WO2014104591A1 - Flame-retardant foam insulating material based on chemically cross-linked polyvinyl chloride and method for producing same - Google Patents

Flame-retardant foam insulating material based on chemically cross-linked polyvinyl chloride and method for producing same Download PDF

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Publication number
WO2014104591A1
WO2014104591A1 PCT/KR2013/010804 KR2013010804W WO2014104591A1 WO 2014104591 A1 WO2014104591 A1 WO 2014104591A1 KR 2013010804 W KR2013010804 W KR 2013010804W WO 2014104591 A1 WO2014104591 A1 WO 2014104591A1
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weight
parts
polyvinyl chloride
flame retardant
resin
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PCT/KR2013/010804
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French (fr)
Korean (ko)
Inventor
김효린
이장훈
박완용
오흥식
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영보화학 주식회사
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Publication of WO2014104591A1 publication Critical patent/WO2014104591A1/en

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    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
    • B29C44/505—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying extruding the compound through a flat die
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • C—CHEMISTRY; METALLURGY
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • 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
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • 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
    • B29K2995/0015—Insulating
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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    • C08J2427/00—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
    • C08J2427/02—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
    • C08J2427/04—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
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a foam insulation and a method for manufacturing the same, and more particularly, to a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation and a method for manufacturing the same, which can be used as a building insulation, due to the excellent heat insulating properties through the production of high magnification foam. will be.
  • thermal insulation materials are largely classified into organic polymer resins and inorganic resins, and their methods of use vary according to their physical properties and properties.
  • organic insulating material has better heat insulation, light weight, water resistance, processability, and impact resistance than inorganic heat insulating material, heat resistance or durability is inferior. Therefore, when a multi-functional insulating material complementary to each characteristic is developed, the limitation of the use range can be greatly alleviated, and new applications are possible.
  • Cross-linked polyvinyl chloride (PVC) -based foams are new functional insulation materials with much improved heat resistance, low temperature resistance, chemical resistance and mechanical strength in addition to the general properties of organic insulation materials, and function well under a wider range of harsh conditions. It is evaluated as an organic insulating material which can exhibit. Therefore, these cross-linked polyvinyl chloride-based foams are widely used as a single structural material in industries such as housing, construction, refrigeration, refrigeration, LNG storage tanks, aircraft, and ships. It is a product made.
  • polyvinyl chloride contains chlorine as a flame retardant element, it is basically a material having excellent flame retardancy.
  • the air present in the foam insulation blocks the heat loss by blocking the entry of heat, so that the more pores therein, the better the thermal insulation.
  • the conventional polyvinyl chloride-based foam insulation has a low cross-linking degree is difficult to foam a high magnification, there is a limit that it is difficult to secure more than a certain level of thermal insulation.
  • the problem to be solved by the present invention is to provide a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation and a method for producing the same, while maintaining excellent flame retardancy, improved thermal insulation due to the foaming of high magnification.
  • a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin; 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture; And 1 to 10 parts by weight of the crosslinking agent; chemical raw material cross-linked polyvinyl chloride-based flame-retardant foam insulation material is extrusion-molded comprising a.
  • PVC polyvinyl chloride
  • CPE chlorinated polyethylene
  • CPO chlorinated paraffin oil
  • the chlorinated paraffin oil (CPO) may be 20 to 80 parts by weight based on 100 parts by weight of the resin mixture.
  • the crosslinking agent may be 2 to 5 parts by weight based on 100 parts by weight of the resin mixture.
  • the crosslinking agent is dicumyl peroxide (DCP), t-butyl peroxy laurate, t-butyl peroxy isopropyl carbonate, benzoyl peroxide, t- butyl peroxy acetate, t- butyl peroxy benzoate, Cyclohexanone peroxide, t-dibutylperoxymaleic acid, t-butylhydroperoxide, 2,3-dimethyl-2,5-dihexane, di-t-butylperoxide, 2,2-bisbenzene, 1, Any one or two or more selected from the group consisting of 3-bisbenzene, 1,1-bis-3,3,5-trimethylcyclohexane, p-chlorobenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide It may be a mixture.
  • DCP dicumyl peroxide
  • t-butyl peroxy laurate t-butyl peroxy
  • the limit oxygen index of the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation may be 28 or more.
  • the chemical crosslinked polyvinyl chloride-based flame retardant foam insulation may have a density of 0.025 g / cm 3 to 0.500 g / cm 3 .
  • thermal conductivity of the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation may be 0.04 W / mK or less.
  • the raw material composition based on 100 parts by weight of the resin mixture, 5 to 50 parts by weight of a flame retardant; And 1 to 5 parts by weight of a thermal stabilizer.
  • the flame retardant may be any one selected from the group consisting of antimony trioxide, decabromophenyl oxide and magnesium hydroxide or a mixture of two or more thereof.
  • the thermal stabilizer may be any one selected from the group consisting of tin maleate, tin laurate, and powder tin maleate esters, or two or more kinds of organotin thermal stabilizers.
  • the resin mixture comprising 30 to 70 parts by weight of (S1) polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin, based on 100 parts by weight of the resin mixture 10 to 100 parts by weight of chlorinated paraffin oil (CPO), 1 to 10 parts by weight of crosslinking agent, 5 to 50 parts by weight of flame retardant, 1 to 5 parts by weight of heat stabilizer, 5 to 50 parts by weight of blowing agent, and 0.1 to 3 parts by weight of foaming aid Kneading to prepare a raw material composition; (S2) preparing the extruded sheet by putting the raw material composition into an extruder and melt extrusion; And (S3) heating the extruded sheet to form a foam by foaming the chemical crosslinking agent and the foaming agent.
  • a method of manufacturing a chemically crosslinked polyvinylchloride-based flame retardant foam insulating material is provided.
  • the step (S1) a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin, based on 100 parts by weight of the resin mixture, 10 to 100
  • PVC polyvinyl chloride
  • CPE chlorinated polyethylene
  • the blowing agent ammonium bicarbonate, sodium bicarbonate, sodium borohydride, azodicarbonamide, dinitrosopentamethylene tetramine, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, toluenesulfonyl semicarba It may be any one selected from the group consisting of zide and oxybis (benzenesulfonyl hydrazide) or a mixture of two or more thereof.
  • the foaming aid may be any one selected from the group consisting of cadmium compounds, calcium compounds, zinc compounds, magnesium compounds, iron compounds, and copper compounds, or a mixture of two or more thereof.
  • the extruder may be a single extruder or a twin extruder, and the extrusion temperature may be maintained at 90 to 140 ° C.
  • the extrusion sheet may be heated to a temperature of 150 to 250 °C to form a foam by foaming the chemical crosslinking and the blowing agent.
  • the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation according to the present invention includes a polyvinyl chloride resin and a chlorinated polyethylene resin having excellent flame retardancy, and thus can be used as a heat insulating material for construction.
  • the chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation according to the present invention contains a chlorinated polyethylene resin excellent in compatibility with the polyvinyl chloride resin, to increase the degree of crosslinking, it is possible to foam high magnification, thereby improving heat insulation do.
  • the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation according to the present invention including a chlorinated paraffin oil as a plasticizer, it is possible to further improve the flame retardancy.
  • Chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation according to the present invention, a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin; 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture; And 1 to 10 parts by weight of the crosslinking agent; is formed by extrusion foam molding.
  • PVC polyvinyl chloride
  • CPE chlorinated polyethylene
  • CPO chlorinated paraffin oil
  • the content of the polyvinyl chloride resin is less than 30 parts by weight, and the content of the chlorinated polyethylene resin is more than 70 parts by weight, the limit oxygen index to be described later is lowered, disadvantageous to ensure flame retardancy, the polyvinyl chloride resin
  • the content of more than 70 parts by weight, and the content of the chlorinated polyethylene resin is less than 30 parts by weight the state of the specimen of the resin mixture is poor, the crosslinking and foaming is not good.
  • the foam made of polyvinyl chloride resin has a property of breaking well, a certain amount of plasticizer should be included, and in the present invention, 10 to 100 parts by weight, or 20 to 80 parts by weight, based on 100 parts by weight of the resin mixture.
  • Chlorinated paraffin oils are included as plasticizers. Outside the numerical range, the limit oxygen index is lowered, which is disadvantageous in securing flame retardancy.
  • the chlorinated paraffin oil is excellent in the flame retardancy of the foam insulation of the present invention, as will be described later, and since degradation does not occur well even if a heat stabilizer is added later, the performance as a foam insulation does not occur.
  • a heat insulating material in order for a heat insulating material to be used for building, it should basically be excellent in flame retardancy and heat insulation.
  • LOI limiting oxygen index
  • the polyvinyl chloride resin, chlorinated polyethylene resin and chlorinated paraffin oil contain chlorine, which is a flame retardant element, has excellent flame retardancy, and the limiting oxygen index of the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation is at least 28 or more.
  • the thermal insulation of the foam insulation means that the air present in the interior of the foam insulation to block the entry of heat to prevent the loss of heat. Therefore, the more air present in the foam insulation, the better the thermal insulation, the conventional foam insulation is composed of polyvinyl chloride resin, since the cross-linking degree of the polymer chain structure is low, about 20 times the foaming, a certain level of insulation It was difficult to secure.
  • a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin as 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin having excellent compatibility with the polyvinyl chloride resin is used as a base resin.
  • PVC polyvinyl chloride
  • CPE chlorinated polyethylene
  • the degree of crosslinking is increased, and foaming with high magnification of about 30 to 40 times is possible, and the heat insulating property is improved.
  • the thermal conductivity of the foam insulation according to the present invention may be 0.04 W / mK or less.
  • the crosslinking agent may contain 1 to 10 parts by weight or 2 to 5 parts by weight, if less than 1 part by weight of the crosslinking degree is low, the foaming ratio is not good, the heat insulation may be lowered, if exceeding 10 parts by weight, This is not good because the surface of the cell is rough because of the popping phenomenon.
  • the crosslinking agent that can be used here is dicumyl peroxide (DCP), t-butylperoxylaurylate, t-butylperoxyisopropylcarbonate, benzoyl peroxide, t-butylperoxyacetate, t-butylperoxybenzo Eights, cyclohexanone peroxide, t-dibutylperoxymaleic acid, t-butylhydroperoxide, 2,3-dimethyl-2,5-dihexane, di-t-butylperoxide, 2,2-bisbenzene, Any one selected from the group consisting of 1,3-bisbenzene, 1,1-bis-3,3,5-trimethylcyclohexane, p-chlorobenzoylperoxide, and 2,4-dichlorobenzoylperoxide; It may be a mixture of species or more.
  • DCP dicumyl peroxide
  • the foam insulation of the present invention due to the foaming of the high magnification, the foam insulation of the present invention, light weight is achieved by showing a relatively small density of 0.025 g / cm 3 to 0.500 g / cm 3 .
  • the raw material composition based on 100 parts by weight of the resin mixture, 5 to 50 parts by weight of a flame retardant; And 1 to 5 parts by weight of a thermal stabilizer.
  • the content of the flame retardant is less than 5 parts by weight, the effect of the flame retardant added is insignificant, if it exceeds 50 parts by weight, the durability of the foam insulation can be lowered.
  • the content of the thermal stabilizer is less than 1 part by weight, the workability during extrusion and foaming is lowered, the resin is decomposed to lower the physical properties, if it exceeds 5 parts by weight, due to the addition of more than necessary, economical of course of the product Mechanical properties may be degraded.
  • the flame retardant may be any one selected from the group consisting of antimony trioxide, decabromophenyl oxide and magnesium hydroxide or a mixture of two or more thereof.
  • the thermal stabilizer may be any one selected from the group consisting of tin maleate, tin laurate, and powder tin maleate esters, or two or more kinds of organotin thermal stabilizers.
  • a resin mixture comprising 30 to 70 parts by weight of a polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of a chlorinated polyethylene (CPE) resin, and 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture.
  • PVC polyvinyl chloride
  • CPE chlorinated polyethylene
  • CPO chlorinated paraffin oil
  • the step (S1) may be performed through the following steps in order to prevent efficient mixing of raw materials and deterioration of physical properties of the product.
  • a resin mixture comprising 30 to 70 parts by weight of a polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of a chlorinated polyethylene (CPE) resin, and 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture.
  • PVC polyvinyl chloride
  • CPE chlorinated polyethylene
  • CPO chlorinated paraffin oil
  • the resultant after the second dispersion step may be prepared in the form of pellets (pellets), so that it can be easily added to the extruder later.
  • foaming agent and the foaming aid satisfy the numerical range, foaming is sufficiently performed, and a decrease in physical properties of the product does not occur.
  • blowing agent although various kinds are already known, should be capable of forming fine and uniform bubbles, and should be used to minimize premature decomposition that may occur during extrusion.
  • blowing agents include inorganic blowing agents such as ammonium bicarbonate, sodium bicarbonate, sodium borohydride, azodicarbonamide, dinitrosopentamethylene tetramine (N, N'-dinitrosopentamethylene tetramine) ), Benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, toluenesulfonyl semicarbazide, oxybis (benzenesulfonyl hydrazide) (P, P ') organic blowing agents such as -oxybis (benzenesulfonyl hydrazide).
  • a cadmium compound As the foaming aid, a cadmium compound, a calcium compound, a zinc compound, a magnesium compound, an iron compound, a copper compound, and the like are used. It is preferable to use zinc oxide, and it is particularly preferable to use zinc oxide among zinc compounds.
  • the raw material composition is introduced into an extruder and melt-extruded to produce an extruded sheet (S2).
  • the step (S2) is a process of extruding the raw material composition prepared in the step (S1) into an extruded sheet having a predetermined width and thickness, the extrusion of the extrusion sheet due to a single extruder (single extruder) or a blowing agent
  • a twin extruder in which the foaming agent is introduced in a side feeding method using a separate screw, and a screw having a temperature of 90 to 140 ° C.
  • an extruder having a die having a temperature of 90 to 140 ° C. thereby kneading and extruding the raw material composition, thereby uniformly mixing the entire composition contained in the raw material composition prepared in the step (S1).
  • the resin mixture may be insignificantly melted to reduce the kneading property of the foam mixture.
  • the temperature of the cylinder and die is kept above 140 ° C., the decomposition of the blowing agent may occur. Therefore, it is preferable to maintain the temperature of the cylinder and die of an extruder at 90-140 degreeC. And, at this time, it is obvious that the width and thickness of the extruded sheet can be variously adjusted according to the judgment of those skilled in the art.
  • the extruded sheet is heated to foam the chemical crosslinking agent and the blowing agent to form a foam (S3).
  • the step (S3) after the chemically crosslinked by heating the extruded sheet to a temperature of 150 to 250 °C through a foaming furnace, it may be to form a foam by foaming the blowing agent. If the temperature at this time is less than 150 °C, the blowing agent is not activated, the foaming is not performed properly, if it exceeds 250 °C, the blowing agent may be decomposed to cause problems in product formation.
  • the step (S3) may be performed by any one method selected from the horizontal foaming method for installing the foaming furnace horizontally, the vertical foaming method for installing the foaming furnace vertically and the salt foaming method using the liquid salt as the heat transfer medium. Can be.
  • the three foaming methods are all made at atmospheric pressure, and are distinguished from each other according to the installation method and the heat transfer medium of the foaming furnace.
  • the foaming furnace is installed horizontally so that the foam is produced horizontally upon foaming, and all the processes proceed horizontally. Since the horizontal foaming method has almost no influence of gravity in the process of arranging and processing the foaming furnace, the expansion ratio in the longitudinal direction during foaming is small, so there is a small change in physical properties in the longitudinal direction and the width direction.
  • the second vertical foaming method is a method in which the foaming furnace is installed vertically and foamed while the extrusion sheet is lowered.
  • the foam foaming method Since the vertical foaming method is foamed in the air at the time of foaming, the appearance is excellent and the deviation in the width direction is small and has an advantage in terms of yield.
  • the foam foaming method shows a large difference in process from the two foaming methods described above in that the liquid foam is used as the heat transfer medium. Unlike the vertical foaming method, the liquid foam does not use air as a heat carrier. Because of the use of sulphate, the heat transfer effect is excellent and the foam is uniformly formed on the sheet. In particular, compared to the foamed product produced by the above-described horizontal or vertical foaming method, the variation in the physical properties in the longitudinal direction and the width direction is very small. It has the advantage that the property is evaluated well.
  • Samples 1 to 5 according to the above formulations were all measured to have a limiting oxygen index of more than 28, and there was no problem in flame retardancy, but the following experiments were performed using sample 3 having the best specimen state.
  • magnesium hydroxide as a flame retardant and 2 parts by weight of dicumyl peroxide (DCP) as a crosslinking agent were added and dispersed at 90 DEG C for 5 minutes, followed by 25 parts by weight of azodicarbonamide as a foaming agent and zinc oxide as a foaming aid. 1 part by weight was added, dispersed for 5 minutes at 110 ° C., and then pelletized.
  • DCP dicumyl peroxide
  • the pelletized foam raw material composition was introduced into a single extruder maintained at 120 ° C., and then melt-extruded to produce an extruded sheet, followed by cross-linking and foaming in an oven maintained at 200 ° C. to prepare a foam insulation. It was.
  • Foam insulation was prepared in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 2 parts by weight of antimony trioxide, and 6 parts by weight of decabromophenyl oxide were added as the flame retardant.
  • Foam insulation was prepared in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant.
  • Foam insulation was prepared in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 4 parts by weight of antimony trioxide, and 16 parts by weight of decabromophenyl oxide were added as the flame retardant.
  • Foaming was carried out in the same manner as in Example 1 except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant, and 10 parts by weight of azodicarbonamide was added as the blowing agent. Insulation was made.
  • Foaming was carried out in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant, and 20 parts by weight of azodicarbonamide was added as the blowing agent. Insulation was made.
  • Foaming was carried out in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant, and 30 parts by weight of azodicarbonamide was added as the blowing agent. Insulation was made.
  • composition of the foam insulation prepared in Examples 1 to 7 are shown in Table 2 below, and the density, limit oxygen index, thermal conductivity and product state of each Example are shown in Table 3 below.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Density (g / cm 3 ) 0.05 0.05 0.05 0.06 0.10 0.07 0.04
  • Marginal oxygen index 28 30
  • 32 34
  • 34 34
  • 34 34
  • the foam insulation was prepared by varying only the content of the flame retardant, but as the amount of the flame retardant increased, the thermal conductivity of the product did not change significantly, but the marginal oxygen index increased, indicating that the flame resistance was improved.
  • the amount of the flame retardant increased, the thermal conductivity of the product did not change significantly, but the marginal oxygen index increased, indicating that the flame resistance was improved.
  • the foam insulation was prepared by changing only the content of the foaming agent. As the amount of the foaming agent was increased, the density of the product was decreased, but it was found that the thermal conductivity was decreased to improve the thermal insulation.
  • PVC polyvinyl chloride
  • CPO chlorinated paraffin oil
  • the pelletized foam raw material composition was introduced into a single extruder maintained at 120 ° C., and then melt-extruded to produce an extruded sheet, followed by cross-linking and foaming in an oven maintained at 200 ° C. to prepare a foam insulation. It was.
  • composition of the foam insulation prepared by Comparative Examples 1 to 3 are shown in Table 4 below, and the density, limit oxygen index, thermal conductivity, and product state of each Comparative Example are shown in Table 5 below.

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Abstract

The present invention relates to a flame-retardant foam insulating material based on chemically cross-linked polyvinyl chloride and a method for producing same. The present invention comprises a polyvinyl chloride resin and a chlorinated polyethylene resin, which have excellent flame retardancy, and thus can be used as an insulating material for construction. By comprising the chlorinated polyethylene resin which is excellent for use in combination with the polyvinyl chloride resin, the present invention increases the degree of cross-linking and thus allows high-magnification foaming and thereby has improved insulating properties.

Description

화학가교 폴리비닐클로라이드계 난연 발포단열재 및 그의 제조방법Chemical crosslinked polyvinyl chloride-based flame retardant foam insulation and its manufacturing method
본 발명은 발포단열재 및 그의 제조방법에 관한 것으로서, 더욱 상세하게는 고배율의 발포체 제조를 통한 우수한 단열성으로 인해, 건축용 단열재로의 사용이 가능한 화학가교 폴리비닐클로라이드계 난연 발포단열재 및 그의 제조방법에 관한 것이다.The present invention relates to a foam insulation and a method for manufacturing the same, and more particularly, to a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation and a method for manufacturing the same, which can be used as a building insulation, due to the excellent heat insulating properties through the production of high magnification foam. will be.
본 출원은 2012년 12월 26일에 출원된 한국특허출원 제10-2012-0153019호에 기초한 우선권 주장을 하며, 해당 출원의 명세서에 개시된 모든 내용은 본 출원에 원용된다.This application claims the priority based on Korean Patent Application No. 10-2012-0153019, filed December 26, 2012, all the contents disclosed in the specification of the application is incorporated in this application.
에너지의 효율적인 이용과 절약의 관점에서 단열재의 개발과 효과적 이용 방안도 매우 중요한 의미를 갖고 있다. 현재 단열재는 유기 고분자 수지계와 무기계로 크게 구분되며, 각각의 물성과 특성에 따라 이용방법도 달라진다. 일반적으로 유기 단열재가 무기 단열재에 비해 단열성, 경량성, 내수성, 가공성, 내충격성이 좋은 반면, 내열성 또는 내구성이 떨어지는 편이다. 따라서 각각의 특성이 보완된 다기능성 단열재가 개발될 경우 사용 범위의 제한이 크게 완화될 수 있고, 보다 새로운 활용이 가능하게 된다.In terms of efficient use and saving of energy, the development and effective use of thermal insulation materials is also very important. Currently, heat insulating materials are largely classified into organic polymer resins and inorganic resins, and their methods of use vary according to their physical properties and properties. In general, while organic insulating material has better heat insulation, light weight, water resistance, processability, and impact resistance than inorganic heat insulating material, heat resistance or durability is inferior. Therefore, when a multi-functional insulating material complementary to each characteristic is developed, the limitation of the use range can be greatly alleviated, and new applications are possible.
한편, 가교 폴리비닐클로라이드(Polyvinyl Chloride, PVC)계 발포체는, 유기 단열재가 가지는 일반적인 특성 외에 내열성, 내저온성, 내약품성 그리고 기계적 강도가 훨씬 보강된 새로운 기능성 단열재로서 보다 광범위하고 가혹한 조건에서도 충분히 기능을 발휘할 수 있는 유기 단열재로 평가되고 있다. 따라서 이러한 가교 폴리비닐클로라이드계 발포체는 주택, 건설, 냉장, 냉동, LNG 저장용 탱크, 항공기, 선박 등 산업 전반에 단일구조재로 다양하게 이용되고 있으며 그 용도가 계속 개발됨에 따라 사용범위의 지속적인 확대가 이루어지고 있는 제품이다.Cross-linked polyvinyl chloride (PVC) -based foams, on the other hand, are new functional insulation materials with much improved heat resistance, low temperature resistance, chemical resistance and mechanical strength in addition to the general properties of organic insulation materials, and function well under a wider range of harsh conditions. It is evaluated as an organic insulating material which can exhibit. Therefore, these cross-linked polyvinyl chloride-based foams are widely used as a single structural material in industries such as housing, construction, refrigeration, refrigeration, LNG storage tanks, aircraft, and ships. It is a product made.
특히, 건축물에 화재가 발생하면 연소시 발생하는 연기나 가스에 의해 인명피해가 발생하는데, 연소가 활발해지면서 주변의 산소가 부족해져, 유해성 가스가 발생하고 불완전 연소에 의해 발생하는 연기는 다량의 인명피해를 발생시킬 수 있다. 따라서, 건축용 단열재는, 화재발생시 위험요인의 발생을 최소화하기 위해 우수한 난연성을 가질 것이 요구되는데, 폴리비닐클로라이드는 난연성 원소인 염소를 포함하고 있어, 기본적으로 난연성이 우수한 재료이다.Particularly, when a fire breaks out in a building, human injury is caused by smoke or gas generated during combustion, and as the combustion becomes active, the surrounding oxygen is deficient, harmful gases are generated and smoke generated by incomplete combustion causes a lot of human injury. Can be generated. Therefore, the building insulation is required to have excellent flame retardancy in order to minimize the occurrence of risk factors in the event of a fire, polyvinyl chloride contains chlorine as a flame retardant element, it is basically a material having excellent flame retardancy.
한편, 발포단열재의 내부에 존재하는 공기가 열의 출입을 차단시킴으로써 열의 손실을 막아주기 때문에, 내부에 기공을 많이 포함할수록 단열성이 좋아진다. 발포단열재의 내부에 기공을 많이 형성시키기 위해서는 고배율로 발포가 이루어져야 한다. 하지만, 종래의 폴리비닐클로라이드계 발포단열재는, 가교도가 낮아서 고배율의 발포가 어려워 일정 수준 이상의 단열성을 확보하기가 어렵다는 한계가 있다.On the other hand, the air present in the foam insulation blocks the heat loss by blocking the entry of heat, so that the more pores therein, the better the thermal insulation. In order to form a lot of pores in the foam insulation should be foamed with a high magnification. However, the conventional polyvinyl chloride-based foam insulation has a low cross-linking degree is difficult to foam a high magnification, there is a limit that it is difficult to secure more than a certain level of thermal insulation.
본 발명이 해결하고자 하는 과제는, 우수한 난연성을 유지하면서, 고배율의 발포로 인해 단열성을 향상시킨 화학가교 폴리비닐클로라이드계 난연 발포단열재 및 그의 제조방법을 제공하는 것이다.The problem to be solved by the present invention is to provide a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation and a method for producing the same, while maintaining excellent flame retardancy, improved thermal insulation due to the foaming of high magnification.
상기 과제를 해결하기 위하여, 본 발명의 일 측면에 따르면, 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물; 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO); 및 1 내지 10 중량부의 가교제;를 포함하는 원료 조성물이 압출 발포 성형된 화학가교 폴리비닐클로라이드계 난연 발포단열재가 제공된다.In order to solve the above problems, according to an aspect of the present invention, a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin; 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture; And 1 to 10 parts by weight of the crosslinking agent; chemical raw material cross-linked polyvinyl chloride-based flame-retardant foam insulation material is extrusion-molded comprising a.
이때, 상기 염소화 파라핀오일(CPO)은, 상기 수지 혼합물 100 중량부를 기준으로 20 내지 80 중량부일 수 있다.In this case, the chlorinated paraffin oil (CPO) may be 20 to 80 parts by weight based on 100 parts by weight of the resin mixture.
그리고, 상기 가교제는, 상기 수지 혼합물 100 중량부를 기준으로 2 내지 5 중량부일 수 있다.The crosslinking agent may be 2 to 5 parts by weight based on 100 parts by weight of the resin mixture.
그리고, 상기 가교제는, 디큐밀퍼옥사이드(DCP), t-부틸퍼옥시라우릴레이트, t-부틸퍼옥시이소프로필카보네이트, 벤조일퍼옥사이드, t-부틸퍼옥시아세테이트, t-부틸퍼옥시벤조에이트, 시클로헥산온퍼옥사이드, t-디부틸퍼옥시말레인산, t-부틸히드로퍼옥사이드, 2,3-디메틸-2,5-디헥산, 디-t-부틸퍼옥사이드, 2,2-비스벤젠, 1,3-비스벤젠, 1,1-비스-3,3,5-트리메틸시클로헥산, p-클로로벤조일퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.And, the crosslinking agent is dicumyl peroxide (DCP), t-butyl peroxy laurate, t-butyl peroxy isopropyl carbonate, benzoyl peroxide, t- butyl peroxy acetate, t- butyl peroxy benzoate, Cyclohexanone peroxide, t-dibutylperoxymaleic acid, t-butylhydroperoxide, 2,3-dimethyl-2,5-dihexane, di-t-butylperoxide, 2,2-bisbenzene, 1, Any one or two or more selected from the group consisting of 3-bisbenzene, 1,1-bis-3,3,5-trimethylcyclohexane, p-chlorobenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide It may be a mixture.
그리고, 상기 화학가교 폴리비닐클로라이드계 난연 발포단열재의 한계산소지수는, 28 이상일 수 있다.In addition, the limit oxygen index of the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation may be 28 or more.
그리고, 상기 화학가교 폴리비닐클로라이드계 난연 발포단열재의 밀도는, 0.025 g/cm3 내지 0.500 g/cm3일 수 있다.The chemical crosslinked polyvinyl chloride-based flame retardant foam insulation may have a density of 0.025 g / cm 3 to 0.500 g / cm 3 .
그리고, 상기 화학가교 폴리비닐클로라이드계 난연 발포단열재의 열전도율은, 0.04 W/mK 이하일 수 있다.In addition, the thermal conductivity of the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation may be 0.04 W / mK or less.
한편, 상기 원료 조성물은, 상기 수지 혼합물 100 중량부를 기준으로, 난연제 5 내지 50 중량부; 및 열안정제 1 내지 5 중량부;를 더 포함할 수 있다.On the other hand, the raw material composition, based on 100 parts by weight of the resin mixture, 5 to 50 parts by weight of a flame retardant; And 1 to 5 parts by weight of a thermal stabilizer.
여기서, 상기 난연제는, 삼산화안티몬, 데카브로모페닐옥사이드 및 수산화마그네슘으로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.Here, the flame retardant may be any one selected from the group consisting of antimony trioxide, decabromophenyl oxide and magnesium hydroxide or a mixture of two or more thereof.
그리고, 상기 열안정제는, 주석 말레이트, 주석 라우레이트 및 분말주석 말레이트 에스테르로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 유기주석계 열안정제일 수 있다.The thermal stabilizer may be any one selected from the group consisting of tin maleate, tin laurate, and powder tin maleate esters, or two or more kinds of organotin thermal stabilizers.
한편, 본 발명의 다른 측면에 따르면, (S1) 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물, 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO), 1 내지 10 중량부의 가교제, 난연제 5 내지 50 중량부, 열안정제 1 내지 5 중량부, 발포제 5 내지 50 중량부, 및 발포조제 0.1 내지 3 중량부를 혼련하여 원료 조성물을 제조하는 단계; (S2) 상기 원료 조성물을 압출기에 투입하고 용융압출하여 압출시트를 제조하는 단계; 및 (S3) 상기 압출시트를 가열하여 화학가교 및 상기 발포제를 발포시켜 발포체를 형성하는 단계;를 포함하는 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법이 제공된다.On the other hand, according to another aspect of the invention, the resin mixture comprising 30 to 70 parts by weight of (S1) polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin, based on 100 parts by weight of the resin mixture 10 to 100 parts by weight of chlorinated paraffin oil (CPO), 1 to 10 parts by weight of crosslinking agent, 5 to 50 parts by weight of flame retardant, 1 to 5 parts by weight of heat stabilizer, 5 to 50 parts by weight of blowing agent, and 0.1 to 3 parts by weight of foaming aid Kneading to prepare a raw material composition; (S2) preparing the extruded sheet by putting the raw material composition into an extruder and melt extrusion; And (S3) heating the extruded sheet to form a foam by foaming the chemical crosslinking agent and the foaming agent. A method of manufacturing a chemically crosslinked polyvinylchloride-based flame retardant foam insulating material is provided.
여기서, 상기 (S1)단계는, 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물, 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO), 및 열안정제 1 내지 5 중량부를 70 내지 150 ℃에서 5 내지 20 분간 혼합하는 혼합단계; 상기 혼합단계 후의 결과물에, 상기 수지 혼합물 100 중량부를 기준으로, 난연제 5 내지 50 중량부 및 가교제 1 내지 10 중량부를 첨가하여 70 내지 150 ℃에서 2 내지 10 분간 분산시키는 제1 분산단계; 및 상기 제1 분산단계 후의 결과물에, 상기 수지 혼합물 100 중량부를 기준으로, 발포제 5 내지 50 중량부, 및 발포조제 0.1 내지 3 중량부를 첨가하여 70 내지 150 ℃에서 2 내지 10 분간 분산시키는 제2 분산단계;를 포함하는 것일 수 있다.Here, the step (S1), a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin, based on 100 parts by weight of the resin mixture, 10 to 100 A mixing step of mixing 1 part by weight of chlorinated paraffin oil (CPO) and 1 to 5 parts by weight of a heat stabilizer at 70 to 150 ° C. for 5 to 20 minutes; A first dispersion step of dispersing 2 to 10 minutes at 70 to 150 ° C by adding 5 to 50 parts by weight of a flame retardant and 1 to 10 parts by weight of a crosslinking agent based on 100 parts by weight of the resin mixture; And a second dispersion in which 5 to 50 parts by weight of the blowing agent and 0.1 to 3 parts by weight of the foaming aid are added to the resultant after the first dispersing step, and dispersed at 70 to 150 ° C. for 2 to 10 minutes based on 100 parts by weight of the resin mixture. It may be to include.
여기서, 상기 발포제는, 탄산수소암모늄, 탄산수소나트륨, 보로수소화나트륨, 아조디카본아미드, 디니트로소펜타메틸렌 테트라민, 벤젠설포닐 하이드라지드, 톨루엔설포닐 하이드라지드, 톨루엔설포닐 세미카바자이드 및 옥시비스(벤젠설포닐 하이드라지드)로 이루어진 군으로부터 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.Here, the blowing agent, ammonium bicarbonate, sodium bicarbonate, sodium borohydride, azodicarbonamide, dinitrosopentamethylene tetramine, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, toluenesulfonyl semicarba It may be any one selected from the group consisting of zide and oxybis (benzenesulfonyl hydrazide) or a mixture of two or more thereof.
그리고, 상기 발포조제는, 카드뮴 화합물, 칼슘 화합물, 아연 화합물, 마그네슘 화합물, 철 화합물 및 구리 화합물로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.The foaming aid may be any one selected from the group consisting of cadmium compounds, calcium compounds, zinc compounds, magnesium compounds, iron compounds, and copper compounds, or a mixture of two or more thereof.
그리고, 상기 압출기는, 싱글 압출기 또는 트윈 압출기이며, 압출온도는 90 내지 140 ℃로 유지되는 것일 수 있다.The extruder may be a single extruder or a twin extruder, and the extrusion temperature may be maintained at 90 to 140 ° C.
그리고 상기 (S3)단계는, 상기 압출시트를 150 내지 250 ℃의 온도로 가열하여 화학가교 및 상기 발포제를 발포시켜 발포체를 형성하는 것일 수 있다.And (S3) step, the extrusion sheet may be heated to a temperature of 150 to 250 ℃ to form a foam by foaming the chemical crosslinking and the blowing agent.
본 발명에 따른 화학가교 폴리비닐클로라이드계 난연 발포단열재는, 난연성이 우수한 폴리비닐클로라이드 수지와 염소화 폴리에틸렌 수지를 포함하고 있어, 건축용 단열재로의 사용이 가능하다.The chemically crosslinked polyvinyl chloride-based flame retardant foam insulation according to the present invention includes a polyvinyl chloride resin and a chlorinated polyethylene resin having excellent flame retardancy, and thus can be used as a heat insulating material for construction.
그리고, 본 발명에 따른 화학가교 폴리비닐클로라이드계 난연 발포단열재는, 폴리비닐클로라이드 수지와 혼용성이 우수한 염소화 폴리에틸렌 수지를 포함하고 있어, 가교도를 상승시켜, 고배율의 발포가 가능하며, 이로써 단열성이 향상된다.In addition, the chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation according to the present invention contains a chlorinated polyethylene resin excellent in compatibility with the polyvinyl chloride resin, to increase the degree of crosslinking, it is possible to foam high magnification, thereby improving heat insulation do.
또한, 본 발명에 따른 화학가교 폴리비닐클로라이드계 난연 발포단열재는, 가소제로서 염소화 파라핀오일을 포함하여, 난연성을 더욱 향상시킬 수 있다.In addition, the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation according to the present invention, including a chlorinated paraffin oil as a plasticizer, it is possible to further improve the flame retardancy.
이하, 본 발명을 상세히 설명하기로 한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
또한, 본 명세서에 기재된 실시예의 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.In addition, the configuration of the embodiments described herein is only one of the most preferred embodiments of the present invention and does not represent all of the technical idea of the present invention, various equivalents and modifications that may be substituted for them at the time of the present application It should be understood that there may be
본 발명에 따른 화학가교 폴리비닐클로라이드계 난연 발포단열재는, 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물; 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO); 및 1 내지 10 중량부의 가교제;를 포함하는 원료 조성물이 압출 발포 성형되어 형성된다.Chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation according to the present invention, a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin; 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture; And 1 to 10 parts by weight of the crosslinking agent; is formed by extrusion foam molding.
이때, 상기 폴리비닐클로라이드 수지의 함량이 30 중량부 미만이고, 상기 염소화 폴리에틸렌 수지의 함량이 70 중량부를 초과하면, 후술하는 한계산소지수가 낮아지게 되어, 난연성 확보에 불리하며, 상기 폴리비닐클로라이드 수지의 함량이 70 중량부를 초과하고, 상기 염소화 폴리에틸렌 수지의 함량이 30 중량부 미만이면, 상기 수지 혼합물의 시편상태가 불량해져서 가교 및 발포가 잘 이루어지지 않는다.In this case, when the content of the polyvinyl chloride resin is less than 30 parts by weight, and the content of the chlorinated polyethylene resin is more than 70 parts by weight, the limit oxygen index to be described later is lowered, disadvantageous to ensure flame retardancy, the polyvinyl chloride resin When the content of more than 70 parts by weight, and the content of the chlorinated polyethylene resin is less than 30 parts by weight, the state of the specimen of the resin mixture is poor, the crosslinking and foaming is not good.
그리고, 폴리비닐클로라이드 수지로 구성된 발포체는 잘 부러지는 특성이 있기 때문에, 일정량의 가소제가 포함되어야 하며, 본 발명에서는 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부, 또는 20 내지 80 중량부의 염소화 파라핀오일이 가소제로서 포함된다. 상기 수치범위를 벗어나면, 한계산소지수가 낮아지게 되어, 난연성 확보에 불리하다. 또한, 상기 염소화 파라핀오일은, 후술하는 바와 같이 본 발명의 발포단열재의 난연성을 우수하게 하며, 추후 열안정제가 첨가되더라도 분해가 잘 일어나지 않기 때문에, 발포단열재로서의 성능 저하가 발생하지 않는다.In addition, since the foam made of polyvinyl chloride resin has a property of breaking well, a certain amount of plasticizer should be included, and in the present invention, 10 to 100 parts by weight, or 20 to 80 parts by weight, based on 100 parts by weight of the resin mixture. Chlorinated paraffin oils are included as plasticizers. Outside the numerical range, the limit oxygen index is lowered, which is disadvantageous in securing flame retardancy. In addition, the chlorinated paraffin oil is excellent in the flame retardancy of the foam insulation of the present invention, as will be described later, and since degradation does not occur well even if a heat stabilizer is added later, the performance as a foam insulation does not occur.
한편, 단열재가 건축용으로 사용되기 위해서는, 기본적으로 난연성 및 단열성이 우수해야 한다.On the other hand, in order for a heat insulating material to be used for building, it should basically be excellent in flame retardancy and heat insulation.
국토해양부에서 제정한 건축기계설비공사 표준시방서에는, 단열재의 난연성과 관련된 시험방법인 KS M ISO 4589-2에 의해 측정되는 난연성 측정지수인 한계산소지수(limiting oxygen index, L.O.I)가 28 이상이 될 것을 요구하고 있다.In the standard standard of construction machinery construction by the Ministry of Land, Transport and Maritime Affairs, the limiting oxygen index (LOI), which is measured by KS M ISO 4589-2, which is a test method related to the flame retardancy of insulation, will be 28 or more. Is asking.
본 발명에 따르면, 상기 폴리비닐클로라이드 수지, 염소화 폴리에틸렌 수지 및 염소화 파라핀오일은, 난연성 원소인 염소를 포함하고 있어, 난연성이 우수하며, 상기 화학가교 폴리비닐클로라이드계 난연 발포단열재의 한계산소지수는 적어도 28 이상이다.According to the present invention, the polyvinyl chloride resin, chlorinated polyethylene resin and chlorinated paraffin oil contain chlorine, which is a flame retardant element, has excellent flame retardancy, and the limiting oxygen index of the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation is at least 28 or more.
한편, 발포단열재의 단열성은, 발포단열재의 내부에 존재하는 공기가 열의 출입을 차단시켜 열의 손실을 막아주는 정도를 의미한다. 따라서, 발포단열재의 내부에 존재하는 공기가 많을수록 단열성이 우수해지는데, 종래 폴리비닐클로라이드 수지로 구성된 발포단열재는, 고분자의 체인구조상 가교도가 낮기 때문에, 20 배 정도의 발포가 이루어져, 일정 수준 이상의 단열성을 확보하기가 어려웠다.On the other hand, the thermal insulation of the foam insulation means that the air present in the interior of the foam insulation to block the entry of heat to prevent the loss of heat. Therefore, the more air present in the foam insulation, the better the thermal insulation, the conventional foam insulation is composed of polyvinyl chloride resin, since the cross-linking degree of the polymer chain structure is low, about 20 times the foaming, a certain level of insulation It was difficult to secure.
그러나, 본 발명에서는, 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부에, 상기 폴리비닐클로라이드 수지와 혼용성이 우수한 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물을 기본 수지로 함으로써, 가교도를 상승시키며, 30 내지 40 배 정도의 고배율의 발포가 가능하여, 단열성이 향상된다. 이때 본 발명에 따른 발포단열재의 열전도율은, 0.04 W/mK 이하일 수 있다.In the present invention, however, a resin mixture comprising 30 to 70 parts by weight of polyvinyl chloride (PVC) resin as 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin having excellent compatibility with the polyvinyl chloride resin is used as a base resin. The degree of crosslinking is increased, and foaming with high magnification of about 30 to 40 times is possible, and the heat insulating property is improved. At this time, the thermal conductivity of the foam insulation according to the present invention may be 0.04 W / mK or less.
그리고, 본 발명에서는, 가교제가 1 내지 10 중량부 또는 2 내지 5 중량부가 포함될 수 있는데, 1 중량부 미만이면 가교도가 낮아져 발포 배율이 좋지 않아 단열성이 저하될 수 있고, 10 중량부를 초과하면, 발포셀이 터지는 현상으로 인해 표면이 거칠게 되기 때문에 좋지 않다.And, in the present invention, the crosslinking agent may contain 1 to 10 parts by weight or 2 to 5 parts by weight, if less than 1 part by weight of the crosslinking degree is low, the foaming ratio is not good, the heat insulation may be lowered, if exceeding 10 parts by weight, This is not good because the surface of the cell is rough because of the popping phenomenon.
여기서 사용될 수 있는 상기 가교제는, 디큐밀퍼옥사이드(DCP), t-부틸퍼옥시라우릴레이트, t-부틸퍼옥시이소프로필카보네이트, 벤조일퍼옥사이드, t-부틸퍼옥시아세테이트, t-부틸퍼옥시벤조에이트, 시클로헥산온퍼옥사이드, t-디부틸퍼옥시말레인산, t-부틸히드로퍼옥사이드, 2,3-디메틸-2,5-디헥산, 디-t-부틸퍼옥사이드, 2,2-비스벤젠, 1,3-비스벤젠, 1,1-비스-3,3,5-트리메틸시클로헥산, p-클로로벤조일퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.The crosslinking agent that can be used here is dicumyl peroxide (DCP), t-butylperoxylaurylate, t-butylperoxyisopropylcarbonate, benzoyl peroxide, t-butylperoxyacetate, t-butylperoxybenzo Eights, cyclohexanone peroxide, t-dibutylperoxymaleic acid, t-butylhydroperoxide, 2,3-dimethyl-2,5-dihexane, di-t-butylperoxide, 2,2-bisbenzene, Any one selected from the group consisting of 1,3-bisbenzene, 1,1-bis-3,3,5-trimethylcyclohexane, p-chlorobenzoylperoxide, and 2,4-dichlorobenzoylperoxide; It may be a mixture of species or more.
그리고, 상기 고배율의 발포로 인해, 본 발명의 발포단열재는, 0.025 g/cm3 내지 0.500 g/cm3의 비교적 작은 밀도를 나타냄으로써 경량성이 달성된다.And, due to the foaming of the high magnification, the foam insulation of the present invention, light weight is achieved by showing a relatively small density of 0.025 g / cm 3 to 0.500 g / cm 3 .
한편, 상기 원료 조성물은, 상기 수지 혼합물 100 중량부를 기준으로, 난연제 5 내지 50 중량부; 및 열안정제 1 내지 5 중량부;를 더 포함할 수 있다.On the other hand, the raw material composition, based on 100 parts by weight of the resin mixture, 5 to 50 parts by weight of a flame retardant; And 1 to 5 parts by weight of a thermal stabilizer.
상기 난연제의 함량이 5 중량부 미만이면, 난연제 첨가의 효과가 미미하며, 50 중량부를 초과하면, 상기 발포단열재의 내구성이 저하될 수 있다.If the content of the flame retardant is less than 5 parts by weight, the effect of the flame retardant added is insignificant, if it exceeds 50 parts by weight, the durability of the foam insulation can be lowered.
그리고, 상기 열안정제의 함량이 1 중량부 미만이면, 압출 및 발포시 가공성이 저하되고 수지가 분해되어 물성이 저하되며, 5 중량부를 초과하면, 필요 이상의 첨가로 인해, 경제성이 저하됨은 물론 제품의 기계적 특성이 저하될 수 있다.And, if the content of the thermal stabilizer is less than 1 part by weight, the workability during extrusion and foaming is lowered, the resin is decomposed to lower the physical properties, if it exceeds 5 parts by weight, due to the addition of more than necessary, economical of course of the product Mechanical properties may be degraded.
여기서, 상기 난연제는, 삼산화안티몬, 데카브로모페닐옥사이드 및 수산화마그네슘으로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.Here, the flame retardant may be any one selected from the group consisting of antimony trioxide, decabromophenyl oxide and magnesium hydroxide or a mixture of two or more thereof.
그리고, 상기 열안정제는, 주석 말레이트, 주석 라우레이트 및 분말주석 말레이트 에스테르로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 유기주석계 열안정제일 수 있다.The thermal stabilizer may be any one selected from the group consisting of tin maleate, tin laurate, and powder tin maleate esters, or two or more kinds of organotin thermal stabilizers.
이하에서는, 본 발명에 따른 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법에 대해 설명하도록 한다.Hereinafter, a method of manufacturing a chemically crosslinked polyvinyl chloride-based flame retardant foam insulation according to the present invention.
우선, 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물, 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO), 1 내지 10 중량부의 가교제, 난연제 5 내지 50 중량부, 열안정제 1 내지 5 중량부, 발포제 5 내지 50 중량부, 및 발포조제 0.1 내지 3 중량부를 혼련하여 원료 조성물을 제조한다 (S1).First, a resin mixture comprising 30 to 70 parts by weight of a polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of a chlorinated polyethylene (CPE) resin, and 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture. ), 1 to 10 parts by weight of the crosslinking agent, 5 to 50 parts by weight of the flame retardant, 1 to 5 parts by weight of the heat stabilizer, 5 to 50 parts by weight of the blowing agent, and 0.1 to 3 parts by weight of the foaming aid to prepare a raw material composition (S1).
이때 상기 (S1)단계는, 원료의 효율적인 혼합 및 제품의 물성저하를 방지하기 위해 아래와 같은 단계를 거쳐 수행될 수 있다.At this time, the step (S1) may be performed through the following steps in order to prevent efficient mixing of raw materials and deterioration of physical properties of the product.
우선, 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물, 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO), 및 열안정제 1 내지 5 중량부를 70 내지 150 ℃에서 5 내지 20 분간 혼합한다. 이러한 혼합과정은 습식의 니더 (kneader)기 내에서 수행될 수 있다.First, a resin mixture comprising 30 to 70 parts by weight of a polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of a chlorinated polyethylene (CPE) resin, and 10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture. ) And 1 to 5 parts by weight of the heat stabilizer are mixed at 70 to 150 ° C. for 5 to 20 minutes. This mixing process can be carried out in a wet kneader group.
그 후, 상기 혼합단계 후의 결과물에, 상기 수지 혼합물 100 중량부를 기준으로, 난연제 5 내지 50 중량부 및 가교제 1 내지 10 중량부를 첨가하여 70 내지 150 ℃에서 2 내지 10 분간 분산시키는 제1 분산단계가 수행된다.Thereafter, the first dispersion step of dispersing at a 70 to 150 ℃ for 2 to 10 minutes by adding 5 to 50 parts by weight of a flame retardant and 1 to 10 parts by weight of a crosslinking agent to the resulting product after the mixing step, based on 100 parts by weight of the resin mixture Is performed.
이어서, 상기 제1 분산단계 후의 결과물에, 상기 수지 혼합물 100 중량부를 기준으로, 발포제 5 내지 50 중량부, 및 발포조제 0.1 내지 3 중량부를 첨가하여 70 내지 150 ℃에서 2 내지 10 분간 분산시키는 제2 분산단계가 수행된다.Subsequently, to the resultant after the first dispersion step, 5 to 50 parts by weight of the blowing agent and 0.1 to 3 parts by weight of the foaming aid are added based on 100 parts by weight of the resin mixture to disperse at 70 to 150 ° C. for 2 to 10 minutes. The dispersing step is performed.
이때, 상기 제2 분산단계 이후의 결과물은, 추후 압출기로의 투입이 용이하도록, 펠릿 (pellet) 형태로 제조될 수도 있다.At this time, the resultant after the second dispersion step, may be prepared in the form of pellets (pellets), so that it can be easily added to the extruder later.
한편, 상기 폴리비닐클로라이드 수지, 상기 염소화 폴리에틸렌 수지 및 상기 염소화 파라핀오일이 상기 수치범위를 만족해야 하는 이유는 전술한 바와 같다.Meanwhile, the reason why the polyvinyl chloride resin, the chlorinated polyethylene resin and the chlorinated paraffin oil should satisfy the numerical range is as described above.
그리고, 상기 발포제 및 상기 발포조제가 상기 수치범위를 만족함으로써, 발포가 충분히 이루어짐과 동시에, 제품의 물성 저하가 발생하지 않게 된다.In addition, since the foaming agent and the foaming aid satisfy the numerical range, foaming is sufficiently performed, and a decrease in physical properties of the product does not occur.
여기서, 상기 발포제는, 다양한 종류가 이미 공지되어 있지만 미세하고 균일한 기포를 형성할 수 있어야 하며, 압출시에 발생될 수 있는 조기분해를 최소화할 수 있는 것이 사용되어야 한다. 이러한 발포제의 비제한적인 예로는, 탄산수소암모늄, 탄산수소나트륨, 보로수소화나트륨 등의 무기 발포제가 있고, 아조디카본아미드(azodicarbonamide), 디니트로소펜타메틸렌 테트라민(N,N'-dinitrosopentamethylene tetramine), 벤젠설포닐 하이드라지드(benzenesulfonyl hydrazide), 톨루엔설포닐 하이드라지드(toluenesulfonyl hydrazide), 톨루엔설포닐 세미카바자이드(toluenesulfonyl semicarbazide), 옥시비스(벤젠설포닐 하이드라지드)(P,P'-oxybis(benzenesulfonyl hydrazide)) 등의 유기 발포제가 있다.Here, the blowing agent, although various kinds are already known, should be capable of forming fine and uniform bubbles, and should be used to minimize premature decomposition that may occur during extrusion. Non-limiting examples of such blowing agents include inorganic blowing agents such as ammonium bicarbonate, sodium bicarbonate, sodium borohydride, azodicarbonamide, dinitrosopentamethylene tetramine (N, N'-dinitrosopentamethylene tetramine) ), Benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, toluenesulfonyl semicarbazide, oxybis (benzenesulfonyl hydrazide) (P, P ') organic blowing agents such as -oxybis (benzenesulfonyl hydrazide).
그리고, 상기 발포조제로서 카드뮴 화합물(cadmium compound), 칼슘 화합물(calsium compound), 아연 화합물(zinc compound), 마그네슘 화합물(magnesium compound), 철 화합물(iron compound), 구리 화합물(copper compound) 등이 사용되는 것이 바람직하며, 특히 아연 화합물 중 산화아연을 사용하는 것이 바람직하다.As the foaming aid, a cadmium compound, a calcium compound, a zinc compound, a magnesium compound, an iron compound, a copper compound, and the like are used. It is preferable to use zinc oxide, and it is particularly preferable to use zinc oxide among zinc compounds.
이어서, 상기 원료 조성물을 압출기에 투입하고 용융압출하여 압출시트를 제조한다 (S2).Subsequently, the raw material composition is introduced into an extruder and melt-extruded to produce an extruded sheet (S2).
여기서, 상기 (S2) 단계는, 상기 (S1) 단계에서 제조된 원료 조성물을 일정의 넓이와 두께를 갖는 압출시트로 압출성형하는 공정으로서, 일반적인 싱글 압출기(single extruder) 또는 발포제로 인한 압출시트의 조기발포를 더욱 방지하기 위하여, 발포제를 별도의 스크류를 이용하여 사이드 피딩방식으로 투입하는 트윈 압출기(twin extruder)를 이용하여 공정처리가 가능하고, 스크류를 내재하며 90 내지 140 ℃의 온도를 갖는 실린더 및 90 내지 140℃의 온도를 갖는 다이스를 구비한 압출기로서 원료 조성물을 혼련하여 압출성형하기 때문에, 상기 (S1) 단계에서 준비된 원료 조성물에 포함된 전체 조성물을 균일하게 혼합하는 효과가 있다. 또한 실린더 및 다이스의 온도를 90 ℃ 미만으로 유지하면 수지 혼합물이 미미하게 용융되어 발포체 혼합물의 혼련성이 감소하는 문제가 발생하고, 140 ℃를 초과하도록 유지하면 발포제의 조기분해가 발생하는 문제가 발생하기 때문에, 압출기의 실린더 및 다이스의 온도를 90 내지 140 ℃로 유지하는 것이 바람직하다. 그리고, 이때, 상기 압출시트의 너비와 두께는 당업자의 판단에 따라 다양하게 조절이 가능함은 자명하다.Here, the step (S2) is a process of extruding the raw material composition prepared in the step (S1) into an extruded sheet having a predetermined width and thickness, the extrusion of the extrusion sheet due to a single extruder (single extruder) or a blowing agent In order to further prevent premature foaming, it is possible to process by using a twin extruder in which the foaming agent is introduced in a side feeding method using a separate screw, and a screw having a temperature of 90 to 140 ° C. And an extruder having a die having a temperature of 90 to 140 ° C., thereby kneading and extruding the raw material composition, thereby uniformly mixing the entire composition contained in the raw material composition prepared in the step (S1). In addition, if the temperature of the cylinder and die is kept below 90 ° C., the resin mixture may be insignificantly melted to reduce the kneading property of the foam mixture. If the temperature of the cylinder and die is kept above 140 ° C., the decomposition of the blowing agent may occur. Therefore, it is preferable to maintain the temperature of the cylinder and die of an extruder at 90-140 degreeC. And, at this time, it is obvious that the width and thickness of the extruded sheet can be variously adjusted according to the judgment of those skilled in the art.
이어서, 상기 압출시트를 가열하여 화학가교 및 상기 발포제를 발포시켜 발포체를 형성한다 (S3).Subsequently, the extruded sheet is heated to foam the chemical crosslinking agent and the blowing agent to form a foam (S3).
여기서, 상기 (S3)단계는, 상기 압출시트를 발포로를 통해 150 내지 250 ℃의 온도로 가열하여 화학적으로 가교시킨 후, 상기 발포제를 발포시켜 발포체를 형성하는 것일 수 있다. 이때의 온도가 150 ℃ 미만이면, 발포제가 활성화되지 않아, 발포가 제대로 이루어지지 않고, 250 ℃를 초과하면, 발포제가 분해되어 제품 형성에 문제가 발생할 수 있다.Here, the step (S3), after the chemically crosslinked by heating the extruded sheet to a temperature of 150 to 250 ℃ through a foaming furnace, it may be to form a foam by foaming the blowing agent. If the temperature at this time is less than 150 ℃, the blowing agent is not activated, the foaming is not performed properly, if it exceeds 250 ℃, the blowing agent may be decomposed to cause problems in product formation.
이때, 상기 (S3)단계는, 발포로를 수평으로 설치하는 수평발포방법, 발포로를 수직으로 설치하는 수직발포방법 및 열전달 매체로 액상의 설트를 이용하는 설트발포방법 중 선택된 어느 하나의 방법으로 진행될 수 있다.At this time, the step (S3) may be performed by any one method selected from the horizontal foaming method for installing the foaming furnace horizontally, the vertical foaming method for installing the foaming furnace vertically and the salt foaming method using the liquid salt as the heat transfer medium. Can be.
이때, 상기 3가지의 발포방법은 모두 상압 상태에서 이루어지며, 발포로의 설치 방법과 열전달 매체에 따라 상호 구분된다. 첫 번째의 상기 수평발포방법은 발포로가 수평으로 설치되어 발포시 발포체가 수평으로 생산되며, 모든 공정이 수평으로 진행된다. 이러한 수평발포방법은 발포로의 배치 및 공정 진행 과정에서 중력에 의한 영향이 거의 없으므로 발포시 길이 방향의 팽창비가 작으므로 길이 방향과 폭 방향의 물성 변화가 작은 장점이 있다. 두 번째의 상기 수직발포방법은 발포로를 수직으로 설치하여, 상기 압출시트를 하강시키면서 발포시키는 방법이다. 이러한 수직발포방법은 발포시 공기중에서 발포가 이루어지므로 외관이 우수하고 아울러 폭 방향으로의 편차가 작게 발생하여 수율면에서 우수한 장점이 있다. 세 번째의 상기 설트발포방법은 열전달매체로 액상 설트를 사용하는 점에서 전술한 두 가지의 발포방법과는 공정상 큰 차이를 보이고 있으며, 수직발포방법과는 달리 공기를 열전달체로 사용하지 않고 액상의 설트를 사용하기 때문에 열전달 효과가 우수하며 시트상에서 균일하게 발포가 이루어지는 장점이 있으며, 특히 전술한 수평 또는 수직발포방법에 의해 생산된 발포제품에 비해 길이 방향이나 폭 방향에서의 물성 편차가 매우 작아 제품 특성이 우수하게 평가되는 장점을 갖는다.At this time, the three foaming methods are all made at atmospheric pressure, and are distinguished from each other according to the installation method and the heat transfer medium of the foaming furnace. In the first horizontal foaming method, the foaming furnace is installed horizontally so that the foam is produced horizontally upon foaming, and all the processes proceed horizontally. Since the horizontal foaming method has almost no influence of gravity in the process of arranging and processing the foaming furnace, the expansion ratio in the longitudinal direction during foaming is small, so there is a small change in physical properties in the longitudinal direction and the width direction. The second vertical foaming method is a method in which the foaming furnace is installed vertically and foamed while the extrusion sheet is lowered. Since the vertical foaming method is foamed in the air at the time of foaming, the appearance is excellent and the deviation in the width direction is small and has an advantage in terms of yield. Third, the foam foaming method shows a large difference in process from the two foaming methods described above in that the liquid foam is used as the heat transfer medium. Unlike the vertical foaming method, the liquid foam does not use air as a heat carrier. Because of the use of sulphate, the heat transfer effect is excellent and the foam is uniformly formed on the sheet. In particular, compared to the foamed product produced by the above-described horizontal or vertical foaming method, the variation in the physical properties in the longitudinal direction and the width direction is very small. It has the advantage that the property is evaluated well.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
1. 실시예 - 수지 혼합물의 제조Example-Preparation of Resin Mixture
폴리비닐클로라이드 (PVC) 수지와 염소화 폴리에틸렌(CPE) 수지의 배합비를 조절하여, 밀롤(mill roll)로 140 ℃의 온도에서 15 분간 배합하여 각각의 수지 혼합물을 제조하였으며, 각 배합비에 따른 수지 혼합물의 한계산소지수 및 시편상태에 대해, 하기 표 1에 나타내었다.The mixture ratio of polyvinyl chloride (PVC) resin and chlorinated polyethylene (CPE) resin was adjusted, and each resin mixture was prepared by milling the mixture at a temperature of 140 ° C. for 15 minutes. For the limit oxygen index and the specimen state, it is shown in Table 1 below.
표 1
구분 시료 1 시료 2 시료 3 시료 4 시료 5
PVC 중량부 70 60 50 40 30
CPE 중량부 30 40 50 60 70
합계 100 100 100 100 100
한계산소지수 38 36 34 31 29
시편상태 △ ○ ◎ ○ △
Table 1
division Sample 1 Sample 2 Sample 3 Sample 4 Sample 5
PVC weight part 70 60 50 40 30
CPE parts by weight 30 40 50 60 70
Sum 100 100 100 100 100
Marginal oxygen index 38 36 34 31 29
Specimen Status △ ○ ◎ ○ △
(시편상태 표시: ◎ 매우 양호, ○ 양호, △ 보통, × 불량)(Indication of specimens: ◎ Very good, ○ Good, △ Normal, × Poor)
상기 각 배합에 따른 시료 1 내지 5 는 모두 한계산소지수가 28이 넘는 것으로 측정되어 난연성에는 문제가 없었지만, 시편상태가 가장 양호한 시료 3을 이용하여 하기 실험들을 수행하였다.Samples 1 to 5 according to the above formulations were all measured to have a limiting oxygen index of more than 28, and there was no problem in flame retardancy, but the following experiments were performed using sample 3 having the best specimen state.
2. 실시예 - 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조2. Example-Preparation of chemically crosslinked polyvinyl chloride-based flame retardant foam insulation
(1) 실시예 1(1) Example 1
상기 시료 3의 배합을 갖는 수지 혼합물 100 중량부, 가소제로 염소화 파라핀오일(CPO) 50 중량부 및 열안정제로 주석 말레이트 2 중량부를 70 ℃의 습식의 니더 (kneader)기 내에서 10 분간 혼합하였다.100 parts by weight of the resin mixture having the formulation of Sample 3, 50 parts by weight of chlorinated paraffin oil (CPO) as a plasticizer and 2 parts by weight of tin maleate as a heat stabilizer were mixed in a wet kneader group at 70 ° C. for 10 minutes. .
그 후, 난연제로서 수산화마그네슘 10 중량부 및 가교제로서 디큐밀퍼옥사이드 (DCP) 2 중량부를 투입하여, 90 ℃에서 5 분간 분산시키고, 이어서, 발포제로서 아조디카본아미드 25 중량부 및 발포조제로서 산화아연 1 중량부를 첨가하여, 110 ℃에서 5 분간 분산시킨 후, 이를 펠릿 (pellet)화하였다.Thereafter, 10 parts by weight of magnesium hydroxide as a flame retardant and 2 parts by weight of dicumyl peroxide (DCP) as a crosslinking agent were added and dispersed at 90 DEG C for 5 minutes, followed by 25 parts by weight of azodicarbonamide as a foaming agent and zinc oxide as a foaming aid. 1 part by weight was added, dispersed for 5 minutes at 110 ° C., and then pelletized.
이어서, 상기 펠릿화된 발포체 원료 조성물을, 120 ℃로 유지되는 싱글 압출기에 투입한 후, 용융압출하여 압출시트를 제조한 후, 200 ℃로 유지되는 오븐에 투입하여 가교 및 발포시킴으로써 발포단열재를 제조하였다.Subsequently, the pelletized foam raw material composition was introduced into a single extruder maintained at 120 ° C., and then melt-extruded to produce an extruded sheet, followed by cross-linking and foaming in an oven maintained at 200 ° C. to prepare a foam insulation. It was.
(2) 실시예 2(2) Example 2
상기 난연제로서 수산화마그네슘 10 중량부, 삼산화안티몬 2 중량부 및 데카브로모페닐옥사이드 6 중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 발포단열재를 제조하였다.Foam insulation was prepared in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 2 parts by weight of antimony trioxide, and 6 parts by weight of decabromophenyl oxide were added as the flame retardant.
(3) 실시예 3(3) Example 3
상기 난연제로서 수산화마그네슘 10 중량부, 삼산화안티몬 3 중량부 및 데카브로모페닐옥사이드 9 중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 발포단열재를 제조하였다.Foam insulation was prepared in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant.
(4) 실시예 4(4) Example 4
상기 난연제로서 수산화마그네슘 10 중량부, 삼산화안티몬 4 중량부 및 데카브로모페닐옥사이드 16 중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 발포단열재를 제조하였다.Foam insulation was prepared in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 4 parts by weight of antimony trioxide, and 16 parts by weight of decabromophenyl oxide were added as the flame retardant.
(5) 실시예 5(5) Example 5
상기 난연제로서 수산화마그네슘 10 중량부, 삼산화안티몬 3 중량부 및 데카브로모페닐옥사이드 9 중량부를 투입하고, 상기 발포제로서 아조디카본아미드 10 중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 발포단열재를 제조하였다.Foaming was carried out in the same manner as in Example 1 except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant, and 10 parts by weight of azodicarbonamide was added as the blowing agent. Insulation was made.
(6) 실시예 6(6) Example 6
상기 난연제로서 수산화마그네슘 10 중량부, 삼산화안티몬 3 중량부 및 데카브로모페닐옥사이드 9 중량부를 투입하고, 상기 발포제로서 아조디카본아미드 20 중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 발포단열재를 제조하였다.Foaming was carried out in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant, and 20 parts by weight of azodicarbonamide was added as the blowing agent. Insulation was made.
(7) 실시예 7(7) Example 7
상기 난연제로서 수산화마그네슘 10 중량부, 삼산화안티몬 3 중량부 및 데카브로모페닐옥사이드 9 중량부를 투입하고, 상기 발포제로서 아조디카본아미드 30 중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 방법으로 발포단열재를 제조하였다.Foaming was carried out in the same manner as in Example 1, except that 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, and 9 parts by weight of decabromophenyl oxide were added as the flame retardant, and 30 parts by weight of azodicarbonamide was added as the blowing agent. Insulation was made.
상기 실시예 1 내지 7에 의해 제조된 발포단열재의 조성에 대해 정리하여 하기 표 2에 나타내었고, 각 실시예의 밀도, 한계산소지수, 열전도율 및 제품상태에 대해 정리하여 하기 표 3에 나타내었다.The composition of the foam insulation prepared in Examples 1 to 7 are shown in Table 2 below, and the density, limit oxygen index, thermal conductivity and product state of each Example are shown in Table 3 below.
표 2
배합물 종류 실시예1 실시예2 실시예3 실시예4 실시예5 실시예6 실시예7
수지 PVC 50 50 50 50 50 50 50
CPE 50 50 50 50 50 50 50
가소제 CPO 50 50 50 50 50 50 50
난연제 삼산화안티몬 - 2 3 4 3 3 3
데카브로모페닐옥사이드 - 6 9 16 9 9 9
수산화마그네슘 10 10 10 10 10 10 10
열안정제 주석 말레이트 2 2 2 2 2 2 2
가교제 디큐밀퍼옥사이드 2 2 2 2 2 2 2
발포제 아조디카본아미드 25 25 25 25 10 20 30
발포조제 산화 아연 1 1 1 1 1 1 1
총 중량부 190 198 202 210 187 197 207
TABLE 2
Formulation Kinds Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Suzy PVC 50 50 50 50 50 50 50
CPE 50 50 50 50 50 50 50
Plasticizer CPO 50 50 50 50 50 50 50
Flame retardant Antimony trioxide - 2 3 4 3 3 3
Decabromophenyl oxide - 6 9 16 9 9 9
Magnesium hydroxide 10 10 10 10 10 10 10
Heat stabilizer Tin maleate 2 2 2 2 2 2 2
Crosslinking agent Dicumyl peroxide 2 2 2 2 2 2 2
blowing agent Azodicarbonamide 25 25 25 25 10 20 30
Foaming aid zinc oxide One One One One One One One
Parts by weight 190 198 202 210 187 197 207
표 3
특성 실시예 1 실시예 2 실시예 3 실시예 4 실시예 5 실시예 6 실시예 7
밀도(g/cm3) 0.05 0.05 0.05 0.06 0.10 0.07 0.04
한계산소지수 28 30 32 34 34 34 34
열전도율(W/mK) 0.035 0.035 0.035 0.035 0.040 0.036 0.034
제품상태 양호 양호 양호 양호 양호 양호 양호
TABLE 3
characteristic Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Density (g / cm 3 ) 0.05 0.05 0.05 0.06 0.10 0.07 0.04
Marginal oxygen index 28 30 32 34 34 34 34
Thermal Conductivity (W / mK) 0.035 0.035 0.035 0.035 0.040 0.036 0.034
Product Status Good Good Good Good Good Good Good
상기 표 3에 나타낸 바와 같이, 실시예에서 제조된 모든 발포단열재는 양호한 상태로 제조되었으며, 적절한 밀도와 열전도율을 나타내었고, 한계산소지수는 28 이상으로 측정되어 건축기계설비공사 표준시방서의 요구치를 모두 만족하였다.As shown in Table 3, all the foam insulation was prepared in a good state, exhibited the proper density and thermal conductivity, and the limiting oxygen index was measured to 28 or more, all of the requirements of the standard specification Satisfied.
특히, 실시예 2 내지 4에서, 난연제의 함량만을 달리하여 발포단열재를 제조하였는데, 난연재의 양이 증가할수록 제품의 열전도율에는 크게 변화가 없었으나, 한계산소지수가 증가되는 것으로 미루어, 난연성이 향상되었음을 알 수 있었다.In particular, in Examples 2 to 4, the foam insulation was prepared by varying only the content of the flame retardant, but as the amount of the flame retardant increased, the thermal conductivity of the product did not change significantly, but the marginal oxygen index increased, indicating that the flame resistance was improved. Could know.
그리고, 실시예 5 내지 7에서, 발포제의 함량만을 달리하여 발포단열재를 제조하였는데, 발포제의 양이 증가할수록 제품의 밀도는 작아졌지만, 열전도율이 감소하여 단열성이 향상되었음을 알 수 있었다.In addition, in Examples 5 to 7, the foam insulation was prepared by changing only the content of the foaming agent. As the amount of the foaming agent was increased, the density of the product was decreased, but it was found that the thermal conductivity was decreased to improve the thermal insulation.
3. 비교예 - 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조3. Comparative Example-Preparation of chemically crosslinked polyvinyl chloride-based flame retardant foam insulation
(1) 비교예 1(1) Comparative Example 1
폴리비닐클로라이드 (PVC) 수지 100 중량부, 가소제로 염소화 파라핀오일(CPO) 40 중량부 및 열안정제로 주석 말레이트 2 중량부를 70 ℃의 습식의 니더 (kneader)기 내에서 10 분간 혼합하였다.100 parts by weight of polyvinyl chloride (PVC) resin, 40 parts by weight of chlorinated paraffin oil (CPO) as a plasticizer and 2 parts by weight of tin maleate as a heat stabilizer were mixed for 10 minutes in a 70 ° C wet kneader group.
그 후, 난연제로서 수산화마그네슘 10 중량부, 삼산화안티몬 3 중량부 및 데카브로모페닐옥사이드 9 중량부와 가교제로서 디큐밀퍼옥사이드 2 중량부를 투입하여, 90 ℃에서 5 분간 분산시키고, 이어서, 발포제로서 아조디카본아미드 25 중량부 및 발포조제로서 산화아연 1 중량부를 첨가하여, 110 ℃에서 5 분간 분산시킨 후, 이를 펠릿 (pellet)화하였다.Subsequently, 10 parts by weight of magnesium hydroxide, 3 parts by weight of antimony trioxide, 9 parts by weight of decabromophenyl oxide and 2 parts by weight of dicumyl peroxide as a crosslinking agent were added as a flame retardant, and dispersed at 90 DEG C for 5 minutes, followed by azo as a blowing agent. 25 parts by weight of dicarbonamide and 1 part by weight of zinc oxide as a foaming aid were added, dispersed for 5 minutes at 110 ° C., and then pelletized.
이어서, 상기 펠릿화된 발포체 원료 조성물을, 120 ℃로 유지되는 싱글 압출기에 투입한 후, 용융압출하여 압출시트를 제조한 후, 200 ℃로 유지되는 오븐에 투입하여 가교 및 발포시킴으로써 발포단열재를 제조하였다.Subsequently, the pelletized foam raw material composition was introduced into a single extruder maintained at 120 ° C., and then melt-extruded to produce an extruded sheet, followed by cross-linking and foaming in an oven maintained at 200 ° C. to prepare a foam insulation. It was.
(2) 비교예 2(2) Comparative Example 2
폴리비닐클로라이드 (PVC) 수지 100 중량부 대신, 상기 시료 3의 배합을 갖는 수지 혼합물 100 중량부를 사용하고, 상기 가소제로서 염소화 파라핀오일 40 중량부 대신 디이소노닐프탈레이트 (DINP) 50 중량부가 혼합되는 것을 제외하고는 비교예 1과 동일한 방법으로 발포단열재를 제조하였다.Instead of 100 parts by weight of polyvinyl chloride (PVC) resin, 100 parts by weight of the resin mixture having the formulation of Sample 3 was used, and 50 parts by weight of diisononylphthalate (DINP) was mixed instead of 40 parts by weight of chlorinated paraffin oil as the plasticizer. Except that the foam insulation was prepared in the same manner as in Comparative Example 1.
(3) 비교예 3(3) Comparative Example 3
폴리비닐클로라이드 (PVC) 수지 100 중량부 대신, 상기 시료 3의 배합을 갖는 수지 혼합물 100 중량부를 사용하고, 상기 가소제로서 염소화 파라핀오일 40 중량부 대신 디옥틸프탈레이트 (DOP) 50 중량부가 혼합되는 것을 제외하고는 비교예 1과 동일한 방법으로 발포단열재를 제조하였다.100 parts by weight of the resin mixture having the formulation of Sample 3 was used instead of 100 parts by weight of polyvinyl chloride (PVC) resin, and 50 parts by weight of dioctylphthalate (DOP) was mixed instead of 40 parts by weight of chlorinated paraffin oil as the plasticizer. And foam insulation was prepared in the same manner as in Comparative Example 1.
상기 비교예 1 내지 3에 의해 제조된 발포단열재의 조성에 대해 정리하여 하기 표 4에 나타내었고, 각 비교예의 밀도, 한계산소지수, 열전도율 및 제품상태에 대해 정리하여 하기 표 5에 나타내었다.The composition of the foam insulation prepared by Comparative Examples 1 to 3 are shown in Table 4 below, and the density, limit oxygen index, thermal conductivity, and product state of each Comparative Example are shown in Table 5 below.
표 4
배합물 종류 비교예 1 비교예 2 비교예 3
수지 PVC 100 50 50
CPE - 50 50
가소제 CPO 40 - -
DINP - 50 -
DOP - - 50
난연제 삼산화안티몬 3 3 3
데카브로모페닐옥사이드 9 9 9
수산화마그네슘 10 10 10
열안정제 주석 말레이트 2 2 2
가교제 디큐밀퍼옥사이드 2 2 2
발포제 아조디카본아미드 25 25 25
발포조제 산화 아연 1 1 1
총 중량부 192 202 202
Table 4
Formulation Kinds Comparative Example 1 Comparative Example 2 Comparative Example 3
Suzy PVC 100 50 50
CPE - 50 50
Plasticizer CPO 40 - -
DINP - 50 -
DOP - - 50
Flame retardant Antimony trioxide 3 3 3
Decabromophenyl oxide 9 9 9
Magnesium hydroxide 10 10 10
Heat stabilizer Tin maleate 2 2 2
Crosslinking agent Dicumyl peroxide 2 2 2
blowing agent Azodicarbonamide 25 25 25
Foaming aid zinc oxide One One One
Parts by weight 192 202 202
표 5
특성 비교예 1 비교예 2 비교예 3
밀도(g/cm3) - 0.06 0.06
한계산소지수 - 25 24
열전도율(W/mK) - 0.050 0.050
제품상태 가소성 부족, 가교 불가, 발포 불가 가소성 양호, 발포시 다량의 가스 발생, 난연성 저하 가소성 양호, 발포시 다량의 가스 발생, 난연성 저하
Table 5
characteristic Comparative Example 1 Comparative Example 2 Comparative Example 3
Density (g / cm 3 ) - 0.06 0.06
Marginal oxygen index - 25 24
Thermal Conductivity (W / mK) - 0.050 0.050
Product Status Lack of plasticity, no crosslinking, no foaming Good plasticity, large amount of gas during foaming, low flame retardancy Good plasticity, large amount of gas during foaming, low flame retardancy
상기 표 5에 나타낸 바와 같이, 비교예 1에서처럼 폴리비닐클로라이드가 100 %인 경우에는, 가교 및 발포가 제대로 이루어지지 않았다.As shown in Table 5, when the polyvinyl chloride is 100% as in Comparative Example 1, crosslinking and foaming was not performed properly.
또한, 비교예 2 및 비교예 3과 같이 가소제로서, 염소화 파라핀오일이 아닌, 프탈레이트계가 사용된 경우에는 가소성은 양호하나, 발포시 다량의 가스가 발생하였으며, 특히, 한계산소지수가 25 이하로 측정되어 기준치에 미달하였다.In addition, in the case of using a phthalate system other than chlorinated paraffin oil as a plasticizer as in Comparative Example 2 and Comparative Example 3, plasticity was good, but a large amount of gas was generated during foaming, and in particular, the limiting oxygen index was measured to be 25 or less. The standard was not met.
한편, 본 명세서에 개시된 본 발명의 실시예들은 이해를 돕기 위해 특정 예를 제시한 것에 지나지 않으며, 본 발명의 범위를 한정하고자 하는 것은 아니다. 여기에 개시된 실시예들 이외에도 본 발명의 기술적 사상에 바탕을 둔 다른 변형예들이 실시 가능하다는 것은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 자명한 것이다.On the other hand, the embodiments of the present invention disclosed herein are not intended to limit the scope of the present invention only presented a specific example to facilitate understanding. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention can be carried out in addition to the embodiments disclosed herein.

Claims (16)

  1. 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물;A resin mixture comprising 30 to 70 parts by weight of a polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of a chlorinated polyethylene (CPE) resin;
    상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO); 및 1 내지 10 중량부의 가교제;를 포함하는 원료 조성물이 압출 발포 성형된 화학가교 폴리비닐클로라이드계 난연 발포단열재.10 to 100 parts by weight of chlorinated paraffin oil (CPO) based on 100 parts by weight of the resin mixture; And 1 to 10 parts by weight of a crosslinking agent; a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation material is extrusion foam molded raw material composition comprising a.
  2. 제1항에 있어서,The method of claim 1,
    상기 염소화 파라핀오일(CPO)은, 상기 수지 혼합물 100 중량부를 기준으로 20 내지 80 중량부인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The chlorinated paraffin oil (CPO) is a chemical crosslinked polyvinyl chloride-based flame retardant foam insulation, characterized in that 20 to 80 parts by weight based on 100 parts by weight of the resin mixture.
  3. 제1항에 있어서,The method of claim 1,
    상기 가교제는, 상기 수지 혼합물 100 중량부를 기준으로 2 내지 5 중량부인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The crosslinking agent is a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation, characterized in that 2 to 5 parts by weight based on 100 parts by weight of the resin mixture.
  4. 제1항에 있어서,The method of claim 1,
    상기 가교제는, 디큐밀퍼옥사이드(DCP), t-부틸퍼옥시라우릴레이트, t-부틸퍼옥시이소프로필카보네이트, 벤조일퍼옥사이드, t-부틸퍼옥시아세테이트, t-부틸퍼옥시벤조에이트, 시클로헥산온퍼옥사이드, t-디부틸퍼옥시말레인산, t-부틸히드로퍼옥사이드, 2,3-디메틸-2,5-디헥산, 디-t-부틸퍼옥사이드, 2,2-비스벤젠, 1,3-비스벤젠, 1,1-비스-3,3,5-트리메틸시클로헥산, p-클로로벤조일퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The crosslinking agent is dicumyl peroxide (DCP), t-butyl peroxylaurylate, t-butyl peroxy isopropyl carbonate, benzoyl peroxide, t-butyl peroxy acetate, t-butyl peroxy benzoate, cyclohexane Onperoxide, t-dibutylperoxymaleic acid, t-butylhydroperoxide, 2,3-dimethyl-2,5-dihexane, di-t-butylperoxide, 2,2-bisbenzene, 1,3- Bisbenzene, 1,1-bis-3,3,5-trimethylcyclohexane, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, any one selected from the group consisting of, or a mixture of two or more thereof Chemically crosslinked polyvinyl chloride-based flame retardant foam insulation.
  5. 제1항에 있어서,The method of claim 1,
    상기 화학가교 폴리비닐클로라이드계 난연 발포단열재의 한계산소지수는, 28 이상인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The limiting oxygen index of the chemically crosslinked polyvinyl chloride flame retardant foam insulation is 28 or more, characterized in that the chemically crosslinked polyvinyl chloride flame retardant foam insulation.
  6. 제1항에 있어서,The method of claim 1,
    상기 화학가교 폴리비닐클로라이드계 난연 발포단열재의 밀도는, 0.025 g/cm3 내지 0.500 g/cm3인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The chemically crosslinked polyvinylchloride-based flame retardant foam insulation has a density of 0.025 g / cm 3 to 0.500 g / cm 3 .
  7. 제1항에 있어서,The method of claim 1,
    상기 화학가교 폴리비닐클로라이드계 난연 발포단열재의 열전도율은, 0.04 W/mK 이하인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The thermal conductivity of the chemically crosslinked polyvinyl chloride-based flame retardant foam insulation is less than 0.04 W / mK.
  8. 제1항에 있어서,The method of claim 1,
    상기 원료 조성물은, 상기 수지 혼합물 100 중량부를 기준으로, 난연제 5 내지 50 중량부; 및 열안정제 1 내지 5 중량부;를 더 포함하는 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The raw material composition, based on 100 parts by weight of the resin mixture, 5 to 50 parts by weight of a flame retardant; And 1 to 5 parts by weight of a heat stabilizer. The chemically cross-linked polyvinyl chloride-based flame-retardant foam insulating material further comprises.
  9. 제8항에 있어서,The method of claim 8,
    상기 난연제는, 삼산화안티몬, 데카브로모페닐옥사이드 및 수산화마그네슘으로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The flame retardant is a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation, characterized in that any one or a mixture of two or more selected from the group consisting of antimony trioxide, decabromophenyl oxide and magnesium hydroxide.
  10. 제8항에 있어서,The method of claim 8,
    상기 열안정제는, 주석 말레이트, 주석 라우레이트 및 분말주석 말레이트 에스테르로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 유기주석계 열안정제인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재.The thermal stabilizer is any one selected from the group consisting of tin maleate, tin laurate and powder tin maleate ester or at least two of these organic tin-based heat stabilizers, characterized in that the chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation .
  11. (S1) 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물, 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO), 1 내지 10 중량부의 가교제, 난연제 5 내지 50 중량부, 열안정제 1 내지 5 중량부, 발포제 5 내지 50 중량부, 및 발포조제 0.1 내지 3 중량부를 혼련하여 원료 조성물을 제조하는 단계;(S1) A resin mixture comprising 30 to 70 parts by weight of a polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of chlorinated polyethylene (CPE) resin, based on 100 parts by weight of the resin mixture, 10 to 100 parts by weight of chlorinated paraffin oil ( CPO), 1 to 10 parts by weight of the crosslinking agent, 5 to 50 parts by weight of the flame retardant, 1 to 5 parts by weight of the heat stabilizer, 5 to 50 parts by weight of the blowing agent, and 0.1 to 3 parts by weight of the blowing aid to prepare a raw material composition;
    (S2) 상기 원료 조성물을 압출기에 투입하고 용융압출하여 압출시트를 제조하는 단계; 및(S2) preparing the extruded sheet by putting the raw material composition into an extruder and melt extrusion; And
    (S3) 상기 압출시트를 가열하여 화학가교 및 상기 발포제를 발포시켜 발포체를 형성하는 단계;를 포함하는 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법.(S3) a method of manufacturing a chemically crosslinked polyvinyl chloride-based flame retardant foam insulation comprising the step of heating the extruded sheet to form a foam by foaming the chemical crosslinking and the blowing agent.
  12. 제11항에 있어서,The method of claim 11,
    상기 (S1)단계는, 폴리비닐클로라이드(PVC) 수지 30 내지 70 중량부 및 염소화 폴리에틸렌(CPE) 수지 30 내지 70 중량부를 포함하는 수지 혼합물, 상기 수지 혼합물 100 중량부를 기준으로, 10 내지 100 중량부의 염소화 파라핀오일(CPO), 및 열안정제 1 내지 5 중량부를 70 내지 150 ℃에서 5 내지 20 분간 혼합하는 혼합단계;The step (S1) may include a resin mixture including 30 to 70 parts by weight of a polyvinyl chloride (PVC) resin and 30 to 70 parts by weight of a chlorinated polyethylene (CPE) resin, and 10 to 100 parts by weight based on 100 parts by weight of the resin mixture. A chlorinated paraffin oil (CPO), and a mixing step of mixing 1 to 5 parts by weight of a heat stabilizer at 70 to 150 ° C. for 5 to 20 minutes;
    상기 혼합단계 후의 결과물에, 상기 수지 혼합물 100 중량부를 기준으로, 난연제 5 내지 50 중량부 및 가교제 1 내지 10 중량부를 첨가하여 70 내지 150 ℃에서 2 내지 10 분간 분산시키는 제1 분산단계; 및A first dispersion step of dispersing 2 to 10 minutes at 70 to 150 ° C by adding 5 to 50 parts by weight of a flame retardant and 1 to 10 parts by weight of a crosslinking agent based on 100 parts by weight of the resin mixture; And
    상기 제1 분산단계 후의 결과물에, 상기 수지 혼합물 100 중량부를 기준으로, 발포제 5 내지 50 중량부, 및 발포조제 0.1 내지 3 중량부를 첨가하여 70 내지 150 ℃에서 2 내지 10 분간 분산시키는 제2 분산단계;를 포함하는 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법.A second dispersion step of dispersing the resultant after the first dispersion step by adding 5 to 50 parts by weight of the blowing agent and 0.1 to 3 parts by weight of the foaming aid based on 100 parts by weight of the resin mixture and dispersing the mixture at 70 to 150 ° C. for 2 to 10 minutes. Method for producing a chemically crosslinked polyvinyl chloride-based flame retardant foam insulating material comprising a.
  13. 제11항에 있어서,The method of claim 11,
    상기 발포제는, 탄산수소암모늄, 탄산수소나트륨, 보로수소화나트륨, 아조디카본아미드, 디니트로소펜타메틸렌 테트라민, 벤젠설포닐 하이드라지드, 톨루엔설포닐 하이드라지드, 톨루엔설포닐 세미카바자이드 및 옥시비스(벤젠설포닐 하이드라지드)로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법.The blowing agent is ammonium bicarbonate, sodium bicarbonate, sodium borohydride, azodicarbonamide, dinitrosopentamethylene tetramine, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, toluenesulfonyl semicarbazide and A method for producing a chemically crosslinked polyvinyl chloride-based flame-retardant foam insulation, characterized in that any one or a mixture of two or more selected from the group consisting of oxybis (benzenesulfonyl hydrazide).
  14. 제11항에 있어서,The method of claim 11,
    상기 발포조제는, 카드뮴 화합물, 칼슘 화합물, 아연 화합물, 마그네슘 화합물, 철 화합물 및 구리 화합물로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법.The foaming aid is any one selected from the group consisting of cadmium compounds, calcium compounds, zinc compounds, magnesium compounds, iron compounds and copper compounds or a mixture of two or more thereof. Method of manufacturing insulation.
  15. 제11항에 있어서,The method of claim 11,
    상기 압출기는, 싱글 압출기 또는 트윈 압출기이며, 압출온도는 90 내지 140 ℃로 유지되는 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법.The extruder is a single extruder or twin extruder, the extrusion temperature is a manufacturing method of a chemically cross-linked polyvinyl chloride-based flame retardant foam insulation characterized in that maintained at 90 to 140 ℃.
  16. 제11항에 있어서,The method of claim 11,
    상기 (S3)단계는, 상기 압출시트를 150 내지 250 ℃의 온도로 가열하여 화학가교 및 상기 발포제를 발포시켜 발포체를 형성하는 것을 특징으로 하는 화학가교 폴리비닐클로라이드계 난연 발포단열재의 제조방법.In the step (S3), the extruded sheet is heated to a temperature of 150 to 250 ℃ chemical crosslinking and foaming the blowing agent to form a foam to form a chemically crosslinked polyvinyl chloride-based flame retardant foam insulation.
PCT/KR2013/010804 2012-12-26 2013-11-26 Flame-retardant foam insulating material based on chemically cross-linked polyvinyl chloride and method for producing same WO2014104591A1 (en)

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CN104072821A (en) * 2014-07-08 2014-10-01 国家电网公司 High-voltage insulating boot
CN105837976A (en) * 2016-04-22 2016-08-10 刘志宏 PVC cross-linking melt-resistant material

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DE112015006834B4 (en) 2015-08-26 2023-06-01 Bizlink Technology (Slovakia) s.r.o. Electrical cable for a device, device and method for manufacturing an electrical cable

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CN104072821A (en) * 2014-07-08 2014-10-01 国家电网公司 High-voltage insulating boot
CN105837976A (en) * 2016-04-22 2016-08-10 刘志宏 PVC cross-linking melt-resistant material

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