Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • 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
• • 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
• • 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
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/10—Encapsulated ingredients
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention relates to a method for producing a recycled resin composition, a method for producing a molded product, a recycled resin composition, and the like.
• resin products it is common for resin products to be downgraded and recycled due to the effects of colored layers and contamination of different types of resin. For example, it is common that film products and sheet products are collected, downgraded and recycled as resin for containers, and container products are collected, further downgraded and recycled as resin for building materials and miscellaneous goods. .
• Patent Document 1 describes a printed matter in which a reversible thermochromic color image using a reversible thermochromic microcapsule pigment as a coloring material is provided on a support.
• the color of the color image can be erased when the temperature is higher than the complete color erasing temperature, but the color develops when the temperature is lower than the complete color development temperature. It does not describe any concept of recycling and reuse.
• the resin used for horizontal recycling should be uncolored in order to have the same appearance as virgin material. have no choice but to recycle. From the viewpoint of effective use of used plastics, it is desirable to carry out horizontal recycling to reuse them for similar purposes without downgrading.
• the problem to be solved by the present invention is to provide a horizontally recyclable recycled resin composition manufacturing method, a molded product manufacturing method, a recycled resin composition, and the like.
• the present inventors have conducted extensive studies and have completed the present invention.
• the present invention includes, for example, the following.
• a recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation, and a step of irreversibly decoloring by thermal stimulation.
• a method of making the composition is a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation, and a step of irreversibly decoloring by thermal stimulation.
• a recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation at a temperature T (° C.) that satisfies the following condition (10): A method of making the composition.
• Condition (10): Ti ⁇ T Ti is the irreversible decoloring temperature of the coloring material.
• the recycled resin composition according to [1] or [2], wherein the coloring material that is irreversibly decolored by thermal stimulation contains (a) an electron-donating color-developing organic compound and (b) an electron-accepting compound. manufacturing method.
• any of [1] to [3], wherein the coloring material that is irreversibly decolored by thermal stimulation comprises (a) an electron-donating color-forming organic compound and (b) a microcapsule encapsulating an electron-accepting compound.
• a method for producing a recycled resin composition according to 1. [5] The recycled resin composition according to any one of [1] to [4], wherein the resin base material contains at least one resin selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester, and aliphatic polyamide. A method of making things.
• the recycled resin composition according to any one of [1] to [5], wherein the molded article comprising a resin substrate and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation is a film or a sheet. manufacturing method.
• a recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation, and a step of irreversibly decoloring by thermal stimulation.
• a recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation at a temperature T (° C.) that satisfies the following condition (10): A recycled resin composition obtained by a method for producing a composition. Condition (10): Ti ⁇ T Ti is the irreversible decoloring temperature of the coloring material.
• L * , a * , b * , ⁇ E are lightness (L * ) and chromaticity (L * ) and chromaticity ( a * and b * ), the color difference ( ⁇ E) (CIE 1976L * a * b * color space).
• Ti is the irreversible decoloring temperature of the coloring material.
• a recycled resin composition that can be horizontally recycled without being downgraded such as film-to-film recycling.
• the present inventors have found a manufacturing method of .
• a recycled resin composition that can be horizontally recycled can be produced. That is, the recycled resin composition and molded article produced by the production method of the present invention and the recycled resin composition of the present invention irreversibly lost the color of the coloring material even at room temperature to low temperature. remain.
• the method for producing the recycled resin composition of the present invention is the following [1] to [6].
• a recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation, and a step of irreversibly decoloring by thermal stimulation.
• a method of making the composition is the following [1] to [6].
• a recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation at a temperature T (° C.) that satisfies the following condition (10): A method of making the composition.
• Condition (10): Ti ⁇ T Ti is the irreversible decoloring temperature of the coloring material.
• the recycled resin composition according to [1] or [2], wherein the coloring material that is irreversibly decolored by thermal stimulation contains (a) an electron-donating color-developing organic compound and (b) an electron-accepting compound. manufacturing method.
• any of [1] to [3], wherein the coloring material that is irreversibly decolored by thermal stimulation comprises (a) an electron-donating color-developing organic compound and (b) a microcapsule encapsulating an electron-accepting compound.
• a method for producing a recycled resin composition according to 1. [5] The recycled resin composition according to any one of [1] to [4], wherein the resin base material contains at least one resin selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester, and aliphatic polyamide. A method of making things.
• the recycled resin composition according to any one of [1] to [5], wherein the molded article comprising a resin substrate and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation is a film or a sheet. manufacturing method.
• the resin substrate used in the present invention is overlaid with a colored layer to support the colored layer.
• the material is not particularly limited, it is preferably a resin film or a resin sheet, for example.
• the thickness of the resin base material is not particularly limited, but is preferably 1 ⁇ m or more and 10 mm or less, more preferably 2 ⁇ m or more and 1 mm or less, further preferably 5 ⁇ m or more and 200 ⁇ m or less, and 10 ⁇ m or more and 100 ⁇ m or less. is most preferred.
• the method for producing the resin base material is not particularly limited, and a conventional method for producing a base material may be used.
• the resin base material is, for example, a resin film or a resin sheet
• the resin base material can be produced by a usual method for producing films or sheets.
• extrusion molding methods such as the inflation method using a blown film manufacturing apparatus and the T die method using a T die cast film manufacturing apparatus can be mentioned.
• Corona treatment, ozone treatment, plasma treatment, flame treatment, electron beam treatment, and anchor coating are applied to the surface of the resin substrate before providing a colored layer printed with ink that is irreversibly decolored by thermal stimulation on the resin substrate.
• a pretreatment such as a treatment or a washing treatment may be performed, and from the viewpoint of adhesion between the resin base material and the colored layer and suppression of repelling of the liquid composition when the colored layer is a cured product of the liquid composition, these are used. Pretreatment is preferred.
• Molded article comprising a resin base material and a colored layer containing a coloring material irreversibly decolored by thermal stimulus
• the resin base material used in the present invention and a coloring material irreversibly decolored by thermal stimulus are included.
• the method for producing the molded article including the colored layer is not particularly limited, and a conventional method for producing a molded article may be used.
• the resin substrate is, for example, a resin film or a resin sheet
• a liquid composition containing a coloring material that is irreversibly decolored by thermal stimulation is applied, printed, dried and cured on the resin substrate to form a colored layer.
• the molded article can be produced by forming the molded article, or by laminating a separately formed colored layer to adhere the molded article.
• the thickness of the colored layer is not particularly limited, but is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, more preferably 0.2 ⁇ m or more and 50 ⁇ m or less, still more preferably 0.5 ⁇ m or more and 10 ⁇ m or less, Particularly preferably, the molded product containing a resin substrate having a thickness of 1 ⁇ m or more and 5 ⁇ m or less and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation is preferably a film or a sheet.
• the thickness of the molded body is not particularly limited, it is preferably 1 ⁇ m or more and 10 mm or less, more preferably 2 ⁇ m or more and 1 mm or less, further preferably 5 ⁇ m or more and 200 ⁇ m or less, and 10 ⁇ m or more and 100 ⁇ m or less. Most preferably.
• a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation may be provided on one (or part) surface of the resin substrate, or may be provided on both (or all) surfaces.
• a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation may be provided on a part of the surface of the resin base material, or may be provided on the entire surface.
• a plurality of colored layers containing a coloring material that is irreversibly decolored by thermal stimulation may be stacked, and it is preferable to stack colored layers of different colors in order to express many colors.
• different layers may be superimposed, for example, a different resin layer may be superimposed on the surface of the colored layer opposite to the resin base material, or a different material may be laminated via an adhesive layer. is mentioned.
• the weight ratio to the resin substrate is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less.
• the resin contained in the resin base material is not particularly limited, for example, Polyolefins such as polypropylene and polyethylene; Methyl (meth)acrylate polymer, ethyl (meth)acrylate polymer, octadecyl (meth)acrylate polymer, hexadecyl (meth)acrylate polymer, tetradecyl (meth)acrylate polymer, polymethyl methacrylate, crosslinked polymethyl methacrylate , acrylic and methacrylic resins such as polymethyl acrylate; Polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth)acrylate-styrene resin, styrene-butadiene-styrene resin, styrene-butadiene copolymer, etc.
• styrenic resin polyamides such as nylon; polycarbonate; Polyesters such as saturated polyesters and unsaturated polyesters; polyphenylene oxide; polyacetal; Chlorine resins such as polyvinyl chloride and polyvinylidene chloride; Vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate resin; Ethylene - methyl (meth) acrylate copolymer, ethylene - ethyl (meth) acrylate copolymer, ethylene - octadecyl (meth) acrylate copolymer, ethylene - hexadecyl (meth) acrylate copolymer, ethylene - tetradecyl ( ethylene-(meth)acrylic acid ester copolymers such as meth)acrylate copolymers, ethylene-octadecyl (meth)acrylate-methyl (meth)acrylate copolymers, and
• polyolefins acrylic/methacrylic resins, styrene resins, polyesters, chlorine resins, vinyl acetate resins, ethylene-(meth)acrylic acid ester copolymers and their ionomer resins, and vinyl alcohol resins are preferred.
• thermoplastic elastomers engineering plastics, polyamides, phenol resins, polyurethanes, urea resins, melamine resins, epoxy resins or silicone resins, more preferably polyolefins, acrylic/methacrylic resins, styrene resins, polyesters, polyamides , thermoplastic elastomer, engineering plastic or polyurethane, and more preferably contains at least one resin selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester, and aliphatic polyamide.
• the resin base material contains at least one resin selected from the group consisting of polyethylene, polypropylene, polyester, and aliphatic polyamide. More particularly preferably, the resin base material contains at least one resin selected from the group consisting of polyethylene, polypropylene and polyester. Most preferably, the resin base material contains at least one resin selected from the group consisting of polyethylene and polypropylene.
• the resin substrate is polyethylene or polypropylene. , polystyrene, polyvinyl chloride, polyester, and aliphatic polyamide in a proportion of 70% by weight or more of the resin contained in the base material, preferably 80% by weight or more. It is more preferably contained in a proportion, more preferably in a proportion of 90% by weight or more, and particularly preferably in a proportion exceeding 95% by weight.
• a polyolefin resin when used, it preferably contains 70 mol% or more, preferably 97 mol% or more, of structural units derived from the same monomer (e.g., ethylene) among the polymers contained in the layer. , more preferably 98 mol % or more, more preferably 99 mol % or more.
• the polymer may be composed of structural units derived from 100 mol % of the same monomer.
• the film formation stability can be enhanced and rigidity can be imparted when the polymer is formed into a film. Two or more types of polymers derived from the same monomer may be used in combination.
• At least one of the two or more polymers should contain 70 mol % or more of structural units derived from the same monomer.
• the content of the polymer containing 70 mol% or more of structural units derived from the same monomer is 100% by weight in total of the two or more types of ethylene polymers. , preferably 60% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more.
• the resin base material may be a single layer or a multilayer consisting of a plurality of layers.
• Materials contained in each layer in the case of a multilayer body are not particularly limited, but examples thereof include resins such as those described above.
• a monomaterial resin base material containing one type of resin as a main component in order to suppress changes in the physical properties of the resin before and after recycling.
• one kind of resin selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester, and aliphatic polyamide is included in the resin contained in the base material at a rate of 70% by weight or more.
• the method for molding the multilayer body is not particularly limited, and a conventional method for manufacturing a multilayer resin molded body may be used.
• the resin substrate is, for example, a resin film or a resin sheet
• the resin substrate can be produced by a usual method for producing multilayer films or sheets. Examples thereof include a multilayer inflation method using a multilayer inflation film manufacturing apparatus and an extrusion molding method such as a multilayer T-die method using a multilayer T die-cast film manufacturing apparatus. Further, it is also possible to manufacture by subsequently applying other layers on a resin molded body formed into a single layer by a method such as coating, printing, laminating, vapor deposition, insert molding, or the like.
• the resin base material may contain at least one additive within a range that does not impair the purpose and effect of the present invention.
• Additives include inorganic fillers, lubricants, stabilizers (antioxidants, HALS), surfactants, antistatic agents, processability improvers, quenchers, ultraviolet absorbers, visible light absorbers, infrared absorbers, and anti-blocking agents and the like.
• the irreversible discoloration temperature (Ti) of the coloring material is not particularly limited, but is preferably 50° C. or higher, more preferably 100° C. or higher, from the viewpoint of preventing discoloration during use of the resin molding. , more preferably 150° C. or higher, and particularly preferably 180° C. or higher. From the viewpoint of reducing energy consumption during melt-kneading, the temperature is preferably 350° C. or lower, preferably 300° C. or lower, and more preferably 250° C. or lower.
• the decomposition temperature (Tp) of the resin base material described later is preferably below the decomposition temperature (Tp) of the resin base material described later, more preferably (Tp-10) ° C. or below, and (Tp-20). It is more preferably not higher than (Tp-30)°C, particularly preferably not higher than (Tp-30)°C, and most preferably not lower than (Tp-50)°C. Furthermore, from the viewpoint of ensuring the irreversibility of decoloration, it is preferably at least the decomposition initiation temperature (Td) of the colored layer, which will be described later.
• the irreversible decoloring temperature is measured by drying the ink on an appropriate base material and setting the oven temperature from 30°C to 10°C in increments. After heating in the oven for 30 minutes, dry ice After performing the cooling operation for 10 minutes above, the color difference ⁇ E in the CIE1976L*a*b* color space from before heating is 5 or more, L* ⁇ 35 after cooling, and (a* 2 + b* 2 ) by finding the lowest temperature that satisfies 0.5 ⁇ 25;
• the decomposition temperature (Tp) of resin base material is not particularly limited, but is preferably 200° C. or higher, more preferably 250° C. or higher, and even more preferably 280° C. or higher, from the viewpoint of heat resistance of the recycled resin.
• the decomposition initiation temperature was measured using a thermogravimetry/differential thermal analysis (TG-DTA) device, with a nitrogen flow rate of 200 mL/min and a temperature increase rate of 10°C/min. The weight change was measured while warming and the temperature at which the weight loss reached 5% of the initial weight of the sample was determined.
• TG-DTA thermogravimetry/differential thermal analysis
• the decomposition initiation temperature (Td) of the colored layer is not particularly limited, but is preferably 50° C. or higher, more preferably 100° C. or higher, more preferably 150° C. or higher, from the viewpoint of preventing deterioration of the resin molding during use. is more preferable, and 180° C. or higher is particularly preferable. Also, the temperature is preferably 350° C. or lower, more preferably 300° C. or lower, and more preferably 250° C. or lower. In addition, from the viewpoint of preventing deterioration of the resin after recycling, it is below the decomposition temperature (Tp) of the resin base material described later, preferably (Tp-10) ° C.
• the decomposition initiation temperature was measured using a thermogravimetry/differential thermal analysis (TG-DTA) device at a nitrogen flow rate of 200 mL/min and a temperature increase rate of 10°C/min. ) was measured while the temperature was raised, and the temperature at which the weight reduction reached 3% of the initial weight of the sample was investigated.
• TG-DTA thermogravimetry/differential thermal analysis
• the resin temperature (T) in the step of melt-kneading a molded body containing a resin base material and a colored layer preferably satisfies the following conditions.
• the decomposition initiation temperature (Td) of the colored layer or higher is preferably the decomposition initiation temperature (Td) of the colored layer or higher, more preferably Td + 10 ° C. or higher, and particularly preferably Td + 20 ° C. or higher.
• the resin temperature (T) can be 150° C. or higher and 350° C. or lower, preferably 180° C. or higher and 330° C. or lower, more preferably 190° C. or higher and 300° C. or lower, and 200° C. or higher. It is particularly preferably 280°C or lower, and most preferably 210°C or higher and 250°C or lower.
• This resin temperature represents the actual temperature of the resin during the heating process, and can be measured by bringing a thermocouple into contact with the resin.
• the melting point of the resin substrate is the apex of the melting peak obtained by analyzing the melting curve of the resin material used for the resin substrate measured by the following differential scanning calorimetry by a method conforming to JIS K7121-1987. is the temperature at which the melting endotherm is maximum.
• the melting peak temperature is the peak temperature of the melting peak with the maximum melting endotherm.
• the midpoint glass transition obtained by analyzing the melting curve measured by the following differential scanning calorimetry by a method conforming to JIS K7121-1987 The temperature is taken as the melting point.
• the shear stress applied in the process of melt-kneading the molded body containing the resin base material and the colored layer causes the resin temperature to rapidly increase and irreversibly decolorize due to shear heat generation.
• the viscosity is preferably 600,000 Pa or less, more preferably 500,000 Pa or less, and even more preferably 400,000 Pa or less.
• the heater setting temperature (Ts) of the processing machine in the melt-kneading step is not particularly limited, but preferably satisfies any one of the following conditions, and more preferably satisfies a plurality of conditions. Ti-100 ⁇ Ts ⁇ Tp Td-100 ⁇ Ts ⁇ Tp More preferably, any one of the following conditions is satisfied. Ti-50 ⁇ Ts ⁇ Tp Td-50 ⁇ Ts ⁇ Tp
• Mixers such as Banbury mixers, super mixers, kneaders, single-screw extruders, twin-screw extruders, multi-screw extruders, planetary mixers, butterfly mixers, dissolvers, roll mills, and mixing pots can be used for melt-kneading. . It is preferred to use a twin-screw extruder or a multi-screw extruder for continuous production at high shear stress. The resulting resin composition may be molded into powder, pellets, lumps, or the like.
• the present invention also provides the following method for producing a molded article. [10] obtaining a recycled resin composition by melt-kneading a first molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation; and a step of molding a recycled resin composition at a resin temperature Tf (° C.) satisfying the following condition (11) to obtain a second molded body.
• Tf ° C.
• Resin base material, colored layer, molded body containing resin base material and colored layer, conditions for melt-kneading, and irreversible decoloring temperature of coloring material which are used in the method for producing the second molded body of the present invention.
• Tf the same as those described above can be applied.
• Tf the resin temperature
• the molding conditions in the step of obtaining the other molded body are not particularly limited, and ordinary conditions for obtaining a molded body may be used.
• the shape of the separate molded body is not particularly limited, but a shape similar to that of the recycled resin composition described below can be applied.
• the shape of the recycled resin composition is not particularly limited, but the recycled resin composition may be, for example, in the form of strands, sheets, films, flat plates, or pellets.
• a pellet-shaped resin composition can be produced, for example, by forming a strand-shaped resin composition and then cutting it into an appropriate length.
• the shape of the recycled resin composition is preferably pellets with a length of about 1 to 50 mm. Moreover, it is preferable that the shape is the same as that of the resin base material, and it is more preferable that the shape is film-like or sheet-like.
• various components may be added during production of the recycled resin composition.
• such components include neutralizers, antioxidants, ultraviolet absorbers, nucleating agents, lubricants, antistatic agents, antiblocking agents, processing aids, organic peroxides, foaming agents, foam nuclei. agents, plasticizers, flame retardants, cross-linking agents, cross-linking aids, brighteners, antibacterial agents and light diffusing agents, thermoplastic resins, and fillers. Only one of these components may be contained, or two or more may be contained.
• the recycled resin composition of the present invention has the following [7] to [9]: [7] A recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation, and a step of irreversibly decoloring by thermal stimulation. A recycled resin composition obtained by a method for producing a composition.
• a recycled resin comprising a step of melt-kneading a molded body containing a resin base material and a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation at a temperature T (° C.) that satisfies the following condition (10): A recycled resin composition obtained by a method for producing a composition. Condition (10): Ti ⁇ T Ti is the irreversible decoloring temperature of the coloring material.
• L * , a * , b * , ⁇ E are lightness (L * ) and chromaticity (L * ) and chromaticity ( a * and b * ), the color difference ( ⁇ E) (CIE 1976L * a * b * color space).
• Ti is the irreversible decoloring temperature of the coloring material.
• the resin substrate, the colored layer, the molded body containing the resin substrate and the colored layer the melt-kneading conditions, the irreversible decoloring temperature (Ti) of the coloring material, and the decomposition initiation temperature
• the decomposition initiation temperature (Tp) of the resin base material, the heating temperature in the heating step, and the shear stress the same ones as described above can be applied.
• Color difference ⁇ E Colorimetric values (L 1 * , a 1 *, b 1 * ) and (L 2 * , a 2 * , b 2 * ) in CIE1976L * a * b * color space at two points measured with a colorimeter are ⁇ E represented by the following formula is defined as the color difference at two points. The larger the color difference, the easier it is to visually distinguish between the colors, and the smaller the color difference, the more difficult it is to visually distinguish.
• ⁇ E (( L2 * -L1 * ) 2+ ( a2 * -a1 * ) 2+ ( b2 * -b1 * ) 2 ) 0.5
• L* ⁇ 70 at 23° C. is preferably ⁇ 75, more preferably ⁇ 80, still more preferably ⁇ 85, and particularly preferably ⁇ 88.
• the values of L* and (a *2 + b *2 ) 0.5 are within the preferable range, the color of the recycled resin composition approaches white, so the recycled resin composition is molded and printed thereon. Good visibility when applied.
• the colored layer in the present invention is not particularly limited, but contains, for example, an organic dye.
• Organic dyes include, for example, azo-, styryl-, anthraquinone-, quinophthalone-, indigo-, polyene-, and cyanine-based dyes having a structure having a coloring system used for dyes.
• the organic pigment used in the colored layer of the present application is preferably an organic pigment in view of printability on resin.
• organic pigments applicable to the present invention include azo lake pigments, azo pigments including insoluble azo pigments or condensed azo pigments, phthalocyanine pigments, quinacdrine pigments, dioxazine pigments, isoindolinone pigments, threne pigments, pyrocholine pigments, Examples include polycyclic pigments including fluorbine pigments, metal complex pigments, quinophthalone pigments, isoindoline pigments, dyeing lake pigments including acid dye lake pigments, basic dye lake pigments, and the like.
• the colored layer in the present invention is not particularly limited, but can be a layer obtained by laminating a coloring agent using pigments that develop yellow, magenta, and cyan colors as coloring materials on a resin substrate. It is preferable to laminate a plurality of colorants that develop different colors in order to express various colors. In particular, it is more preferable to use all of the coloring agents that develop the three colors described above and print in layers, because full-color printing can be performed. It is also preferable to use a colorant that develops a black color, since a clear monochrome image can be obtained. All of the coloring materials used in the colored layer in the invention are preferably irreversibly decolorable. More preferably, all of the colorants used are colorants that are irreversibly decolorized by heat.
• yellow organic pigments include the following pigments. Hansa Yellow, Hansa Brilliant Yellow, Permanent Yellow, Fast Yellow, Lionol Yellow, Disazo Yellow, Cromophthal Yellow, Hostapalm Yellow, Irgadin Yellow, Fastogen Super Yellow, Sandrine Yellow, Flavanthrone, Phthaloylamide Anthraquinone, Anthrapyrimidine , paliotol yellow, phthalimidoquinophthalone, isoindoline.
• magenta organic pigments include the following pigments.
• cyan organic pigments include the following pigments. Phthalocyanine blue, phthalocyanine green, phthalocyanine lake, dioxane violet, methyl violet lake, indanthrone blue, methyl violet phosphomolybdate lake, methyl violet phosphotungstate lake, methyl violet tannate lake. It is also preferred that the organic dye contains (a) an electron-donating color-developing organic compound and (b) an electron-accepting compound. Furthermore, the colored layer in the present invention preferably contains microcapsules encapsulating (a) an electron-donating color-developing organic compound and (b) an electron-accepting compound.
• the colored layer in the present invention is, for example, "(a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, A coloring material using thermochromic microcapsule pigments that develop colors in yellow, magenta, and cyan, respectively, containing a reversible thermochromic composition consisting of a compound that is a reaction medium generated in the base material. It can be a layer obtained by printing.
• the heating temperature in the method for producing a recycled resin composition of the present invention is preferably higher than the above-mentioned "specific temperature range".
• the color change in the "specific temperature range" of the thermochromic microcapsule pigment may be reversible, and in the present invention, it is preferable that "reversible” becomes “irreversible” by heating at a higher temperature.
• thermochromic microcapsule pigment As the reversible thermochromic microcapsule pigment, a predetermined temperature (color change point) described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc. It changes color before and after that, exhibits a decoloring state in a temperature range above the high temperature side color change point, and a color development state in a temperature range below the low temperature side color change point.
• a reversible thermochromic microcapsule pigment encapsulating a color-changing composition can also be applied.
• the complete discoloration temperature (t 4 ) in order to allow only a specific one state of the reversible thermochromic microcapsule pigment to exist in the ordinary temperature range (around 25°C), the complete discoloration temperature (t 4 ) must be 40°C or higher. And, the color development start temperature (t 2 ) is preferably 5° C. or less.
• the complete color disappearance temperature (t 4 ) is 40° C. or more and the color development start temperature (t 2 ) is 5° C. or less in order to maintain the color development state at room temperature will be explained. If the heating is stopped after passing through the decoloring start temperature (t 3 ) and before reaching the complete decoloring temperature (t 4 ), a phenomenon of returning to the first state occurs again, and coloring starts from the decolored state.
• the complete color disappearance temperature (t 4 ) exceeds the normal temperature range. If it is 40° C. or higher, the coloring state is maintained under normal use conditions, and if the color development start temperature (t 2 ) is 5° C. or less below the normal temperature range, the color disappearing state is maintained under normal use conditions. maintained.
• a higher temperature is preferable in order to maintain the coloring state under normal use conditions, and 50° C. or higher is preferable, and 55° C. or higher is preferable. It is more preferable, and 60° C. or higher is even more preferable.
• a lower temperature is preferable in order to maintain the decolored state under normal use conditions, preferably 0° C. or less, and ⁇ 5° C. or less. is more preferred.
• the complete coloring temperature (t 1 ) is -50°C to 5°C, preferably -50°C to 0°C, more preferably -50°C to -5°C.
• the hysteresis width ( ⁇ H) is in the range of 40°C to 100°C, preferably 50°C to 100°C, more preferably 60°C to 100°C.
• Examples of the yellow (a) electron-donating color-forming organic compound include pyridine-based compounds, quinazoline-based compounds, and bisquinazoline-based compounds.
• pyridine-based compound 4-(4′-methylbenzylaminophenyl)-pyridine, 2,6-diphenyl-4-(4′-dimethylaminophenyl)-pyridine, 2,6-diphenyl-4-(4′-phenyl,methylaminophenyl)-pyridine, 2,6-bis(2′-methyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine, 2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine, 2,6-bis(2′-propyloxyphenyl)-4-(4′-dimethylaminophenyl)-pyridine, 2,6-bis(2′-butyloxyphenyl)-4-(4′-d
• Benzofluorane-based compounds and indolylphthalide-based compounds can be exemplified as the (a) component for magenta.
• benzofluorane-based compound 6-dimethylamino-1,2-benzofluorane, 6-diethylamino-1,2-benzofluorane, 6-di-n-propylamino-1,2-benzofluorane, 6-di-n-butylamino-1,2-benzofluorane, 6-di-n-hexylamino-1,2-benzofluorane, 6-N-isobutyl-N-ethylamino-1,2-benzofluorane, 6-N-isoamyl-N-ethylamino-1,2-benzofluorane, 6-Nn-hexyl-N-ethylamino-1,2-benzofluorane, 6-dimethylamino-3,4-benzofluorane, 6-diethylamino
• indolylphthalide compound 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-propyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-isobutyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-pentyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-hexyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-octyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-ethyl-2-ethylindol-3-yl)phthalide, 3,3-bis(1-propyl-2-ethylindol-3-yl)phthalide, 3,3-
• Examples of the cyan (a) component include indolylphenylphthalide compounds and indolylphenylazaphthalide compounds. Indolylphenylazaphthalide-based compounds are preferred as the cyan component (a) from the viewpoint of color development.
• indolylphenylphthalide compound 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-di-n-butylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-N-phenyl-N-ethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-n-butyl-2-methylindol-3-yl)phthalide, 3-(4-di-n-butylaminophenyl)-3-(1-n-butyl-2-methylindol-3-yl)phthalide, 3-(4-N-phenyl-N-ethylaminophenyl)-3-(1-n-butyl-2-methyl
• indolylphenylazaphthalide compound 3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylamino-2-ethylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-di-n-butylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-di-n-butylamino-2-ethylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylamino-2-methylphenyl)-3-(1-n-butyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethy
• a fluoran-based compound can be exemplified as the black-colored (a) component, 2-anilino-3-methyl-6-dimethylamino-fluorane, 2-anilino-3-methyl-6-diethylamino-fluorane, 2-anilino-3-methyl-6-di-n-butylamino-fluorane, 2-anilino-3-methyl-6-N-ethyl-N-propylamino-fluorane, 2-anilino-3-methyl-6-N-ethyl-N-isobutylamino-fluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylamino-fluorane, 2-an
• Examples of the electron-accepting compound of the component (b) include a group of compounds having an active proton, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as acids in the composition to develop a color in the component (a)), There is a group of compounds having electron vacancies.
• a compound having an active proton is preferably a compound having a phenolic hydroxyl group.
• Compounds having a phenolic hydroxyl group include monophenols to polyphenols, and further have alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and their esters or amide groups, halogen groups, etc. as their substituents.
• a compound having a bis-type phenol structure is more preferable as the compound having a phenolic hydroxyl group.
• a compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazoles and derivatives thereof, and the like.
• Component (c) is preferably alcohols or esters.
• the coloring material may contain only one kind of component (c), or may contain two or more kinds. It is preferable that the coloring material contains two or more kinds of the component (c).
• low-molecular-weight components evaporate out of the capsule when subjected to high heat treatment, so a compound having 10 or more carbon atoms is preferably used in order to stably retain the component in the capsule.
• aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective, and specific examples include decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and hexadecyl. alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol and the like.
• aliphatic monovalent saturated alcohols having 12 or more carbon atoms are more preferable
• aliphatic monovalent saturated alcohols having 14 or more carbon atoms are more preferable
• aliphatic monovalent saturated alcohols having 16 or more carbon atoms are particularly preferred.
• esters esters having 10 or more carbon atoms are effective, and any combination of monohydric carboxylic acid having aliphatic and alicyclic or aromatic ring and monohydric alcohol having aliphatic and alicyclic or aromatic ring Esters obtained from any combination of polycarboxylic acids having aliphatic and alicyclic or aromatic rings and monohydric alcohols having aliphatic and alicyclic or aromatic rings, aliphatic and alicyclic Alternatively, esters obtained from any combination of a monovalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aliphatic, alicyclic or aromatic ring can be mentioned, specifically ethyl caprylate, octyl caprylate, capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, stearyl
• esters obtained from a combination of an aliphatic monohydric carboxylic acid and an aliphatic monohydric alcohol are preferred.
• both the carboxylic acid and the alcohol constituting these groups preferably have 10 or more carbon atoms, more preferably 12 or more carbon atoms, and even more preferably 14 or more carbon atoms.
• esters of saturated fatty acids and branched fatty alcohols, esters of unsaturated fatty acids or branched or substituted saturated fatty acids with branched or branched fatty alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate, and Ester compounds selected from behenyl butyrate are also effective.
• a carboxylic acid ester compound exhibiting a ⁇ T value (melting point - cloud point) of 5°C or higher and lower than 50°C such as A carboxylic acid ester containing a substituted aromatic ring, an ester of a carboxylic acid containing an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester containing a cyclohexyl group in the molecule, a fatty acid having 6 or more carbon atoms and Esters of unsubstituted aromatic alcohols or phenols, fatty acids with 8 or more carbon atoms and branched aliphatic alcohols or esters, esters of dicarboxylic acids and aromatic alcohols or branched aliphatic alcohols, dibenzyl cinnamate, heptyl stearate, didecyl adipate
• Fatty acid ester compounds having 17 to 23 total carbon atoms obtained from group carboxylic acids are also effective.
• ketones aliphatic ketones having a total carbon number of 10 or more are effective.
• ethers As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether.
• ditridecyl ether ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decanediol dimethyl ether, undecanediol dimethyl ether, dodecanediol dimethyl ether, tridecanediol dimethyl ether, decanediol diethyl ether, undecanediol diethyl ether etc. can be mentioned.
• a compound represented by the following general formula (1) can also be used as the component (c).
• R 1 represents a hydrogen atom or a methyl group
• m represents an integer of 0 to 2
• one of X 1 and X 2 is -(CH 2 ) n OCOR 2 or -(CH 2 ) n COOR 2 and the other represent a hydrogen atom
• n represents an integer of 0 to 2
• R 2 represents an alkyl group or alkenyl group having 4 or more carbon atoms
• Y 1 and Y 2 represent a hydrogen atom, and have 1 to 4 carbon atoms.
• r and p are integers of 1-3.
• R 1 when R 1 is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R 1 is a hydrogen atom, and , m are more preferably 0.
• the compounds represented by the formula (1) the compounds represented by the following general formula (2) are more preferably used.
• R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.
• the compounds include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, and dodecanoic acid.
• a compound represented by the following general formula (3) can also be used as the component (c).
• R represents an alkyl group or alkenyl group having 8 or more carbon atoms
• m and n each represent an integer of 1 to 3
• X and Y are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon Alkoxy groups of numbers 1 to 4, halogen.
• Specific examples of the compounds include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, and 1,1-dodecanoate.
• Diphenylmethyl, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, octadecanoic acid 1,1-diphenylmethyl can be exemplified.
• a compound represented by the following general formula (4) can also be used as the component (c).
• X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom
• m represents an integer of 1 to 3
• n represents an integer of 1 to 20.
• the compounds include a diester of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl)]ethanol, a diester of succinic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of succinic acid and 2- [4-(3-methylbenzyloxy)phenyl)]ethanol diester, glutaric acid and 2-(4-benzyloxyphenyl)ethanol diester, glutaric acid and 2-[4-(4-chlorobenzyloxy) phenyl)]ethanol, adipic acid with 2-(4-benzyloxyphenyl)ethanol, pimelic acid with 2-(
• a compound represented by the following general formula (5) can also be used as the component (c).
• R represents an alkyl or alkenyl group having 1 to 21 carbon atoms
• n represents an integer of 1 to 3.
• the compounds include diesters of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, diesters of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, 1,3-bis(2 -hydroxyethoxy)benzene with lauric acid, 1,3-bis(2-hydroxyethoxy)benzene with myristic acid, 1,4-bis(hydroxymethoxy)benzene with butyric acid, 1,4 - the diester of bis(hydroxymethoxy)benzene with isovaleric acid, the diester of 1,4-bis(2-hydroxyethoxy)benzene with acetic acid, the diester of 1,4-bis(2-hydroxyethoxy)benzene with propionic acid Diesters, diesters of 1,4
• a compound represented by the following general formula (6) can also be used as the component (c).
• X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom
• m represents an integer of 1 to 3
• n represents 1 to 20 indicates an integer of Examples of the compounds include diesters of succinic acid and 2-phenoxyethanol, diesters of suberic acid and 2-phenoxyethanol, diesters of sebacic acid and 2-phenoxyethanol, diesters of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, A diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol can be exemplified.
• a compound represented by the following general formula (7) can also be used as the component (c).
• R represents an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms
• X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom
• n is 0 or 1.
• Specific examples of the compounds include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, -decyl biphenyl acetate, lauryl 4-biphenyl acetate, myristy
• a compound represented by the following general formula (8) can also be used as the component (c).
• R represents either an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms
• X is a hydrogen atom
• an alkyl group having 1 to 3 carbon atoms, 1 or 2 carbon atoms is either an alkoxy group or a halogen atom
• Y is a hydrogen atom or a methyl group
• Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, a halogen atom indicates either.
• Specific examples of the compounds include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, esters of phenoxyethyl 4-hydroxybenzoate and dodecanoic acid, and vanillin
• a compound represented by the following general formula (9) can also be used as the component (c).
• R represents an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group
• X represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom
• Y is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom
• n is 0 or 1.
• Specific examples of the compounds include benzoate of octyl 4-hydroxybenzoate, decyl 4-hydroxybenzoate, 4-methoxy benzoate of heptyl 4-hydroxybenzoate, and dodecyl 4-hydroxybenzoate. and cyclohexylmethyl benzoate of 4-hydroxybenzoate.
• a compound represented by the following general formula (10) can also be used as the component (c).
• R is an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or an alkenyl group having 3 to 18 carbon atoms
• X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom
• Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or an ethoxy group; , indicates one of the halogen atoms.
• Specific examples of the compounds include phenoxyethyl ether of nonyl 4-hydroxybenzoate, phenoxyethyl ether of decyl 4-hydroxybenzoate, phenoxyethyl ether of undecyl
• a compound represented by the following general formula (11) can also be used as the component (c).
• R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms
• n represents an integer of 1 to 3.
• Specific examples of the compounds include a diester of 1,3-bis(2-hydroxyethoxy)benzene and cyclohexanecarboxylic acid, a diester of 1,4-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid, 1, A diester of 3-bis(2-hydroxyethoxy)benzene and cyclohexanepropionic acid can be exemplified.
• a compound represented by the following general formula (12) can also be used as the component (c).
• R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkylalkyl group having 5 to 8 carbon atoms
• X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, group, methoxy group, ethoxy group, halogen atom, and n is an integer of 1 to 3.
• Specific examples of the compound include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenoldiethylene glycol ether and lauric acid, and a diester of 4-phenylphenoltriethylene glycol ether and cyclohexanecarboxylic acid.
• diesters diesters of 4-phenylphenol ethylene glycol ether and octanoic acid, diesters of 4-phenylphenol ethylene glycol ether and nonanoic acid, diesters of 4-phenylphenol ethylene glycol ether and decanoic acid, 4-phenylphenol ethylene glycol Diesters of ethers and myristic acid can be exemplified.
• the decolorizing compound shown below can also be used as the component (c).
• the decolorant compound typically includes a compound having a bulky molecular skeleton like a steroid skeleton and having an alcoholic hydroxyl group, such as a sterol compound.
• sterol compounds include cholesterol, stigmasterol, pregnenolone, methylandrostenediol, estradiol benzoate, epiandrostene, stenolone, ⁇ -sitosterol, pregnenolone acetate, ⁇ -cholesterol, 5,16-pregnadiene-3 ⁇ .
• cholic acid cholic acid methyl ester, sodium cholate, lithocholic acid, lithocholic acid methyl ester, sodium lithocholic acid, hyodeoxycholic acid, hyodeoxycholic acid methyl ester, testosterone, methyltestosterone, 11 ⁇ -hydroxymethyl Testosterone, hydrocortisone, cholesterol methyl carbonate, ⁇ -cholestanol and the like.
• a substance (phase separation inhibitor) that has an effect of inhibiting phase separation between an electron-donating color-forming organic compound and an electron-accepting compound can be used in combination with another decolorizing agent.
• D-glucose D-mannose, D-galactose, D-fructose, L-sorbose, L-rhamnose, L-fucose, D-ribodeose, ⁇ -D-glucose pentaacetate, acetoglucose, diacetone.
• the blending ratio of the components (a), (b), and (c) depends on the concentration, discoloration temperature, and the type of each component, but generally the component ratio that provides the desired discoloration property is For component 1, (b) component 0.1 to 50, preferably 0.5 to 20, more preferably 1 to 10, (c) component 1 to 800, preferably 5 to 200, more preferably It ranges from 10 to 100 (all the above proportions are parts by weight). Also, each component may be used in combination of two or more.
• the reversible thermochromic composition is used as a reversible thermochromic microcapsule pigment encapsulated in microcapsules. This is because the reversible thermochromic composition can be maintained at the same composition under various conditions of use and can exhibit the same effect.
• Examples of the method for microencapsulating the reversible thermochromic composition include an isocyanate interfacial polymerization method, an in situ polymerization method using a melamine-formalin system, etc., a liquid curing coating method, a phase separation method from an aqueous solution, an organic There are a phase separation method from a solvent, a melting dispersion cooling method, an aerial suspension coating method, a spray drying method, an interfacial polycondensation method, and the like, which are appropriately selected according to the application.
• the surface of the microcapsules may be further provided with a secondary resin film to impart durability, or the surface characteristics may be modified for practical use.
• the microcapsule pigment may have a circular cross-sectional shape or a non-circular cross-sectional shape.
• the mass ratio of the reversible thermochromic composition to the microcapsule wall film satisfies the range of 7:1 to 1:1, preferably 6:1 to 1:1. If the ratio of the reversible thermochromic composition to the wall film is greater than the above range, the thickness of the wall film becomes too thin and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition is larger than the above range, the color density and sharpness are likely to be lowered during color development.
• the microcapsule pigment has an average particle size of 0.1 to 100 ⁇ m, preferably 3 to 30 ⁇ m, more preferably 0.1 to 10 ⁇ m, still more preferably 0.1 to 8 ⁇ m, particularly preferably 0.5 to 6 ⁇ m. satisfies the practicality. If the average particle size exceeds 10 ⁇ m, the microcapsules may lack dispersion stability, and if the average particle size is less than 0.1 ⁇ m, it becomes difficult to exhibit high-concentration color development. As the average particle diameter of the microcapsule pigment, the average particle diameter (median diameter) of particles equivalent to a sphere of equal volume is used.
• measurement can be performed using a laser diffraction/scattering particle size distribution analyzer SALD7000 manufactured by Shimadzu Corporation, which is a laser diffraction/scattering particle size distribution analyzer calibrated by a direct measurement method.
• SALD7000 laser diffraction/scattering particle size distribution analyzer calibrated by a direct measurement method.
• SALD7000 laser diffraction/scattering particle size distribution analyzer calibrated by a direct measurement method.
• SALD7000 laser diffraction/scattering particle size distribution analyzer calibrated by a direct measurement method.
• SALD7000 laser diffraction/scattering particle size distribution analyzer calibrated by a direct measurement method.
• Measurement of the average particle size by the image analysis method for example, using the image analysis type particle size distribution measurement software "Macview” manufactured by Mountec Co., Ltd. to determine the area of particles, from the area of the area of the particles, the projected area circle equivalent diameter ( Heywood diameter) can be calculated, and the average particle diameter of particles equivalent to a sphere of equal volume can be measured.
• the measurement of the average particle size by the Coulter method is applicable when the particle size of all particles or most of the particles exceeds 0.2 ⁇ m. 4e" can be used.
• said microcapsule pigment has less than 20% by volume of particles larger than 15 ⁇ m, preferably less than 15% by volume, more preferably less than 10% by volume of the total microcapsulated pigment.
• Each of the pigments is used as a coloring material and contained in the coloring material.
• the coloring material include gravure printing ink, offset printing ink, process printing ink, screen printing ink, inkjet ink, toner, etc. dispersed in a vehicle containing an additive as necessary.
• a thermochromic printed matter can be obtained by forming a thermochromic color image.
• the vehicle used in the present invention comprises a solvent, a resin, and various additives if necessary.
• the resin is preferably 0.1 to 10 parts per coloring material, more preferably 0.5 to 5 parts (all the above proportions are parts by mass).
• the solvent include water and various organic solvents.
• organic solvent examples include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol.
• the resin examples include ionomer resins, isobutylene-maleic anhydride copolymer resins, acrylonitrile-acrylonitrile-styrene copolymer resins, acrylonitrile-styrene copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, acrylonitrile-chlorinated polyethylene-styrene copolymer resins.
• Polymerized resin ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinyl acetate resin, vinyl chloride resin, vinylidene chloride resin , chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polycarbonate resin, polybutadiene, polyethylene terephthalate resin, polybutylene terephthalate resin, polystyrene resin, high impact polystyrene resin , styrene-maleic acid copolymer resin, acrylic-styrene copolymer resin, polypropylene resin, polymethylstyrene resin, acrylic acid ester resin, polymethylmethacrylate resin, epoxy acrylate resin, alkyl
• Synthetic middle molecular weight polymers such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene, coumarone plastic, polybutene, phenoxy plastic, liquid polybutadiene, liquid rubber, petroleum hydrocarbon resin, cyclopentadiene petroleum resin.
• Natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubber, shellac, agar, casein, glue, gelatin, polyterpene, and the like.
• a resin having a structure derived from any of a vinyl chloride monomer, an unsaturated carboxylic acid ester monomer, an isocyanate group, and an epoxy group is preferred, and a resin having a structure derived from an unsaturated carboxylic acid ester monomer is more preferred.
• a resin having a structure derived from an acrylic acid ester monomer or a methacrylic acid ester monomer is more preferable.
• resin emulsions except for resin emulsions, some medium-molecular-weight polymers, and some reactive resins such as epoxy resins, these resins are in a solid state at room temperature, so water, aliphatic hydrocarbons, aromatic hydrocarbons, It can be made liquid by dissolving or dispersing it in a solvent such as alcohols, glycols, glycol derivative esters, ketones, etc.
• Additives are added as necessary to prepare a liquid composition.
• the additives include non-thermochromic coloring agents, cross-linking agents, curing agents, desiccants, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, anti-settling agents, and smoothing agents. .
• a resin molding can be obtained by forming a colored layer on a resin substrate by means of coating or the like.
• the colored layer is a layer formed by a compound other than the solvent in the liquid composition volatilized, and the coloring material is fixed to the resin in a dispersed state.
• the surface of the colored layer, the back surface of the colored layer, the surface and the back surface of the colored layer may be coated with an ultraviolet absorber, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, and a visible light absorber. It is also possible to provide a light stabilizer layer in which an appropriate amount of one or more agents selected from infrared absorbing agents are dispersed in a binder resin.
• the back surface of the colored layer includes the surface between the colored layer and the resin base layer and the surface of the resin base layer.
• the laminate of the present invention is the following [12] to [19].
• a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation On the resin base layer, a colored layer containing a coloring material that is irreversibly decolored by thermal stimulation, and a barrier layer having a thickness of 50% or less of the resin base layer on the colored layer (however, aluminum excluding foil) and laminates.
• a colored layer containing a coloring material that is irreversibly decolored by thermal stimulus is provided on the resin base layer, an adhesive layer is provided on the colored layer, and a resin of the same type as the resin base layer is provided on the adhesive layer.
• a laminate obtained by laminating a sealant layer [14] The laminate according to [13], wherein a barrier layer is interposed between the resin base layer and the sealant layer.
• the combination of the resin base layer and the sealant layer is any one selected from the combinations described below, [13] to [17].
• laminate Uniaxially oriented polyethylene/Polyethylene with a density of 880 to 930 kg/m 3
• Unoriented polypropylene oriented polyester/Non Crystalline polyester for the resin substrate layer and colored layer contained in the laminate of the present invention, the same resin substrate and colored layer as described in the above " ⁇ Method for producing recycled resin composition>" can be used. .
• the barrier layer laminated in the barrier layer laminate [12] is a barrier layer laminated on the colored layer containing a coloring material that is irreversibly decolored by thermal stimulation of the laminate [12], may be a single layer barrier layer or may be a multilayer barrier layer.
• the film thickness of the barrier layer is 50% or less of the film thickness of the resin base material layer, assuming that the film thickness of the resin base material layer is 100%. (However, the film thickness of the aluminum foil layer is excluded.)
• the barrier layer is a layer that prevents permeation of gases such as oxygen and water vapor.
• the barrier layer includes, for example, a metal oxide layer formed by vapor deposition of an inorganic compound, and a layer formed from a composition containing an inorganic layered compound and/or a polyvinyl alcohol-based resin.
• layers formed by vapor-depositing an inorganic compound include layers formed from silicon oxide, alumina, and spinel.
• the barrier layer may be, for example, a layer formed from a composition containing an inorganic stratiform compound and a polyvinyl alcohol-based resin.
• examples of inorganic layered compounds include kaolinite group, smectite group, and mica group.
• smectites such as layered silicate minerals, hectorites, and sabonites are preferred, and resins are incorporated between the layers of the inorganic layered compound to facilitate formation of a composite.
• layered silicate minerals are preferable and can provide high oxygen gas barrier properties.
• a polyvinyl alcohol-based resin is a polymer whose main component is a structural unit derived from vinyl alcohol.
• polyvinyl alcohol examples include polymers obtained by hydrolyzing the acetate moiety of vinyl acetate polymers, trifluorovinyl acetate polymers, vinyl formate polymers, vinyl pivalate polymers, t- Examples thereof include polymers obtained by hydrolyzing butyl vinyl ether polymers, trimethylsilyl vinyl ether polymers, and the like (for details of "polyvinyl alcohol", see, for example, Poval Kai, "The World of PVA", 1992, Co., Ltd.
• the degree of "saponification" of the ester portion of the polymer is preferably 70 mol % or more, more preferably 85 mol % or more, and even more preferably 98 mol % or more.
• the degree of polymerization of the polymer used is preferably 100 or more and 5000 or less, more preferably 200 or more and 3000 or less.
• the vinyl alcohol may be a so-called vinyl alcohol derivative having a functional group other than a hydroxyl group.
• examples include carboxylate groups, sulfonate ion groups, phosphate ion groups, ammonium groups, phosphonium groups, silyl groups, siloxane groups, alkyl groups, allyl groups, fluoroalkyl groups, alkoxy groups, carbonyl groups, halogen groups and the like.
• the polyvinyl alcohol-based resin may be a copolymer containing structural units derived from vinyl alcohol and structural units derived from ⁇ -olefins such as ethylene and propylene.
• the content of structural units derived from the ⁇ -olefin contained in the copolymer is preferably 40 mol % or less, more preferably 15 mol % or less.
• the content of the structural unit derived from the ⁇ -olefin contained in the copolymer is 0 to 0. It is more preferably 50 mol %, preferably 20 to 45 mol %.
• the adhesive layer laminated in the adhesive layer laminate [13] is an adhesive layer laminated on the colored layer containing a coloring material that is irreversibly decolored by thermal stimulation of the laminate [13].
• the adhesive layer may be a single adhesive layer or multiple adhesive layers.
• the adhesive layer may be formed from a water-based or solvent-based dry laminating adhesive, or may be formed from a non-solvent laminating adhesive.
• Adhesives for forming the adhesive layer include, for example, polyurethane-based adhesives such as polyether-based polyurethane adhesives and polyester-based polyurethane adhesives, polyester-based adhesives, imine-based adhesives, titanate-based adhesives, and the like. can be mentioned.
• polyurethane-based adhesives include Takelac (registered trademark) (manufactured by Mitsui Chemicals) and Takenate (registered trademark) (manufactured by Mitsui Chemicals).
• Other adhesive layers include high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, ultra-low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene.
• the sealant layer laminated in the sealant layer laminate [13] is a sealant layer laminated on the adhesive layer of the laminate [13], and is the resin used for the resin base layer of the molded article [13]. It is a sealant layer made of the same kind of resin.
• the sealant layer may be a single layer sealant layer or multiple layers of sealant layers.
• "the same kind" means resins with the same name even if the weight average molecular weights are different.
• resins of the same type include resins with the same name from different lots, resins with the same name from different manufacturers, and the like.
• the colored layer, the sealant layer, and the barrier layer laminated in the colored layer, sealant layer, and barrier layer laminate [14] are barrier layers in which the barrier layer is interposed between the resin base layer and the sealant layer, and the colored layer and the It is preferably a barrier layer interposed between the sealant layers.
• the thickness of the resin substrate layer used in the laminate [15] is 10-100 ⁇ m, preferably 10-40 ⁇ m.
• the resin used in the resin base layer and the resin used in the sealant layer of the resin base layer/sealant layer laminate [16] are the same type of resin, and the same type of resin includes polyethylene, polypropylene, polystyrene, polyvinyl chloride, It is at least one resin selected from the group consisting of polyesters and aliphatic polyamides.
• the term "homogeneous” as used herein means that resins selected from the above polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester, and aliphatic polyamide are of the same type.
• the polyethylene used for the resin substrate layer includes the following ethylene polymer (A), and the polyethylene used for the sealant layer is includes the following ethylene polymer (B).
• Ethylene polymer (A) [A-1] Mole Fraction of Monomer Units Derived from Ethylene
• the ethylene polymer (A) contained in the resin substrate layer contains 80 mol% or more, and 97 mol% or more, of structural units derived from ethylene. preferably 98 mol% or more, more preferably 99 mol% or more.
• the ethylene polymer (A) may be composed of structural units derived from 100 mol % of ethylene.
• two or more ethylene polymers described later may be used in combination. In this case, at least one of the two or more ethylene polymers should contain 80 mol % or more of structural units derived from ethylene as the ethylene polymer (A).
• A-2 Density of Ethylene Polymer The density of the ethylene polymer (A) is measured according to A method described in JIS K7112-1980 after performing annealing treatment specified in JIS K6760-1995.
• the density of the ethylene polymer (A) contained in the resin substrate layer is preferably 930 kg/m 3 or more, more preferably 935 kg/m 3 or more. Also, it is preferably 970 kg/m 3 or less, more preferably 940 kg/m 3 or less.
• melt flow rate of Ethylene Polymer The melt flow rate (MFR) of the ethylene polymer (A) is measured according to JIS K7210-1-2014 at a temperature of 190° C. and a load of 21.18 N.
• the melt flow rate (MFR) of the ethylene polymer (A) is preferably 0.01 g/10 minutes or more, more preferably 0.1 g/10 minutes or more. Also, it is preferably less than 3 g/10 minutes, more preferably less than 2 g/10 minutes.
• the ethylene polymer (A) includes high-pressure low-density polyethylene, high-density polyethylene, ethylene- ⁇ -olefin copolymer, and ethylene-vinyl ester copolymer. , ethylene-unsaturated carboxylic acid ester copolymers, and other ethylene polymers can be used.
• Ethylene polymer (A) is preferably an ethylene- ⁇ -olefin copolymer, high-pressure low-density polyethylene, or high-density polyethylene. more preferably used.
• the ⁇ -olefins having 3 to 20 carbon atoms used in the constituent units of the ethylene- ⁇ -olefin copolymer include propylene, 1- butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like, These may be used alone or in combination of two or more. Preferred are 1-butene and 1-hexene.
• ethylene- ⁇ -olefin copolymers examples include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-1 -Butene-1-hexene copolymer, ethylene-1-butene-1-octene copolymer, etc., may be used alone, or two or more thereof may be used in combination. Further, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-butene-1-hexene copolymer are preferable.
• Examples of methods for producing ethylene- ⁇ -olefin copolymers include production methods by known polymerization methods using known radical polymerization catalysts and ionic polymerization catalysts.
• Examples of known catalysts include peroxide catalysts, Ziegler-Natta catalysts, metallocene catalysts, etc.
• Examples of known polymerization methods include solution polymerization, slurry polymerization, high-pressure ion polymerization, high-pressure A radical polymerization method, a vapor phase polymerization method, and the like can be mentioned.
• Ziegler-Natta catalysts include, for example, catalysts composed of solid catalyst components for olefin polymerization containing titanium atoms, magnesium atoms and halogen atoms, and organometallic compounds.
• No. 322833 discloses a catalyst.
• metallocene-based catalysts include the following catalysts (1) to (4).
• a catalyst comprising a component containing a transition metal compound having a group having a cyclopentadiene skeleton and a component containing an alumoxane compound (2) A component containing the transition metal compound and ions such as trityl borate and anilinium borate (3) A catalyst comprising a component containing the transition metal compound, a component containing the ionic compound, and an organometallic compound (4)
• Each of the above components is combined with SiO 2 , Al 2 O 3 and the like, and particulate polymer supports such as olefin polymers such as ethylene and styrene, and catalysts obtained by supporting or impregnating the above organometallic compounds, for example, butyllithium, triethyl Aluminum etc. are mentioned.
• the ethylene- ⁇ -olefin copolymer is preferably an ethylene- ⁇ -olefin copolymer produced by a gas phase polymerization method using a metallocene catalyst.
• Specific examples of the ethylene- ⁇ -olefin copolymer include ethyne- ⁇ -olefin copolymers described in JP-A-9-183816.
• the production method includes polymerizing ethylene and an ⁇ -olefin having 3 to 12 carbon atoms by a known polymerization method using a known catalyst.
• known catalysts include Ziegler-Natta catalysts
• known polymerization methods include, for example, gas phase-solid phase polymerization in the presence or absence of a solvent, liquid phase-solid phase polymerization. , a homogeneous liquid phase polymerization method, and the like.
• the polymerization temperature is usually 30 to 300° C.
• the polymerization pressure is usually normal pressure to 3000 kg/cm 2 .
• ethylene polymers such as high-pressure low-density polyethylene, ethylene-vinyl ester copolymers, and ethylene-unsaturated carboxylic acid ester copolymers may be produced by known production methods, and commercially available products may be used. .
• Ethylene polymer (B) [B-1] Mole Fraction of Ethylene-Derived Monomer Units
• the ethylene polymer (B) contained in the sealant layer contains 70 mol % or more, preferably 90 mol % or more of ethylene-derived structural units.
• the ethylene polymer (B) may be composed of structural units derived from 100 mol % of ethylene. When the ethylene polymer (B) contains 70 mol % or more of structural units derived from ethylene, it can be uniformly compatible with the ethylene polymer (A) contained in the resin substrate layer.
• the density of the ethylene polymer (B) is measured according to A method described in JIS K7112-1980 after performing an annealing treatment specified in JIS K6760-1995. be.
• the density of the ethylene polymer (B) is preferably 880 kg/m 3 or more, more preferably 890 kg/m 3 or more, still more preferably 895 kg/m 3 or more, or 930 kg/m 3 . It is preferably less than
• the melt flow rate (MFR) of the ethylene polymer (B) is measured in accordance with JIS K7210-1-2014 at a temperature of 190°C and a load of 21.18N. be done.
• the MFR of the ethylene polymer (B) is preferably 0.01 g/10 min or more, more preferably 0.1 g/10 min or more, still more preferably 0.5 g/10 min or more, and , preferably less than 10 g/10 min, more preferably 7 g/10 min or less, and even more preferably 5 g/10 min or less.
• the ethylene polymer (B) is an ethylene polymer similar to the ethylene polymer (A) from the molar fraction, density, and MFR of structural units derived from ethylene. can be used. That is, the ethylene polymer (B) includes high-pressure low-density polyethylene, high-density polyethylene, ethylene- ⁇ -olefin copolymer, ethylene-vinyl ester copolymer, ethylene-unsaturated carboxylic acid ester copolymer, and the like.
• Ethylene polymers can be used, and high-pressure low-density polyethylene, high-density polyethylene, and ethylene- ⁇ -olefin copolymers are preferably used, and high-density polyethylene and ethylene- ⁇ -olefin copolymers are more preferably used. be done.
• the ethylene polymer (B) can be produced by the same production method as the ethylene polymer (A).
• the ethylene polymer (B) and an ethylene polymer other than the ethylene polymer (B) may be used in combination.
• the content of the ethylene polymer (B) is preferably 60% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more.
• the content of the inorganic filler is preferably less than 20% by weight when the total content of the ethylene polymer (B) and the inorganic filler is 100% by weight. Although not required, it is more preferred that the sealant layer does not contain inorganic fillers.
• Examples of the inorganic filler contained in the resin substrate layer of the inorganic filler laminate [17] include calcium carbonate, kaolin, metakaolin, hydrotalcite, mica, talc, and fibrous basic magnesium sulfate particles.
• the inorganic filler is preferably hydrotalcite, talc or fibrous basic magnesium sulfate particles, more preferably talc.
• the inorganic filler may be carbon fiber. These inorganic fillers may be used alone or in combination of two or more.
• the inorganic filler may be surface-treated with, for example, a coupling agent.
• color pigments such as titanium oxide and iron oxide may be included as inorganic fillers.
• the median diameter (d50) of the inorganic filler is not particularly limited, and may be 0.5 ⁇ m to 10 ⁇ m.
• the median diameter (d50) of the inorganic filler can be measured as a volume-based median diameter by a laser diffraction method.
• the inorganic filler is fibrous basic magnesium sulfate particles
• the fiber length may be 8 ⁇ m to 30 ⁇ m and the fiber diameter may be 0.5 ⁇ m to 1.0 ⁇ m.
• the content of the inorganic filler is preferably 20 parts by mass to 80 parts by mass with respect to the total of 100 parts by mass of the resin content and the inorganic filler content contained in the resin base layer, and 30 parts by mass. More preferably, it is up to 70 parts by mass.
• the electron beam treatment applied to the resin substrate layer of the electron beam treated laminate [17] is a treatment of irradiating the polymer film used for the resin substrate layer with an electron beam.
• the reason why the crosslink density of the polymer differs depending on the presence or absence of electron beam irradiation is not clear, it is considered as follows. That is, when a polymer film is irradiated with an electron beam, carbon-hydrogen bonds in the polymer near the surface of the film are cut, and radicals are generated at the cut bond ends.
• an electron beam may be irradiated from one surface to allow the electron beam to penetrate the polymer film to improve the crosslink density not only on the irradiated surface but also on the surface opposite to the irradiated surface.
• the irradiation energy of the electron beam varies depending on the intended use of the package. If it is too much, the molecular chains of the polymer will be cut too much, and the physical properties of the film, such as strength, will remarkably decrease.
• the dose of the electron beam is preferably in the range of 10 to 2000 kGy, more preferably 20 to 1000 kGy, and the acceleration voltage of the electron beam is preferably in the range of 30 to 300 kV, more preferably 50 to 300 kV, particularly preferably 50 to 300 kV. 250 kV.
• the electron beam irradiation energy is preferably 20 to 750 keV, more preferably 25 to 400 keV, still more preferably 30 to 300 keV, and particularly preferably 20 to 200 keV.
• the electron beam irradiation device As the electron beam irradiation device, a conventionally known one can be used, for example, a curtain type electron irradiation device (LB1023, manufactured by I Electron Beam Co., Ltd.) and a line irradiation type low energy electron beam irradiation device (EB-ENGINE, Hamamatsu Photonics). (manufactured by Hamamatsu Photonics Co., Ltd.) can be preferably used, and in particular, a line irradiation type low-energy electron beam irradiation apparatus (EB-ENGINE, manufactured by Hamamatsu Photonics Co., Ltd.) can be preferably used.
• EB-ENGINE line irradiation type low-energy electron beam irradiation apparatus
• the oxygen concentration in the electron beam irradiation device is preferably 500 ppm or less, more preferably 100 ppm or less.
• the polymer film is prone to thermal shrinkage, it is preferable to use a cooling drum or the like to irradiate the electron beam at the same time as cooling.
• the electron beam may be irradiated from the polymer film substrate side.
• the stretching treatment applied to the resin base layer of the stretched laminate [17] is a process of stretching the polymer film used for the resin base layer by a known method.
• the stretching method include a uniaxial stretching method and a biaxial stretching method, and from the viewpoint of the strength of the polymer film, a biaxially stretched polymer film is preferable.
• the stretching ratio in the longitudinal direction (MD) of the polymer film used for the resin substrate layer is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
• the draw ratio in the transverse direction (TD) is preferably 2 times or more and 10 times or less, and preferably 3 times or more and 7 times or less.
• the resin used for the laminate [18] 90% by mass or more of the resin is the same kind of resin, with the total amount of the resin used for the molded body being 100% by mass.
• the combination of the resin used for the resin substrate layer and the resin used for the sealant layer of the laminate [19] is any one selected from the combinations described below.
• the combination is indicated by "resin used for resin substrate layer/resin used for sealant layer”.
• Laminate film manufacturing method Laminates [12] to [19] of the present invention are a step of laminating a resin base layer, a colored layer and a barrier layer in this order (step of manufacturing molded body [12]); A step of laminating a resin base layer, a colored layer, an adhesive layer and a sealant layer in this order (manufacturing step of molded body [13]); A step of laminating a resin base layer, a colored layer, a barrier layer, an adhesive layer, and a sealant layer in this order, or laminating a resin base layer, a colored layer, an adhesive layer, a barrier layer, and a sealant layer in this order. It can be manufactured by a manufacturing method exemplified by a dry lamination method or an extrusion lamination method, including the step of (manufacturing step of molded product [14]).
• the method for producing the film-forming resin composition for forming the resin substrate layer, the adhesive layer, and the sealant layer is not particularly limited, and the components used in each film-forming resin composition are separately prepared. Alternatively, they may be melt-blended (melt-kneaded) in advance, may be dry-blended individually, or may be dry-blended as a masterbatch of one or more types.
• Various blenders such as Henschel mixers and tumbler mixers are used for dry blending, and various mixers such as single-screw extruders, twin-screw extruders, Banbury mixers and hot rolls are used for melt blending.
• Example 1 Manufacture of Molded Body Containing Resin Base Material and Colored Layer
• a film (1) was prepared by forming a high-density polyethylene (KEIYO Polyethylene E8080, manufactured by Keiyo Polyethylene Co., Ltd., melting point 136° C.) to a thickness of 100 ⁇ m.
• the lightness and chromaticity of film (1) were measured with a colorimeter (spectro-guide 45/0 gloss manufactured by BYK-Gardner GmbH) based on CIE1976L * a * b * color space.
• One side of the film (1) was subjected to corona treatment so that the wettability was 58 dyn or more , and a temperature-sensitive ink (Metamocolor manufactured by Pilot Ink Co., Ltd. (registered (trademark))) was applied in a uniform thickness and dried sufficiently at room temperature to form a colored layer (irreversible discoloration temperature Ti: 200°C, decomposition initiation temperature Td: 191°C) to obtain film (2). . At this time, the weight of the colored layer was 3.1 parts with respect to 100 parts of film (2).
• a temperature-sensitive ink Metalocolor manufactured by Pilot Ink Co., Ltd. (registered (trademark)
• thermochromic microcapsule pigment blue at 42° C. or lower, colorless at 45° C. or higher
• Manufacturing film (2) of recycled resin composition 75 g of film (2) and 0.075 g of antioxidant (Sumilyzer GP) are processed in Labo Plastomill (manufactured by Toyo Seiki Seisakusho, model 65C150) at a rotation speed of 80 rpm and a resin temperature of 210° C. for 8 minutes. The mixture was kneaded to produce a recycled resin composition. The shear stress at this time was 149000Pa.
• the recycled resin composition was press molded at 180° C. and 10 MPa to form a film (3) having a thickness of 100 ⁇ m.
• the brightness and chromaticity of this film were measured at temperatures of 0°C, 23°C and 100°C.
• the lightness L * is 89.3
• the chromaticity a * is ⁇ 0.6
• b * is 4.3 . 3.
• the color difference ⁇ E 100 between 23°C and 100°C was 0.4
• the color difference ⁇ E 0 between 23°C and 0 °C was 0.7.
• the recycled resin composition was press molded at 210° C. and 10 MPa to form a film (4) having a thickness of 100 ⁇ m.
• the color difference ⁇ E R0 at 0° C. between film (1) and film (4) was 4.0
• the color difference ⁇ E R23 at 23° C. was 3.7
• the color difference ⁇ E R100 at 100° C. was 3.9.
• the difference in visual appearance between (1) and film (4) is such that a very slight difference in color can be visually recognized at any temperature, and the color and the difference do not change depending on the temperature, giving a sense of discomfort. Since there was nothing to remember, it was determined that horizontal recycling for the same purpose is fully possible.
• Example 2 In the production of the recycled resin composition, the resin temperature is 180 ° C., the shear stress is 260000 Pa, and the press molding temperature in the evaluation of the horizontal recycling of the recycled resin composition is 180 ° C., except that the temperature is 180 ° C. conducted in the same way.
• Example 1 shows that the recycled resin composition of Example 1 has a low color difference ( ⁇ E R0 , ⁇ E R23 , ⁇ E R100 ) between the resin substrate alone and the recycled composition, and the color tone sensory evaluation is 4.
• the difference in appearance by visual observation was such that a very slight difference in color was recognizable at any temperature. is shown. From this, it was confirmed that Example 1 (the present invention) is excellent in horizontal recycling for the same use.
• the color differences ( ⁇ E R0 , ⁇ E R23 , ⁇ E R100 ) between the resin substrate alone and the recycled composition are larger than those in Example 1, but are comparable at any temperature.
• the sensory evaluation of color tone was 3, which means that although the appearance was slightly different at each temperature, there was only a slight sense of discomfort. Accordingly, it was confirmed that Example 2 (the present invention) is sufficiently applicable to horizontal recycling for the same use.
• Adhesive coating and laminate production 12 parts by mass of Takelac (registered trademark) A310 (manufactured by Mitsui Chemicals), 1 part by mass of Takenate (registered trademark) A3 (manufactured by Mitsui Chemicals), and 12 parts by mass and ethyl acetate to prepare an adhesive for dry lamination.
• the adhesive for dry lamination is applied to the barrier layer side of the barrier layer laminated sealant 1 in a uniform thickness and dried at room temperature to form an adhesive layer.
• a film (2') was obtained by laminating such that one side was in close contact with the adhesive layer. At this time, the weight of the adhesive layer was 1 part by weight with respect to 1,95 parts by weight of the sealant.
• the layer structure of the film (2') was resin substrate 1/colored layer/adhesive layer/barrier layer/sealant 1, and the ratio of the same kind of resin (polyethylene resin) was 91% by weight.
• laminate recycled resin composition 85 g of film (2′) and 0.085 g of antioxidant (Sumilizer GP) were kneaded for 8 minutes at a rotation speed of 80 rpm and a resin temperature of 210° C. in the lab plastomill to prepare a laminate. A recycled resin composition was produced. The shear stress at this time was 66000Pa.
• the recycled laminate resin composition was press molded at 180° C. and 10 MPa to form a film (3′) having a thickness of 160 ⁇ m.
• the brightness and chromaticity of this film were measured at temperatures of 0°C, 23°C and 100°C.
• Lightness L* at 23° C. is 82.2
• chromaticity a* is 0.2
• b* is 18.1
• (a*2+b*2) 0.5 corresponding to the distance from the origin of chromaticity is 18.1
• the color difference ⁇ E100 between 23°C and 100°C was 0.9
• the color difference ⁇ E0 between 23°C and 0°C was 0.8.
• the recycled laminate resin composition was press-molded under conditions of 210° C. and 10 MPa to form a film (4′) having a thickness of 160 ⁇ m.
• a film (1') was prepared in the same manner as the film (2') except that the colored layer was not applied, and the film (1') was heated to 0°C, 23°C, and 100°C. ) and the film (4') were measured.
• the color difference ⁇ ER0 at 0° C. was 19.9
• the color difference ⁇ ER23 at 23° C. was 19.7
• the color difference ⁇ ER100 at 100° C. was 20.6.
• Color sensory evaluation 5: There is no visual difference at room temperature, no change with temperature, and no discomfort. 4: Slight color difference is felt at room temperature, but there is no change with temperature, and there is no discomfort. 3: Slight color difference at room temperature or slight temperature change is felt, but only slight discomfort is felt 2: Color difference at room temperature or color change depending on temperature is felt and discomfort is felt. 1: Difference in color tone at room temperature and color change due to temperature are felt, and there is a noticeable sense of discomfort.
• Example 3 the color difference between 23° C. and 100° C. was 0.9 for the laminate recycled resin composition of Example 3, which was an extremely low value, while for Comparative Example 2 it was 17.4. shows a much higher value.
• Example 3 the color disappeared and an "irreversible" change in color was observed, and it could be determined that horizontal recycling is sufficiently possible.
• the recycled laminate resin composition of Example 3 although there are color differences ( ⁇ ER0, ⁇ ER23, ⁇ ER100) between the film (1′) and the recycled laminate composition, the color and the difference change depending on the temperature. It shows that there was no feeling of discomfort. From this, it was confirmed that Example 3 (the present invention) is excellent in horizontal recycling for the same use.
• a horizontally recyclable recycled resin composition can be produced by treating a molded article including a resin base material and a colored layer under specific conditions.
• the recycled resin composition and molded article produced by the production method of the present invention and the recycled resin composition of the present invention are, for example, heavy bags, shrink wraps, general packaging, thin films, protective films (protective films), extrusion laminated films, Horizontally recyclable into a wide variety of products such as extruded film, foamed film, etc., packaging materials for various products, various parts of home appliances, various housing equipment parts, various industrial parts, and various building materials. It is suitable for applications such as parts, interior and exterior parts of various automobiles, and has high applicability in various industrial fields such as the electrical and electronic industry, household goods, food industry, transportation machinery industry, and construction industry.

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