KR100369440B1 - Method of manufacturing white porous polyester film for paper - Google Patents
Method of manufacturing white porous polyester film for paper Download PDFInfo
- Publication number
- KR100369440B1 KR100369440B1 KR10-1998-0045112A KR19980045112A KR100369440B1 KR 100369440 B1 KR100369440 B1 KR 100369440B1 KR 19980045112 A KR19980045112 A KR 19980045112A KR 100369440 B1 KR100369440 B1 KR 100369440B1
- Authority
- KR
- South Korea
- Prior art keywords
- resin
- film
- paper
- weight
- polyester film
- Prior art date
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229920001225 polyester resin Polymers 0.000 claims abstract description 33
- 239000004645 polyester resin Substances 0.000 claims abstract description 32
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 239000010419 fine particle Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920001971 elastomer Polymers 0.000 claims abstract description 4
- 239000000806 elastomer Substances 0.000 claims abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 24
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 229920000098 polyolefin Polymers 0.000 description 10
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229940117969 neopentyl glycol Drugs 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- LEVONNIFUFSRKZ-UHFFFAOYSA-N 3-(carboxymethyl)-2,2-dimethylcyclobutane-1-carboxylic acid Chemical compound CC1(C)C(CC(O)=O)CC1C(O)=O LEVONNIFUFSRKZ-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 종이 대용 백색 다공성 폴리에스테르 필름의 제조방법에 관한 것으로써, 폴리에스테르수지를 주성분으로한 백색의 종이 대용 백색 다공성 필름을 제조함에 있어, 필름 내에 존재하는 기공의 크기와 모양 및 분포가 적절하게 형성될 수 있도록함으로써 백색도와 질감 및 경량성이 우수할 뿐만 아니라 폴리에스테르 필름 특유의 뻣뻣함을 크게 개선하여 종이와 유사하게 부드러운 질감을 나타낼 수 있도록 한 종이대용 백색 다공성 폴리에스테르 필름의 제조방법을 제공함에 그 목적이 있는 것으로, 상기한 목적을 달성하기 위한 본 발명은 용융온도가 170 내지 230℃이며 무기미립자가 함유되어 있는 폴리에스테르 수지와 평균직경이 8μm이하인 입상의 폴리올레핀수지를 1차 혼합하여 수지혼합물을 제조한 후, 무수숙신산 또는 무수말레인산이 그라프트 중합된 에라스토머 공중합체를 상기 수지혼합물 전체 중량 기준으로 0.3 내지 2.0중량%로 첨가하여 혼합한 다음 용융, 압출 및 연신시키는 공정을 포함함을 특징으로 하는 종이 대용 백색 다공성 폴리에스테르 필름의 제조방법을 제공한다.The present invention relates to a method for producing a paper-substituted white porous polyester film, wherein in preparing a white paper-substituted white porous film mainly composed of a polyester resin, the size, shape and distribution of pores present in the film are appropriate. It provides a method of manufacturing a white porous polyester film for paper substitutes not only excellent in whiteness, texture, and light weight, but also greatly improved the stiffness peculiar to the polyester film to exhibit a smooth texture similar to paper. In order to achieve the above object, the present invention provides a resin obtained by first mixing a polyester resin containing a melting temperature of 170 to 230 ° C. and containing inorganic fine particles and a granular polyolefin resin having an average diameter of 8 μm or less. After preparing the mixture, succinic anhydride or maleic anhydride Preparation of a white-substituted white porous polyester film, comprising the step of adding, mixing, melting, extruding, and stretching the raft polymerized elastomer copolymer to 0.3 to 2.0% by weight based on the total weight of the resin mixture. Provide a method.
Description
본 발명은 백색의 다공성 폴리에스테르 필름의 제조방법에 관한 것으로써, 보다 상세하게는 경량성과 질감이 우수하고 제전 특성 및 인쇄 적성이 양호할 뿐만 아니라 은폐성이 우수하여 종이 대용으로 사용될 수 있는 백색 다공성 폴리에스테르 필름 및 그의 제조방법에 관한 것이다.The present invention relates to a method for producing a white porous polyester film, and more particularly, a white porous that can be used as a substitute for paper because of excellent light weight and texture, good antistatic properties and printability, as well as excellent hiding properties. A polyester film and its manufacturing method are related.
일반적으로 폴리에스테르수지에 백색 무기입자를 혼합하여 제조된 백색 폴리에스테르 필름은 기계적 성질, 내열성, 수치 안정성 면에서 폴리에스테르 고유의 특성을 유지하면서 빛 차단성과 백색도가 우수하고 종이와 유사한 색상과 질감을 나타낼 수 있으므로 달력, 광고지, 고급 포장지, 인쇄 장식 용지, 벽지 등에 종이 대용으로 주로 사용되어 왔다.In general, a white polyester film prepared by mixing white inorganic particles with a polyester resin maintains polyester's inherent properties in terms of mechanical properties, heat resistance, and numerical stability, and has excellent light blocking property, whiteness, and color and texture similar to paper. Since it can be displayed, it has been mainly used as a paper substitute for calendars, flyers, high-quality wrapping paper, printed decorative paper, wallpaper, and the like.
이와함께 폴리올레핀계 필름 역시 경량성 및 표면 특성이 우수한 장점을 가지고 있으므로 상기의 폴리에스테르 수지와 더불어 포장재 및 인쇄 재료에 종이 대용으로 널리 사용되어 왔다.In addition, since the polyolefin-based film also has advantages of light weight and excellent surface properties, it has been widely used as a substitute for paper in packaging materials and printing materials together with the polyester resin.
그러나, 이러한 백색 폴리에스테르 필름의 경우 상기 설명한 바의 장점이 있기는 하지만, 재질이 뻣뻣하고 접촉시의 촉감이 매끄러워 종이와 흡사한 질감을 나타내지 못하는 단점이 있으며 경량성이 부족한 문제점이 있었다.However, such a white polyester film has the advantages described above, but has a disadvantage in that the material is stiff and the touch is smooth and does not exhibit a texture similar to paper, and the light weight is insufficient.
또한 종이 대용으로 이용되는 폴리올레핀계 필름의 경우 기계적 특성 및 열적 특성이 떨어지는 단점이 있다.In addition, the polyolefin-based film used as a substitute for paper has a disadvantage in that the mechanical and thermal properties are poor.
상기한 바의 두가지 수지에서 나타나는 단점을 상호 보완하기 위한 방법으로써, 폴리에스테르 필름의 우수한 특성을 유지하면서 종이와 같은 질감을 낼 수 있고 단위 면적당 질량을 폴리올레핀계 필름 정도로 경량화시킬 수 있는 방법이 공지되었는 바, 일본국 공개특허공보 소화 62-243120호 및 평성 2-206622호에는 폴리에스테르에 무기 입자를 첨가하는 방법이 개시되어 있고, 일본 공개 특허공보 소화 58-50625호에는 폴리에스테르에 발포재를 배합하여 경량화 시키는 방법이 개시되어 있다. 또한 일본 공개 특허 공보 소화 57-49648호에는 폴리에스테르에 폴리올레핀계 수지를 배합하고 연신함으로써 이종(異種) 수지간의 단점을 보완하고 필름 표면 및 내부에 미세 기공을 형성하여 필름의 표면성을 개선하고 필름 자체를 경량화 시키는 방법이 개시되어 있다.As a method for compensating the disadvantages of the two resins as described above, it is possible to produce a paper-like texture while maintaining the excellent properties of the polyester film and to reduce the weight per unit area to a weight of polyolefin-based film. Bars Japanese Patent Laid-Open No. 62-243120 and Japanese Patent Laid-Open No. 2-206622 disclose a method of adding inorganic particles to polyester, and Japanese Laid-open Patent No. 58-50625 combine foams with polyester. To reduce the weight is disclosed. In addition, Japanese Unexamined Patent Publication No. 57-49648 discloses that by blending and stretching a polyolefin-based resin in polyester, the disadvantages between dissimilar resins are compensated for, and fine pores are formed on the surface and inside of the film to improve the surface of the film and A method of making itself lighter is disclosed.
상기한 바의 종래기술은 폴리올레핀 수지가 폴리에스테르 수지에 혼합되어 압출, 성형, 연신 공정을 거치는 과정에서 두 수지 상호간의 상용성 불량으로 인하여 필름 표면 및 내부에 미세한 기공이 형성되므로 이와 같은 성질을 이용하여 필름의 표면성을 개선하고 경량화를 실현할 수 있다는데 착안하여 폴리에스텔 수지에 폴리올레핀 수지를 배합하여 사용하였으나, 기공의 형성에 한계가 있고 기공 자체가 불균일하여 표면에 기공이 부분적으로 노출되거나 움푹 들어간 부분이 많아서 필름 표면에의 인쇄가 불균일 해지는 문제점이 있었다.The prior art as described above uses such properties because fine pores are formed on the surface and inside of the film due to the incompatibility between the two resins in the process of the polyolefin resin is mixed with the polyester resin and subjected to the extrusion, molding and stretching process. By using polyolefin resin in combination with polyester resin, it is possible to improve the surface property of the film and realize weight reduction. However, there is a limit in the formation of pores and the pores themselves are uneven, so that the pores are partially exposed or recessed on the surface. There were many problems that printing to the film surface became uneven.
뿐만 아니라, 종이와 같은 질감과 표면 특성은 필름 중에 존재하는 기공의 형태와 분포에 따라 매우 민감하게 변화될 수 있는데, 상기한 바의 종래 기술에 의하여 제조된 필름은 기공의 형성시 기공의 분포가 적절하게 설계되지 않을 경우 원하는 종이의 질감을 얻을 수 없고 경량화 및 공정성에도 좋지 않은 영향을 미치게 된다.In addition, the texture and surface characteristics such as paper can be changed very sensitively depending on the shape and distribution of the pores present in the film, the film prepared by the prior art as described above has a pore distribution in the formation of pores If not properly designed, the desired texture of the paper will not be obtained, and the weight and fairness will be adversely affected.
이는 필름 중에 존재하는 기공의 크기가 작으면 비중이 높아져 무거운 반면, 기공이 지나치게 크면 파단 등으로 인해 공정성에 문제가 발생하기 때문으로, 종이 대용으로 이용되기에 부족함이 없는 필름을 얻기 위해서는 상기한 바와 같이 필름 중에 존재하는 기공의 분포에 관한 사항이 적절히 설계되어야 하는 것이다.This is because if the size of the pores present in the film is small, the specific gravity becomes high and heavy, whereas if the pores are too large, problems occur in the processability due to breakage, etc., in order to obtain a film that is not sufficient for use as a substitute for paper. Similarly, matters concerning the distribution of pores existing in the film should be properly designed.
본 발명은 상기한 바의 종래기술의 문제점을 해결하고, 폴리에스테르수지를 주성분으로한 백색의 종이 대용 백색 다공성 필름을 제조함에 있어, 필름 내에 존재하는 기공의 크기와 모양 및 분포가 적절하게 형성될 수 있도록함으로써 백색도와 질감 및 경량성이 우수할 뿐만 아니라 폴리에스테르 필름 특유의 뻣뻣함을 크게 개선하여 종이와 유사하게 부드러운 질감을 나타낼 수 있도록 한 다공성의 백색 폴리에스테르 필름을 제공하는 것을 목적으로 한다.The present invention solves the problems of the prior art as described above, and in preparing a white paper substitute white porous film mainly composed of a polyester resin, the size, shape and distribution of pores present in the film may be appropriately formed. It is an object of the present invention to provide a porous white polyester film that not only has excellent whiteness, texture, and light weight, but also greatly improves the stiffness peculiar to a polyester film to exhibit a soft texture similar to paper.
상기와 같은 목적을 달성하기 위하여, 본 발명에서는 용융온도가 170 내지 230℃이며 무기미립자가 함유되어 있는 폴리에스테르 수지 65 내지 95중량%와 평균직경이 8μm이하인 입상의 폴리올레핀수지 5 내지 35중량%를 1차 혼합하여 수지혼합물을 제조한 후, 무수숙신산 또는 무수말레인산이 그라프트 중합된 에라스토머 공중합체를 상기 수지혼합물 전체 중량 기준으로 0.3 내지 2.0중량%로 첨가하여 혼합한 다음 용융, 압출 및 연신시키는 공정을 포함함을 특징으로 하는 종이 대용 백색 다공성 폴리에스테르 필름의 제조방법을 제공한다.In order to achieve the above object, in the present invention, the melting temperature is 170 to 230 ℃ and 65 to 95% by weight of the polyester resin containing inorganic fine particles and 5 to 35% by weight of the granular polyolefin resin having an average diameter of 8μm or less After first mixing to prepare a resin mixture, the succinic anhydride or maleic anhydride graft polymerized elastomer copolymer is added in an amount of 0.3 to 2.0% by weight based on the total weight of the resin mixture, followed by melting, extrusion, and stretching. It provides a process for producing a paper-substitute white porous polyester film, characterized in that it comprises a step of making.
본 발명에 있어서, 폴리에스테르 수지는 폴리에틸렌테레프탈레이트(PolyethylentTerephthalate)를 주성분으로 하는 공중합 수지로써 힌더드 페놀계 화합물을 0.005 내지 0.5중량% 포함하는 것이 바람직하다. 또한, 바람직하기로는, 상기 폴리에스테르계 수지는 직경이 0.1 내지 10μm인 무기 미립자를 0.1 내지 10중량% 포함한다. 이러한 무기미립자는 이산화티탄, 황산바륨, 탄산칼슘, 실리카, 카올린, 탈크 또는 제올라이트중 어느 하나 또는 둘이 상의 혼합물인 것이 바람직하다.In the present invention, the polyester resin is a copolymer resin mainly composed of polyethylene terephthalate (Polyethylent Terephthalate), it is preferable to include a hindered phenol compound of 0.005 to 0.5% by weight. Also preferably, the polyester-based resin contains 0.1 to 10% by weight of inorganic fine particles having a diameter of 0.1 to 10 μm. Such inorganic fine particles are preferably a mixture of any one or two of titanium dioxide, barium sulfate, calcium carbonate, silica, kaolin, talc or zeolite.
바람직하기로는 상기 폴리올레핀계 수지의 함량이 수지 총량에 대해 5 내지 35중량%이고, 용융지수가 1 내지 25gr/분 이다. 또한 상기 폴리올레핀계 수지는 에틸렌, 프로필렌, 부텐, 펜텐, 헥센 또는 옥텐 중에서 선택된 적어도 1종이상의 단량체로부터 중합 또는 공중합된 것이 바람직하다.Preferably the content of the polyolefin-based resin is 5 to 35% by weight based on the total amount of the resin, the melt index is 1 to 25gr / min. In addition, the polyolefin resin is preferably polymerized or copolymerized from at least one monomer selected from ethylene, propylene, butene, pentene, hexene or octene.
또한 폴리에스테르계 수지 및 폴리올레핀계 수지로 된 백색 다공성 폴리에스테르 필름을 제조하는 공정에 있어서, 폴리에스테르계 수지와 폴리올레핀계 수지를 95:5 내지 65:35의 중량비로 혼합하여 1차 혼합 수지를 제조하는 단계에서 1차 혼합수지 기준으로 무수 숙신산 또는 무수 말레인산이 그라프트된 공중합체 0.3 내지 2.0중량%를 투입한다. 상기와 같이 제조된 1차 혼합수지를 용융압출하여 필름 시이트를 형성하고, 상기 필름 시이트가 2축 연신되는 공정을 거쳐 백색 다공성 폴리에스테르 필름이 제조된다.In the process for producing a white porous polyester film made of a polyester resin and a polyolefin resin, a primary mixed resin is prepared by mixing a polyester resin and a polyolefin resin in a weight ratio of 95: 5 to 65:35. 0.3 to 2.0% by weight of the copolymer grafted with succinic anhydride or maleic anhydride on the basis of the primary mixed resin in the step. The primary mixed resin prepared as described above is melt-extruded to form a film sheet, and a white porous polyester film is manufactured through a process of biaxially stretching the film sheet.
상기 필름 시이트를 형성하는 단계에 있어서, 필름 시이트 내의 폴리올레핀의 평균 직경은 20μm이하, 더욱 바람직하기로는 8μm이하이고, 필름 시이트 25,000μm2내에 폴리올레핀의 평균 입자수가 50개 이상, 더욱 바람직하기로는 80개 이상인 것이 바람직하다.In the step of forming the film sheet, the average diameter of the polyolefin in the film sheet is 20 μm or less, more preferably 8 μm or less, and the average number of polyolefins in the film sheet 25,000 μm 2 is 50 or more, more preferably 80 pieces. It is preferable that it is above.
이하 본 발명의 백색 다공성 필름의 제조방법과 본 발명의 원리에 대해 상세히 설명하기로 한다.Hereinafter, a method of manufacturing a white porous film of the present invention and the principle of the present invention will be described in detail.
본 발명에서 이용되는 폴리에스테르계수지는 폴리에틸렌테레프탈레이트로써 방향족 디카르복시산을 주성분으로 하는 산성분과 알킬렌글리콜을 주성분으로 하는 글리콜 성분을 중축합시킴으료써 제조할 수 있으며, 상기의 방향족 디카르복시산으로써는 디메틸테레프탈레이트, 테레프탈산, 이소프탈산, 싸이클로헥산디카르복실산, 디페녹시에탄디카르복실산, 디페닐디카르복실산, 디페닐에테르디카르복실산 등이 사용 가능하며, 이중에서 디메틸테레프탈레이트, 테레프탈레이트산이 바람직하다.The polyester resin used in the present invention can be prepared by polycondensing an acid component having aromatic dicarboxylic acid as a main component and a glycol component having alkylene glycol as a main component as polyethylene terephthalate, and as the aromatic dicarboxylic acid, dimethyl tere Phthalate, terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid and the like can be used, among which dimethyl terephthalate and tere Phthalate acid is preferred.
또한 상기 알킬렌글리콜의 예로는 에틸렌글리콜, 트리메틸렌글리콜, 테트라 메틸렌글리콜, 펜타메틸렌글리콜, 헥사메틸렌글리콜, 헥실렌글리콜 등을 들 수 있으나 이들 중 에틸렌글리콜이 바람직하다.In addition, examples of the alkylene glycol may include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, hexylene glycol, and ethylene glycol is preferable.
본 발명의 폴리에스테르계 수지는 통상의 폴리에스테르 합성법에 따라 제조되는데, 70중량%이상은 폴리에틸렌테레프탈레이트이고 30중량% 이내에서 공중합 되도록 하는 것이 바람하다. 보다 바람직하게는 5 내지 20중량% 공중합되도록 한다. 이러한 공중합 성분의 구체적인 예로서는 디에틸렌글리콜, 프로필렌글리콜, 네오펜틸글리콜, 폴리에틸렌글리콜, p-키실렌글리콜, 1,4-싸이클로헥산디메탄올, 5-나트륨술포레졸신 등의 디올화합물과 이소프탈산, 아지핀산, 5-나트륨술포이소프탈산 등의 디카르복실산 성분, 트리메틸산, 피로메틸산 등의 다관능 디카르복실산 성분 등을 들 수 있다.The polyester resin of the present invention is prepared according to a conventional polyester synthesis method, 70% by weight or more is preferably polyethylene terephthalate and copolymerized within 30% by weight. More preferably 5 to 20% by weight copolymerization. Specific examples of such copolymerization components include diol compounds such as diethylene glycol, propylene glycol, neopentyl glycol, polyethylene glycol, p-xylene glycol, 1,4-cyclohexanedimethanol and 5-sodium sulfolezocin, isophthalic acid and azi And polyfunctional dicarboxylic acid components such as dicarboxylic acid components such as pinic acid and 5-sodium sulfoisophthalic acid, trimethyl acid and pyromethyl acid.
본 발명의 폴리에스테르계 수지를 제조하는데 있어서 무기 입자가 첨가될 수 있다. 무기 입자는 빛의 투과율이나 색상과 같은 광학적 특성의 조절 및 마찰계수, 표면 조도 및 미세한 촉감의 조절을 목적으로 폴리에스테르 수지에 첨가되는데 그 입경은 0.1 내지 10μm 범위인 것이 바람직하며 첨가량은 0.1 내지 10중량% 바람직하기로는 0.1 내지 5중량%로 한다.In order to prepare the polyester resin of the present invention, inorganic particles may be added. The inorganic particles are added to the polyester resin for the purpose of controlling optical properties such as light transmittance or color, and controlling friction coefficient, surface roughness and fine touch, and the particle size is preferably in the range of 0.1 to 10 μm, and the amount of addition is 0.1 to 10 % By weight is preferably 0.1 to 5% by weight.
또한 첨가량이 0.1중량% 미만인 경우에는 첨가 효과가 미미하고 10중량%를 초과하는 경우에는 필름의 표면 특성이 떨어져서 종이와 같은 질감을 얻을 수 없다.In addition, when the amount is less than 0.1% by weight, the effect of addition is insignificant, and when the amount is more than 10% by weight, the surface characteristics of the film are inferior, and thus a paper-like texture cannot be obtained.
사용 가능한 무기 미립자의 예로는 이산화티탄, 탄산칼슘, 황산바륨, 실리카, 카올린, 탈크, 제오라이트 등을 들 수 있다.Examples of the inorganic fine particles that can be used include titanium dioxide, calcium carbonate, barium sulfate, silica, kaolin, talc, zeolite and the like.
이외에도, 본 발명의 폴리에스테르계 수지 제조시 상기 주성분들 외에 첨가제로써 중축합촉매, 분산제, 정전인가제, 결정화촉진제, 블로킹방지제 및 무기활제들이 더 첨가될 수 있음은 물론이며, 이들 첨가제로는 통상 이러한 용도로 사용되는 물질들이 사용된다.In addition, polycondensation catalysts, dispersants, electrostatic agents, crystallization accelerators, antiblocking agents and inorganic lubricants may be further added as additives in addition to the main components when preparing the polyester resin of the present invention. Materials used for this purpose are used.
본 발명에서 폴리에스테르 수지에 혼합되는 폴리올레핀계 수지로는 에틸렌, 폴리메틸펜틴, 프로필렌, 부텐, 펜텐, 헥센, 옥텐 중에서 1성분 이상의 단량체로부터 중합된 것이 바람직하며, 특히, 프로필렌을 주성분으로 하고 그 외의 단량체를 보조성분으로 하여 중합된 것이 보다 바람직하다. 또한 용융지수가 1 내지 25gr/분 인 것이 기공 형성에 효율적이고, 수지 총량에 대해 5 내지 35중량%를 차지하는 것이 바람직한데, 5중량% 미만인 경우에는 기공의 형성이 전반적으로 불균일하고 전체 기공의 함량이 적어서 필름이 뻣뻣해지며, 35중량%를 초가하는 경우에는 기공의 형성은 충분하나 내열성과 기계적 성질이 떨어지는 폴리올레핀의 양이 많아지기 때문에 필름의 내열성과 기계적 성질이 떨어지고 공정성도 불량해 진다.In the present invention, the polyolefin resin mixed with the polyester resin is preferably polymerized from at least one component monomer among ethylene, polymethylpentine, propylene, butene, pentene, hexene, and octene, and in particular, propylene is a main component. It is more preferable that it superposed | polymerized using the monomer as an auxiliary component. In addition, it is preferable that the melt index is 1 to 25 gr / min, which is efficient for pore formation, and occupies 5 to 35% by weight based on the total amount of resin. When it is less than 5% by weight, the formation of pores is generally uneven and the content of total pores. When the film is less, the film becomes stiff, and when the weight ratio is higher than 35% by weight, the formation of pores is sufficient, but the heat resistance and mechanical properties of the polyolefin are reduced, resulting in poor heat resistance and mechanical properties and poor processability.
본 발명의 핵심은 폴리에스테르 수지와 폴리올레핀 수지를 혼합할 때 상용화제 첨가에 의해 폴리올레핀 수지가 폴리에스테르 수지 내에서 작고 균일하게 다량 분포되고, 폴리에스테르 수지와 접하는 폴리올레핀의 접촉면적도 증가하게 되어 전체 기공율도 높아지고, 이들 기공들이 균일하게 분포된다. 따라서 최종적으로 얻어지는 필름의 밀도가 낮아져서 경량화가 이루어지며 필름의 유연성도 증가된다.The core of the present invention is that when the polyester resin and the polyolefin resin are mixed, a large amount of polyolefin resin is uniformly distributed in the polyester resin by the addition of a compatibilizer, and the contact area of the polyolefin in contact with the polyester resin is also increased, thereby increasing the total porosity. Also, these pores are uniformly distributed. Therefore, the density of the finally obtained film is lowered, thereby making it lighter and increasing the flexibility of the film.
상기와 같은 방식으로만 제조된 백색 다공성 필름은 종이와 같은 질감을 내기에는 아직 뻣뻣한 먼제점이 있다. 이것은 본질적으로 이 필름에 65중량% 이상 사용되는 폴리에스테르 수지가 폴리올레핀계 수지에 비해 보다 뻣뻣하기 때문이다.The white porous film produced only in the above manner has a far stiff point to still be textured like a paper. This is essentially because the polyester resins used in the film at 65% by weight or more are stiffer than the polyolefin resins.
따라서 전술한 바와 같이 본 발명에 사용되는 폴리에스테르 수지를 30중량% 내에서 공중합시켜 상기 폴리에스테르 수지의 용융온도를 170 내지 230℃ 범위로 조절하여 유연성을 증가시켰다. 상기 용융온도가 170℃ 이하에서는 유연성은 증가하지만 내열성이 떨어지고 230℃ 이상에서는 유연성이 증가되지 않는다.Therefore, as described above, the polyester resin used in the present invention was copolymerized within 30% by weight to adjust the melting temperature of the polyester resin in the range of 170 to 230 ° C. to increase flexibility. If the melting temperature is 170 ° C or less, the flexibility is increased, but heat resistance is lowered, and the flexibility is not increased above 230 ° C.
전술한 바와 같이 폴리에스테르 수지와 폴리올레핀 수지 및 상용화제를 혼합하게되면 혼합수지가 얻어지게 되는데, 이 혼합수지에 대해 통상의 폴리에스테르 제조방법과 마찬가지의 방법으로 건조, 용융, 압출 공정을 실시하여 필름 시이트를 얻은 다음, 이 시이트를 종방향과 횡방향으로 각각 2배 내지 5배, 바람직하게는 3배 내지 3.5배 연신한다.As described above, when the polyester resin, the polyolefin resin, and the compatibilizer are mixed, a mixed resin is obtained. The mixed resin is dried, melted, and extruded in the same manner as in the conventional polyester manufacturing method to obtain a film. After the sheet is obtained, the sheet is stretched 2 to 5 times, preferably 3 to 3.5 times, respectively in the longitudinal and transverse directions.
상기 혼합수지, 특히 연신 전의 필름 시이트에 대한 폴리올레핀 수지의 분산상태는 최종적으로 얻어지는 필름의 특성에 중대한 영향을 미치게 된다. 폴리올레핀 수지의 분산상태는 컴파운딩 칩 또는 재용융 후 만들어진 시이트를 전자현미경으로 관찰함으로써 알 수 있다. 즉, 컴파운딩 칩 또는 재용융된 시이트를 전자현미경을 이용하여 관찰, 시이트에 분산되어 있는 폴리올레핀 입자의 평균직경과 입자 수를 측정하여 분산상태를 평가할 수 있다.The dispersion state of the polyolefin resin in the mixed resin, especially the film sheet before stretching, has a significant influence on the properties of the film finally obtained. The dispersion state of the polyolefin resin can be known by observing a compounding chip or a sheet made after remelting with an electron microscope. In other words, the compounding chip or the remelted sheet can be observed using an electron microscope, and the dispersion state can be evaluated by measuring the average diameter and the number of particles of the polyolefin particles dispersed in the sheet.
폴리올레핀 입자의 평균 직경이 20μm 이하일 때 균일한 분산성과 필름물성의 개선효과가 뚜렷이 나타나며, 25000μm2내에 폴리올레핀 평균 수가 80개 이상인 경우에 밀도 감소와 유연성 향상이 뚜렷이 나타났다.When the average diameter of the polyolefin particles is 20μm or less, the uniform dispersibility and the improvement of film properties are apparent, and when the average number of polyolefins is more than 80 in 25000μm 2 , the density decrease and the flexibility improvement are apparent.
이하, 실시예, 비교에 및 실험예를 통해 본 발명을 더욱 상세히 설명하기로 한다. 단, 본 발명의 범위가 이하의 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples, comparisons, and experimental examples. However, the scope of the present invention is not limited to the following Examples.
<실시예 1><Example 1>
당량비로 디메텔테레프탈레이트 1에 에틸렌글리콜을 1.8, 네오펜틸글라이콜을 0.2 비율로 혼합한 뒤, 여기에 에스테르 교환반응 촉매를 첨가하여 에스테르 교환반응을 시킨다. 여기에 평균입경이 0.8μm인 이산화티탄을 폴리에스테르 기준으로 2중량%와 중축합 촉매를 첨가하여 중축합 반응을 완결시켜 극한점도가 0.66dl/gr인 폴리에스테르 수지를 제조하였다.Ethylene glycol was mixed in dimethel terephthalate 1 at an equivalent ratio of 1.8 and neopentyl glycol at a ratio of 0.2, and then transesterification was performed by adding a transesterification catalyst. Here, 2 wt% of titanium dioxide having an average particle diameter of 0.8 μm and a polycondensation catalyst were added to complete the polycondensation reaction to prepare a polyester resin having an intrinsic viscosity of 0.66 dl / gr.
이렇게 제조된 폴리에스테르 수지 90중량%와 용융지수 3.5인 호모 폴리프로필렌 수지 15중량%를 혼합한 다음, 여기에 무수말레인산이 그라프트된 엘라스토머 1중량%를 첨가하여 컴파운딩 방식에 의해 혼합수지를 만들고, 다시 통상의 폴리에스테르 필름 제조방식에 따라 건조, 용융, 압출하여 시이트 형태로 형성한 후, 종연신비 3.5배, 횡연신비 3.8배로 연신시켜 두께 120μm의 이축연신 고분자 필름을 제조하였다. 이 필름의 특성을 하기한 실험예에서 정한 방법에 따라 기공의 크기와 수, 무기미립자의 평균입경, 겉보기 밀도, 필름의 유연성 및 수지 용융온도를 측정하여 그 결과를 하기 표 1에 나타내었다.90% by weight of the polyester resin thus prepared and 15% by weight of homopolypropylene resin having a melt index of 3.5 were mixed, and then 1% by weight of maleic anhydride-grafted elastomer was added thereto to form a mixed resin by compounding. After drying, melting, and extruding according to a conventional polyester film production method to form a sheet, stretching was performed at 3.5 times the longitudinal draw ratio and 3.8 times the transverse draw ratio to prepare a biaxially stretched polymer film having a thickness of 120 μm. The characteristics of this film were measured in the following experimental example, the size and number of pores, the average particle diameter of the inorganic fine particles, the apparent density, the flexibility of the film and the resin melting temperature were measured and the results are shown in Table 1 below.
<실험예>Experimental Example
-기공의 크기와 수-Pore size and number
일본 JEOL사의 전자 주사 현미경을 사용하여 단면을 관찰 후 영상 분석기를 통해 측정한다.The cross section is observed using an electron scanning microscope manufactured by JEOL of Japan, and then measured by an image analyzer.
-무기미립자의 평균입경-Average particle size of inorganic particles
일본 시마쥬사의 원심분리 입도 측정기를 이용하여 에틸렌 글리콜에 분산된 무기 미립자의 슬러리를 측정하여 체적평균 입경으로써 나타낸다.The slurry of the inorganic fine particles dispersed in ethylene glycol was measured using the centrifugal particle size measuring device of Shimadzu, Japan, and is represented as a volume average particle diameter.
-겉보기 밀도--Apparent density-
사염화탄소와 노르말헵탄으로 이루어진 밀도구배관을 25℃로 유지하고 부침법에 의해 측정한다.A density gradient tube consisting of carbon tetrachloride and normal heptane is maintained at 25 ° C. and measured by ups and downs.
-필름 유연성-Film Flexibility
종이와 비교하여 다공성 필름의 유연성을 양호, 보통, 불량으로 구분하였다.Compared to paper, the flexibility of the porous film was classified into good, normal, and poor.
-수지 용융온도-Resin Melting Temperature
시차주사 열량분석기를 이용하여 측정하였다.It was measured using a differential scanning calorimeter.
<실시예 2><Example 2>
상기 실시예 1과 동일한 방법으로 실시하되, 상기의 네오펜틸글라이콜 대신 폴리에틸렌글라이콜 0.4 당량비를 첨가한 다음, 실시예 1과 동일한 방법으로 실시하여 두께 120μm인 이축연신 고분자 필름을 얻었다. 이 필름에 대해 전술한 것과 마찬가지 방법으로 여러 가지 특성을 평가하여 그 결과를 하기 표 1에 나타내었다.The same procedure as in Example 1 was carried out, but 0.4 equivalent ratio of polyethylene glycol was added instead of the neopentyl glycol, and the same procedure as in Example 1 was performed to obtain a biaxially stretched polymer film having a thickness of 120 μm. Various properties were evaluated in the same manner as described above for this film, and the results are shown in Table 1 below.
<실시예 3 내지 5><Examples 3 to 5>
공중합 모노머 및 각종 첨가제의 첨가량을 하기 표 1에서와 같이 변화시키는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하여 고분자 필름을 얻은 다음, 이 필름에 대해 마찬가지로 특성을 평가하여 그 결과를 하기 표 1에 나타내었다.Except for changing the addition amount of the copolymerization monomer and various additives as shown in Table 1, to obtain a polymer film in the same manner as in Example 1, and then to evaluate the characteristics of the film in the same manner to the results Table 1 shows.
<비교예 1 내지 5><Comparative Examples 1 to 5>
공중합 비율 및 각종 첨가제의 첨가량을 하기 표 1에서와 같이 변화시킨 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 고분자 필름을 얻을 다음, 이 필름에 대해 마찬가지로 특성을 평가하여 그 결과를 하기 표 1에 나타내었다.A polymer film was obtained by performing the same method as Example 1 except that the copolymerization ratio and the amount of various additives were changed as shown in Table 1 below. Shown in
상기 표 1에서 상용화제는 (스틸렌-에틸렌/부틸렌-스틸렌)-말레익안하이드라이드이며, NG는 네오펜틸글리콜이며, PG는 폴리에틸렌글리콜이고, CD는 헥사메틸렌디메탄올을 의미한다.In Table 1, the compatibilizer is (styrene-ethylene / butylene-styrene) -maleic hydride, NG is neopentylglycol, PG is polyethyleneglycol, and CD is hexamethylenedimethanol.
상기 표 1에 나타난 바와 같이 본 발명에 의한 상기 실시예 1 내지 5로부터 제조된 필름은 질감과 유연성이 우수하고 외관이 양호한 수준이었으며, 각종 첨가제의 첨가량이 본 발명에서 한정된 범위를 유지하는 한 기공의 분포가 바람직한 수준으로 유지되어 필름의 질감과 외관이 모두 양호하고, 또한 경량화도 어느 정도 이루어지며, 공정성도 우수함을 알 수 있다.As shown in Table 1, the films prepared from Examples 1 to 5 according to the present invention had excellent texture, flexibility, and good appearance, and included pores as long as the amount of various additives was maintained in a limited range in the present invention. It can be seen that the distribution is maintained at a desirable level, so that both the texture and appearance of the film are good, the weight is made to some extent, and the processability is excellent.
그러나 하기 표 1로부터 알 수 있듯이, 실시예의 경우와는 달리 각종 첨가제의 첨가량이 본 발명에서 한정된 바람직한 범위를 벗어나는 경우에는 얻어지는 필름이 평가된 여러 가지 특성 중 적어도 하나 이상의 항목에서 불량한 것으로 나타났다. 특히, 폴리에스테르수지의 중합시 첨가되는 공중합물질의 몰%를 35중량%이상으로 과다하게 첨가한 비교예 1 내지 비교예 2의 경우 파단강도가 크게 낮아졌으며 폴리에스테르의 용융온도가 230℃를 초과한 비교예 3, 4 및 5의 경우에는 유연성이 크게 저하되었을 뿐만 아니라 기공의 평균수가 매우 낮게 나타났다.However, as can be seen from Table 1, unlike the case of the embodiment, when the amount of the additives added is outside the preferred range defined in the present invention, the obtained film was found to be poor in at least one or more of the various properties evaluated. In particular, in the case of Comparative Examples 1 to 2 in which the mol% of the copolymer added at the time of polymerization of the polyester resin was added in excess of 35% by weight, the breaking strength was significantly lowered and the melting temperature of the polyester exceeded 230 ° C. In Comparative Examples 3, 4 and 5, not only the flexibility was greatly reduced but also the average number of pores was very low.
이상 설명한 바와 같이 본 발명은 폴리에스테르수지를 주성분으로한 백색의 종이 대용 백색 다공성 필름을 제조함에 있어, 필름 내에 존재하는 기공의 크기와 모양 및 분포가 적절하게 형성될 수 있도록함으로써 백색도와 질감 및 경량성이 우수할 뿐만 아니라 폴리에스테르 필름 특유의 뻣뻣함을 크게 개선하여 종이와 유사하게 부드러운 질감을 나타낼 수 있도록 한 다공성의 백색 폴리에스테르 필름의 제조방법을 제공하는 유용한 발명인 것이다.As described above, the present invention provides a white paper substitute white porous film mainly composed of a polyester resin, so that the size, shape, and distribution of pores present in the film can be appropriately formed. It is a useful invention to provide a method for producing a porous white polyester film that not only has excellent properties but also greatly improves the stiffness peculiar to a polyester film to exhibit a soft texture similar to paper.
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| KR (1) | KR100369440B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230024173A (en) | 2021-08-11 | 2023-02-20 | 소윤섭 | Paper substitute highly absorbent plastic film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020066110A (en) * | 2001-02-09 | 2002-08-14 | 주식회사 한진피앤씨 | Improvement radiation of far-infrared light of air permeability film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02276841A (en) * | 1989-04-18 | 1990-11-13 | Oji Yuka Synthetic Paper Co Ltd | Orientated film |
| US5618881A (en) * | 1995-01-09 | 1997-04-08 | Du Pont Canada Inc. | Compatibilizer composition |
| KR100193690B1 (en) * | 1997-02-26 | 1999-06-15 | 장용균 | White porous polyester film and its manufacturing method |
| KR100193691B1 (en) * | 1997-02-26 | 1999-06-15 | 장용균 | White porous polyester film and its manufacturing method |
-
1998
- 1998-10-27 KR KR10-1998-0045112A patent/KR100369440B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02276841A (en) * | 1989-04-18 | 1990-11-13 | Oji Yuka Synthetic Paper Co Ltd | Orientated film |
| US5618881A (en) * | 1995-01-09 | 1997-04-08 | Du Pont Canada Inc. | Compatibilizer composition |
| KR100193690B1 (en) * | 1997-02-26 | 1999-06-15 | 장용균 | White porous polyester film and its manufacturing method |
| KR100193691B1 (en) * | 1997-02-26 | 1999-06-15 | 장용균 | White porous polyester film and its manufacturing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230024173A (en) | 2021-08-11 | 2023-02-20 | 소윤섭 | Paper substitute highly absorbent plastic film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20000027220A (en) | 2000-05-15 |
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