JP5278046B2 - Recycled resin composition, method for producing the same, and resin molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a regenerated resin composition excellent in flame retardancy and impact resistance. <P>SOLUTION: The regenerated resin composition includes (A) a recycled resin containing a first polycarbonate/styrenic alloy resin, (B) a second polycarbonate/styrenic alloy resin, (C) a composite rubber-based graft copolymer which is a core-shell type composite rubber including a core which is a composite rubber containing a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component and a shell in which a vinyl monomer is graft-polymerized to the core, the content thereof being 0.5 mass% or more and 10 mass% or less based on 100 mass% of the sum of the component (A) and the component (B), and (D) an organic phosphorous flame retardant, the content thereof being 1 mass% or more and 10 mass% or less based on 100 mass% of the sum of the component (A) and the component (B). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a recycled resin composition, a method for producing the same, and a resin molded body.

  Polycarbonate (PC) resins are excellent in heat resistance and impact resistance, and thus are used in various applications, and in particular, used in home appliances, various parts of automobiles, casings, and the like. In addition, for parts such as electronic and electrical equipment casings, resin molding made of a resin composition containing an alloy resin of polycarbonate resin and styrene resin, taking into account mechanical properties such as impact strength. The body is used a lot.

  For this reason, when the above-mentioned parts are manufactured or after the parts are used, a large amount of PC-based resin and alloy resin waste materials are discharged. Conventionally, this waste material has been reused by methods such as (1) chemical recycling (monomer / raw material, blast furnace reducing agent, etc.) and (2) thermal recycling (cement kiln, waste power generation, RDF, RPF, etc.). However, in recent years, material recycling (recycling) that makes more effective use of these has been desired from the viewpoint of resource reuse and environmental protection.

  As a method of recycling the resin waste material, the recovered PC / ABS alloy resin is blended with the flame retardant and the polycarbonate / acrylonitrile-butadiene-styrene copolymer system (PC / ABS system) alloy resin which is a virgin material. A PC-based resin composition has been proposed (see, for example, Patent Document 1).

  Moreover, as a resin composition excellent in moldability, impact resistance, and recyclability, a resin composition comprising (A) an aromatic polycarbonate, (B) a styrene polymer, and (C) a core-shell elastic polymer. (I) A component is 50 parts by weight or more and 99 parts by weight or less and B component is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total of A component and B component, and C component is 0.5 part by weight or more and 20 parts by weight or less, and (ii) one or more carbon atoms of 1 or more in the rubber core in which the C component is composed of 2 or more kinds of polyalkyl (meth) acrylate rubbery polymers An aromatic polycarbonate resin composition which is a core-shell elastic polymer obtained by graft polymerization of an alkyl (meth) acrylate monomer having 3 or less alkyl groups is known (for example, Patent Document 2). Irradiation).

  Furthermore, as a recycled resin composition excellent in long-term physical property retention and mechanical strength, it is a crushed product of a molded product having an aromatic polycarbonate resin content of 30 wt% to 98 wt%, A recycled resin composition comprising a crushed product (component A) having a viscosity average molecular weight of 000 or less and a wet heat retention of 60% or more, and an aromatic polycarbonate resin (component B) is known ( For example, see Patent Document 3).

  Further, as a recycled resin composition excellent in molded product processing characteristics and molded product mechanical characteristics, rubber polymer (component A-1) in 2% by weight to 10% by weight and inorganic filler (A) in 100% by weight of the molded product -2 component) is pulverized product (component A), virgin thermoplastic resin (component B), and virgin inorganic filler (component C) of a molded thermoplastic resin composition containing 0 wt% or more and 15 wt% or less. A regenerated resin composition (component D) produced by melt-kneading a rubber polymer (D-1 component) in an amount of 0.1% by weight to 2% by weight in 100% by weight of the regenerated resin composition A recycled resin composition containing 15% by weight or more and 50% by weight or less of an inorganic filler (D-2 component) is known (for example, see Patent Document 4).

JP 2003-160724 A JP 2003-96288 A International Publication No. 01/072900 Pamphlet JP 2004-323825 A

  The subject of this invention is providing the recycled resin composition excellent in the flame retardance and impact resistance.

The above problem is solved by the following means. That is,
The invention according to claim 1
(A) a recovered resin containing a first polycarbonate / styrene alloy resin;
(B) a second polycarbonate / styrene alloy resin;
(C) The content when the total of the component (A) and the component (B) is 100% by mass is 0.5% by mass to 10% by mass, and the polyorganosiloxane rubber component and the polyalkyl ( A core-shell type composite rubber which is a composite rubber-based graft copolymer including a core which is a composite rubber containing a (meth) acrylate rubber component, and a shell obtained by graft polymerization of a vinyl monomer to the core. When,
(D) An organic phosphorus flame retardant having a content of 1% by mass to 10% by mass when the total of the component (A) and the component (B) is 100% by mass;
Contain,
The ratio of the component (A) in the total of the component (A) and the component (B) is 60% by mass or more and 90% by mass or less,
The temperature at which the mass reduction rate in the TGA measurement of the component (C) is 50% is the temperature at which the mass reduction rate in the TGA measurement of the component (A) is 50%, and in the TGA measurement of the component (B). A recycled resin composition having a mass reduction rate lower than 50% .

The invention according to claim 2
at least,
(A) a recovered resin containing a first polycarbonate / styrene alloy resin;
(B) a second polycarbonate / styrene alloy resin;
(C) The content when the total of the component (A) and the component (B) is 100% by mass is 0.5% by mass to 10% by mass, and the polyorganosiloxane rubber component and the polyalkyl ( A core-shell type composite rubber which is a composite rubber-based graft copolymer including a core which is a composite rubber containing a (meth) acrylate rubber component, and a shell obtained by graft polymerization of a vinyl monomer to the core. When,
(D) An organic phosphorus flame retardant having a content of 1% by mass to 10% by mass when the total of the component (A) and the component (B) is 100% by mass;
Have a step of melt-kneading,
The ratio of the component (A) in the total of the component (A) and the component (B) is 60% by mass or more and 90% by mass or less,
The temperature at which the mass reduction rate in the TGA measurement of the component (C) is 50% is the temperature at which the mass reduction rate in the TGA measurement of the component (A) is 50%, and in the TGA measurement of the component (B). A method for producing a recycled resin composition lower than a temperature at which the mass reduction rate is 50% .

The invention according to claim 3
The regeneration according to claim 2 , wherein the melt-kneading is performed under a condition that a temperature of a mixture including the component (A), the component (B), the component (C), and the component (D) is 260 ° C or less. A method for producing a resin composition.

The invention according to claim 4
A resin molded product comprising the recycled resin composition according to claim 1 .

According to the invention which concerns on Claim 1, compared with the case where it does not have this structure, the recycled resin composition excellent in the flame retardance and impact resistance is provided.
According to the invention which concerns on Claim 1 , compared with the case where the ratio of the said (A) component in the sum total of the said (A) component and the said (B) component does not have this structure, flame retardance and resistance A recycled resin composition having excellent impact properties and excellent reusability is provided.
According to the invention of claim 1 , the temperature at which the mass reduction rate in the TGA measurement of the component (C) is 50% is superior in flame retardancy and impact resistance compared to the case where this configuration is not provided. A recycled resin composition is provided.
According to the invention which concerns on Claim 2 , compared with the case where it does not have this structure, the manufacturing method of the recycled resin composition excellent in the flame retardance and impact resistance is provided.
According to the invention of claim 3 , when the temperature of the mixture containing the component (A), the component (B), the component (C), and the component (D) during melt kneading exceeds 260 ° C. In comparison, a method for producing a recycled resin composition excellent in flame retardancy and impact resistance is provided.
According to the invention which concerns on Claim 2 , compared with the case where the ratio of the said (A) component in the sum total of the said (A) component and the said (B) component does not have this structure, it has a flame retardance and resistance. A method for producing a recycled resin composition having excellent impact properties is provided.
According to the invention which concerns on Claim 2 , compared with the case where the temperature from which the mass reduction rate in the TGA measurement of the said (C) component becomes 50% does not have this structure, it was excellent in the flame retardance and impact resistance. A method for producing a recycled resin composition is provided.
According to the invention which concerns on Claim 4 , compared with the resin molding which contains the reproduction | regeneration resin composition which does not have this structure, the resin molding excellent in the flame retardance and impact resistance is provided.

It is a schematic diagram which shows an example of the resin composition manufacturing apparatus for enforcing the manufacturing method of the resin composition of this embodiment. It is a schematic diagram which shows an example of the components of an electronic / electric equipment provided with the resin molding of this embodiment.

Hereinafter, the recycled resin composition of the present invention, the production method thereof, and the resin molded body will be described.
≪Recycled resin composition and production method thereof≫
The recycled resin composition of the present embodiment includes (A) a recovered resin containing a first polycarbonate / styrene alloy resin (hereinafter also referred to as “component (A)”), and (B) a second polycarbonate / styrene system. Alloy resin (hereinafter also referred to as “component (B)”), and (C) content of 0.5% by mass or more when the total of component (A) and component (B) is 100% by mass A core that is 10% by mass or less and is a composite rubber containing a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component, and a shell obtained by graft polymerization of a vinyl monomer to the core. The total of the core-shell type composite rubber (hereinafter also referred to as “component (C)”), which is a composite rubber-based graft copolymer, and (D) the component (A) and the component (B) is 100 masses. Content when% 1% by weight to 10% by weight or less is an organic phosphorus-based flame retardant (hereinafter, also referred to as "component (D)") and contains.
Moreover, the manufacturing method of the recycled resin composition of this embodiment has the process of melt-kneading at least said (A) component, said (B) component, said (C) component, and said (D) component.

So far, although the regenerated resin composition has been studied, the conventional regenerated resin composition is limited to the case where the ratio of the recovered resin in the regenerated resin composition is low (for example, about 30% by mass). In some cases, the recovered resin and the virgin resin are limited to the same type, or the flame retardancy is insufficient.
The recycled resin composition and the production method thereof according to the present embodiment can obtain an effect excellent in flame retardancy and impact resistance by the above-described configuration. In particular, even when a large amount of the collected resin is blended (for example, when 50% by mass or more is blended in the entire matrix resin), flame retardancy and impact resistance that are close to virgin resin can be obtained.

In the present embodiment, the first polycarbonate / styrene alloy resin and the second polycarbonate / styrene alloy resin may be the same or different. In the present embodiment, the above effect can be obtained even if the two are different species. In the present embodiment, it is preferable that the second polycarbonate / styrene alloy resin is a virgin resin (virgin material) from the viewpoint of obtaining the above effect more effectively.
Here, the virgin resin (virgin material) refers to a resin that has not been used since it was manufactured.
In this embodiment, the component (A) and the component (B) may be referred to as “matrix resin”, respectively, and the sum of the component (A) and the component (B) may be referred to as “all matrix resin”. .
Details of each component will be described below.

<(A) First Polycarbonate / Recovered Resin Containing Styrene Alloy Resin>
In the present embodiment, as the recovered resin according to the component (A), for example, a market recovered material (recycled material) containing the first polycarbonate / styrene alloy resin is used.
The recovered resin is preferably used after being pulverized using a crusher such as a dry or wet crusher. At this time, the size of the resin material obtained after pulverization is preferably 10 mm or less, and more preferably 5 mm or less.

The first polycarbonate / styrene alloy resin contained in the recovered resin is not particularly limited as long as it is an alloy resin in which at least one polycarbonate resin and at least one styrene resin are combined.
Here, examples of the polycarbonate (hereinafter also referred to as “PC”) resin include aromatic polycarbonate, polyorganosiloxane-containing aromatic polycarbonate, aliphatic polycarbonate, and alicyclic polycarbonate.
Among these, aromatic polycarbonate is preferable from the viewpoint of excellent heat resistance and low colorability during processing.
Examples of the styrene resin include GPPS resin (general polystyrene resin), HIPS resin (impact polystyrene), SBR resin (styrene butadiene rubber), ABS resin (acrylonitrile-butadiene rubber-styrene copolymer), AES. Resin (acrylonitrile-ethylene propylene rubber-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer), AS resin (acrylonitrile-styrene) Copolymer), MS resin (methyl methacrylate-styrene copolymer), and the like.
Among the above, HIPS resin, ABS resin, AS resin, and the like are preferable from the viewpoint of balance between heat resistance and impact resistance and workability.

  Commercially available products of the first polycarbonate / styrene alloy resin include “TN7300”, a PC / ABS alloy resin manufactured by Teijin Chemicals Ltd., “X-3325”, a PC / AS alloy resin manufactured by Teijin Chemicals Ltd., and Idemitsu “NN2710AS” which is a PC / HIPS alloy resin manufactured by Kosan Co., Ltd., “ZFJ61” which is a PC / ABS alloy resin manufactured by UMGABS, “C6600” which is a PC / ABS alloy resin manufactured by SABIC, and the like.

The ratio of the component (A) in the total matrix resin (the sum of the components (A) and (B)) of the present embodiment is preferably 50% by mass or more and 90% by mass or less.
When the ratio is 50% by mass or more, reusability is excellent, and when the ratio is 90% by mass or less, flame retardancy and impact resistance are excellent.
From the viewpoint of further improving flame retardancy and impact resistance, the ratio is preferably 50% by mass or more and 70% by mass or less, and more preferably 50% by mass or more and 60% by mass or less.
On the other hand, from the viewpoint of further improving reusability, the ratio is preferably 60% by mass or more and 90% by mass or less, and more preferably 70% by mass or more and 90% by mass or less.

In the present embodiment, the temperature at which the mass reduction rate in the TGA measurement (thermogravimetry) of the recovered resin relating to the component (A) is 50% (hereinafter also referred to as “temperature A”) is preferably higher. Specifically, the temperature is preferably 450 ° C. or higher and 550 ° C. or lower, and more preferably 460 ° C. or higher and 540 ° C. or lower.
Within the above range, excellent flame retardancy and impact resistance tend to be obtained even when the content of the recovered resin in the recycled resin composition is high.
In the present embodiment, the temperature A indicates a value obtained as follows. In addition, it calculates | requires by the same method also in the temperature B and the temperature C which are mentioned later.
That is, using TGA-DTA2000S (trade name) manufactured by Seiko Co., Ltd., the temperature was increased from 23 ° C. to 600 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen stream, and the mass reduction rate at each temperature was measured. The temperature at which the mass reduction rate reaches 50% is defined as temperature A.
Here, the mass reduction rate at a certain temperature X is obtained by the following equation 1.
Mass reduction rate at temperature X (%) = ((mass of sample at 23 ° C.−mass of sample at temperature X) / mass of sample at 23 ° C.) × 100 (Equation 1)

<(B) Second Polycarbonate / Styrene Alloy Resin>
In the present embodiment, the second polycarbonate / styrene-based alloy resin related to the component (B) is not particularly limited, but as described above, from the viewpoint of more effectively obtaining the effects of the present embodiment, a virgin resin (virgin Material).
As the second polycarbonate / styrene alloy resin, the resins exemplified for the first polycarbonate / styrene alloy resin can be used, and the preferred range is also the same.
However, as described above, the first polycarbonate / styrene alloy resin and the second polycarbonate / styrene alloy resin may be the same or different.

The ratio of the component (B) in the total matrix resin (the sum of the components (A) and (B)) of the present embodiment is preferably 10% by mass or more and 50% by mass or less.
When the ratio is 50% by mass or less, reusability is excellent, and when the ratio is 10% by mass or more, flame retardancy and impact resistance are excellent.
From the viewpoint of further improving flame retardancy and impact resistance, the ratio is preferably 30% by mass or more and 50% by mass or less, and more preferably 40% by mass or more and 50% by mass or less.
On the other hand, from the viewpoint of further improving reusability, the ratio is preferably 10% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 30% by mass or less.

In the present embodiment, the temperature at which the mass reduction rate in the TGA measurement (thermogravimetric analysis) of the recovered resin relating to the component (B) is 50% (hereinafter also referred to as “temperature B”) is preferably higher. Specifically, the temperature is preferably 450 ° C. or higher and 550 ° C. or lower, and more preferably 460 ° C. or higher and 540 ° C. or lower.
Within the above range, excellent flame retardancy and impact resistance are easily obtained even when the content of the recovered resin in the recycled resin composition is high.

<(C) Core-shell type composite rubber>
In this embodiment, the component (C) includes a core that is a composite rubber including a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component, and a shell formed by graft polymerization of a vinyl monomer on the core. And a core-shell type composite rubber which is a composite rubber-based graft copolymer.

  The core-shell type composite rubber has a two-layer structure composed of a core and a shell, and the core portion is in a soft rubber state, and the shell portion on the surface thereof is a hard resin. The core-shell type composite rubber itself is in a powder form (particle state). The core-shell type composite rubber, for example, is largely in its original form even after being melt-blended with, for example, a polycarbonate / styrene alloy resin. Since most of the blended core-shell type composite rubber maintains the original form, the dispersion uniformity is improved and the effect of preventing surface peeling is obtained. This effect particularly improves the impact resistance.

Examples of the polyorganosiloxane rubber component in the core include polydialkylsiloxanes such as polydimethylsiloxane, polydiethylsiloxane, polydipropylsiloxane, polydibutylsiloxane, and polydipentylsiloxane.
Among these, polydialkylsiloxane is preferable from the viewpoint of improving heat resistance and from the viewpoint of improving impact resistance. Furthermore, the number of carbon atoms in the two alkyl moieties of the dialkylsiloxane is preferably 1 or more and 6 or less.
The polyorganosiloxane rubber component in the core may be only one type or two or more types.

Examples of the polyalkyl (meth) acrylate rubber component in the core include poly (meth) acrylic acid such as polybutyl acrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, and 2-ethylhexyl polyacrylate. Alkyl is mentioned.
From the viewpoint of improving the heat resistance and the viewpoint of improving the impact resistance, the alkyl moiety of the alkyl poly (meth) acrylate preferably has 1 to 6 carbon atoms.
Further, the polyalkyl (meth) acrylate rubber component in the core may be only one type or two or more types.
In the present specification, “(meth) acrylate” represents acrylate or methacrylate, and “(meth) acrylic acid” represents acrylic acid or methacrylic acid.

Examples of vinyl monomers that form a shell by graft polymerization to the core include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyltoluene, and methacrylic acid such as methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl methacrylate. Examples thereof include acrylic esters such as esters, methyl acrylate, ethyl acrylate and butyl acrylate, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Hereinafter, the methacrylic acid ester and the acrylic acid ester may be collectively referred to as “alkyl (meth) acrylate”.
Among these, alkyl (meth) acrylate, (meth) acrylonitrile, and styrene are preferable from the viewpoint of improving heat resistance and impact resistance. Further, the number of carbon atoms in the alkyl portion of the alkyl (meth) acrylate is preferably 1 or more and 6 or less independently.
The vinyl monomer that forms a shell by graft polymerization with respect to the core may be one kind or two or more kinds.

  Examples of the core-shell type elastomer include “EXL2603”, “KM-330” (trade name, manufactured by Rohm & Haas), “MR-01”, “MR-02” (trade name, manufactured by Kaneka). ), “Metabrene S-2001”, “S-2006”, “S-2030”, “S-2100”, “SRK-200”, “SX-006”, “SX-005”, “W-300A” , “W-450A”, “W-341”, “E-901”, “C-223A”, “C-323A”, “C-215A”, “C-201A”, “C-202”, “ C-102 "," C-140A "," C-132 "," F-410 "," H-602 "(all manufactured by Mitsubishi Rayon Co., Ltd.).

The content of the component (C) in the recycled resin composition of the present embodiment is 0.5% by mass or more and 10% by mass when the total of the component (A) and the component (B) is 100% by mass. It is necessary that:
When the content is less than 0.5% by mass, sufficient impact resistance cannot be obtained. When the content exceeds 10% by mass, the flame retardancy and impact resistance of the thermoplastic resin tend to be lost.
From the viewpoint of the balance of impact resistance, flame retardancy, and workability, the content is preferably 0.5% by mass or more and 5.0% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass. The following is more preferable.

In the present embodiment, the temperature at which the mass reduction rate in the TGA measurement (thermogravimetric analysis) of the recovered resin relating to component (C) is 50% (hereinafter also referred to as “temperature C”) is preferably lower. Specifically, the temperature is preferably 380 ° C. or higher and 450 ° C. or lower, and more preferably 390 ° C. or higher and 440 ° C. or lower.
Within the above range, excellent flame retardancy and impact resistance can be easily obtained even when the ratio of the recovered resin in the entire matrix resin is high (for example, when the ratio is 50% by mass or more). .

In the present embodiment, the temperature C is preferably lower than the temperature A and the temperature B. At this time, the temperature C is more preferably 40 ° C. or more, and particularly preferably 50 ° C. or more, lower than the lower one of the temperature A and the temperature B.
When the relationship between the temperature A, the temperature B, and the temperature C is the above relationship, the ratio of the recovered resin in the entire matrix resin is high (for example, the ratio is 50% by mass or more). However, excellent flame retardancy and impact resistance are easily obtained.

  Further, the ratio of the core in the component (C) is preferably 45% by mass or more and 95% by mass or less, and more preferably 60% by mass or more and 95% by mass or less from the viewpoint of heat resistance.

In the component (C), the ratio of the polyorganosiloxane rubber component in the core is preferably 5% by mass or more and 70% by mass or less, and more preferably 5% by mass or more and 50% by mass or less. . Thereby, it becomes easy to adjust the said temperature C to the said range, and a flame retardance and impact property are improved more.
Examples of the component (C) in which the content of the polyorganosiloxane rubber component in the core is 5% by mass or more and 50% by mass or less include the “SRK-200”, the “S-2006”, and the “SX-”. 006 "and" S-2001 ".

<(D) Organophosphorous flame retardant>
In the present embodiment, the organic phosphorus flame retardant according to the component (D) is not particularly limited. For example, melamine polyphosphate, aromatic phosphorus compound, phosphate ester, condensed phosphate ester, phosphinate, phosphone Acid salts, phosphazene compounds, ammonium polyphosphate and the like can be mentioned. In the present embodiment, in view of the situation that it is required not to contain a halogen-based compound due to the problem of generation of harmful substances at the time of combustion, a condensed phosphate ester that does not contain a halogen and can express high flame retardancy is used. It is preferable to use it as a flame retardant.

  Examples of the condensed phosphate ester include pentaerythritol diphosphate and phosphate ester compounds represented by the following general formulas (I) and (II).

In formula (I), Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q ⁵ , Q ⁶ , Q ⁷ and Q ⁸ are each Independently represents a hydrogen atom or a methyl group, m1, m2, m3 and m4 each independently represents an integer of 0 to 3, m5 and m6 each independently represents an integer of 0 or more and 2 or less, and n1 is Represents an integer of 0 or more and 10 or less.

In formula (II), Q ⁹ , Q ¹⁰ , Q ¹¹ and Q ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ¹³ represents a hydrogen atom or a methyl group, m7, m8, m9 and m10 each independently represents an integer of 0 or more and 3 or less, m11 represents an integer of 0 or more and 4 or less, and n2 represents an integer of 0 or more and 10 or less.

  In the present embodiment, for example, aromatic condensed phosphate esters such as bisphenol A type, biphenylene type, and isophthal type are preferably used. Commercially available products such as PX-200, PX-201, PX-202, CR-733S, CR-741, CR747 manufactured by Daihachi Chemical Co., Ltd. may be used as the condensed phosphate ester.

The content of the component (D) in the recycled resin composition of the present embodiment is 1% by mass or more and 10% by mass or less when the total of the component (A) and the component (B) is 100% by mass. It is necessary to be.
When the content is less than 1% by mass, flame retardancy is deteriorated. When the content exceeds 10% by mass, impact resistance deteriorates.
From the viewpoint of achieving both impact resistance and flame retardancy, the content is preferably 3% by mass or more and 9% by mass or less.

<Other ingredients>
The recycled resin composition of this embodiment may contain other components other than the component (A), the component (B), the component (C), and the component (D).
However, from the viewpoint of obtaining the effect of the present embodiment more effectively, the content of other components in the recycled resin composition is preferably 0% by mass or more and 10% by mass or less, and 0% by mass or more and 5% by mass. The following is more preferable. Here, “0 mass%” means a form that does not contain other components.
Examples of the other components include various pigments, modifiers, anti-drip agents, compatibilizers, antistatic agents, antioxidants, weathering agents, antihydrolysis agents, fillers, reinforcing agents (glass fibers, Carbon fiber, talc, clay, mica, glass flake, milled glass, glass beads, crystalline silica, alumina, silicon nitride, alumina nitride, boron nitride, etc.). Moreover, the recycled resin composition of this embodiment contains, for example, 0.1% by mass or more and 1% by mass of polytetrafluoroethylene (PTFE) as another component from the viewpoint of further improving the flame retardancy. Also good.

<< Method for Producing Recycled Resin Composition >>
The method for producing a recycled resin composition of the present embodiment includes at least a step of melt-kneading the component (A), the component (B), the component (C), and the component (D).
Here, a known means can be used as the melt kneading means, and examples thereof include a twin screw extrusion, a Henschel mixer, a Banbury mixer, a single screw extruder, a multi-screw extruder, and a kneader.

In the melt kneading, the temperature of the mixture containing the component (A), the component (B), the component (C), and the component (D) (hereinafter also simply referred to as “resin temperature”) is 260 ° C. or less. It is preferable to carry out under the following conditions.
Here, the resin temperature refers to a value measured using a value measured by winding a strand extruded from a twin-screw extruder around a handy type resin thermometer by 50 g.
When the resin temperature exceeds 260 ° C., the components (C) and (D) may be poorly dispersed.
The resin temperature is preferably 170 ° C. or higher and 260 ° C. or lower, and more preferably 190 ° C. or higher and 240 ° C. or lower, from the viewpoint of preventing thermal degradation of the resin.

Hereinafter, an example of a recycled resin composition production apparatus for carrying out the method for producing a recycled resin composition of the present embodiment will be described with reference to FIG.
FIG. 1 is a schematic view showing an example of a resin composition production apparatus for carrying out the method for producing a resin composition of the present embodiment. The resin composition production apparatus 10 shown in FIG. 1 is a raw material of a recycled resin composition (the component (A), the component (B), the component (C), and the component (D) (and other if necessary). The component)) is provided with a raw material supply unit 5 that can be individually supplied, and a twin-screw extruder 6 that melts and kneads the supplied material. In the resin composition manufacturing apparatus 10, the recovered resin 1 as the component (A), the virgin resin 2 as the component (B), and the core-shell type composite as the component (C) supplied to the raw material supply unit 5. The rubber 3 and the organophosphorus flame retardant 4 as the component (D) are melt-kneaded to obtain a recycled resin composition 7.

≪Resin molded body≫
The resin molded body of the present embodiment includes the recycled resin composition of the present embodiment described above.
That is, the resin molded body of the present embodiment is obtained by molding the recycled resin composition of the present embodiment. For example, the recycled resin composition of this embodiment is molded by a molding method such as injection molding, extrusion molding, blow molding, heat press molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding, transfer molding, etc. The resin molding which concerns on embodiment is obtained.
The injection molding is performed using, for example, a commercially available apparatus such as NEX150 manufactured by Nissei Plastic Industry, NEX70000 manufactured by Nissei Plastic Industry, SE50D manufactured by Toshiba Machine.
At this time, the cylinder temperature is preferably 220 ° C. or higher and 280 ° C. or lower, and more preferably 230 ° C. or higher and 270 ° C. or lower, from the viewpoint of preventing thermal deterioration of the resin.
The mold temperature is preferably 40 ° C. or higher and 80 ° C. or lower, more preferably 50 ° C. or higher and 70 ° C. or lower, from the viewpoint of productivity.

  Since the resin molded body of this embodiment can be excellent in impact resistance and flame retardancy, it is suitably used for applications such as electronic / electric equipment, home appliances, containers, and automobile interior materials. More specifically, housings such as home appliances and electronic / electrical equipment, various parts, wrapping films, storage cases such as CD-ROMs and DVDs, tableware, food trays, beverage bottles, chemical wrap materials, etc. Especially, it is suitable for parts of electronic / electric equipment. Many parts of electronic and electrical equipment have complicated shapes, and are heavy, so extremely high impact strength and surface impact strength are required. However, according to the resin molded body of this embodiment, Thus, such required characteristics can be sufficiently satisfied.

FIG. 2 is an external perspective view of an image forming apparatus, which is an example of a part of an electronic / electric device including the molded body of the present embodiment, as viewed from the front side.
The image forming apparatus 100 in FIG. 2 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 freely opened and closed so that an operator can operate the inside of the apparatus. Thus, the operator replenishes the toner when the toner is exhausted, replaces the exhausted process cartridge, or removes the jammed paper when a paper jam occurs in the apparatus. FIG. 2 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. In addition, the main body device 110 includes an automatic document conveying device 134 that conveys a document on the copy glass 132 at the top thereof. 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 is 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 is 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 supply unit 136 is provided on a side surface of the main apparatus 110, and paper is 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 that forms part of the main body device 110 and is in contact with each other. Paper is discharged to the outside. The main body device 110 is provided with a plurality of paper discharge sections 138 on the side opposite to the side where the paper supply section 136 is provided, and the paper after image formation is discharged to these paper discharge sections.

  In the image forming apparatus 100, for example, members for office equipment such as the front covers 120a and 120b, the exterior of the process cartridge 142, the housing 150, and the housing 152 have various performances such as impact resistance and flame retardancy. Required. In addition, the usage rate of recycled materials is increasing in the above parts. For this reason, the resin molding of this embodiment is used suitably as components of these electronic / electrical devices. In addition, the above components are likely to deteriorate due to external light or heat generated in the apparatus. For this reason, the resin molding of this embodiment is useful also for the recycling of the said components.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Matrix resin>
The matrix resins used in the present examples and comparative examples are shown in Table 1 below.
Table 1 shows the temperature at which the mass reduction rate in TGA measurement is 50% for each matrix resin. Here, TGA measurement was performed as follows.
That is, using TGA-DTA2000S (trade name) manufactured by Seiko, the temperature was increased from 23 ° C. to 600 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen stream, and the mass reduction rate at each temperature was measured. The temperature at which the mass reduction rate reached 50% was defined as temperature A.

In Table 1, “recovered PC / HIPS alloy resin” is a resin contained in the component (A) of this embodiment. All other resins are resins contained in the component (B) of this embodiment.
Moreover, the meaning of the abbreviation in Table 1 is as follows.
・ PC ・ ・ ・ Polycarbonate ・ ABS ・ ・ ・ Acrylonitrile butadiene styrene ・ HIPS ・ ・ ・ Impact-resistant polystyrene ・ AS ・ ・ ・ Acrylonitrile styrene

<Additives>
The additives used in the present examples , reference examples and comparative examples are shown in Table 2 below.
Table 2 shows the temperature at which the mass reduction rate in the TGA measurement is 50% for each additive. TGA measurement was performed in the same manner as the TGA measurement of the matrix resin.
Table 2 shows the composition of each additive.

  In Table 2, all except for “Z-6018” are core-shell type composite rubbers contained in the component (C) of this embodiment.

[ Reference Example 1]
<Preparation of resin composition>
Using a super mixer, 1,3-phenylene-tetrakis (2,6-dimethylphenyl phosphate as an flame retardant (organophosphorus flame retardant manufactured by Daihachi Chemical Industry Co., Ltd., trade name “PX-200”, particulate form; (D ) Component) and additives (core-shell type composite rubber manufactured by Mitsubishi Rayon Co., Ltd., trade name “SRK-200”; component (C)) were mixed at a mass ratio shown in Table 3 to obtain a mixture.

Next, the mixture obtained above, PC / ABS alloy resin (trade name “TN-7300” manufactured by Teijin Chemicals Ltd .; component (B)), which is a virgin material, and market recovery material (PC / HIPS alloy resin ( Idemitsu Kosan Co., Ltd., trade name "NN2710AS") copier cover was collected, metal parts were removed, and pulverized to a size of about 4 mm with a pulverizer; Supplyed to the raw material supply part of a shaft extruder (manufactured by Nippon Steel Works, product name “TEX44αII”, screw diameter 44 mm) at the mass ratio shown in Table 3, extruder supply part temperature: 150 to 180 ° C., extruder compression part Temperature: 180-220 ° C., extruder melting part temperature: 180-220 ° C., extruder head temperature: 250 ° C., melt-kneaded at an extrusion throughput of 100 kg / h, pellets that are recycled resin compositions Diameter 3 mm, to prepare a length 3 mm).
The resin temperature at the time of the melt kneading was measured by measuring 50 g of a strand extruded from a twin-screw extruder around a handy type resin thermometer and measuring 250 ° C. Here, the “resin temperature” is the temperature of the mixture of the component (A), the component (B), the component (C), and the component (D) (the same applies hereinafter).

<Preparation of resin molding and its evaluation>
The pellets obtained above were injection molded using an injection molding machine (product name “NEX500” manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 235 ° C. and a mold temperature of 60 ° C. 4 mm, width 10 mm) and UL test piece (thickness 1.5 mm) for V-test in UL-94.
The following evaluation was performed using these test pieces. The evaluation results are shown in Table 3.

(Flame retardancy test)
UL-V test and UL-5V test were performed in accordance with the method defined in UL-94 using the above V test UL test piece.
In Table 3, the display of the results of the UL-V test is V-0, V-1, and V-2 in descending order of flame retardancy. As a result of the test, the case where it was inferior to V-2, that is, the case where the test piece had spread, was indicated as not-V.
Moreover, the display of the result of UL-5V test in Table 3 is 5VA and 5VB in order from the one with the higher flame retardancy. As a result of the test, the case where it was inferior to 5 VB, that is, the case where the test piece was spread was indicated as not-5 VB.

(Charpy impact strength)
Charpy impact strength (kJ / m ² ) was measured by an impact resistance test apparatus (DG-5, manufactured by Toyo Seiki Co., Ltd.) using a notched ISO multipurpose dumbbell test piece. The larger the measured value, the better the impact resistance.

(Measurement of fluidity)
The fluidity (MVR (melt volume flow rate)) under the conditions shown in Table 3 was measured by the method specified in ISO-1133 (1997). The larger the measured value, the better the fluidity.

[Examples 8 to 13, Reference Examples 2 to 7, Reference Examples 14 to 15 ]
The matrix resin, the type and amount of each component of the flame retardant, and additives, except for changing as shown in Table 3 or Table 4 in the same manner as in Reference Example 1 to prepare a recycled resin composition, Reference Examples In the same manner as in No. 1, a resin molded body was produced and evaluated. The evaluation results are shown in Table 3 or 4 below.

[Comparative Examples 1 to 5]
The matrix resin, the type and amount of each component of the flame retardant, and additives, except for changing as shown in Table 3 or Table 4 in the same manner as in Reference Example 1 to prepare a recycled resin composition, Reference Examples In the same manner as in No. 1, a resin molded body was produced and evaluated. The evaluation results are shown in Table 3 or 4 below.

As shown in Tables 3 and 4, Reference Examples 1 to 7, Example 8 to Example 13, Reference Example 14 and Reference Example 15 are excellent in flame retardancy and impact resistance, and further flow. It was also excellent in performance. In particular, Reference Examples 1 to 5, Reference Example 7, and Examples 8 to 13 exhibited high flame retardancy of 5 VB.

Next, the same evaluation as in Reference Example 1 was performed on the matrix resin alone and the reference matrix resin used in the above Examples , Reference Examples, and Comparative Examples. The evaluation results are shown in Table 5 below.

As can be seen from the comparison between the results of Table 5 and the results of Reference Example 1 to Reference Example 7, Example 8 to Example 13, and Reference Example 14 to Reference Example 15 , Reference Example 1 to Reference Example 7, In Examples 8 to 13 and Comparative Examples 14 to 15 , the flame retardancy, impact resistance, and fluidity that are similar to virgin materials are maintained despite the large amount of recovered resin. It had been.

[ Reference Example 1-1, Reference Example 1-2, Reference Example 1-3]
Reference Example 1, the resin temperature during melt-kneading, 210 ° C., 230 ° C., 280 ° C., except for changing the respective temperatures in the same manner as in Reference Example 1 to prepare a recycled resin composition, as in Reference Example 1 The resin molded body was produced and evaluated by the same method. The evaluation results are shown in Table 6 below.

As shown in Table 6, in Reference Example 1, Reference Example 1-2, and Reference Example 1-3 in which the resin temperature during melt-kneading was 260 ° C. or less, Reference Example 1-1 in which the resin temperature was 280 ° C. Compared with it, it was more excellent in flame retardancy and impact resistance.

DESCRIPTION OF SYMBOLS 1 Recovery resin 2 Virgin resin 3 Core-shell type composite rubber 4 Organophosphorus flame retardant 5 Raw material supply part 6 Twin screw extruder 7 Recycled resin composition 100 Image forming apparatus 110 Main body apparatus 120a, 120b Front cover 136 Paper supply part 138 Paper discharge unit 142 Process cartridge 150, 152 Case

Claims (4)

(A) a recovered resin containing a first polycarbonate / styrene alloy resin;
(B) a second polycarbonate / styrene alloy resin;
(C) The content when the total of the component (A) and the component (B) is 100% by mass is 0.5% by mass to 10% by mass, and the polyorganosiloxane rubber component and the polyalkyl ( A core-shell type composite rubber which is a composite rubber-based graft copolymer including a core which is a composite rubber containing a (meth) acrylate rubber component, and a shell obtained by graft polymerization of a vinyl monomer to the core. When,
(D) An organic phosphorus flame retardant having a content of 1% by mass to 10% by mass when the total of the component (A) and the component (B) is 100% by mass;
Contain,
The ratio of the component (A) in the total of the component (A) and the component (B) is 60% by mass or more and 90% by mass or less,
The temperature at which the mass reduction rate in the TGA measurement of the component (C) is 50% is the temperature at which the mass reduction rate in the TGA measurement of the component (A) is 50%, and in the TGA measurement of the component (B). A recycled resin composition having a mass reduction rate lower than 50% . at least,
(A) a recovered resin containing a first polycarbonate / styrene alloy resin;
(B) a second polycarbonate / styrene alloy resin;
(C) The content when the total of the component (A) and the component (B) is 100% by mass is 0.5% by mass to 10% by mass, and the polyorganosiloxane rubber component and the polyalkyl ( A core-shell type composite rubber which is a composite rubber-based graft copolymer including a core which is a composite rubber containing a (meth) acrylate rubber component, and a shell obtained by graft polymerization of a vinyl monomer to the core. When,
(D) An organic phosphorus flame retardant having a content of 1% by mass to 10% by mass when the total of the component (A) and the component (B) is 100% by mass;
Have a step of melt-kneading,
The ratio of the component (A) in the total of the component (A) and the component (B) is 60% by mass or more and 90% by mass or less,
The temperature at which the mass reduction rate in the TGA measurement of the component (C) is 50% is the temperature at which the mass reduction rate in the TGA measurement of the component (A) is 50%, and in the TGA measurement of the component (B). A method for producing a recycled resin composition lower than a temperature at which the mass reduction rate is 50% . The regeneration according to claim 2 , wherein the melt-kneading is performed under a condition that a temperature of a mixture including the component (A), the component (B), the component (C), and the component (D) is 260 ° C or less. A method for producing a resin composition. A resin molded product comprising the recycled resin composition according to claim 1 .

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