KR102456135B1 - Manufacturing method of flame retardant polyureyhane foam sheet - Google Patents
Manufacturing method of flame retardant polyureyhane foam sheet Download PDFInfo
- Publication number
- KR102456135B1 KR102456135B1 KR1020200127135A KR20200127135A KR102456135B1 KR 102456135 B1 KR102456135 B1 KR 102456135B1 KR 1020200127135 A KR1020200127135 A KR 1020200127135A KR 20200127135 A KR20200127135 A KR 20200127135A KR 102456135 B1 KR102456135 B1 KR 102456135B1
- Authority
- KR
- South Korea
- Prior art keywords
- foam sheet
- polyurethane foam
- flame retardant
- surface treatment
- treatment agent
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 92
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000006260 foam Substances 0.000 title description 9
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 69
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 69
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- -1 polyethylene terephthalate Polymers 0.000 claims description 8
- 229920003002 synthetic resin Polymers 0.000 claims description 8
- 239000000057 synthetic resin Substances 0.000 claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 5
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- LRZPQLZONWIQOJ-UHFFFAOYSA-N 10-(2-methylprop-2-enoyloxy)decyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOC(=O)C(C)=C LRZPQLZONWIQOJ-UHFFFAOYSA-N 0.000 claims description 3
- PYLRGSOFJMYQNO-UHFFFAOYSA-N 14-(2-methylprop-2-enoyloxy)tetradecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCCCCCOC(=O)C(C)=C PYLRGSOFJMYQNO-UHFFFAOYSA-N 0.000 claims description 3
- YJVIKVWFGPLAFS-UHFFFAOYSA-N 9-(2-methylprop-2-enoyloxy)nonyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCCCCCCCCOC(=O)C(C)=C YJVIKVWFGPLAFS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- UBRPGRAGAZVZKQ-UHFFFAOYSA-N 8-(2-methylprop-2-enoyloxy)octyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCOC(=O)C(C)=C UBRPGRAGAZVZKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003226 polyurethane urea Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004804 winding Methods 0.000 abstract description 7
- 238000005538 encapsulation Methods 0.000 abstract description 5
- 239000002335 surface treatment layer Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- QMRNDFMLWNAFQR-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid;styrene Chemical compound C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 QMRNDFMLWNAFQR-UHFFFAOYSA-N 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical class C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IRCAZSRWCCDLJN-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.CCOC(=O)C=C IRCAZSRWCCDLJN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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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 폴리우레탄 발포시트의 일면에 코팅하는 코팅단계 및 상기 코팅단계를 통해 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 난연제가 함유되지 않아 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 and a curing step of curing the surface treatment agent coated on the polyurethane foam sheet through the coating step.
The method for producing a flame-retardant polyurethane foam sheet comprising the above process applies 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 polyurethane foam sheet. It has excellent flame retardant performance and provides a surface treatment layer that exhibits effects such as reducing stickiness, suppressing wrinkling during winding or use. To provide a polyurethane foam sheet with improved restoring force and tensile strength.
Description
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 난연제가 함유되지 않아 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 having improved elasticity, compressive recovery force and tensile strength due to stabilization.
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, the 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.This 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 a flame retardant is added in the same amount as that of a 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 for polymer materials include a method of synthesizing a polymer with 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.Currently, flame retardants mainly used are divided into organic and inorganic types according to their components. Organic types are mainly classified into phosphorus-based, bromine-based and chlorine-based flame retardants, 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. 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 degree of curing of the polymer material was lowered by ultraviolet rays, so that stickiness was left on the surface.
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 난연제가 함유되지 않아 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 not only flame retardant performance but also stickiness Polyurethane with improved elasticity, compression recovery, and tensile strength due to stabilization of the pore layer because a flame retardant is not contained in the foam seat, and wrinkles are suppressed during the winding or use process by providing a surface treatment layer that exhibits effects such as reduction To provide a method for manufacturing a flame-retardant polyurethane foam sheet to provide a foam sheet.
본 발명의 목적은 캡슐화된 난연제와 멜라민으로 이루어진 난연제혼합물이 함유된 자외선 경화형 표면처리제를 제조하는 표면처리제제조단계, 상기 표면처리제제조단계를 통해 제조된 표면처리제를 폴리우레탄 발포시트의 일면에 코팅하는 코팅단계 및 상기 코팅단계를 통해 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, and coating the surface treatment agent prepared through the surface treatment agent manufacturing step on one surface of a polyurethane foam sheet. It is achieved by providing a method for manufacturing a flame-retardant polyurethane foam sheet, characterized in that it comprises a curing step of curing the surface treatment agent coated on the polyurethane foam sheet through the coating step and 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 surface treatment agent manufacturing step, 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 직쇄상의 탄소수가 9 내지 30인 탄화수소를 포함하는 1,9-노난디올디메타아크릴레이트, 1,6-헥산디올디메타아크릴레이트, 1,8-옥탄디올디메타아크릴레이트, 1,10-데칸디올디메타아크릴레이트 및 1,14-테트라데칸디올디메타아크릴레이트로 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-decanediol dimethacrylate and 1,14-tetradecanediol dimethacrylate.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 캡슐화된 난연제는 난연제 100 중량부의 표면을 합성수지 100 내지 0.005 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 100 to 0.005 to 100 parts by weight of the 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 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 난연제가 함유되지 않아 기공층의 안정화로 인해 탄성, 압축복원력 및 인장강도 등이 향상된 폴리우레탄 발포시트를 제공하는 탁월한 효과를 나타낸다.The method for producing 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, which suppresses wrinkling during winding or use. And it exhibits an excellent effect of providing a polyurethane foam sheet with improved tensile strength and the like.
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 of 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 폴리우레탄 발포시트(10)의 일면에 코팅하는 코팅단계(S103) 및 상기 코팅단계(S103)를 통해 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 is 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
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 radical polymerization by a photoinitiator reaction and provides a coating film having excellent elasticity and strength. In particular, on the surface of the
상기 아크릴게 모노머는 50 내지 150 중량부가 함유되며, 직쇄상의 탄소수가 9 내지 30인 탄화수소를 포함하는 1,9-노난디올디메타아크릴레이트, 1,6-헥산디올디메타아크릴레이트, 1,8-옥탄디올디메타아크릴레이트, 1,10-데칸디올디메타아크릴레이트 및 1,14-테트라데칸디올디메타아크릴레이트로 이루어지는데, 상기의 성분으로 이루어지는 아크릴계 모노머는 자외선 경화형 표면처리제의 유연성, 밀착성, 가교밀도 적정성 등을 고려하여, 직쇄상의 탄소수 9 내지 30인 탄화수소를 포함하는 2관능 (메타)아크릴레이트계가 사용되었다.The acrylic monomer contains 50 to 150 parts by weight, and 1,9-nonanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1, It consists of 8-octanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,14-tetradecanediol dimethacrylate. In consideration of adhesion, crosslinking density, appropriateness, and the like, a bifunctional (meth)acrylate system containing a linear hydrocarbon having 9 to 30 carbon atoms was used.
이때, 3관능을 넘는 측쇄상 모노머의 사용은 도막 경화물의 경도가 높아지거나 유연성이 감소되어, 도막의 두께가 5㎛ 이상 형성되면 폴리우레탄 발포시트(10)의 권취과정이나 사용과정에서 표면주름이 발생할 수 있다.At this time, the use of a branched-chain monomer that exceeds trifunctionality increases the hardness or flexibility of the cured coating film, and when the thickness of the coating film is formed to be 5 μm or more, the surface wrinkle in the winding process or use process of the
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 undesirable because the content of the encapsulated flame retardant is relatively reduced.
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 100 내지 0.005 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
더욱 바람직하게는 상기 캡슐화된 난연제는 난연제 100 중량부, 합성수지 0.005 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, 0.005 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 폴리우레탄 발포시트(10)의 일면에 코팅하는 단계로, 상기 표면처리제제조단계(S101)를 통해 제조된 표면처리제(20)를 폴리우레탄 발포시트(10)의 일면에 2 내지 20㎛의 두께로 코팅하여 이루어진다.The coating step (S103) is a step of coating the
상기 표면처리제(20)의 코팅두께가 2㎛ 미만이면 폴리우레판 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.When the coating thickness of the
이때, 상기 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 조성물과 이소시아네이트를 혼합하는 과정에서 발포 조촉매인 질소를 추가 투입하여 반응시키는 과정을 통해 제조된 것을 사용하는 것이 바람직하나, 이에 한정되지는 않는다.At this time, the
또한, 상기 폴리우레판 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
상기 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.When the expansion ratio of the
상기 경화단계(S105)는 상기 코팅단계(S103)를 통해 폴리우레탄 발포시트(10)에 코팅된 표면처리제(20)를 경화하는 단계로, 상기 코팅단계(S103)를 통해 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
이때, 상기 자외선의 조사는 자외선 램프를 이용하여 이루어질 수 있으며, 이때 자외선 조사시 온도조건은 50 내지 60℃가 바람직하다.In this case, the irradiation of the ultraviolet rays may be made using an ultraviolet lamp, and the temperature condition during 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>
두께가 1.5mm인 폴리우레판 발포시트(밀도 0.2g/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.On the surface of a polyurethane foam sheet having a thickness of 1.5 mm (density 0.2 g/cm 3 , expansion ratio 6 times), the UV-curable surface treatment agent prepared in Preparation Example 3 was applied to a thickness of 5 μm, and the temperature of 55° C. A flame-retardant polyurethane foam sheet was prepared by irradiating an ultraviolet light of 1000 mj/cm 2 in.
<실시예 2><Example 2>
두께가 1.5mm인 폴리우레판 발포시트(밀도 0.18g/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.On the surface of a polyurethane foam sheet having a thickness of 1.5 mm (density 0.18 g/cm 3 , expansion ratio 7 times), the UV-curable surface treatment agent prepared in Preparation Example 3 was applied to a thickness of 10 μm, and a temperature of 55° C. A flame-retardant polyurethane foam sheet was prepared by irradiating an ultraviolet light of 1000 mj/cm 2 in.
<비교예 1><Comparative Example 1>
두께가 1.5mm인 폴리우레판 발포시트(밀도 0.22g/cm3, 발포배율 5배).Polyurethane foam sheet with a thickness of 1.5mm (density 0.22g/cm 3 , expansion ratio 5 times).
상기 실시예 1 내지 2를 통해 제조된 난연성 폴리우레탄 발포시트와 상기 비교예 1을 통해 제조된 폴리우레탄 발포시트의 난연성과 영구압축줄음율을 측정하여 아래 표 1에 나타내었다.The flame-retardant polyurethane foam sheet prepared in Examples 1 and 2 and the polyurethane foam sheet prepared in Comparative Example 1 were measured for flame retardancy and compression set, and are 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 permanent compression set tester.}
<표 1><Table 1>
상기 표 1에 나타낸 것처럼, 본 발명의 실시예 1 내지 2를 통해 제조된 난연성 폴리우레탄 발포시트는 비교예 1의 폴리우레탄발포시트와 대등한 영구압축줄음율을 나타내면서도 난연성이 월등하게 향상되는 것을 알 수 있다.As shown in Table 1, the flame-retardant polyurethane foam sheet prepared through Examples 1 and 2 of the present invention exhibits a permanent compression set equivalent to that of the polyurethane foam sheet of Comparative Example 1, while the flame retardancy is significantly improved. Able to know.
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 함유되지 않아 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. It has excellent adhesion and provides a surface treatment layer that exhibits effects such as reducing stickiness as well as flame retardant performance to suppress wrinkles during winding or use. To provide a polyurethane foam sheet with improved compressive resilience and tensile strength.
S101 ; 표면처리제제조단계
S103 ; 코팅단계
S105 ; 경화단계
10 ; 표면처리제
20 ; 폴리우레탄 발포시트S101; Surface treatment manufacturing step
S103; coating step
S105 ; hardening stage
10 ; surface treatment agent
20 ; polyurethane foam sheet
Claims (8)
상기 표면처리제제조단계를 통해 제조된 표면처리제를 폴리우레탄 발포시트의 일면에 코팅하는 코팅단계; 및
상기 코팅단계를 통해 폴리우레탄 발포시트에 코팅된 표면처리제를 경화하는 경화단계;로 이루어지며,
상기 표면처리제제조단계는 우레탄계 올리고머 100 중량부 대비 아크릴계 모노머 50 내지 150 중량부, 광개시제 2 내지 15 중량부 및 캡슐화된 난연제와 멜라민으로 이루어진 난연제 혼합물 25 내지 300 중량부를 혼합하여 이루어지고,
상기 캡슐화된 난연제는 난연제의 표면을 합성수지로 코팅하여 제조되며,
상기 합성수지는 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.
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; and
A curing step of curing the surface treatment agent coated on the polyurethane foam sheet through the coating step;
The surface treatment agent manufacturing step is performed by mixing 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 relative to 100 parts by weight of the urethane-based oligomer,
The encapsulated flame retardant is prepared by coating the surface of the flame retardant with a synthetic resin,
The synthetic resin is at least one selected from the group consisting of polycarbonate, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polymethyl methacrylate, polyamide, epoxy, melamine, polyurethane and polyurea. A method for producing a flame-retardant polyurethane foam sheet, characterized in that consisting of.
상기 난연제 혼합물은 캡슐화된 난연제 100 중량부 대비 멜라민 30 내지 100 중량부로 이루어지는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.
The method according to claim 1,
The flame retardant mixture is a method of manufacturing a flame retardant polyurethane foam sheet, characterized in that consisting of 30 to 100 parts by weight of melamine relative to 100 parts by weight of the encapsulated flame retardant.
상기 아크릴계 모노머는 직쇄상의 탄소수가 9 내지 30인 탄화수소를 포함하는 1,9-노난디올디메타아크릴레이트, 1,6-헥산디올디메타아크릴레이트, 1,8-옥탄디올디메타아크릴레이트, 1,10-데칸디올디메타아크릴레이트 및 1,14-테트라데칸디올디메타아크릴레이트로 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, A method for producing a flame-retardant polyurethane foam sheet comprising 1,10-decanediol dimethacrylate and 1,14-tetradecanediol dimethacrylate.
상기 코팅단계는 상기 표면처리제제조단계를 통해 제조된 표면처리제를 폴리우레탄 발포시트의 일면에 2 내지 20㎛의 두께로 코팅하여 이루어지는 것을 특징으로 하는 난연성 폴리우레탄 발포시트의 제조방법.
The method according to claim 1,
The coating step is a method of manufacturing a flame-retardant polyurethane foam sheet, characterized in that it is made by coating the surface treatment agent prepared through the surface treatment agent manufacturing step to a thickness of 2 to 20㎛ on one surface of the polyurethane foam sheet.
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 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012007109A (en) | 2010-06-25 | 2012-01-12 | Kiyoshi Adachi | Powder for fire resistances and foaming type fire prevention composition containing the same |
| JP2014524954A (en) * | 2011-06-28 | 2014-09-25 | ダウ グローバル テクノロジーズ エルエルシー | Sprayable flame retardant polyurethane coating composition |
| KR101927926B1 (en) | 2018-06-08 | 2018-12-11 | 이동룡 | A coating method and coating apparatus for functional coating composition for foamed urethane sponge |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100756217B1 (en) * | 2004-11-17 | 2007-09-06 | 제일모직주식회사 | Encapsulated phosphorus-based flame retardant and Flameproof thermoplastic resin composition containing the same |
| KR100926834B1 (en) | 2009-02-06 | 2009-11-12 | 광스틸 주식회사 | A complex heat insulator made of rigid polyurethane foam and manufacturing method thereof |
| BR112013012211A2 (en) | 2010-11-18 | 2020-10-13 | Dow Global Technologies Inc | reactive formulation to prepare a flame resistant polyurethane foam, process to prepare a flame resistant flexible polyurethane foam and flame resistant polyurethane foam |
| KR20150120773A (en) * | 2014-04-18 | 2015-10-28 | 안문준 | Incombustible powder and expanded type incombustible compositions containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012007109A (en) | 2010-06-25 | 2012-01-12 | Kiyoshi Adachi | Powder for fire resistances and foaming type fire prevention composition containing the same |
| JP2014524954A (en) * | 2011-06-28 | 2014-09-25 | ダウ グローバル テクノロジーズ エルエルシー | Sprayable flame retardant polyurethane coating composition |
| KR101927926B1 (en) | 2018-06-08 | 2018-12-11 | 이동룡 | A coating method and coating apparatus for functional coating composition for foamed urethane sponge |
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