KR102405705B1 - Manufacturing method of flame retardant polyurethane foam sheet - Google Patents

Manufacturing method of flame retardant polyurethane foam sheet Download PDF

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KR102405705B1
KR102405705B1 KR1020200149857A KR20200149857A KR102405705B1 KR 102405705 B1 KR102405705 B1 KR 102405705B1 KR 1020200149857 A KR1020200149857 A KR 1020200149857A KR 20200149857 A KR20200149857 A KR 20200149857A KR 102405705 B1 KR102405705 B1 KR 102405705B1
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flame retardant
foam sheet
polyurethane foam
surface treatment
treatment agent
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KR20220064436A (en
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김기성
박서규
고세윤
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주식회사 켐코
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    • 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
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B29C44/5681—Covering the foamed object with, e.g. a lining
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/0017—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor characterised by the choice of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • 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
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets

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Abstract

본 발명은 난연성 폴리우레탄 발포시트의 제조방법에 관한 것으로, 더욱 상세하게는 캡슐화된 난연제와 멜라민으로 이루어진 난연제혼합물이 함유된 자외선 경화형 표면처리제를 제조하는 표면처리제제조단계, 상기 표면처리제제조단계를 통해 제조된 표면처리제를 난연제가 함유된 폴리우레탄 발포시트의 일면에 코팅하는 코팅단계 및 상기 코팅단계를 통해 난연제가 함유된 폴리우레탄 발포시트에 코팅된 표면처리제를 경화하는 경화단계로 이루어진다.
상기의 과정으로 이루어지는 난연성 폴리우레탄 발포시트의 제조방법은 캡슐화를 통해 표면개질된 난연제와 멜라민으로 이루어진 난연제 혼합물이 함유된 표면처리제를 폴리우레탄 발포시트의 표면에 도포하여 폴리우레탄 발포시트와의 도막 밀착성이 우수하며, 난연성능 뿐만 아니라 끈적임 감소 등의 효과를 나타내는 표면처리층이 제공되어 권취 혹은 사용과정에서 주름발생이 억제되며, 발포시트 내부에 난연제의 함량이 낮아 난연성이 우수하면서도 기공층의 안정화로 인해 탄성, 압축복원력 및 인장강도 등이 향상된 폴리우레탄 발포시트를 제공한다.The present invention relates to a method for manufacturing a flame-retardant polyurethane foam sheet, and more particularly, a surface treatment agent manufacturing step for preparing a UV curable surface treatment agent containing a flame retardant mixture consisting of an encapsulated flame retardant and melamine, through the surface treatment agent manufacturing step A coating step of coating the prepared surface treatment agent on one surface of the polyurethane foam sheet containing a flame retardant and a curing step of curing the surface treatment agent coated on the polyurethane foam sheet containing a flame retardant through the coating step.
The method for producing a flame-retardant polyurethane foam sheet comprising the above process is to apply a surface treatment agent containing a flame retardant mixture consisting of a flame retardant and melamine surface-modified through encapsulation on the surface of the polyurethane foam sheet to adhere to the coating film with the polyurethane foam sheet. It has excellent flame retardancy and provides a surface treatment layer that exhibits effects such as reduction of stickiness and suppression of wrinkles during winding or use. To provide a polyurethane foam sheet with improved elasticity, compressive resilience, and tensile strength.

Description

난연성 폴리우레탄 발포시트의 제조방법 {MANUFACTURING METHOD OF FLAME RETARDANT POLYURETHANE FOAM SHEET}Manufacturing method of flame-retardant polyurethane foam sheet {MANUFACTURING METHOD OF FLAME RETARDANT POLYURETHANE FOAM SHEET}

본 발명은 난연성 폴리우레탄 발포시트의 제조방법에 관한 것으로, 더욱 상세하게는, 캡슐화를 통해 표면개질된 난연제와 멜라민으로 이루어진 난연제 혼합물이 함유된 표면처리제를 폴리우레탄 발포시트의 표면에 도포하여 폴리우레탄 발포시트와의 도막 밀착성이 우수하며, 난연성능 뿐만 아니라 끈적임 감소 등의 효과를 나타내는 표면처리층이 제공되어 권취 혹은 사용과정에서 주름발생이 억제되며, 발포시트 내부에 난연제의 함량이 낮지만 난연성이 우수하면서도 기공층의 안정화로 인해 탄성, 압축복원력 및 인장강도 등이 향상된 폴리우레탄 발포시트를 제공하는 난연성 폴리우레탄 발포시트의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a flame-retardant polyurethane foam sheet, and more particularly, by applying a surface treatment agent containing a flame retardant mixture consisting of a flame retardant and melamine surface-modified through encapsulation on the surface of the polyurethane foam sheet to polyurethane It has excellent adhesion to the foam sheet, and a surface treatment layer that exhibits effects such as reducing stickiness as well as flame retardant performance is provided to suppress wrinkles during winding or use. It relates to a method for manufacturing a flame-retardant polyurethane foam sheet that provides a polyurethane foam sheet with improved elasticity, compressive recovery force, and tensile strength due to stabilization of the pore layer while being excellent.

일반적으로 박막 폴리우레탄 발포시트는 주로 모바일 기기나 TV 가전 및 자동차 등에 적용되어 완충재 및 씰링재로서의 역할을 하는 것으로, 사용과정 중 발생될 수 있는 발화를 방지하기 위하여 폴리우레탄 발포시트 내부에 일체형으로 난연제를 일정량 혼합하여 제조된다.In general, thin-film polyurethane foam sheet is mainly applied to mobile devices, TV home appliances and automobiles, and serves as a cushioning material and sealing material. It is prepared by mixing a certain amount.

이러한 종래의 폴리우레탄 발포시트는 난연제가 이물질로 작용하여 기공층에 함유됨으로써, 기공층의 크기가 불균일하며, 복원력이 저하되고, 표면이 거칠어지는 문제점이 있었다.The conventional polyurethane foam sheet has problems in that the flame retardant acts as a foreign material and is contained in the pore layer, so that the size of the pore layer is non-uniform, the restoring force is lowered, and the surface is rough.

또한, 폴리우레탄 수지의 팽창과정에서 난연제 입자간의 거리가 멀어짐으로 인해 난연성이 저하될 뿐만 아니라 특히, 1.5mm 이하의 박막 폴리우레탄 발포 시트의 경우 두께가 두꺼운 발포시트와 동일한 함량의 난연제를 첨가하더라도 난연성이 저하되는 바, 이의 난연성을 충족시키기 위해서는 난연제가 과다 충전됨으로 인해 상기에 언급한 문제점들이 더욱 부각되는 단점들이 있었다.In addition, in the case of a thin film polyurethane foam sheet of 1.5 mm or less, in particular, in the case of a thin foam sheet of 1.5 mm or less, flame retardancy is added even if the same amount of flame retardant is added to the thick foam sheet as the distance between the flame retardant particles increases in the expansion process of the polyurethane resin. This is lowered, there were disadvantages in which the above-mentioned problems are further emphasized due to the excessive filling of the flame retardant in order to satisfy its flame retardancy.

한편, 최근에는 각종 고분자 재료가 전기, 전자부품, 차량, 항공기 및 선박 등에 광범위하게 적용되고 있으며, 효과적인 난연화에 대한 필요성이 크게 부각되고 있는 상황이다. Meanwhile, in recent years, various polymer materials have been widely applied to electric and electronic parts, vehicles, aircraft, and ships, and the need for effective flame retardancy has been greatly emphasized.

일반적으로 고분자 재료의 난연화 방법에는 고분자의 구조를 변경시켜 내열, 난연성을 가진 고분자를 합성하는 방법, 화학결합을 통해 난연성을 가진 물질을 제조하는 방법, 난연제를 고분자에 첨가시키는 방법, 최종제품에 난연제를 코팅하는 방법 등이 있다. 이중 고분자에 난연제를 첨가하는 방법이 가장 효과적으로 난연성을 부여하는 방법중의 하나로 알려져 있다.In general, flame retardant methods of polymer materials include a method of synthesizing a polymer having heat resistance and flame retardancy by changing the structure of the polymer, a method of manufacturing a flame retardant material through chemical bonding, a method of adding a flame retardant to a polymer, and a method of adding a flame retardant to a final product There is a method of coating a flame retardant. A method of adding a flame retardant to a double polymer is known as one of the most effective methods for imparting flame retardancy.

현재 주로 사용되는 난연제는 구성성분에 따라 유기계와 무기계로 나뉘는데, 유기계는 주로 인계, 브롬계, 염소계로 분류되고, 무기계는 수산화알루미늄, 산화안티몬, 수산화마그네슘 등으로 분류된다.Flame retardants currently used mainly are divided into organic and inorganic types according to their components. Organic types are mainly classified into phosphorus, bromine, and chlorine types, and inorganic types are classified into aluminum hydroxide, antimony oxide, magnesium hydroxide, and the like.

상기에 나열된 난연제들을 고분자 재료에 직접 혼합되는 경우 고분자 재료의 투명도를 저하시켜 외관이 뿌옇게 보이는 현상이 발생되며, 난연제의 고르게 분산되지 못해 균일한 난연성을 나타내기가 어렵고, 고분자 소재와의 접착성이 낮에 쉽게 탈리되거나 자외선에 의한 고분자 소재의 경화도가 저하시켜 표면에 끈적임이 남기 때문에 도막 내구성 및 내오염성이 감소되는 문제점이 있었다.When the flame retardants listed above are directly mixed with the polymer material, the transparency of the polymer material is lowered and the appearance is cloudy, and the flame retardant is not evenly dispersed, so it is difficult to show a uniform flame retardancy, and the adhesiveness with the polymer material is low There was a problem in that the durability and stain resistance of the coating film were reduced because it was easily detached from the surface or the curing degree of the polymer material was reduced by ultraviolet rays, leaving stickiness on the surface.

한국특허등록 제10-0926834호(2009.11.06)Korean Patent Registration No. 10-0926834 (2009.11.06) 한국특허등록 제10-1865980호(2018.06.01)Korean Patent Registration No. 10-1865980 (2018.06.01)

본 발명의 목적은 캡슐화를 통해 표면개질된 난연제와 멜라민으로 이루어진 난연제 혼합물이 함유된 표면처리제를 폴리우레탄 발포시트의 표면에 도포하여 폴리우레탄 발포시트와의 도막 밀착성이 우수하며, 난연성능 뿐만 아니라 끈적임 감소 등의 효과를 나타내는 표면처리층이 제공되어 권취 혹은 사용과정에서 주름발생이 억제되며, 발포시트 내부에 난연제의 함량이 낮지만 난연성이 우수하면서도 기공층의 안정화로 인해 탄성, 압축복원력 및 인장강도 등이 향상된 폴리우레탄 발포시트를 제공하는 난연성 폴리우레탄 발포시트의 제조방법을 제공하는 것이다.An object of the present invention is to apply a surface treatment agent containing a flame retardant mixture consisting of a flame retardant and melamine surface-modified through encapsulation on the surface of a polyurethane foam sheet to have excellent adhesion to the polyurethane foam sheet, and has excellent flame retardant performance as well as stickiness A surface treatment layer that exhibits effects such as reduction is provided to suppress wrinkling during winding or use, and although the content of flame retardant inside the foam sheet is low, it has excellent flame retardancy and elasticity, compression recovery and tensile strength due to stabilization of the pore layer It is to provide a method for manufacturing a flame-retardant polyurethane foam sheet that provides an improved polyurethane foam sheet.

본 발명의 목적은 캡슐화된 난연제와 멜라민으로 이루어진 난연제혼합물이 함유된 자외선 경화형 표면처리제를 제조하는 표면처리제제조단계, 상기 표면처리제제조단계를 통해 제조된 표면처리제를 난연제가 함유된 폴리우레탄 발포시트의 일면에 코팅하는 코팅단계 및 상기 코팅단계를 통해 난연제가 함유된 폴리우레탄 발포시트에 코팅된 표면처리제를 경화하는 경화단계로 이루어지는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법을 제공함에 의해 달성된다.An object of the present invention is a surface treatment agent manufacturing step for preparing a UV curable surface treatment agent containing a flame retardant mixture consisting of an encapsulated flame retardant and melamine, a surface treatment agent prepared through the surface treatment agent manufacturing step of a polyurethane foam sheet containing a flame retardant It is achieved by providing a method for manufacturing a flame-retardant polyurethane foam sheet, characterized in that it comprises a coating step of coating one surface and a curing step of curing the surface treatment agent coated on the polyurethane foam sheet containing the flame retardant through the coating step. .

본 발명의 바람직한 특징에 따르면, 상기 표면처리제제조단계는 우레탄계 올리고머 100 중량부, 아크릴계 모노머 50 내지 150 중량부, 광개시제 2 내지 15 중량부 및 캡슐화된 난연제와 멜라민으로 이루어진 난연제 혼합물 25 내지 300 중량부를 혼합하여 이루어지는 것으로 한다.According to a preferred feature of the present invention, in the step of preparing the surface treatment agent, 100 parts by weight of a urethane-based oligomer, 50 to 150 parts by weight of an acrylic monomer, 2 to 15 parts by weight of a photoinitiator, and 25 to 300 parts by weight of a flame retardant mixture consisting of an encapsulated flame retardant and melamine are mixed. to be done by

본 발명의 더 바람직한 특징에 따르면, 상기 난연제 혼합물은 캡슐화된 난연제 100 중량부 및 멜라민 30 내지 100 중량부로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the flame retardant mixture shall consist of 100 parts by weight of the encapsulated flame retardant and 30 to 100 parts by weight of melamine.

본 발명의 더욱 바람직한 특징에 따르면, 상기 아크릴계 모노머는 1,9-노난디올디메타아크릴레이트, 1,6-헥산디올디메타아크릴레이트, 1,8-옥탄디올디메타아크릴레이트, 1,10-데칸디올디메타아크릴레이트 및 1,14-테트라데칸디올디메타아크릴레이트로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the acrylic monomer is 1,9-nonanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,8-octanediol dimethacrylate, 1,10- It shall consist of at least one selected from the group consisting of decanediol dimethacrylate and 1,14-tetradecanediol dimethacrylate.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 캡슐화된 난연제는 난연제 100 중량부의 표면을 합성수지 5 내지 100 중량부로 코팅하여 제조되는 것으로 한다.According to an even more preferred feature of the present invention, the encapsulated flame retardant is to be prepared by coating the surface of 100 parts by weight of the flame retardant with 5 to 100 parts by weight of a synthetic resin.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 합성수지는 폴리스티렌, 아크릴로니트릴부타디엔스티렌 공중합체, 하이임펙트 폴리스티렌, 아크릴로니트릴스티렌아크릴레이트 공중합체, 아크릴로니트릴스티렌 공중합체, 메틸메타크릴레이트부타디엔스티렌 공중합체, 아크릴로니트릴에틸아크릴레이트스티렌 공중합체, 폴리카보네이트, 폴리페닐렌에테르, 폴리에틸렌 테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리비닐클로라이드, 폴리메틸메타아크릴레이트, 폴리아미드, 에폭시, 멜라민, 폴리우레탄 및 폴리우레아로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the synthetic resin is polystyrene, acrylonitrile butadiene styrene copolymer, high-impact polystyrene, acrylonitrile styrene acrylate copolymer, acrylonitrile styrene copolymer, methyl methacrylate butadiene styrene copolymer Copolymer, acrylonitrile ethyl acrylate styrene copolymer, polycarbonate, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polymethyl methacrylate, polyamide, epoxy, melamine, polyurethane and It shall be made of at least one selected from the group consisting of polyurea.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 코팅단계는 상기 표면처리제제조단계를 통해 제조된 표면처리제를 폴리우레탄 발포시트의 일면에 2 내지 20㎛의 두께로 코팅하여 이루어지는 것으로 한다.According to an even more preferred feature of the present invention, the coating step is made by coating the surface treatment agent prepared through the surface treatment agent manufacturing step on one surface of the polyurethane foam sheet to a thickness of 2 to 20 μm.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 난연제가 함유된 폴리우레탄 발포시트에는 상기 난연제가 함유된 폴리우레탄 발포시트 100 중량부 대비 난연제 3 내지 5 중량부가 함유되는 것으로 한다.According to an even more preferred feature of the present invention, the flame retardant-containing polyurethane foam sheet contains 3 to 5 parts by weight of the flame retardant relative to 100 parts by weight of the polyurethane foam seat containing the flame retardant.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 난연제가 함유된 폴리우레탄 발포시트에 함유되는 난연제는 인계난연제인 것으로 한다.According to an even more preferred feature of the present invention, the flame retardant contained in the polyurethane foam sheet containing the flame retardant is a phosphorus-based flame retardant.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 경화단계는 상기 코팅단계를 통해 폴리우레탄 발포시트에 코팅된 표면처리제에 800 내지 1200mj/cm2의 자외선을 조사하여 이루어지는 것으로 한다.According to an even more preferred feature of the present invention, the curing step is made by irradiating UV rays of 800 to 1200 mj/cm 2 to the surface treatment agent coated on the polyurethane foam sheet through the coating step.

본 발명에 따른 난연성 폴리우레탄 발포시트의 제조방법은 캡슐화를 통해 표면개질된 난연제와 멜라민으로 이루어진 난연제 혼합물이 함유된 표면처리제를 폴리우레탄 발포시트의 표면에 도포하여 폴리우레탄 발포시트와의 도막 밀착성이 우수하며, 난연성능 뿐만 아니라 끈적임 감소 등의 효과를 나타내는 표면처리층이 제공되어 권취 혹은 사용과정에서 주름발생이 억제되며, 발포시트 내부에 난연제의 함량이 낮아 난연성이 우수하면서도 기공층의 안정화로 인해 탄성, 압축복원력 및 인장강도 등이 향상된 폴리우레탄 발포시트를 제공하는 탁월한 효과를 나타낸다.The method for manufacturing a flame-retardant polyurethane foam sheet according to the present invention is to apply a surface treatment agent containing a flame retardant mixture consisting of a flame retardant and melamine surface-modified through encapsulation on the surface of the polyurethane foam sheet to improve the adhesion of the coating film with the polyurethane foam sheet. It has excellent flame retardant performance as well as a surface treatment layer that exhibits effects such as reducing stickiness to suppress wrinkles during winding or use. It shows an excellent effect of providing a polyurethane foam sheet with improved elasticity, compressive resilience, and tensile strength.

도 1은 본 발명에 따른 난연성 폴리우레탄 발포시트의 제조방법을 나타낸 순서도이다.
도 2는 본 발명에 따른 난연성 폴리우레탄 발포시트의 제조방법으로 제조된 발포시트를 나타낸 사시도이다.1 is a flowchart showing a method of manufacturing a flame-retardant polyurethane foam sheet according to the present invention.
Figure 2 is a perspective view showing a foam sheet manufactured by the method for manufacturing a flame-retardant polyurethane foam sheet according to the present invention.

이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a preferred embodiment of the present invention and the physical properties of each component will be described in detail, which is intended to describe in detail enough that a person of ordinary skill in the art to which the present invention pertains can easily carry out the invention, This does not mean that the technical spirit and scope of the present invention is limited.

본 발명에 따른 난연성 폴리우레탄 발포시트의 제조방법은 캡슐화된 난연제와 멜라민으로 이루어진 난연제혼합물이 함유된 자외선 경화형 표면처리제를 제조하는 표면처리제제조단계(S101), 상기 표면처리제제조단계(S101)를 통해 제조된 표면처리제(20)를 난연제가 함유된 폴리우레탄 발포시트(10)의 일면에 코팅하는 코팅단계(S103) 및 상기 코팅단계(S103)를 통해 난연제가 함유된 폴리우레탄 발포시트(10)에 코팅된 표면처리제(20)를 경화하는 경화단계(S105)로 이루어진다.The method for manufacturing a flame-retardant polyurethane foam sheet according to the present invention comprises a surface treatment agent manufacturing step (S101) of preparing a UV-curable surface treatment agent containing a flame retardant mixture consisting of an encapsulated flame retardant and melamine, through the surface treatment agent manufacturing step (S101) The polyurethane foam sheet 10 containing the flame retardant through the coating step (S103) and the coating step (S103) of coating the prepared surface treatment agent 20 on one side of the polyurethane foam sheet 10 containing the flame retardant. It consists of a curing step (S105) of curing the coated surface treatment agent (20).

상기 표면처리제제조단계(S101)는 캡슐화된 난연제와 멜라민으로 이루어진 난연제 혼합물이 함유된 자외선 경화형 표면처리제를 제조하는 단계로, 우레탄계 올리고머 100 중량부, 아크릴계 모노머 50 내지 150 중량부, 광개시제 2 내지 15 중량부 및 난연제 혼합물 25 내지 300 중량부를 혼합하여 이루어진다.The surface treatment agent manufacturing step (S101) is a step of preparing a UV-curable surface treatment agent containing a flame retardant mixture consisting of an encapsulated flame retardant and melamine, 100 parts by weight of a urethane-based oligomer, 50 to 150 parts by weight of an acrylic monomer, 2 to 15 parts by weight of a photoinitiator and 25 to 300 parts by weight of the flame retardant mixture.

상기 우레탄계 올리고머는 우레탄아크릴레이트로 이루어지는데, 상기의 우레탄아크릴레이트는 광개시제 반응에 의한 라디칼 중합반응이 빠르게 진행되며 탄성 및 강도가 우수한 도막을 제공하며 특히, 상기 폴리우레탄 발포시트(10)의 표면에 대한 우수한 밀착력을 나타낸다.The urethane-based oligomer is made of urethane acrylate, and the urethane acrylate rapidly undergoes a radical polymerization reaction by a photoinitiator reaction and provides a coating film having excellent elasticity and strength. In particular, on the surface of the polyurethane foam sheet 10 It shows excellent adhesion to

상기 아크릴게 모노머는 50 내지 150 중량부가 함유되며, 1,9-노난디올디메타아크릴레이트, 1,6-헥산디올디메타아크릴레이트, 1,8-옥탄디올디메타아크릴레이트, 1,10-데칸디올디메타아크릴레이트 및 1,14-테트라데칸디올디메타아크릴레이트로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는데, 상기의 성분으로 이루어지는 아크릴계 모노머는 자외선 경화형 표면처리제의 유연성, 밀착성, 가교밀도 적정성 등을 고려하여 사용되었다.The acrylic monomer contains 50 to 150 parts by weight, 1,9-nonanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,8-octanediol dimethacrylate, 1,10- It consists of at least one selected from the group consisting of decanediol dimethacrylate and 1,14-tetradecanediol dimethacrylate, and the acrylic monomer composed of the above components has the flexibility, adhesion, crosslinking density, etc. of the UV curable surface treatment agent. was used taking into account.

상기 아크릴계 모노머의 함량이 50 중량부 미만이면 자외선 경화형 표면처리제의 유연성, 밀착성, 가교밀도 적정성 등이 저하될 수 있으며, 상기 아크릴계 모노머의 함량이 150 중량부를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 상대적으로 캡슐화된 난연제의 함량이 줄어들기 때문에 바람직하지 못하다.If the content of the acrylic monomer is less than 50 parts by weight, the flexibility, adhesion, crosslinking density, and the like of the UV curable surface treatment agent may be reduced, and if the content of the acrylic monomer exceeds 150 parts by weight, the above effect is not significantly improved It is not preferable because the content of the relatively encapsulated flame retardant is reduced in the present invention.

삭제delete

상기 광개시제는 2 내지 15 중량부가 함유되며, 상기 우레탄계 올리고머의 라디칼 중합을 개시하여 탄성 및 강도 등이 우수하며, 상기 폴리우레탄 발포시트의 표면과 우수한 밀착을 나타내는 도막을 제공하는 역할을 하는데, 아세토페논 계열, 벤조인에테르 계열 및 벤질케톤 계열 등으로 이루어진 그룹에서 선택된 하나 이상을 사용하는 것이 바람직하다.The photoinitiator contains 2 to 15 parts by weight, and by initiating radical polymerization of the urethane-based oligomer, it has excellent elasticity and strength, and serves to provide a coating film exhibiting excellent adhesion to the surface of the polyurethane foam sheet, acetophenone It is preferable to use at least one selected from the group consisting of series, benzoin ether series, and benzyl ketone series.

상기 난연제 혼합물은 캡슐화된 난연제 100 중량부 및 멜라민 30 내지 100 중량부로 이루어지며, 자외선 경화형 표면처리제(20)로 이루어지는 도막에 난연성능을 부여하는 역할을 하는데, 난연제 100 중량부의 표면을 합성수지 5 내지 100 중량부로 코팅하여 제조되는 것이 바람직하다.The flame retardant mixture consists of 100 parts by weight of the encapsulated flame retardant and 30 to 100 parts by weight of melamine, and serves to impart flame retardant performance to the coating film made of the UV curable surface treatment agent 20. The surface of 100 parts by weight of the flame retardant is synthetic resin 5 to 100 It is preferably prepared by coating in parts by weight.

더욱 바람직하게는 상기 캡슐화된 난연제는 난연제 100 중량부, 합성수지 5 내지 100 중량부 및 유화제 1 내지 10 중량부를 혼합하여 혼합물을 제조하고, 상기 혼합물에 경화제 1 내지 10 중량부를 혼합한 후에 30 내지 100℃의 온도에서 교반시키는 과정을 통해 제조된다.More preferably, the encapsulated flame retardant is prepared by mixing 100 parts by weight of a flame retardant, 5 to 100 parts by weight of a synthetic resin, and 1 to 10 parts by weight of an emulsifier, and after mixing 1 to 10 parts by weight of a curing agent in the mixture, 30 to 100° C. It is prepared through a process of stirring at a temperature of

이때, 상기 난연제는 인계난연제를 사용하거나, 인계난연제와 수산화알루미늄 및 수산화마그네슘 등의 무기계 난연제를 혼합하여 사용하는 것이 바람직하다.In this case, the flame retardant is preferably a phosphorus-based flame retardant or a mixture of a phosphorus-based flame retardant and an inorganic flame retardant such as aluminum hydroxide and magnesium hydroxide.

또한, 상기 합성수지는 폴리스티렌, 아크릴로니트릴부타디엔스티렌 공중합체, 하이임펙트 폴리스티렌, 아크릴로니트릴스티렌아크릴레이트 공중합체, 아크릴로니트릴스티렌 공중합체, 메틸메타크릴레이트부타디엔스티렌 공중합체, 아크릴로니트릴에틸아크릴레이트스티렌 공중합체, 폴리카보네이트, 폴리페닐렌에테르, 폴리에틸렌 테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리비닐클로라이드, 폴리메틸메타아크릴레이트, 폴리아미드, 에폭시, 멜라민, 폴리우레탄 및 폴리우레아로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것이 바람직하다.In addition, the synthetic resin is polystyrene, acrylonitrile butadiene styrene copolymer, high-impact polystyrene, acrylonitrile styrene acrylate copolymer, acrylonitrile styrene copolymer, methyl methacrylate butadiene styrene copolymer, acrylonitrile ethyl acrylate One selected from the group consisting of styrene copolymer, polycarbonate, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polymethyl methacrylate, polyamide, epoxy, melamine, polyurethane and polyurea It is preferable to consist of the above.

또한, 상기 유화제는 소듐라우릴레이트, 소듐올레이트, 포타슘올레이트, 포타슘스테아레이트 등과 같은 지방산금속, 소듐라우릴설페이트 및 로진산칼륨으로 이루어진 그룹에서 선택된 하나로 이루어지는 것이 바람직하며, 상기 경화제는 헥사메틸렌디아민으로 이루어지는 것이 바람직하다In addition, the emulsifier is preferably made of one selected from the group consisting of fatty acid metals such as sodium laurylate, sodium oleate, potassium oleate, potassium stearate, sodium lauryl sulfate and potassium rosinate, and the curing agent is hexamethylene It is preferably made of diamine

상기 코팅단계(S103)는 상기 표면처리제제조단계(S101)를 통해 제조된 표면처리제(20)를 난연제가 함유된 폴리우레탄 발포시트(10)의 일면에 코팅하는 단계로, 상기 표면처리제제조단계(S101)를 통해 제조된 표면처리제(20)를 난연제가 함유된 폴리우레탄 발포시트(10)의 일면에 2 내지 20㎛의 두께로 코팅하여 이루어진다.The coating step (S103) is a step of coating the surface treatment agent 20 prepared through the surface treatment agent manufacturing step (S101) on one surface of the polyurethane foam sheet 10 containing a flame retardant, the surface treatment agent manufacturing step ( It is made by coating the surface treatment agent 20 prepared through S101) to a thickness of 2 to 20 μm on one surface of the polyurethane foam sheet 10 containing the flame retardant.

상기 표면처리제(20)의 코팅두께가 2㎛ 미만이면 폴리우레탄 발포시트(10)의 난연성과 끈적임 감소 등의 효과가 미미하며, 권취 혹은 사용과정에서 주름이 발생할 수 있으며, 상기 표면처리제(20)의 코팅두께가 20㎛를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 표면처리제(20)의 코팅두께가 지나치게 증가하여 제조비용을 증가시킬 수 있다.If the coating thickness of the surface treatment agent 20 is less than 2 μm, the effects such as flame retardancy and stickiness reduction of the polyurethane foam sheet 10 are insignificant, and wrinkles may occur during winding or use, and the surface treatment agent 20 When the thickness of the coating exceeds 20 μm, the coating thickness of the surface treatment agent 20 is excessively increased without significantly improving the above effect, thereby increasing the manufacturing cost.

이때, 상기 난연제가 함유된 폴리우레탄 발포시트(10)는 저밀도 박막 폴리우레탄 발포시트를 사용하는 것이 바람직하며, 폴리에스테르 폴리올, 폴리에테르 폴리올, 기포를 안정시키는 정포제, 중합반응을 촉진 시키는 경화성 촉매, 경도 및 치수안정성을 향상시키는 필러, 색상을 표현하는 안료 등을 혼합한 조성물 및 난연제와 이소시아네이트를 혼합하는 과정에서 발포 조촉매인 질소를 추가 투입하여 반응시키는 과정을 통해 제조된 것을 사용하는 것이 바람직하나, 이에 한정되지는 않는다.At this time, it is preferable to use a low-density thin-film polyurethane foam sheet for the polyurethane foam sheet 10 containing the flame retardant, polyester polyol, polyether polyol, a foam stabilizer for stabilizing bubbles, a curable catalyst for accelerating the polymerization reaction , It is preferable to use a composition mixed with a filler to improve hardness and dimensional stability, a pigment expressing color, etc. However, the present invention is not limited thereto.

또한, 상기 난연제가 함유된 폴리우레탄 발포시트(10)는 두께범위가 0.07 내지 5.0mm 일 수 있으며, 적용분야로 인해 박막의 기준이 요구되므로, 1.5mm이하의 두께를 나타내는 것이 바람직하고, 밀도범위는 0.1 내지 0.5g/cm3를 나타내는 것이 바람직한데, 발포배율이 2 내지 10인 폴리우레탄 발포시트(10)를 사용하는 것이 바람직하다.In addition, the polyurethane foam sheet 10 containing the flame retardant may have a thickness range of 0.07 to 5.0 mm, and since a thin film standard is required due to the field of application, it is preferable to exhibit a thickness of 1.5 mm or less, and the density range It is preferable to represent 0.1 to 0.5 g/cm 3 , and it is preferable to use the polyurethane foam sheet 10 having a foaming ratio of 2 to 10.

상기 난연제가 함유된 폴리우레탄 발포시트(10)의 발포배율은 발포배율이 2배 미만이면 기공의 수가 너무 적어 중량이 무겁고 탄성 및 단열성이 저하되며, 폴리우레탄 발포시트(10)의 발포배율이 10배를 초과하게 되면 중량은 가벼우나 기계적 물성이 지나치게 저하될 수 있다.If the expansion ratio of the polyurethane foam sheet 10 containing the flame retardant is less than 2 times, the number of pores is too small, the weight is heavy, the elasticity and thermal insulation properties are lowered, and the expansion ratio of the polyurethane foam sheet 10 is 10 If it exceeds twice, the weight may be light, but mechanical properties may be excessively deteriorated.

이때, 상기 난연제가 함유된 폴리우레탄 발포시트(10)는 상기 난연제가 함유된 폴리우레탄 발포시트(10) 100 중량부 대비 난연제 3 내지 5 중량부가 함유될 수 있는데, 상기 난연제는 특별히 한정되지 않고, 무기계 난연제나 유기계 난연제 모두가 사용될 수 있으나, 인계 난연제를 사용하는 것이 가장 바람직하다.At this time, the polyurethane foam sheet 10 containing the flame retardant may contain 3 to 5 parts by weight of the flame retardant relative to 100 parts by weight of the polyurethane foam sheet 10 containing the flame retardant, the flame retardant is not particularly limited, Both inorganic flame retardants and organic flame retardants may be used, but it is most preferable to use a phosphorus flame retardant.

상기 난연제가 함유된 폴리우레탄 발포시트(10)에 함유되는 난연제의 함량이 3 중량부 미만이면 본 발명에 따른 난연성 폴리우레탄 발포시트의 제조방법을 통해 제조되는 발포시트의 난연성 향상효과가 미미하며, 상기 난연제의 함량이 5 중량부를 초과하게 되면 기공층의 안정화가 저하되어 발포시트의 탄성, 압축복원력 및 인장강도 등이 저하될 수 있다.If the content of the flame retardant contained in the polyurethane foam sheet 10 containing the flame retardant is less than 3 parts by weight, the flame retardant improvement effect of the foam sheet manufactured through the method for manufacturing the flame retardant polyurethane foam sheet according to the present invention is insignificant, When the content of the flame retardant exceeds 5 parts by weight, the stabilization of the pore layer is lowered, and the elasticity, compressive recovery force, and tensile strength of the foam sheet may be lowered.

상기 경화단계(S105)는 상기 코팅단계(S103)를 통해 난연제가 함유된 폴리우레탄 발포시트(10)에 코팅된 표면처리제(20)를 경화하는 단계로, 상기 코팅단계(S103)를 통해 난연제가 함유된 폴리우레탄 발포시트(10)에 코팅된 표면처리제(20)에 800 내지 1200mj/cm2의 자외선을 조사하거나, 열풍건조기를 통해 발생하는 120 내지 150℃의 열풍으로 경화시키는 과정으로 이루어진다. 또한, 경우에 따라서는 상기의 조건의 자외선 조사후 상기 온도범위의 열풍을 순차적으로 적용하는 방법을 이용할 수도 있다.The curing step (S105) is a step of curing the surface treatment agent 20 coated on the polyurethane foam sheet 10 containing the flame retardant through the coating step (S103). It consists of a process of irradiating 800 to 1200 mj/cm 2 of UV light to the surface treatment agent 20 coated on the polyurethane foam sheet 10 contained therein, or curing it with hot air of 120 to 150° C. generated through a hot air dryer. In addition, in some cases, a method of sequentially applying hot air in the above temperature range after UV irradiation under the above conditions may be used.

이때, 상기 자외선의 조사는 자외선 램프를 이용하여 이루어질 수 있으며, 이때 자외선 조사시 온도조건은 50 내지 60℃가 바람직하다.At this time, the irradiation of the ultraviolet rays may be made using an ultraviolet lamp, and the temperature condition at the time of ultraviolet irradiation is preferably 50 to 60°C.

이하에서는, 본 발명에 따른 난연성 폴리우레탄 발포시트의 제조방법 및 그 제조방법을 통해 제조된 발포시트의 물성을 실시예를 들어 설명하기로 한다.Hereinafter, the method for manufacturing a flame-retardant polyurethane foam sheet according to the present invention and the physical properties of the foam sheet manufactured through the manufacturing method will be described with reference to examples.

<제조예 1> 캡슐화된 난연제의 제조<Preparation Example 1> Preparation of encapsulated flame retardant

난연제(인계난연제) 100 중량부, 합성수지(폴리스티렌) 50 중량부 및 유화제(소듐라우릴레이트) 5 중량부를 혼합하여 혼합물을 제조하고, 상기 혼합물에 경화제(헥사메틸렌디아민) 5 중량부를 혼합한 후에 60℃의 온도에서 교반시켜 캡슐화된 난연제를 제조하였다.A mixture is prepared by mixing 100 parts by weight of a flame retardant (phosphorus flame retardant), 50 parts by weight of a synthetic resin (polystyrene), and 5 parts by weight of an emulsifier (sodium laurylate), and after mixing 5 parts by weight of a curing agent (hexamethylenediamine) to the mixture, 60 parts by weight The encapsulated flame retardant was prepared by stirring at a temperature of °C.

<제조예 2> 난연제 혼합물의 제조<Preparation Example 2> Preparation of flame retardant mixture

상기 제조예 1을 통해 제조된 캡슐화된 난연제 100 중량부에 멜라민 70 중량부를 혼합하여 난연제 혼합물을 제조하였다.70 parts by weight of melamine was mixed with 100 parts by weight of the encapsulated flame retardant prepared in Preparation Example 1 to prepare a flame retardant mixture.

<제조예 3> 자외선 경화형 표면처리제의 제조<Preparation Example 3> Preparation of UV-curable surface treatment agent

우레탄계 올리고머(우레탄아크릴레이트) 100 중량부, 아크릴계 모노머(1,6-헥산디올디메타아크릴레이트) 100 중량부, 광개시제(2, 2-디메톡시-2-페닐아세토페논) 8 중량부 및 상기 제조예 2를 통해 제조된 난연제 혼합물 120 중량부를 혼합하여 자외선 경화형 표면처리제를 제조하였다.100 parts by weight of a urethane-based oligomer (urethane acrylate), 100 parts by weight of an acrylic monomer (1,6-hexanediol dimethacrylate), 8 parts by weight of a photoinitiator (2,2-dimethoxy-2-phenylacetophenone) and the above preparation An ultraviolet curable surface treatment agent was prepared by mixing 120 parts by weight of the flame retardant mixture prepared in Example 2.

<실시예 1><Example 1>

폴리우레탄 발포시트 100 중량부 대비 난연제가 4 중량부 함유되며, 두께가 3.0mm인 폴리우레탄 발포시트(밀도 0.24g/cm3, 발포배율 6배)의 표면에 상기 제조예 3를 통해 제조된 자외선 경화형 표면처리제를 5㎛의 두께로 도포하고 55℃의 온도에서 1000mj/cm2의 자외선을 조사하여 난연성 폴리우레탄 발포시트를 제조하였다.4 parts by weight of a flame retardant is contained relative to 100 parts by weight of the polyurethane foam sheet, and the UV produced in Preparation Example 3 on the surface of the polyurethane foam sheet having a thickness of 3.0 mm (density 0.24 g/cm 3 , expansion ratio 6 times) A curable surface treatment agent was applied to a thickness of 5 μm and irradiated with UV light of 1000 mj/cm 2 at a temperature of 55° C. to prepare a flame-retardant polyurethane foam sheet.

<비교예 2><Comparative Example 2>

두께가 3.0mm인 폴리우레탄 발포시트(밀도 0.22g/cm3, 발포배율 7배)의 표면에 상기 제조예 3를 통해 제조된 자외선 경화형 표면처리제를 5㎛의 두께로 도포하고 55℃의 온도에서 1000mj/cm2의 자외선을 조사하여 난연성 폴리우레탄 발포시트를 제조하였다.The UV curable surface treatment agent prepared in Preparation Example 3 was applied to the surface of a 3.0 mm thick polyurethane foam sheet (density 0.22 g/cm 3 , expansion ratio 7 times) to a thickness of 5 μm, and at a temperature of 55° C. A flame-retardant polyurethane foam sheet was prepared by irradiating an ultraviolet light of 1000 mj/cm 2 .

<비교예 3><Comparative Example 3>

두께가 3.0mm인 폴리우레탄 발포시트(밀도 0.25g/cm3, 발포배율 7배)의 표면에 상기 제조예 3를 통해 제조된 자외선 경화형 표면처리제를 10㎛의 두께로 도포하고 55℃의 온도에서 1000mj/cm2의 자외선을 조사하여 난연성 폴리우레탄 발포시트를 제조하였다.The UV curable surface treatment agent prepared in Preparation Example 3 was applied to the surface of a 3.0 mm thick polyurethane foam sheet (density 0.25 g/cm 3 , expansion ratio 7 times) to a thickness of 10 μm, and at a temperature of 55° C. A flame-retardant polyurethane foam sheet was prepared by irradiating an ultraviolet light of 1000 mj/cm 2 .

<비교예 3><Comparative Example 3>

두께가 1.5mm인 폴리우레탄 발포시트(밀도 0.19g/cm3, 발포배율 5배).Polyurethane foam sheet with a thickness of 1.5 mm (density 0.19 g/cm 3 , expansion ratio 5 times).

상기 실시예 1 및 비교예 1 내지 3을 통해 제조된 폴리우레탄 발포시트의 난연성과 영구압축줄음율을 측정하여 아래 표 1에 나타내었다.The flame retardancy and compression set of the polyurethane foam sheets prepared in Example 1 and Comparative Examples 1 to 3 were measured and shown in Table 1 below.

{단, 난연성은 UL-94 수평 테스트 방법을 이용하였으며, 영구압축줄음율은 영구압축줄음율시험기인 LT170D을 이용하여 측정하였다.}{However, the UL-94 horizontal test method was used for flame retardancy, and the compression set was measured using LT170D, a compression set tester.}

<표 1><Table 1>

Figure 112020120478884-pat00001
Figure 112020120478884-pat00001

상기 표 1에 나타낸 것처럼, 본 발명의 실시예 1을 통해 제조된 난연성 폴리우레탄 발포시트는 비교예 1 내지 3을 통해 제조된 폴리우레탄 발포시트와 대등한 영구압축줄음율을 나타내면서도 난연성이 월등하게 향상되는 것을 알 수 있다.As shown in Table 1, the flame-retardant polyurethane foam sheet prepared in Example 1 of the present invention has excellent flame retardancy while exhibiting a compression set equivalent to that of the polyurethane foam sheet prepared in Comparative Examples 1 to 3 improvement can be seen.

따라서, 본 발명에 따른 난연성 폴리우레탄 발포시트의 제조방법은 캡슐화를 통해 표면개질된 난연제와 멜라민으로 이루어진 난연제 혼합물이 함유된 표면처리제를 폴리우레탄 발포시트의 표면에 도포하여 폴리우레탄 발포시트와의 도막 밀착성이 우수하고, 난연성능 뿐만 아니라 끈적임 감소 등의 효과를 나타내는 표면처리층이 제공되어 권취 혹은 사용과정에서 주름발생이 억제되며, 발포시트 내부에 난연제가 적정량 함유되어 난연성이 우수하면서도 기공층의 안정화로 인해 탄성, 압축복원력 및 인장강도 등이 향상된 폴리우레탄 발포시트를 제공한다.Therefore, in the method for manufacturing a flame-retardant polyurethane foam sheet according to the present invention, a surface treatment agent containing a flame retardant mixture consisting of a flame retardant and melamine surface-modified through encapsulation is applied to the surface of the polyurethane foam sheet to make a coating film with the polyurethane foam sheet. A surface treatment layer that has excellent adhesion and exhibits effects such as reducing stickiness as well as flame retardant performance is provided to suppress wrinkling during winding or use. As a result, there is provided a polyurethane foam sheet having improved elasticity, compressive resilience, and tensile strength.

S101 ; 표면처리제제조단계
S103 ; 코팅단계
S105 ; 경화단계
10 ; 표면처리제
20 ; 난연제가 함유된 폴리우레탄 발포시트S101; Surface treatment manufacturing step
S103; coating step
S105 ; hardening stage
10 ; surface treatment agent
20 ; Polyurethane foam sheet containing flame retardant

Claims (10)

캡슐화된 난연제와 멜라민으로 이루어진 난연제혼합물이 함유된 자외선 경화형 표면처리제를 제조하는 표면처리제제조단계;
상기 표면처리제제조단계를 통해 제조된 표면처리제를 난연제가 함유된 폴리우레탄 발포시트의 일면에 코팅하는 코팅단계; 및
상기 코팅단계를 통해 난연제가 함유된 폴리우레탄 발포시트에 코팅된 표면처리제를 경화하는 경화단계;로 이루어지며,
상기 표면처리제제조단계는 우레탄계 올리고머 100 중량부, 아크릴계 모노머 50 내지 150 중량부, 광개시제 2 내지 15 중량부 및 난연제 혼합물 25 내지 300 중량부를 혼합하여 이루어지고,
상기 난연제 혼합물은 캡슐화된 난연제 100 중량부 및 멜라민 30 내지 100 중량부로 이루어지며,
상기 코팅단계는 상기 표면처리제제조단계를 통해 제조된 표면처리제를 폴리우레탄 발포시트의 일면에 2 내지 20㎛의 두께로 코팅하여 이루어지고,
상기 난연제가 함유된 폴리우레탄 발포시트에는 상기 난연제가 함유된 폴리우레탄 발포시트 100 중량부 대비 난연제 3 내지 5 중량부가 함유되는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.
A surface treatment agent manufacturing step of preparing a UV-curable surface treatment agent containing a flame retardant mixture consisting of an encapsulated flame retardant and melamine;
A coating step of coating the surface treatment agent prepared through the surface treatment agent manufacturing step on one surface of the polyurethane foam sheet containing a flame retardant; and
A curing step of curing the surface treatment agent coated on the polyurethane foam sheet containing the flame retardant through the coating step;
The surface treatment agent manufacturing step is made by mixing 100 parts by weight of a urethane-based oligomer, 50 to 150 parts by weight of an acrylic monomer, 2 to 15 parts by weight of a photoinitiator, and 25 to 300 parts by weight of a flame retardant mixture,
The flame retardant mixture consists of 100 parts by weight of encapsulated flame retardant and 30 to 100 parts by weight of melamine,
The coating step is made by coating the surface treatment agent prepared through the surface treatment agent manufacturing step to a thickness of 2 to 20 μm on one surface of the polyurethane foam sheet,
The flame retardant-containing polyurethane foam sheet contains 3 to 5 parts by weight of a flame retardant based on 100 parts by weight of the polyurethane foam sheet containing the flame retardant.
 삭제delete 삭제delete 청구항 1에 있어서,
상기 아크릴계 모노머는 1,9-노난디올디메타아크릴레이트, 1,6-헥산디올디메타아크릴레이트, 1,8-옥탄디올디메타아크릴레이트, 1,10-데칸디올디메타아크릴레이트 및 1,14-테트라데칸디올디메타아크릴레이트로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.
The method according to claim 1,
The acrylic monomer is 1,9-nonanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,8-octanediol dimethacrylate, 1,10-decanediol dimethacrylate and 1, 14- A method for producing a flame-retardant polyurethane foam sheet, comprising at least one selected from the group consisting of 14-tetradecanediol dimethacrylate.
 청구항 1에 있어서,
상기 캡슐화된 난연제는 난연제 100 중량부의 표면을 합성수지 5 내지 100 중량부로 코팅하여 제조되는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.
The method according to claim 1,
The encapsulated flame retardant is a method of manufacturing a flame retardant polyurethane foam sheet, characterized in that it is prepared by coating the surface of 100 parts by weight of the flame retardant with 5 to 100 parts by weight of a synthetic resin.
 청구항 5에 있어서,
상기 합성수지는 폴리스티렌, 아크릴로니트릴부타디엔스티렌 공중합체, 하이임펙트 폴리스티렌, 아크릴로니트릴스티렌아크릴레이트 공중합체, 아크릴로니트릴스티렌 공중합체, 메틸메타크릴레이트부타디엔스티렌 공중합체, 아크릴로니트릴에틸아크릴레이트스티렌 공중합체, 폴리카보네이트, 폴리페닐렌에테르, 폴리에틸렌 테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리비닐클로라이드, 폴리메틸메타아크릴레이트, 폴리아미드, 에폭시, 멜라민, 폴리우레탄 및 폴리우레아로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.
6. The method of claim 5,
The synthetic resin is polystyrene, acrylonitrile butadiene styrene copolymer, high-impact polystyrene, acrylonitrile styrene acrylate copolymer, acrylonitrile styrene copolymer, methyl methacrylate butadiene styrene copolymer, acrylonitrile ethyl acrylate styrene copolymer At least one selected from the group consisting of coal, polycarbonate, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polymethyl methacrylate, polyamide, epoxy, melamine, polyurethane and polyurea Method for producing a flame-retardant polyurethane foam sheet, characterized in that made.
 삭제delete 삭제delete 청구항 1에 있어서,
상기 난연제가 함유된 폴리우레탄 발포시트에 함유되는 난연제는 인계난연제인 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.
The method according to claim 1,
The flame retardant contained in the polyurethane foam sheet containing the flame retardant is a method for producing a flame retardant polyurethane foam sheet, characterized in that the phosphorus-based flame retardant.
 청구항 1에 있어서,
상기 경화단계는 상기 코팅단계를 통해 폴리우레탄 발포시트에 코팅된 표면처리제에 800 내지 1200mj/cm2의 자외선을 조사하여 이루어지는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.The method according to claim 1,
The curing step is a method of manufacturing a flame-retardant polyurethane foam sheet, characterized in that made by irradiating an ultraviolet light of 800 to 1200 mj / cm 2 to the surface treatment agent coated on the polyurethane foam sheet through the coating step.
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JP2010261042A (en) 2009-05-11 2010-11-18 Eternal Chemical Co Ltd Microencapsulated fire retardant and use thereof

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KR100360208B1 (en) * 2000-10-05 2002-11-11 주식회사 사나테크 Organic Phosphorus Flame Retardant and Flame Retardant Thormoplastic Resin Composition Containing the Same
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