WO2001072900A1 - Composition de resine regeneree - Google Patents
Composition de resine regeneree Download PDFInfo
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- WO2001072900A1 WO2001072900A1 PCT/JP2001/002474 JP0102474W WO0172900A1 WO 2001072900 A1 WO2001072900 A1 WO 2001072900A1 JP 0102474 W JP0102474 W JP 0102474W WO 0172900 A1 WO0172900 A1 WO 0172900A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/911—Recycling consumer used articles or products
Definitions
- the present invention relates to a recycled resin composition. More specifically, the present invention relates to a recycled resin composition having excellent mechanical strength and recycling efficiency by using a crushed molded product satisfying specific conditions as a recycled resin composition.
- Conventional technology relates to a recycled resin composition having excellent mechanical strength and recycling efficiency by using a crushed molded product satisfying specific conditions as a recycled resin composition.
- Aromatic polycarbonate resins are widely used industrially because of their excellent mechanical and thermal properties.
- many aromatic flame retardant polycarbonate resin compositions have been developed for blending aromatic polycarbonate with other thermoplastic resins, and a flame retardant polycarbonate resin composition with a flame retardant added to enhance flame retardancy has been developed.
- 'It is widely used in the fields of electronic devices, automobiles, and other miscellaneous goods.
- resin compositions in which aromatic polystyrene resin is blended with ABS measuring agent and Nada flame retardant have been increasing remarkably in parts such as housings of OA equipment and electronic and electrical equipment.
- phosphates phosphate esters are becoming mainstream.
- the recovered equipment is likely to be placed in an environment where the deterioration of the aromatic polycarbonate resin progresses in the process of obtaining the recovered resin.
- the ratio of the recovered resin to the purge resin must be set at the lower limit of the dispersion, and as a result, the recycling efficiency is reduced.
- CD and the like are substantially composed of only an aromatic polycarbonate resin except for a very small amount of additives, and are basically unlikely to cause the above-mentioned problem of inferiority, and are therefore unlikely to cause a problem of quality variation.
- An object of the present invention is to provide a highly recyclable resin composition in which a molded article made of a resin composition containing an aromatic polycarbonate resin is collected, and the collected resin is mixed with another virgin resin to produce a recycled resin composition. It is an object of the present invention to provide a recycled resin composition that enables the efficiency and the properties substantially equal to those of the member before the regeneration.
- the present inventor has used, as a collected crushed product, a product that satisfies specific conditions in terms of molecular weight and moisture and heat resistance.
- the present inventors have found that the above problems can be solved by producing a resin composition composed of a polycarbonate resin, and have completed the present invention.
- Means for solving the problem According to the present invention, the object of the present invention is:
- the crushed material has a viscosity average molecular weight of 17,000 to 30,000, and (3) the crushed material has a wet heat retention of 60% or more.
- the crushed product of the component A in the present invention will be described.
- the crushed molded product used in the present invention is particularly limited in the properties required for the product in which the molded product is used, such as the use, shape, and hue of the molded product, and in the use period and environment of the molded product. It does not. Furthermore, not only the crushed product of a specific molded product but also a crushed product of one or more types of molded products can be used in combination.
- the “article” as the component A means: (1) the article is used in the market as a part of the product, and the article is recovered by the consumer after the use period of the product has expired; and This refers to molded products that have undergone at least one step of molding and processing pergin resin pellets, such as defective products generated in the process and molded products collected as inventory during the distribution process of products in the market.
- molded products generated during the molding process such as prototypes, defective products, sprues, and runners, are mixed into the recycled resin composition within the range normally used in the molding industry. It can be done.
- A— 1 component polycarbonate resin in A component
- A-3-A component Phosphate ester as flame retardant in A component
- A-3-b component Organic siloxane compound as flame retardant in A component A-3-c component Alkaline (earth) metal salt as flame retardant in A component A-4 component; Impact in A component Improver
- A-5 component inorganic filler in A component
- Component C—3-c Component Alkaline (earth) metal salt as flame retardant in component C 1-4
- crushed molded product (A component) of the present invention contains 30 to 98% by weight or more of an aromatic polycarbonate resin (A-1 component). is there. Furthermore, (1) a crushed material having a viscosity average molecular weight of 170,000 to 30,000, and a wet heat retention of 60% or more, as defined in (2) or less, You need to use
- the effect of the present invention is exhibited when the proportion of the aromatic polycarbonate resin (A-1 component) in the crushed product (A component) is 30 to 98% by weight, preferably 40 to 90% by weight. .
- the content of the aromatic polyphenol resin in the crushed product of the molded product of component A can be determined by separation methods such as alkali decomposition treatment, thermal decomposition treatment, and heat treatment, IR analysis, NMR analysis, pyrolysis gas chromatography analysis, Near infrared analysis, UV analysis, SIMS Analysis can be performed by arbitrarily combining a method of comparing specific peaks based on relative intensity, such as analysis, ESCA analysis, etc., and the ratio involved can be easily determined.
- the viscosity average molecular weight is from 17,000 to 30,000, preferably from 18,000 to 26,000. If the viscosity average molecular weight is lower than 17,000, the ratio of the A component to the virgin resin is reduced to increase the mechanical strength of the recycled resin composition, and the recycling efficiency cannot be sufficiently increased. Further, when the molecular weight is reduced due to deterioration of the resin composition before regeneration, such a deteriorated product becomes a deterioration factor of the recycled resin composition, and the deterioration can progress during the production of the recycled resin composition. It is difficult to stably obtain the target strength and the like. On the other hand, if the viscosity average molecular weight is higher than 30,000, the molding processability is reduced, and the thermal load during the production of the recycled resin composition is increased, which is not preferable. Causes a decline.
- the viscosity average molecular weight used to specify the component A is defined as the following: First, the component A, which is a crushed molded product, is dissolved in methylene chloride 20 to 30 times the weight of the component A. Is collected by filtration through celite, the solvent is removed and the residue is sufficiently dried to obtain a solid soluble in methylene chloride. From a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride, a specific viscosity at 20 ° C. calculated by the following equation is determined using an Ostwald viscometer.
- the viscosity average molecular weight M is determined by inserting the specific viscosity determined above into the following equation.
- V SP / c [77] +0.45 X [77] 2 c
- the moist heat retention rate specified for specifying the component A in the present invention is measured after the crushed article is left for 24 hours in a wet heat pressurized environment of 120 ° C and 100% RH, and after the treatment. It is a value defined by the following formula from the above viscosity average molecular weight obtained.
- Moist heat retention (%) (viscosity average molecular weight after wet heat treatment Z viscosity average molecular weight before wet heat treatment) X 100
- the moist heat retention rate is less than 60%, the mechanical properties of a molded article made from the recycled resin composition will decrease. The reason why the value of the wet heat retention cannot be satisfied is that deterioration during the production of the regenerated resin composition is likely to occur. More preferably, the moist heat retention is 70% or more.
- the present invention uses a molded article broken frame (component A) containing a specific amount of an aromatic polycarbonate resin, having a specific viscosity average molecular weight, and having the wet heat retention of the present invention.
- component A a molded article broken frame
- the selection of the crushed molded product that satisfies such conditions can be performed by the simple method as described above, and the recovered resin composition having a variety of qualities and compositions or compositions containing the aromatic polycarbonate resin can be selected. It can be used very effectively.
- the recycled resin composition obtained by mixing with a virgin resin such as an aromatic polycarbonate shelf (Component B) stably achieves good mechanical properties.
- the shape of the broken frame of the molded product which is the component A of the present invention, is not particularly limited, but from the viewpoint of workability, handleability, etc., the maximum particle length of the crushed product is in the range of 1 to 30 mm.
- the pulverization can be performed using a known pulverizer. For example, rotary katsuyuichi mill, roll crusher, hammer crusher, disk mill, pin mill, turbo mill, jet mill, etc. can be used.
- the proportion of the component A in the recycled resin composition (component C) is preferably 5 to 60% by weight in 100% by weight of the recycled resin composition. It is more preferably from 6 to 50% by weight, still more preferably from 7 to 40% by weight, still more preferably from 10 to 40% by weight, and particularly preferably from 10 to 35% by weight.
- the proportion of the component A is 5 to 60% by weight, it is possible to achieve both good recycling efficiency and mechanical properties and long-term properties.
- the aromatic polycarbonate resin (part B) of pergin in the regenerated resin composition (component C) is 5 to 90% by weight, preferably 10 to 85% by weight, particularly Preferably it is 20 to 85% by weight.
- crushed materials Components other than the resin composition originating from the surface treatment of the molded product such as packaging, conductive plating, metal deposition, etc. are removed so that the content is 1% by weight or less in the crushed product. It is preferable, especially when higher impact resistance is required.
- a method for removing such surface coating components such as a printed coating film and a paint
- a method of rolling between two rolls a method of contacting with heated / pressurized water, various solvents, an acid / alkali aqueous solution, etc.
- the method include a method of mechanically shaving the material, a method of irradiating an ultrasonic wave, and a method of blasting, and a combination of these methods.
- the crushed product of the component A may be substantially composed of only the aromatic polycarbonate resin, but the crushed product of the normal product is a product in which the aromatic polycarbonate resin contains other components.
- Other components are not particularly limited, for example, other thermoplastic resins, flame retardants, anti-dripping agents, reinforcing fillers, impact modifiers, lubricants, stabilizers, coloring agents, ultraviolet absorbers, antioxidants And release agents.
- a crushed molded article containing a flame retardant or another thermoplastic resin a crushed molded article containing these can be suitably used in that the present invention provides a good regenerated resin composition.
- the component A of the present invention contains a styrene resin (A-2-PS component) or an aromatic polyester resin (A-2-PE component) in addition to the aromatic polycarbonate resin (A-1 component).
- a styrene resin A-2-PS component
- an aromatic polyester resin A-2-PE component
- the content of the styrene resin (A-2-PS component) or the aromatic polyester resin (A-2-PE component) in the component A is 1 to 65% by weight, preferably 5 to 50% by weight. %, Particularly preferably from 10 to 40% by weight.
- a flame retardant (A-3 component) may be contained in addition to the aromatic polycarbonate resin (A-1 component) and the styrene-based resin (A-2-PS component) or the aromatic polyester resin (A-2-PE component).
- a flame retardant (A-3 component) may be contained.
- Flame retardant (A— Phosphoric acid esters (A-3-a component), organic siloxane compounds (A-3-b component) or alkali (earth) metal salts (A-3-c component) are the three components. Preferred for The proportions of these three types of flame retardants contained in the component A each have a preferable range.
- the content of the phosphoric acid ester (A-3-a component) in the A component is preferably in the range of 1 to 30% by weight, and particularly preferably in the range of 5 to 20% by weight.
- the flame retardant is an organic siloxane compound (A-3-b component)
- the content of the component A is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and 0.5 to 3 times. Amount% is particularly preferred.
- the flame retardant is an alkali (earth) metal salt (A-3-c component)
- the amount of the component A is preferably 0.0005 to 1% by weight, more preferably 0.001 to 0.2% by weight, 002-0.1% by weight is particularly preferred.
- composition of the component A include the following (1), (II) and (III). Particularly preferred compositions are the following (I) and (II).
- a crushed product of a molded article formed from the composition comprising the following (1) to (5).
- Aromatic polyphenol resin (A-1 component) 30 to 98% by weight, preferably 40 to 90% by weight
- Styrene resin (A-2 PS component) 1 to 65% by weight, preferably 5 to 50% by weight
- Impact modifier (A-4 component) 0 to 20% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight
- Reinforcing filler (A-5 component) 0-60% by weight, preferably 1-60% by weight, more preferably 2-50% by weight
- composition of component A (II) A crushed product of a molded article formed from the composition comprising the following (1) to (5).
- Aromatic polycarbonate resin (A-1 component) 30 to 98% by weight, preferably 40 to 90% by weight
- Aromatic polyester resin (A-2-PE component) 1 to 65% by weight, preferably 5 to 50% by weight
- Impact modifier (A-4 component) 0 to 20% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight
- Reinforcing filler (A-5 component) 0-60% by weight, preferably 1-60% by weight, more preferably 2-50% by weight
- a crushed molded article formed from the composition comprising the following (1) to (4).
- Aromatic polycarbonate resin (A-1 component) 50 to 98% by weight, preferably 55 to 98% by weight
- Impact modifier (A-4 component) 0 to 20% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight
- Reinforcing filler (A-5 component) 0-30% by weight, preferably 1-30% by weight, more preferably 2-25% by weight
- the component B of the present invention refers to a so-called virgin aromatic polycarbonate resin which is polymerized as a resin, granulated into powders and pellets, and not formed as a molded product. Therefore, it is clearly distinguished from the A component of the present invention which was once used in the market and collected as an article.
- the component A and the component B may be mixed in the above ratio, but it is also possible to further mix other additives other than the component B. It is.
- additives include, for example, other thermoplastic aspects, flame retardants, anti-dripping agents, reinforcing fillers, impact modifiers, lubricants, stabilizers, colorants, UV absorbers, antioxidants, mold release Agents, antibacterial agents, antifungal agents, antistatic agents and the like. These can be compounded in an iffi manner in accordance with the desired properties of the recycled resin composition.
- An object of the present invention is to provide a recycled resin composition that can be used for a purpose equivalent to that of a molded product before pulverization of the A component, using the A component satisfying specific conditions. Therefore, the composition of the recycled resin composition (component C) of the present invention is preferably close to the composition of component A. More preferably, the ratio of the aromatic polycarbonate resin, the styrene-based resin, the aromatic polyester resin, and the flame retardant in the C component, which are at least the main constituent components, to 0% of the ratio in the A component, respectively. It is preferably in the range of 7 to 1.5 times, more preferably in the range of 0.75 to 1.45 times, and more preferably in the range of 0.8 to 1.3 times. More preferred. It is preferable to add the above component B and an additive of pergin other than the component B so as to achieve such a composition ratio.
- the regenerated resin composition (C component) of the present invention is obtained by mixing the A component and the B component in the ratio described above, and finally (1), (II) or ( It has been found that it is appropriate to use the composition of III), and a molded article having good long-term physical stability and mechanical strength can be obtained.
- Particularly preferred regenerated resin compositions are the following (I) or (II).
- Aromatic polyphenol resin (C-1 component) 30 to 96% by weight, preferably Is 35-90% by weight, more preferably 45-90% by weight, even more preferably 55-90% by weight
- Styrene resin (C-2-PS component) 3 to 40% by weight, preferably 5 to 35% by weight, more preferably 5 to 30% by weight and
- the recycled resin composition (I) also contains an impact modifier (C-14 component) in an amount of 0.5. -20% by weight, preferably 1-15% by weight. Further, the recycled resin composition (I) may contain 1 to 60% by weight, preferably 2 to 50% by weight, particularly preferably 3 to 45% by weight of a reinforcing filler (C-5 component). .
- the flame retardant (C-3 component) in this recycled resin composition (I) is suitably a phosphate ester (C-3-a component), and its content is preferably 1 to 30% by weight. Advantageously, it is 2 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 5 to 15% by weight.
- Aromatic polycarbonate resin (C-1 component) 30 to 96% by weight, preferably 35 to 90% by weight, more preferably 45 to 90% by weight, and still more preferably 35 to 90% by weight
- aromatic polyester resin (C-1-PE component) 3 to 40% by weight, preferably 5 to 35% by weight, more preferably 5 to 30% by weight and
- the reclaimed resin composition (II) also contains an impact modifier (C-4 component) of 0.5. -20% by weight, preferably 1-15% by weight.
- the recycled resin composition (II) may contain 1 to 60% by weight, preferably 2 to 50% by weight, particularly preferably 3 to 45% by weight of a reinforcing filler (C-15 component).
- the flame retardant (C-13 component) in the recycled resin composition (II) is suitably a phosphate ester (C-3-a component), and its content is 1 to 30% by weight, Advantageously, it is preferably 2-20% by weight, more preferably 5-20% by weight, even more preferably 5-15% by weight.
- Aromatic polycarbonate resin (C-1 component) 50 to 98% by weight, preferably 55 to 98% by weight
- Impact modifier (C-4 component) 0-20% by weight, preferably 1-15% by weight
- the recycled resin composition (III) may further contain 1 to 30% by weight, preferably 2 to 25% by weight of a reinforcing filler (C-5 component).
- the flame retardant (C-3 component) in the recycled resin composition (III) is suitably ester phosphate (C-3-a component), and its content is 1 to 30% by weight.
- it is preferably 2-20% by weight, more preferably 5-20% by weight, even more preferably 5-15% by weight.
- the above-mentioned recycled resin compositions (1), (II) and (III) of the present invention are preferred compositions, and molded articles formed from these compositions have excellent physical properties. That is, the molded article formed from the above composition has a wet heat retention of 60% or more under suitable conditions and 70% or more under suitable conditions, and the flame retardancy test according to UL 94 standard satisfies V-0 under suitable conditions. . In addition, the molded product has an impact value retention of 60% or more, and 70% or more under suitable conditions.
- Aromatic polycarbonate resins (A-1 component, B component and C-1 component) are obtained, for example, by reacting a divalent phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. It is obtained by polymerizing a carbonate prepolymer by a solid-phase ester exchange method, or obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.
- divalent phenol used here include: Sorsinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis ⁇ (4-hydroxy-1,3,5-dimethyl) phenyl ⁇ methane, 1,1-bis (4-hydroxyphenyl) methane Enyl) ethane, 1,1-bis (4-hydroxyphenyl) 1-1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis ⁇ (4-hydroxy 1,3-methyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-3,5-dimethyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-1,3,5 —Jib mouth m) Phenyl ⁇ propane, 2,2-bis ⁇ (3-isopropyl-14-hydroxy) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-13-phenyl) phenyl ⁇ Propane, 2,
- Bisphenol A 2, 2-bis ⁇ (4-hydroxy-3-methyl) Phenyl ⁇ propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -13-methylbutane, 2,2-bis (4-hydroxyphenylyl) 1,3,3-Dimethylbutane, 2,2-bis (4-hydroxyphenyl) 1,4-methylpentane, 1,1-bis (4-hydroxyphenyl) 1,3,3,5-trimethylcyclohexane and 1,1-bis (4 -Hydroxyphenyl)
- a homopolymer or copolymer obtained from at least one kind of bisphenol selected from the group consisting of 1 m-diisopropylbenzene is preferable, and particularly, a homopolymer of bisphenol A and 1,1- Bis (4-hydroxyphenyl) -1,3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇ Pan or a, alpha
- carbonate precursor carbanol phenol, carbonate ester or octaform formate and the like are used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of divalent phenol.
- Aromatic polycarbonate is also intended to be a branched polyfunctional monoponate obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, but is also intended to be a polyester carbonate obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid. It may be a resin, or a mixture of two or more of the obtained aromatic polycarbonate resins.
- trifunctional or higher polyfunctional aromatic compounds examples include fluorodarucine, phloroglucide, and 4,6-dimethyl-1,2,4,6-tris (4-hydrokidiphenyl) heptene-1,2,2,4,6- Trimethylate 2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1, 1, 1—Tris (3,5-Dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-1-5-methylbenzyl) -4-methylphenol, 4- ⁇ 4 -— [1,1-bis (4- [Hydroxyphenyl) ethyl] benzene ⁇ -a, ⁇ -Dimethylpenzylphenol, etc., trisphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone,
- the proportion is preferably 0.001 to 1 mol%, preferably 0.05 to 0.5 mol%, based on the total amount of the aromatic polycarbonate resin. Particularly preferably, it is 0.01 to 0.3 mol%.
- a branched structure may be generated as a side reaction.
- the amount of such a branched structure is also 0.001-1% by mole, preferably 0.01% by mole of the total amount of the aromatic polycarbonate resin. It is preferably from 0.5 to 0.5 mol%, particularly preferably from 0.1 to 0.3 mol%. Note that such a ratio can be calculated by 1 H—N MR measurement.
- the reaction by the interfacial polycondensation method is usually a reaction between divalent phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent.
- an acid binder for example, an alkali metal hydroxide such as sodium hydroxide or hydroxylating hydroxide or an amine compound such as pyridine is used.
- an organic solvent for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
- tertiary amines such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds, etc.
- the reaction temperature is usually 0 to 40 ° C.
- the reaction time is preferably about 10 minutes to 5 hours
- the pH during the reaction is preferably maintained at 9 or more.
- a terminal stopper is usually used.
- Monofunctional phenols can be used as such a terminal stopper.
- Monofunctional phenols are generally used as a terminating agent for controlling the molecular weight.
- Such monofunctional phenols are generally phenol or lower alkyl-substituted phenols, Monofunctional phenols represented by the formula (1) can be shown.
- A is a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms or a phenyl-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3.
- monofunctional phenols include phenol, p-tert-butyl phenol, P-cumyl phenol and isooctyl phenol.
- phenols or benzoic acid chlorides having a long-chain alkyl group or an aliphatic polyester group as a substituent may be used. it can. Among them, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.
- X is one R—CO— ⁇ one or one R—O—CO—, where R is a single bond or carbon number:! -10, preferably 1-5 divalent fats Represents a group hydrocarbon group, and n represents an integer of 10 to 50.
- substituted phenols of the general formula (2) those wherein n is from 10 to 30, especially from 10 to 26 are preferred, and specific examples thereof are, for example, decylphenol, dodecylphenol, tetradecylphenol, hexene Examples include decylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontyl'phenol.
- a compound in which X is one R—CO—0— and R is a single bond is suitable, and n is 10 to 30, especially 10 to 2 6 are preferred.
- Specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and hydroxybenzoate. Acid triacontyl.
- the terminal stoppers may be used alone or in combination of two or more.
- the reaction by the melt transesterification method is usually a transesterification reaction between a divalent phenol and a carbonate ester, and the alcohol formed by mixing the divalent phenol and the carbonate ester while heating in the presence of an inert gas. Or fenault This is carried out by a method of distilling the oil.
- the reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the pressure of the reaction system is reduced to about 1.33 ⁇ 10 3 to 13.3 Pa to facilitate the distillation of alcohol or phenol produced.
- the reaction time is usually about 1 to 4 hours.
- carbonate ester examples include an ester such as an optionally substituted aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms.
- Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthylcapone, bis (diphenyl) carbonate, dimethylcarbonate, getylcarbonate, dibutylcarbonate and the like. Nilcaponate is preferred.
- a polymerization catalyst can be used to increase the polymerization rate.
- a polymerization catalyst include sodium metal, potassium hydroxide, sodium salts of divalent phenol, alkali metal compounds such as potassium salt, and the like.
- Alkaline earth metal compounds such as caffeium hydroxide, 7j ⁇ barium oxide, magnesium hydroxide, etc., nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, triethylamine, etc.
- Alkoxides of alkaline metals and alkaline earth metals, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds , Lead compounds, osmium compounds, antimony compounds Manganese compounds, may be used titanium compounds, typically esters Kahan response, such as zirconium compounds, the catalyst used in the transesterification reaction.
- the catalyst may be used alone or in combination of two or more.
- the amount of the polymerization catalyst, to divalent phenol 1 mole of the raw material preferably 1 X 1 0 _ 8 ⁇ 1 X 1 0- 3 equivalents, more preferably 1 X 1 0- 7 ⁇ 5 X 1 0 — Selected in a range of 4 equivalents.
- 2-chlorophenylphenylcarbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenylcarbonate are preferred, and 2-methoxycarbonylphenylphenylcarbonate is particularly preferred. used.
- a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction.
- the deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butylbenzenesulfonate, octyl benzenesulfonate, benzenesulfonic acid phenyl, p-toluene Sulfonates such as methyl toluenesulfonate, ethyl P-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; and trifluoromethanesulfonic acid and naphthalen
- the amount of such a catalyst is preferably used in a ratio of 0.5 to 50 mol per mol of the remaining catalyst, and a ratio of 0.01 to 500 ppm with respect to the polycarbonate resin after polymerization. It is more preferably used at a rate of 0.01 to 300 ppm, particularly preferably at a rate of 0.01 to L: 00 ppm.
- the molecular weight of the aromatic polycarbonate resin is not specified, in the case of measuring the aromatic polycarbonate used as the component B, if the molecular weight is less than 14,000, the impact resistance and the like decrease, and the molecular weight is reduced by 40,000. If it exceeds the above range, the moldability deteriorates, so that the viscosity average molecular weight is preferably from 14,000 to 40,000, and particularly preferably from 17,000 to 35,000. In addition, two or more aromatic polycarbonate resins having different molecular weights may be mixed.
- the viscosity average molecular weight referred to in the present invention is determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride in 201 ml of a specific viscosity (7? SP ). SP ) is calculated by the following equation to determine the viscosity average molecular weight M.
- thermoplastic resins include, but are not limited to, aromatic polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin; polystyrene, AS resin, ABS resin, ASA resin, and AES resin. And polyolefin resins such as polyamide resin, acrylic resin, polyethylene resin and polypropylene resin.
- engineering plastics such as polyphenyl ether and polyacetal, polyetheretherketone, polyetherimide, polyetheramide, polysulfone, polyethersulfone, polyphenylenesulfide and the like, so-called super engineering plastics, may also be used. .
- thermoplastic resins As these other thermoplastic resins, styrene-based resins (A-2-PS component or C-2-PS component) and aromatic polyester resins (A-2-PE component or C-12-PE component) are particularly preferable. It is.
- aromatic polyester resin polyethylene terephthalate resin or polybutylene terephthalate resin is preferable. Styrene resins are particularly preferred as other thermoplastic resins in the present invention, and specific compounds will be described below.
- the styrene resin refers to a homopolymer or copolymer of styrene derivatives such as styrene, ⁇ -methylstyrene, and ⁇ -methylstyrene. And a vinyl monomer such as acrylonitrile and methyl methacrylate.
- styrene resin A-2-PS component or C-2-PS component
- a vinyl monomer such as acrylonitrile and methyl methacrylate.
- it has a structure in which gen-based rubber such as polybutadiene, ethylene / propylene-based rubber, acrylic rubber, and polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated.
- styrene resin examples include, for example, polystyrene, styrene butadiene styrene copolymer (SBS), hydrogenated styrene butadiene styrene copolymer (hydrogenated SBS), hydrogenated styrene isoprene styrene copolymer.
- SBS styrene butadiene styrene copolymer
- hydrogenated SBS hydrogenated styrene butadiene styrene copolymer
- hydrogenated SBS hydrogenated styrene isoprene styrene copolymer
- Polymer (hydrogenated SIS), impact polystyrene (HIPS), acrylonitrile styrene copolymer (AS resin), acrylonitrile styrene butadiene styrene copolymer (ABS resin), methyl methacrylate butadiene styrene copolymer (MB S resin), Chilmetyl acrylate ⁇ acrylonitrile ⁇ butadiene ⁇ styrene copolymer (MA BS resin), acrylonitrile ⁇ acrylic rubber ⁇ styrene copolymer (AA S resin), acrylonitrile ⁇ ethylene propylene rubber 'styrene copolymer (AES resin) And a resin such as styrene / IPN type rubber copolymer, or a mixture thereof.
- HIPS impact polystyrene
- AS resin acrylonitrile styrene butadiene styrene cop
- the styrenic resin may have a high stereoregularity, such as syndiotactic polystyrene, by using a catalyst such as a meta-mouth catalyst at the time of its production.
- a catalyst such as a meta-mouth catalyst
- polymers and copolymers having a narrow molecular weight distribution, block copolymers, and polymers and copolymers having a high stereoregularity obtained by methods such as anion living polymerization and radical living polymerization may be used. You may. Also poly power
- a compound having a functional group such as maleic anhydride / N-substituted maleimide may be copolymerized with a strong styrene resin.
- AS resin acrylonitrile-styrene copolymer
- ABS resin acrylonitrile-butadiene-styrene copolymer
- the AS resin is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound.
- a vinyl cyanide compound acrylonitrile can be particularly preferably used.
- the aromatic vinyl compound include those described above, but styrene and ⁇ -methylstyrene are preferred.
- the ratio of each component in the AS resin when the whole is 100% by weight, the vinyl cyanide compound is 5 to 50% by weight, preferably 15 to 35% by weight, 95 to 50% by weight, preferably 85 to 65% by weight.
- these vinyl compounds may be copolymerized with other copolymerizable vinyl compounds described above. The content of these is preferably 15% by weight or less in the AS resin component.
- the initiator, chain transfer agent and the like used in the reaction various conventionally known ones can be used as necessary.
- Such AS resin was manufactured by any method of bulk polymerization, suspension polymerization, and emulsion polymerization. Although it may be one, it is preferably by bulk polymerization.
- the method of copolymerization may be either one-step copolymerization or multi-step copolymerization.
- the reduced viscosity of the AS resin is from 0.2 to 1.0 dlZg, preferably from 0.3 to 0.5 dlZg.
- the reduced viscosity was measured by precisely measuring 0.25 g of AS resin and dissolving it in 50 ml of dimethylformamide over 2 hours at 30 ° C. using an Ubbelohde viscometer. Use a viscometer with a solvent flow time of 20 to 100 seconds.
- the reduced viscosity is determined from the number of seconds flowing down of the solvent (t.) And the number of seconds flowing down of the solution (t) according to the following equation.
- ABS resin is a mixture of a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound onto a gen-based rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is.
- a rubber having a glass transition temperature of ⁇ 10 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and the proportion thereof is ABS resin. It is preferably from 5 to 80% by weight, more preferably from 8 to 50% by weight, particularly preferably from 10 to 30% by weight, based on 100% by weight of the components.
- the vinyl cyanide compound to be grafted to the gen-based rubber component acrylonitrile is particularly preferred.
- aromatic vinyl compound to be grafted to the gen-based rubber component the above-mentioned ones can be similarly used, but styrene and ⁇ -methylstyrene are particularly preferable.
- the proportion of the component grafted to the gen-based rubber component is preferably 95 to 20% by weight, particularly preferably 50 to 90% by weight, in 100% by weight of the ABS resin component.
- the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl aldehyde compound is 95 to 50% by weight based on 100% by weight of the total amount of the biel cyanide compound and the aromatic pinyl compound. .
- Methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc. can be mixed and used for some of the components grafted to the gen-based rubber component described above. Is preferably 15% by weight or less in the ABS resin component. Further, conventionally known various initiators, chain transfer agents, emulsifiers and the like can be used as necessary.
- the rubber particle diameter is preferably from 0.1 to 5.0 m, more preferably from 0.2 to 3.0 im, and particularly preferably from 0.3 to 1.5 m.
- the distribution of the rubber particle diameter either a single distribution or a distribution having two or more peaks can be used, and the rubber particles also form a single phase in the morphology. It may have a salami structure by containing an occluded phase around rubber particles.
- ABS resin contains a bi-cyanide compound and an aromatic vinyl compound which are not grafted to the gen-based rubber component. It may contain a polymer component.
- the reduced viscosity of the copolymer comprising the free vinyl cyanide compound and the aromatic vinyl compound is such that the reduced viscosity (at 30) determined by the method described above is 0.2 to 1.0 dl Zg, More preferably, it is 0.3 to 0.7 dl Zg.
- the ratio of the grafted vinyl cyanide compound and aromatic Bier compound is preferably 20 to 200%, more preferably 20 to 20%, expressed as a graft ratio (% by weight) with respect to the gen-based rubber component. ⁇ 70%.
- Such ABS resin may be one produced by any of bulk polymerization, suspension polymerization and emulsion polymerization, but is preferably one produced by bulk polymerization.
- the copolymerization method may be one-step copolymerization or multi-step copolymerization. Further, a blend of a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component with the ABS resin obtained by such a production method may be used.
- ABS resin When the ABS resin is compounded as a virgin resin in the regenerated resin composition, 100 to 30% by weight of the entire ABS resin contains 10 to 30% by weight of a gen-based rubber component, and Acrylonitrile is in the range of 15 to 35% by weight and styrene is in the range of 85 to 65% by weight in 100% by weight of the components other than the rubber-based rubber component. It is produced by bulk polymerization and has a reduced viscosity of 0.3. What is ⁇ 0.7 dl Zg can be preferably used.
- examples of the flame retardant (A-3 component or C-3 component) include ester phosphate, an alkali (earth) metal salt of an inorganic acid, an alkali (earth) metal salt of an organic acid, and an organic halogen compound. , Red phosphorus, organic siloxane compounds, inorganic phosphates, and hydrates of inorganic metal compounds. Of these, preferred are phosphate esters, alkali (earth) metal salts, or organosiloxane compounds. Examples of the phosphate ester include one or more phosphate esters represented by the following general formula (4).
- Y in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol ⁇ , dihydroxydiphenyl, dihydroxyxinaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) A) a divalent group derived from ketone or bis (4-hydroxyphenyl) sulfide; j, k, 1, and m are each independently 0 or 1, and n is an integer of 0 to 5; Yes, or in the case of a mixture of n different phosphate esters, the average value is 0 to 5, and I 1 , 2 , R and R 4 are each independently substituted or substituted with one or more halogen atoms. Not derived from phenol, cresol, xylenol, isopropylphenol, butylphenol or p-cumylphenol Is a monovalent group.
- Y in the above formula is preferably hydroquinone, resorcinol or Is a group derived from bisphenol A, j, k, 1, and m are each 1, n is an integer of 0 to 3, or in the case of a blend of n different phosphate esters, R 1, R 2 , R 3 , and R 4 are each independently a group derived from phenol, cresol, or xylenol with or without one or more halogen atoms. It is.
- Y is a group derived from resorcinol or bisphenol A
- j, k, 1, m are each 1
- n is 0 or 1
- RR 2 , R 3 , and R 4 is each independently a group derived from phenol or xylenol.
- monophosphate compounds include triphenyl phosphate
- phosphate ester oligomers include resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate).
- phosphate ester oligomers include resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate).
- Alkali metals in the alkali (earth) metal salts of inorganic acids as flame retardants include lithium, sodium, potassium and cesium, and alkali (earth) metals include calcium, magnesium and barium .
- examples of the inorganic acids H 3 A 1 F 6, H 3 BF 6, H 3 SbF 6, H 2 T i F 6, H 2 S i F 6, H 3 PO, H 2 Z rF 6, H 2 WF 6 or HBF 4 .
- Preferred inorganic alkali metal salts or inorganic earth metal salts include Na 3 A 1 F 6 and Ca 3 (Al F 6 ) 2 .
- Alkali metals in alkali (earth) metal salts of organic acids as flame retardants include lithium, sodium, potassium and cesium, and alkali (earth) metals include calcium, magnesium and palladium.
- organic acids include aliphatic sulfonic acids, aliphatic sulfate esters, aromatic sulfonic acids, aromatic sulfonamides, aromatic carboxylic acids, and aliphatic carboxylic acids. Specific examples include methylsulfonic acid and lauryl sulfate ester.
- Mono- or di-sulfates such as hexadecyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, ethylene glycol, propylene glycol, and butanediol; , Tri- or tetrasulfate, stearic acid monoglyceride monosulfate, 1,3-bis (2-ethylhexyl) glycerin ether monosulfate, trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoro Propanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesul Acid, dodecanesulfonic acid, benzenesulfonic acid
- Preferred organic alkali metal salts or organic alkaline earth metal salts include potassium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, diphenylsulfonate and the like.
- organic halogen compound as a flame retardant examples include tetrabromobisphenol A (TBA) monomer oligomer, decabromodiphenyl ether, octabromodiphenyl ether, tetrabromodiphenyl ether, Hexasub mouth Cyclododecan, Ethylene bistetrabromophthalimide, Tris (pentabromobenzyl) isocyanurate, Promoted polystyrene, TBA epoxy tree Fat, tetrabromophenol-terminated TBA epoxy resin, and the like.
- TSA tetrabromobisphenol A
- tetra-bromobisphenol A is a polyponate oligomer which has good flame retardancy and generates little harmful substances during combustion, and is compatible with aromatic poly-polycarbonate resin. Good flame retardancy without deteriorating mechanical properties such as impact resistance, and little decrease in long-term mechanical properties.
- a preferred organic octalogen compound When compounded as a product, it can be mentioned as a preferred organic octalogen compound.
- red phosphorus as a flame retardant examples include red phosphorus in which the surface of red phosphorus is microencapsulated with a thermosetting resin and / or an inorganic material in addition to general red phosphorus.
- a master pellet is preferably used to improve safety and workability.
- the average particle size of the red phosphorus is from l to 100 m, preferably from 1 to 40 m.
- microphosphorous red phosphorus-based flame retardants include NOVA-EXCEL 140, NO-BA-EXCEL F-5 (trade name, manufactured by Rin-I-Dagaku Kogyo Co., Ltd.), Hishigard TP-10 (Japan Chemical Industry Co., Ltd .: trade name), Hostafram RP 614 (Clariant, Japan Co., Ltd .: trade name), and the like.
- organosiloxane compound as a flame retardant examples include those having a basic structure represented by the following general formula (5).
- R 5 , R 6 , and R 7 each represent a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group having 1 to 12 carbon atoms, and a carbon group having 2 to 12 carbon atoms.
- Each respective substituents R 5 and R 6 are either the same or may be different dates.
- R 8 represents an alkyl group having 1 to 4 carbon atoms.
- alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an n-propyl group, an isopropyl group, various butyl groups, various hexyl groups, and a cyclohexyl group.
- alkenyl group examples include a vinyl group, an aryl group and a cyclohexenyl group.
- aryl group examples include a phenyl group, a naphthyl group, and a tolyl group.
- Specific examples of the group include a benzyl group, a j8-phenyl group, a 2-phenylpropyl group and the like.
- phenyl, vinyl, and methyl groups are particularly preferred because they exhibit more effective flame retardancy, and particularly preferably contain a phenyl group.
- a phenyl group is at least 15 mol%, preferably at least 20 mol%, more preferably 25 to 90 mol%, of the organic groups (R 5 , R 6 , R 7 and R 8 ) in the organosiloxane. It is particularly preferable to use those containing 25 to 70 mol%.
- phenolic hydroxyl group-containing monovalent organic groups examples include 2- (0-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 2- (m-hydroxyphenyl) ethyl group, 1- (o-hydroxyphenyl) ethyl group, 1- (p-hydroxyphenyl) ethyl group, 1- (m-hydroxyphenyl) ethyl group, 3- (o-hydroxyphenyl) propyl group, 3 — (P-hydroxyphenyl) propyl, 3- (m-hydroxyphenyl) propyl, 2- (o-hydroxyphenyl) propyl, 2- (p-hydroxyphenyl) propyl and 2- (M-hydroxyphenyl) propyl group and the like.
- c and d are not simultaneously 0.
- 0.1.l ⁇ e ⁇ 0.5 for (a + b + c + d) 1.
- the organic siloxane compound has a kinematic viscosity at 25 ° C of 1 to 10, It is preferably OOO c St (centistokes), more preferably 5 to 100 cSt, still more preferably 5 to 300 cSt, and particularly preferably 5 to 100 cS. It becomes t.
- OOO c St centistokes
- an inorganic phosphate such as ammonium polyphosphate can be used.
- aluminum hydroxide, magnesium hydroxide, dolomite, octasite talcite, calcium hydroxide, water Inorganic metal hydroxides such as barium oxide, basic magnesium carbonate, zirconium hydroxide and hydrates of tin oxide can be used.
- the impact modifier (A-4 component or C-4 component) in the present invention has a glass transition temperature of 10 ° C or lower, preferably -10 ° C or lower, more preferably -30 ° C or lower. It is a rubber polymer or a rubber polymer component-containing copolymer in which a component copolymerizable with the rubber polymer is copolymerized and contains 40% by weight or more of the rubber polymer component.
- the rubber polymer include polybutadiene, polyisoprene, and gen-based copolymers (for example, random and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymer, and acryl / butadiene rubber (acrylic).
- Preferred examples of the monomer component copolymerized with the rubber component include an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylate compound, and a (meth) acrylic oxide compound.
- Other monomer components include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methyl maleimide, N-phenyl maleimide, acrylic acid, methacrylic acid, and maleic acid. And 0 !, j8-unsaturated carboxylic acids such as maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof.
- SB styrene-butadiene polymer
- ABS acrylonitrile-butadiene-styrene
- MBS methyl ⁇ / methacrylate-butanediene-styrene
- MAB S methyl Methacrylate-acrylonitrile-butadiene-styrene
- MB methyl methacrylate-butene
- ASA acrylonitrile-styrene-acrylic rubber
- AES acrylonitrile-ethylene propylene rubber-styrene
- MA meth> remethacrylate-acrylic rubber
- MAS methyl methacrylate-acrylic rubber-styrene
- methyl methacrylate-acrylic-butene gen-rubber copolymer methyl methacrylate-acrylic-butadienego Moustylene copolymer, methyl methacrylate
- methyl methacrylate And the
- thermoplastic elastomers such as styrene thermoplastic elastomers, olefin thermoplastic elastomers, polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, and polyamide thermoplastic elastomers.
- the resin composition of the present invention may contain an anti-dripping agent for improving the flame retardancy, and the anti-dripping agent may be a fluorinated polyolefin having a fibril-forming ability.
- the anti-dripping agent may be a fluorinated polyolefin having a fibril-forming ability.
- examples of such polymers include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (eg, tetrafluoroethylene z-hexafluoropropylene copolymer, etc.).
- partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, and polyphenol resins produced from fluorinated diphenols. It is Lochlen.
- Polytetrafluoroethylene having fibril-forming ability is classified into type 3 in the ASTM standard. Further, the polytetrafluoroethylene having the ability to form fibrils preferably has a primary particle diameter in the range of 0.05 to 10 jm, and a secondary particle diameter of 50 to 700 im. Are preferred. Such polytetrafluoroethylene has the ability to prevent dripping at the time of a test specimen burning test in the UL standard vertical combustion test. Polytetrafluoroethylene having such a fibril-forming ability is, for example, Mitsui DuPont Fluorochemical ( Co., Ltd. as Teflon 6J or Daikin Industries, Ltd. as Polyflon.
- PTFE polytetrafluoroethylene
- a virgin product When such polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is used as a virgin product, it can be used in the form of an aqueous dispersion in addition to the usual solid form.
- PPTFE having such fibril-forming ability can improve the dispersibility in a resin, and in order to obtain better flame retardancy and mechanical properties, it is also possible to use a PPTFE mixture of the following form.
- a coagulated mixture of a PPTFE dispersion and a dispersion of a Piel polymer can be mentioned.
- a PTFE dispersion having an average particle size of 0.05 to 5 m and a dispersion of a vinyl polymer are mixed as disclosed in Japanese Patent Application Laid-Open No.
- a method for obtaining a PTFE mixture by coagulating PTFE particles without purification and drying the coagulated product is described, and such a mixture can be used.
- a mixture obtained by mixing a PTFE dispersion and dried polymer particles can be mentioned.
- polymer particles various types can be used, but more preferred. In other words, it uses a poly-carbon resin resin powder or an ABS resin powder.
- JP-A-4-272957 describes a mixture of a PTFE dispersion and an ABS resin powder, and such a method can be used.
- a PTFE mixture obtained by simultaneously removing the respective media from the mixture of the PTFE dispersion and the thermoplastic resin solution can be mentioned.
- the media was removed by using a spray dryer.
- Mixtures can be mentioned, and such mixtures are described in JP-A-08-188653.
- a PTFE mixture obtained by polymerizing another vinyl monomer in a PTFE dispersion is disclosed in JP-A-9-95583 in PTFE latex.
- a method for obtaining a PTFE mixture by supplying styrene and acrylonitrile is specifically described, and such a mixture can be used.
- a method of mixing a PTFE dispersion and a polymer-particle dispersion and then polymerizing a butyl monomer in the mixed dispersion can be cited. It can be mentioned as a preferable PTFE mixture in terms of achieving both fine dispersion. The details of such a mixture are described in JP-A-11-29679, that is, in a dispersion obtained by mixing a PTFE dispersion having a particle size of 0.05 to 1.
- a PTFE mixture pulverized by emulsion polymerization of a monomer having an unsaturated bond and then coagulation or spray drying can be mentioned as a preferable example.
- the polymer particles include block copolymers composed of polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, ASA resin, polyalkyl (meth) acrylate, styrene and butadiene, and the like.
- Hydrogenated copolymer block copolymer composed of styrene and isoprene, and its hydrogenated copolymer, acrylonitrile-butadiene copolymer, random copolymer of ethylene-propylene and block copolymer, ethylene- Butene random copolymer and block copolymer, ethylene and ⁇ -olefin copolymer, ethylene-unsaturated copolymer such as ethylene-butyl acrylate copolymer with ruponic acid ester, acrylate monobutadiene Copolymers, composite rubbers containing polyorganosiloxanes and polyalkyl (meth) acrylates, and copolymers obtained by grafting vinyl monomers such as styrene, acrylonitrile, and polyalkyl methacrylate onto the composite rubbers, and the like can be given.
- polyalkyl (meth) acrylate, polystyrene, AS resin
- monomers having an ethylenically unsaturated bond include styrene such as styrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene and ⁇ -methylstyrene.
- Monomers methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 1-ethylhexyl methacrylate, Acrylic ester monomers such as dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; bier methyl ether, vinyl Vinyl ether monomer such as ethyl ether; vinyl acetate Vinyl carboxylate monomers of vinyl butyrate, ethylene, Orefin monomers such as propylene Ren, isobutylene-butadiene, may be selected isoprene, from such diene-based monomer of dimethyl butadiene. These monomers can be used alone or in combination of two or more.
- the compounding amount is preferably 0.05 to 1% by weight based on 100% by weight of the recycled resin composition of the present invention. ⁇ In ingredients Even when the anti-dripping agent component is contained, the intended prevention of dripping tends to be insufficient at 0.05% by weight or less, and the upper limit of 1% by weight is sufficient for this purpose. That's why.
- Reinforcing fillers include talc, mai power, cle — wollastonite, montmonillonite, smectite, kaolin, calcium carbonate, glass fiber, glass beads, and glass Balloon, Mild fiber, Glass flake, Carbon fiber, Carbon flake, Carbon beads, Carbon milled fiber, Metal flake, Metal fiber, Metal coated glass fiber, Metal coated carbon fiber, Metal coated glass flake, Silica, Ceramic particles, Ceramic Fibers, ceramic particles, aramide particles, aramide conceals, polyarylate fibers, graphite, conductive carbon black, carbon black, potassium titanate whiskers, aluminum borate whiskers, basic magnesium sulfate, etc. Various ui Car, and the like. These reinforcing fillers may be used alone or in combination of two or more.
- talc or wollastonite which is a highly safe fine filler, is hardly destroyed in the kneading step for obtaining the crushed and / or regenerated resin composition and that the talc is particularly preferable. is there.
- talc is preferably used, and a higher purity product is more preferably used.
- the resin composition of the present invention may further contain various stabilizers. Particularly, when various kinds of powder products are mixed to produce a shelf composition, various kinds of heat stabilizers and oxidizing agents are used. It is preferable to further add an inhibitor.
- Examples of such a heat stabilizer include a phosphorus-based heat stabilizer.
- a phosphorus-based heat stabilizer any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.
- phosphite-based stabilizer examples include, for example, those represented by the general formula (6)
- R 8 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkali group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, (The alkyl group has 1 to 30 carbon atoms) or a substituent of a hydroxy substituent.
- the three R 8 s can be the same or different from each other, and must be derived from divalent phenols.
- the cyclic structure can also be selected by the formula.
- R 9 and R 1Q is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, Ariru group or an alkyl ⁇ aryl group having 6 to 20 carbon atoms, indicates Ararukiru group having 7 to 30 carbon atoms, R 9 and R 1Q is not a hydrogen atom at the same time, and may be any of the same or different from each other.
- R 12 is each hydrogen, an alkyl group having 1 to 20 carbon atoms, Ariru group or an alkyl ⁇ aryl group of carbon number 6-20, Ararukiru group of 7 to 30 carbon atoms, cycloalkyl of carbon number 4-20 Alkyl group, 2- (4-methoxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms, which may be the same or different from each other, wherein cycloalkyl group and aryl group are substituted with alkyl group. And a compound substituted with an alkyl group can be selected.).
- R 13 and R 14 are an alkyl group having 12 to 15 carbon atoms.
- R 13 and R 14 may be the same or different from each other.
- Examples of the phosphonite-based stabilizer include a phosphonite compound represented by the following general formula (10) and a phosphonite compound represented by the following general formula (11).
- Ar 1 and Ar 2 represent an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms; Ar 1 may be the same as or different from each other. Or, two Ar 2 may be the same or different from each other. ]
- more preferred phosphorus-based stabilizers include a phosphite compound represented by the above general formula (7) and a phosphonite represented by the above general formula (10) and the above general formula (11).
- Compounds can be listed, and these can be used alone or in combination of two or more. More preferably, the phosphite compound represented by the above general formula (7) is used in 100% by weight of the E component. At least 5% by weight.
- Preferred specific examples of the phosphite compound corresponding to the general formula (6) include diphenylisooctylphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, diphenyl Rumono (tridecyl) phosphite, phenyldiisodecylphosphite and phenyldi (Tridecyl) phosphite.
- More preferred specific examples corresponding to the above general formula (7) include trifenyl phosphite, tris (dimethylenephenyl) phosphite, tris (getylphenyl) phosphite, and tris (di-iso-propylphenyl) phosphite.
- the above phosphite compounds can be used alone or in combination of two or more.
- phosphite compound corresponding to the above general formula (8) include distearyl pentyl erythryl] rudiphosphite, bis (2,4-di-tert-butylphenyl) penyl erythritol diphosphite, bis (2, 6-Gy tert-butyl-4-methylphenyl) pentaerythryl 1 ⁇ -yldiphosphite, phenylbisphenol A pentyl erythritol monodiphosphite, dicyclohexylpentaerythritol diphosphite, and the like, preferably distearylpentaerythritol Diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol dip
- phosphite compound corresponding to the above general formula (9) include 4,4′-isopropylidenediphenol ditridecyl phosphite.
- Preferred specific examples of the phosphonite compound corresponding to the above general formula (10) include tetrakis (2,4-di-iso-propylphenyl) -4,4, -biphenylenediphosphonite, tetrakis ( 2,4-di-n-butylphenyl) 1,4,4-biphenylenediphosphonite, tetrakis (2,4-di-tert-) Butylphenyl) 1,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) 1,4,3,1-biphenylenediphosphonite, tetrakis (2,4-di-tert-) Butylphenyl) 1,3, -biphenylene diphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2
- the tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenyl Di-diphosphonite (X 1 component), tetrakis (2,4-di-tert-butylphenyl) —4,3'-biphenylenediphosphonite (x2 component) and tetrakis (2,4-di-tert-butylphenyl) ) 3,3, -Biphenylenediphosphonite (x3 component) can be used alone or in combination of two or more, but preferably a mixture of three.
- the mixing ratio of the xl component, the x2 component and the X3 component is preferably in the range of 100: 37 to 64: 4 to 14, and 100: 40 to 60: 5 to 11 by weight. Is more preferable.
- Preferred specific examples of the phosphonite compound corresponding to the above general formula (11) include bis (2,4-di-iso-propylphenyl) -14-phenyl-phenylphosphonite, bis (2,4-diphenyl) n-Butylphenyl) 1-3-phenyl-1-phenylphosphonite, bis (2,4-di-tert-butylphenyl) —4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) 13-phenyl -Phenylphosphonite bis (2,6-di-iso-propylphenyl 1) 4-phenyl-1-phenylphosphonite, bis (2,6-di-n-butylphenyl) 1-3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) 14- Phenyl-phenylphosphonite, bis (2,6-di-tert-butylphen
- Bis (2,4-di-tert-butylphenyl) -phenylphenylphosphonite is more preferred.
- This bis (2,4-di-tert-butylphenyl) -monophenylphenylphosphonite is preferably a mixture of two or more kinds.
- One or two kinds of monophenyl phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-1-phenylphosphonite can be used in combination, but preferably two kinds are used. It is a mixture.
- phosphate-based stabilizers include tributyl phosphate, trimethyl phosphate, trichloride rephosphate, triphenyl ⁇ / phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate. , Tributyl toxyl phosphate, dibutyl phosphate, octyl phosphate, diisopropyl phosphate and the like, and preferably trimethyl phosphate.
- the phosphorus-based heat stabilizers may be used alone or in combination of two or more.
- the phosphorus-based heat stabilizer is contained in the regenerated resin composition of the present invention in an amount of 0.001 to 0.5% by weight, more preferably 0.05 to 0.3% by weight, based on 100% by weight. It is preferable to mix them.
- antioxidants may be blended as a virgin product to obtain a recycled resin composition having good mechanical properties and the like.
- antioxidants include, for example, vitamin E, n-octadecyl / 3- (4'-hydroxy-13,5, di-tert-butylfel) propionate, 21-tert-butyl-6- (3, -tert-butyl) One 5 '—Methyl-2, One 4-hydroxyphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-1-hydroxybenzyl Phosphonate getyl ester, 2,2, -methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2, 6-di-tert-butylphenol, 2,2'-methylenebis (4-methyl-6-cycl
- UV absorbers can be appropriately compounded as virgin products.
- UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-14-methoxybenzophenone, 2-hydroxy-14-n-octoxybenzophenone, and 2-hydroxy-4-phenone.
- n-Dodecyloxybenzophenone 2-hydroxy-4-benzyloxybenzophenone, 2,2,1-dihydroxy-14-methoxybenzophenone, 2-hydroxy-4-methoxy-1'-caproloxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2,1-dihydroxy-4,4,1-dimethoxybenzophenone, 2,2,4,4,1-tetrahydroxybenzophenone , 2,2, dihydroxy-4,4'dimethoxy-5-sodiumsulfoxybenzophenone and bis (5-benzoyl-4-hydroxy-12-methoxyphenyl) Benzophenone ultraviolet absorbers represented by methane and the like can be mentioned.
- Examples of the ultraviolet absorber include 2- (2,1-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5, -tert-butylphenyl) benzotriazole, and 2- (2, -hydroxy).
- release agent examples include an olefin wax, a silicone oil, an organopolysiloxane, a higher fatty acid ester of a monohydric or polyhydric alcohol, a paraffin box, and a honey.
- the recycled resin composition of the present invention can be used for mixing various virgin products such as crushed molded products and aromatic polycarbonate resins with a mixer such as a tumbler, a V-type blender, a Nowaichi mixer, a Henschel mixer, and a bread palli mixer. It can be produced by blending with a mixer, melt-kneading with a heating kneader such as a kneading nozzle or an extruder. Also, a method in which the crushed molded product is melt-kneaded in advance and granulated, and then blended or melt-kneaded with various virgin products can be applied.
- a mixer such as a tumbler, a V-type blender, a Nowaichi mixer, a Henschel mixer, and a bread palli mixer. It can be produced by blending with a mixer, melt-kneading with a heating kneader such as a kneading nozzle or
- the heating temperature for melting and kneading is usually 220 to 340. Is selected in the range.
- the reclaimed resin composition thus obtained has mechanical strength by applying injection molding, injection compression molding, extrusion molding, compression molding, hollow molding, calendar molding, professional molding, vacuum molding, rotary molding, etc. It can be used for a wide range of applications, such as electrical, electronic, and OA equipment, where recycled products that require mechanical properties are preferably used, and achieves effective recycling.
- Moist heat retention (%) (viscosity average molecular weight after wet heat treatment Z viscosity average molecular weight before wet heat treatment) X 100
- Impact value retention (%) (Long-term accelerated impact value Z Initial impact value) X 100
- composition analysis was performed on the crushed molded product containing aromatic polycarbonate resin recovered from the market by the following method.
- Tables 8 and 9 show the results of the following composition analysis.
- the main resin components were analyzed by the FT-IR method and the DSC method.
- Hydazine immersion treatment of the crushed molded product at 130 for 2 hours mainly decomposes the poly-polycarbonate resin, other components such as ABS, inorganic components such as pigments, and anti-drip agents such as PTFE And the total amount was calculated.
- the amount was calculated by the iodine monochloride method.
- the hydrazine decomposition residue in the above (ii) was further subjected to pyrolysis gas mouth chromatography at 590 ° C and mass spectrometry to identify monomer components derived from ABS resin, MBS resin and the like.
- the approximate content of the crushed molded product was determined by the ion chromatography method, assuming that all was PTFE as an anti-drip agent (The PTFE content was determined by DSC measurement of the hydrazine decomposition residue. confirmed).
- the molded product was checked for the presence of bromine compounds by the pile-staine method and X-ray fluorescence measurement.
- the amount of bromine was determined for the molded article by combustion ion chromatography.
- the amount of the bromine compound was determined from the bromine content of the corresponding bromine compound.
- a crushed product model, polycarbonate resin, styrene resin, flame retardant, impact modifier, and anti-dripping agent with the composition shown in Table 1 are mixed, and a vented twin-screw extruder with a diameter of 3 ⁇ (manufactured by Nippon Steel Works; TEX30XSST) And melt-extruded at a cylinder temperature of 260 to form pellets.
- the obtained pellets are dried at 100 ° C for 5 hours using a hot air circulation type dryer, and the temperature of the cylinder is 260 ° C and the mold temperature is 60 ° C by an injection molding machine (Sumitomo Heavy Industries, Ltd .; SGI50U).
- a test piece for evaluation was obtained. Table 1 shows the evaluation results.
- a crushed material model, a polycarbonate resin, a polyester resin, a flame retardant, an impact modifier, an anti-dripping agent and other components are mixed with the composition shown in Table 2, and a vented twin screw extruder with a diameter of 30 ⁇ (Nippon Steel (30XSST) and melt extruded at a cylinder temperature of 280 ° C to pelletize.
- the obtained pellet was dried at 105 ° C for 5 hours with a hot air circulating drier, and evaluated by an injection molding machine (manufactured by Sumitomo Heavy Industries, SG1 50U) at a cylinder temperature of 270 and a mold temperature of 70 ° C. Get the test piece Was.
- Table 2 shows the evaluation results. Table 2
- the composition shown in Table 3 is a regenerated product of a crushed material model or a crushed material model, poly-force—Pontate resin, styrene resin, flame retardant, impact modifier, reinforcing agent, and anti-drip agent It was charged into a vented twin-screw extruder (Nippon Steel Works; ⁇ 30XSS ⁇ ) and melt extruded at a cylinder temperature of 260 to form pellets. The obtained pellets were dried at 100 ° C for 5 hours using a hot air circulation type dryer, and the cylinder temperature was 260 and the mold temperature was 60 ° C using an injection molding machine (Sumitomo Heavy Industries, SG 150 U). A test piece for evaluation was obtained. Table 3 shows the evaluation results. Table 3
- the crushed product and polycarbonate resin were mixed with the composition shown in Table 4, and the mixture was charged into a 30 mmd) bent twin-screw extruder (TEX30XSST, manufactured by Nippon Steel Works), melt-extruded at a cylinder temperature of 290 ° C, and pelletized. .
- the obtained pellets are dried at 120 ° C for 5 hours using a hot air circulating dryer, and evaluated with an injection molding machine (Sumitomo Heavy Industries, SG150U) at a cylinder temperature of 290 ° C and a mold temperature of 70 ° C. A test piece was obtained. Table 4 shows the evaluation results.
- the obtained pellets are dried at 100 ° C for 5 hours using a hot air circulation type dryer, and the cylinder temperature is 25'0 'and the mold temperature is 60 ° C using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .; SG150U). A test piece for evaluation was obtained. The evaluation results are shown in Tables 5 and 6.
- the extruder is used to obtain the crushed molded product, aromatic polycarbonate resin, styrene-based resin pellet, impact modifier, flame retardant, reinforcing material, dripping inhibitor, and coloring agent.
- pellets were obtained by a strand cutter to obtain pellets.
- the obtained pellets were dried at 100 ° C for 5 hours using a hot air drier, and then subjected to a specified temperature at a cylinder temperature of 250 ° C and a mold temperature of 60 using an injection molding machine (Sumitomo Heavy Industries, SG-150U). A test piece for evaluation was obtained.
- Table 7 shows the composition and evaluation results of the materials supplied to the extruder, and Table 9 shows the composition analysis results of the crushed molded product.
- the kneading conditions for the extruder were as follows.
- the extruder used was a twin screw extruder with a diameter of 3 ⁇ ⁇ ⁇ ⁇ with a vent (Nippon Steel Works; ⁇ 30XSST).
- a cassette wing feeder (CWF-1) (Kubota Tekko; CE-II-10S01), which is a raw material supply device with a two-screw screw, was installed above the first supply port.
- a side feeder with a twin screw is connected to the second feed port in the middle of the extruder, and a cassette weighing feeder (CWF-2, CWF-2), which is a material feeder with a twin screw, is connected above the side feeder. -3) were installed.
- the crushed material, polycarbonate resin, polyethylene terephthalate resin pellets (hot-air dried at 120 for 5 hours), impact modifier, flame retardant, and anti-drip agent Extrusion was performed under the same conditions as in Example 18 except that the section from the first supply port to the side feeder was set to 260, and the section after that was set to 245, to obtain pellets.
- the obtained pellets are dried at 120 ° C for 5 hours with a hot air circulating drier, and then heated by an injection molding machine (Sumitomo Heavy Industries, SG-150U) at a cylinder temperature of 260 ° C and a mold temperature of 60 ° C. Evaluation A test piece was obtained.
- Table 7 shows the composition and evaluation results of the materials supplied to the extruder, and Table 9 shows the composition analysis results of the crushed molded product. Table 7
- MS-1 68.7% by weight of a polycarbonate resin shown below as PC-2, and a phosphate ester manufactured by Daihachi Chemical Industry; CR-733S (phosphate ester Rigoma 1)
- PC-2 polycarbonate resin
- ST-1 phosphate ester manufactured by Daihachi Chemical Industry
- MD-1 5% by weight of rubber elastic body shown as MD-1
- anti-drip agent shown as PTFE 0.3 % By weight and charged into a vented twin-screw extruder with a diameter of 3 3 ⁇ (manufactured by Nippon Steel Works; ⁇ 30XSST), and pelletized by melt extrusion at a cylinder temperature of 260 ° C.
- the obtained pellets were dried at 100 ° C for 5 hours using a hot air circulating drier.
- the conditions were as follows: cylinder temperature 260 ° C, mold temperature 60 using an injection molding machine (Sumitomo Heavy Industries, SG150U).
- a molded product for evaluation having a side of 150 mm and a thickness of 3 mm was obtained.
- the molded product was left for 1000 hours in a constant temperature and humidity tester (Tapa Ispec; Platinous F) under the conditions of 65% and 85% RH to obtain an accelerated deteriorated molded product in a moist heat environment. .
- MS-1 had a viscosity average molecular weight of 21,500 and a wet heat retention of 55%.
- MS-2 In MS-1, instead of 68.7% by weight of polycarbonate resin shown as PC-2, 66.7% by weight of polycarbonate resin shown below as PC-1 and 2% by weight of TD were used. Other than the above, molding, wet heat treatment, and crushing were performed in the same manner as MS-1, to obtain a model of crushed molded product (MS-2). MS-2 had a viscosity average molecular weight of 21,800 and a wet heat retention of 86%.
- MS-3 95.3% by weight of polycarbonate resin shown below as PC-2, 4% by weight of silicon-based flame retardant (manufactured by Toshiba Silicone; XC99-B5664), N- (p-tolylsulfonyl) -p —After uniformly mixing 0.4% by weight of the potassium salt of toluenesulfoimide and 0.3% by weight of PTFE (anti-drip agent), the mixture was passed through a vented twin-screw extruder with a diameter of 30 ⁇ (manufactured by Nippon Steel Works; ⁇ 30XSST). It was charged and melt-extruded at a cylinder temperature of 290 ° C to pelletize.
- PC-2 polycarbonate resin shown below as PC-2, 4% by weight of silicon-based flame retardant (manufactured by Toshiba Silicone; XC99-B5664), N- (p-tolylsulfonyl) -p —After uniformly mixing 0.4% by weight of
- the obtained pellets are dried at 120 for 5 hours using a hot air circulating drier, and the cylinder temperature is 290 ° C and the mold temperature is 80 ° C using an injection molding machine (manufactured by Sumitomo Heavy Industries, SG 150 U).
- a molded product for evaluation having a side length of 15 Omm and a thickness of 3 mm was obtained.
- the molded product is kept at a constant temperature.
- the product was left standing for 1000 hours in a constant humidity tester (Tabayespec; Platinous F) under the conditions of 65 ° C and 85% RH to obtain an accelerated deteriorated molded product in a moist heat environment.
- the treated molded product is crushed with a mill (SB-210 manufactured by Horai Tekkosho Co., Ltd.) at a processing capacity of 70 kg / h, uniformly blended with a V-type blender, and a model of crushed molded product (MS — 3) MS-3 had a viscosity average molecular weight of 21,800 and a wet heat retention of 58%.
- MS-4 Code shown below PC-1 (Polycarbonate resin) 97.64% by weight, Silicon flame retardant (Shin-Etsu Chemical; X-40-9243) 2% by weight, Alkyri metal salt flame retardant ( Made by Dainippon Inki Danigaku Kogyo; Megafac F-l 14P) 0.0 1% by weight, PTFE (Drip inhibitor) 0.3% by weight, S-1 (Phosphite antioxidant) 0.05% by weight % Was molded, wet-heat treated and crushed in the same manner as in 3-3 to obtain a model of crushed molded product (MS-4). MS-4 had a viscosity average molecular weight of 19,100 and a wet heat retention of 88%.
- MS-5 Code shown below PC-2 (polycarbonate resin) 62.6% by weight, PET (polyethylene terephthalate resin) 16.7% by weight, PBT (polyethylene terephthalate resin) 1% by weight, SIS (Styrene-based elastomer) 4.2% by weight, COMP (polyester-styrene-based elastomer-copolymer-containing additive) 5.8% by weight, FR-4 (flame retardant) 9.2% by weight, PTFE (anti-drip agent) ) 0.4% by weight and 0.1% by weight of S-1 (Song's fixed agent) were uniformly mixed, and then charged into a vented twin-screw extruder with a diameter of 30mm ⁇ (manufactured by Nippon Steel Works; TEX30XSST).
- the mixture was melt extruded at a cylinder temperature of 290 ° C. and pelletized.
- the obtained pellets were dried in a hot air circulating dryer at 105 for 5 hours, and the cylinder temperature was 270 ° C and the mold temperature was 70 ° C using an injection molding machine (Sumitomo Heavy Industries, SG 150U).
- a molded product for evaluation having a side of 150 mm and a thickness of 3 mm was obtained. After that, the molded product is left for 1000 hours at 65 ° C and 85% RH in a constant temperature and humidity tester (Tapaiespec; Platinous F) to obtain an accelerated deteriorated molded product in a moist heat environment.
- Tapaiespec constant temperature and humidity tester
- the treated product is crushed with a grinding machine (TORAI KOKOKU; SB-210) at a processing capacity of 70 kg / h, and uniformly blended with a V-type blender to obtain a molded product.
- Dell (MS-5) was obtained.
- MS-5 had a viscosity average molecular weight of 14,300 and a wet heat retention of 53%.
- MS-6 In MS-5, use PC-1 instead of PC-2, and replace FR-4 (flame retardant) 9.2% by weight with FR-3 (flame retardant) 8.4 weight% Except for using 0.8% by weight of TD and 0.8% by weight, molding, wet heat treatment and crushing were carried out in the same manner as MS-5 to obtain a model of a crushed molded product (MS-6). MS-6 had a viscosity average molecular weight of 18,400 and a wet heat retention of 84%.
- MS-1-1 MS-1, polycarbonate resin, styrene resin, flame retardant, impact modifier at the ratios shown in Table 2
- the mixture was added to a vent-type twin-screw extruder having a diameter of 3 ⁇ ⁇ (manufactured by Nippon Steel Works; ⁇ ⁇ 30XSST) and melt-extruded at a cylinder temperature of 260 ° C to be pelletized.
- the obtained pellets are dried at 100 ° C for 5 hours using a hot air circulating drier, and the cylinder temperature is 260 ° C and the mold temperature is 60 by using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .; SGI 50U).
- an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd .; SGI 50U.
- a molded product for evaluation having a side of 150 mm and a thickness of 3 mm was obtained.
- the molded product is left for 1000 hours under the condition of 65% and 85% RH in a constant temperature and humidity tester (Platinus F manufactured by Tapaye Spec Co., Ltd.) to obtain an accelerated deteriorated molded product in a moist heat environment.
- a constant temperature and humidity tester Platinum F manufactured by Tapaye Spec Co., Ltd.
- MS-1-1 had a viscosity average molecular weight of 21,200 and a wet heat retention of 51%.
- MS—1-2 Same as MS—1-1 except that the shredded material was changed to MS_1 and replaced with MS—1-1. A crushed product (MS-1-2) was obtained. MS-112 had a viscosity average molecular weight of 21,000 and a wet heat retention of 50%.
- MS—1—3 Same as MS—1-1 except that the crushed material was changed to MS—1 instead of MS—1, molding, wet heat treatment, and crushing, and the third regeneration crushing of the crushed product model Product (MS-1-3) was obtained.
- MS-1-3 has a viscosity average molecular weight of 20,800, And wet heat retention were 48%.
- MS-2-1 MS-2, poly-carbonate resin, styrene-based resin, flame retardant, impact modifier, reinforced filler, anti-drip agent are mixed at the ratio shown in Table 2, and the diameter is 30 ⁇
- a vented twin-screw extruder Nippon Steel Works Ltd .; # 30XSST
- melt extruded at a cylinder temperature of 260 to pelletize The resulting pellets are dried at 100 ° C for 5 hours with a hot air circulating dryer, and the cylinder temperature is 260 ° C and the mold temperature is 60 ° C using an injection molding machine (Sumitomo Heavy Industries, SG1 50U).
- a molded product for evaluation having a side of 150 mm and a thickness of 3 mm was obtained.
- the molded product is left for 1,000 hours at 65 ° C and 85% RH in a constant temperature and humidity tester (Tapaiespec; Platinous F), and the accelerated deteriorated molded product in a moist heat environment is obtained. Obtained.
- the processed molded product is broken by a mill (SB-210 manufactured by Torai Tekkosho Co., Ltd.) with a processing capacity of 70 kgh, and is uniformly blended with a V-type blender to produce a model of a molded product crushed product.
- the first regenerated crushed product (MS-2-1) was obtained.
- MS-2-1 had a viscosity average molecular weight of 21,700 and a wet heat retention of 84%.
- MS-2-2 Same as MS-2-1, except that the crushed material was changed to MS-2 and replaced with MS-2-1. Product (MS-2-2) was obtained. MS-2-2 had a viscosity average molecular weight of 21,600 and a wet heat retention of 83%.
- MS—2—3 Same as MS—2-1 except that the crushed material was replaced with MS—2 and replaced with MS—2-2—3rd regeneration and crushing of the crushed product model by molding, wet heat treatment and crushing Product (MS-2-3) was obtained.
- MS-2-3 had a viscosity average molecular weight of 21,400 and a wet heat retention of 81%.
- Table 8 shows the analysis results for RE-1 to RE-5 and Table 9 shows the analysis results for RE-6 to RE-8. Table 8
- RE-1 A polycarbonate resin molded product used for bathroom light covers in the market was washed with tap water, dried with a hot air dryer, and then crushed with a grinder (TORAI KOKOKU; SB-210) at 70 kg / kg. The mixture was ground with a processing capacity of h and uniformly blended with a V-type blender to obtain a crushed product (RE-1). Table 8 shows the results of the composition analysis of RE-1. RE-1 had a viscosity average molecular weight of 16,100 and a wet heat retention of 90%.
- RE-2 The molded product used in the battery pack of the notebook computer in the market was washed, dried, crushed and blended in the same manner as R E-1 to obtain a crushed product (RE-2).
- Table 8 shows the results of the composition analysis of RE-2.
- RE-2 had a viscosity average molecular weight of 19,000 and a wet heat retention of 8.7%.
- RE-3 A molded product that is used for notebook PC housing in the market and has a conductive coating film and a metal plating film is immersed in an aqueous nitric acid solution, and then the molded product is washed with water to remove these metal components. I got Then, it was crushed and blended in the same manner as RE-1 to obtain a crushed product (RE-3).
- the results of a compositional analysis of E-3 are shown in Table 8.
- R E-3 had a viscosity average molecular weight of 18,100 and a wet heat retention of 85%.
- RE-4 The molded product used for the copier housing in the market was washed, dried, crushed and blended in the same manner as RE-1 to obtain a crushed product (RE-4). Table 8 shows the results of a compositional analysis of RE-4. RE-4 had a viscosity average molecular weight of 19,300 and a wet heat retention of 52%.
- RE-5 The molded product used for the printer housing at the factory was washed with water, dried, crushed, and blended in the same manner as in RE-1 to obtain a crushed product (RE-5). The results of a compositional analysis of RE-5 are shown in Table 8, and were found to be almost the same as RE-4. RE-5 had a viscosity average molecular weight of 16,300 and a wet heat retention of 43%.
- RE-6 A molded article that is used for notebook PC housing in the field and has a conductive coating film and a metal plating film is immersed in an aqueous nitric acid solution, and then the molded article is washed with water to remove these metallic components. The molded product of one color was washed with water, dried, crushed and blended in the same manner as RE-1, to obtain a crushed product (RE-6). .
- Table 9 shows the results of a composition analysis of RE-6.
- RE-6 has a viscosity average molecular weight of 18,900, wet The heat retention was 88%.
- RE-7 The molded product of the copier housing (I-poly) was washed with water, dried, crushed, and blended as in RE-1, to obtain a crushed product (RE-7). Table 9 shows the results of a composition analysis of RE-7. RE-7 had a viscosity average molecular weight of 17,700 and a wet heat retention of 80%.
- RE-8 The molded product of the internal parts of the printer (black) was washed with water, dried, crushed and blended in the same manner as RE-1, to obtain a crushed product (RE-8). Table 9 shows the results of a composition analysis of RE-8. RE-8 had a viscosity average molecular weight of 20,300 and a wet heat retention of 88%.
- PET polyethylene terephthalate resin
- PBT Polybutylene terephthalate resin
- FR-2 Resin ⁇ / cinol bis (dixylenyl phosphate)
- FR-3 Bisphenol A bis (diphenyl phosphate) Daihachi Chemical Industries; CR-741
- FR-4 Resorcinol bis (diphenyl phosphate)
- MD-1 Methyl methyl acrylate-ethyl acrylate-butene gen copolymer Kureha Chemical Industry; Paraloid EXL-2602
- MD-2 2-Ethylhexyl acrylate 'butadiene ⁇ methyl methacrylate ⁇ styrene multistage graft copolymer
- MD-3 Composite elastic body of polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component
- Hayashi Kasei HS—TO. 8 (average particle size of about 5 m by laser diffraction method)
- PTFE Polytetrafluoroethylene capable of forming fibrils
- DC-1 A dry color mask in which the following dyes (i) to (V), pigments, and PC-1 are uniformly mixed with a supermixer.
- the reclaimed resin composition of the present invention has the excellent characteristics of an aromatic polysiloxane resin, and is excellent in initial mechanical strength, particularly impact resistance, as well as long-term mechanical strength and flame retardancy retention effect.
- initial mechanical strength particularly impact resistance
- long-term mechanical strength and flame retardancy retention effect As a result, it is not only possible to efficiently recycle poly-polycarbonate resin-based molded products generated from used products such as electrical and electronic equipment and OA equipment, but also to have sufficient properties that can be widely reused for these products. Therefore, it is very useful from the viewpoint of environmental protection and resource recycling, and the industrial effects achieved are outstanding.
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60108825T DE60108825T2 (de) | 2000-03-28 | 2001-03-27 | Regenerierte harzzusammensetzung |
JP2001571822A JP4881531B2 (ja) | 2000-03-28 | 2001-03-27 | 再生樹脂組成物の製造方法 |
EP01915833A EP1191065B1 (en) | 2000-03-28 | 2001-03-27 | Reclaimed resin composition |
US10/742,388 US7045555B2 (en) | 2000-03-28 | 2003-12-22 | Regenerated resin composition |
Applications Claiming Priority (2)
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JP2000-88195 | 2000-03-28 | ||
JP2000088195 | 2000-03-28 |
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US09/979,555 A-371-Of-International US20030065092A1 (en) | 2000-03-28 | 2001-05-27 | Reclaimed resin composition |
US10/742,388 Division US7045555B2 (en) | 2000-03-28 | 2003-12-22 | Regenerated resin composition |
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WO2001072900A1 true WO2001072900A1 (fr) | 2001-10-04 |
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PCT/JP2001/002474 WO2001072900A1 (fr) | 2000-03-28 | 2001-03-27 | Composition de resine regeneree |
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US (2) | US20030065092A1 (ja) |
EP (1) | EP1191065B1 (ja) |
JP (1) | JP4881531B2 (ja) |
KR (1) | KR100718853B1 (ja) |
CN (1) | CN1205267C (ja) |
DE (1) | DE60108825T2 (ja) |
WO (1) | WO2001072900A1 (ja) |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08311326A (ja) * | 1995-05-16 | 1996-11-26 | Teijin Chem Ltd | 芳香族ポリカーボネート樹脂組成物および成形品 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0531008A1 (en) | 1991-08-22 | 1993-03-10 | General Electric Company | Compositions derived from recycled polycarbonate and polyester |
DE4244027A1 (de) * | 1992-12-24 | 1994-06-30 | Bayer Ag | Thermoplastische Formmassen mit wiederaufgearbeiteten Bestandteilen |
DE4311138C2 (de) * | 1993-04-05 | 1995-03-30 | Bayer Ag | Recycling von Thermoplasten mit dünnen Beschichtungen aus Schmelze-inerten Fremdstoffen |
JPH06298991A (ja) | 1993-04-16 | 1994-10-25 | Sumitomo Chem Co Ltd | リサイクル用樹脂の回収方法 |
DE4338282A1 (de) * | 1993-11-10 | 1995-05-11 | Buna Gmbh | Schlagzähe Polycarbonat-Regenerate |
JP3262983B2 (ja) * | 1996-02-27 | 2002-03-04 | 帝人化成株式会社 | ポリカーボネート樹脂成形品の再利用方法 |
DE19717878A1 (de) * | 1997-04-28 | 1998-10-29 | Basf Ag | Verwendung von CD-Rezyklat als Einsatzstoff für Flittereinfärbungen |
ES2268878T3 (es) | 1998-08-28 | 2007-03-16 | Teijin Chemicals, Ltd. | Una composicion de resina de policarbonato y articulo moldeado. |
DE69914431T2 (de) | 1998-09-29 | 2004-07-15 | Idemitsu Petrochemical Co., Ltd. | Thermoplastische Harzzusammensetzungen und ihre Spritzgussteile |
JP2000159900A (ja) | 1998-11-26 | 2000-06-13 | Ricoh Co Ltd | 再生成形品及びその製造方法 |
DE19958974B4 (de) | 1998-12-11 | 2011-06-22 | Idemitsu Kosan Co., Ltd. | Flammhemmende thermoplastische Harz-Zusammensetzung und ihre Verwendung |
US6498228B1 (en) | 1999-01-11 | 2002-12-24 | Idemitsu Petrochemical Co., Ltd. | Flame-retardant polycarbonate resin composition and molded product |
JP2001026719A (ja) | 1999-05-07 | 2001-01-30 | Mitsubishi Engineering Plastics Corp | リサイクル樹脂組成物及びその製造方法 |
JP4627833B2 (ja) | 2000-02-10 | 2011-02-09 | 旭化成ケミカルズ株式会社 | ポリカーボネート組成物 |
-
2001
- 2001-03-27 JP JP2001571822A patent/JP4881531B2/ja not_active Expired - Lifetime
- 2001-03-27 WO PCT/JP2001/002474 patent/WO2001072900A1/ja active IP Right Grant
- 2001-03-27 DE DE60108825T patent/DE60108825T2/de not_active Expired - Lifetime
- 2001-03-27 KR KR1020017014944A patent/KR100718853B1/ko not_active IP Right Cessation
- 2001-03-27 CN CNB018013589A patent/CN1205267C/zh not_active Expired - Fee Related
- 2001-03-27 EP EP01915833A patent/EP1191065B1/en not_active Expired - Lifetime
- 2001-05-27 US US09/979,555 patent/US20030065092A1/en not_active Abandoned
-
2003
- 2003-12-22 US US10/742,388 patent/US7045555B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08311326A (ja) * | 1995-05-16 | 1996-11-26 | Teijin Chem Ltd | 芳香族ポリカーボネート樹脂組成物および成形品 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1191065A4 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1302510A1 (en) * | 2001-10-11 | 2003-04-16 | Asahi Kasei Kabushiki Kaisha | Flame retardant resin composition |
US6956073B2 (en) | 2001-11-22 | 2005-10-18 | Teijin Chemicals, Ltd. | Flame-retardant resin composition |
JP2006335890A (ja) * | 2005-06-02 | 2006-12-14 | Teijin Chem Ltd | 再生樹脂組成物および再生樹脂組成物の製造方法 |
US8877850B2 (en) | 2006-06-19 | 2014-11-04 | Idemitsu Kosan Co., Ltd. | Light-diffusing polycarbonate resin composition and light-diffusing plate |
JP2009132892A (ja) * | 2007-11-09 | 2009-06-18 | Canon Inc | 熱可塑性樹脂構造体の製造方法及び熱可塑性樹脂組成物 |
JP2013163813A (ja) * | 2007-11-09 | 2013-08-22 | Canon Inc | 再生樹脂及び再生樹脂の製造方法 |
US8735456B2 (en) | 2007-11-09 | 2014-05-27 | Canon Kabushiki Kaisha | Process for producing thermoplastic resin composition, and thermoplastic resin composition produced by the same |
JP2017110045A (ja) * | 2015-12-14 | 2017-06-22 | 帝人株式会社 | ポリカーボネート樹脂組成物 |
JP7486308B2 (ja) | 2019-12-03 | 2024-05-17 | 三星電子株式会社 | トリアジン環含有ポリマーならびにこれを含む熱可塑性成形品および光学部品 |
EP4019576A1 (en) | 2020-12-28 | 2022-06-29 | Trinseo Europe GmbH | Recycling method for elastomer toughened thermoplastic polymers |
WO2022144158A1 (en) | 2020-12-28 | 2022-07-07 | Trinseo Europe Gmbh | Recycling method for elastomer toughened thermoplastic polymers |
Also Published As
Publication number | Publication date |
---|---|
KR100718853B1 (ko) | 2007-05-16 |
JP4881531B2 (ja) | 2012-02-22 |
EP1191065B1 (en) | 2005-02-09 |
US7045555B2 (en) | 2006-05-16 |
KR20020018670A (ko) | 2002-03-08 |
EP1191065A1 (en) | 2002-03-27 |
CN1380895A (zh) | 2002-11-20 |
EP1191065A4 (en) | 2003-05-02 |
US20040138378A1 (en) | 2004-07-15 |
CN1205267C (zh) | 2005-06-08 |
DE60108825T2 (de) | 2006-01-19 |
US20030065092A1 (en) | 2003-04-03 |
DE60108825D1 (de) | 2005-03-17 |
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