WO2008013266A1 - Particules de résine ayant une poudre combinée à celles-ci et leur procédé de formation, objet moulé contenant les particules, matière en forme de feuille contenant les particules et leur procédé de formation et feuille fonctionnelle et procédé servant à la prod - Google Patents

Particules de résine ayant une poudre combinée à celles-ci et leur procédé de formation, objet moulé contenant les particules, matière en forme de feuille contenant les particules et leur procédé de formation et feuille fonctionnelle et procédé servant à la prod Download PDF

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Publication number
WO2008013266A1
WO2008013266A1 PCT/JP2007/064769 JP2007064769W WO2008013266A1 WO 2008013266 A1 WO2008013266 A1 WO 2008013266A1 JP 2007064769 W JP2007064769 W JP 2007064769W WO 2008013266 A1 WO2008013266 A1 WO 2008013266A1
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WO
WIPO (PCT)
Prior art keywords
powder
integrated
resin particles
granular carrier
particle
Prior art date
Application number
PCT/JP2007/064769
Other languages
English (en)
Japanese (ja)
Inventor
Tatsuya Ogawa
Hitoshi Otomo
Yuriko Morinaka
Minoru Fujita
Kunio Nakatsubo
Midori Fujisaki
Original Assignee
Kyodo Printing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2007193402A external-priority patent/JP2008050592A/ja
Priority claimed from JP2007193403A external-priority patent/JP2008080793A/ja
Application filed by Kyodo Printing Co., Ltd. filed Critical Kyodo Printing Co., Ltd.
Publication of WO2008013266A1 publication Critical patent/WO2008013266A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/02—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose in the form of fibres or filaments
    • 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
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule

Definitions

  • the present invention relates to powder-integrated resin particles and a granulating method thereof, and a particle-containing molded body, a particle-containing sheet material, and a molding method thereof.
  • a thermoplastic resin and a powder are preferable.
  • a powder-integrated resin particle integrated with a functional material (including a pigment), a granulation method of the powder-integrated resin particle, a particle-containing molded body comprising the powder-integrated resin particle, and a powder The present invention relates to a particle-containing sheet material molded from body-integrated resin particles and a molding method thereof.
  • the present invention also relates to a functional sheet and a method for producing the same, and more particularly to a functional sheet provided with functionality such as adsorptivity and a method for producing the same.
  • compositions having various resins and powders are widely known.
  • a method of producing such a composition a method of forming a film by mixing a certain amount of resin and powder, a method of uniformly kneading and holding these components, although a method of simply mixing and molding can be mentioned, it is not satisfactory to exert the function of the powder and consequently the functional material.
  • Patent Document 1 and Patent Document 2 disclose a method of molding a resin and powder mixedly. Since these all use a thermosetting resin as the resin part, the steps of hardening and liquefaction are indispensable. In addition, since there is little fluidity and extensibility due to heat, it is difficult to carry a high concentration of powder in the mixing process, and there is a possibility that the performance of the functional material in the molded body may be reduced. Furthermore, when thermoplastic resin and powder are mixed and processed with a mixer such as a Henschel mixer, crosslinking occurs between the molecules due to frictional heat with the rotating blades and the wall of the granulation tank. Curing could occur and the integration process could be difficult. In addition, since thermosetting resins are formed using a curing reaction by heating, the molding method is limited, and post-processing such as biaxial stretching of the molded body is difficult.
  • Patent Document 3 describes a fine microlite powder of zeolite. Disclosed is a technology that uses a mixture of a thermoplastic resin and a thermoplastic resin, and sandwiches it between two nonwoven fabrics for molding.
  • the zeolite powder if a fine powder having an average particle diameter of 1 to 100 m is used as the zeolite powder, the agglomeration effect is likely to occur as compared with a powder made of another substance. There is a tendency to become non-uniform. In addition, the zeolite powder from the gap between the nonwoven fabric fibers In order to escape, there was a problem in practical and functional aspects.
  • thermoplastic resin when a mixture of zeolite powder and a thermoplastic resin is used, the thermoplastic resin is biased and exposed due to uneven mixing due to the action such as aggregation described above, and adhesion between the nonwoven fabrics. There was a problem that defects occurred. However, in order to prevent this, if the proportion of the thermoplastic resin in the entire nonwoven fabric is increased, the amount of zeolite adsorbed and the adsorption speed are reduced, and the nonwoven fabric has poor air permeability.
  • Patent Document 1 JP-A-11 246672
  • Patent Document 2 Japanese Patent Laid-Open No. 09-067155
  • Patent Document 3 Japanese Patent Application Laid-Open No. 09-276897
  • the present invention has been made in view of the above problems, and is a powder integration that is produced by a simple method while exhibiting the function of a powder, preferably a functional material (including a pigment).
  • the object is to provide resin particles.
  • the present invention can easily perform integration processing without requiring resin curing and liquefaction processing, and further post-processing such as film forming by biaxial extrusion, etc. without deteriorating the properties of the functional material.
  • the object is to provide a method for granulating powder-integrated resin particles.
  • Another object of the present invention is to provide a particle-containing molded body comprising such powder-integrated resin particles, a particle-containing sheet material molded from the powder-integrated resin particles, and a molding method thereof.
  • Another object of the present invention is to provide a functional sheet that maintains its shape as a sheet and that exhibits functionality such as adsorptivity uniformly and continuously, and a method for producing the functional sheet.
  • the powder-integrated resin particles according to the present invention include a granular carrier made of a thermoplastic resin, and the particles. And a powder integrated on the surface of the carrier. This makes it possible to fully exhibit the characteristics of the powder.
  • the average particle diameter of the powder integrated resin particles is 10 m or more. As a result, it is advantageous to handle the powder-integrated resin particles such that the particles do not scatter during post-treatment.
  • the weight of the powder is from 50% by weight to 900% by weight with respect to the weight of the thermoplastic resin. This makes it possible to fully exhibit the characteristics of the powder.
  • thermoplastic resin particles In the powder-integrated resin particles according to the present invention, a volume ratio of the thermoplastic resin to the powder is 1:;! To 1:20. As a result, the power S can be fully demonstrated.
  • a particle-containing molded article according to the present invention is characterized by comprising the above-mentioned powder-integrated resin particles and a water-soluble organic resin. As a result, a molded article containing particles having excellent strength while exhibiting the characteristics of the powder can be obtained.
  • the content of the water-soluble organic resin is 2% by weight or more and 50% by weight or less based on the weight of the powder-integrated resin particles. It is characterized by. Thereby, the particle
  • the method for granulating powder-integrated resin particles comprises a granular support made of a thermoplastic resin, and a powder-integrated resin having a powder integrated on the surface of the granular support.
  • the step of applying heat to the granular carrier includes a rotating member that rotates in a sealed space and the granular carrier. It is a process performed by frictional heat generated by contact with. This makes it possible to supply heat to the granular carrier by using frictional heat generated in one step of the granulation method without requiring a further apparatus, thereby reducing the complexity of the process. Can be reduced It becomes ability.
  • the method for molding a particle-containing molded body according to the present invention is characterized by having a step of adding a water-soluble organic resin to the powder-integrated resin particles, kneading, and pressurizing. As a result, the degree of integration of the powder-integrated resin particles can be further improved.
  • the particle-containing sheet material according to the present invention is characterized by comprising powder-integrated resin particles having a granular carrier made of a thermoplastic resin and powder integrated on the surface of the granular carrier. And As a result, even when the content of the powder is high, handling is facilitated while fully exhibiting the characteristics of the powder.
  • the film thickness of the particle-containing sheet material is 10 m or more and 5 mm or less. As a result, handling as a sheet is improved.
  • the particle-containing sheet material further includes a second resin.
  • the second resin is a thermoplastic resin.
  • the method for forming a particle-containing sheet material comprises powder-integrated resin particles having a granular carrier made of a thermoplastic resin and powder integrated on the surface of the granular carrier.
  • a method for forming a particle-containing sheet material the step of applying heat to the granular carrier so that the surface of the granular carrier is at least softened; and a powder on the surface of the softened granular carrier And a step of obtaining powder-integrated resin particles; and a step of forming a composition comprising the powder-integrated resin particles so as to obtain a sheet shape. This makes it possible to obtain a sheet-like product while fully exhibiting the characteristics of the powder.
  • the step of molding the composition comprising the powder-integrated resin particles is a step of performing extrusion molding by adding a second resin.
  • the second resin is heatable. It is a plastic resin. This makes it possible to adjust the heat seal temperature.
  • the functional sheet according to the present invention includes powder-integrated resin particles having a granular carrier made of a thermoplastic resin and powder integrated on the surface of the granular carrier on a base sheet. It is characterized by being held. As a result, the powder, particularly the functional material, can perform its function without dropping off from the sheet.
  • a powder integrated body having a granular carrier made of a thermoplastic resin and a powder integrated on the surface of the granular carrier between a plurality of substrate sheets. Resin particles are supported. This can further prevent the powder-integrated resin particles from falling off.
  • the functional sheet according to the present invention is characterized in that a layer made of a thermoplastic resin is further disposed between the base sheet and the powder-integrated resin particles.
  • the functional sheet according to the present invention is characterized in that the substrate sheet and the powder-integrated resin particles are supported by hot pressing. This facilitates the loading of the powder-integrated resin particles.
  • the weight of the powder is 30 wt% or more and 80 wt% or less with respect to the total weight of the functional sheet.
  • the weight of the powder is 50 wt% or more and 900 wt% or less with respect to the weight of the thermoplastic resin. This facilitates maintenance of the shape of the powder-integrated resin particles in the sheet.
  • the volume ratio of the thermoplastic resin and the powder is:
  • the average particle diameter of the powder-integrated resin particles is 10 111 or more. This facilitates handling of the powder integrated resin particles.
  • the method for producing a functional sheet according to the present invention comprises a thermoplastic resin on a base sheet.
  • the step of applying heat to the granular carrier is the contact between the rotating member that rotates in a sealed space and the granular carrier. It is a process performed by the frictional heat generated by. This makes it possible to supply heat to the granular carrier by using the frictional heat generated during the process without requiring a further device, thereby reducing the complexity of the process. Become.
  • the characteristics of the powder can be sufficiently exhibited.
  • the powder can be handled in an arbitrary shape.
  • such powder-integrated resin particles can be easily obtained without performing treatments such as curing and liquefaction treatment.
  • the powder-integrated resin particles having a powder having certain characteristics can be maintained without falling off the base sheet, and the function derived from the powder can be exhibited. It becomes.
  • FIG. 1 is a schematic view showing powder-integrated resin particles according to the present invention.
  • FIG. 2 is a schematic view showing an example of a functional sheet according to the present invention.
  • 3] It is a schematic diagram showing an example of a functional sheet according to the present invention.
  • FIG. 5 is a schematic view showing an example of a process for producing a functional sheet according to the present invention.
  • the powder-integrated resin particles according to the present invention have a granular carrier made of a thermoplastic resin and a powder integrated on the surface of the granular carrier, and have a particulate form. It is.
  • the form of the powder integrated resin particle according to the present invention is not particularly limited as long as it is particulate.
  • the form of the powder-integrated resin particles is not particularly limited, and as shown in FIG. 1, the powder 4 is integrated on the surface of the granular support 2 with the granular support 2 as the center. It may be in a different form.
  • the state "integrated on the surface of the granular carrier” means that the thermoplastic resin and the powder constituting the granular carrier are solidified from the thermoplastic resin. It refers to a state of continuous bonding at a possible temperature. As such a state, After applying heat to the thermoplastic resin constituting the granular carrier to change from a solid state to at least a molten state, the powder adheres to the surface of the molten thermoplastic resin, and these compositions are used as the thermoplastic resin. The state which is formed when the temperature at which becomes a solid state is used.
  • the thermoplastic resin may be polyethylene.
  • PE low density polyethylene
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • PP polypropylene
  • EVA ethylene acetate butyl
  • EMMA ethylene-methacrylic acid copolymer
  • EMMA Ethylene-methyl methacrylic acid copolymer
  • EMA ethylene methyl acrylic acid copolymer
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • PAN polyacrylonitrile
  • thermoplastic resins are preferably those having a softening property at 200 ° C or lower.
  • the thermoplastic resin of these materials fluidity and extensibility are imparted to the resin part, the dispersibility between the resin part and the powder, preferably the functional material, is increased, and further, a granular material made of a thermoplastic resin is used. It becomes possible to carry a functional material at a high concentration on the carrier.
  • the granular carrier made of the thermoplastic resin is not particularly limited as long as it can form a granular shape, Granules and pebbles are exemplified.
  • any inorganic powder can be used as long as the powder can maintain a solid state upon integration with the following thermoplastic resin.
  • any of organic compounds may be sufficient.
  • the functional material used as the powder is a simple substance or compound, or any of these, as long as it is an inorganic or organic substance having a function desired to be imparted to the powder-integrated resin particles. It may be a mixture.
  • functions desired to be given include odor absorption, hygroscopicity, hydrophobicity, heat resistance, color development, hydrophilicity, adsorptivity, and impact resistance.
  • the functional material that is the above-mentioned inorganic substance Silica, colloidal silica, zeolite, montmorillonite, hectorite, talc, aerosil, my power, bentonite, aluminum compound, magnesium compound, norium compound, calcium carbonate, alumina, silicon nitride, boron nitride, etc.
  • Functional materials iron oxide (valve), mercury sulfide (sandstone), natural mineral pigments such as amber, sienna, kaolin, white mica, cadmium yellow, nickel titanium, viridian, ultramarine, carbon black, lead white, etc. These synthetic inorganic pigments can also be used.
  • examples of the functional material that is an organic substance include synthetic organic pigments such as powdered ink toners, phosphors, phthalocyanine-based, azo-based, and polycyclic compounds used in copying machines and laser printers, lakes, and the like.
  • thermosetting resins such as natural organic pigments such as synthetic dyes, polyimides, urea resins, phenol resins, epoxy resins, urethane resins, melamine resins, unsaturated polyester resins, and alkyd resins.
  • the functional material used as the powder may be treated with a surface modifier such as a coupling agent so as to appropriately modify the properties thereof.
  • a surface modifier such as a coupling agent
  • examples of such surface modifiers include methylating agents and silylating agents.
  • zeolite is used as a powder and is methylated, it is possible to impart hydrophobicity to the powder-integrated resin particles.
  • the average particle size of the powder is usually from 0.;! To 5 OO ⁇ m, particularly from ! to 100 m.
  • the average particle diameter may be measured using a known measuring method such as a wet method! /.
  • the particle size of the powder-integrated resin particles according to the present invention is 0.5 to 70 mm, in particular;! To 40 mm, and the average particle size of the powder-integrated resin particles according to the present invention is It is preferably ⁇ or more, more preferably 1 to 30 mm.
  • the average particle size is less than 10 m, the entire amount cannot be automatically discharged when taken out from a closed space where granulation is performed, such as a granulation tank.
  • the twin screw extruder used in the subsequent process cannot be used for a screw such as a fine film film forming machine.
  • the weight of the powder is not particularly limited, but for example, it is preferably 50 to 900% by weight with respect to the weight of the thermoplastic resin. ⁇ ; More preferably, it is 100% by weight. If it is less than 50% by weight, the thermoplastic resin, which will be described later, has been melted, and the surface of the powder-integrated resin particles has become bullet marks, and the adhesion of the surface has increased. You may not be able to remove it from the space where you perform. If it exceeds 900% by weight, integration of the thermoplastic resin and the powder may not proceed and granulation may not be possible.
  • the volume ratio of the thermoplastic resin to the inorganic or organic functional material powder is preferably 1: 1 to 1:20. Outside these ranges, it may become impossible to remove from the space for granulation, such as a granulation tank, during production.
  • the particle-containing molded article according to the present invention is a particle-containing molded article composed of the above-mentioned powder-integrated resin particles according to the present invention and a water-soluble organic resin such as polyhydric alcohol (PVA).
  • PVA polyhydric alcohol
  • the form of the particle-containing molded body is not particularly limited, and examples thereof include a cylinder and a pyramid.
  • Examples of the water-soluble organic resin in the particle-containing molded body according to the present invention include polybulal alcohol (PVA), acrylic acid, polyester, and the like.
  • the solid content of the water-soluble organic resin is preferably 1% to 25%.
  • the weight of the water-soluble organic resin is preferably 10% by weight or more and 50% by weight or less with respect to the weight of the powder-integrated resin particles. If the amount is less than 10% by weight, the adhesive strength is insufficient. If the amount exceeds 50% by weight, the characteristics of the powder, especially the function of the functional material, will deteriorate.
  • the above-mentioned powder integrated resin particles and a water-soluble organic resin are molded into a certain shape using a molding method known in the art.
  • a molding method known in the art kneading, baking, heating, pressurizing and the like without particular restrictions may be used alone or in an appropriate combination.
  • the heating temperature is not particularly limited as long as it can volatilize the solvent used for molding, for example, about 100 ° C.
  • the pressure range of this pressurization includes lkg / cm 2 or more.
  • the method for granulating powder-integrated resin particles according to the present invention includes a step of applying heat to the granular carrier so as to at least soften the surface of the granular carrier made of the thermoplastic resin, and then the softening. A step of attaching the above-mentioned powder, preferably a functional material, to the surface of the granular carrier.
  • the powder-integrated resin particles having a granular carrier made of a thermoplastic resin and a powder integrated on the surface of the granular carrier can be obtained.
  • the granular carrier used for granulation of the powder-integrated resin particles, and the powder exemplified by the functional material include: During this method, the powder exemplified by the functional material is already introduced into the system when performing the step of applying heat to the granular carrier, which should be appropriately introduced into the granulating system. Alternatively, after this step is performed, a step of introducing the powder into the system and attaching the powder to the surface of the granular carrier may be performed.
  • thermoplastic resin is introduced first for the purpose of suppressing the scattering of the powder exemplified as the functional material or promoting the softening of the thermoplastic resin in the granulating system. It is preferable. Regarding the method of introducing these components into the granulation system, there is no particular restriction. Depending on the method, it is selected as appropriate from the method of direct injection into the system. Further, the form of the granular carrier made of the above-mentioned powder and thermoplastic resin introduced into the sealed space for granulation is appropriately selected according to the desired form of the powder-integrated resin particles. For example, examples of the form of the granular carrier made of thermoplastic resin include pellets and granules.
  • the method of applying a heat to the granular carrier is as follows. There is no particular limitation as long as it softens at least.
  • a method of directly applying heat to the thermoplastic resin constituting the granular carrier may be used.
  • a method of introducing a granular carrier made of a thermoplastic resin into the sealed space and raising the temperature of the sealed space may be used.
  • a mixing granulator such as a Henschel mixer
  • a rotating member such as a rotary blade that rotates in a sealed space of this machine is brought into contact with the granular carrier,
  • the granular carrier may be heated by the frictional heat generated at this time!
  • the temperature of the step of applying heat to the granular carrier is the thermoplastic resin used for granulation and the physical properties of the powder.
  • the glass transition point, the melting temperature, etc. may be selected as appropriate.
  • the temperature when heat is applied to a granular carrier made of polyethylene, polypropylene or the like as a thermoplastic resin, the temperature may be 80 ° C to 200 ° C. If the temperature is less than 80 ° C, it becomes difficult to soften the granular carrier made of thermoplastic resin at least, and integration with the powder to be performed later does not proceed.
  • the temperature of the step of applying heat to the granular carrier is lower than the melting point of the powder. May be. This makes it possible to prevent the granular carrier from being melted and integrated into the thermoplastic resin when heat is applied to the granular carrier.
  • the step of applying heat to the granular carrier is a powder exemplified by a thermoplastic resin and preferably a functional material.
  • a known mixing granulator for mixing and granulating examples include a mixing granulator provided with a granulating tank.
  • a Henschel mixer is preferably used.
  • the size of the granulation tank provided in such a mixing granulator may be appropriately selected according to the amount of components such as the thermoplastic resin and powder to be introduced, the specific gravity of the powder, etc. ⁇ 200cm, height may be 80% to 200% of diameter.
  • the step of applying heat to the granular carrier includes a rotating member that rotates in a sealed space where granulation is performed, and The frictional heat generated by the contact with the granular carrier may be used.
  • a rotating member such as a rotary blade provided at the bottom of the granulation tank and rotating in the tank. It may be performed by heat.
  • the tip of the rotating member be applied so as to give a shearing force to the granular carrier.
  • the rotation speed of the rotating member may be appropriately selected according to the material of the granular carrier, the glass transition point, the melting temperature, etc.
  • the rotating speed of the tip of the rotating member is from 1 Om / sec to You may set it so that it may become 100m / second, especially 30m / second-60m / second. Within such a range, it is preferable in terms of controlling the softening temperature of the thermoplastic resin and increasing the contact probability with the powder exemplified by the functional material or functional pigment derived from inorganic or organic. .
  • the granulation is performed for the purpose of at least softening the surface of the granular carrier made of a thermoplastic resin. It may be performed by applying heat to the tank.
  • the temperature of the granulation tank may be appropriately selected according to the material of the granular carrier, the glass transition point, the melting temperature, etc. For example, when polyethylene, polypropylene or the like is used as the thermoplastic resin, 80 ° C to 200 ° C.
  • the method for controlling the temperature of the granulation tank may be a method of directly heating the granulation tank, or a method of achieving this temperature range by cooling the granulation tank.
  • thermoplastic resin and the powder are transferred in the tank as the rotary blade in the granulation tank rotates.
  • a blade may be provided at a position vertically above the rotating member. This blade lowers the thermoplastic resin and powder below the granulation tank in order to bring the powder exemplified by the thermoplastic resin and functional material into contact with the rotating member provided at the lower part of the granulation tank. It is.
  • one or more choppers may be installed, which may have a crushing action on the side of the granulation tank or from the top. May be.
  • the size of the rotating member is preferably 50% to 95% of the diameter of the granulation tank and has a shape and strength sufficient to cut a softened thermoplastic resin. Used Yes
  • the rotating member and the blade are both installed at a position within a range of 20% to 60% of the height of the tank from the bottom of the granulation tank. From the bottom, the rotary blade and the blade are parallel to each other in this order. Don't touch! /, You can set it up! /.
  • the chopper is installed for the purpose of disturbing the movement of the mixture of the thermoplastic resin in the centrifugal direction generated by the rotary blade and the powder, preferably the functional material. It does not matter, but it is preferable that the tip of the tank is installed so that the tip is directed toward the bottom. Moreover, if the said objective is achieved, the presence or absence of rotation will not be ask
  • the particle-containing sheet material according to the present invention comprises the above-described powder-integrated resin particles according to the present invention, and has various sheet-like shapes.
  • the particle-containing sheet material according to the present invention is formed into a sheet shape using a composition comprising powder-integrated resin particles obtained according to the granulation method of powder-integrated resin particles according to the present invention described above.
  • the composition may be molded by a molding method known in the art. This molding method is not particularly limited, and examples include extrusion molding, cast molding, T-die molding, inflation molding, injection molding, and blow molding.
  • the film thickness is not particularly limited as long as it can exhibit the characteristics of the powder.
  • it is 30 111 or more and 300 111 or less. It is preferable. If it is within this range, the properties of the powder, particularly the effect of the functional material, and the handling as a sheet will be good.
  • the composition comprising the powder-integrated resin particles may have various materials in addition to the powder-integrated resin particles.
  • various inorganic / organic compounds may be added to impart fluidity.
  • a second resin such as a polyethylene resin may be added in addition to the thermoplastic resin constituting the powder-integrated resin particles.
  • a second resin is not particularly limited, and examples thereof include a thermoplastic resin such as polyethylene.
  • the second resin may be a thermoplastic resin that constitutes the powder-integrated resin particles.
  • thermoplastic resin fluidity, heat It is preferable at the point which has the same property, and the point which can maintain the integrity as a sheet
  • the addition amount of the second resin is preferably 10 to 30% by weight with respect to the total amount of the powder-integrated resin particles. If it is within this range, it is determined by the force that imparts fluidity to the second resin during extrusion molding.
  • the functional sheet according to the present invention is characterized by having a sheet-like form in which powder-integrated resin particles are supported on a base sheet. The outline is shown in Figs.
  • the functional sheet 12 according to the present invention may include a base sheet 14 and powder-integrated resin particles 1 supported on the base sheet. Good.
  • the functional sheet 12 according to the present invention further includes a thermoplastic resin layer 16 made of a thermoplastic resin between the base sheet 14 and the powder integrated resin particles 1. It may be arranged.
  • the functional sheet 12 according to the present invention may be one in which powder-integrated resin particles 1 are supported between a plurality of substrate sheets 14.
  • the weight of the powder constituting the powder-integrated resin particles is preferably 30% by weight or more and 80% by weight or less with respect to the total weight of the functional sheet.
  • the weight of the nonwoven fabric to be used may be set as appropriate.
  • a known sheet is not particularly limited and can be used.
  • synthetic fibers such as aramid, cellulose, polyamide, polybutyl alcohol, polyester, polyolefin, rayon, phenol, natural fibers such as cotton, silk, hemp, etc., and carbon fibers of these fibers are spunbonded. Spun lace, needle punch, etc. Physical, resin bond, chemical method such as thermal bond, etc. It is done.
  • Polyethylene terephthalate (PET), polyethylene (PE), poly salt It may be a sheet-like substrate made of a synthetic resin such as plasticized bull (PVC). The type and weight of these components, and the aspect of the substrate sheet such as the number of voids inside the substrate sheet may be appropriately selected depending on the application.
  • Examples thereof include nonwoven fabrics and sheet-like substrates.
  • Examples of the base material sheet include heat resistance at about 100 ° C. or more, thermal stability, weight per unit area, air permeability (porous), thickness, and the like.
  • polyester, cotton, polyamide, aramide, and phenol are preferably used as the material constituting the base sheet.
  • a known roughened surface such as a blast method may be used as the base material sheet.
  • the powder-integrated resin particles carried on the base sheet are integrated with a granular carrier made of a thermoplastic resin and the surface of the granular carrier. And has a particulate form.
  • the form of the powder-integrated resin particle is not particularly limited as long as it is particulate.
  • the form of the powder-integrated resin particles is not particularly limited, as shown in Fig. 1, with the granular support 2 being the center and the powder 4 being integrated on the surface of the granular support 2. It may be.
  • the state of "integrated on the surface of the granular carrier” means that the thermoplastic resin and the powder constituting the granular carrier are thermoplastic.
  • the powder adheres to the surface of the molten thermoplastic resin, The state formed when these compositions are set to a temperature at which the thermoplastic resin is in a solid state.
  • thermoplastic resin polyethylene (PE) as mentioned in the powder-integrated resin particles, Low density polyethylene (LDPE), High density polyethylene (HDPE), Linear low density polyethylene (LLDPE), Polypropylene (PP), Ethylene acetate butyl (EVA), Ethylene monometatalic acid copolymer (EMAA), Ethylene Methyl methacrylic acid copolymer (EMMA), ethylene-methyl acrylic acid copolymer (EMA), butyl chloride, butyl acetate, butyl acetate Examples include a butyl copolymer, acrylic, methacrylic resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyacrylonitrile (PAN).
  • the thermoplastic resin may be a combination of these materials as appropriate. Good. Among these, PE, LDPE, LLDPE, PP, EVA, EMAA, EMMA, EMA, and talyl resin are desirable for integration with functional materials. These thermoplastic resins are preferably those having a softening property at 200 ° C or lower. By using thermoplastic resins of these materials, fluidity and extensibility are imparted to the resin part, the dispersibility between the resin part and the powder, preferably the functional material, is increased, and the resin part is made of thermoplastic resin. It becomes possible to carry the functional material at a high concentration on the granular carrier.
  • the granular carrier made of the thermoplastic resin is not particularly limited as long as it can form a granular shape. Shapes, granules, and pebbles.
  • the powder may be any material that can maintain a solid state when integrated with the following thermoplastic resin.
  • Either an inorganic compound or an organic compound may be used.
  • the functional material used as the powder as long as it is an inorganic substance or an organic substance having a function desired to be imparted to the powder-integrated resin particles, there is no particular limitation, a simple substance or a compound, or a mixture thereof. It may be.
  • examples of the function desired to be given include odor absorption, hygroscopicity, hydrophobicity, heat resistance, color development, hydrophilicity, adsorptivity, and impact resistance.
  • the functional material that is the above-mentioned inorganic compound or metal includes silica, colloidal silica, zeolite, montmorillonite, hectorite, talc, and aerosol.
  • the functional material that is an organic substance described above, synthesis of powdered ink toners, phosphors, phthalocyanine-based, azo-based, polycyclic compounds, and the like used in copying machines and laser printers is possible.
  • examples include organic pigments, natural organic pigments such as lakes, synthetic dyes, polyimides, urea resins, phenol resins, epoxy resins, urethane resins, melamine resins, unsaturated polyester resins, alkyd resins, and other thermosetting resins.
  • the functional material used as the powder is treated with a surface modifier such as a coupling agent so as to appropriately modify the properties thereof.
  • a surface modifier such as a coupling agent
  • examples of such surface modifiers include methylating agents and silylating agents.
  • zeolite when used as a powder and is methylated, it is possible to impart hydrophobicity to the powder-integrated resin particles.
  • the average particle diameter of the powder (usually, 0 to 500 mm, and especially 100 to 100 mm).
  • the particle diameter of the powder-integrated resin particles used in the functional sheet according to the present invention is 0.5 to 7 mm, and the average particle diameter of the powder-integrated resin particles used in the functional sheet according to the present invention.
  • the diameter is preferably 10 111 to 5111 111, more preferably 100 111 to 1.5 mm. If the average particle size is less than 10 m, the entire amount cannot be discharged automatically when taken out from a closed space where granulation is performed, such as a granulation tank. On the other hand, if the average particle diameter exceeds 40 mm, the surface unevenness becomes remarkable when the sheet is supported on the sheet, and it becomes impossible to obtain good sheet characteristics.
  • powder-integrated resin particles used in the functional sheet according to the present invention those having an average particle size of !! to 30 mm may be used as they are for the purpose of extrusion. It can be suitably used for processing, and can also be used effectively for film formation.
  • the weight of the powder is not particularly limited, but is, for example, 50% by weight or more with respect to the weight of the thermoplastic resin. It is preferably 80% by weight or less; more preferably 100% by weight. If it is less than 50% by weight, the above-mentioned thermoplastic resin will be melted and the surface of the powder-integrated resin particles will become bullet marks, or the adhesion of the surface will increase. There is a case where it adheres in the space where it is performed and cannot be removed from the granulation tank. If it exceeds 900% by weight, the integration of the thermoplastic resin and the powder may not proceed and granulation may not be possible.
  • the powder-integrated resin particles used in the functional sheet according to the present invention The volume ratio between the resin and the inorganic or organic functional material powder is preferably 1:;! ⁇ 1: 20. Outside these ranges, it may become impossible to remove from the space for granulation, such as a granulation tank, during production.
  • the method for granulating the powder integrated resin particles used in the functional sheet according to the present invention is not particularly limited as long as it is a method capable of obtaining the above-described powder integrated resin particle embodiment! / ,.
  • this granulation method heat is applied to the granular carrier so as to at least soften the surface of the granular carrier made of the thermoplastic resin, and then the surface of the softened granular carrier is
  • the powder described above, preferably a functional material may be attached. That is, as the granulation method for the powder-integrated resin particles used in the functional sheet according to the present invention, the granulation method for the powder-integrated resin particles according to the present invention may be used. As a result, the powder-integrated resin particles having a granular carrier made of a thermoplastic resin and a powder integrated on the surface of the granular carrier are obtained.
  • the functional sheet according to the present invention may have various components as long as the above-described aspect is not affected.
  • a thermoplastic resin layer 16 made of a thermoplastic resin may be provided between the base sheet 14 and the powder-integrated resin particles 1.
  • Any thermoplastic resin may be used as long as it does not hinder the support of the powder integrated resin particles 1 and the base sheet 14, and the thermoplastic resin constituting the powder integrated resin particles 1 is not particularly limited. A resin is preferred.
  • FIG. 5 is a schematic view showing an example of a process for producing a functional sheet according to the present invention.
  • the powder integrated resin particles are fed from the feeder 44 onto the base sheet 14 supplied from the primary unwinding section 41. Distribute evenly. Thereafter, the base sheet 14 having the powder-integrated resin particles uniformly distributed is supported on the base sheet 14 by, for example, the oven 46 in which heat is applied.
  • the whole base sheet may be preheated by passing through the inside, and may be hot pressed or pressed by the hot press roll 48. The obtained sheet Then, it may be wound up by the winding unit 49.
  • thermoplastic resin layer made of a thermoplastic resin may be laminated on the base sheet 14.
  • a material obtained by previously laminating a thermoplastic resin layer on the base sheet 14 may be supplied from the primary unwinding portion 41.
  • the powder-integrated resin particles are uniformly distributed from the feeder 44 onto the base sheet 14, and then conveyed to the oven 46 before the secondary side winding.
  • a base sheet 14 of the same or different type as that of the primary side unwinding part 41 may be placed from above on the spreading surface from the unloading part 42.
  • the substrate sheet wound up by the winding unit 49 is supplied again to the primary-side unwinding unit 41, and each of the above steps is repeated or a feeder is provided.
  • Up to 44 forces and up to the heat and pressure roll 48 may be continuously arranged a plurality of times. This makes it possible to produce a functional sheet having a multilayer structure.
  • winding unit 49 which is the final step, may be omitted, and after pressing the base material sheet obtained up to the hot-pressing roll 48, sheet cutting may be performed using a cutting machine or the like, and then sequentially stacked. .
  • the heating temperature by the oven 46 may be appropriately selected according to the type of base material sheet and powder-integrated resin particles used.
  • the heating temperature is higher than the glass transition point of the powder-integrated resin particles which may be set in consideration of the glass transition point of the base-material sheet or the powder-integrated resin particles. May be set so that the glass transition point of the base sheet is lower than the heating temperature.
  • the clearance distance between the hot press rolls 48 is not particularly limited.
  • the line speed may be set according to the type of base material sheet and powder integrated resin particles used. There is no particular limitation as long as the particles are distributed and hot pressed well.
  • the force S described to be performed by applying heat using the oven 46, the hot press roll 48, etc. As long as it is possible to achieve such a supporting mode, it is not limited to heat, and examples thereof include UV curing, high frequency, ultrasonic waves, and electron beams.
  • powders (average particle size 2 mm) obtained by kneading and pulverizing the following components were supplied to a mixing granulator to obtain powder integrated resin particles having the composition shown in Table 1.
  • Table 2 shows the average particle diameter after processing and the results of microscopic observation.
  • the mixing granulator has a mixing granulation tank having a diameter of 40 cm at the bottom and a height of 40 cm, a rotating blade having a diameter of 30 cm is provided at the center of the bottom, and the rotating blade A blade having a diameter of 20 cm was installed in the upper part in parallel with the rotary blade.
  • the rotation speed of the rotary blade edge was set to 40 m / second
  • the rotation speed of the blade edge was set to 30 m / second
  • one chopper was installed on the top of the tank lid.
  • the temperature was controlled so that the temperature in the tank was 140 ° C.
  • the grinding time was 20 minutes.
  • thermoplastic resin in the formulation shown in Table 1 was pulverized and then dry blended with the powder using a stirrer, and pelletized by a twin screw extruder as a subsequent step.
  • the charged amount was about 4 kg in total of the powder and the thermoplastic resin in both Examples and Comparative Examples.
  • the functional material used as the powder is molecular sieve 4A (Union Showa)
  • thermoplastic resin LDPE (manufactured by Tosoichi Co., Ltd.) and PP (Nippon Polychem BC06C) were used.
  • Example 1 1 1 1 1 1 Molecular sieve 4 A 90 parts LDFE 10 parts
  • Example 1 1 1-3 Molecular sieve 4 A 70 parts LDPE 30 parts
  • Ratio reduction example 1-2-1 Molecular sheep 4 A 90 parts P P 10 parts
  • Example 1 1 3-1 CaO 90 parts LDPE 10 parts
  • Example 1 1 4-1 Alumina 90 parts LDPE 10 parts
  • Example 1 -4 1 2 Alumina 80 parts LDPE 20 parts
  • Example 1 -4 1 3 Alumina 70 parts LDPE 30 parts
  • Example 1-1-3 In all cases, falling evenly Stable production ⁇
  • Comparative Example 1 1-1 1-3 Resin falls faster and clogging occurs
  • Example 1 1 In all cases, falling evenly Stable production ⁇
  • Comparative Example 1-2-1 Resin falls earlier and clogging occurs
  • Example 1-2-3 In all cases, evenly dropped Stable production ⁇
  • Comparative Example 1 1 2-3 Resin falls faster and clogging occurs
  • Example 1-3-3 In all cases, falling evenly Stable production ⁇
  • Comparative Example 1 3-3 Resin falls earlier and clogging occurs
  • Example 1-4-1 In all cases, falling evenly Stable production ⁇
  • Comparative Example 1-4-1 Resin falls faster and clogging occurs
  • the quantitative feeding into the extruder could be easily performed.
  • the thermoplastic resin and the powder were put separately, the ratio of the particles having a large particle size relative to the charging ratio increased, and the fine powder remained in the transport system, which was a good master. The batch could not be made.
  • Example 1 1 1 to 1 4 3 In the same manner as in Examples 1 1 1 to 1 4 3 using the powder and thermoplastic resin shown in Table 4 instead of the powder and thermoplastic resin shown in Table 1. To obtain powder-integrated resin particles. Next, the water-soluble organic resin shown in Table 4 was added to 100 parts of the powder integrated resin particles and kneaded. The obtained kneaded product was filled in a mold and a pressure of 10 kg / cm 2 or more was applied. This was sintered at 200 ° C. for 1 hour to obtain a solidified product.
  • a cylindrical solid product with a diameter of 2 mm and a height of 3 mm and a tablet containing triethylamine (active ingredient content 10%) are placed in a sealed container and left in an environment at a temperature of 25 ° C and a relative humidity of 50% for 2 40 hours. did. Thereafter, the presence or absence of adsorption of the triethylamine component was detected using a GC-MS apparatus (Automass, manufactured by JEOL Ltd.), and the odor absorption property of the solidified product was evaluated. The results are shown in Table 5. In Table 5, ⁇ indicates that the product has sufficient odor absorption, and symbol indicates that evaluation was not possible.
  • a cylindrical solid product with a diameter of 2 mm and a height of 3 mm was prepared, and the hardness of this solid product was measured as a peak value at the time of crushing fracture using a digital force gauge (FGC-50, manufactured by SHIMPO). did.
  • the results are shown in Table 5.
  • Example 1 1 1 to 1 4 3 except that 30 parts of A-type silica gel (manufactured by Tokuma Corporation) and 70 parts of PE were used instead of the powder and thermoplastic resin shown in Table 1. Were carried out in the same manner as in Examples 1 1 1 to 1 4 3 to obtain powder integrated resin particles. 10 parts of PE is further added to the powder-integrated resin particles, and a 100 m thick film is formed by extrusion molding. Molded into rum. When this film was moisture-absorbed at a temperature of 40 ° C and a relative humidity of 90%, it showed a moisture absorption of 9. Og / m 2 .
  • Example 2 For Example 2— ;! to 2-2-2, the components in Table 6 were ground using the Henschel mixer (Mitsui Mining Co., Ltd.) under the following conditions! / ⁇ Forming powder integrated resin particles did.
  • thermoplastic resin polyethylene (PE)
  • E-integrated resin particles thermoplastic resin: polyethylene (PE)
  • zeolite powder and a thermoplastic resin ethylene butyl acetate copolymer
  • composition obtained by dry blending with (EVA) was sandwiched between base sheets in the same manner as in the examples and sheeted and tested in the same manner as in the examples. The results are shown in Table 6.
  • Measurement method Using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), the adhesion between 25 mm wide substrate sheets was measured.
  • Table 6 shows the tensile strength at which the base sheets peeled off.
  • the obtained base material sheet was cut into a 10 cm square and allowed to stand for 48 hours in an oven at a temperature of 40 ° C./90% relative humidity, and the weight increase due to moisture absorption was measured with an electronic balance.
  • Examples 2-3 to 2-5 those obtained by granulating Zeolite molecular sieve 13X (manufactured by Union Showa Co., Ltd.) as a functional material and polyethylene as a thermoplastic resin with a weight ratio of 8: 2 were used. Using. In addition, each of Comparative Examples 2-3 to 2-5 was used alone. Using et Scott Fine CO60NA0 2 as the base sheet (manufactured by Yuyuchika Co.), based on the above hot pressing step, under the following conditions, subjected to hot pressing to obtain a functional sheet. [0146] [Hot press conditions]
  • Hot press temperature 200 ° C
  • Example 2 except that the components shown in Table 8 were used instead of the powder-integrated resin particles of Examples 2-6 to 2-8. — Perform in the same way as 6 to 2-8. I got a job.
  • T-type peeling was performed at 1 N / m 2 or more.
  • the obtained functional sheet or sheet and a tablet containing triethylamine (active ingredient content: 10%) were placed in a sealed container and allowed to stand for 240 hours in an environment of a temperature of 25 ° C. and a relative humidity of 50%. Thereafter, the presence or absence of adsorption of the triethylamine component was detected using a GC-MS apparatus (Automass, manufactured by Nippon Denshi), and the functional sheet or sheet odor absorption was evaluated. The results are shown in Table 8. In Table 8, ⁇ indicates that it has sufficient odor absorption.
  • the functional sheet according to the present invention can be suitably used mainly for filters for air-conditioning machines, medicines, desiccants for electronic and electrical members, and the like.
  • it since it is supported on a non-woven fabric, it can be easily processed into a desired shape and can be applied to a wide range of fields.

Abstract

L'invention concerne des particules de résine ayant une poudre combinée à celles-ci, lesquelles sont produites par un procédé simple tout en conservant la fonction de la poudre, de préférence une matière fonctionnelle (dont un pigment). L'invention concerne des particules de résine ayant une poudre combinée à celles-ci, caractérisées en ce qu'elles comprennent un support particulaire comprenant une résine thermoplastique et des particules de poudre combinées à la surface du support particulaire.
PCT/JP2007/064769 2006-07-28 2007-07-27 Particules de résine ayant une poudre combinée à celles-ci et leur procédé de formation, objet moulé contenant les particules, matière en forme de feuille contenant les particules et leur procédé de formation et feuille fonctionnelle et procédé servant à la prod WO2008013266A1 (fr)

Applications Claiming Priority (8)

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JP2006-206016 2006-07-28
JP2006206016 2006-07-28
JP2006-235640 2006-08-31
JP2006235640 2006-08-31
JP2007193402A JP2008050592A (ja) 2006-07-28 2007-07-25 粉体一体化樹脂粒子及びその造粒方法、並びに粒子含有成形体及び粒子含有シート材並びにこれらの成形方法
JP2007-193403 2007-07-25
JP2007-193402 2007-07-25
JP2007193403A JP2008080793A (ja) 2006-08-31 2007-07-25 機能性シート及び機能性シートの製造方法

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WO2010146820A1 (fr) * 2009-06-19 2010-12-23 三井・デュポンポリケミカル株式会社 Pastille de résine et méthode de production de celle-ci
WO2019055304A1 (fr) * 2017-09-18 2019-03-21 Dow Global Technologies Llc Compositions contenant des particules de polymère enrobées et compositions de tpo formées à partir de celles-ci
EP4015181A1 (fr) * 2020-12-17 2022-06-22 Schlenk Metallic Pigments GmbH Procédé de génération in situ des pigments dans une matière plastique

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JPS62149727A (ja) * 1985-12-24 1987-07-03 Nikko Rika Kk プラスチツク複合化粒子およびその製造方法
JPS62298443A (ja) * 1986-06-17 1987-12-25 Nara Kikai Seisakusho:Kk 固体粒子の表面改質方法
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WO2010146820A1 (fr) * 2009-06-19 2010-12-23 三井・デュポンポリケミカル株式会社 Pastille de résine et méthode de production de celle-ci
JP4801221B2 (ja) * 2009-06-19 2011-10-26 三井・デュポンポリケミカル株式会社 樹脂ペレットおよびその製造方法
KR101138928B1 (ko) 2009-06-19 2012-04-30 듀폰-미츠이 폴리케미칼 가부시키가이샤 수지 펠릿 및 그 제조 방법
CN102803353A (zh) * 2009-06-19 2012-11-28 三井-杜邦聚合化学株式会社 树脂颗粒及其制造方法
CN102803353B (zh) * 2009-06-19 2013-10-09 三井-杜邦聚合化学株式会社 树脂颗粒及其制造方法
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WO2019055304A1 (fr) * 2017-09-18 2019-03-21 Dow Global Technologies Llc Compositions contenant des particules de polymère enrobées et compositions de tpo formées à partir de celles-ci
US11236241B2 (en) 2017-09-18 2022-02-01 Dow Global Technologies Llc Compositions containing coated polymer particles and TPO compositions formed from the same
EP4015181A1 (fr) * 2020-12-17 2022-06-22 Schlenk Metallic Pigments GmbH Procédé de génération in situ des pigments dans une matière plastique
WO2022128261A1 (fr) * 2020-12-17 2022-06-23 Schlenk Metallic Pigments Gmbh Procédé de production d'un granulé plastique contenant des pigments

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