WO2011071110A1 - 着色樹脂組成物および成形体 - Google Patents
着色樹脂組成物および成形体 Download PDFInfo
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- WO2011071110A1 WO2011071110A1 PCT/JP2010/072129 JP2010072129W WO2011071110A1 WO 2011071110 A1 WO2011071110 A1 WO 2011071110A1 JP 2010072129 W JP2010072129 W JP 2010072129W WO 2011071110 A1 WO2011071110 A1 WO 2011071110A1
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- polypropylene
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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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
- C08K5/0041—Optical brightening agents, organic pigments
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
Definitions
- the present invention relates to a colored resin composition and a molded body containing a polypropylene resin.
- the present invention claims priority based on Japanese Patent Application No. 2009-279562 filed in Japan on December 09, 2009 and Japanese Patent Application No. 2010-270702 filed in Japan on December 03, 2010. The contents are incorporated here.
- Resin moldings are used in a wide range of fields, for example, ABS resin is widely used as the material for housings of home appliances, and polycarbonate is widely used as the material for exterior parts of stationery, and is usually molded by injection molding. Yes.
- ABS resin has a problem in color developability when a colorant is blended.
- polycarbonate is concerned about the influence of residual bisphenol A on the living body, and the molding temperature must be increased, so that the colorant may deteriorate.
- a polypropylene resin having excellent mechanical properties at low cost particularly a copolymer with ethylene (for example, random copolymer polypropylene, Block copolymer type polypropylene) may be used (see, for example, Patent Document 1).
- the present invention provides a colored resin composition that can obtain a molded article excellent in both impact resistance and color developability despite containing a polypropylene resin as a main component and having injection molding suitability. The purpose is to do. It is another object of the present invention to provide a molded article that is particularly excellent in both low temperature impact and color developability despite containing a polypropylene resin as a main component.
- the colored resin composition of the present invention contains 90 to 99.9% by mass of a polypropylene resin that satisfies the following conditions (a) to (d) and 0.1 to 10% by mass of a colorant ( However, the total of the polypropylene resin and the colorant is 100% by mass).
- the polypropylene resin is a reaction blend type polypropylene obtained by polymerizing a copolymer rubber of ethylene and an ⁇ -olefin having 3 to 10 carbon atoms in the presence of homopolypropylene or random polypropylene in a reactor.
- melt flow rate (temperature 230 ° C., load 21.6 N) is 4 g / 10 min or more.
- the low temperature embrittlement temperature is 0 ° C. or less.
- the total light transmittance measured at 1 mm thickness is 25% or more.
- the melting peak temperature (Tmp) is 140 ° C. or higher.
- the colored resin composition of the present invention contains a polypropylene resin as a main component, both the impact resistance and the color developability are excellent, and it has injection molding suitability.
- black coloring can sufficiently increase jet blackness, so that so-called piano black color can be obtained, and pearl coloring can provide vivid gloss.
- the molded article of the present invention contains a polypropylene resin as a main component, both impact resistance and color developability are excellent.
- the colored resin composition of the present invention contains a polypropylene resin and a colorant as essential components.
- the polypropylene resin is a reaction blend type polypropylene obtained by polymerizing a copolymer rubber of ethylene and an ⁇ -olefin having 3 to 10 carbon atoms in the presence of homopolypropylene or random polypropylene in the reactor.
- the polypropylene resin satisfies the following conditions (a) to (d).
- the melt flow rate (hereinafter referred to as “MFR”) is 4 g / 10 minutes or more.
- MFR is a value measured in accordance with JIS K 7210 under conditions of a temperature of 230 ° C. and a load of 21.6 N. If the MFR is less than 4 g / 10 minutes, the moldability when the injection molding method is applied is impaired.
- the MFR is preferably 7 g / 10 minutes or more, more preferably 15 g / 10 minutes or more, and further preferably 25 g / 10 minutes or more. Moreover, it is preferably 110 g / 10 min or less, more preferably 75 g / 10 min or less, and further preferably 55 g / 10 min or less. If MFR is 110 g / 10 min or less, sufficient low-temperature impact property as a molded article can be obtained.
- the low temperature embrittlement temperature is 0 ° C. or less.
- the low temperature embrittlement temperature is a value measured in accordance with JIS K 7216 using a test piece of width 6.0 mm ⁇ thickness 2.0 mm ⁇ length 38 mm cut out from an injection-molded plate. . If the low-temperature embrittlement temperature is 0 ° C. or higher, the low-temperature impact property is impaired.
- the total light transmittance measured with a 1 mm-thick test piece is 25% or more.
- the total light transmittance is a value measured according to JIS K 7105.
- a polypropylene resin having a total light transmittance of less than 25% measured with a 1 mm thick test piece is a conventional block copolymer polypropylene resin.
- incident light is scattered, and light emitted from the colorant is reduced.
- the total light transmittance is preferably 30% or more, more preferably 35% or more. If the total light transmittance is 30% or more, sufficient color developability as a molded product can be obtained.
- the melting peak temperature (Tmp) is 140 ° C. or higher.
- the melting peak temperature (Tmp) is a value obtained by increasing the temperature from room temperature at a rate of 10 ° C./min using a differential scanning calorimeter (DSC) in accordance with JIS K 7121.
- a high MFR polypropylene matrix is finely dispersed with an ethylene / ⁇ -olefin copolymer rubber as a dispersed phase.
- a resin that is dispersed or dispersed in a stretched state may be used.
- the content of the polypropylene resin in the colored resin composition is in the range of 90 to 99.9% by mass when the total of the polypropylene resin and the colorant is 100% by mass, and 97 to 99.8% by mass. A range is preferable.
- the content of the polypropylene resin is less than 90% by mass, the impact resistance is impaired, and when it exceeds 99.9% by mass, the content of the colorant is decreased, so that coloring is insufficient.
- the colorant contained in the colored resin composition changes the color of the polypropylene resin, and examples thereof include a color pigment, a pearl pigment, and metal powder.
- examples of the color pigment include carbon black and iron black as black colorants; titanium oxide, zinc white, lithbon, lead white as white colorants; bitumen, ultramarine blue, cobalt blue, and phthalocyanine blue as blue colorants.
- Indanthrene Blue RS First Sky Blue Lake, Alkaline Blue Lake, Victoria Blue Lake; red colorant, petal, lead charcoal, molybdenum red, cadmium red, lake red C, lake red D, brilliant carmine 6B, Resor Red, Permanent Red 4R, Watching Red, Thioindigo Red, Alizarin Red, Quinacridone Red, Rhodamine Lake, Orange Lake, Benzimidazolone Red, Pyrazolone Red, Condensed Azo Red, Perylene Red, Permanent Car FB, quinacridone magenta; yellow colorants such as yellow lead, cadmium yellow, titanium yellow, iron yellow, isoindolinone yellow, benzidine yellow, first yellow, flavonthrone yellow, naphthol yellow, quinoline yellow, benzimidazolone yellow, HR yellow, condensed azo yellow; as green colorant, chrome green, chromium oxide, guine green, spinel green, phthalocyanine green, pigment green B, naphthol
- pearl-like pigments include natural or synthetic mica, pearl mica in which natural or synthetic mica is coated with a metal oxide such as titanium oxide and iron oxide, and the thickness of the film layer of the metal oxide is changed.
- examples include interference mica that uses the difference in refractive index and interference of reflected light for color development, colored mica coated with a colored oxide such as iron oxide, and glass flakes.
- the metal powder include aluminum powder, copper powder, zinc powder, Fronz powder, and stainless steel powder.
- the content of the colorant in the colored resin composition is in the range of 0.1 to 10% by mass and the range of 0.2 to 3% by mass when the total of the polypropylene resin and the colorant is 100% by mass. It is preferable that When the content of the colorant is less than 0.1% by mass, the content of the colorant is decreased, so that coloring is insufficient. When the content exceeds 10% by mass, mechanical properties are impaired.
- the colored resin composition of the present invention may contain, for example, other thermoplastic resins as optional components.
- other thermoplastic resins include ethylene or ⁇ -olefin homopolymers, ethylene or ⁇ -olefin copolymers having 3 to 10 carbon atoms, mixtures thereof, polyamides, polycarbonates, polyphenylene oxides, petroleum resins, and the like. Can be mentioned.
- ethylene or ⁇ -olefin homopolymers include high-density polyethylene, low-density polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, and poly (3-methyl-1-pentene.
- Polystyrene Poly (3-methyl-1-butene), poly (4-methyl-1-pentene), poly-1-hexene, poly-1-heptene, poly-1-octene, poly-1-decene, polystyrene Can be mentioned.
- the content of other thermoplastic resins in the colored resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the entire colored resin composition. If content of another thermoplastic resin is 10 mass% or less, the impact resistance of a colored resin composition and the fall of a moldability can be prevented. When the colored resin composition contains another thermoplastic resin, the lower limit of the content is preferably 1% by mass or more.
- the colored resin composition of the present invention may contain a known inorganic filler as an optional component.
- the inorganic filler include natural silicic acid or silicate such as talc, kaolinite, calcined clay, virophilite, serinite, and wollastonite; carbonates such as precipitated calcium carbonate, heavy calcium carbonate, and magnesium carbonate; water Hydroxides such as aluminum oxide and magnesium hydroxide; oxides such as zinc oxide and magnesium oxide; and powder fillers such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, anhydrous silicic acid and the like synthetic silicate or silicate, Flaky filler such as mica; basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Filler), zonotlite, potassium titanate, and elastadite Which fibrous filler; and can be used Garasubarun, balloon-like fillers such as fly ash balloon and the like.
- These inorganic fillers may be used alone or in combination of two or more. Moreover, these inorganic fillers may be untreated or may be surface-treated in advance. Examples of the surface treatment method include a chemical or physical method using a surface treatment agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, or polyethylene glycol.
- a surface treatment agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, or polyethylene glycol.
- the content of the inorganic filler in the colored resin composition is preferably 30% by mass or less, more preferably 20% by mass or less when the entire colored resin composition is 100% by mass. If content of an inorganic filler is 30 mass% or less, the impact resistance of a colored resin composition and the fall of a moldability can be prevented.
- the lower limit of the content when the colored resin composition contains an inorganic filler is preferably 1% by mass or more.
- the colored resin composition of the present invention includes, as optional components, for example, an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an internal lubricant, an external lubricant, an antistatic agent, a flame retardant, You may contain additives, such as a dispersing agent, copper damage prevention agent, a neutralizing agent, a plasticizer, a foaming agent, a foam
- additives such as a dispersing agent, copper damage prevention agent, a neutralizing agent, a plasticizer, a foaming agent, a foam
- the colored resin composition of the present invention is produced by mixing a polypropylene resin and a colorant, if necessary, with other thermoplastic resins and additives.
- the colorant is preferably made into a master batch and mixed with a polypropylene resin in a later step.
- the master batch is produced by blending a diluent resin with a colorant.
- the dilution resin include the other thermoplastic resins.
- the mixing method include a method of dry blending using a mixer such as a Henschel mixer, a tumbler and a ribbon mixer, and a method of mixing while melting using a mixer such as an extrusion mixer, a kneader and a Banbury.
- the melting temperature is preferably in the range of 160 to 350 ° C., more preferably in the range of 170 to 260 ° C., and still more preferably in the range of 190 to 230 ° C.
- the polypropylene resin is contained as a main component. Regardless, it has excellent impact resistance and color development.
- the colored resin composition is particularly excellent in color developability when colored in black, white, brown, or gray with a colorant.
- blending a pearl tone pigment as a coloring agent is exhibited notably.
- the reason why the color developability is excellent is not clear, but it is presumed that the reaction blend type polypropylene has little scattering of incident light on the rubber and light emitted from the colorant easily reaches.
- the said colored resin composition is excellent in fluidity
- Such a colored resin composition can be suitably used as an alternative material for ABS resin and polycarbonate.
- the molded body of the present invention is obtained by molding the colored resin composition.
- the molding method of the colored resin composition is not particularly limited, and for example, an injection molding method, an extrusion molding method, a compression molding method, a hollow molding method, and the like can be applied. Further, after forming into a sheet shape using an extruder, the sheet may be formed into a desired shape by a secondary processing method such as a vacuum forming method or a pressure forming method. Since the colored resin composition is suitable for the injection molding method, the injection molding method is preferable among the molding methods.
- the molded body of the present invention can be applied to various fields, and is particularly suitable for, for example, a housing for home appliances and an exterior part for stationery.
- Example 1 Polypropylene resin (reaction blend type polypropylene, Cylell EC348P manufactured by Lion Delbacell) and black colorant masterbatch (manufactured by Tokyo Ink; 9AK028 BLACK) or pearl pigment masterbatch (manufactured by Tokyo Ink; 1AK298 PEARL)
- the colorant content was blended so as to be 5% by mass when the total of the polypropylene resin and the colorant was 100% by mass.
- the resulting mixture was melt kneaded at 230 ° C. using an extruder to obtain a colored resin composition.
- Example 2 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene-based resin was changed to a reaction blend type polypropylene (Cylell EC440P manufactured by Lion Delbacell).
- Example 3 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a reaction blend type polypropylene (Cylell EC340Q manufactured by Lion Delbacell).
- Example 4 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a reaction blend type polypropylene (Crylell EC440R manufactured by Lion Delbacell).
- Example 5 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a reaction blend type polypropylene (Crylell EC140R manufactured by Lion Delbacell).
- Example 6 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a reaction blend type polypropylene (Qualar CM646V manufactured by Sun Allomer Co., Ltd.).
- Example 7 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a reaction blend type polypropylene (Qualar PP2228 manufactured by Sun Allomer Co., Ltd.).
- Example 8 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a reaction blend type polypropylene (Quareal CMA70V manufactured by Sun Allomer Co., Ltd.).
- Example 9 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to the reaction blend type polypropylene prototype 1 shown in Table 1.
- Example 10 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to the reaction blend type polypropylene prototype 2 shown in Table 1.
- Example 1 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to random copolymer polypropylene (PM731V manufactured by Sun Allomer Co., Ltd.).
- Example 2 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to random copolymer polypropylene (PM931V manufactured by Sun Allomer Co., Ltd.).
- Example 3 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a random copolymer polypropylene (PM741R manufactured by Sun Allomer Co., Ltd.).
- Example 4 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to block copolymerized polypropylene (PM580X manufactured by Sun Allomer Co., Ltd.).
- Example 5 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to a block copolymer type polypropylene (PM771M manufactured by Sun Allomer Co., Ltd.).
- Example 6 A colored resin composition was obtained in the same manner as in Example 1 except that the polypropylene resin was changed to block copolymer polypropylene (PM972Z manufactured by Sun Allomer Co., Ltd.).
- MFR MFR was measured under the conditions of temperature: 230 ° C. and load: 21.6 N in accordance with JIS K 7210.
- Low temperature embrittlement temperature The colored resin composition was injection molded (molding temperature: 230 ° C., molding machine: FANUC100B) to produce a molded product having a width of 130 mm ⁇ length of 130 mm ⁇ thickness of 2.0 mm.
- the low temperature embrittlement temperature was measured in accordance with JIS K 7216 using a test piece having a width of 6.0 mm, a thickness of 2.0 mm and a length of 38 mm punched out from the molded product in the flow direction.
- Total light transmittance The total light transmittance is obtained by injection molding a colored resin composition (molding temperature: 230 ° C., molding machine: FANUC100B) to produce a molded product having a width of 70 mm ⁇ a length of 150 mm ⁇ a thickness of 1.0 mm. Used and measured according to JIS K 7105.
- MFR and low temperature embrittlement temperature were measured, and fluidity
- the evaluation results are shown in Table 2.
- the measuring method of MFR and low temperature embrittlement temperature is the same as the measuring method of MFR and low temperature embrittlement temperature of polypropylene resin.
- the color developability was evaluated by the following method. [Color development] A colored resin composition is injection-molded (molding temperature: 230 ° C., molding machine: FANUC100B) to produce a molded product having a width of 70 mm ⁇ length of 150 mm ⁇ thickness of 1.0 mm, and having a 60 ° specular gloss according to JIS7105. It was measured.
- the black or pearl color was evaluated in three stages based on a color obtained by coloring a random copolymer polypropylene material.
- O Random copolymer type polypropylene equivalent or better
- X Inferior to random copolymer type polypropylene
- ⁇ Intermediate between O and X.
- the product was excellent in all of moldability, impact resistance and color development.
- the colored resin compositions of Comparative Examples 1 and 2 using a random copolymer type polypropylene resin having a low temperature embrittlement temperature of 0 ° C. or higher had low impact resistance.
- the colored resin composition of Comparative Example 3 having a low-temperature embrittlement temperature of 0 ° C. or lower had a low melting peak temperature (heat resistance).
- the colored resin compositions of Comparative Examples 4, 5, and 6 using a block copolymer type polypropylene resin having a total light transmittance of less than 25% had low color developability.
- the colored resin composition of Example 5 is excellent in color developability.
- 1A is a colored resin composition of Comparative Example 6, FIG.
- 1B is a colored resin composition of Example 5, the horizontal axis of the graph is coordinates passing through the position irradiated with laser light, and the vertical axis is scattered light. Of strength.
- the coordinates irradiated with the laser light are about 280 pixels.
- the colored resin composition molded body of Example 5 had a scattered light intensity lower than that of the colored resin composition molded body of Comparative Example 6. That is, in the molded body of the colored resin composition of Example 5, the jetness is high because the amount of light reaching the eyes is small.
- strength of the laser beam of the film-form molded object of the colored resin composition of the comparative example 6 and Example 5 containing a pearl tone pigment was measured.
- the scattered light intensity of the laser beam of the polypropylene resin used in Comparative Example 6 in which no colorant was blended and the polypropylene resin used in Example 5 was measured.
- the scattered light intensity of the laser light of the film-shaped molded article not containing the pearl-like pigment was subtracted from the scattered light intensity of the laser-shaped molded article containing the pearl-colored pigment.
- FIGS. 2A and 2B shows the results obtained from the colored resin composition of Comparative Example 6
- FIG. 2B shows the results obtained from the colored resin composition of Example 5.
- the graphs of FIG. 2A and FIG. 2B show the intensity of scattered light based on the pearl pigment, and the stronger the scattered light intensity, the greater the effect of the pearl tone.
- the colored resin composition molded body of Example 5 has a scattered light intensity stronger than that of the colored resin composition molded body of Comparative Example 6, and a pearl-like effect appears greatly. It was.
- the conventional polypropylene block copolymer contains ethylene / propylene rubber particles, but the composition of the rubber is away from homopolypropylene, so the refractive index is also away, and the shape of the rubber particles is spherical. Close to. Therefore, as shown in FIG. 3A, the incident light is scattered by the rubber particles G, and looks whitish due to the scattered light. Therefore, it seems that jet blackness becomes insufficient when black is colored. In the conventional polypropylene block copolymer, the light incident on the pearl pigment P and the light scattered from the pigment are blocked by the rubber particles G, and are not easily observed as scattered light.
- the colored resin composition of the present invention and a molded product formed therefrom are excellent in both impact resistance and color developability despite containing a polypropylene resin as a main component.
- black coloring can sufficiently increase jet blackness, so that so-called piano black color can be obtained, and pearl coloring can provide vivid gloss.
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Abstract
Description
本発明は、2009年12月09日に日本に出願された特願2009-279562号、および2010年12月03日に日本に出願された特願2010-270702号に基づき優先権を主張し、その内容をここに援用する。
しかしながら、ABS樹脂は着色剤を配合した際の発色性に問題があった。また、ポリカーボネートは残留ビスフェノールAの生体への影響が懸念される上に、成形温度を高くしなければならないため、着色剤が劣化することがあった。
また、近年、コストダウンの観念から、ABS樹脂やポリカーボネートの代わりに、安価でありながらも優れた機械的物性を有するポリプロピレン系樹脂、とりわけエチレンとの共重合体(例えば、ランダム共重合型ポリプロピレン、ブロック共重合型ポリプロピレン)を用いることがある(例えば特許文献1参照)。
そこで、本発明は、ポリプロピレン系樹脂を主成分として含有するにもかかわらず、耐衝撃性および発色性が共に優れた成形体を得ることができ、しかも射出成形適性を有する着色樹脂組成物を提供することを目的とする。また、ポリプロピレン系樹脂を主成分として含有するにもかかわらず、特に低温衝撃性および発色性が共に優れた成形体を提供することを目的とする。
(1)本発明の着色樹脂組成物は、下記(a)~(d)の条件を満たすポリプロピレン系樹脂90~99.9質量%と、着色剤0.1~10質量%とを含有し(ただし、ポリプロピレン系樹脂と着色剤との合計を100質量%とする。)、
前記ポリプロピレン系樹脂は、反応器内でホモポリプロピレン又はランダムポリプロピレンの存在下、エチレンと炭素数3~10のαオレフィンとの共重合体ゴムを重合して得た反応ブレンド型ポリプロピレンである。
(a)メルトフローレート(温度230℃、荷重21.6N)が4g/10分以上である。
(b)低温脆化温度が0℃以下である。
(c)1mm厚で測定した全光線透過率が25%以上である。
(d)融解ピーク温度(Tmp)が140℃以上である。
(2)また、本発明は上記(1)に記載の着色樹脂組成物が成形された成形体である。
本発明の成形体は、ポリプロピレン系樹脂を主成分として含有するにもかかわらず、耐衝撃性および発色性のいずれもが共に優れている。
本発明の着色樹脂組成物は、ポリプロピレン系樹脂と着色剤とを必須成分として含有する。
ここで、ポリプロピレン系樹脂は、反応器内でホモポリプロピレン又はランダムポリプロピレンの存在下、エチレンと炭素数3~10のαオレフィンとの共重合体ゴムを重合して得た反応ブレンド型ポリプロピレンである。
本発明においては、ポリプロピレン系樹脂が下記(a)~(d)の条件を満たす。
ここで、MFRは、JIS K 7210に準拠し、温度230℃、荷重21.6Nの条件で測定した値である。MFRが4g/10分未満であると、射出成形法を適用した際の成形性が損なわれる。
MFRは、好ましくは7g/10分以上、より好ましくは15g/10分以上であり、さらに好ましくは25g/10分以上である。また、好ましくは110g/10分以下、より好ましくは75g/10分以下、さらに好ましくは55g/10分以下である。MFRが110g/10分以下であれば、成形品として十分な低温衝撃性が得られる。
全光線透過率は、好ましくは30%以上、より好ましくは35%以上である。全光線透過率が30%以上であれば、成形品として充分な発色性が得られる。
着色顔料としては、例えば、黒色の着色剤として、カーボンブラック、鉄黒;白色の着色剤として、酸化チタン、亜鉛華、リトボン、鉛白;青色の着色剤として紺青、群青、コバルトブルー、フタロシアニンブルー、インダンスレンブルーRS、ファーストスカイブルーレーキ、アルカリブルーレーキ、ビクトリアブルーレーキ;赤色の着色剤として、弁柄、鉛炭、モリブデンレッド、カドミウムレッド、レーキレッドC、レーキレッドD、ブリリアントカーミン6B、リソールレッド、パーマネントレッド4R、ウォッチングレッド、チオインジゴレッド、アリザリンレッド、キナクリドンレッド、ローダミンレーキ、オレンジレーキ、ベンズイミダゾロンレッド、ピラゾロンレッド、縮合アゾレッド、ペリレンレッド、パーマネントカーミンFB、キナクリドンマゼンダ;黄色の着色剤として、黄鉛、カドミウムイエロー、チタンイエロー、鉄黄、イソインドリノンイエロー、ベンジジンイエロー、ファーストイエロー、フラボンスロンイエロー、ナフトールイエロー、キノリンイエロー、ベンズイミダゾロンイエロー、HRイエロー、縮合アゾイエロー;緑色の着色剤として、クロムグリーン、酸化クロム、ギネグリーン、スピネルグリーン、フタロシアニングリーン、ピグメントグリーンB、ナフトールグリーン、アッシッドグリーンレーキ、マラカイトグリーンレーキ;橙色の着色剤として、クロムオレンジ、カドミウムオレンジ、ベンズイミダゾロンオレンジ、ペリノンオレンジ;茶色の着色剤として亜鉛フェライト;紫色の着色剤として、マンガン紫、コバルト紫、紫弁柄、ファーストバイオレットB、メチルバイオレットレーキ、ジオキサジンバイオレットなどが挙げられる。
パール調顔料としては、例えば、天然または合成雲母、天然または合成雲母に酸化チタン、酸化鉄などの金属酸化物をコーティングしたパールマイカ、金属酸化物の皮膜層の厚みを変化させ基材と皮膜の屈折率差を利用し、反射光の干渉を発色に利用する干渉マイカ、酸化鉄などの有色酸化物で被覆した着色マイカ、ガラスフレークなどが挙げられる。
金属粉としては、例えば、アルミニウム粉、銅粉、亜鉛粉、フロンズ粉、ステンレス粉などが挙げられる。
エチレン又はα-オレフィン単独重合体としては、例えば、高密度ポリエチレン、低密度ポリエチレン、ポリプロピレン、ポリ-1-ブテン、ポリ-1-ペンテン、ポリ-1-ヘキセン、ポリ(3-メチル-1-ペンテン)、ポリ(3-メチル-1-ブテン)、ポリ(4-メチル-1-ペンテン)、ポリ-1-ヘキセン、ポリ-1-ヘプテン、ポリ-1-オクテン、ポリ-1-デセン、ポリスチレンが挙げられる。
無機フィラーとしては、例えば、タルク、カオリナイト、焼成クレー、バイロフィライト、セリナイト、ウォラストナイトなどの天然珪酸または珪酸塩;沈降性炭酸カルシウム、重質炭酸カルシウム、炭酸マグネシウムなどの炭酸塩;水酸化アルミニウム、水酸化マグネシウムなどの水酸化物;酸化亜鉛、酸化マグネシウムなどの酸化物;及び、含水珪酸カルシウム、含水珪酸アルミニウム、含水珪酸、無水珪酸などの合成珪酸または珪酸塩などの粉末状フィラー、マイカなどのフレーク状フィラー;塩基性硫酸マグネシウムウィスカー、チタン酸カルシウムウィスカー、ホウ酸アルミニウムウィスカー、セピオライト、PMF(Processed Mineral Filler)、ゾノトライト、チタン酸カリウム、及びエレスタダイトなどの繊維状フィラー;並びに、ガラスバルン、フライアッシュバルンなどのバルン状フィラー等を用いることができる。これら無機フィラーは、単独でも2種類以上併用してもよい。
また、これら無機フィラーは未処理であってもよいし、予め表面処理されていてもよい。表面処理方法の例としては、シランカップリング剤、高級脂肪酸、脂肪酸金属塩、不飽和有機酸、有機チタネート、ポリエチレングリコールなどの表面処理剤を用いる化学的または物理的方法が挙げられる。
混合方法としては、ヘンシェルミキサー、タンブラーおよびリボンミキサー等の混合機を使用してドライブレンドする方法、押出混合機、ニーダーおよびバンバリー等の混合機を用いて溶融しながら混合する方法が挙げられる。溶融する場合の溶融温度は160~350℃の範囲であることが好ましく、170~260℃の範囲であることがより好ましく、更に好ましくは190~230℃の範囲である。
特に、上記着色樹脂組成物は、着色剤により黒色、白色、茶色、灰色に着色した際の発色性にとりわけ優れている。また、着色剤としてパール調顔料を配合した際のパール調の効果が顕著に発揮される。発色性に優れる理由は明らかではないが、上記反応ブレンド型ポリプロピレンでは、ゴムでの入射光の散乱が少なく、着色剤から発する光も到達しやすいためと推測する。
しかも、上記着色樹脂組成物は、流動性に優れ、射出成形適性を有する。
このような着色樹脂組成物は、ABS樹脂やポリカーボネートの代替材料として好適に使用できる。
本発明の成形体は、上記着色樹脂組成物が成形されたものである。
着色樹脂組成物の成形方法としては、特に制限されるものではなく、例えば、射出成形法、押出成形法、圧縮成形法、中空成形法等を適用できる。また、押出成形機を用いてシート状に成形した後、このシートを真空成形法、圧空成形法等の二次加工方法によって所望の形状に成形してもよい。上記の着色樹脂組成物は射出成形法に適したものであるため、上記成形方法の中でも射出成形法が好ましい。
本発明の成形体は各種分野に適用でき、例えば、家電製品のハウジング、文具の外装部品にとりわけ好適である。
ポリプロピレン系樹脂(反応ブレンド型ポリプロピレン、ライオンデルバセル社製Clyrell EC348P)と、黒着色剤マスターバッチ(東京インキ社製;9AK028 BLACK)またはパール調顔料マスターバッチ(東京インキ社製;1AK298 PEARL)とを、着色剤の含有量が、ポリプロピレン系樹脂と着色剤との合計を100質量%とした際の5質量%になるように配合した。これにより得られた混合物を、押出機を用い、230℃で溶融混練して、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、反応ブレンド型ポリプロピレン(ライオンデルバセル社製Clyrell EC440P)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、反応ブレンド型ポリプロピレン(ライオンデルバセル社製Clyrell EC340Q)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、反応ブレンド型ポリプロピレン(ライオンデルバセル社製Clyrell EC440R)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、反応ブレンド型ポリプロピレン(ライオンデルバセル社製Clyrell EC140R)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、反応ブレンド型ポリプロピレン(サンアロマー社製Qualear CM646V)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、反応ブレンド型ポリプロピレン(サンアロマー社製Qualear PP2228)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、反応ブレンド型ポリプロピレン(サンアロマー社製Qualear CMA70V)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、表1に示す反応ブレンド型ポリプロピレンの試作材1に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、表1に示す反応ブレンド型ポリプロピレンの試作材2に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、ランダム共重合型ポリプロピレン(サンアロマー社製PM731V)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、ランダム共重合型ポリプロピレン(サンアロマー社製PM931V)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、ランダム共重合型ポリプロピレン(サンアロマー社製PM741R)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、ブロック共重合型ポリプロピレン(サンアロマー社製PM580X)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、ブロック共重合型ポリプロピレン(サンアロマー社製PM771M)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
ポリプロピレン系樹脂を、ブロック共重合型ポリプロピレン(サンアロマー社製PM972Z)に変更した以外は実施例1と同様にして、着色樹脂組成物を得た。
[MFR]
MFRは、JIS K 7210に準拠し、温度:230℃、荷重:21.6Nの条件で測定した。
[低温脆化温度]
着色樹脂組成物を射出成形して(成形温度:230℃、成形機:FANUC100B)幅130mm×長さ130mm×厚さ2.0mmの成形品を作製した。低温脆化温度は、この成形品から流動方向に打ち抜いて切り出された幅6.0mm×厚さ2.0mm×長さ38mmの試験片を用い、JIS K 7216に準拠して測定した。
[全光線透過率]
全光線透過率は、着色樹脂組成物を射出成形して(成形温度:230℃、成形機:FANUC100B)幅70mm×長さ150mm×厚さ1.0mmの成形品を作製し、この成形品を用い、JIS K 7105に準拠して測定した。
[融解ピーク温度]
230℃で熱プレスしてシート状にしたポリプロピレン系樹脂の融解ピーク温度(セカンドラン)を、JIS K 7121に準拠して示差走査熱量計(DSC)(ティー・エイ インストルメント DSC Q2000)を用いて、常温から10℃/分の速度で昇温して測定した。
なお、MFRおよび低温脆化温度の測定方法は、ポリプロピレン系樹脂のMFRおよび低温脆化温度の測定方法と同様である。また、発色性について以下の方法により評価した。
[発色性]
着色樹脂組成物を射出成形して(成形温度:230℃、成形機:FANUC100B)幅70mm×長さ150mm×厚さ1.0mmの成形品を作製し、JIS7105に準拠した60°鏡面光沢度を測定した。また黒色またはパール色の鮮明さについて、ランダム共重合型ポリプロピレン材料を着色したものを基準にして3段階で評価した。(○:ランダム共重合型ポリプロピレン同等以上、×:ランダム共重合型ポリプロピレンに劣る。△:○と×との中間。)
ランダム共重合型で低温脆化温度が0℃以上のポリプロピレン系樹脂を用いた比較例1,2の着色樹脂組成物は、耐衝撃性が低かった。低温脆化温度が0℃以下の比較例3の着色樹脂組成物は、融解ピーク温度(耐熱性)が低かった。
ブロック共重合型で全光線透過率が25%未満のポリプロピレン系樹脂を用いた比較例4,5,6の着色樹脂組成物は、発色性が低かった。
具体的には、黒着色した比較例6および実施例5の着色樹脂組成物のフィルム状の成形体(縦50mm、横20mm、厚さ0.1mm)にレーザー光(波長: 632.8nm)を照射し、その散乱光の強度を測定した。その結果を図1Aおよび図1Bのグラフに示す。なお、図1Aは比較例6の着色樹脂組成物、図1Bは実施例5の着色樹脂組成物であり、グラフの横軸は、レーザー光が照射された位置を通る座標、縦軸は散乱光の強度である。レーザー光が照射された座標は約280ピクセルの位置である。
図1Aおよび図1Bに示すように、実施例5の着色樹脂組成物の成形体は、比較例6の着色樹脂組成物の成形体よりも散乱光強度が弱かった。すなわち、実施例5の着色樹脂組成物の成形体では、目に届く光の量が少ないため、漆黒性が高い。
図2Aおよび図2Bのグラフは、パール調顔料に基づく散乱光の強度を示しており、散乱光強度が強い程、パール調の効果が大きいことを意味する。
図2Aおよび図2Bに示すように、実施例5の着色樹脂組成物の成形体は、比較例6の着色樹脂組成物の成形体よりも散乱光強度が強く、パール調の効果が大きく現れていた。
また、従来のポリプロピレンブロック共重合体では、パール顔料Pに入射する光および顔料から散乱した光がゴム粒子Gに遮られ、散乱光として観察されにくい。そのため、パール調の効果が小さくなると思われる。
これに対し、図3Bに示すように、本発明で用いる反応ブレンド型ポリプロピレンにおいてはゴムの粒子Gのゴムの密度はポリプロピレンに近いため、屈折率も近く、さらにその形状は扁平状に引き伸ばされている。そのため、入射した光はゴム粒子Gによって散乱しにくい。したがって、黒着色した場合には漆黒性が高くなると思われる。
また、本発明で用いる反応ブレンド型ポリプロピレンでは、パール顔料Pから散乱した光がゴム粒子Gに遮られにくく、パール調の効果が大きくなると思われる。
G:ゴム粒子
Claims (2)
- メルトフローレート(温度230℃、荷重21.6N)が4g/10分以上であって、低温脆化温度が0℃以下であって、1mm厚の試験片で測定した全光線透過率が25%以上であって、及び融解ピーク温度(Tmp)が140℃以上であるポリプロピレン系樹脂90~99.9質量%と、
ポリプロピレン系樹脂と着色剤との合計を100質量%とした場合に、着色剤0.1~10質量%とを含有し、
前記ポリプロピレン系樹脂は、反応器内でホモポリプロピレン又はランダムポリプロピレンの存在下、エチレンと炭素数3~10のα-オレフィンとの共重合体ゴムを重合して得た反応型ポリプロピレンである着色樹脂組成物。 - 請求項1に記載の着色樹脂組成物が成形された成形体。
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| JP6094847B2 (ja) * | 2010-12-15 | 2017-03-15 | サンアロマー株式会社 | 射出成形用ポリプロピレン樹脂組成物、成形品、容器および蓋 |
| JP6928682B2 (ja) | 2017-08-22 | 2021-09-01 | エルジー・ケム・リミテッド | プラスチック樹脂の射出物性評価方法および射出成形用ポリエチレン樹脂 |
| JP7114361B2 (ja) | 2018-06-19 | 2022-08-08 | サンアロマー株式会社 | ポリプロピレン組成物および成形品 |
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2010
- 2010-12-03 JP JP2010270702A patent/JP5770996B2/ja active Active
- 2010-12-09 KR KR1020127014677A patent/KR20120105466A/ko not_active Withdrawn
- 2010-12-09 CN CN2010800554854A patent/CN102666712A/zh active Pending
- 2010-12-09 WO PCT/JP2010/072129 patent/WO2011071110A1/ja not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239549A (ja) * | 1995-03-01 | 1996-09-17 | Toyoda Gosei Co Ltd | 高光沢・高耐衝撃性樹脂組成物及び樹脂成形体 |
| JP2000072950A (ja) * | 1998-09-02 | 2000-03-07 | Chisso Corp | 高発色性ポリプロピレン系組成物 |
| JP2004027217A (ja) * | 2002-05-10 | 2004-01-29 | Sunallomer Ltd | ポリプロピレン樹脂組成物 |
| JP2005530901A (ja) * | 2002-06-26 | 2005-10-13 | バセル ポリオレフィン イタリア エス.ピー.エー. | 耐衝撃性ポリオレフィン組成物 |
| JP2005530900A (ja) * | 2002-06-26 | 2005-10-13 | バセル ポリオレフィン イタリア エス.ピー.エー. | 耐衝撃性ポリオレフィン組成物 |
| JP2004083608A (ja) * | 2002-08-22 | 2004-03-18 | Mitsui Chemicals Inc | 自動車部品用樹脂組成物 |
| JP2009138113A (ja) * | 2007-12-07 | 2009-06-25 | Japan Polypropylene Corp | プロピレン系共重合体組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102666712A (zh) | 2012-09-12 |
| JP2011140640A (ja) | 2011-07-21 |
| KR20120105466A (ko) | 2012-09-25 |
| JP5770996B2 (ja) | 2015-08-26 |
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