WO2023243589A1 - Composition de résine noire et corps moulé - Google Patents

Composition de résine noire et corps moulé Download PDF

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Publication number
WO2023243589A1
WO2023243589A1 PCT/JP2023/021705 JP2023021705W WO2023243589A1 WO 2023243589 A1 WO2023243589 A1 WO 2023243589A1 JP 2023021705 W JP2023021705 W JP 2023021705W WO 2023243589 A1 WO2023243589 A1 WO 2023243589A1
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Prior art keywords
pigment
red
resin composition
black
pigments
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PCT/JP2023/021705
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English (en)
Japanese (ja)
Inventor
竜太 大橋
大輔 草間
Original Assignee
東洋インキＳｃホールディングス株式会社
トーヨーカラー株式会社
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Priority claimed from JP2022094866A external-priority patent/JP7184221B1/ja
Priority claimed from JP2022194064A external-priority patent/JP2024080813A/ja
Application filed by 東洋インキＳｃホールディングス株式会社, トーヨーカラー株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Publication of WO2023243589A1 publication Critical patent/WO2023243589A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • 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
    • 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

Definitions

  • the present invention relates to a black resin composition and a molded article formed from the same.
  • plastic is easy to mold, it is used in a wide range of fields such as electrical and electronic equipment parts, automobile parts, medical parts, and food containers, and plastic molded objects are often colored to enhance their decorative properties. ing. Particularly in the field of caps and bottles, the trend is toward multicolored products to differentiate products, and molded products with various colors and designs are on the market.
  • Patent Documents 1 and 2 are known as methods for forming a black resin composition using a plurality of organic pigments without using carbon black.
  • a polyolefin resin when a polyolefin resin is colored with a plurality of pigments, it not only has excellent shielding properties in the visible light region, low brightness, and excellent design properties, but also has high shielding properties in the near-infrared region.
  • the object of the present invention is to provide a black resin composition capable of forming a molded object that exhibits transmittance while suppressing an increase in dimensional stability and opening torque, and a molded object formed from the black resin composition.
  • one embodiment of the present invention includes a polyolefin resin (A) and a pigment (B), and a molded article having a length of 150 mm, a width of 120 mm, and a thickness of 2 mm formed by molding a black resin composition using an injection molding machine is as follows.
  • the average transmittance in the wavelength range of 380 nm to 800 nm is 1% or less
  • the average transmittance in the wavelength range of 800 nm to 2500 nm is 25% or more
  • ⁇ MDS expressed by the following formula (1) is 0.35% or less
  • the following formula The present invention relates to a black resin composition having a ⁇ TDS expressed by (2) of 0.35% or less.
  • Formula (1) ⁇ MDS
  • Formula (2) ⁇ TDS
  • the subsequent shrinkage rate in the same direction as the injection direction (MD direction) and the contraction rate in the direction perpendicular to the injection direction (TD direction), X0 and Y0 are respectively obtained by molding a polyolefin resin (A) using an injection molding machine, after leaving a molded body of 150 mm in length, 120 mm in width, and 2 mm in thickness at 23° C.
  • Another embodiment of the present invention relates to a molded article formed from the above black resin composition. Yet another embodiment of the present invention relates to a cap that is the above-mentioned molded article.
  • a polyolefin resin when a polyolefin resin is colored with a plurality of pigments, it exhibits high transmittance in the near-infrared region while providing good design properties and increasing dimensional stability and opening torque. It becomes possible to provide a black resin composition that can form a molded body with suppressed oxidation, and a molded body formed from the black resin composition.
  • the black resin composition of the present invention contains a polyolefin resin (A) and a pigment (B), and a molded article having a length of 150 mm, a width of 120 mm, and a thickness of 2 mm formed by molding the black resin composition using an injection molding machine is as follows:
  • the average transmittance in the wavelength range of 380 nm to 800 nm is 1% or less
  • the average transmittance in the wavelength range of 800 nm to 2500 nm is 25% or more
  • ⁇ MDS expressed by the following formula (1) is 0.35% or less
  • Formula (1) ⁇ MDS
  • Formula (2) ⁇ TDS
  • X1 is the same as the injection direction after a molded body of 150 mm long, 120 mm wide, and 2 mm thick, formed by molding a black resin composition using an injection molding machine, is left at 23°C and 50% RH for 24 hours. It is the shrinkage rate in the direction (MD direction), and Y1 is the shrinkage rate in the direction perpendicular to the injection direction (TD direction).
  • X0 is the injection direction after a molded body of 150 mm in length, 120 mm in width, and 2 mm in thickness, formed by molding polyolefin resin (A) using an injection molding machine, is allowed to stand at 23°C and 50% RH for 24 hours. This is the shrinkage rate in the same direction (MD direction), and Y0 is the shrinkage rate in the direction perpendicular to the injection direction (TD direction).
  • X0 and Y0 can be determined using a molded product containing only the polyolefin resin (A) that contains the highest resin ratio in the polyolefin resin (A).
  • the molded article using the polyolefin resin (A) having the smallest shrinkage rate is used as a reference.
  • ⁇ MDS and ⁇ TDS are 0.35% or less, it can be said that the molded article maintains dimensional stability with high precision and dimensional changes due to coloring with pigment are controlled.
  • ⁇ MDS is more preferably 0.3% or less, even more preferably 0.2% or less, and the closer it is to 0%, the more preferable it is.
  • ⁇ TDS is more preferably 0.3% or less, preferably 0.2% or less, and the closer it is to 0%, the more preferable it is.
  • the molded product has a controlled shrinkage difference at the same level as a molded product made of uncolored resin.
  • the average transmittance in the wavelength range of 380 nm to 800 nm, which is the visible light region, is 1% or less, more preferably 0.07% or less, and even more preferably 0.06% or less.
  • the lower limit is preferably substantially 0%. Within this range, a molded article with lower brightness and excellent design can be obtained.
  • the average transmittance in the wavelength range of 800 nm to 2500 nm, which is the near-infrared region, is 25% or more, more preferably 27% or more, and even more preferably 28% or more. Although not particularly limited, it is preferably 80% or less. Within this range, mechanical visibility is better and the accuracy of sorting waste plastics can be increased.
  • the average transmittance is determined by measuring, using a spectrophotometer, a molded article having a length of 150 mm, a width of 120 mm, and a thickness of 2 mm, which is molded from a black resin composition using an injection molding machine.
  • a spectrophotometer for example, an ultraviolet-visible spectrophotometer UV-3150 manufactured by Shimadzu Corporation can be used.
  • the black resin composition is obtained by kneading the pigment (B) and the polyolefin resin (A) at a temperature at which the polyolefin resin (A) melts.
  • the method for producing the black resin composition includes, for example, adding polyolefin resin (A) and pigment (B), and further adding various additives as necessary, using a kneader, roll mill, super mixer, high speed mixer, ball mill, sand mill, etc.
  • a batch kneader such as an attriter or a Banbury mixer, a single-screw extruder, a twin-screw extruder, a rotor-type twin-screw kneader, etc.
  • a batch kneader such as an attriter or a Banbury mixer
  • a single-screw extruder such as an attriter or a Banbury mixer
  • twin-screw extruder twin-screw extruder
  • a rotor-type twin-screw kneader etc.
  • the black resin composition may be a compound prepared by blending the pigment (B) with the polyolefin resin (A) in an amount as required and used as it is for molding, or it may be a compound containing the pigment (B) at a high concentration. It may be a masterbatch, or it may be diluted with a diluent resin and used for molding.
  • the polyolefin resin (A) in the present invention is a polymer of olefin monomers such as ethylene, propylene, butylene, and may be a block or random copolymer having a melting point in the range of 40 to 200°C, a bipolymer, or It may be a terpolymer or the like.
  • ⁇ -olefin polymers such as linear low-density polyethylene resin (LLDPE), low-density polyethylene resin (LDPE), high-density polyethylene resin (HDPE), and polypropylene resin (PP) are mentioned. It will be done.
  • the polypropylene resin (PP) may be any of homo PP (h-PP), block PP (b-PP), and random PP (r-PP).
  • the polyolefin resin (A) is preferably HDPE or PP with high crystallinity because the effects of the present invention can be easily obtained.
  • the melting point in this specification is a value measured using a differential scanning calorimeter "DSC6200" (manufactured by Seiko Instruments) under conditions of a temperature range of 40 to 200°C and a heating rate of 10°C/min.
  • the MFR (melt flow rate, also referred to as melt viscosity) of the polyolefin resin (A) is preferably 5 to 100 g/10 minutes, more preferably 10 to 60 g/10 minutes. If the MFR of the polyolefin resin (A) is 5 g/10 minutes or more, the masterbatch will be sufficiently distributed when added to the diluted resin, causing appearance defects such as color unevenness in the molded product. This can be further suppressed. On the other hand, if the MFR is 100 g/10 minutes or less, it is possible to prevent the melt viscosity of the entire system from decreasing during molding and affecting moldability.
  • the polyolefin resin (A) and the diluent resin used in the masterbatch are the same type of polyolefin resin.
  • the polyolefin resin (A) that is the diluent resin is HDPE
  • the polyolefin resin (A) in the masterbatch is also HDPE.
  • the MFR of the polyolefin resin (A) is preferably 5 g/10 minutes or less, more preferably 0.1 to 5 g/10 minutes. When the MFR of the polyolefin resin (A) is within the above range, both moldability and dimensional stability can be achieved.
  • the MFR of the polyolefin resin (A) is The rate is preferably 5 g/10 minutes or less, and more preferably 0.1 to 5 g/10 minutes. Note that the MFR in the present invention is a value measured according to JIS (Japanese Industrial Standard) K-7210.
  • polyolefin resin (A) examples include Novatec LL UJ580 (LLDPE, MFR: 20 g/10 min, manufactured by Japan Polyethylene Co., Ltd.), Suntec LD M2270 (LDPE, MFR: 7 g/10 min, manufactured by Asahi Kasei Co., Ltd.), Suntec HD J240 (HDPE, MFR: 5g/10 min, Asahi Kasei Co., Ltd.), Suntec HD J300 (HDPE, MFR: 42 g/10 min, Asahi Kasei Co., Ltd.), Prime Polypro J229E (PP, MFR: 50 g/10 min, Prime Polymer Co., Ltd.) ), etc. Furthermore, Nipolon Hard 6530 (HDPE, MFR: 0.1 g/10 minutes, manufactured by Tosoh Corporation) can be mentioned.
  • the content of the polyolefin resin (A) in 100% by mass of the resin composition is preferably 60% by mass or more and less than 100% by mass, more preferably 90% by mass or more.
  • the blending amount of the polyolefin resin (A) is 60% by mass or more, it is easy to maintain sufficient strength of the molded article.
  • Pigment (B) At least one selected from the group consisting of inorganic pigments (B1) and organic pigments (B2) can be used.
  • Preferred embodiments of the pigment (B) include the following Embodiment I and Embodiment II.
  • an organic pigment (B2) or an inorganic pigment (B1) can be used without particular limitation, and includes blue pigments, red pigments, yellow pigments, green pigments, purple pigments, etc.
  • a black pigment composition can be obtained by combining a plurality of these.
  • the red pigment and purple pigment it is more preferable to include a red pigment.
  • the red pigment and the purple pigment are C.I. I. Pigment Red 122, C. I. Pigment Red 254, and C.I. I. It is preferable from the viewpoint of dimensional stability that at least one selected from the group consisting of Pigment Violet 19 is included.
  • inorganic pigment (B1) examples include titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, carbon black, Cadmium red, red iron, molybdenum red, molybdate orange, chrome vermilion, chlorine, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Examples include navy blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.
  • organic pigment (B2) examples include diketopyrrolopyrrole pigments, azo pigments (e.g., azo, disazo, polyazo, etc.), phthalocyanine pigments (e.g., copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc.) , anthraquinone pigments (e.g., aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthrone, indanthrone, pyrantrone, violanthrone, etc.), quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments Examples include pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, and metal complex pigments.
  • diketopyrrolopyrrole pigments from the viewpoint of dimensional stability, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, and quinacridone pigments are preferred, and diketopyrrolopyrrole pigments, monoazo pigments, disazo pigments, and copper phthalocyanine pigments are preferred. , halogenated copper phthalocyanine pigments, and quinacridone pigments are more preferred.
  • the pigment (B) preferably does not contain carbon black, and the content of carbon black is 0.05% by mass or less in 100% by mass of the pigment (B). It is preferable that there be.
  • Preferred combinations of pigments (B) include a phthalocyanine-based blue pigment or a cobalt-based blue pigment, a quinacridone red pigment, a diketopyrrolopyrrole-based red pigment, and a quinacridone-based red pigment, from the viewpoint of visible light shielding properties and near-infrared transmittance. It is preferable that at least one of a purple pigment is included, and it is more preferable that a monoazo yellow pigment or a disazo yellow pigment is included.
  • a more preferable combination of pigments (B) is a monoazo yellow pigment, a quinacridone red pigment, or a phthalocyanine blue pigment, a monoazo yellow pigment, a diketopyrrolopyrrole red pigment, or a phthalocyanine blue pigment, and a monoazo yellow pigment.
  • a combination of a pigment, a quinacridone-based purple pigment, and cobalt blue is preferred in terms of shrinkage rate.
  • the pigments (B) include monoazo yellow pigments, quinacridone red pigments, and phthalocyanine blue pigments, monoazo yellow pigments, diketopyrrolopyrrole red pigments, and phthalocyanine blue pigments.
  • a monoazo yellow pigment, a quinacridone purple pigment, a phthalocyanine blue pigment, a disazo yellow pigment, a quinacridone red pigment, a phthalocyanine blue pigment, a disazo yellow pigment, a diketopyrrolopyrrole red pigment, and a phthalocyanine More preferred are combinations of blue pigments, disazo yellow pigments, quinacridone purple pigments, and phthalocyanine blue pigments.
  • blue pigment red pigment, yellow pigment, green pigment, and purple pigment, and further specific examples of the orange pigment will be described later.
  • each pigment is such that a molded body of 150 mm in length, 120 mm in width, and 2 mm in thickness is formed from a black resin composition using an injection molding machine, and has an average transmittance of 1% or less in the wavelength range of 380 nm to 800 nm, and There is no particular restriction as long as the average transmittance at 800 nm to 2500 nm satisfies 25% or more, but if it contains at least one of a blue pigment, a red pigment, and a violet pigment, based on the total amount of pigment (B) 100% by mass.
  • the content of the blue pigment is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
  • the content of the red pigment or purple pigment is preferably 20 to 50% by mass, more preferably 30 to 40% by mass. In addition, when both a red pigment and a purple pigment are included, it is preferable that the total amount of the red pigment and the purple pigment is within the above range.
  • the content of other pigments other than the blue pigment, red pigment and purple pigment is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.
  • Other pigments in this case are pigments other than blue pigments, red pigments, and purple pigments, and include, for example, yellow pigments, green pigments, orange pigments, and the like.
  • the content of the blue pigment may be 100 to 300 parts by mass per 100 parts by mass of the red pigment and the violet pigment. , is preferable from the viewpoint of the light-shielding property of the molded article in the visible light region, and 150 to 250 parts by mass is more preferable.
  • the blending amount of each color pigment is preferably 0.05 to 0.8% by mass of the blue pigment in 100% by mass of the molded product, since it can achieve both dimensional stability and design. More preferably, it is .1 to 0.5% by mass.
  • the content of the red pigment is preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.4% by mass.
  • the content of the yellow pigment is preferably 0 to 0.5% by mass, more preferably 0.05 to 0.4% by mass.
  • the content of the pigment (B) is preferably 0.01% by mass or more, and preferably 0.1% by mass or more based on 100% by mass of the molded product, from the viewpoint of achieving both dimensional stability and design.
  • the content is more preferably 0.3% by mass or more. Further, it is preferably 1% by mass or less, and more preferably less than 0.8% by mass.
  • pigment (B) is C.I. I. Pigment Brown 29, C. I. Pigment Black 11, C. I. Pigment Black 27, C. I. Pigment Black 33, C. I. Pigment Black 36, and C.I. I. Contains an inorganic pigment (B1x) that is at least one selected from the group consisting of Pigment Green 17. Thereby, it is possible to suppress the occurrence of warpage, shrinkage, etc. in the molded product when coloring the polyolefin resin, and achieve highly accurate dimensional stability. From the viewpoint of design, when the pigment (B) contains the inorganic pigment (B1x), it is preferable that the pigment (B) further contains other pigments.
  • the other pigment in this case is at least one of the organic pigment (B2) and the other inorganic pigment (B1y) other than the inorganic pigment (B1x), and more preferably includes the organic pigment (B2).
  • the inorganic pigment (B1x) is C.I. I. Pigment Brown 29, C. I. Pigment Black 11, C. I. Pigment Black 27, C. I. Pigment Black 33, C. I. Pigment Black 36, and C.I. I. Pigment Green 17, and may be used alone or in combination of two or more. From the viewpoint of design, C. I. Pigment Brown 29 or C.I. I. Pigment Black 33 is preferred.
  • C. I. Pigment Brown 29 includes PS24-3950 (manufactured by Faroe Co.)
  • C. I. Pigment Black 11 includes Byferox 306 (manufactured by LANXESS)
  • C.I. I. Pigment Black 27 includes Dipyroxide Black #9590 (manufactured by Dainichiseika Chemical Industry Co., Ltd.)
  • C.I. I. Pigment Black 33 includes Byferox 303T (manufactured by LANXESS)
  • C.I. I. Pigment Black 36 includes Taipei Black SG-101 (manufactured by Ishihara Sangyo Co., Ltd.)
  • C.I. I. Examples of Pigment Green 17 include Shepard Black 10P922 (manufactured by Shepard).
  • the inorganic pigment (B1x) is preferably blended in an amount of 1.0 to 3.0% by mass, more preferably 1.2 to 2.0% by mass, in 100% by mass of the molded article. When the inorganic pigment (B1x) is within the above range, higher designability can be obtained.
  • the content of the inorganic pigment (B1x) is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more based on 100% by mass of the pigment (B). , 95% by mass or more is particularly preferred. Further, it is preferably less than 100% by mass, and more preferably 99.99% by mass or less. When the inorganic pigment (B1x) is within the above range, higher designability can be obtained.
  • the inorganic pigment (B1y) is an inorganic pigment other than the inorganic pigment (B1x), such as titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay.
  • talc bentonite, cadmium red, red iron, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Examples include Victoria green, ultramarine blue, navy blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.
  • green inorganic pigments or blue inorganic pigments are preferred, including viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green ultramarine, navy blue, cobalt blue, cerulean blue, and cobalt silica blue. , or cobalt zinc silica blue is preferred.
  • the pigment (B) preferably does not contain carbon black, and the content of carbon black is preferably 0.05% by mass or less in 100% by mass of the pigment (B). .
  • Organic pigment (B2) As the organic pigment (B2), the examples of the organic pigment (B2) mentioned in Embodiment I can be applied. Preferred examples are also as listed in Embodiment I.
  • pigments organic pigment (B2) and inorganic pigment (B1y), are not particularly limited, and blue pigments, red pigments, purple pigments, yellow pigments, green pigments, orange pigments, etc. can be used, and inorganic pigments
  • a black resin composition can be obtained.
  • blue pigments, red pigments, purple pigments, yellow pigments, or green pigments are preferred.
  • the other pigment preferably contains at least one of a blue pigment and a green pigment, and more preferably contains a blue pigment.
  • the blue pigment and the green pigment are preferably a phthalocyanine-based blue organic pigment or a phthalocyanine-based green organic pigment, and C.I. I. Pigment Blue 15, 15:1, 15:3, or C.I. I. Pigment Green 7 is more preferred.
  • the other pigments include at least one of a red pigment and a purple pigment.
  • the red pigment and the purple pigment are preferably diketopyrrolopyrrole-based red pigments, azo-based red pigments, quinacridone-based red pigments, azo-based yellow pigments, or quinacridone-based purple pigments, and C.I. I. Pigment Red 122, C. I. Pigment Red 254, or C.I. I. Pigment Violet 19 is more preferred.
  • blue pigment red pigment, purple pigment, yellow pigment, green pigment, and orange pigment.
  • the total content of the organic pigment (B2) and the inorganic pigment (B1y) is preferably 0.001% by mass or more based on 100% by mass of the molded product from the viewpoint of achieving both dimensional stability and designability.
  • the content is more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more. Further, it is preferably 1% by mass or less, and more preferably less than 0.8% by mass.
  • the total content of the organic pigment (B2) or inorganic pigment (B1y) is preferably 50% by mass or less based on 100% by mass of the pigment (B) from the viewpoint of achieving both dimensional stability and designability, It is more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Further, it is preferably 0.01% by mass or more.
  • each pigment is such that a molded body of 150 mm in length, 120 mm in width, and 2 mm in thickness is formed from a black resin composition using an injection molding machine, and has an average transmittance of 1% or less in the wavelength range of 380 nm to 800 nm, and There is no particular restriction as long as the average transmittance from 800 nm to 2500 nm satisfies 25% or more, but if at least one of a blue pigment and a green pigment is included, the design quality is From this point of view, the content of the blue pigment is preferably 0.1 to 1.2% by mass, more preferably 0.5 to 1.0% by mass.
  • the content of the green pigment is preferably 0.1 to 1.0% by mass, more preferably 0.3 to 0.8% by mass.
  • the content of other color pigments other than the blue pigment and the green pigment is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.
  • the amount of blue pigment is 0.1 to 1.2 parts by mass per 100 parts by mass of the inorganic pigment (B1x). It is preferably 0.5 to 1.0 parts by mass, more preferably 0.5 to 1.0 parts by mass.
  • the amount of the green pigment is preferably 0.1 to 1.0 parts by mass, more preferably 0.3 to 0.8 parts by mass.
  • [Blue pigment] As a blue pigment, C. I. Phthalocyanine-based blue organic pigments such as Pigment Blue 15, 15:1, 15:3, C. I. Cobalt-based blue inorganic pigments such as Pigment Blue 28, C. I. Ultramarine blue inorganic pigments such as Pigment Blue 29, etc. Among these, phthalocyanine-based blue organic pigments or cobalt-based blue inorganic pigments are preferred from the viewpoint of dimensional stability. Furthermore, from the viewpoint of near-infrared transmittance, phthalocyanine-based blue organic pigments are more preferred. Among them, C. I. Pigment Blue 15:3 is more preferred.
  • Red pigment As a red pigment, C. I. Quinacridone red organic pigments such as Pigment Red 122, 207, 209, C. I. Diketopyrrolopyrrole red organic pigments such as Pigment Red 254 and 264, C. I. Perylene-based red organic pigments such as Pigment Red 149 and 178, C. I. Pigment Red 48: Azo red organic pigments such as 2, 144, 151, 166, 208, 221, C. I. Anthraquinone red organic pigment such as Pigment Red 177, C. I. Examples include pyrazolone-based red organic pigments such as Pigment Red 38.
  • quinacridone red organic pigments or diketopyrrolopyrrole red organic pigments are preferred from the viewpoint of dimensional stability.
  • C. I. Pigment Red 122, or C.I. I. Pigment Red 254 is more preferred.
  • C. I. Pigment Red 122 includes TCR12203 Red (manufactured by Trustchem)
  • C.I. I. Pigment Red 207 includes Sincacious Scarlet L3080 (manufactured by DIC)
  • C.I. I. Pigment Red 209 includes Hostapalm Red EG Transparent (manufactured by Clariant)
  • C.I. I. Pigment Red 149 includes Sincacious Scarlet L3080 (manufactured by DIC)
  • C.I. I. Pigment Red 178 includes Palyogen Red K3911 (manufactured by BASF)
  • C.I. I. Pigment Red 48:2 includes Lionor Red DWG (manufactured by Toyo Color Co., Ltd.), C.I. I.
  • Pigment Red 144 includes Chromophthal Red D3635 (manufactured by BASF), C.I. I. Pigment Red 151 includes Red 202 (manufactured by Arimoto Kagaku Kogyo Co., Ltd.), C.I. I. Pigment Red 166 includes Chromophthal Scarlet D3540 (manufactured by BASF), C.I. I. Pigment Red 208 includes Shimla Fast Red 4598 (manufactured by DIC), C.I. I. Pigment Red 221 includes Chromophthal Red K3830 (manufactured by BASF), C.I. I. Pigment Red 177 includes First Gen Super Red ATY (manufactured by Clariant), C.I. I.
  • Pigment Red 38 includes Graftol Red HFG (manufactured by Clariant), C.I. I. Pigment Red 254 includes Chromophthal Red 2028 (manufactured by BASF), C.I. I. Pigment Red 264 includes Irgazin DPP Rubin TR (manufactured by BASF) and the like.
  • C. I. Pigment Violet 15 includes Ultramarine Violet 12 (manufactured by Faroe)
  • C.I. I. Pigment Violet 19 includes Chromofine Violet 6845 (manufactured by Dainichiseika Chemical Co., Ltd.)
  • C.I. I. Pigment Violet 23 includes PV Fast Violet RL (manufactured by Clariant) and the like.
  • [Yellow pigment] As a yellow pigment, C. I. Monoazo yellow organic pigments such as Pigment Yellow 150, 151, 168, 169, 181, 183, C. I. Disazo yellow organic pigments such as Pigment Yellow 83, 180, 214, C. I. Nickel titanium yellow inorganic pigment such as Pigment Yellow 53, C. I. Condensed azo yellow organic pigments such as Pigment Yellow 93 and 95, C. I. Quinophthalone-based yellow organic pigments such as Pigment Yellow 138, C. I. Isoindolinone yellow organic pigments such as Pigment Yellow 109, 110, and 139, C. I. Bismuth-based yellow organic pigment such as Pigment Yellow 184, etc.
  • monoazo yellow organic pigments or disazo yellow organic pigments are preferred from the viewpoint of dimensional stability.
  • C. I. Pigment Yellow 180 or. I. Pigment Yellow 181 is more preferred.
  • C. I. Pigment Yellow 150 includes Chromophthal Yellow D 1085 J (manufactured by BASF), C. I. Pigment Yellow 151 includes Chromophthal Yellow L 1061 HD (manufactured by BASF), C.I. I. Pigment Yellow 168 includes Paliotol Yellow K1070 (manufactured by BASF), C.I. I. Pigment Yellow 169 includes Lionor Yellow K2R (manufactured by Toyo Color Co., Ltd.), C.I. I. Pigment Yellow 181 includes TCY18001E Yellow (manufactured by Trustchem), C.I. I. Pigment Yellow 183 includes Paliotol Yellow 1700 (manufactured by BASF), C.I. I.
  • Pigment Yellow 83 includes Chromofine Yellow (manufactured by Dainichiseika Kaisha), C.I. I. Pigment Yellow 180 includes Chromophthal Yellow K1410 (manufactured by BASF), C.I. I. Pigment Yellow 214 has P. V. First Yellow H9G VP2430 (manufactured by Clariant), C. I. Pigment Yellow 53 includes Shikotan Yellow K1010 (manufactured by BASF), C.I. I. Pigment Yellow 93 includes Chromofine Yellow 5930 (manufactured by Dainichiseika Chemical Co., Ltd.), C.I. I.
  • Pigment Yellow 95 includes Chromofine Yellow 5900 (manufactured by Dainichiseika Chemical Co., Ltd.), C.I. I. Pigment Yellow 138 includes Paliotol Yellow K0961 (manufactured by BASF), C.I. I. Pigment Yellow 109 includes Irgazin Yellow K1170 (manufactured by BASF), C.I. I. Pigment Yellow 110 is Irgazin Yellow K2060 (manufactured by BASF) C. I. Pigment Yellow 139 includes Paliotol Yellow K1841 (manufactured by BASF), C.I. I. Pigment Yellow 184 includes Lithopac Yellow 6601B (manufactured by Faroe Co., Ltd.).
  • Green pigment As a green pigment, C. I. Phthalocyanine-based green organic pigments such as Pigment Green 7 and 36, C. I. Cobalt green inorganic pigment such as Pigment Green 50, etc. Among these, phthalocyanine-based green organic pigments are preferred from the viewpoint of dimensional stability. Among them, C. I. Pigment Green 7 is more preferred.
  • Pigment Green 7 includes First Gen Green BN (manufactured by DIC)
  • Pigment Green 36 includes First Gen Green 2YK (manufactured by DIC)
  • Pigment Green 50 includes Cico Pearl Green L9715 (manufactured by BASF).
  • orange pigment As an orange pigment, C. I. Examples include monoazo orange organic pigments such as Pigment Orange 64.
  • the black resin composition of the present invention includes alkali metal, alkaline earth metal, or zinc metal soap, hydrotalcite, nonionic surfactant, cationic surfactant, anionic surfactant, and so on, as long as the effects of the present invention are not impaired.
  • Additives such as a polyamide surfactant, an amphoteric surfactant, an antistatic agent, a halogen-based, phosphorus-based or metal oxide flame retardant, an antioxidant, an ultraviolet absorber, and a filler can be contained.
  • a molded article is molded using the black resin composition of the present invention.
  • the molding method is not particularly limited, and the molded article can be obtained by extrusion molding, compression molding, injection molding, blow molding, and the like.
  • the molded article may be formed as it is from a black resin composition kneaded with the pigment (B) at a temperature at which the polyolefin resin (A) melts, or a master batch containing the pigment (B) at a high concentration may be used.
  • a molded body may be formed from a black resin composition which is then kneaded with a polyolefin resin as a diluted resin at a prescribed ratio during molding of the molded body. Further, the diluent resin at this time may be the same resin as the polyolefin resin (A) constituting the masterbatch, or may be a different resin, but it is preferably the same resin.
  • the content of the polyolefin resin (A) in 100% by mass of the masterbatch is preferably 20% by mass or more, more preferably 30 to 60% by mass. When the blending amount of the polyolefin resin (A) is 20% by mass or more, the processability during masterbatch production will be better.
  • the content of the polyolefin resin (A) is more preferably 40% by mass or more. Moreover, it is preferable that it is 80 mass % or less. When the blending amount of the polyolefin resin (A) is within this range, the processability during masterbatch production will be better.
  • the content of pigment (B) in 100% by mass of the masterbatch is preferably 1 to 60% by mass, more preferably 5 to 50% by mass based on 100% by mass of the black resin composition.
  • the content of the polyolefin resin (A) in 100% by mass of the molded product is preferably 60% by mass or more and less than 100% by mass, more preferably 90% by mass or more.
  • the blending amount of the polyolefin resin (A) is 60% by mass or more, it is easy to maintain sufficient strength of the molded article.
  • the molded article formed from the black resin composition of the present invention is excellent in suppressing warpage and shrinkage and has good dimensional stability, so it can be molded by compression molding or injection molding. It can be suitably used for automobile parts, nozzles, caps, pallets, mechanical parts, etc., as well as bottles, pots, tanks, etc. molded by blow molding (direct blow, injection blow).
  • the molded product has excellent design and dimensional stability, it can be used in a variety of applications such as automobile parts, nozzles, caps, pallets, mechanical parts, bottles, pots, and tanks. Among these, it is preferable to use it as a cap, and furthermore, it can suppress the cap from shrinking over time and increasing the torque when opening the cap, so it is a cap for beverages that requires higher precision and dimensional stability. can also be suitably used.
  • a black resin composition containing a polyolefin resin (A) and a pigment (B), A molded article with a length of 150 mm, a width of 120 mm, and a thickness of 2 mm formed from a black resin composition by an injection molding machine has an average transmittance of 1% or less in the wavelength range of 380 nm to 800 nm, and an average transmittance of the wavelength of 800 nm to 2500 nm.
  • Formula (1) ⁇ MDS
  • Formula (2) ⁇ TDS
  • the subsequent shrinkage rate in the same direction as the injection direction (MD direction) and the contraction rate in the direction perpendicular to the injection direction (TD direction), X0 and Y0 are respectively obtained by molding a polyolefin resin (A) using an injection molding machine, after leaving a molded body of 150 mm in length, 120 mm in width, and 2 mm in thickness at 23° C. and 50% RH for 24 hours. , the shrinkage rate in the same direction as the injection direction (MD direction), and the shrinkage rate in the direction perpendicular to the injection direction (TD direction).
  • the pigment (B) includes a blue pigment, and at least one of a red pigment and a purple pigment, The red pigment and the purple pigment are C.I. I.
  • Pigment Red 122, C. I. Pigment Red 254, and C.I. I. The black resin composition as described in [1] above, comprising at least one selected from the group consisting of Pigment Violet 19.
  • the black resin composition according to [2] above which contains 100 to 300 parts by mass of a blue pigment based on 100 parts by mass of the red pigment and the purple pigment.
  • [6] A cap that is the molded article described in [5] above.
  • the polyolefin resin when the polyolefin resin is colored with a plurality of pigments, it exhibits high transmittance in the near-infrared region, provides good design, and suppresses increases in dimensional stability and opening torque. It becomes possible to provide a black resin composition capable of forming a body, and a molded body formed from the same.
  • the pigment (B) is C.I. I. Pigment Brown 29, C. I. Pigment Black 11, C. I. Pigment Black 27, C. I. Pigment Black 33, C. I. Pigment Black 36, and C.I. I.
  • a molded article with a length of 150 mm, a width of 120 mm, and a thickness of 2 mm formed from a black resin composition by an injection molding machine has an average transmittance of 1% or less in the wavelength range of 380 nm to 800 nm, and an average transmittance of the wavelength of 800 nm to 2500 nm. 25% or more
  • Formula (1) ⁇ MDS
  • Formula (2) ⁇ TDS
  • the subsequent shrinkage rate in the same direction as the injection direction (MD direction) and the contraction rate in the direction perpendicular to the injection direction (TD direction), X0 and Y0 are respectively obtained by molding a polyolefin resin (A) using an injection molding machine, after leaving a molded body of 150 mm in length, 120 mm in width, and 2 mm in thickness at 23° C.
  • the pigment (B) further includes other pigments, The black resin composition according to [1] above, wherein the other pigment is at least one of an organic pigment (B2) and an other inorganic pigment (B1y) other than the inorganic pigment (B1x).
  • the other pigment includes at least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, a yellow pigment, and a green pigment.
  • the organic pigment (B2) consists of a phthalocyanine blue pigment, a phthalocyanine green pigment, a diketopyrrolopyrrole red pigment, an azo red pigment, a quinacridone red pigment, an azo yellow pigment, and a quinacridone purple pigment.
  • [5] A molded article formed from the black resin composition according to any one of [1] to [4] above.
  • [6] A cap that is the molded article described in [5] above.
  • the polyolefin resin when the polyolefin resin is colored with a pigment, it exhibits high transmittance in the infrared region, provides good design, has excellent dimensional stability, and suppresses increase in opening torque. It becomes possible to provide a black resin composition that can be formed into a molded object, and a molded object formed therefrom.
  • MFR Melt viscosity of polyolefin resin (A)
  • JIS Japanese Industrial Standard
  • B-3 Paliogenlet K3580 (manufactured by BASF, C.I. Pigment Red 149, perylene red pigment)
  • Pigment Red 166, condensed azo red pigment B-5: TCR12203 Red (manufactured by Trustchem, C.I. Pigment Red 122, quinacridone-based red pigment)
  • Pigment Yellow 110 isoindolinone yellow pigment
  • B-9 Paliotol Yellow K0961 (manufactured by BASF, C.I. Pigment Yellow 138, quinophthalone yellow pigment)
  • B-10 TCY18001E (manufactured by Trustchem, C.I. Pigment Yellow 181, monoazo yellow pigment)
  • B-11 Chromophthal Yellow K1410 (manufactured by BASF, C.I. Pigment Yellow 180, disazo yellow pigment)
  • B-12 Chromophthal Yellow K1500 (manufactured by BASF, C.I. Pigment Yellow 95, condensed azo yellow pigment) [Other pigments]
  • B-13 First Gen Green BN (manufactured by DIC, C.I.
  • B-14 Chromophthal Orange K2960 (manufactured by BASF, C.I. Pigment Orange 64, monoazo orange pigment)
  • B-15 High black 200B (manufactured by Orion Engineered Carbons, C.I. Pigment Black 7, carbon black)
  • B1x-1 PS24-3950 (manufactured by Faroe Co., Ltd., C.I. Pigment Brown 29, iron-chromium composite pigment)
  • B1x-2 Byferox 306 (manufactured by LANXESS, C.I. Pigment Black 11, iron oxide pigment)
  • B1x-3 Dipyroxide black #9590 (manufactured by Dainichiseika Kagyo Co., Ltd., C.I.
  • B1x-4 Byferox 303T (manufactured by LANXESS, C.I. Pigment Black 33, manganese iron oxide composite pigment)
  • B1x-5 Taipei Black SG-101 (manufactured by Ishihara Sangyo Co., Ltd., C.I. Pigment Black 36, calcium titanium manganese composite pigment)
  • B1x-6 Shepard Black 10P922 (manufactured by Shepard Co., Ltd., C.I. Pigment Green 17, iron-chromium composite pigment), and the like.
  • B1y Inorganic pigment (B1y)] (Inorganic pigments other than inorganic pigments (B1x)) (red pigment)
  • B1y-1 Bayferox 105M (manufactured by LANXESS, C.I. Pigment Red 101, iron oxide) (blue pigment)
  • B1y-2 Shico Pearl Blue K6210 (manufactured by BASF, C.I. Pigment Blue 28, Cobalt Blue) (yellow pigment)
  • B1y-3 Dipyroxide Yellow #9120 (manufactured by Dainichiseika Chemical Industry Co., Ltd., C.I. Pigment Yellow 53, titanium nickel antimony composite pigment) (black pigment)
  • B1y-4 High black 200B (manufactured by Orion Engineered Carbons, C.I. Pigment Black 7, carbon black)
  • Example I Polyolefin resin (A-1) 99.4 parts, blue pigment (B-2) "Lionol Blue FG-7350 (manufactured by Toyo Color Co., Ltd., C.I. Pigment Blue 15:3, phthalocyanine blue pigment)" 0. 3 parts, red pigment (B-5) "TCR12203 manufactured by Red Trustchem Co., Ltd., C.I. Pigment Red 122, quinacridone red pigment)” 0.2 parts, yellow pigment (B-10) "TCY18001E (manufactured by Trustchem Co., Ltd.)” , C.I.
  • Pigment Yellow 181, monoazo yellow pigment were mixed and extruded at 200°C using a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) and granulated to form black pellets.
  • a resin composition (C-1) was obtained.
  • Examples I-2 to 16 Comparative Examples I-1 to 5> Pellet-shaped black resin compositions (C-2 to 21) were obtained in the same manner as in Example 1, except that the materials and amounts (parts by mass) shown in Tables I-1 and 2 were changed.
  • molded body (cap-shaped molded body)
  • the manufacturing conditions for the molded product (cap-shaped molded product) were as follows: 20 pieces were continuously injection molded using an injection molding machine (manufactured by Toshiba Machinery Co., Ltd.) at a molding temperature of 220°C and a mold temperature of 20°C. A thermoplastic resin suitable as a sealing material was in-shell molded on the inner surface, a liner was formed, and a cap-shaped molded body with a nominal diameter of 28 mm that could be wrapped around the mouth of a container was produced.
  • six of the 14th to 19th cap-shaped molded products were used after being molded and stored in a constant temperature room at 23° C. and 50% RH for one day.
  • ⁇ Measurement of shrinkage rate> Using six of the obtained plate-shaped molded bodies, the distance between the marked lines was measured using a precision caliper, and the average value of the shrinkage percentage in the injection direction and in the direction perpendicular to the injection direction was determined from the measured value.
  • the formula for calculating the shrinkage difference rate is as follows.
  • Formula (1) ⁇ MDS
  • Formula (2) ⁇ TDS
  • the subsequent shrinkage rate in the same direction as the injection direction (MD direction) and the contraction rate in the direction perpendicular to the injection direction (TD direction), X0 and Y0 are respectively obtained by molding a polyolefin resin (A) using an injection molding machine, after leaving a molded body of 150 mm in length, 120 mm in width, and 2 mm in thickness at 23° C. and 50% RH for 24 hours. , the shrinkage rate in the same direction as the injection direction (MD direction), and the shrinkage rate in the direction perpendicular to the injection direction (TD direction). )
  • Example I-1 a plate-shaped molded body 1 having a length of 150 mm, a width of 120 mm, and a thickness of 2 mm formed by molding a black resin composition (C-1) using an injection molding machine was molded for 23 hours after molding. After standing at 50% RH for 24 hours, the shrinkage rate in the same direction as the injection direction (MD direction) is X1, and the shrinkage rate in the direction perpendicular to the injection direction (TD direction) is Y1.
  • ⁇ Visible light average transmittance and near-infrared average transmittance> Using an ultraviolet-visible spectrophotometer UV-3150 manufactured by Shimadzu Corporation, the transmittance of the obtained plate-shaped molded body was measured at a pitch of 1 nm in the wavelength range of 380 nm to 2500 nm, and the average value of the measured transmittance was determined. I asked for The average transmittance in the wavelength range of 380 nm to 800 nm is listed in the table as the average transmittance in the visible light region, and the average transmittance in the wavelength range of 800 nm to 2500 nm as the near-infrared average transmittance.
  • ⁇ Cap opening torque> The obtained cap-shaped molded body was wrapped with a capper into a heat-resistant 350ml PET bottle manufactured by Toyo Seikan Co., Ltd. filled with 87°C hot water, and then heated at 75°C for 3.5 minutes and at 55°C for 4.5 minutes for 40 minutes. °C - 4.0 minutes, 30 °C - 6.0 minutes, 25 °C - 2.5 minutes with cooling shower treatment, using a torque meter (Nidec-Shimpo Corporation TNX-2), The cap was turned in the opening direction of the evaluation sample at room temperature, and the opening torque T0 at the beginning of movement was measured. Thereafter, the opening torque T1 of the sample was stored in a constant temperature room at 23° C.
  • T1-T0 is less than 0.2N ⁇ m ++: T1-T0 is 0.2N ⁇ m or more and less than 0.4N ⁇ m +: T1-T0 is 0.4N ⁇ m or more and less than 0.6N ⁇ m NG: T1-T0 is 0.6N ⁇ m or more
  • Pigment Green 7, phthalocyanine green pigment was mixed and extruded at 200 ° C. using a twin screw extruder (manufactured by Japan Steel Works, Ltd.) and granulated. A pellet-shaped black resin composition (D-1) was obtained.
  • Examples II-2 to 17 Pellet-shaped black resin compositions (D-2 to D-24) were obtained in the same manner as in Example 1, except that the materials and blending amounts (parts by mass) shown in Tables II-1 to II-3 were changed.
  • Example II-1 a molded body (plate-shaped molded body 1) with a length of 150 mm, a width of 120 mm, and a thickness of 2 mm is molded from a black resin composition (D-1) using an injection molding machine. After being allowed to stand at 23° C. and 50% RH for 24 hours, the shrinkage percentage in the same direction as the injection direction (MD direction) is X1, and the shrinkage percentage in the direction perpendicular to the injection direction (TD direction) is Y1.
  • the black resin composition of the present invention not only has excellent shielding properties in the visible light region, low brightness, and excellent design properties, but also The molded product was prevented from warping and had good dimensional stability.
  • waste plastics can be separated with high accuracy because it shows high transmittance in the near-infrared region and has excellent mechanical visibility under IR (infrared rays).
  • IR infrared rays

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Abstract

Un mode de réalisation de la présente invention concerne une composition de résine noire comprenant une résine de polyoléfine (A) et un pigment (B). Lorsque la composition de résine noire est moulée par une machine de moulage par injection pour former un corps moulé de 150 mm de long, de 120 mm de large et de 2 mm d'épaisseur, le corps moulé satisfait les caractéristiques suivantes : la transmittance moyenne dans une plage de longueurs d'onde de 380 à 800 nm est de 1 % ou moins, la transmittance moyenne dans une plage de longueurs d'onde de 800 à 2 500 nm est de 25 % ou plus, ΔMDS représenté par la formule (1) est de 0,35 % ou moins, et ΔTDS représenté par la formule (2) est de 0,35 % ou moins.
PCT/JP2023/021705 2022-06-13 2023-06-12 Composition de résine noire et corps moulé WO2023243589A1 (fr)

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JP2022-094866 2022-06-13
JP2022094866A JP7184221B1 (ja) 2022-06-13 2022-06-13 黒色樹脂組成物、および成形体
JP2022-194064 2022-12-05
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04345626A (ja) * 1991-05-23 1992-12-01 Achilles Corp シート状物
JP2014214244A (ja) * 2013-04-26 2014-11-17 クラリアント・ファイナンス・（ビーブイアイ）・リミテッド 顔料組成物及び顔料樹脂混合物
JP2022092732A (ja) * 2020-12-11 2022-06-23 東洋インキＳｃホールディングス株式会社 着色樹脂組成物および成形体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04345626A (ja) * 1991-05-23 1992-12-01 Achilles Corp シート状物
JP2014214244A (ja) * 2013-04-26 2014-11-17 クラリアント・ファイナンス・（ビーブイアイ）・リミテッド 顔料組成物及び顔料樹脂混合物
JP2022092732A (ja) * 2020-12-11 2022-06-23 東洋インキＳｃホールディングス株式会社 着色樹脂組成物および成形体

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