JP2008189766A - Resin composition, resin-molded article, box body and method for producing resin-molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in flame retardance, mechanical characteristics and thermal characteristics even in the case of containing a recycled material. <P>SOLUTION: This resin composition contains (A) a polyorganosiloxane-containing aromatic polycarbonate resin, (B) an aromatic polycarbonate resin other than the component (A), and (C) a phosphorus-based flame retardant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition, a resin molded body, a housing, and a method for manufacturing the resin molded body.

  Resin moldings are widely used in fields such as the office equipment field, the electrical / electronic equipment field, and the automobile field. Particularly in recent years, an alloy resin (hereinafter sometimes referred to as “PC / ABS alloy”) of a polycarbonate resin and an acrylonitrile-butadiene-styrene resin excellent in mechanical properties such as impact resistance strength, or a polycarbonate resin and a polystyrene resin. A resin molded body made of a resin composition blended with a polycarbonate-based resin such as an alloy resin (hereinafter sometimes referred to as “PC / PS alloy”) is often used for parts such as cases of office equipment and electronic / electric equipment. It has become so.

  In addition, since a high degree of flame retardancy is required for molded articles of office equipment and home appliances, a flame retardant for imparting flame retardancy is usually blended in the resin molded body. Recently, phosphorus-based flame retardants have been actively developed as non-halogen flame retardants in order to avoid corrosion during processing and generation of toxic gases during combustion. In addition, for the purpose of satisfying the heat resistance, impact resistance and flame retardancy of a resin molded body, for example, a technique for containing a specific phosphorus compound in a resin composition containing an aromatic polycarbonate and a styrene resin has been proposed. (For example, see Patent Document 1).

  On the other hand, in the field of office equipment such as computers, printers, and copiers, from the viewpoint of resource reuse and environmental protection, there is a growing demand for recycling to reuse products collected from the market. However, a resin molded body used for a housing of office equipment has high demands on mechanical characteristics such as impact strength and thermal characteristics such as heat resistance. For this reason, satisfying the above characteristics even for a resin molded body using a recycled material (hereinafter sometimes referred to as “recycled material”) is the key to improving the utilization rate of the recycled material.

  In the production of resin moldings, the resin composition is molded using a mold corresponding to each part, but the same mold can be used when only new materials are used and when recycled materials are included. Is desirable in terms of manufacturing cost. Therefore, the resin composition containing the recycled material is required to have excellent thermal characteristics such as low thermal shrinkage.

Japanese Patent No. 3432069

  An object of this invention is to provide the resin composition which is excellent in a flame retardance, a mechanical characteristic, and a thermal characteristic even if it is a case where a recycled material is included. Moreover, an object of this invention is to provide the manufacturing method and housing | casing of a resin molding which consists of such a resin composition, a resin molding, and a housing | casing.

  In order to achieve the above object, the invention described in claim 1 includes (A) a polyorganosiloxane-containing aromatic polycarbonate resin, (B) an aromatic polycarbonate resin other than the component (A), and (C) a phosphorus-based resin. A resin composition comprising a flame retardant is provided.

  Further, the invention according to claim 2 is the invention according to claim 1, wherein the resin is an alloy resin of an aromatic polycarbonate resin other than the component (A) and an acrylonitrile-butadiene-styrene resin and / or other than the component (A). Provided is a resin composition containing a recycled material of a resin molded article comprising an alloy resin of an aromatic polycarbonate resin and a polystyrene resin and a phosphorus flame retardant.

  The invention according to claim 3 comprises (A) a polyorganosiloxane-containing aromatic polycarbonate resin, (B) an aromatic polycarbonate resin other than the component (A), and (C) a phosphorus-based flame retardant. A resin molded body is provided.

  The invention according to claim 4 comprises (A) a polyorganosiloxane-containing aromatic polycarbonate resin, (B) an aromatic polycarbonate resin other than the component (A), and (C) a phosphorus-based flame retardant. There is provided a method for producing a resin molded body comprising a step of molding a resin composition.

  The invention according to claim 5 is the invention according to claim 4, wherein the resin composition is an alloy resin of an aromatic polycarbonate resin other than the component (A) and an acrylonitrile-butadiene-styrene resin and / or ( There is provided a method for producing a resin molded product comprising a recycled material of a resin molded product comprising an alloy resin of an aromatic polycarbonate resin and a polystyrene resin other than the component A) and a phosphorus flame retardant.

  The invention according to claim 6 is the resin molding according to claim 5, wherein the resin composition contains a recycled material in an amount of 1% by mass to 50% by mass based on the total amount of the resin composition. A method for manufacturing a body is provided.

  Moreover, this invention of Claim 7 provides the housing | casing characterized by using the resin molding of Claim 3 for part or all.

  The invention according to claim 1 is excellent in mechanical characteristics as compared with a resin composition containing a conventional PC / ABS alloy or PC / PS alloy that does not have this configuration even when a recycled material is included. And it has the effect that a flame retardance and a thermal characteristic are enough.

  The invention according to claim 2 is excellent in mechanical properties as compared with a conventional resin composition containing PC / ABS alloy or PC / PS alloy that does not have this configuration, while containing a recycled material. And it has the effect that a flame retardance and a thermal characteristic are enough. In addition, the invention described in claim 2 has an effect of being excellent in solvent resistance and thermal characteristics as compared with the polyorganosiloxane-containing aromatic polycarbonate resin composition not having this configuration. The effect of the invention according to claim 2 that is excellent in solvent resistance is that the polycarbonate-based resin is weak against chemical irritation, is susceptible to cracking, and silicone has the property of absorbing solvent and has no cracking. Considering that the probability of occurrence may be further increased, it can be said that this is an unexpected effect.

  Further, the invention according to claim 3 is a machine as compared with a conventional resin molded body containing PC / ABS alloy or PC / PS alloy which does not have this configuration even when recycled material is included. It has the effect that it is excellent in thermal characteristics and has sufficient flame retardancy and thermal characteristics. Furthermore, in the invention according to claim 3, when the resin composition according to claim 2 is used, a conventional PC / ABS alloy or PC / PS alloy which does not have this configuration while containing a recycled material. An aromatic polycarbonate resin containing a polyorganosiloxane that has excellent mechanical properties and sufficient flame retardancy and thermal properties as compared with a resin molded article comprising Compared to the resin molded body, it has the effect of being excellent in solvent resistance and thermal characteristics.

  The invention according to claim 4 is a method for producing a resin molded body using a conventional PC / ABS alloy or PC / PS alloy which does not have this configuration even when a recycled material is used. In comparison, it has an effect that a resin molded article having excellent mechanical properties and sufficient flame retardancy and thermal properties can be obtained.

  In addition, the invention according to claim 5 is a machine that uses a recycled material and has a mechanical machine as compared with a conventional method of manufacturing a resin molded body using a PC / ABS alloy or a PC / PS alloy that does not have this configuration. It has the effect that the resin molding which is excellent in a physical characteristic and has sufficient flame retardance and a thermal characteristic is obtained. In addition, the invention according to claim 5 has improved solvent resistance and thermal characteristics as compared with a method of producing a resin molded article using a polyorganosiloxane-containing aromatic polycarbonate resin composition not having this configuration. It has the effect of being excellent. The effect of the invention according to claim 5 that is excellent in solvent resistance is that the polycarbonate-based resin is weak against chemical irritation and is susceptible to cracking, and that silicone has a property of absorbing solvent and has no cracking. Considering that the probability of occurrence may be further increased, it can be said that this is an unexpected effect.

  The invention according to claim 6 is a resin molding using a conventional PC / ABS alloy or PC / PS alloy which does not have this configuration while using a recycled material at a high content (1% by mass or more). Compared with the method for producing a body, the effect of obtaining a resin molded body having excellent mechanical properties and sufficient flame retardancy and thermal properties, and polyorganosiloxane not having this structure Compared to a method for producing a resin molded body using an aromatic polycarbonate resin composition, the resin composition has an effect of being excellent in solvent resistance and thermal characteristics.

  Further, the invention according to claim 7 has a mechanical characteristic as compared with a case made of a conventional PC / ABS alloy or PC / PS alloy which does not have this configuration even when a recycled material is included. It has the effect of being excellent and having sufficient flame retardancy and thermal properties. Furthermore, in the invention according to claim 7, when a resin molded body made of the resin composition according to claim 2 is used, a conventional PC / ABS that does not have this configuration while containing a recycled material. Compared to a housing comprising an alloy or PC / PS alloy, it has excellent mechanical properties, sufficient flame retardancy and thermal properties, and contains polyorganosiloxane that does not have this structure Compared to a housing containing an aromatic polycarbonate resin, it has an effect of being excellent in solvent resistance and excellent in thermal characteristics.

  Hereinafter, preferred embodiments of the resin composition, the resin molded body, the method for producing the resin molded body, and the housing of the present invention will be described.

<Resin composition>
The resin composition of this embodiment contains (A) a polyorganosiloxane-containing aromatic polycarbonate resin, (B) an aromatic polycarbonate resin other than the component (A), and (C) a phosphorus-based flame retardant.

  (A) The polyorganosiloxane-containing aromatic polycarbonate resin is composed of a polycarbonate part and a polyorganosiloxane part. For example, a polyorganosiloxane having a reactive group at a terminal constituting a polycarbonate oligomer and a polyorganosiloxane part is used. It can be prepared by dissolving in a solvent such as methylene chloride, adding an aqueous sodium hydroxide solution of bisphenol A, and performing an interfacial polycondensation reaction using a catalyst such as triethylamine. About a polycarbonate part, it can prepare similarly to the case where the aromatic polycarbonate resin as (B) component mentioned later is obtained. Polyorganosiloxane-containing aromatic polycarbonate resins are disclosed in, for example, JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, JP-A-8-302178, and JP-A-10-. No. 7897 can be used.

  Examples of commercially available polyorganosiloxane-containing aromatic polycarbonate resins include “FC1700” (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.).

  In the polyorganosiloxane-containing aromatic polycarbonate resin used in the present embodiment, the polyorganosiloxane is preferably polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, or the like, and particularly preferably polydimethylsiloxane.

  The degree of polymerization of the polycarbonate part of the polyorganosiloxane-containing aromatic polycarbonate resin is preferably from 3 to 100, and the degree of polymerization of the polyorganosiloxane part is preferably from 2 to 500. The polyorganosiloxane content of the polyorganosiloxane-containing aromatic polycarbonate resin is usually in the range of 0.1 to 2% by mass, preferably 0.3 to 1.5% by mass. .

The viscosity average molecular weight of the polyorganosiloxane-containing aromatic polycarbonate resin used in the present embodiment is usually from 5,000 to 100,000, preferably from 10,000 to 30,000, particularly preferably from 12,000 to 30,000. 000 or less. The viscosity average molecular weight (Mv) means a value obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] from this, and calculating by the following formula.
[Η] = 1.23 × 10 ⁻⁵ Mv0.83

  The content of the (A) polyorganosiloxane-containing aromatic polycarbonate resin in the resin composition of the present embodiment is preferably 1% by mass or more and 80% by mass or less based on the total amount of the resin composition in terms of fluidity, and 3% by mass. It is more preferably 75% by mass or less, and even more preferably 5% by mass or more and 70% by mass or less.

  (B) As aromatic polycarbonate resin other than (A) component, there is no restriction | limiting in particular and various things can be mentioned. Usually, an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor can be used. It is possible to use a product produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol and phosgene, or a transesterification method of a dihydric phenol and diphenyl carbonate or the like. .

  Various dihydric phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4 -Hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) ) Sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether and bis (4-hydroxyphenyl) ketone.

  Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, particularly bisphenol A.

  Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like, and specifically phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.

  The polycarbonate resin may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-bidro Xylphenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid and isatin bis (o-cresol). Moreover, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. are used for adjustment of molecular weight.

  As the aromatic polycarbonate resin other than the components (B) and (A), the resin composition of the present embodiment is a recycled material of a resin molded body containing an aromatic polycarbonate resin, an aromatic polycarbonate resin and acrylonitrile-butadiene- described later. A styrene resin or an alloy resin with a polystyrene resin, or a recycled material of a resin molded body containing the alloy resin may be included.

  The content of the aromatic polycarbonate resin other than the components (B) and (A) in the resin composition of the present embodiment is preferably 1% by mass or more and 80% by mass or less based on the total amount of the resin composition in terms of fluidity. The mass% is more preferably 75% by mass or less and even more preferably 5% by mass or more and 70% by mass or less.

  Moreover, the resin composition of this embodiment is obtained by changing a part of dihydric phenol to dihydroxybiphenyl during the polymerization of the aromatic polycarbonate resin as the aromatic polycarbonate resin other than the components (B) and (A). It is preferable to include.

式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、炭素数５〜７のシクロアルキル基、炭素数６〜１２の置換又は無置換のアリール基及びハロゲン原子から選ばれる基を示す。また、ｍ及びｎは１〜４の整数である。 Examples of dihydroxybiphenyl include compounds represented by the following general formula (1).

In formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a substituted or unsubstituted aryl having 6 to 12 carbon atoms. A group selected from a group and a halogen atom; M and n are integers of 1 to 4.

  Specifically, 4,4′-dihydroxybiphenyl, 3,3′-dimethyl-4,4′-dihydroxybiphenyl, 3,5,3 ′, 5′-tetramethyl-4,4′-dihydroxybiphenyl, 3 3,3'-diphenyl-4,4'-dihydroxybiphenyl and 2,3,5,6,2 ', 3', 5 ', 6'-hexafluoro-4,4'-dihydroxybiphenyl. These dihydroxybiphenyls are used in combination with dihydric phenol at the time of aromatic polycarbonate polymerization, and the amount used is usually about 5 mol% to 50 mol%, preferably 5 mol%, based on the total amount of dihydric phenol. It is mol% or more and 30 mol% or less. When the content of dihydroxybiphenyl is 5 mol% or more, a flame-retardant effect is easily obtained, and when it is 50 mol% or less, good impact resistance is easily obtained.

  The content of the aromatic polycarbonate resin using dihydroxybiphenyl as a part of the dihydric phenol in the resin composition of this embodiment is other than the components (B) and (A) in the resin composition in terms of fluidity. 1 to 80 parts by mass is preferable with respect to a total of 100 parts by mass of the aromatic polycarbonate resin, and 5 to 70 parts by mass is more preferable.

  As the aromatic polycarbonate resin (polyorganosiloxane-containing aromatic polycarbonate resin and other aromatic polycarbonate resins) used in the present embodiment, those having a molecular terminal having an alkyl group having 10 to 35 carbon atoms can also be used.

  Here, the polycarbonate resin having an alkyl group having 10 to 35 carbon atoms at the molecular end can be obtained by using an alkylphenol having an alkyl group having 10 to 35 carbon atoms as a terminal terminator in the production of the polycarbonate resin. These alkylphenols include decylphenol, undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol, icosylphenol, docosylphenol. , Tetracosylphenol, hexacosylphenol, octacosylphenol, triacontylphenol, dotriacontylphenol and pentatriacontylphenol. The alkyl group of these alkylphenols may be o-, m-, or p-position with respect to the hydroxyl group, but the p-position is preferred. The alkyl group may be linear, branched or a mixture thereof. As this substituent, at least one may be the alkyl group having 10 to 35 carbon atoms described above, and the other four are not particularly limited, and are alkyl groups having 1 to 9 carbon atoms and aryl having 6 to 20 carbon atoms. It may be a group, a halogen atom or unsubstituted.

  This aromatic polycarbonate resin having an alkyl group having 10 to 35 carbon atoms at its molecular end is, for example, end-capped with these alkylphenols in order to adjust the molecular weight in the reaction of a dihydric phenol with phosgene or a carbonate compound. It is obtained by using as an agent.

  For example, it can be obtained by reaction of a dihydric phenol with phosgene or a polycarbonate oligomer in a methylene chloride solvent in the presence of a triethylamine catalyst and the phenol having an alkyl group having 10 to 35 carbon atoms. Here, the phenol having an alkyl group having 10 to 35 carbon atoms seals one end or both ends of the polycarbonate resin, and the end is modified. In this case, the terminal modification is 20% or more, preferably 50% or more with respect to all terminals. That is, the other end is a hydroxyl end or an end sealed with the following other end-capping agent.

  As other end-capping agents, phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, p-tert-amyl, which are commonly used in the production of polycarbonate resins Phenol, bromophenol, tribromophenol, pentabromophenol and the like can be mentioned. Among these, a compound containing no halogen is preferable because of environmental problems.

  For high fluidization, the aromatic polycarbonate resin preferably has a molecular terminal having an alkyl group having 10 to 35 carbon atoms. When the molecular terminal is an alkyl group having 10 or less carbon atoms, the effect of improving the fluidity of the polycarbonate resin composition is difficult to obtain. On the other hand, when the molecular terminal is an alkyl group having 36 or more carbon atoms, the heat resistance and impact resistance are reduced. Tend to.

  The content ratio of the component (A) and the component (B) in the resin composition of the present embodiment is 5 parts by mass of the component (B) with respect to 100 parts by mass of the component (A) in terms of compatibility and fluidity. The amount is preferably 50 parts by mass or less, and more preferably 10 parts by mass or more and 30 parts by mass or less.

  Examples of the (C) phosphorus flame retardant include condensed phosphate ester and triphenyl phosphate (TPP). In the present embodiment, it is preferable to use a condensed phosphate ester in terms of less contamination of the mold and the like.

  The content of the (C) phosphorus flame retardant in the resin composition of the present embodiment is preferably 1% by mass or more and 30% by mass or less, based on the total amount of the resin composition, in that the mechanical strength of the resin is difficult to decrease. The mass% is more preferably 25% by mass or less and even more preferably 5% by mass or more and 20% by mass or less.

  Moreover, the resin composition of this embodiment may contain a phosphorus flame retardant and its hydrolyzate. These content ratios may be the same as long as the phosphorus element content of the phosphorus-based flame retardant and the phosphorus element content of the hydrolyzate of the phosphorus-based flame retardant are the same by fluorescent X-ray analysis. Here, “same degree” means that the difference in content is within 10% based on the content of phosphorus element in the phosphorus-based flame retardant. Moreover, in the resin composition of this embodiment, it is preferable that a phosphorus flame retardant and its hydrolyzate are supplied in the said ratio from the recycled material of the resin molding containing a phosphorus flame retardant. According to such a resin composition, even when the content of the recycled material is increased (particularly, 30% by mass or more and 50% by mass or less based on the total amount of the resin composition), flame retardancy and mechanical strength are achieved. Can be obtained at a high level.

  It is preferable that the resin composition of this embodiment further contains a styrene resin. As the styrene resin, a rubber-modified styrene copolymer or a rubber-unmodified styrene copolymer obtained by using acrylonitrile or methyl methacrylate in combination with another monomer in addition to the styrene monomer is an aromatic polycarbonate resin. It is preferable from the viewpoint of improving the compatibility. Moreover, solvent resistance and mechanical strength can be improved more because a resin composition contains a styrene resin further. The reason why the solvent resistance is improved is that by combining the styrene resin with the above components (A) and (C), the styrene resin having a low viscosity is extruded together with the component (C) to the flow front at the time of formation. The present inventors speculate that a certain kind of protective layer was formed by flowing on the mold wall surface and coming out on the surface of the molded body. In addition, the mechanical strength is improved because the presence of a material that easily flows, a material that does not easily flow, and the component (C) causes a concentration gradient of the material, a so-called gradient, and a different material is strong. The present inventors infer that it has a structure in which the strength increases as it goes to the center and further has elasticity.

  Specific examples of the styrene resin include, for example, ABS resin (acrylonitrile-butadiene rubber-styrene copolymer), AES resin (acrylonitrile-ethylenepropylene rubber-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer). Polymer), MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), MS resin (methyl methacrylate-styrene copolymer), and the like.

  The content of the styrenic resin in the resin composition of the present embodiment is 1% by mass or more and 50% by mass based on the total amount of the resin composition from the viewpoint of improving fluidity, heat resistance, and impact resistance (Charpy impact strength) in a well-balanced manner. % Or less is preferable, and 5 mass% or more and 40 mass% or less are more preferable.

  The resin composition of the present embodiment preferably contains a recycled material of a resin molded body.

  Examples of the resin molded body include an alloy resin of a polycarbonate resin and an acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “PC / ABS alloy”) or an alloy resin of a polycarbonate resin and a polystyrene resin (hereinafter referred to as “ PC / PS alloy ”may also be included.

  In the present embodiment, an alloy resin of an aromatic polycarbonate resin other than the component (A) and an acrylonitrile-butadiene-styrene resin and / or an alloy resin of an aromatic polycarbonate resin other than the component (A) and a polystyrene resin, and It is preferable to use a recycled material of a resin molded body containing the phosphorus-based flame retardant described above. By using such a recycled material, while increasing the content ratio of the recycled material, compared with a conventional resin composition containing PC / ABS alloy or PC / PS alloy that does not have this configuration, the mechanical properties are improved. Excellent, flame retardant, sufficient thermal properties (specifically, the molding temperature is sufficiently low and the thermal shrinkage rate is sufficiently small), and this configuration is provided. Compared to non-polyorganosiloxane-containing aromatic polycarbonate resin compositions, it has superior solvent resistance and thermal characteristics (specifically, the molding temperature is lower and the thermal shrinkage is lower) Is played.

  The reason why the solvent resistance is improved is that by combining the recycled material with the component (A), the ABS resin or PS resin having a low viscosity is extruded together with the phosphorus-based flame retardant at the time of formation to the mold mainly. The present inventors speculate that a certain kind of protective layer was formed by flowing on the wall surface and coming out on the surface of the molded body. In addition, the mechanical strength is improved because of the presence of a material that easily flows, a material that does not easily flow, and a phosphorus-based flame retardant, a concentration gradient of the material, a so-called gradient, occurs, and different types of materials are strong. The present inventors infer that it has a structure in which the strength increases as it goes to the center and further has elasticity. Moreover, the present inventors speculate that the reason why the thermal characteristics are improved is that the thermal conductivity of the surface is increased by the above structure.

  The content of the phosphorus-based flame retardant in the resin molded body is preferably 1% by mass or more and 30% by mass or less, preferably 3% by mass or more and 25% by mass, based on the total amount of the resin molded body, in that the impact strength of the resin is difficult to decrease. The following is more preferable, and 5% by mass or more and 20% by mass or less is even more preferable.

  Further, in the resin composition of the present embodiment, if a resin molded body that has undergone excessive hydrolysis as a recycled material is contained, it is difficult to control the fluidity of the resin. It is preferable to use those having a melt flow index (MI) of 4 times or less, more preferably 2 times or less. Here, MI is a value measured under conditions of a cylinder temperature of 260 ° C. and a load of 2.16 kg in accordance with ASTM D1238.

  From the viewpoint of satisfying all of the mechanical properties, thermal properties, flame retardancy and solvent resistance while effectively using the recycled materials, the content of the recycled materials in the resin composition of the present embodiment, 1 mass% or more and 50 mass% or less are preferable on the basis of the total amount of the resin composition, 5 mass% or more and 50 mass% or less are more preferable, and 10 mass% or more and 40 mass% or less are even more preferable.

  In order to improve rigidity and flame retardancy, an inorganic filler can be blended in the resin composition of the present embodiment as necessary. As the inorganic filler, talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, potassium titanate and the like are used. Among these inorganic fillers, talc and mica whose form is plate-like are particularly preferable. Talc is a hydrated silicate of magnesium, and a commercially available product can be used. In addition, talc having an average particle size of about 0.1 to 50 μm is usually used, but a talc having an average particle size of 0.2 to 20 μm is particularly preferably used.

  The content of the inorganic filler in the resin composition of the present embodiment is usually about 1 part by mass or more and 20 parts by mass or less, preferably 2 parts by mass or more and 15 parts by mass or less when the total amount of the resin composition is 100 parts by mass. It is.

  Moreover, the impact resistance improver can be mix | blended with the resin composition of this embodiment as needed for the purpose of improving impact resistance. As the impact resistance improver, a core-shell type elastomer is preferable. The core-shell type elastomer has a two-layer structure composed of a core and a shell, the core part is in a soft rubber state, and the shell part on the surface is a hard resin. The elastomer itself is an elastic body in the form of powder (particle state). The core-shell type elastomer remains largely in its original form after melt blending with the polycarbonate resin. Since most of the blended elastomer maintains the original form, an effect of uniformly dispersing and preventing surface peeling can be obtained.

  Examples of the core-shell type elastomer that are commercially available include “EXL2603” (trade name, manufactured by Kureha Chemical Industry Co., Ltd.), “Hybrene B621” (trade name, manufactured by Nippon Zeon Co., Ltd.), and “KM”. -330 "(trade name, manufactured by Rohm & Haas)," Metabrene W529 "," Metabrene S2001 "," Metabrene C223 "," Metabrene B621 "(all trade names, manufactured by Mitsubishi Rayon Co., Ltd.)," MR01 "," MR02 "(both manufactured by Kaneka Corporation).

  The content of the impact resistance improver in the resin composition of the present embodiment is usually about 1 part by mass or more and 20 parts by mass or less, preferably 2 parts by mass or more and 15 parts by mass when the total amount of the resin composition is 100 parts by mass. It is as follows. By setting the content of the impact resistance improver to 1 part by mass or more, an effect of improving impact resistance can be easily obtained, and by setting the content to 20 parts by mass or less, flame retardancy, heat resistance and rigidity can be maintained. Easy to do.

  Moreover, at least 1 type chosen from an organic alkali metal salt and an organic alkaline-earth metal salt can be mix | blended with the resin composition of this embodiment as needed for the purpose of improving a flame retardance further. Examples of the organic alkali metal salt and the organic alkaline earth metal salt include an alkali metal salt and an organic alkaline earth metal salt of an organic acid or organic acid ester having at least one carbon atom. Examples of organic acids or organic acid esters include organic sulfonic acids and organic carboxylic acids. On the other hand, examples of the alkali metal include lithium, sodium, potassium, and cesium, and examples of the alkaline earth metal include magnesium, calcium, strontium, and barium. Among these, sodium and potassium salts are preferably used. The salt of the organic acid may be substituted with a halogen such as fluorine, chlorine or bromine. Alkali metal salts and organic alkaline earth metal salts can be used singly or in combination of two or more.

In the present embodiment, when an alkali metal salt or alkaline earth metal salt of organic sulfonic acid is used, an alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid represented by the following general formula (2) is preferably used. It is done.
(CaF _{2a + 1} SO ₃ ) _b M (2)
In the formula (2), a represents an integer of 1 to 10, M represents an alkaline metal such as lithium, sodium, potassium or cesium, or an alkaline earth metal such as magnesium, calcium, stronadium or barium, and b represents The valence of M is shown.

  As the compound represented by the general formula (2), for example, those described in JP-B-47-40445 can be used.

  Examples of the perfluoroalkanesulfonic acid in the general formula (2) include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, and perfluoro. Examples thereof include hexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid. In particular, these potassium salts are preferably used.

  In addition, alkali metal salts of organic sulfonic acids other than the above include 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3 ′. -Disulfonic acid, naphthalene trisulfonic acid, etc. can be used.

  Examples of the organic carboxylic acid include perfluoroformic acid, perfluoromethanecarboxylic acid, perfluoroethanecarboxylic acid, perfluoropropanecarboxylic acid, perfluorobutanecarboxylic acid, perfluoromethylbutanecarboxylic acid, perfluorohexanecarboxylic acid. Perfluoroheptanecarboxylic acid, perfluorooctanecarboxylic acid, and the like, and alkali metal salts of these organic carboxylic acids are used.

式（３）中、Ｘはスルホン酸塩基、Ｙは水素又は炭素数１〜１０の炭化水素基を示す。ｃは１〜５の整数である。また、式（３）中、ｄはモル分率を表し、０＜ｄ≦１の関係を満たす。すなわち、スルホン酸塩基（Ｘ）は、芳香環に対して、全置換したものであっても、部分置換したものであってもよい。 Further, the resin composition of the present embodiment can be blended with an alkali metal salt and / or an alkaline earth metal salt of polystyrene sulfonic acid. Specifically, the sulfone represented by the following general formula (3): An acid-base-containing aromatic vinyl resin can be blended.

In formula (3), X represents a sulfonate group, Y represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. c is an integer of 1-5. In formula (3), d represents a mole fraction and satisfies the relationship 0 <d ≦ 1. That is, the sulfonate group (X) may be a fully substituted or partially substituted aromatic ring.

  Here, the sulfonate group is an alkali metal salt and / or alkaline earth metal salt of sulfonic acid, and examples of the metal include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. It is done.

  In order to effectively improve the flame retardancy, the substitution ratio of the sulfonate group is preferably determined in consideration of the content of the sulfonate group-containing aromatic vinyl resin, generally 10 to 100. % Substitution is preferred.

  In addition, the sulfonate group-containing aromatic vinyl resin as the alkali metal salt and / or alkaline earth metal salt of polystyrene sulfonic acid is not limited to the polystyrene resin represented by the general formula (3), It may be a copolymer with another monomer copolymerizable with the styrenic monomer.

  As a method for producing the sulfonate group-containing aromatic vinyl resin, (i) the above aromatic vinyl monomer having a sulfonic acid group or the like, or another monomer copolymerizable therewith is polymerized. Or (ii) an aromatic vinyl polymer, or a copolymer of an aromatic vinyl monomer and another copolymerizable monomer, or a mixed polymer thereof, There is a method of neutralizing with an alkali metal compound and / or an alkaline earth metal compound.

  As a specific example of the above method (ii), a mixture of concentrated sulfuric acid and acetic anhydride is added to a 1,2-dichloroethane solution of polystyrene resin, heated, and reacted for several hours to produce polystyrene sulfone oxide. Then, a method of obtaining polystyrene sulfonate potassium salt or sodium salt by neutralizing with sulfonic acid group and equimolar amount of potassium hydroxide or sodium hydroxide can be mentioned.

  The weight average molecular weight of the sulfonate group-containing aromatic vinyl resin used in the present embodiment is preferably 1,000 to 300,000, and more preferably about 2,000 to 200,000. The weight average molecular weight can be measured by the GPC method.

  In the resin composition of the present embodiment, the content of the alkali metal salt and / or alkaline earth metal salt is usually about 0.01 part by mass or more and about 1 part by mass or less when the resin composition is 100 parts by mass, Preferably they are 0.03 mass part or more and 0.9 mass part or less, More preferably, they are 0.05 mass part or more and 0.8 mass part or less. By setting the content of the alkali metal salt and / or alkaline earth metal salt in the above range, an effect of improving flame retardancy commensurate with the blending amount can be obtained.

In the resin composition of the present embodiment, a reactive group-containing silicone compound can be blended as necessary for further improving flame retardancy. The reactive group-containing silicone compound is a (poly) organosiloxane having a reactive group, and its skeleton is a polymer or copolymer having a basic structure represented by the following general formula (4).
^{_{R 3 e R 4 f SiO (}} 4-e-f) / 2 ... (4)
In Formula (4), R ³ represents a reactive group, R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, and e and f are 0 <e ≦ 3, 0 ≦ f <3 and 0 <e + f ≦. The relationship of 3 is satisfied.

  Examples of the reactive group include an alkoxy group, aryloxy, polyoxyalkylene group, hydrogen group, hydroxyl group, carboxyl group, silanol group, amino group, mercapto group, epoxy group, and vinyl group. Among these, an alkoxy group, a hydrogen group, a hydroxyl group, and an epoxy group are preferable, and a methoxy group and a vinyl group are particularly preferable.

As the reactive group-containing silicone compound, a silicone compound having a plurality of reactive groups and a silicone compound having different reactive groups can be used in combination. This reactive group-containing silicone compound has a reactive group (R ³ ) / hydrocarbon group (R ⁴ ) of generally 0.1 to 3, preferably about 0.3 to 2. These silicone compounds are liquids, howders, etc., but those having good dispersibility in melt kneading are preferred. For example, a liquid material having a kinematic viscosity at room temperature of about 10 to 500,000 mm ² / s can be exemplified.

  The content of the reactive group-containing silicone compound in the resin composition of the present embodiment is usually about 1 part by mass or more and 30 parts by mass or less, preferably 3 parts by mass or more and 25 parts by mass when the total amount of the resin composition is 100 parts by mass. It is not more than part by mass, more preferably not less than 5 parts by mass and not more than 20 parts by mass. By setting the content of the reactive group-containing silicone compound in the above range, an effect of improving flame retardancy commensurate with the blending amount can be obtained.

  Moreover, the polytetrafluoroethylene (PTFE) can be mix | blended with the resin composition of this embodiment as needed for the further flame retardance improvement (for example, V-0, 5V in UL94). The average molecular weight of PTFE is preferably 500,000 or more, particularly preferably 500,000 to 10,000,000.

  When PTFE having the ability to form a small fiber structure is used, it is possible to impart even higher melt drip prevention. Although there is no restriction | limiting in particular in PTFE which has the formation ability of a small fiber structure, For example, what is classified into type 3 in ASTM standard is mentioned. Specific examples thereof include, for example, “Teflon (registered trademark) 6-J” (trade name, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), “Polyflon D-1”, “Polyflon F-103”, “Polyflon F201” ( As mentioned above, Daikin Industries, Ltd., brand name), "CD076" (Asahi Glass Fluoropolymers, brand name) etc. are mentioned.

  Other than those classified as type 3, for example, “Algoflon F5” (manufactured by Montefluos, product name), “Polyflon MPA”, “Polyflon FA-100” (manufactured by Daikin Industries, Ltd., product name). ) And the like. These PTFE may be used independently and may combine 2 or more types.

  The PTFE having the ability to form a fibril structure as described above is, for example, 6.9 to 690 kPa (1 to 100 psi) in the presence of sodium, potassium, or ammonium peroxydisulfide in tetrafluoroethylene in an aqueous solvent. It is obtained by polymerizing at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. under the pressure of

  The content of polytetrafluoroethylene in the resin composition of the present embodiment is usually about 0.1 parts by mass or more and 1 part by mass or less, preferably 0.15 parts by mass or more, with respect to 100 parts by mass of the resin. It is 0.5 mass part or less, More preferably, it is 0.16 mass part or more and 0.45 mass part or less. By setting the content of polytetrafluoroethylene in the above range, an effect of improving flame retardancy commensurate with the blending amount can be obtained, and the adverse effects on impact resistance and molded product appearance can be sufficiently reduced.

  In addition to the above-mentioned components, the resin composition of the present embodiment includes appropriate amounts of general thermoplastic resin and additives used in the composition depending on the properties required for the resin molded product. It can be included. Examples of such additives include antioxidants, antistatic agents, ultraviolet absorbers, light stabilizers (weathering agents), plasticizers, antibacterial agents, compatibilizers, and colorants (dyes and pigments). It is done.

As a particularly preferable aspect of the resin composition of the present embodiment,
(A) a polyorganosiloxane-containing aromatic polycarbonate resin;
(A) aromatic polycarbonate resin (B-1) other than component,
(A) An alloy resin of an aromatic polycarbonate resin other than the component and an acrylonitrile-butadiene-styrene resin and / or an alloy resin of an aromatic polycarbonate resin other than the component (A) and a polystyrene resin, and a phosphorus flame retardant Recycled resin molded body (B-2 / C-1)
One or more styrenic resins (D) selected from the group consisting of ABS resin, AES resin, AAS resin, MBS resin, AS resin and MS resin;
The thing containing is mentioned.

  The resin composition in this case can satisfy a high level of mechanical properties, flame retardancy, thermal properties, and solvent resistance while containing a recycled material.

  The preferable contents of the component (A), the component (B-1), the component (B-2 / C-1), and the component (D) in the above resin composition are respectively the preferable contents of the respective components described above. It is the same.

  The resin composition of the present embodiment can be obtained by blending and kneading each component described above. At this time, the mixing and kneading are premixed with a commonly used equipment such as a ribbon blender or a drum tumbler, and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. It can be performed by a method using a machine, a conida or the like. The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C. Moreover, each component may be added as a master batch prepared in advance.

<Production method of resin molding>
Next, a preferred embodiment of the method for producing a resin molded body of the present invention will be described.

  The method for producing a resin molded body of the present embodiment includes (A) a polyorganosiloxane-containing aromatic polycarbonate resin, (B) an aromatic polycarbonate resin other than the component (A), and (C) a phosphorus flame retardant. A step of molding the resin composition.

  In addition to the components (A), (B), and (C), the above-described components can be contained in the resin composition. Moreover, what was obtained by mix | blending and knead | mixing each component can be used for the resin composition, for example. At this time, the mixing and kneading are premixed with a commonly used equipment such as a ribbon blender or a drum tumbler, and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. It can be performed by a method using a machine, a conider or the like. The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C. The resin composition may be one in which each component is added as a master batch prepared in advance.

  The resin composition can be molded by a known molding method such as injection molding, injection compression molding, press molding, extrusion molding, blow molding, calendar molding, coating molding, cast molding, dipping molding, or the like.

  Moreover, in the manufacturing method of the resin molding of this embodiment, the resin composition is an alloy resin of an aromatic polycarbonate resin other than the component (A) and an acrylonitrile-butadiene-styrene resin and / or a component other than the component (A). It is preferable to include an alloy resin of an aromatic polycarbonate resin and a polystyrene resin, and a recycled material of a resin molded body containing a phosphorus-based flame retardant.

  Furthermore, it is preferable that the resin composition further includes one or more styrenic resins selected from the group consisting of ABS resin, AES resin, AAS resin, MBS resin, AS resin, and MS resin.

  Specific examples of the method for producing a resin molded body in this case include the following methods. First, (A) component, (B) component, and other components (for example, styrenic resin, inorganic filler, impact resistance improver, flame retardant, other additives, etc.) as necessary, A first resin composition is prepared by kneading, and on the other hand, a resin molded body made of PC / ABS alloy or PC / PS alloy recovered from a product used on the market and containing a phosphorus-based flame retardant A recycled material is prepared by pulverizing the powder to a size of about 1 to 12 mm using a pulverizer.

  Next, the first resin composition and the recycled material are mixed at a mass ratio of preferably 99: 1 to 50:50, more preferably 95: 5 to 60:40. Mixing can be carried out by dry mixing by simply mixing with a tumbler or by granulating and using a single screw extruder, a twin screw extruder, a multi-screw extruder, a kneader or the like. The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C.

  In the present embodiment, if a resin molded body that has undergone excessive hydrolysis is used as a recycled material, it is difficult to control the fluidity of the resin. Therefore, the melt flow index (MI) as an index of the degree of deterioration due to hydrolysis is difficult. Is preferably 4 times or less, more preferably 2 times or less. Here, MI is a value measured under conditions of a cylinder temperature of 260 ° C. and a load of 2.16 kg in accordance with ASTM D1238.

  Next, a dry mixture comprising the first resin composition and the recycle material or the granulated material is injection-molded, for example, under conditions of a cylinder temperature of 220 ° C. or higher and 300 ° C. or lower, preferably 230 ° C. or higher and 280 ° C. or lower. Thus, a resin molded body can be obtained. In addition, all the above components may be melt-kneaded to produce a granular molding raw material, and then injection molding or injection compression molding may be performed using the granular molding raw material. Further, when a gas injection molding method is employed as the injection molding method, it is possible to obtain a resin molded product that is excellent in appearance without shrinkage and reduced in weight.

  Further, according to the method for producing a resin molded body of the present embodiment, by using the resin composition of the present embodiment, the concentration of the phosphorus-based flame retardant in the vicinity of the surface of the resin molded body is changed to the phosphorus in the resin molded body. The concentration can be higher than the concentration of the system flame retardant. In addition, the density | concentration of the phosphorus flame retardant in a resin molding can be calculated | required, for example using the fluorescent X-ray apparatus (Simultics 12, Rigaku Co., Ltd.) etc. about the surface of the molded body cut | disconnected mechanically.

  For example, by applying the method for producing a resin molded body of the present embodiment and manufacturing a resin molded body from a recycled material containing 2.6% by mass of a phosphorus flame retardant and a material not containing a phosphorus flame retardant, The content of the phosphorus-based flame retardant on the surface of the obtained resin molded body can be 2.6% by mass.

<Case>
FIG. 1 is an external perspective view of an image forming apparatus provided with a housing and office equipment parts according to an embodiment of the resin molded body of the present invention, as viewed from the front side. The image forming apparatus 100 in FIG. 1 includes front covers 120 a and 120 b on the front surface of the main body device 110. These front covers 120a and 120b can be opened and closed so that an operator can operate the inside of the apparatus. Thus, the operator can replenish the toner when the toner is exhausted, replace the exhausted process cartridge, and remove the jammed paper when a paper jam occurs in the apparatus. FIG. 1 shows the apparatus with the front covers 120a and 120b opened.

  On the upper surface of the main body 110, there are provided an operation panel 130 on which various conditions relating to image formation such as a paper size and the number of copies are input by an operation of an operator, and a copy glass 132 on which a document to be read is placed. Yes. Further, the main body device 110 includes an automatic document feeder 134 that can automatically convey a document on the copy glass 132. Further, main device 110 includes an image reading device that scans a document image placed on copy glass 132 and obtains image data representing the document image. Image data obtained by the image reading apparatus is sent to the image forming unit via the control unit. Note that the image reading device and the control unit are housed in a housing 150 that forms part of the main body device 110. The image forming unit is provided in the housing 150 as a detachable process cartridge 142. The process cartridge 142 can be attached and detached by turning the operation lever 144.

  A toner container 146 is attached to the casing 150 of the main body device 110, and toner can be replenished from the toner supply port 148. The toner stored in the toner storage unit 146 is supplied to the developing device.

  On the other hand, sheet storage cassettes 140a, 140b, and 140c are provided at the lower portion of the main unit 110. In addition, the main body apparatus 110 has a plurality of conveying rollers formed of a pair of rollers arranged in the apparatus, thereby forming a conveying path through which the sheets of the sheet storage cassette are conveyed to the upper image forming unit. ing. The paper in each paper storage cassette is taken out one by one by a paper take-out mechanism disposed near the end of the transport path and sent out to the transport path. Further, a manual paper tray 136 is provided on the side surface of the main body 110, and paper can be supplied from here.

  The paper on which the image is formed by the image forming unit is sequentially transferred between two fixing rolls that are supported by a casing 152 constituting a part of the main body device 110 and abut against each other. Paper is discharged to the outside. The main body device 110 is provided with a plurality of discharge trays 138 on the side opposite to the side on which the paper tray 136 is provided, and paper after image formation is discharged to these trays.

  When the resin molding of this embodiment formed from the resin composition of this embodiment described above contains a recycled material (particularly, the content of the recycled material is 1% by mass or more and 50% by mass or less, preferably 5% by mass or more and 50% by mass or less), it is possible to sufficiently retain excellent mechanical properties, heat resistance, and flame retardancy. ), A member constituting a housing (front cover, rear cover, etc.), a toner cartridge, and a paper feed tray. In this case, the amount of recycled material used in the electrophotographic apparatus can be further increased.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Raw material of resin composition>
The following raw materials were prepared as components for preparing the resin composition.

  Polyorganosiloxane-containing aromatic polycarbonate resin: “FC1700” (made by Idemitsu Petrochemical Co., Ltd., viscosity average molecular weight 17500, PDMS (polydimethylsiloxane) content 3 mass%, PDMS chain length (n) 30 PC-PDMS-containing bisphenol A) Polycarbonate) (hereinafter referred to as “PC-A”).

  Aromatic polycarbonate resin: “FN1700A” (made by Idemitsu Petrochemical Co., Ltd., bisphenol A polycarbonate having a viscosity average molecular weight of 17500) (hereinafter referred to as “PC-B1”).

  Aromatic polycarbonate resin: Polycarbonate biphenol copolymer (hereinafter referred to as “PC-B2”) having a viscosity average molecular weight of 17500 and a biphenol content of 15.9 mol% obtained in Production Example 1 below.

(Production Example 1)
(1) Polycarbonate oligomer synthesis step To a sodium hydroxide aqueous solution having a concentration of 5.6% by mass, 0.2% by mass of sodium dithionite is added to bisphenol A (BPA) to be dissolved later. BPA was dissolved to 13.5% by mass to prepare an aqueous sodium hydroxide solution of BPA. A sodium hydroxide aqueous solution of BPA was continuously passed through a tubular reactor having an inner diameter of 6 mm and a pipe length of 30 m at a flow rate of 40 L / hr and methylene chloride at a flow rate of 15 L / hr, and phosgene was continuously supplied at a flow rate of 4.0 kg / hr. Passed through. The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.

  Next, the reaction liquid sent out from the tubular reactor was continuously introduced into a tank reactor with a baffle having an internal volume of 40 L equipped with a receding blade, and 2.8 L of an aqueous sodium hydroxide solution of BPA was further added thereto. / Hr, 25 mass% sodium hydroxide aqueous solution was supplied at a flow rate of 0.07 L / hr, water was 17 L / hr, and 1 mass% triethylamine aqueous solution was supplied at a flow rate of 0.64 L / hr, and the reaction was performed at 29 to 32 ° C. The reaction liquid was continuously extracted from the tank reactor and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 338 g / L and a chloroformate group concentration of 0.71 mol / L.

(2) Polycarbonate-biphenol copolymer polymerization step In a 50 L tank reactor equipped with baffle plates and paddle type stirring blades, 15.0 L of the oligomer solution, 10.5 L of methylene chloride, PTBP (p-tert- Butylphenol (132.7 g) and triethylamine (1.4 mL) were charged, and an aqueous solution of biphenol in sodium hydroxide (640 g of NaOH and 1.8 g of sodium dithionite Na ₂ S ₂ O ₄ in 9.3 L of water) 4'-biphenol dissolved in 890 g) was added, and a polymerization reaction was carried out for 1 hour. After adding 10.0 L of methylene chloride for dilution, the mixture was allowed to stand to separate into an organic phase containing polycarbonate and an aqueous phase containing excess 4,4′-biphenol and NaOH, and the organic phase was isolated.

(3) Washing step The methylene chloride solution of the polycarbonate-biphenol copolymer obtained in the step (2) above was mixed with 15% by volume of 0.03 mol / L sodium hydroxide aqueous solution, 0.2 mol / Washing was sequentially performed with L hydrochloric acid, and then washing with pure water was repeated until the electrical conductivity in the aqueous phase after washing was 0.05 μS / m or less.

(4) Grinding step A methylene chloride solution of the polycarbonate-biphenol copolymer obtained in the step (3) above was concentrated and ground to obtain a ground product of the polycarbonate-biphenol copolymer. The obtained flakes were dried at 120 ° C. under reduced pressure for 12 hours. The biphenyl content measured by NMR was 15.9 mol%.

  ABS resin: “B600N” (Ube Saikon Co., Ltd., acrylonitrile butadiene styrene copolymer having a rubber content of 60% by mass) (hereinafter referred to as “ABS-1”).

  Core-shell type elastomer: “EXL2603” (manufactured by Kureha Chemical Co., Ltd., core-shell type graft rubber-like elastic body) (hereinafter referred to as “elastomer-1”).

  Inorganic filler: “TP-A25” (manufactured by Fuji Talc Kogyo Co., Ltd., talc, average particle size 4.9 μm) (hereinafter referred to as “inorganic filler-1”).

  Metal salt: “Megafac F-114” (manufactured by Dainippon Ink Co., Ltd., potassium perfluoroalkanesulfonate) (hereinafter referred to as “metal salt-1”).

  Silicone compound: “X40-2664A” (manufactured by Shin-Etsu Chemical Co., Ltd., methyl hydrogen silicone) (hereinafter referred to as “silicone-1”).

  Polytetrafluoroethylene: “CD076” (manufactured by Asahi ICI Fluoropolymers) (hereinafter referred to as “PTFE-1”).

  Recycled material: Copying machine cover (used for about 2 years) made by PC / ABS alloy "TN7300" (manufactured by Teijin Kasei Co., Ltd.) was collected, metal parts were removed, and pulverized to a size of about 8 mm using a pulverizer. , Pulverized product (MI measured under conditions of cylinder temperature 260 ° C. and load 2.16 kg according to ASTM D1238: less than 1.5 times, content of condensed phosphate ester having aromatic ring: 13%, Hydrolysis rate: 5%) (hereinafter referred to as “recycled material-1”).

  In addition, the quantitative determination of the condensed phosphate ester was carried out by connecting a gas chromatograph (GC: HP6890, manufactured by Agilent) and a mass spectrometer (MS: JMS-Q1000GC K9, manufactured by JEOL Ltd.) (GC-MS). . The capillary column was HP-5 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), and the temperature was raised from 100 ° C. to 320 ° C. at 10 ° C./min. The ionization voltage was 70 eV, and the scan range was m / z = 29 to 900. Moreover, since condensed phosphate ester produces | generates acidic phosphate ester by hydrolysis, the hydrolysis rate of condensed phosphate ester was measured by carrying out neutralization titration of this. Specifically, in accordance with MIL standard H-19457, the pulverized product / distilled water (mass ratio: 75/25) is put into a sealed glass bottle, heated at 93 ° C. for 48 hours, and the acid value of the organic phase and the aqueous phase. Were measured with an alkali solution (potassium hydroxide solution) and added together to obtain a total acid value.

  Recycled material: Copying machine cover (used for about 3 years) made by PC / PS alloy “NN2710AS” (made by Idemitsu Kosan Co., Ltd.) was collected, metal parts were removed, and pulverized to a size of about 8 mm using a pulverizer. , Pulverized product (MI measured under conditions of cylinder temperature 260 ° C. and load 2.16 kg according to ASTM D1238: less than 1.5 times, content of condensed phosphate ester having aromatic ring: 13%, Hydrolysis rate: 5%) (hereinafter referred to as “recycled material-2”).

<Manufacture of resin molding>
(Examples 1 to 12, Comparative Examples 1 and 2)
Each raw material was mixed at the blending ratio (parts by mass) shown in Tables 1 and 2 and supplied to a vent type twin screw extruder (TEM 35, manufactured by Toshiba Machine Co., Ltd.), and melt kneaded and granulated at 260 ° C. Prior to melt kneading, 0.1 parts by mass of Irganox 1076 (manufactured by Ciba Specialty Chemicals) and 0.1 part by mass of ADK STAB C (manufactured by Asahi Denka Kogyo Co., Ltd.) were added as antioxidants in all compositions. did.

  Next, after drying the obtained granular molding raw material at 120 ° C. for 5 hours, injection molding was performed under the conditions of the predetermined molding temperature (cylinder temperature) and the mold temperature of 60 ° C. shown in Tables 1 and 2. Test pieces of Examples 1 to 12 and Comparative Examples 1 and 2 were obtained.

  About the granular forming raw materials obtained in Examples 1 to 12 and Comparative Examples 1 and 2, or the test pieces obtained in Examples 1 to 12 and Comparative Examples 1 and 2, mechanical properties (Charpy impact strength), thermal Characteristics (thermal deformation temperature (HDT), spiral flow length (SFL), shrinkage), flame retardancy and solvent resistance were evaluated by the following various tests. The results are shown in Tables 1 and 2.

(1) Charpy impact strength An ISO multi-purpose dumbbell test piece was created and notched, using a digital impact tester (manufactured by Toyo Seiki Seisakusho) in accordance with JIS K7111, a lifting angle of 150 degrees, hammer used Charpy impact strength (kJ / m ² ) was measured under the conditions of 2.0 J and the number of measurements n = 10.

(2) HDT (thermal deformation temperature)
Measurement was performed at a load of 1.83 MPa according to ASTM D648. This value is a measure of heat resistance, and although it depends on the purpose of use of the resin composition, 90 ° C. or higher is usually a practically preferable range.

(3) SFL (spiral flow length)
Using each granular forming raw material, a test was performed at a molding temperature of 280 ° C., a mold temperature of 80 ° C., a wall thickness of 2 mm, a width of 1 cm, and an injection pressure of 7.84 MPa (80 kg / cm ² ). A larger numerical value indicates better fluidity, preferably 35 cm or more. The thickness of the exterior cover is usually about 2.4 mm, but since the thickness has been reduced to 2 mm or less with the recent reduction in weight, the evaluation with a thickness of 2 mm was performed.

(4) Shrinkage rate When molding with a rectangular parallelepiped mold (150 mm x 150 mm x 3 mm), measure how much the vertical and horizontal lengths were shorter than the mold dimensions with calipers, and the shrinkage rate Was calculated. In general, the shrinkage rate is preferably about 0.6%, and if it is 0.7% or more, the shrinkage must be taken into account, and a die specific to the material is required.

(5) Flame Retardancy Test A test piece with an outer dimension of 127 mm x 12.7 mm and a wall thickness of 1.5 mm is prepared, and a vertical combustion test is conducted in accordance with Underwriters Laboratory Subject 94 (UL94 standard). went.

(6) Solvent resistance An ISO multipurpose dumbbell specimen was prepared and notched. Next, a solvent was applied to the surface of the test piece, and the sample was left in an environment at 23 ° C. for 72 hours with a strain of 1%, and thereafter, the presence or absence of cracking was visually confirmed. As the solvent, silicone oil manufactured by Shin-Etsu Chemical was used. The results are shown in the table as “C” when cracking occurs and “N” when cracking does not occur.

Moreover, about the test piece obtained in Examples 1-12, when the content rate of the polycarbonate resin in each place of a molded object was computed by FT-IR (infrared absorption) analysis, content of the polycarbonate resin in the surface part of a molded object is It was confirmed that it was 70% of the content of the polycarbonate resin in the center of the molded body. Incidentally, in the FT-IR spectra, since the intrinsic absorption of the polycarbonate resin is observed in 1200 cm ^-1 and 1780 cm ^-1, it was determined the ratio of the the magnitude of the peak.

1 is an external perspective view of an image forming apparatus including a casing and office equipment parts according to an embodiment of a resin molded body of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 ... Image forming apparatus, 110 ... Main body apparatus, 120a, b ... Front cover, 136 ... Paper tray, 138 ... Discharge tray, 142 ... Process cartridge, 150, 152 ... Case.

Claims (7)

(A) a polyorganosiloxane-containing aromatic polycarbonate resin;
(B) an aromatic polycarbonate resin other than the component (A);
(C) a phosphorus-based flame retardant,
A resin composition comprising:   An alloy resin of an aromatic polycarbonate resin other than the component (A) and an acrylonitrile-butadiene-styrene resin and / or an alloy resin of an aromatic polycarbonate resin other than the component (A) and a polystyrene resin, a phosphorus flame retardant, The resin composition according to claim 1, comprising a recycled material of a resin molded body comprising (A) a polyorganosiloxane-containing aromatic polycarbonate resin;
(B) an aromatic polycarbonate resin other than the component (A);
(C) a phosphorus-based flame retardant,
A resin molded body. (A) a polyorganosiloxane-containing aromatic polycarbonate resin;
(B) an aromatic polycarbonate resin other than the component (A);
(C) a phosphorus-based flame retardant, and a resin composition,
The manufacturing method of a resin molding provided with the process of shape | molding. The resin composition is
An alloy resin of an aromatic polycarbonate resin other than the component (A) and an acrylonitrile-butadiene-styrene resin and / or an alloy resin of an aromatic polycarbonate resin other than the component (A) and a polystyrene resin, and a phosphorus flame retardant, A recycled material for a resin molded body,
The manufacturing method of the resin molding of Claim 4 containing this.   The method for producing a resin molded body according to claim 5, wherein the resin composition contains the recycled material in an amount of 1% by mass to 50% by mass based on the total amount of the resin composition. The housing | casing in which the resin molding of Claim 3 was used for part or all.

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