WO2011122646A1 - Resin composition, molded article and housing for electric/electronic device - Google Patents

Abstract

Disclosed is a resin composition that can provide a molded article superior in all the characteristics of moldability, flame resistance, impact strength and hygroscopicity. The disclosed resin composition contains: a cellulose ester (A); a thermoplastic resin (B) having an aromatic ring on the main chain; a low-molecular weight plasticizer (C1) formed from a compound with a molecular weight of 450 or less; an oligomer plasticizer (C2) formed from a compound with a mass average molecular weight of 500 - 5000; and a phosphorus-based flame retardant (D) formed from a phosphorus-containing compound with a molecular weight of 400 - 800.

Description

Resin composition, molded body, and casing for electrical and electronic equipment

The present invention relates to a resin composition, a molded body, and a housing for electric 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. Are used in large quantities. 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 1).
However, further improvements are required from the perspective of aiming for a more complete carbon neutral material.

Cellulose is gaining great attention as a biomass material that can be regenerated on the earth obtained from plants and as a biodegradable material in the environment. Cellulose is not only used for paper, but cellulose derivatives, for example, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate phthalate are used as film materials and the like.

In Patent Document 2, in a resin composition containing cellulose ester, polylactic acid resin, aromatic polycarbonate resin, and condensed phosphate ester as a flame retardant, ethylene bislauric acid amide (molecular weight 425) or polyethylene / propylene glycol as a plasticizer It is described that a molded body is formed using (average molecular weight 8400).
Patent Document 3 discloses 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). To form a film from a coating solution containing
Patent Document 4 describes that a film is formed from a coating solution containing triphenyl phosphate (molecular weight 326) as a plasticizer and ditrimethylolpropane tetraacetate (molecular weight 305) as another plasticizer in a cellulose acetate solution. Has been.

Japanese Unexamined Patent Publication No. 2008-24919 Japanese Unexamined Patent Publication No. 2006-111858 Japanese Unexamined Patent Publication No. 2006-291192 Japanese Patent Laid-Open No. 2002-265636

However, as a result of studies by the present inventors, it has been found that the plasticizer used in the resin composition described in Patent Document 2 reduces the flame retardancy of a molded product obtained from the resin composition. 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 patent document 3 and 4 also reduces the flame retardance of a molded object similarly to the plasticizer of patent document 2. FIG.
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 resin composition of Patent Document 2 contains one type of plasticizer, but when the plasticizer has a higher molecular weight than the specific molecular weight range, the molded article obtained has poor moisture absorption resistance (moisture absorption rate). ) Rises. On the other hand, it was found that when the plasticizer has a relatively low molecular weight, the resulting molded article has poor impact resistance. Thus, the balance between impact strength and hygroscopicity has also been a problem with molded articles containing cellulose esters.
In addition, in the cellulose ester films as described in Patent Documents 3 and 4, since there is a concern that transparency is lowered by phase separation, a high-molecular plasticizer is not usually used in many cases.

The present invention has been made by paying attention to the above-mentioned problems in a resin composition using a cellulose derivative, and the purpose thereof is as a novel resin composition that can be used in various applications, as moldability, flame retardancy, and the like. It is providing the resin composition from which the molded object excellent in all the characteristics of property, impact strength, and moisture absorption resistance 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 studies to achieve the above object, the present inventors have found that a cellulose ester, a thermoplastic resin having a specific structure, a low molecular plasticizer having a specific molecular weight, and a specific range The present inventors have found that the above problems can be solved by a resin composition containing an oligomer plasticizer having a molecular weight and a phosphorus-based flame retardant having a specific range of molecular weight, and have completed the present invention.
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, (C1) a low molecular plasticizer comprising a compound having a molecular weight of 450 or less, and (C2) a compound having a mass average molecular weight of 500 to 5,000. And (D) a phosphorus-based flame retardant comprising a phosphorus-containing compound having a molecular weight of 400 to 800.
2.
2. The resin composition according to 1 above, wherein (A) the cellulose ester is cellulose diacetate, cellulose acetate propionate, or cellulose acetate butyrate.
3.
3. The resin composition as described in 1 or 2 above, wherein (A) the cellulose ester is cellulose diacetate.
4).
4. The resin composition as described in any one of 1 to 3 above, wherein the content of the cellulose ester (A) is 30 to 70% by mass with respect to the total solid content of the resin composition.
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 as described in any one of 1 to 6 above, wherein the water-n-octanol partition coefficient (ClogP) of the (C1) low molecular plasticizer is 2 to 6.
8).
8. The resin composition according to any one of 1 to 7 above, wherein the (C2) oligomer plasticizer has a water-n-octanol partition coefficient (ClogP) of 2 to 6.
9.
9. The resin composition as described in any one of 1 to 8 above, wherein the (C2) oligomer plasticizer has a repeating structure.
10.
10. The resin composition according to any one of 1 to 9 above, wherein the phosphorus-containing compound in (D) is a phosphate ester.
11.
Any one of 1 to 10 above, wherein the total content of the (C1) low molecular plasticizer and the (C2) oligomer plasticizer is 5% by mass to 30% by mass with respect to the total solid content of the resin composition. The resin composition according to item.
12
The total content of the (C1) low molecular plasticizer, the (C2) oligomer plasticizer and the (D) phosphorus flame retardant is 10% by mass to 40% by mass with respect to the total solid content of the resin composition. 12. The resin composition according to any one of 1 to 11 above.
13.
The value of (C1) low molecular plasticizer content / ((C1) low molecular plasticizer content and (C2) oligomer plasticizer content) is 0.2 to 0.8. The resin composition according to any one of 1 to 12.
14
((C1) low molecular plasticizer content and (C2) oligomer plasticizer content) / ((C1) low molecular plasticizer, (C2) oligomer plasticizer and (D) phosphorus flame retardant 14. The resin composition as described in any one of 1 to 13 above, wherein the value of (total content) is from 0.15 to 0.7.
15.
15. The resin composition according to any one of 1 to 14, further comprising (E) a compatibilizing agent.
16.
16. The resin composition according to any one of 1 to 15, further comprising (F) a stabilizer.
17.
The resin composition according to any one of 1 to 16, further comprising (G) a fluororesin.
18.
18. A resin composition for injection molding comprising the resin composition according to any one of 1 to 17 above.
19.
18. A molded product obtained by molding the resin composition according to any one of 1 to 17 above or the resin composition for injection molding according to 18 above.
20.
20. A housing for electrical and electronic equipment, comprising the molded body as described in 19 above.

Since the resin composition of the present invention is a resin composition from which a molded body excellent in all of moldability, flame retardancy, impact strength, and hygroscopic properties can be obtained, for example, the configuration of automobiles, home appliances, electrical and electronic devices, etc. It can be suitably used as parts, machine parts, housing / building materials, and 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 comprises (A) a cellulose ester, (B) a thermoplastic resin having an aromatic ring in the main chain, (C1) a low molecular plasticizer comprising a compound having a molecular weight of 450 or less, and (C2) a molecular weight. An oligomer plasticizer comprising a compound of 500 to 5000 and (D) a phosphorus flame retardant comprising a phosphorus-containing compound having a molecular weight of 400 to 800.

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 that provides a desired degree of acylation (eg, degree of acetylation). For example, 230 to 300 parts by mass, preferably 240 parts per 100 parts by mass of pulp (cellulose). The amount is about 290 parts by mass, more preferably about 250-280 parts by mass. 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 amount of sulfuric acid used is usually about 0.5 to 15 parts by mass, preferably about 5 to 15 parts by mass, and more preferably about 5 to 10 parts by mass with respect to 100 parts by mass of cellulose. The saponification / ripening temperature can be selected from the range of 40 to 160 ° C., 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 and the like, and a 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, etc.), 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, cellulose organic acid esters modified with an organic acid are preferable, and cellulose organic acid esters modified with an organic acid having 2 to 12 carbon atoms are 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, and cellulose diacetate and cellulose propionate are preferable. , Cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose propionate butyrate are more preferable, and cellulose diacetate, cellulose acetate propionate, and cellulose acetate butyrate are still more preferable. Of these, cellulose diacetate is particularly preferable from the viewpoints of flame retardancy and easy shape control when it is compatible with a thermoplastic resin having an aromatic ring in the main chain (leading to improvement in impact strength).

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%. It is preferably 45 to 62.5% (average substitution degree 1.8 to 3), more preferably 48 to 62.5% (average substitution degree 2 to 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 acetate butyrate. Aldrich's “cellulose acetate butyrate (acetyl substitution degree: 0.4, butyrate substitution degree: 1.1, Mn: 70000)” is a cellulose diacetate, “L-70 (acetyl). Degree of substitution: 2.45, Mn: 65000, Mw: 200000) ", manufactured by Daicel Chemical," FRM (acetyl substitution degree: 2.79, Mn: 66000, Mw: 186000) ", manufactured by Daicel Chemical, “LT-35” (acetylated) Degree: 2.87), and the like.

The content of the cellulose ester contained in the resin composition of the present invention is not particularly limited. Preferably, the cellulose ester is contained in an amount of 30 to 70% by mass, more preferably 40 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 molded object excellent in impact resistance, a flame retardance, and a moldability can be obtained. Moreover, it is excellent in terms of moisture absorption resistance when the content of the cellulose ester is 70% by mass or less.

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. This is because the resin composition can be molded by imparting thermoplasticity, which cannot be obtained with cellulose alone, to impart impact strength and flame retardancy to the resulting molded article.
The thermoplastic resin having an aromatic ring in the main chain in the present invention is not particularly limited. For example, a polycarbonate resin, a polymer containing an aromatic vinyl monomer component as a constituent component of the polymer, an aromatic polyester, polyphenylene Ether, polyether imide, polyphenylene sulfide, etc. can be mentioned, and among them, polycarbonate resin is excellent in balance of rigidity, impact resistance, heat resistance, moisture absorption resistance and moldability when used with cellulose ester. Preferred for reasons.
The number average molecular weight of the thermoplastic resin having an aromatic ring is preferably 15000 to 30000. This is because when the number average molecular weight is 15000 or more, impact strength and flame retardancy are further improved, and when the number average molecular weight is 30000 or less, 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.
The thermoplastic resin melt flow rate having an aromatic ring (MFR) is ² ~ 40cm 3 / 10min is preferred. MFR tends to correlate with the molecular weight, with respect to the preferred range 15000-30000 of the number average molecular weight, is considered as a range to be correlated MFR2 ^~ 40cm 3 / 10min.
MFR is an index of melt viscosity, and is obtained by applying a load (1.2 kg) to a resin melted at 300 ° C. in a cylinder and measuring the volume of the resin flowing out in 10 minutes. The larger the MFR value, the higher the fluidity, and the smaller the value, the lower the fluidity. The MFR measurement is also described in JIS7210.
In the present invention, a thermoplastic resin having no aromatic ring, such as polypropylene, or a thermoplastic resin having an aromatic ring only in the side chain, such as polystyrene, is preferable from the viewpoint of impact strength and flame retardancy. Absent.

(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 and 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. 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, for the reason of increasing the compatibility with the cellulose derivative.
The aliphatic polycarbonate resin that can be used for the copolymerization of the aromatic-aliphatic polycarbonate resin is preferably composed of 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 virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins can be used. Used products include optical recording media such as optical discs, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, eyeglass 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 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 Examples thereof include polycarbonate resin (Mn = 21000) (manufactured by Teijin Chemicals Ltd.), Panlite AD-5503, Panlite L-1250Y, L1225LL, Panlite K1300Y (manufactured by Teijin Chemicals Ltd.), and the like.

(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.
Examples of the aromatic dicarboxylic acid that is a raw material of the aromatic polyester in the present invention include 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 acids 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 it is a small amount, 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 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, etc. 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, commercially available products 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, in accordance with 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, it is carried out by discharging lower alcohol 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 wide range of molecular weight polymers 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 are preferable, and Is particularly preferably poly (2,6-dimethyl-1,4-phenylene) ether.

As an example of the method for producing the polyphenylene ether used in the present invention, there is a method of oxidative polymerization of 2,6-xylenol 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 may be used as it is after the polymerization step, or may be melt kneaded in a nitrogen gas atmosphere or a non-nitrogen gas atmosphere under devolatilization or non-devolatilization using an extruder or the like. You may use it by pelletizing.

Polyphenylene ether also includes polyphenylene ether modified with dienophile compounds. 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 products 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 15 to 40% by mass, and still more preferably 20 to 40% 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 includes a plasticizer comprising a compound having a molecular weight of 450 or less (also referred to as “low molecular plasticizer”) and a plasticizer comprising a compound having a molecular weight of 500 to 5000 (“oligomer plasticizer”). (Also referred to as “agent”). These plasticizers contribute to improving the moldability of the resin composition of the present invention. Furthermore, low molecular weight plasticizers can control the hygroscopicity of cellulose esters and impart moisture resistance, and oligomer plasticizers provide impact strength by supplementing the mechanical strength of molded articles containing cellulose esters. Can do.

(C1) Low molecular plasticizer The low molecular plasticizer is not particularly limited as long as it has a molecular weight of 450 or less, and is preferably a plasticizer having a molecular weight of 350 or more and 450 or less. Those commonly used for polymer molding can be used. Examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

The water-n-octanol partition coefficient (ClogP) of the low molecular plasticizer (C1) is preferably 2-6. By setting the value of ClogP within this range, the moisture absorption resistance can be further improved. Moreover, the flame retardance fall by addition of a plasticizer can be suppressed more by making ClogP into 6 or less.
The ClogP value, which is a water-n-octanol partition coefficient, refers to a common logarithmic value of n-octanol / water partition coefficient P indicating the ratio between the equilibrium concentrations of the compound in n-octanol and in water. This ClogP value is determined by a fragment approach based on the chemical structure of the compound (A. Leo, Comprehensive Medical Chemistry, Vol. 4; C. Hansch, P. G. Sammens, JB Taylor and CA A. Ramden, Eds. , P. 295, Pergramon Press, 1990), etc., and is defined as a value calculated by the “CLOGP” program available from Daylight Chemical Information Systems.

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. As the glycerin plasticizer, glyceryl tribenzoate can be preferably used.

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 dicyclohexyl phthalate. , Trimellitic acid esters such as tributyl trimellitic acid, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diadipate Adipic acid esters such as glycol, benzylbutyl diglycol adipate, citrate esters such as triethyl acetylcitrate, tributyl acetylcitrate, and di-2-ethylhexyl azelate Line esters, dibutyl sebacate, and 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 benzoate 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.
A low molecular plasticizer may use only 1 type, and may mix and use 2 or more types.

(C2) Oligomer Plasticizer The oligomer plasticizer is not particularly limited as long as it is a plasticizer having a mass average molecular weight of 500 to 5000, but is preferably a plasticizer having a mass average molecular weight of 600 to 1500. The measurement of the mass average molecular weight of an oligomer plasticizer can be performed using gel permeation chromatography (GPC). Specifically, tetrahydrofuran (THF) is used as a solvent, polystyrene gel is 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.
As the oligomer plasticizer, those commonly used for molding a polymer can be used, and like the above-mentioned low molecular plasticizer, polyester plasticizer, glycerin plasticizer, polyvalent carboxylic ester plasticizer, polyalkylene. Examples include glycol plasticizers and epoxy plasticizers.
The water-n-octanol partition coefficient (ClogP) of the oligomer plasticizer (C2) is preferably 2-6. By setting the value of ClogP within this range, an increase in hygroscopicity can be further suppressed. Moreover, the fall of the flame retardance and impact strength by addition of a plasticizer can be suppressed more by making ClogP into 6 or less.

Furthermore, as an oligomer plasticizer of this invention, what has a repeating structural unit is more preferable.
Usually, a plasticizer reduces the flame retardancy and impact strength of a resin molded article. However, when a polymer having a repeating structural unit is added as a plasticizer, it is easy to suppress a decrease in flame retardancy and impact strength. Become. This effect is considered to be derived from the fact that the repeating structural units are polymerized, so that the molecules easily have a linear structure.

As the plasticizer containing 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 can be preferably used. . 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.
Specific examples of the polyester oligomer preferably include a divalent carboxylic acid, a divalent alcohol, and a hydroxy group-containing carboxylic acid as components. 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 dihydric 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. Like the divalent carboxylic acid, it is more preferable that the compatibility with the cellulose ester is high, 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. Like the divalent carboxylic acid, it is more preferable that the compatibility with the cellulose ester is high. Specifically, glycolic acid, lactic acid, 3-hydroxybutyric acid, and 4-hydroxybutyric acid are preferable.
Furthermore, preferred examples include polyester oligomers using hydroxycarboxylic acids such as polycaprolactone and polylactic acid or cyclic lactones as raw materials.

The ends of these polyester oligomers may remain OH residues without being sealed, or may be sealed, but they are end-capped from the viewpoint of moisture absorption resistance, and have hydroxyl groups and carboxyl groups. It is preferable not to contain.
Sealing can be performed by any method such as ester sealing or ether sealing. 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, naphthoic acid and the like. it can. Examples of monoalcohols used for sealing include methanol, ethanol, propanol, isopropanol, butanol, and isobutanol.
Only one kind of oligomer plasticizer may be used, or two or more kinds may be mixed and used.

The content of the plasticizer contained in the resin composition of the present invention is not particularly limited. Preferably, the total content of (C1) low molecular plasticizer and (C2) oligomer plasticizer is 5 to 30% by mass, more preferably 10 to 20% by mass, based on the total solid content of the resin composition. . By setting it within this range, the moldability becomes more excellent, and bleeding out during kneading and molding processes can be suppressed.

The value of (C1) low molecular plasticizer content / ((C1) low molecular plasticizer content and (C2) oligomer plasticizer content) is 0.2 to 0.8. It is preferably 0.4 to 0.6. By setting it as this range, it is possible to obtain a better balance between moisture absorption resistance and impact strength of the molded article obtained. In addition, the said content is a mass reference | standard.

4). (D) Phosphorus flame retardant The resin composition of the present invention contains a phosphorus flame retardant comprising a phosphorus-containing compound. The molecular weight of the phosphorus-containing compound is 400 to 800, preferably 500 to 700. By setting the molecular weight within this range, flame retardancy can be imparted while maintaining the excellent impact strength of the molded article.

Phosphorus flame retardants are thermally decomposed when combined with resins or during molding, and generate hydrogen halide, compared to other flame retardants such as bromine flame retardants and chlorine flame retardants that are usually used. There is no possibility of corroding processing machines or molds or deteriorating the work environment, and halogens may be volatilized during incineration and disposal, which may adversely affect the environment due to the generation of harmful substances such as dioxins. There is an advantage that there are few. Moreover, compared with other flame retardants, such as a silicon containing flame retardant normally used, a nitrogen compound flame retardant, an inorganic flame retardant, there exists an advantage that the fall of a bending elastic modulus and impact resistance is suppressed.

The phosphorus-containing compound 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 thermal stability, phosphate esters are preferred, and condensed phosphate esters (particularly phosphate esters in the molecule). A compound having two or more units) is more preferable.

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 -2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate Can be mentioned.

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

The molecular weight of these phosphate esters is preferably 500 to 700 from the viewpoint that volatilization during molding and bleeding out of the molded product can be suppressed.

In addition, polyphosphates composed of salts of phosphoric acid, polyphosphoric acid and metals of Groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines 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 flame retardants can be produced by a known method. Commercially available products can also be used, for example, “PX-200, 1,3-phenylenebis (di-2,6-xylenyl phosphate) (manufactured by Daihachi Chemical)” “CR733S (manufactured by Daihachi Chemical). ) "," FP-600 (manufactured by Adeka) ".

The total content of the low molecular plasticizer, the oligomer plasticizer, and the phosphorus flame retardant contained in the resin composition of the present invention is not particularly limited, but is preferably 10 with respect to the total solid content of the resin composition. -40% by mass, more preferably 20-30% by mass. By setting it as this range, it is preferable from the viewpoints of impact resistance, brittleness, combustibility, and the like. Further, volatilization during molding and bleed-out of the molded body can be further suppressed.

The value of (low molecular plasticizer content + oligomer plasticizer content) / (low molecular plasticizer content + oligomer plasticizer content + phosphorus flame retardant content) is 0.15 to It is preferably 0.7, and more preferably 0.3 to 0.5. By setting it as this range, it is possible to obtain a better balance between moisture absorption resistance, impact strength, and flame retardancy of the molded article obtained. In addition, the said content is a mass reference | standard.

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. 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 from 0.1 to 30% by mass, more preferably from 0.5 to 20% 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.
The content of the stabilizer in the resin composition of the present invention is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition.

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, especially 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, and when mixed with other resin compositions mechanically with 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 mass or more of a monomer, and may be a mixture thereof. The polytetrafluoroethylene content in the polytetrafluoroethylene-containing mixed powder is 0.1% by mass to 90% by mass. It is preferable that it is mass%.

The content of the fluororesin in the resin composition of the present invention is preferably 0.01 to 3% by mass, more preferably 0.02 to 2% by mass, based on the total solid content of the resin composition. More preferably, it is 0.03 to 1% by mass. 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, 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, polymers other than the cellulose ester, 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 polyolefins, fatty acid amides, 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, antibacterial agent, antifungal agent, etc. Can be mentioned. Further, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose ester, either a thermoplastic polymer or 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), polyolefins 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 homopolymers and copolymers), polyurethane, aromatic and aliphatic polyketones, polyphenylene sulfide, polyether ether ketone, thermoplastic starch resin, polymethyl methacrylate, methacrylate ester-acrylate ester 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.
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 content is preferably not more than mass%, more preferably 2 to 10 mass%.

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.

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

<Manufacture of oligomer plasticizer>
Using the dicarboxylic acid component and the diol component shown in Table 1 in each part by mass shown in Table 1, an oligomer plasticizer having the terminal structure, mass average molecular weight, and ClogP value shown in Table 1 (oligomer plasticizers 1 to 4) Manufactured.

[Method for measuring mass average molecular weight]
Gel permeation chromatography (GPC) was used for measurement of the mass average molecular weight of the oligomer plasticizer. Specifically, THF was used as a solvent, polystyrene gel was used, and a molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene constituent curve was used. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.

[Measurement method of ClogP value]
The ClogP value of the oligomer plasticizer used was a value calculated with the “CLOGP” program available from Daylight Chemical Information Systems.

<Examples 1 to 27, 29 to 54, Comparative Examples 1 to 18 and 28>
[Production of molded body]
Cellulose ester, thermoplastic resin, low molecular weight plasticizer, oligomer plasticizer, flame retardant and other components were mixed at the blending ratios (mass%) shown in Tables 2 to 7 to prepare resin compositions. This resin composition was supplied to a twin-screw kneading extruder (manufactured by Technobel Co., Ltd., Ultranano) to produce pellets, and then the obtained pellets were injected into an injection molding machine (FANUC Corporation Robot S-2000i, automatic injection molding). A test piece for Charpy impact test (length: 80 mm, width: 10 mm, thickness: 4.0 mm), and a test piece for flame retardancy test (length: 120 mm, width: 13 mm, (Thickness: 1.6 mm).

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

(Charpy impact strength)
In accordance with ISO 179, a notch with an incident angle of 45 ± 0.5 ° and a tip of 0.25 ± 0.05 mm is formed on a specimen for Charpy impact test molded 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.
Moreover, those Charpy impact strength of 10 kJ / m ² or more ◎, 6 kJ / m ² or more of the ○, 4 kJ / m ² or more of the △, was × those less than 4 kJ / m ^2.

(Hygroscopic rate)
The kneaded pellets were stored in an environment of 32 ° C. and 85% for 7 days. The pellet mass before and after storage was measured, and the moisture absorption (%) was measured by (increased mass / original pellet mass) × 100.
Moreover, the thing of moisture absorption 2.5% or less was made into (circle), less than 3% was made into (triangle | delta), and 3% or more was made into x.

(Flame retardance)
Using a test piece for a flame retardant test, 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, V-2 for resin composition drip during combustion test and self-extinguishing within a predetermined time V-2, no self-extinguishing resin composition drip for self-extinguishing within a predetermined time during combustion V-1 (combustion time within 30 seconds) and V-0 (combustion time within 10 seconds).
In addition, V-0 is indicated by ○, V-1 and V-2 are indicated by Δ, and V-not is indicated by ×.

(Formability)
The moldability evaluation shows the moldability in an injection molding machine. A resin composition that is excellent in both mold transportability and injection property is indicated by ○, a resin composition that has a problem in either one, and a problem in both. A certain resin composition was set as x.
In addition, (circle) is what can shape | mold without deterioration, such as coloring, at the temperature of 230 degrees C or less at the time of shaping | molding, (triangle | delta) can be shape | molded without deterioration, such as coloring, at 240 degrees C or less at the time of shaping | molding, * Molding can be performed at a temperature higher than 240 ° C. without deterioration such as coloring, and xx cannot be molded.

In the ^table, over a MFR (cm 3 / 10min) the load to the molten resin to 300 ° C. in the cylinder (1.2 kg), by measuring the volume of flow out come resin for 10 minutes, was determined.

From the above results, when the thermoplastic resin does not have an aromatic ring in the main chain, good impact strength and flame retardancy cannot be obtained, there is no low molecular plasticizer, and there is no specified molecular weight In this case, it was confirmed that the moisture absorption resistance was not obtained, and the impact strength was inferior in the absence of the oligomer plasticizer or in the absence of the prescribed molecular weight. Furthermore, it was confirmed that in the absence of a flame retardant, the flame retardancy deteriorates.

Since the resin composition of the present invention is a resin composition from which a molded body excellent in all of moldability, flame retardancy, impact strength, and hygroscopic properties can be obtained, for example, the configuration of automobiles, home appliances, electrical and electronic devices, etc. It can be suitably used as parts, machine parts, housing / building materials, and 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.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on March 30, 2010 (Japanese Patent Application No. 2010-079928), the contents of which are incorporated herein by reference.

Claims (20)

1. (A) a cellulose ester, (B) a thermoplastic resin having an aromatic ring in the main chain, (C1) a low molecular plasticizer comprising a compound having a molecular weight of 450 or less, and (C2) a compound having a mass average molecular weight of 500 to 5,000. And (D) a phosphorus-based flame retardant comprising a phosphorus-containing compound having a molecular weight of 400 to 800.
2. The resin composition according to claim 1, wherein the cellulose ester (A) is cellulose diacetate, cellulose acetate propionate, or cellulose acetate butyrate.
3. The resin composition according to claim 1 or 2, wherein the (A) cellulose ester is cellulose diacetate.
4. The resin composition according to any one of claims 1 to 3, wherein the content of the cellulose ester (A) is 30 to 70 mass% with respect to the total solid content of the resin composition.
5. The resin composition according to any one of claims 1 to 4, wherein the (B) thermoplastic resin is a polycarbonate resin.
6. 6. The resin composition according to claim 1, wherein the number average molecular weight of the (B) thermoplastic resin is 15000 to 30000.
7. 7. The resin composition according to claim 1, wherein the (C1) low molecular plasticizer has a water-n-octanol partition coefficient (ClogP) of 2 to 6.
8. The resin composition according to any one of claims 1 to 7, wherein the (C2) oligomer plasticizer has a water-n-octanol partition coefficient (ClogP) of 2 to 6.
9. The resin composition according to any one of claims 1 to 8, wherein the (C2) oligomer plasticizer has a repeating structure.
10. The resin composition according to any one of claims 1 to 9, wherein the phosphorus-containing compound in (D) is a phosphate ester.
11. The total content of the (C1) low molecular plasticizer and the (C2) oligomer plasticizer is 5% by mass to 30% by mass with respect to the total solid content of the resin composition. 2. The resin composition according to item 1.
12. The total content of the (C1) low molecular plasticizer, the (C2) oligomer plasticizer and the (D) phosphorus flame retardant is 10% by mass to 40% by mass with respect to the total solid content of the resin composition. The resin composition according to any one of claims 1 to 11.
13. The value of (C1) content of low molecular plasticizer / ((C1) content of low molecular plasticizer and (C2) content of oligomer plasticizer) is 0.2 to 0.8. The resin composition according to any one of 1 to 12.
14. ((C1) low molecular plasticizer content and (C2) oligomer plasticizer content) / ((C1) low molecular plasticizer, (C2) oligomer plasticizer and (D) phosphorus flame retardant The resin composition according to any one of claims 1 to 13, which has a value of (total content) of 0.15 to 0.7.
15. The resin composition according to any one of claims 1 to 14, further comprising (E) a compatibilizing agent.
16. The resin composition according to any one of claims 1 to 15, further comprising (F) a stabilizer.
17. The resin composition according to any one of claims 1 to 16, further comprising (G) a fluororesin.
18. An injection molding resin composition comprising the resin composition according to any one of claims 1 to 17.
19. A molded product obtained by molding the resin composition according to any one of claims 1 to 17 or the resin composition for injection molding according to claim 18.
20. A housing for electrical and electronic equipment comprising the molded body according to claim 19.