Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
  • C08L93/04—Rosin
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
  • C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
  • C09F1/04—Chemical modification, e.g. esterification

Definitions

• the present invention relates to a composite plastic molding.
• Composite plastic moldings have excellent mechanical strength, so they are processed into injection molded products, films, sheets, fibers, etc., and are used in a wide range of applications such as mobile phones, personal computers, and LED devices.
• the base material of the composite plastic molding includes general-purpose plastics such as polyvinyl chloride and polyethylene; engineering plastics such as polyamide, polycarbonate and polyester; super engineering plastics such as polyamideimide, polyphenylsulfone and polyethersulfone.
• engineering plastics are highly reliable base materials with excellent heat resistance, and are used in liquid crystal television parts, electronic parts such as optical fibers, clothing fibers, automobile parts, and the like.
• a phthalic acid plasticizer or the like is added in order to easily process and impart flexibility.
• phthalate-based plasticizers may not be fully compatible with plastic substrates, and plasticizers may ooze out from the substrate (referred to as “bleed out”) and may have a detrimental effect on human health and the environment. It can affect.
• thermoplastic resin composition using a specific amount of organosiloxane with respect to a resin composition containing a styrene resin and a thermoplastic resin is known (Patent Document 1).
• a thermoplastic resin composition containing a thermoplastic resin that is a polyamide resin, an aliphatic polyester resin, or a semi-aromatic polyester resin, a filler, and rosin is also known (Patent Document 2).
• Patent Document 1 cannot sufficiently suppress bleed-out when a styrene resin is used, and is inferior in moldability. Further, the invention described in Patent Document 2 is colored at the time of molding.
• the composite plastic molding of one embodiment of the present invention is a reaction product of (A) engineering plastic and (B) rosins and a monohydric alcohol having 1 to 9 carbon atoms, and does not have an aromatic ring.
• An abietic acid type resin acid having a conjugated double bond and an ester thereof are less than 1% by weight, and include a rosin ester having a glass transition temperature of ⁇ 15 ° C. or lower.
• a composite plastic molded product (hereinafter also referred to as a molded product) according to an embodiment of the present invention includes an engineering plastic (A) (hereinafter referred to as component (A)) and a specific rosin ester (B) (hereinafter referred to as (B). Component).
• the component (A) has a structure containing not only carbon but also oxygen and nitrogen in the molecular chain. Therefore, the component (A) has excellent heat resistance.
• the component (A) is not particularly limited.
• the component (A) preferably has thermoplasticity. Examples of the component (A) having thermoplasticity include polyamide, polyester, polycarbonate, polyacetal and the like. A plurality of these may be used.
• Polyamide is not particularly limited. Various known polyamides can be used. Examples of the polyamide include 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, 9-nylon, polyamide 4, polyamide 12 and the like. Examples of the polyamide include aromatic nylon such as polyamide 6T, polyamide 9T, and polyamide 10T.
• the weight average molecular weight of the polyamide is not particularly limited.
• the weight average molecular weight is preferably about 10,000 to 60,000, more preferably about 20,000 to 50,000 from the viewpoint of compatibility with the component (B).
• Polyester is not particularly limited. Various known polyesters can be used. Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polybutylene isophthalate, poly-p-phenylene adipate, poly-p-phenylene terephthalate; polyethylene adipate, polybutylene adipate, poly- Examples thereof include aliphatic polyesters such as ⁇ -caprolactone, polylactic acid, polyhydroxybutyrate, and polybutylene succinate.
• aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polybutylene isophthalate, poly-p-phenylene adipate, poly-p-phenylene terephthalate; polyethylene adipate, polybutylene adipate, poly- Examples thereof include aliphatic polyesters such as ⁇ -caprolactone, polylactic acid, polyhydroxybutyrate, and poly
• the weight average molecular weight of the polyester is not particularly limited.
• the weight average molecular weight is preferably about 10,000 to 200,000, more preferably about 15,000 to 150,000, from the viewpoint of compatibility with the component (B).
• Polycarbonate is not particularly limited. Various known polycarbonates can be used. Polycarbonate is obtained, for example, by a method of copolymerizing an aromatic dihydroxy compound and an aliphatic dihydroxy compound by a transesterification reaction using a carbonic acid diester as a carbonate source in the presence of a transesterification catalyst; an aromatic dihydroxy compound and phosgene. What is obtained by making it react is mentioned. Further, the polycarbonate may have a branched structure.
• a carbonic acid diester may be used as a carbonate source.
• the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. A plurality of these may be used.
• aromatic dihydroxy compounds include bisphenol-A, tetrabromobisphenol-A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxy).
• Phenyl) butane 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) )
• Propane 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro) -4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis
• a known catalyst is appropriately used.
• the catalyst include basic compounds and transesterification catalysts.
• the catalyst is preferably a metal compound such as an alkali metal compound, an alkaline earth metal compound, a nitrogen-containing metal compound, or a tin compound.
• the weight average molecular weight of the polycarbonate is not particularly limited.
• the weight average molecular weight is preferably about 10,000 to 100,000, more preferably about 15,000 to 80,000, from the viewpoint of compatibility with the component (B).
• the polyacetal is not particularly limited. Various known polyacetals can be used. Examples of the polyacetal include polyoxymethylene, polyoxyethylene, polyoxyphenylene, poly-1,3-dioxolane and the like.
• the weight average molecular weight of polyacetal is not particularly limited.
• the polyacetal is preferably about 30,000 to 16000, more preferably about 50,000 to 130,000, from the viewpoint of compatibility with the component (B).
• the component (A) preferably contains at least one selected from the group consisting of polycarbonate, polyamide and polyester, more preferably polycarbonate, from the viewpoint of high transparency.
• antioxidants include a sulfur-containing acidic compound or a derivative formed from the acidic compound, a phenol-based stabilizer, a phosphorus-based antioxidant, a thioether-based stabilizer, a hindered amine-based stabilizer, an epoxy-based stabilizer, and the like.
• UV absorber include benzotriazole UV absorbers and triazine UV absorbers.
• Component (B) is a rosin ester, which is a reaction product of rosin and a monohydric alcohol having 1 to 9 carbon atoms.
• rosins that are constituents of the component (B)
• various known rosins can be used without particular limitation.
• examples of rosins include natural rosin such as Nesia rosin, gum rosin, tall oil rosin, and wood rosin, purified rosin obtained by purifying natural rosin, hydrogenated rosin obtained by hydrogenating natural rosin, and natural rosin. And disproportionated rosin obtained by the reaction.
• a plurality of rosins may be used. Among these, rosins are preferably disproportionated rosin and hydrogenated rosin from the viewpoint of suppressing coloring of the molded product.
• the purified rosin can be obtained using various known means such as a distillation method, an extraction method, and a recrystallization method.
• the distillation method include a method of distilling the natural rosin usually at a temperature of about 200 to 300 ° C. and a reduced pressure of about 0.01 to 3 kPa.
• the extraction method include a method of neutralizing the aqueous layer after extracting the natural rosin as an alkaline aqueous solution and extracting an insoluble unsaponified product with various organic solvents.
• the recrystallization method include a method in which the natural rosin is dissolved in an organic solvent as a good solvent, the solvent is then distilled off to obtain a concentrated solution, and an organic solvent as a poor solvent is added.
• the disproportionated rosin can be obtained using various known means.
• Examples of the disproportionated rosin include a method in which a raw natural rosin or a purified purified rosin is subjected to a heat reaction in the presence of a disproportionation catalyst.
• the disproportionation catalyst various known catalysts such as supported catalysts such as palladium-carbon, rhodium-carbon, platinum-carbon; metal powders such as nickel and platinum; iodides such as iodine and iron iodide can be used.
• the amount of the catalyst used is usually about 0.01 to 5 parts by weight, preferably about 0.01 to 1 part by weight, based on 100 parts by weight of rosin.
• the reaction temperature is about 100 to 300 ° C, preferably about 150 to 290 ° C.
• the disproportionated rosin is preferably purified by the above distillation method from the viewpoint of increasing the color tone of the obtained rosin ester.
• the hydrogenated rosin can be obtained by hydrogenating rosins using known hydrogenation conditions.
• a method for obtaining a hydrogenated rosin includes a method in which rosins are heated to about 100 to 300 ° C. at a hydrogen pressure of about 2 to 20 MPa in the presence of a hydrogenation catalyst.
• the hydrogen pressure is preferably about 5 to 20 MPa
• the reaction temperature is preferably about 150 to 300 ° C.
• the hydrogenation catalyst various known catalysts such as a supported catalyst, metal powder, iodine, and iodide can be used.
• the supported catalyst include palladium-carbon, rhodium-carbon, ruthenium-carbon, platinum-carbon and the like.
• the metal powder include nickel and platinum.
• Examples of the iodide include iron iodide.
• palladium, rhodium, ruthenium, and platinum-based catalysts are preferable because the hydrogenation rate of the obtained rosins is high and the hydrogenation time is short.
• the amount of the hydrogenation catalyst used is usually preferably about 0.01 to 5 parts by weight and more preferably about 0.01 to 2 parts by weight with respect to 100 parts by weight of rosins.
• Alcohol that is a component of component (B) is a monohydric alcohol having 1 to 9 carbon atoms.
• the monohydric alcohol having 9 or more carbon atoms is used, the obtained component (B) is difficult to be compatible with the component (A), and the liquid component (B) separated from the molded product is likely to exude.
• the monohydric alcohol having 1 to 8 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol and the like. It is done. A plurality of these may be used. From the same point, a monohydric alcohol having 1 to 4 carbon atoms is more preferable, and methanol or ethanol is particularly preferable.
• the component (B) has a Gardner color number of 1 or less, preferably a Hazen color number of 200 H or less.
• a Gardner color number of 1 or less When the Gardner color number of the rosin ester is 1 or less, the molded product is difficult to be colored.
• the Gardner color number and the Hazen color number are measured in Gardner units and Hazen units, respectively, according to JIS K0071.
• Component (B) has a glass transition temperature (Tg) of ⁇ 15 ° C. or lower.
• Tg glass transition temperature
• Tg is preferably ⁇ 40 to ⁇ 15 ° C. from the viewpoint that the molded product is excellent in bleed-out resistance.
• the glass transition temperature is measured by the method specified in JIS K7121.
• the component (B) is not particularly limited.
• Component (B) usually has a degree of esterification of 94% by weight or more, preferably 96% by weight or more.
• the degree of esterification is obtained by calculating the formula (1) from the total peak area at the time of gel permeation chromatography (GPC) measurement of the component (B) and the peak area corresponding to the monoester body in the component (B). It is calculated using.
• GPC gel permeation chromatography
• Esterification degree (%) [A / total total peak area] ⁇ 100 (1)
• A shows the peak area (peak area corresponding to the monoester body in rosin ester) of the weight average molecular weight (polystyrene conversion value) 240.
• the content of the abietic acid type resin acid having a conjugated double bond having no aromatic ring and its ester is less than 1% by weight. By doing so, the molded product is difficult to be colored. Further, from the same viewpoint, the content is preferably less than 0.5% by weight, more preferably substantially 0% by weight (a level that cannot be detected).
• the content is determined by gas chromatographic analysis (GC) by preparing a solution of rosin ester subjected to the following pretreatment.
• sample pretreatment method 10 mg of rosin ester is thoroughly examined, and 2 mL of MeOH / toluene (50/50) mixture is added and dissolved. Next, a 10% hexane solution of trimethylsilyldiazomethane is dropped, and the sample is methylesterified and analyzed.
• the abietic acid type resin acid having a conjugated double bond having no aromatic ring includes abietic acid and isomers thereof.
• isomers of abietic acid include neoabietic acid, levopimaric acid, and parastolic acid.
• the isomer of abietic acid does not include dehydroabietic acid having an aromatic ring.
• the isomers of abietic acid do not include pimaric acid type resin acids such as pimaric acid, isopimaric acid, and sandaracopimalic acid.
• (B) It does not specifically limit as a manufacturing method of a component.
• a known esterification method can be adopted as the production method.
• the amount of each of the rosins and alcohol charged is not particularly limited. The amount charged is usually determined so that the OH group of alcohol / COOH group (equivalent ratio) of rosins is about 0.8 to 8, preferably about 3 to 7.
• the reaction temperature of the esterification reaction is usually about 150 to 320 ° C., preferably about 150 to 300 ° C.
• the reaction time is usually about 2 to 24 hours, preferably about 2 to 7 hours. Furthermore, for the purpose of shortening the reaction time, the esterification reaction can proceed in the presence of a catalyst.
• the catalyst examples include acid catalysts such as p-toluenesulfonic acid; metal hydroxides such as calcium hydroxide and magnesium hydroxide; metal oxides such as calcium oxide and magnesium oxide. Since water is produced as a result of the esterification reaction, the reaction can proceed while removing the produced water out of the system. In consideration of the color tone of the rosin ester obtained, it is desirable to carry out the reaction under an inert gas stream. The reaction can be performed under pressure if necessary. Moreover, you may make it react in the organic solvent non-reactive with rosins and alcohol. Examples of the organic solvent include hexane, cyclohexane, toluene, xylene and the like. When an organic solvent is used, the organic solvent or unreacted raw material can be distilled off under reduced pressure as necessary.
• purification, disproportionation or hydrogenation of natural rosin is carried out after esterification of natural rosin and alcohols, or natural rosin.
• the rosin can be purified, disproportionated or hydrogenated and the resulting rosins and alcohols can be esterified.
• the acid value of the component (B) is preferably 2 mgKOH / g or less, more preferably 1 mgKOH / g or less. Thereby, a softness
• the acid value is measured according to JIS K 0070.
• the component (B) contains a dihydroabietic acid ester content of 15% by weight or more or a tetrahydroabietic acid ester content of 10% by weight or more (provided that the resin acid and its ester in the component (B)
• the total content is preferably 100% by weight).
• the component (B) preferably includes the dehydroabietic acid ester content of 40% by weight or more (however, the total content of the resin acid and the ester in the component (B) is 100% by weight). . Thereby, when shape
• component (B) other additives may be included as necessary within the range not impairing the effects of the present embodiment.
• other additives include an antioxidant, a polymerization inhibitor, and a sensitizer.
• the other additive is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component (B).
• the composite plastic molded product of the present embodiment is not particularly limited.
• the composite plastic molding can be produced by various known methods.
• the composite plastic molded product can be obtained by, for example, a method in which the components (A) and (B) are kneaded at a temperature of about 220 to 280 ° C. for 0.5 to 6 hours, or (B) ) Component may be added and then molded after kneading.
• the content ratio (solid content weight) of the component (A) and the component (B) is not particularly limited.
• the molding conditions cannot be uniquely defined, but the temperature and pressure may be appropriately adjusted in consideration of the deformation of the target molded product.
• Examples of the molding method include injection molding, extrusion molding, transfer molding, blow molding, heat press molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding, transfer molding, and the like.
• the embodiment of the present invention has been described above.
• the present invention is not particularly limited to the above embodiment.
• the above-described embodiments mainly describe the invention having the following configuration.
• (A) engineering plastics, and (B) abietic acid resin acid and ester thereof, which are a reaction product of rosins and monohydric alcohols having 1 to 9 carbon atoms and have a conjugated double bond having no aromatic ring Is a composite plastic molding comprising a rosin ester having a glass transition temperature of -15 ° C. or lower.
• Item (A) The composite plastic molded article according to Item 1, wherein the component is at least one selected from the group consisting of polycarbonate, polyamide and polyester.
• Item 3 The composite plastic molded article according to Item 1 or 2, wherein the degree of esterification of the component is 94% by weight or more.
• Item 4 The composite plastic molded article according to any one of Items 1 to 3, wherein the acid value of the component (B) is 2 mgKOH / g or less.
• Item 5 The composite plastic molded article according to any one of Items 1 to 4, wherein the rosins include at least one of disproportionated rosin and hydrogenated rosin.
• the rosin ester contains dihydroabietic acid ester in an amount of 15% by weight or more, or tetrahydroabietic acid ester in an amount of 10% by weight or more (however, the total content of the resin acid and its ester in component (B)) Item 8) is a composite plastic molded article according to any one of Items 1 to 5.
• Production Example 1 (Production of rosin ester 1) 100 g of Chinese disproportionated rosin (manufactured by Guangxi Zhengzhou Arakawa Chemical Co., Ltd.) and 300 g of methanol were charged into a 1 L autoclave to remove oxygen in the system, and the temperature was raised to 290 ° C. The internal pressure of the autoclave reached up to 14 MPa. The esterification reaction was carried out for 2 hours while depressurizing every 20 minutes and removing water vapor.
• Production Example 2 (Production of rosin ester 2) 64 g of rosin ester 2 was obtained in the same manner as in Production Example 1, except that the Chinese disproportionated rosin was changed to a highly hydrogenated rosin (Forest Chemical Co., Ltd.).
• Production Example 3 (Production of rosin ester 3) 64 g of rosin ester 3 was obtained in the same manner as in Production Example 1 except that it was changed to low hydrogenated rosin (Forest Chemical Co., Ltd.).
• Production Example 4 (Production of rosin ester 4) 64 g of rosin ester 4 was obtained in the same manner as in Production Example 1 except that it was changed to distilled disproportionated rosin (Arakawa Chemical Industries, Ltd.).
• Production Example 5 (Production of rosin ester 5) 100 g of rosin ester 4 obtained in Production Example 4 and 100 g of 2-propanol were added to a 300 ml flask equipped with a stirrer, a cooling tube and a nitrogen introducing tube, heated to 40 ° C. and dissolved, and then the container was placed in a constant temperature circulator. Soaked. The temperature was lowered from 40 ° C., and seed crystals were added on the way. After the flocculent white crystals increased rapidly, the temperature of the apparatus was lowered to 5 ° C. and held for 1.5 hours.
• Production Example 6 (Production of rosin ester 6) 65 g of rosin ester 6 was obtained in the same manner as in Production Example 1 except that Chinese disproportionated rosin was changed to distilled disproportionated rosin (manufactured by Arakawa Chemical Industries, Ltd.) and methanol was changed to ethanol.
• Comparative Production Example 1 (Production of rosin ester 7) 65 g of rosin ester 6 was obtained in the same manner as in Production Example 1 except that the Chinese disproportionated rosin was changed to a Chinese hydrogenated rosin (manufactured by Guangxi Zhengzhou Nislin Forest Products Chemical Co., Ltd.).
• Comparative Production Example 2 (Production of rosin ester 8) 65 g of rosin ester 7 was obtained in the same manner as in Production Example 1, except that the Chinese disproportionated rosin was changed to a Chinese gum rosin (manufactured by Guangxi Zhengzhou Arakawa Chemical Co., Ltd.).
• rosin ester 10 Hercolin D (hydrogenated rosin methyl ester, manufactured by Eastman Chemical Co.) (Reference Comparative Example 4) and DOP (Reference Comparative Example 4) as other compounds were used.
• Tg glass transition temperature
• Model Product name “HLC-8220”, manufactured by Tosoh Corp. Column: product name “TSKgel G2500HXL”, manufactured by Tosoh Corp., 1 product and product name “TSKgel G2000HXL”, manufactured by Tosoh Corp., 2 products Name “TSKgel G1000HXL”, manufactured by Tosoh Corporation, one connected developing solvent flow rate: tetrahydrofuran, 1 mL / min measuring temperature: 40 ° C. Detector: RI
• A represents a peak area having a weight average molecular weight (polystyrene equivalent value) 240 (peak area corresponding to a monoester in rosin esters 1 to 8).
• ⁇ Analysis of rosin ester composition ratio> The composition ratio of the rosin component (resin acid component) in the rosin ester was analyzed by gas chromatographic analysis (GC). The rosin ester was subjected to the following pretreatment, a solution was prepared, and GC measurement was performed under the following conditions. The results are shown in Table 2.
• sample pretreatment method 10 mg of rosin ester was carefully examined, and 2 mL of a methanol / toluene (50/50) mixed solution was added and dissolved. A 10% hexane solution of trimethylsilyldiazomethane was added dropwise, and the sample was methylesterified and analyzed.
• composition ratio of the rosin ester was calculated by dividing every retention time (hereinafter also referred to as RT).
• Neutral component Peak detected at RT 0 to 4.1 minutes
• Tetrahydroabietic acid ester Among peaks detected at RT 4.1 minutes to 10 minutes, 4.6 minutes, 5.1 minutes, 5.3 minutes Peak dihydroabietic acid ester detected at 5.6 minutes, 5.8 minutes, 6.0 minutes, 6.1 minutes, 6.4 minutes, 7.0 minutes: detected at RT 4.1 minutes to 10 minutes Among those peaks, those other than tetrahydroabietic acid ester Abietic acid ester: peak detected at RT 11.2 minutes
• Dehydroabietic acid ester peak detected at RT 11.7 minutes
• A-Component (A-1) Polycarbonate, trade name "PC (made by Stella)", made by Nippon Test Panel Co., Ltd.-DOP: Dioctyl phthalate-Tuftec: Hydrogenated styrene thermoplastic resin, Tradename “Tuftech H1062” , Made by Asahi Kasei Co., Ltd., Methbrene: Rubber-based resin, trade name “Metbrene L-1000”, made by Mitsubishi Chemical
• Example 8 and Comparative Examples 9 to 10 A reaction vessel equipped with a thermometer and a cooling tube was charged with 45 g of polyamide (trade name “Unitika Nylon 6 A1030FR”, manufactured by Unitika Ltd.) and 55 g of rosin ester 35, respectively, and the temperature was raised to 240 ° C. The mixture was stirred for 1 hour and cooled to room temperature, and then press-molded using a heating press (temperature: 230 ° C., preheating time: 2 minutes, pressure: 10 MPa ⁇ 1 minute) to obtain a composite plastic molded product.
• composite plastic moldings were also prepared with the compositions shown in Table 4. Bleed-out resistance, flexibility and moldability were evaluated under the same conditions as above.

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