylene terephthalate resin “Duranex 2002”, Nippon Polyplastics Co., Ltd. Made)
PSt: Polystyrene resin “PSJ-polystyrene HI (AGI02)”, PS Japan Co., Ltd. ABS: ABS resin “UMG ABS EX10U”, UMG ABS Co., Ltd.
PX-200: condensed phosphate ester flame retardant “PX-200”, molecular weight 701, manufactured by Daihachi Chemical Co., Ltd.
CR-741: condensed phosphate ester flame retardant “CR-741”, molecular weight 693 (main component), FP-600 manufactured by Daihachi Chemical Co., Ltd .: condensed phosphate ester flame retardant “FP-600”, molecular weight 692 ADEKA Corporation FP-700: condensed phosphate ester flame retardant “FP-700”, molecular weight 692, Adeka Corporation TPP: phosphate ester flame retardant “TPP”, molecular weight 326, Daihachi Chemical ( Modiper Co., Ltd .: Compatibilizer “Modiper A4400” Irganox 1010 manufactured by NOF Co., Ltd .: Phenol antioxidant “Irganox 1010”, Ciba Specialty Chemicals Co., Ltd.
6J: Fluorine-containing polymer “Teflon (registered trademark) 6J”, manufactured by Mitsui & DuPont Fluorochemical Co., Ltd. Metablene: Fluorine-containing polymer “Metabrene A-3000”, manufactured by Mitsubishi Rayon Co., Ltd.

  Moreover, what was described in following Table 1 was used for the plasticizers 1-14. The plasticizers 1 to 9, 12, and 13 are polyester compounds obtained by using the dicarboxylic acid component and the diol component shown in Table 1 at a mass ratio shown in Table 1, and the end capping shown in Table 1 to the polyester compound. I used what I did.

[Measurement method of number average molecular weight]
The number average molecular weight of the plasticizer was measured using gel permeation chromatography (GPC). Specifically, N-methylpyrrolidone was used as a solvent, a polystyrene gel was used, and the molecular weight was determined using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.

[Evaluation]
The following items were evaluated using the obtained resin composition and multipurpose test piece. The evaluation results are shown in Tables 2-7.

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

(Bending strength)
In accordance with ISO178, after adjusting a test piece (multipurpose test piece) molded by injection molding at 23 ° C. ± 2 ° C. and 50% ± 5% RH for 48 hours or more, Instron (manufactured by Toyo Seiki, Strograph V50) The bending test was performed at a distance between fulcrums of 64 mm and a test speed of 2 mm / min, and the maximum stress during the test was defined as the bending strength. The measurement is an average of three measurements.

(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 (multipurpose test piece) formed by injection molding, and 23 ° C. ± 2 ° C., 50 After leaving still for 48 hours or more at% ± 5% RH, the impact strength was measured edgewise by a Charpy impact tester (manufactured by Toyo Seiki Seisakusho). The measurement is an average of three measurements.

(Flame retardance)
Using a multi-purpose test piece, a vertical combustion test based on UL94 was performed as an index of flame retardancy. The number of tests is five. V-not for non-self-extinguishing material, V-2 for resin composition drip during combustion test, self-extinguishing within a predetermined time V-2, no resin composition drip during combustion, self-extinguishing within a predetermined time V-1 (combustion time within 30 seconds) and V-0 (combustion time within 10 seconds).

(Volatile)
When kneading and molding the resin composition, volatile components were visually confirmed by white smoke or the like. The case where no volatile component was observed was marked with ◯, the case where slight white smoke was seen was marked with Δ, and the case where white smoke was clearly seen was marked with ×.

(Formability)
The moldability evaluation indicates moldability in an injection molding machine. Good molding transportability means that the resin composition can be stably supplied when charged into the molding machine, and the load is not excessive. Also, good injection means that the resin can be molded into a desired shape without deterioration such as coloring. A resin composition having good molding transportability and injection property was indicated by ◯, a resin composition having a problem in either one was indicated by Δ, and a resin composition having a problem in both was indicated by ×.

(Bleed out)
Letters (ABC) were written with oil-based ink on the surface of a test piece (multipurpose test piece) obtained by kneading and molding, and this test piece was left under conditions of 65 ° C. and 90% RH for 6 hours. And the bleed-out state of the plasticizer on the surface of the test piece was evaluated visually according to the following criteria. When bleed-out occurs, changes such as an increase in gloss on the surface of the test piece, a sticky feeling, powder blowing, and crystal precipitation are observed.
○: Almost no change caused by bleed-out, and ink characters are hardly blurred.
Δ: Some change caused by bleed-out is observed, or ink characters are blurred.
X: A change caused by bleed-out is remarkably observed, or ink characters are blurred to an unreadable level.

  From the above results, when the thermoplastic resin is a side chain aromatic resin (PSt, ABS), good impact strength and flame retardancy cannot be obtained, and when the resin composition does not contain a thermoplastic resin, the phase of the flame retardant It was confirmed that the solubility was poor and kneading and molding became impossible. Also, if the resin composition does not contain a plasticizer, the thermoplasticity will be insufficient and kneading / molding will be impossible, and if the molecular weight of the plasticizer is lowered, the volatility and bleedout will deteriorate, whereas the molecular weight of the plasticizer will be too high It was confirmed that the moldability deteriorated. Furthermore, when there was no flame retardant, it was confirmed that flame retardance deteriorates.

Claims (18)

  (A) a cellulose ester, (B) a thermoplastic resin having an aromatic ring in the main chain, (C) a plasticizer comprising a polymer having a repeating structural unit and a number average molecular weight of 500 to 5000, and (D) a molecular weight. The resin composition containing the phosphorus containing flame retardant which is 400-1500.   The resin composition according to claim 1, wherein the (A) cellulose ester is cellulose acetate or cellulose acetate propionate.   The resin composition according to claim 1 or 2, wherein the acyl substitution degree of the (A) cellulose ester is 1.3 to 2.65.   Content of the said (A) cellulose ester is 30-70 mass%, The resin composition of any one of Claims 1-3.   The resin composition according to claim 1, wherein the thermoplastic resin (B) is a polycarbonate resin.   The number average molecular weight of said (B) thermoplastic resin is 15000-30000, The resin composition of any one of Claims 1-5.   The resin composition according to claim 1, wherein the repeating units in the (C) plasticizer are linked to each other by an ester bond.   The resin composition according to any one of claims 1 to 7, wherein the polymer in the (C) plasticizer does not contain a hydroxyl group and a carboxyl group.   The resin composition according to any one of claims 1 to 8, wherein the (D) phosphorus-containing flame retardant is a phosphate ester.   The resin composition according to claim 9, wherein the phosphate ester is a condensed phosphate ester.   The resin composition according to any one of claims 1 to 10, wherein a total content of the (C) plasticizer and the (D) phosphorus-containing flame retardant is 10 to 40% by mass.   The content of the (C) plasticizer with respect to the total content of the (C) plasticizer and the (D) phosphorus-containing flame retardant is 15 to 75% by mass. The resin composition as described.   Furthermore, (E) The resin composition of any one of Claims 1-12 containing a compatibilizing agent.   Furthermore, (F) The resin composition of any one of Claims 1-13 containing a stabilizer.   Furthermore, (G) The resin composition of any one of Claims 1-14 containing a fluorine resin.   The resin composition for injection molding which consists of a resin composition of any one of Claims 1-15.   The molded object obtained by shape | molding the resin composition of any one of Claims 1-15, or the resin composition for injection molding of Claim 16.   A housing for electrical and electronic equipment comprising the molded body according to claim 17.