Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• • 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
  • B32B5/18—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 features of a layer of foamed material
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
  • C08J9/0038—Use of organic additives containing phosphorus
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding ingredients
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/22—After-treatment of expandable particles; Forming foamed products
  • C08J9/228—Forming foamed products
  • C08J9/236—Forming foamed products using binding agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
  • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
  • C09J127/22—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers modified by chemical after-treatment
  • C09J127/24—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers modified by chemical after-treatment halogenated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
  • B29K2027/06—PVC, i.e. polyvinylchloride
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2065/00—Use of polyphenylenes or polyxylylenes as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
  • B29K2995/0016—Non-flammable or resistant to heat
• • 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
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08J2327/06—Homopolymers or copolymers of vinyl chloride
• • 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
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/22—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment
  • C08J2327/24—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment halogenated
• • 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
  • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
  • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

Definitions

• the present invention relates to flame-retardant articles.
• organic heat insulating materials there are organic heat insulating materials and inorganic heat insulating materials, but organic heat insulating materials are more preferred because they are lightweight and have excellent heat insulating properties.
• foamed plastics thermoplastic resin foamed members
• foamed plastics also have the characteristic of being ignited by contact with flames when a fire occurs and/or during welding, and the fire can spread.
• Patent Document 1 a phenolic resin containing boric acid and aluminum hydroxide is mixed with pre-expanded beads to form coated beads whose surface is coated with a coating layer containing boric acid, aluminum hydroxide and phenolic resin. Techniques are disclosed.
• a primary coating layer composed of a non-boric acid flame retardant and a curing agent-added resol resin is formed on the surface of foamed resin beads, and the film thickness of the primary coating layer is formed on the surface of the primary coating layer.
• a technique is disclosed for coating beads for flame-barrier and heat-insulating materials by forming a secondary coating layer made of a resol resin containing a curing agent with a thinner film thickness.
• Patent Document 3 discloses a structural material made of a combustible foamed resin whose foaming degree is larger than 66% and smaller than 100% of the volume when foamed without pressure, wherein the combustible foamed resin is flame-retardant.
• a vibration-absorbing structural material is disclosed which is partitioned by a non-combustible partition containing microvoids composed of a non-combustible resin and non-combustible fine particles.
• One embodiment of the present invention has been made in view of the above problems, and its object is to provide a novel flame-retardant article with excellent flame-retardant properties.
• the foamed member is formed by foaming a composition containing a thermoplastic resin that does not burn out when burned in a specific high-temperature environment, and the foamed member
• the present inventors have found that the above problems can be solved by providing a cured resin member capable of forming an oxygen-blocking carbonized layer upon combustion on at least a part of the surface of the body, and have completed the present invention.
• the flame-retardant article comprises a foam member obtained by foaming a thermoplastic resin composition containing a thermoplastic resin, and a thermosetting resin composition containing a thermosetting resin. and a cured resin member, wherein the thermoplastic resin produces a residue when heated from 35 ° C. to 600 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere, and the cured resin
• the member forms an oxygen-blocking carbonized layer upon combustion, and the cured resin member is present on at least a portion of the surface of the foamed member.
• the structural units include a structural unit derived from the X1 monomer, a structural unit derived from the X2 monomer, ... and an Xn monomer (where n is An integer of 2 or more) is also referred to as "X 1 /X 2 /.../X n copolymer".
• the X 1 /X 2 /.../X n copolymer is not particularly limited in its polymerization mode unless otherwise specified, and may be a random copolymer or a block copolymer. may be a graft copolymer.
• One of the indices of flame retardancy of a certain article is the evaluation criteria for noncombustible materials, etc., in the Building Standards Law of Japan.
• it in order for an article to be certified as a non-combustible building material, it must be determined by the cone calorimeter method at the General Building Research Institute, a public institution stipulated in Article 108-2 of the Enforcement Order of the Building Standards Law.
• Patent Documents 1 and 2 can satisfy the above criteria if they are composite materials of beads and aluminum members such as aluminum plates. However, the beads themselves cannot meet the above criteria and are not articles that can be qualified as non-combustible materials. That is, the techniques described in Patent Documents 1 and 2 have room for further improvement in terms of flame retardancy.
• the present inventors provide an article that is excellent in flame retardancy, specifically, a novel article that can be certified as a noncombustible material by satisfying the above-mentioned criteria without including an aluminum member as a component. In order to do so, we conducted an intensive study.
• thermoplastic resin in a nitrogen atmosphere, at a temperature increase rate of 10 ° C./min, 35 ° C. to 600 ° C.
• a thermoplastic resin that forms a residue when heated to a temperature of A flame-retardant article obtained by allowing the cured resin member to exist on at least a part of the surface of the foamed member formed by the above-mentioned criteria must be satisfied.
• the reason why the flame-retardant article described above can satisfy the above-mentioned criteria is not clear, but it is speculated as follows: At the time of combustion, the cured resin member is first rapidly carbonized, and carbonized. form a layer.
• the carbonized layer has oxygen blocking performance.
• the carbonized layer can thus act as an oxygen barrier to prevent the foam member from being exposed to oxygen. This results in the foam member being exposed to high temperatures under oxygen deprivation or hypoxic conditions.
• a foamed member such as general polystyrene foam disappears because a combustible low-molecular-weight compound is generated by thermal decomposition from the base resin in an environment exposed to high temperatures.
• the foamed member contains the thermoplastic resin that produces the residue described above, the generation of the low-molecular-weight compound can be suppressed, thereby reducing the calorific value and causing unburned residue even under high-temperature combustion. As a result, the flame-retardant article does not ignite and can reduce the calorific value even during combustion in which it is continuously exposed to an ignition source and high temperature. .
• a flame-retardant article comprises a foamed member formed by foaming a thermoplastic resin composition containing a thermoplastic resin, and a cured thermosetting resin composition containing a thermosetting resin.
• a cured resin member wherein the thermoplastic resin produces a residue when heated from 35° C. to 600° C. at a rate of temperature increase of 10° C./min in a nitrogen atmosphere, and the cured resin member However, it forms an oxygen-blocking carbonized layer when burned, and the cured resin member exists on at least part of the surface of the foamed member.
• the "flame-retardant article according to one embodiment of the present invention” may be referred to as the "present flame-retardant article”.
• “heating from 35°C to 600°C at a heating rate of 10°C/min in a nitrogen atmosphere” may be referred to as “performing a thermal analysis evaluation test”.
• the “residue” when simply described as “residue”, is “residue when the temperature is raised from 35 ° C. to 600 ° C. at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere.” is intended, in other words, "carbide when a thermal analysis evaluation test is performed” is intended.
• total calorific value when simply referred to as “total calorific value”, the “total calorific value” is defined as 20 at a radiant heat intensity of 50 kW/m 2 by a method conforming to "ISO5660-1:2002.””total calorific value when heated per minute” is intended.
• the flame-retardant article itself preferably has a total calorific value of 8.00 MJ/m 2 or less, more preferably 7.70 MJ/m 2 or less, even more preferably 7.60 MJ/m 2 or less, 7.50 MJ/m 2 or less is even more preferred, 7.40 MJ/m 2 or less is particularly preferred, and 7.30 MJ/m 2 or less is most preferred.
• This flame-retardant article does not contain a non-combustible face material such as metal foil as a constituent element, and has the advantage that the flame-retardant article itself satisfies the certification criteria as a non-combustible material under the Building Standards Law. As a result, a flame-retardant article that is low in cost and excellent in lightness can be obtained.
• one embodiment of the present invention also has the advantage of providing safe and inexpensive housing. Thereby, an embodiment of the present invention also has the advantage that it can contribute to achieving the Sustainable Development Goals (SDGs).
• SDGs Sustainable Development Goals
• the foamed member is obtained by foaming a thermoplastic resin composition containing a thermoplastic resin.
• the method for producing the foamed member that is, the method for foaming the thermoplastic resin composition will be described later.
• thermoplastic resin composition Other configurations of the thermoplastic resin composition are not particularly limited as long as it contains a thermoplastic resin.
• the thermoplastic resin composition may contain, in addition to the thermoplastic resin, (a) a foaming agent for foaming the thermoplastic resin composition, and (b) other components such as a processing aid.
• thermoplastic resin can also be said to be a resin that substantially constitutes the foamed member.
• Other constitutions of the thermoplastic resin are not particularly limited as long as they produce a residue.
• a residue is produced intends "a carbide remains when a thermal analysis evaluation test is carried out”.
• thermoplastic resins that produce residues include vinyl halide resins and acrylonitrile resins.
• the vinyl halide resin is not particularly limited.
• (b) a copolymer consisting of one or more monomers selected from the group and one or more other monomers; or (c) post-halogenation A (co)polymer obtained by (for example, post-chlorination) can be mentioned.
• a vinyl chloride resin is more preferable as the vinyl halide resin.
• the vinyl chloride resin used in the present invention is not particularly limited, but examples include polyvinyl chloride (vinyl chloride homopolymer); vinyl chloride/vinyl acetate copolymer, vinyl chloride/(meth)acrylic acid copolymer, Vinyl chloride/methyl (meth)acrylate copolymer, vinyl chloride/ethyl (meth)acrylate copolymer, vinyl chloride/maleate copolymer, vinyl chloride/ethylene copolymer, vinyl chloride/propylene copolymer coalescence, vinyl chloride/styrene copolymer, vinyl chloride/isobutylene copolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/styrene/maleic anhydride terpolymer, vinyl chloride/styrene/acrylonitrile terpolymer Polymers, vinyl chloride/butadiene copolymers, vinyl chloride/isoprene copolymers, vinyl chloride/
• Polyvinyl chloride vinyl chloride polymers such as post-chlorinated polyvinyl chloride and post-chlorinated vinyl chloride copolymers (polyvinyl chloride and polyvinyl chloride copolymers are collectively referred to as “vinyl chloride ) modified (chlorinated, etc.) (for example, chlorinated vinyl chloride polymer); vinylidene chloride polymer such as post-chlorinated vinylidene chloride polymer modified (chlorinated, etc.), and the like.
• vinyl chloride polymers such as post-chlorinated polyvinyl chloride and post-chlorinated vinyl chloride copolymers (polyvinyl chloride and polyvinyl chloride copolymers are collectively referred to as “vinyl chloride ) modified (chlorinated, etc.) (for example, chlorinated vinyl chloride polymer); vinylidene chloride polymer such as post-chlorinated vinylidene chloride polymer modified (chlor
• chlorinated polyolefins having a chemical structure similar to that of polyvinyl chloride, such as chlorinated polyethylene, and modified (chlorinated, etc.) chlorinated olefins may be used.
• the viewpoint of flame retardancy it is preferable that at least one selected from the group consisting of vinyl chloride polymers, chlorinated vinyl chloride polymers and vinylidene chloride polymers is included, especially flame retardant.
• Chlorinated vinyl chloride-based polymers are particularly preferred from the viewpoint of excellent properties and foamability.
• the vinyl chloride resin one of these may be used alone, or two or more of them may be used in combination.
• vinyl chloride polymer means polyvinyl chloride and/or vinyl chloride copolymer.
• a chlorinated vinyl chloride-based polymer may be referred to as a chlorinated vinyl chloride-based resin.
• the average degree of polymerization of the vinyl halide resin is not particularly limited.
• the lower limit of the average degree of polymerization is preferably 300 or more, more preferably 400 or more.
• the upper limit of the average degree of polymerization is preferably 3000 or less, more preferably 1500 or less.
• the average degree of polymerization of the halogenated vinyl halide resin is the average of the vinyl halide resin before halogenation (for example, vinyl chloride resin before chlorination). Considered substantially the same as the degree of polymerization.
• the average degree of polymerization of the vinyl halide resin is measured according to JIS K6720-2.
• the chlorinated vinyl chloride resin is usually produced by using a vinyl chloride resin as a raw material and by the following methods (a) and (b): (a) dissolving the vinyl chloride resin in an aqueous medium; Chlorine is supplied to the aqueous medium in a state dispersed therein, and (i) the resulting mixture is irradiated with a mercury lamp for photo-chlorination, or (ii) the obtained mixture is heated and chlorinated. and (b) a method of chlorinating the vinyl chloride resin in an air space such as chlorination under irradiation with a mercury lamp.
• the chlorine content of the vinyl chloride resin is preferably 50% by weight or more and 75% by weight or less, more preferably 60% by weight or more and 75% by weight or less, and 64% by weight or more and 70% by weight or less. It is more preferable to have The higher the chlorine content of the vinyl chloride resin, the higher the residue rate, and the less the amount of combustible gas produced when heated to a high temperature and in the absence of oxygen. As a result, the total calorific value of the resulting flame-retardant article can be reduced. On the other hand, when the chlorine content of the vinyl chloride resin is 75% by weight or less, the melt viscosity of the thermoplastic resin composition containing these resins is not too high.
• thermoplastic resin compositions containing these resins tend to have good processability during extrusion.
• the chlorine content of the vinyl chloride resin is measured according to JIS K7385 B method. Also, the "residue rate" will be described later.
• the hydrogen substitution rate is defined as the rate at which hydrogen atoms bonded to the main chain are substituted with halogen atoms.
• the hydrogen substitution rate is preferably 0.25 or more and 0.55 or less.
• the hydrogen substitution rate is 0.55 or less, the melt viscosity of the thermoplastic resin composition containing the vinyl halide resin is not too high. Therefore, the thermoplastic resin composition containing the vinyl halide resin tends to have good processability during extrusion.
• Acrylonitrile-based resin as used herein means a resin containing 50 mol% or more of structural units derived from acrylonitrile in 100 mol% of all structural units.
• acrylonitrile-based resins include (a) polyacrylonitrile, which is a homopolymer of acrylonitrile, and (b) a copolymer of acrylonitrile and a monomer other than acrylonitrile, the main component of which is a structural unit derived from acrylonitrile. Preferred, more preferred is polyacrylonitrile.
• the release of combustible gas from the foamed member can be further suppressed when heated to a high temperature and in the absence of oxygen, and as a result, the total calorific value of the resulting flame-retardant article can be further reduced.
• the amount of structural units derived from acrylonitrile in the acrylonitrile-based resin may be 60 mol% or more, 70 mol% or more, or 80 mol% or more in 100 mol% of all structural units. well, or it may be 90 mol % or more.
• the thermoplastic resin preferably contains a vinyl halide resin and/or an acrylonitrile resin, more preferably a vinyl halide resin. According to this configuration, when heated to a high temperature and in the absence of oxygen, it is difficult for the thermoplastic resin to release flammable gas, and as a result, the resulting flame-retardant article has the advantage of being able to reduce the total calorific value.
• the thermoplastic resin preferably contains one or more selected from the group consisting of vinyl chloride resins, chlorinated vinyl chloride resins, vinylidene chloride resins and polyacrylonitrile. It more preferably contains a vinyl resin, and more preferably contains a chlorinated vinyl chloride resin. According to this configuration, it is possible to further suppress the release of combustible gas from the foamed member when heated to a high temperature and in the absence of oxygen. have
• the total amount of the vinyl halide resin and the acrylonitrile resin in 100% by weight of the thermoplastic resin is preferably 50% by weight or more, more preferably 65% by weight or more, and 80% by weight or more. is more preferable, and 95% by weight or more is even more preferable.
• the total amount of the vinyl halide resin and the acrylonitrile resin in 100% by weight of the thermoplastic resin may be 100% by weight, that is, the thermoplastic resin is composed only of the vinyl halide resin and/or the acrylonitrile resin.
• thermoplastic resin is less likely to release flammable gas when heated to a high temperature and in the absence of oxygen. , has the advantage that the total heating value of the resulting flame retardant article can be reduced.
• the total amount of vinyl chloride-based resin, chlorinated vinyl chloride-based resin, vinylidene chloride-based resin and polyacrylonitrile in 100% by weight of the thermoplastic resin is preferably 50% by weight or more, and is 65% by weight or more. is more preferably 80% by weight or more, and even more preferably 95% by weight or more.
• the total amount of vinyl chloride-based resin, chlorinated vinyl chloride-based resin, vinylidene chloride-based resin and polyacrylonitrile in 100% by weight of thermoplastic resin may be 100% by weight, that is, the thermoplastic resin is vinyl chloride-based resin. , chlorinated vinyl chloride resin, vinylidene chloride resin and/or polyacrylonitrile alone.
• the foam member becomes flammable when heated at high temperature and in the absence of oxygen. It has the advantage that the release of gas can be suppressed more, resulting in a lower total heat value of the resulting flame-retardant article.
• thermoplastic resin leaves a residue when heated from 35° C. to 600° C. at a heating rate of 10° C./min in a nitrogen atmosphere.
• the term “residue” refers to carbides remaining after the thermoplastic resin is not completely thermally decomposed when the thermoplastic resin is heated from 35° C. to 600° C. at a heating rate of 10° C./min in a nitrogen atmosphere. . This is because the thermoplastic resin releases less combustible gas due to thermal decomposition when heated to a high temperature and in the absence of oxygen.
• the thermoplastic resin is heated from 35° C. to 600° C. at a heating rate of 10° C./min in a nitrogen atmosphere, the thermoplastic resin is not completely thermally decomposed and remains as carbide. It is preferable because the nonflammability of the flame-retardant article is excellent.
• the residue of the thermoplastic resin can be expressed by the residue rate when the temperature is raised from 35 ° C. to 600 ° C. at a heating rate of 10 ° C./min. It can be rephrased as exceeding.
• the residue rate (%) exceeds 0%, preferably 2% or more, more preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. , more preferably 17% or more, and particularly preferably 20% or more. According to this configuration, it is possible to further suppress the release of combustible gas from the foamed member when heated to a high temperature and in the absence of oxygen. It has the advantage of being able to
• the residue rate of the thermoplastic resin is the residue rate obtained when the thermal analysis evaluation test is performed, and is calculated from the amount of change in the weight of the thermoplastic resin before and after the thermal analysis evaluation test.
• the thermal analysis evaluation test can be performed, for example, by using a simultaneous differential thermogravimetric measurement device in the following manner: (1) Measure the weight of a certain amount of thermoplastic resin, and compare the obtained value with the weight before heating. (2) Place the thermoplastic resin after measuring the weight in an aluminum pan; (3) Blow nitrogen into the pan at a flow rate of 100 mL / min, and raise the temperature in the pan to 35 ° C. at 10 ° C./min.
• Vinyl halide resins which have low side chain bond dissociation energy and tend to form polyenes, and/or acrylonitrile resins, whose main chain tends to have a ring structure, are characterized by being easily carbonized. These thermoplastic resins release little combustible gas when thermally decomposed and tend to leave residues.
• polyvinylidene fluoride (vinylidene fluoride homopolymer), which is a type of vinyl halide resin, has a residue rate of 34%.
• Polyvinyl chloride (vinyl chloride homopolymer), which is a vinyl chloride resin, has a residue rate of 17%, polyvinylidene chloride (vinylidene chloride homopolymer) has a residue rate of 20%, and chlorinated polyvinyl chloride has a residue rate of 20%.
• the residue rate is 23%.
• Acrylonitrile-based resin (63% by weight of polyacrylonitrile) has a residue rate of 44%.
• thermoplastic resin composition may contain a foaming agent for foaming the thermoplastic resin composition.
• a known foaming agent can be used as the foaming agent, and is not particularly limited.
• the foaming agent include (a) (i) hydrocarbons such as normal butane, isobutane, normal pentane, isopentane, neopentane, cyclopentane, normal hexane, and cyclohexane, and (ii) dimethyl ether, diethyl ether, and methyl ethyl ether.
• the content of the foaming agent in the thermoplastic resin composition is not particularly limited, and may be appropriately set according to the type of thermoplastic resin to be used, the desired expansion ratio, and the like.
• thermoplastic resin composition may optionally contain various other components other than the thermoplastic resin and the foaming agent within a range that does not impair the effects of one embodiment of the present invention.
• Such other components include, for example, processing aids, flame retardants, stabilizers, lubricants, nucleating agents, foaming aids, antistatic agents, radiation heat transfer inhibitors, plasticizers, solvents, colorants (pigments and dyes). and weathering agents.
• (processing aid) In one embodiment of the present invention, (a) a copolymer having structural units derived from aromatic vinyl monomers and structural units derived from unsaturated nitrile monomers, such as styrene/acrylonitrile copolymers; (b) acrylic resins, (c) methyl methacrylate/butadiene/styrene polymers, and (d) chlorinated polyethylene may also be used. These can function as processing aids when vinyl halide-based resins and/or acrylonitrile-based resins are used as the thermoplastic resin. In addition, the methyl methacrylate/butadiene/styrene polymer can also function as an impact modifier when a vinyl halide resin and/or an acrylonitrile resin is used as the thermoplastic resin.
• stabilizers examples include (a) tin-based stabilizers (e.g., butyltin mercapto-based stabilizers), (b) antioxidants such as phosphorus-based compounds and amine-based compounds, (c) epoxy-based stabilizers, and (d ) zeolite and the like.
• tin-based stabilizers e.g., butyltin mercapto-based stabilizers
• antioxidants such as phosphorus-based compounds and amine-based compounds
• epoxy-based stabilizers examples include epoxy-based stabilizers.
• Lubricants include (a) waxes such as ester wax and polyethylene wax, and (b) fatty acid metal salts such as calcium stearate and zinc stearate.
• Radiation heat transfer inhibitors include substances having properties of reflecting, scattering or absorbing light in the near-infrared or infrared region. Examples of such substances (radiation heat transfer inhibitors) include graphite, graphene, carbon black, expanded graphite, titanium oxide, and aluminum.
• thermoplastic resin composition contents of processing aids, stabilizers, lubricants and radiation heat transfer inhibitors in the thermoplastic resin composition are not particularly limited.
• the thermoplastic resin composition may be pelletized when molding the foam member.
• the shape of the pelletized thermoplastic resin composition is not particularly limited.
• the shape of the thermoplastic resin composition is preferably particulate because it facilitates the production of foamed particles, which are an example of the foamed member, by foaming the thermoplastic resin composition.
• the term "particulate” as used herein includes not only rounded small particle shapes such as spherical, approximately spherical, convex lens, concave lens, and spindle shapes, but also concave particle shapes.
• the "particulate thermoplastic resin composition” may be referred to as "thermoplastic resin particles”. That is, the foam member is preferably a member formed by foaming thermoplastic resin particles.
• the particle weight of the thermoplastic resin particles is preferably 0.5-10.0 mg/particle, more preferably 1.0-8.0 mg/particle, and even more preferably 3.0-7.0 mg/particle. According to this configuration, the foamed member (expanded particles) obtained by foaming the thermoplastic resin particles can be easily filled into the molding die, and the surface of the foamed molded product obtained by molding the foamed member (expanded particles) is beautiful. It has the advantage that moldability such as flexibility is improved.
• thermoplastic resin composition for example, a particulate thermoplastic resin composition
• the preparation method is not particularly limited.
• An example of a method for preparing a thermoplastic resin composition in other words, a method for preparing thermoplastic resin particles will be described with reference to the case where the thermoplastic resin composition is in the form of particles.
• a particulate thermoplastic resin composition can be obtained, for example, by a method of sequentially performing the following (a1) to (a4): (a1) supplying a thermoplastic resin and, if necessary, various other components to an extruder, and melt-kneading the supplied raw materials; (a2) supplying a foaming agent to the extruder or a dispersing facility after the extruder, and dissolving and dispersing the foaming agent in the melt-kneaded product obtained in (a1); (a3) extruding the melt-kneaded material through a die having one or more small holes mounted after the extruder into a cutter chamber filled with pressurized circulating water; (a4) Immediately after the melt-kneaded product is extruded, the melt-kneaded product is cut by a rotating cutter in contact with the die, and the melt-kneaded product is cooled and solidified by pressurized circulating water to obtain a particulate thermoplastic resin composition.
• the region from which the melted and kneaded material is extruded may not be in the cutter chamber filled with pressurized circulating water, but may be in the gas phase (in the air).
• General extruders can be used as extruders, and specific examples include single-screw extruders, twin-screw extruders, and tandem extruders.
• tandem extruder examples include one in which two single screw extruders are connected, and one in which a twin screw extruder is connected to a single screw extruder.
• an extruder may be used in combination with dispersion equipment such as a static mixer and/or a stirrer without a screw.
• a foamed member can be obtained by foaming a thermoplastic resin composition (for example, a particulate thermoplastic resin composition) by a conventionally known method.
• the method for preparing the foamed member in other words, the method for foaming the thermoplastic resin composition is not particularly limited.
• a particulate thermoplastic resin composition is expanded by a factor of 2 to 110 with a heating medium such as heated air and/or water vapor to form a foamed member (expanded particles). can.
• the expanded particles obtained by expanding thermoplastic resin particles can be filled into a mold or the like, and then heated with steam (saturated steam, superheated steam, etc.) to form a foamed molded product.
• a foam molded article is also a foam member. That is, the shape of the foamed member is not particularly limited, and may be particulate (for example, foamed particles), or may be plate-shaped, box-shaped, or any other shape (for example, foamed molding). Also, the foam member may be a laminate composed of a plurality of foam members.
• the foam member is preferably composed of foam particles. It is easy to apply (coat) the thermosetting resin composition to the surface of the expanded beads, and in particular, the thermosetting resin composition can be easily applied (coated) to most of the surfaces of the expanded beads. . Therefore, it is possible to easily obtain foamed particles (foamed member) in which the cured resin member exists on most of the surface.
• foam molding foamed particles having a thermosetting resin composition applied to most of the surface, not only the cured resin member exists on most of the surface of the molded body, but also the inside of the molded body It is possible to easily obtain a foam-molded article (that is, a flame-retardant article) in which the cured resin member is present even in the Alternatively, a cured resin member may be present on the surface by applying a thermosetting resin composition to the surface of a foam-molded article obtained by in-mold foam molding of foamed particles and heating the same. Such a flame-retardant article can exhibit excellent non-combustible performance because a carbonized layer can be formed on most of the surface of the foamed member during combustion. It should be noted that the phrase "the foamed member is composed of expanded particles" means that the expanded member may be the expanded particles themselves, or may be a foamed article formed by molding the expanded particles.
• thermoplastic resin composition and the preparation of the foam member may be carried out in continuous equipment.
• the preparation of the thermoplastic resin composition and the preparation of the foamed member are continuously performed, and a sheet-shaped, plate-shaped or film-shaped foamed member (extruded foam ) can be obtained: (b1) supplying a thermoplastic resin and, if necessary, various other components to an extruder, and melt-kneading the supplied raw materials; (b2) supplying a foaming agent to the extruder or a dispersing facility subsequent to the extruder, and dissolving and dispersing the foaming agent in the melt-kneaded product obtained in (b1); (b3) extruding the melt-kneaded material through a die having a desired shape installed after the extruder, under a region of lower pressure
• the foamed member may be obtained by known injection molding, thermoforming, calendar molding, press molding, or the like.
• the cured resin member is obtained by curing a thermosetting resin composition, and forms an oxygen-blocking carbonized layer during combustion.
• combustion refers to a state in which oxygen and a substance combine to generate heat, such as in a normal fire. Examples include conditions exposed to high temperatures.
• oxygen-blocking carbonized layer means a carbonized layer having oxygen-blocking properties. Whether or not the carbonized layer has the ability to block oxygen can be determined, for example, by the degree of cracks present on the surface of the carbonized layer.
• carbonized layer means a layer formed by carbonizing a cured resin member. That is, most of the cured resin member is carbonized without being thermally decomposed during combustion.
• the cured resin member should be present on at least a part of the surface of the foamed member.
• the cured resin part By having the cured resin part present on at least a part of the surface of the foamed member, the above-described effects of the embodiment of the present invention can be expected. Further, as long as the cured resin member exists on at least a part of the surface of the foamed member, the cured resin member may exist inside the foamed member, in other words, the cured resin member impregnates the foamed member.
• a cured resin member is provided on at least a portion of the surface of the foam member corresponding to the surface that can come into contact with oxygen when the flame-retardant article is finally used (or when burned). preferably present.
• the foam member may have a form in which substantially the entire surface is covered with a cured resin member. That is, in one embodiment of the present invention, the surface of the foamed member on which the cured resin member is preferably present, or the ratio thereof, can be appropriately set according to the final use scene of the flame-retardant article.
• the cured resin member accounts for 50% or more of the surface (100%) of the foamed member corresponding to the surface that can come into contact with oxygen when the flame-retardant article is finally used. It is preferably present, more preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and 90% or more. is particularly preferred.
• the cured resin member preferably exists in 50% or more, more preferably 60% or more, of the surface (100%) of the foamed member. It is more preferably present in 70% or more, still more preferably in 80% or more, and particularly preferably in 90% or more.
• the cured resin member is present in 50% or more of at least one plate surface (100%) (preferably all plate surfaces 100%) of the foamed member.
• the cured resin member is present in 60% or more, more preferably present in 70% or more, more preferably present in 80% or more, and present in 90% or more is particularly preferred.
• the separate member is not particularly limited, and may be an inorganic metal such as aluminum, an inorganic salt such as silicate, or an organic substance such as plastic.
• thermosetting resin composition Other configurations of the thermosetting resin composition are not particularly limited as long as it contains a thermosetting resin.
• the thermosetting resin composition contains, in addition to the thermosetting resin, (a) a flame retardant, (b) a phenolic compound, (c) a curing agent for curing the thermosetting resin composition, and (d) Other components such as antistatic agents may also be included.
• thermosetting resin is not particularly limited.
• Thermosetting resins include phenol resins, epoxy resins, polyurethanes, unsaturated polyesters, urea resins, melamine resins, guanamine resins, silicone resins, polyimide resins, polyamideimide resins, silicon resins, diallyl phthalate resins, and the like.
• thermosetting resin preferably contains one or more selected from the group consisting of phenolic resin, epoxy resin and polyurethane, and more preferably contains phenolic resin.
• This configuration has the advantage that the cured resin member can retain its shape even when burned, and as a result, the cured resin member can form a carbonized layer with high strength when burned.
• the total amount of phenolic resin, epoxy resin and polyurethane in 100% by weight of the thermosetting resin is preferably 50% by weight or more, more preferably 65% by weight or more, and 80% by weight or more. is more preferable, and 95% by weight or more is even more preferable.
• the total amount of phenolic resin, epoxy resin and polyurethane in 100% by weight of thermosetting resin may be 100% by weight, i.e. the thermosetting resin is selected from the group consisting of phenolic resin, epoxy resin and polyurethane.
• the cured resin member can retain its shape even when burned, and as a result, the cured resin member has high strength when burned. It has the advantage of being able to form a carbonized layer.
• thermosetting resin composition preferably contains a flame retardant. This configuration has the advantage that the total calorific value of the resulting flame-retardant article can be further reduced.
• the flame retardant is not particularly limited.
• flame retardants include phosphorus-based flame retardants, organic flame retardants other than phosphorus-based flame retardants, boron-based inorganic compounds, and inorganic flame retardants other than boron-based inorganic compounds.
• Phosphorus-based flame retardants include polyphosphoric acid, polyphosphates, red phosphorus, condensed phosphates, phosphates and metal phosphates.
• polyphosphate include ammonium polyphosphate and sodium polyphosphate.
• organic flame retardants other than phosphorus flame retardants include melamine phosphate, melamine sulfate, and uncured novolak resins.
• Boron - based inorganic compounds include boric acid ( H3BO3 ), borax ( Na2B4O7.10H2O ), zinc borate and sodium polyborate .
• Inorganic flame retardants other than boron-based inorganic compounds include aluminum hydroxide (Al(OH) 3 ), magnesium hydroxide (Mg(OH) 2 ), silicon (Si), silica soil, silica (SiO 2 ), silicone , ceramics, graphite, carbon, carbon black, vermiculite, low-melting silicate glass, shirasu balloons that are fine hollow glass spheres, mica that is a silicate mineral with a foil-like structure, alumina (Al 2 O 3 ), clay (such as kaolin or china clay), calcium carbonate (CaCO 3 ), chromium oxide (such as Cr 2 O 3 or CrO 2 ), zeolite, perlite, tin (Sn), talc (talc), titanium ( Ti), carbon fiber, and the like.
• Al(OH) 3 aluminum hydroxide
• Mg(OH) 2 magnesium hydroxide
• Si silicon
• silica soil silica soil
• the flame retardant preferably contains a phosphorus-based flame retardant, more preferably one or more selected from the group consisting of red phosphorus and polyphosphate, and even more preferably ammonium polyphosphate.
• a phosphorus-based flame retardant more preferably one or more selected from the group consisting of red phosphorus and polyphosphate, and even more preferably ammonium polyphosphate.
• the content of the flame retardant in the thermosetting resin composition is not particularly limited, and may be appropriately set according to the envisaged usage environment of the flame-retardant article and the desired non-combustible performance.
• the content of the flame retardant in the thermosetting resin composition is, for example, preferably 0.1 parts by weight to 200.0 parts by weight with respect to 100 parts by weight of the thermosetting resin, and 2.0 parts by weight to It is more preferably 100.0 parts by weight, even more preferably 5.0 to 60.0 parts by weight, and particularly preferably 10.0 to 40.0 parts by weight.
• thermosetting resin composition may contain a curing agent for curing the thermosetting resin composition.
• the curing agent is not particularly limited, and conventionally known curing agents can be used.
• curing agents include organic acids such as phenolsulfonic acid, toluenesulfonic acid (e.g., p-toluenesulfonic acid monohydrate), and benzenesulfonic acid. And from the viewpoint of ease of handling, p-toluenesulfonic acid monohydrate is preferred.
• the content of the curing agent in the thermosetting resin composition is not particularly limited, and may be appropriately set according to the type and amount of the thermosetting resin and the curing method.
• the content of the curing agent in the thermosetting resin composition is, for example, preferably 0.1 to 100.0 parts by weight, preferably 2.0 to 100.0 parts by weight, with respect to 100 parts by weight of the thermosetting resin. It is more preferably 60.0 parts by weight, still more preferably 5.0 to 40.0 parts by weight, and particularly preferably 8.0 to 20.0 parts by weight.
• thermosetting resin composition preferably contains a phenolic compound.
• This configuration has the advantage that the total calorific value of the resulting flame-retardant article can be further reduced.
• the phenolic compound blended in the thermosetting resin composition can function as a flame retardant aid. Therefore, "phenolic resin” and “phenolsulfonic acid” are not regarded as phenolic compounds to be blended in thermosetting resin compositions.
• the phenolic compound is not particularly limited, and conventionally known phenolic compounds can be used.
• phenolic compounds include monohydric phenols and polyhydric phenols.
• Monohydric phenols include phenol, cresol, trimethylphenol, thymol, xylenol, carvacrol and p-tert-butylphenol.
• Polyhydric phenols include tannins, flavones, catechins, anthocyanidins and chalcones. Tannins include hydrolyzed tannins (eg, tannic acid) and condensed tannins (eg, persimmon tannins).
• the phenolic compound preferably contains monohydric phenol and/or polyhydric phenol, more preferably monohydric phenol and/or polyhydric phenol.
• the phenolic compound preferably contains polyhydric phenol, which has a high flame retardant effect, more preferably tannins, and even more preferably tannic acid. This configuration has the advantage of further reducing the total calorific value of the resulting flame-retardant article.
• the phenolic compound may be polyhydric phenol, tannins, or tannic acid.
• the content of the phenolic compound in the thermosetting resin composition is not particularly limited, and may be set as appropriate according to the envisaged usage environment of the flame-retardant article and the desired non-combustible performance.
• the content of the phenolic compound in the thermosetting resin composition is, for example, preferably 0.1 to 50.0 parts by weight with respect to 100 parts by weight of the thermosetting resin, and 1.0 part by weight. It is more preferably from 3.0 to 10.0 parts by weight, more preferably from 3.0 to 10.0 parts by weight.
• thermosetting resin composition may optionally contain a thermosetting resin, a flame retardant, a curing agent, and a phenolic compound other than the thermosetting resin within a range that does not impair the effects of one embodiment of the present invention.
• Various other ingredients may also be included. Examples of such other components include stabilizers, lubricants, antistatic agents, radiation heat transfer inhibitors, plasticizers, solvents, colorants (pigments and dyes), weathering agents and nucleating agents.
• thermosetting resin composition is obtained by mixing (a) a thermosetting resin and (b) optionally a flame retardant, a curing agent, a phenolic compound and/or other components by a conventionally known method. be able to.
• the device used for the mixing is not particularly limited, and examples thereof include a ribbon blender, a homogenizer and a mixer.
• a cured resin member can be obtained by curing the thermosetting resin composition by a conventionally known method.
• the means for curing the thermosetting resin composition is not particularly limited, and includes heat, heated water such as steam, and the like.
• a method for curing the thermosetting resin composition will be described in detail in the method for producing a flame-retardant article, which will be described later.
• Methods for producing flame-retardant articles include the following methods (c1), (c2), (c3) or (c4): (c1) After curing the thermosetting resin composition to form a cured resin member, the cured resin member and the foamed member are joined (bonded) so that the cured resin member covers at least a part of the surface of the foamed member.
• thermosetting resin composition before curing the thermosetting resin composition, applying (coating) the thermosetting resin composition to the foam member so that the obtained cured resin member covers at least part of the surface of the foam member; After that, a method of curing the thermosetting resin composition (if the foam member has gaps into which a liquid substance can enter, the thermosetting resin composition also penetrates into the gaps, and a part of the gap surface may also be covered with a cured resin member); (c3) A foamed member having gaps through which a liquid substance can enter is submerged in a thermosetting resin composition before curing, and the thermosetting resin composition is impregnated into the foamed member, and then the thermosetting A method of curing a resin composition; (c4) A thermosetting resin composition before curing is applied to the surface of the foamed member, the foamed member is subjected to an in-mold molding machine, steam and pressure are applied to the foamed member by the in-mold molding machine, and thermosetting is performed.
• a method for manufacturing a flame-retardant article according to an embodiment of the present invention may be configured as follows: including any one of the following steps 1 to 4; After curing a thermosetting resin composition containing a thermosetting resin to form a cured resin member, the cured resin member forms at least the surface of a foamed member formed by foaming a thermoplastic resin composition containing a thermoplastic resin.
• the thermosetting resin composition containing a thermosetting resin Before curing the thermosetting resin composition containing a thermosetting resin, the thermosetting resin composition is applied to a foamed member formed by foaming a thermoplastic resin composition containing a thermoplastic resin, and then step 2 of curing the thermosetting resin composition to form a cured resin member, and covering at least part of the surface of the foamed member with the cured resin member;
• a foamed member obtained by foaming a thermoplastic resin composition containing a thermoplastic resin in the thermosetting resin composition before curing the thermosetting resin composition containing the thermosetting resin, A foamed member having gaps through which substances can enter is submerged, and the thermosetting resin composition is impregnated into the foamed member, and then the thermosetting resin composition is cured to form a cured resin member, and the cured resin is obtained.
• thermosetting resin composition containing a thermosetting resin Before curing the thermosetting resin composition containing a thermosetting resin, the thermosetting resin composition is applied to a foamed member formed by foaming a thermoplastic resin composition containing a thermoplastic resin, and then The foamed member is supplied to an in-mold molding machine, steam and pressure are applied to the foamed member by the in-mold molding machine, the thermosetting resin composition is cured to form a cured resin member, and the cured resin member step 4, covering at least part of the surface of the foam member;
• the thermoplastic resin forms a residue when heated from 35° C. to 600° C. at a rate of 10° C./min in a nitrogen atmosphere, A method for producing a flame-retardant article, wherein the cured resin member forms an oxygen-blocking carbonized layer when burned.
• thermosetting resin composition to the foam member.
• the foamed member is foamed particles, or foamed moldings or foams having a certain size.
• thermosetting resin composition by mixing and stirring the thermosetting resin composition and the foam member, it is possible to obtain a foam member in which at least part of the surface of the foam member is coated with the thermosetting resin composition.
• a device for mixing and stirring the thermosetting resin composition and the foam member is not particularly limited, and examples thereof include a ribbon blender, a mixer and a homogenizer.
• a "foamed member having at least part of the surface of the foamed member coated with the thermosetting resin composition” is also referred to as a "thermosetting resin composition-containing foamed member".
• thermosetting resin composition-containing foamed member can be obtained by applying the thermosetting resin composition to the foamed member using a trowel, roller, rake, caulking gun, spray gun, or the like.
• thermosetting resin composition in the thermosetting resin composition-containing foamed member, it is possible to obtain a flame-retardant article in which the cured resin member exists on at least part of the surface of the foamed member.
• thermosetting resin composition in the thermosetting resin composition-containing foamed member is not particularly limited, and conventionally known methods can be used depending on the type and amount of the thermosetting resin and the type and amount of the curing agent. Any suitable curing method may be employed.
• a foamed member containing a thermosetting resin composition is left in an oven at 90° C. to 130° C. for 0.2 hours to 2.0 hours, so that at least part of the surface of the foamed member is coated with a cured resin member.
• a flame-retardant article can be obtained in which is present.
• the flame-retardant article itself has a total calorific value of 8.00 MJ/m 2 or less, even if it does not contain a non-combustible face material such as a metal foil (e.g., aluminum foil) as a constituent element. has the advantage of Therefore, the present flame-retardant article can be particularly suitably used as a lightweight and low-cost building material. In addition, it is also possible to use the present flame-retardant article as a laminate in which a non-flammable face material such as a metal foil (for example, aluminum foil) is further laminated.
• a non-flammable face material such as a metal foil (for example, aluminum foil) is further laminated.
• the flame-retardant article can be particularly suitably used in various applications such as, for example, a heat insulating material for buildings, a ceiling material, a core material for metal sandwich panels, a heat insulating material for bathrooms, and a heat insulating material for hot water storage tanks.
• An embodiment of the present invention may have the following configuration.
• a foamed member formed by foaming a thermoplastic resin composition containing a thermoplastic resin, and a cured resin member formed by curing a thermosetting resin composition containing a thermosetting resin,
• the thermoplastic resin forms a residue when heated from 35° C. to 600° C. at a rate of 10° C./min in a nitrogen atmosphere,
• the cured resin member forms an oxygen-blocking carbonized layer during combustion, A flame-retardant article, wherein the cured resin member exists on at least part of the surface of the foamed member.
• the difficulty according to [1] wherein the thermoplastic resin has a residue rate of 10% or more when heated from 35 ° C. to 600 ° C.
• thermosetting resin composition further contains a flame retardant.
• flame retardant contains a phosphorus-based flame retardant.
• amount of the flame retardant is 0.1 to 200.0 parts by weight with respect to 100 parts by weight of the thermosetting resin. .
• thermosetting resin contains at least one selected from the group consisting of phenolic resins, epoxy resins and polyurethane resins. Goods.
• thermosetting resin composition further contains a phenolic compound.
• thermoplastic resin composition further contains a radiation heat transfer inhibitor.
• thermoplastic resins First, methods for measuring various physical properties of thermoplastic resins, expanded members (chlorinated vinyl chloride expanded particles or polystyrene expanded particles), and flame-retardant articles will be described.
• thermogravimetric analyzer manufactured by Hitachi High-Tech Science Co., Ltd.: STA200RV. Specifically, it was as follows: (1) 5 to 8 mg of the thermoplastic resin was weighed, and the obtained value was taken as the weight before heating; (2) the thermoplastic resin after measuring the weight The resin was placed in an aluminum pan; (3) while blowing nitrogen into the pan at a flow rate of 100 mL/min, the temperature inside the pan was raised from 35°C to 600°C at a rate of 10°C/min; (4).
• the temperature in the pan reached 600 ° C., it was cooled to room temperature, and the combustion residue was taken out from the pan; (5) The weight of the combustion residue taken out from the pan was measured, and the obtained value was (6) The weight after heating was divided by the weight before heating, multiplied by 100, and the resulting value was defined as the residue rate (%). Note that if there is no combustion residue in the pan after combustion, the residue rate is 0%.
• the flame-retardant article obtained in each example was molded into a size of 10 cm x 10 cm x 3 cm to obtain a foam molded article.
• the total calorific value was measured when the resulting foamed molded article (flame-retardant article) was heated for 20 minutes at a radiant heat intensity of 50 kW/m 2 by a method conforming to ISO5660-1:2002.
• the measurement method is a test method prescribed as a method corresponding to the standard by the cone calorimeter method at the General Building Research Institute, which is a public institution prescribed in Article 108-2 of the Enforcement Ordinance of the Building Standards Law.
• Thermoplastic resin (A-1) Chlorinated vinyl chloride resin [manufactured by Kaneka Corporation, H716S, average degree of polymerization 600, chlorine content 67.6% by weight] (Thermosetting resin) (B-1) Phenolic resin (manufactured by DIC Corporation, product name: GG-1448) (curing agent) (C-1) p-toluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (Flame retardants) (D-1) Ammonium polyphosphate (manufactured by Clariant Chemicals Co., Ltd., product name: EXOLIT AP423) (Phenolic compound) (E-1) Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (Other ingredients) (F-1) Graphite (manufactured by Hayashi Kas
• Example 1 expandable chlorinated vinyl chloride resin particles were produced as a thermoplastic resin composition.
• the resulting formulation was blended to obtain a formulation in which each component was uniformly dispersed. After that, the blend was supplied to an intermeshing co-rotating twin-screw extruder to melt-knead the blend. Then, the melt-kneaded mixture was extruded from an extruder and cut to obtain pellets having the above-described compounding ratio of each component.
• the obtained pellets are pellets of chlorinated vinyl chloride resin, and are sometimes called base resin.
• the obtained pellets were supplied to a twin-screw extruder at a feed rate of 40 kg/hr to melt-knead the pellets.
• the twin-screw extruder used was an intermeshing co-rotating twin-screw extruder with a shaft diameter of ⁇ 40 mm.
• the temperature was 60 ° C. and 1.3 MPa at a discharge rate of 45 kg / hr.
• the melt-kneaded product was extruded into pressurized circulating water of .
• the pressure at the tip of the extruder was 10 MPa
• the resin temperature of the melt was 160°C.
• the extruded melt kneaded material was cut and pulverized using a rotating cutter in contact with the die.
• thermoplastic resin composition having a particle weight of 5.5 mg.
• the residual rate (%) of the thermoplastic resin (chlorinated vinyl chloride resin (A-1)) used was measured by the method described above. Table 1 shows the results.
• ⁇ Preparation of chlorinated vinyl chloride expanded particles 1000 g of expandable chlorinated vinyl chloride resin particles were put into a pre-expanding machine (manufactured by Daikai Kogyo Co., Ltd.). Steam of 0.18 MPa is introduced into the pre-foaming machine, and the expandable chlorinated vinyl chloride resin particles are expanded under the conditions of a temperature of 90 ° C. to 110 ° C. inside the pre-foaming machine, and the chlorinated vinyl chloride foam is expanded 30 times. Particles were obtained. The expansion ratio of the chlorinated vinyl chloride foamed particles was measured by the method described above.
• Chlorinated vinyl chloride foamed particles obtained by coating the surface of vinyl chloride foamed particles (foaming member) and coating most of the surface with a blend solution (thermosetting resin composition) member) was obtained.
• the resulting chlorinated vinyl chloride foamed particles are heated in an oven at 100° C. for 1 hour to cure the blend solution (thermosetting resin composition), thereby forming a foamed member.
• a flame-retardant article in which a cured resin member exists on most of the surface (at least 80% or more) was obtained.
• the resulting flame-retardant article was evaluated for total calorific value by the method described above. Table 1 shows the results.
• Example 2 A flame-retardant article in which a cured resin member exists on most of the surface of the foamed member (at least 80% or more) was obtained by the same method as in Example 1, except that the other component (F-1) was not used. . The resulting flame-retardant article was evaluated for total calorific value by the method described above. Table 1 shows the results.
• Polystyrene-based foamed particles which are foaming members, were prepared by putting expandable polystyrene-based resin particles into a pre-foaming machine (manufactured by Daikai Kogyo Co., Ltd.), introducing 0.10 MPa steam into the pre-foaming machine, and adjusting the temperature inside the pre-foaming machine. Polystyrene foamed particles were obtained under the conditions of 90 to 110°C.
• the polystyrene-based expanded particles had expansion ratios of 30, 50, and 70, respectively.
• a flame-retardant article having a cured resin member present on most of the surface of the foamed member was obtained in the same manner as in Example 1, except that polystyrene foam particles with an expansion ratio of 30 times were used as the foamed member.
• the resulting flame-retardant article was evaluated for total calorific value by the method described above. Table 1 shows the results.
• Example 2 A flame-retardant article having a cured resin member present on most of the surface of the foamed member was obtained in the same manner as in Example 1, except that polystyrene-based foamed particles with an expansion ratio of 50 times were used as the foamed member. The resulting flame-retardant article was evaluated for total calorific value by the method described above. Table 1 shows the results.
• Example 3 A flame-retardant article having a cured resin member on most of the surface of the foamed member was obtained in the same manner as in Example 1, except that polystyrene-based foamed particles with an expansion ratio of 70 times were used as the foamed member. The resulting flame-retardant article was evaluated for total calorific value by the method described above. Table 1 shows the results.
• thermoplastic resin was calculated using a general polystyrene resin [PS680, manufactured by PS Japan Co., Ltd.].
• the flame-retardant article according to one embodiment of the present invention can be used, for example, in various building materials such as building insulation materials, ceiling materials, core materials of metal sandwich panels, bathroom insulation materials, and hot water storage tank insulation materials. It can be used particularly preferably as

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• 2022
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