WO2013035439A1 - Polycarbonate resin composition and molded body - Google Patents

Abstract

Provided are: a polycarbonate resin composition characterized by containing (C) 1-50 parts by mass of a lignophenol having a particular structure for every 100 parts by mass of a resin mixture comprising (A) 99-30 mass% of a polycarbonate resin and (B) 1-70 mass% of an aromatic polyester resin; and a molded body formed by molding the polycarbonate resin composition. The polycarbonate resin composition has a high biomass degree (vegetation degree), superior environmental performance such as a reduction in the amount of carbon dioxide emission and a reduction in fossil starting materials, superior resistance to moist heat, fluidity, impact resistance, and incombustibility, while maintaining high heat resistance, is capable of high fluidization, is capable of an increase in solvent resistance, has increased lignophenol dispersiveness, has favorable compatibility with polycarbonate resins and polyester resins, and obtains a molded body having gloss and transparency.

Description

Polycarbonate resin composition and molded body

The present invention relates to a polycarbonate resin composition and a molded body using the same. More specifically, by using a biomass material, it has excellent environmental performance, high fluidity and high impact resistance, excellent heat resistance and flame resistance, and excellent solvent resistance and moisture and heat resistance, and molded appearance. The present invention also relates to a good polycarbonate resin composition and a molded body using the same.

Polycarbonate resins are excellent in mechanical properties such as heat resistance and impact resistance, and thus are used as materials for various parts in the electric / electronic field, automobile field, and the like. Polycarbonate resins may be used in combination with polycarbonate resins. In order to make a composition in which a polyester resin is blended with such a polycarbonate resin, a flame retardant such as an organic phosphate is used instead of a halogen flame retardant because of a request for non-halogenation. .
However, there is a problem in that the heat resistance and heat-and-moisture resistance of the obtained polycarbonate resin composition are reduced by blending a phosphorus-based flame retardant such as an organic phosphate ester into the composition of such a polycarbonate resin and a polyester-based resin. was there.
From the viewpoint of environmental protection, polylactic acid may be used as a biodegradable polyester resin. For example, in Patent Documents 1 and 2, by blending lignophenol having a specific structure with polycarbonate resin or polycarbonate resin containing polylactic acid, it has excellent environmental performance, and has high fluidity and high impact resistance. A polycarbonate resin composition having excellent flame retardancy and heat resistance is described. However, these documents do not describe blending polyester resins other than polylactic acid and the effects thereof. Moreover, the low gloss of the polycarbonate resin and polylactic acid may result in a decrease in physical properties or a decrease in the dispersibility of lignophenol, resulting in a decrease in gloss of the molded product.

JP 2010-150424 A JP 2010-202712 A

The present invention relates to a resin composition in which a polyester resin is blended with a polycarbonate resin, and has a high degree of biomass (vegetation degree) without using a halogen-based flame retardant and a phosphorus-based flame retardant, reducing carbon dioxide emissions and fossil raw materials. In addition to excellent environmental performance such as reduction, it also has excellent heat and moisture resistance, fluidity, impact resistance and flame retardancy, and can be highly fluidized while maintaining high heat resistance, and can also improve solvent resistance. Disclosed is a polycarbonate resin composition in which the dispersibility of lignophenol is improved and the compatibility between a polycarbonate resin and a polyester resin is good, and a molded article having a transparent feeling and gloss can be obtained, and a molded article using the same. For the purpose.

As a result of intensive studies, the present inventors have achieved the above object by blending (A) polycarbonate resin, (B) aromatic polyester resin, and (C) lignophenol at a specific ratio. As a result, the present invention has been completed.
That is, the present invention provides the following polycarbonate resin composition.

1. (A) 99-30% by mass of polycarbonate resin and (B) 1-70% by mass of aromatic polyester resin
Consisting of 100 parts by mass of the resin mixture,
(C) A polycarbonate resin composition comprising 1 to 50 parts by mass of lignophenol having a structure represented by the following general formula (I).

[Wherein R ¹ and R ⁴ represent an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a phenoxy group, R ² represents a hydroxyaryl group or an alkyl-substituted hydroxyaryl group, and R ³ represents a hydroxyalkyl group or an alkyl group. Group, an aryl group, an alkyl-substituted aryl group or —OR ⁵ (R ⁵ represents a hydrogen atom, an alkyl group or an aryl group), and R ¹ to R ⁵ other than a hydrogen atom may have a substituent. Often, p and q are integers from 0 to 4. However, when p is 2 or more, the plurality of R ¹ may be the same or different, and when q is 2 or more, the plurality of R ⁴ are the same or different. May be. ]
2. (A) The polycarbonate resin composition as described in 1 above, wherein the polycarbonate resin is an aromatic polycarbonate resin.
3. (B) The polycarbonate resin composition according to 1 or 2 above, wherein the aromatic polyester resin is polyethylene terephthalate or polybutylene terephthalate.
4). A molded product obtained by molding the polycarbonate resin composition according to any one of the above 1 to 3.

According to the present invention, by using lignophenol, which is an environmentally friendly biomass raw material, without using a halogen-based flame retardant and a phosphorus-based flame retardant, a resin composition in which a polyester resin is blended with a polycarbonate resin, (Vegetable degree) is high, and it has excellent environmental performance such as carbon dioxide emission reduction and fossil raw material reduction. It also has excellent heat and moisture resistance, fluidity, impact resistance and flame resistance, and maintains high heat resistance. Fluidization is possible, solvent resistance can be improved, lignophenol dispersibility is improved, and compatibility between the polycarbonate resin and the polyester resin is good. can get.

It is a perspective view of the jig | tool which fixes the test piece used for evaluation of the grease resistance of this invention composition.

The polycarbonate resin composition of the present invention is a polycarbonate resin composition containing (A) a polycarbonate resin, (B) an aromatic polyester resin, and (C) a lignophenol. Hereinafter, each component and other components that can be added will be described.

[(A) Polycarbonate resin]
In the present invention, the (A) polycarbonate resin may be an aromatic polycarbonate resin or an aliphatic polycarbonate resin, but it is preferable to use an aromatic polycarbonate resin because it is more excellent in impact resistance and heat resistance.
(Aromatic polycarbonate resin)
As the aromatic polycarbonate resin, an aromatic polycarbonate resin usually produced by a reaction between a dihydric phenol and a carbonate precursor can be used. The aromatic polycarbonate resin can be a main component of the resin composition because it has better heat resistance, flame retardancy, and impact resistance than other thermoplastic resins.

Examples of the dihydric phenol include various compounds such as 4,4′-dihydroxydiphenyl; 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, And bis (4-hydroxyphenyl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane [bisphenol A]; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) oxide; bis (4 -Hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ketone. Of these, bisphenol A is preferred. The dihydric phenol may be a homopolymer using one of these dihydric phenols or a copolymer using two or more. Further, it may be a thermoplastic random branched polycarbonate resin obtained by using a polyfunctional aromatic compound in combination with a dihydric phenol.
Examples of the carbonate precursor include carbonyl halide, haloformate, carbonate ester and the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.

In the production of the aromatic polycarbonate resin used in the present invention, a terminal terminator can be used as necessary, and examples thereof include a monohydric phenol compound represented by the following general formula (II).

(Wherein R ¹⁰ represents an alkyl group having 1 to 35 carbon atoms, and a represents an integer of 0 to 5)
As the monohydric phenol compound represented by the general formula (II), a para-substituted product is preferable. Specific examples of monohydric phenol compounds include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. it can. These monohydric phenols may be used alone or in combination of two or more.

The aromatic polycarbonate resin used in the present invention may have a branched structure. In order to introduce a branched structure, a branching agent may be used. For example, 1,1,1-tris (4-hydroxyphenyl) ethane; α, α ′, α ″ -tris (4-hydroxyphenyl) -1, 3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; phloroglucin, A compound having three or more functional groups such as trimellitic acid and isatin bis (o-cresol) can be used.
The viscosity average molecular weight of the aromatic polycarbonate resin used in the present invention is preferably 10,000 to 40,000, more preferably 13,000 to 30,000, from the viewpoint of physical properties of the resin composition.

In the present invention, as the aromatic polycarbonate resin, an aromatic polycarbonate-polyorganosiloxane copolymer or a resin containing an aromatic polycarbonate-polyorganosiloxane copolymer is used so that the flame retardancy and low temperature are reduced. The impact resistance can be further improved. The polyorganosiloxane constituting the copolymer is more preferably polydimethylsiloxane from the viewpoint of flame retardancy.

[(B) Aromatic polyester resin]
In the present invention, the (B) aromatic polyester-based resin is a component that improves the solvent resistance of the polycarbonate resin composition and increases the fluidity so as to obtain a molded article having a sense of transparency and gloss.

As the aromatic polyester-based resin of the present invention, various resins can be used, and a polyester resin obtained by polycondensation of a bifunctional carboxylic acid component and an alkylene glycol component is particularly preferable. Here, the following can be mentioned as a bifunctional carboxylic acid component and an alkylene glycol component.

Examples of the bifunctional carboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Among these, terephthalic acid is preferable, and other difunctional carboxylic acids can be used in combination as long as the effects of the present invention are not impaired.

Next, the alkylene glycol component is not particularly limited. Specifically, ethylene glycol, propylene-1,2-glycol, propylene-1,3-glycol, butylene-1,4-glycol, butylene-2 , 3-glycol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, decane-1,10-diol, aliphatic diol having 2 to 10 carbon atoms, etc. may be used. it can. Of these, ethylene glycol and butylene glycol are preferred.

In the present invention, the (B) aromatic polyester-based resin includes polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyarylate, etc., among them, polyethylene terephthalate or polybutylene. Terephthalate is preferred.

The production of the aromatic polyester resin as the component (B) can be carried out by a usual method in the presence or absence of a polycondensation catalyst containing titanium, germanium, antimony or the like. For example, polyethylene terephthalate usually undergoes an esterification reaction between terephthalic acid and ethylene glycol or transesterifies a lower alkyl ester such as dimethyl terephthalate with ethylene glycol to produce a glycol ester of terephthalic acid and / or its low weight. It is produced by a first stage reaction for producing a coalescence and a second stage reaction by further polymerizing the glycol ester and / or its low polymer to form a polymer having a high degree of polymerization.

[(C) lignophenol]
In the present invention, (C) lignophenol has a structure represented by the following general formula (I).

In the general formula (I), R ¹ and R ⁴ are alkyl groups (preferably alkyl groups having 1 to 4 carbon atoms, specifically methyl group, ethyl group, propyl group, etc.), aryl groups (preferably carbon atoms). An aryl group having a number of 6 to 10, specifically a phenyl group, etc.), an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, specifically a methoxy group, an ethoxy group, a propoxy group, etc.), An aralkyl group (preferably an aralkyl group having 12 to 20 carbon atoms, specifically a benzyl group or the like) or a phenoxy group is shown.

R ² is a hydroxyaryl group (preferably a hydroxyaryl group having 6 to 14 carbon atoms, specifically 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, etc.) or alkyl-substituted hydroxyaryl Group (preferably a hydroxyaryl group having 7 to 18 carbon atoms, specifically 2-hydroxy-5-methylphenyl group, 3-hydroxy-5-methylphenyl group, 4-hydroxy-5-methylphenyl group, etc. R ³ represents a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 4 carbon atoms, specifically hydroxymethyl group, hydroxyethyl group, etc.), an alkyl group (preferably having 1 to 4 carbon atoms). An alkyl group, specifically a methyl group, an ethyl group, a propyl group, or the like) or an aryl group (preferably having 6 to 1 carbon atoms) An aryl group of 0, specifically a phenyl group, etc., an alkyl-substituted aryl group (preferably an aryl group substituted with an alkyl group having 1 to 10 carbon atoms, specifically a toluyl group, a xylyl group, etc. ) Or —OR ⁵ (R ⁵ represents a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group, preferably an aryl group having 6 to 10 carbon atoms).

R ¹ to R ⁵ other than a hydrogen atom may each have a substituent, and p and q each represents an integer of 0 to 4.
However, when p is 2 or more, the plurality of R ¹ may be the same or different, and when q is 2 or more, the plurality of R ⁴ are the same or different. May be.

In the present invention, the structure represented by the general formula (I) is preferably a naturally derived structure.
In the case of a naturally derived structure, R ¹ and R ⁴ in the above general formula (I) are determined by the tree species, the substituent represented by R ¹ and R ⁴ is a methoxy group, and p and q are each 1 or 2 There are only structures or structures that do not have one or both of the substituents represented by R ¹ and R ⁴ .
For example, in general, softwood is a 3-substituted product with one methoxy group, and broad-leaved trees and herbs are 1: 1 with a 3-substituted product with one methoxy group and two 3,5-substituted products with two methoxy groups. Exists. In addition, in the case where any tree species is a young tree, a structure that does not have a part of the substituent that is a methoxy group may be included.

R ³ is a hydroxymethyl group in the naturally derived structure.
As described above, R ² is a hydroxyaryl group (preferably a hydroxyaryl group having 6 to 14 carbon atoms, specifically 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4 -Hydroxyphenyl group or the like) or alkyl-substituted hydroxyaryl group (preferably a hydroxyaryl group having 7 to 18 carbon atoms, specifically 2-hydroxy-5-methylphenyl group, 3-hydroxy-5-methylphenyl group) , 4-hydroxy-5-methylphenyl group and the like.
In the present invention, the variation as (C) lignophenol can be increased by freely controlling R ² of the naturally derived structure.

The mass average molecular weight of the lignophenol represented by the general formula (I) is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, in terms of polystyrene. The both end groups of lignophenol represented by the general formula (I) are preferably phenolic hydroxyl groups, that is, one is a hydroxyl group and the other is a hydrogen atom.
Moreover, as a specific structure represented by the said general formula (I) of (C) component which can be used in this invention, the lignocresol structure represented, for example by following formula (III) is mentioned.

(Lignophenol)
Lignophenol is a compound derived from lignin contained in timber, paper, etc., and lignin, for example, acts as an intercellular adhesion substance filled in the gaps of carbohydrates that form the cytoskeleton of trees. is there. Since the structure of lignin is very complex and difficult to use as it is, it is useful to convert it to lignophenol.

((C) Lignophenol production method)
The component (C) of the present invention can be obtained by adding a phenol derivative to a lignocellulosic material such as wood or paper and then hydrolyzing it with an acid to separate it into lignophenol and a carbohydrate. The component (C) includes an alkali-treated derivative of the above lignophenol, or a derivative in which the hydroxyl group in the above-mentioned lignophenol or the above-mentioned alkali-treated derivative of lignophenol is protected.

Examples of lignocellulosic substances include wooded materials, various materials mainly wood, such as wood flour, chips, waste materials, and mill ends. Moreover, as wood to be used, any kind of wood such as conifers and hardwoods can be used. Furthermore, various herbaceous plants and related samples such as agricultural wastes can be used.
When lignophenol is separated using these materials, those obtained without heating and pressurization in the separation process are preferably used.

As the phenol derivative, a monovalent phenol derivative, a divalent phenol derivative, a trivalent phenol derivative, or the like can be used. Specific examples of the monovalent phenol derivative include phenol, naphthol, anthrol, anthroquinoneol and the like, and each may have one or more substituents. Specific examples of the divalent phenol derivative include resorcinol, hydroquinone and the like, each of which may have one or more substituents. Specific examples of the trivalent phenol derivative include pyrogallol and the like, which may have one or more substituents.
For example, those including those other than those mentioned above such as hydroxyanthracene, methoxyphenol (mono-di-tri), methylcatechol, biphenyl, dimethylhydroxyaryl, trimethylhydroxyaryl, etc. can also be used as the phenol derivative.

The type of substituent that the phenol derivative may have is not particularly limited, and may have any substituent, but is preferably a group other than an electron-withdrawing group (such as a halogen atom), For example, an alkyl group (methyl group, ethyl group, propyl group, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, etc.), an aryl group (phenyl group etc.), etc. are mentioned. Moreover, it is preferable that at least one of the two ortho positions of the phenolic hydroxyl group on the phenol derivative is unsubstituted. Particularly preferred examples of phenol derivatives are cresol, in particular m-cresol or p-cresol.

As the acid, an acid having swelling property with respect to cellulose is preferable. Specific examples of the acid include sulfuric acid having a concentration of 65% by mass or more (for example, 72% by mass sulfuric acid), 85% by mass or more of phosphoric acid, 38% by mass or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, Examples thereof include trichloroacetic acid and formic acid.

Examples of the method for extracting and separating lignophenol obtained as described above include the following two methods.
The first method is the method described in Japanese Patent No. 2895087. Specifically, lignin is solvated into a phenol derivative by infiltrating a lignocellulosic material such as wood flour, and then concentrated acid is added to dissolve the lignocellulosic material. At this time, the cation at the side chain α-position of the lignin basic structural unit is attacked by the phenol derivative, and lignophenol in which the phenol derivative is introduced at the benzyl position is generated in the phenol derivative phase. And it is the method of extracting lignophenol from a phenol derivative phase.
In the extraction of lignophenol from the phenol derivative phase, the precipitate obtained by adding the phenol derivative phase to a large excess of ethyl ether is collected and dissolved in acetone. The acetone insoluble part is removed by centrifugation, and the acetone soluble part is concentrated. The acetone soluble part is dropped into a large excess of ethyl ether, and the precipitate section is collected. After the solvent is distilled off from this precipitation section, it is dried and lignophenol is obtained as a dried product. The crude lignophenol can be obtained by simply removing the phenol derivative phase by distillation under reduced pressure. Moreover, an acetone soluble part can also be used for a derivatization process (alkali process) as a lignophenol solution as it is.

The second method is a method described in Japanese Patent Laid-Open No. 2001-64494. Specifically, a lignocellulosic material is infiltrated with a solvent in which a solid or liquid phenol derivative is dissolved, and then the solvent is distilled off (phenol derivative sorption step). Next, a concentrated acid is added to this lignocellulosic material to dissolve the cellulose component, and lignophenol is produced in the phenol derivative phase and the lignophenol is extracted as in the first method.
Extraction of lignophenol can be performed in the same manner as in the first method. Alternatively, as another extraction method, the entire reaction solution after the concentrated acid treatment is put into excess water, insoluble sections are collected by centrifugation, deoxidized and dried. Acetone or alcohol is added to the dried product to extract lignophenol. Further, as in the first method, this soluble segment is dropped into excess ethyl ether or the like to obtain lignophenol as an insoluble segment.

In these first and second two methods, the second method is the latter extraction method, in particular, the method of extracting and separating lignophenol with acetone or alcohol, the amount of phenol derivative used is It is economical because it requires less. Moreover, since this method can process many lignocellulosic materials with a small amount of a phenol derivative, it is suitable for large-scale synthesis of lignophenol.

The component (C) of the present invention obtained by the above method generally has the following characteristics. However, the characteristics of the component (C) used in the present invention are not limited to the following.
(1) The mass average molecular weight is about 1,000 to 200,000.
(2) Almost no conjugated system in the molecule, and the color tone is extremely light.
(3) About 170 ° C. derived from conifers and about 130 ° C. derived from broad-leaved trees.
(4) As a result of selective grafting of the phenol derivative to the α position of the side chain, it is a lignin derivative that has a very large amount of phenolic hydroxyl groups and is imparted with high phenol characteristics.
(5) The aromatic nucleus of the lignin structural unit and the aromatic nucleus of the phenol derivative grafted at the side chain α-position form a diphenylmethane type structure, and self-condensation is suppressed.
(6) Easily dissolved in various solvents such as methanol, ethanol, acetone, dioxane, pyridine, THF (tetrahydrofuran), DMF (dimethylformamide) and the like.

Further, the component (C) obtained by the above method can be used after being derivatized by further alkali treatment.
Lignophenol obtained from natural lignin by a phase separation process is stable as a whole because the α-position of its activated carbon is blocked with a phenol derivative. However, the phenolic hydroxyl group readily dissociates under alkaline conditions, and the resulting phenoxide ion attacks the β-position of the adjacent carbon when it is sterically possible. As a result, the β-position aryl ether bond is cleaved, the lignophenol is reduced in molecular weight, and the phenolic hydroxyl group in the introduced phenol nucleus moves to the lignin matrix. Accordingly, the alkali-treated derivative is expected to have improved hydrophobicity compared to lignophenol before the alkali treatment.
At this time, the alkoxide ion present in the carbon at the γ-position or the carbanion of the lignin aromatic nucleus is also expected to attack the β-position, but this requires much higher energy than the phenoxide ion. Therefore, the adjacent group effect of the phenolic hydroxyl group of the introduced phenol nucleus preferentially appears under mild alkaline conditions, and further reaction occurs under severer conditions, and the phenolic hydroxyl group of the once etherified cresol nucleus is regenerated. As a result, it is expected that lignophenol is further reduced in molecular weight and hydrophilicity is increased by increasing the number of hydroxyl groups.

Furthermore, lignophenol and lignophenol derivatives obtained by alkali treatment thereof have various characteristics due to the presence of phenolic and alcoholic hydroxyl groups. By protecting this hydroxyl group, a derivative having different characteristics can be obtained. Examples of the method for protecting the hydroxyl group include protecting the hydroxyl group with a protecting group such as an acyl group (eg, acetyl group, propionyl group, benzoyl group). Further, by performing hydroxymethylation, a new benzyl structure is generated, and variations can be further expanded.

[A blending ratio of (A) polycarbonate resin, (B) aromatic polyester resin and (C) lignophenol]
The blending ratio of (A) polycarbonate resin, (B) aromatic polyester-based resin and (C) lignophenol is a resin mixture 100 comprising 99 to 30% by mass of component (A) and 1 to 70% by mass of component (B). The component (C) is 1 to 50 parts by mass with respect to parts by mass. When the component (A) in the total amount of the component (A) and the component (B) exceeds 99% by mass, the effect of improving fluidity and solvent resistance is reduced, and when it is less than 30% by mass, the impact resistance is decreased. , Heat resistance and flame retardancy are not preferable. Preferably, the component (A) is 90 to 70% by mass, the component (B) is 10 to 30% by mass, and the component (A) is 95 to 70% by mass, and the component (B) is 5 to 30% by mass. .
In addition, when the component (C) is less than 1 part by mass, flame retardancy and fluidity cannot be improved, and when it exceeds 50 parts by mass, the fluidity becomes extremely high, so that the moldability deteriorates and the molding is difficult. Since it becomes difficult, it is not preferable. Component (C) is preferably 3 to 35 parts by mass, and more preferably 10 to 30 parts by mass.

[Additive component]
The polycarbonate resin composition of the present invention may contain an additive component as necessary in addition to the components (A) to (C). For example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (permanent antistatic performance imparted), benzotriazole-based or benzophenone-based UV absorbers, hindered amine-based light stabilizers (Weathering agent), antibacterial agent, compatibilizer, colorant (dye, pigment) and the like. The amount of additive component added is not particularly limited as long as the properties of the polycarbonate resin composition of the present invention are maintained.

[Kneading / Molding]
The polycarbonate resin composition of the present invention can be obtained by blending the components (A) to (C) in the above proportions, and adding the additive components used as necessary in an appropriate proportion and kneading. Mixing and kneading at this time are premixed with a commonly used equipment such as a ribbon blender, a drum tumbler, etc., then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. This method can be performed by a method using a machine and a conider. The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C.
The polycarbonate resin composition of the present invention is obtained by using the above melt-kneading molding machine or the obtained pellet as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method. Various molded bodies can be produced by a foam molding method or the like. In particular, the above-mentioned melt-kneading method can be used to produce a pellet-shaped molding raw material, and then use the pellet to suitably produce an injection-molded body by injection molding or injection compression molding.

The present invention also provides a molded article obtained by molding the above-described polycarbonate resin composition of the present invention.
A molded article formed by molding the polycarbonate resin composition of the present invention, preferably an injection molded article (including injection compression), a copying machine, a fax machine, a television, a radio, a tape recorder, a video deck, a personal computer, a printer, a telephone, Used for OA equipment such as information terminals, refrigerators, microwave ovens, home appliances, housings and various parts of electrical / electronic equipment.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The performance test of the resin composition obtained in each example was performed as follows.
(1) Melt index (MI): fluidity Measurement conditions: Measured according to ASTM standard D-1238 at a resin temperature of 260 ° C. and a load of 21.18 N.
(2) Izod impact strength (IZOD): Impact resistance Measured at a measurement temperature of 23 ° C. according to ASTM standard D-256 using a test piece having a thickness of 1/8 inch.
(3) Thermal deformation temperature (deflection temperature under load): heat resistance Measured at a bending stress of 1.8 MPa according to ASTM standard D-648.
(4) Oxygen index (LOI): Flame retardancy Measured according to ASTM standard D-2863. The oxygen index is a value indicating the minimum oxygen concentration necessary for the test piece to maintain combustion in terms of volume% in air.
(5) Moisture and heat resistance The moisture and heat resistance was determined by visually observing the presence or absence of surface deformation after leaving a flat test piece (80 mm × 80 mm × 1 mm) in an environment of 60 ° C. and 80% humidity for 300 hours.
○ indicates no deformation of the surface.
In x, surface swelling and deformation are recognized.
(6) Molding appearance It observed visually. The case where no appearance defect such as pearly luster or silver was observed was rated as “◯”, and the case where an appearance defect such as pearly luster or silver was observed was marked as “X”.
(7) Grease resistance: Conforms to the solvent resistance chemical resistance evaluation method (limit strain due to 1/4 ellipse).
A test piece (thickness = 3 mm) was fixed to a quarter ellipse surface shown in FIG. 1 (perspective view), and Albania grease (manufactured by Showa Shell Sekiyu KK) was applied to the test piece and held for 48 hours. The minimum length (X) at which cracks occurred was read, and the critical strain (%) was determined from the following formula (1).

Moreover, each component used in each example is as follows.
(A) Polycarbonate resin Aromatic polycarbonate resin: Product name Toughlon A1900 [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 19,500]
(B) Aromatic polyester-based resin Polyethylene terephthalate (PET): [Mitsui Chemicals, Inc.] trade name J125
Polybutylene terephthalate (PBT): [Mitsubishi Rayon Co., Ltd.] Trade name N1300
(C) Lignophenol Lignocresol:
Lignocresol represented by the formula (III):
Beech wood flour was immersed in an acetone solution containing p-cresol, so that p-cresol was sorbed onto the wood flour. 72% by mass sulfuric acid was added to the wood powder after sorption and stirred vigorously. After the stirring was stopped, purified water was added and allowed to stand, and the operation of decanting the supernatant was repeated 6 times to remove acid and excess p-cresol. The precipitate in the container was dried, acetone was added thereto to extract lignocresol having the structure of formula (III), and then acetone was distilled off. Specifically, it was performed in the same manner as in Example 1 of JP-A-2001-64494.
Other components (polylactic acid PLA): [manufactured by Nature Works] product name 3001D
(Phosphorus flame retardant BDP): Bisphenol A bis (diphenyl phosphate) [manufactured by ADEKA Corporation]

[Examples 1 to 4 and Comparative Examples 1 to 5]
The above components were blended in the proportions shown in Table 1, supplied to an extruder (model name: VS40, manufactured by Tanabe Plastic Machinery Co., Ltd.), melt-kneaded at 240 ° C., and pelletized. In all examples and comparative examples, 0.2 parts by mass of Irganox 1076 (manufactured by BASF) as a phenol-based antioxidant and 0.1 parts by mass of Adekastab C (manufactured by ADEKA) as a phosphorus-based antioxidant Respectively. The obtained pellets were dried at 120 ° C. for 12 hours, and then injection molded under conditions of an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model: IS100N) cylinder temperature 260 ° C. and mold temperature 80 ° C. to obtain a test piece. It was. The performance was evaluated by the performance test using the obtained test piece, and the results are shown in Table 1.

Table 1 shows the following.
Examples 1 to 4
(A) Addition of (B) aromatic polyester resin and (C) lignophenol to polycarbonate resin is excellent in fluidity, impact resistance and heat resistance, as well as flame resistance, solvent resistance and moisture and heat resistance. Moreover, a polycarbonate resin composition having a good molded appearance can be obtained.
Comparative examples 1 to 5
(B) If an aromatic polyester resin is not used, fluidity and impact resistance are lowered, and silver is generated to cause poor appearance (Comparative Example 1). (B) Polylactic acid instead of the aromatic polyester resin Even in the case of using, the impact resistance is low, there is no gloss and the appearance is poor (Comparative Example 5), and if the amount of (C) lignophenol is too large, molding becomes difficult and injection molding cannot be performed (Comparative Example 3). . Moreover, when the compounding ratio of (A) polycarbonate resin decreases, fluidity is too high, impact resistance and heat resistance are lowered, and flame retardancy is also lowered (Comparative Example 2). And even if it changes to (B) lignophenol and a phosphorus flame retardant is used, it will be inferior in impact resistance, heat resistance, and heat-and-moisture resistance (comparative example 4).

The polycarbonate resin composition of the present invention can be suitably used as various materials in electronic / electrical equipment, information / communication equipment, OA equipment, automobile field, building material field, and the like.

Claims (4)

(A) 99-30% by mass of polycarbonate resin and (B) 1-70% by mass of aromatic polyester resin
Consisting of 100 parts by mass of the resin mixture,
(C) A polycarbonate resin composition comprising 1 to 50 parts by mass of lignophenol having a structure represented by the following general formula (I).

[Wherein R ¹ and R ⁴ represent an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a phenoxy group, R ² represents a hydroxyaryl group or an alkyl-substituted hydroxyaryl group, and R ³ represents a hydroxyalkyl group or an alkyl group. Group, an aryl group, an alkyl-substituted aryl group or —OR ⁵ (R ⁵ represents a hydrogen atom, an alkyl group or an aryl group), and R ¹ to R ⁵ other than a hydrogen atom may have a substituent. Often, p and q are integers from 0 to 4. However, when p is 2 or more, the plurality of R ¹ may be the same or different, and when q is 2 or more, the plurality of R ⁴ are the same or different. May be. ] The polycarbonate resin composition according to claim 1, wherein (A) the polycarbonate resin is an aromatic polycarbonate resin. (B) The polycarbonate resin composition of Claim 1 whose aromatic polyester-type resin is a polyethylene terephthalate or a polybutylene terephthalate. A molded article formed by molding the polycarbonate resin composition according to any one of claims 1 to 3.

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