KR20070048396A - Process for the producing insoulble polyvinyl alcohol films - Google Patents
Process for the producing insoulble polyvinyl alcohol films Download PDFInfo
- Publication number
- KR20070048396A KR20070048396A KR1020050105436A KR20050105436A KR20070048396A KR 20070048396 A KR20070048396 A KR 20070048396A KR 1020050105436 A KR1020050105436 A KR 1020050105436A KR 20050105436 A KR20050105436 A KR 20050105436A KR 20070048396 A KR20070048396 A KR 20070048396A
- Authority
- KR
- South Korea
- Prior art keywords
- polyvinyl alcohol
- pva
- reaction
- producing
- resin
- Prior art date
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 93
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 11
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 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
- 238000004528 spin coating Methods 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000007127 saponification reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- QZJVWTNHFOMVHX-UHFFFAOYSA-N methanol;methyl acetate Chemical compound OC.COC(C)=O QZJVWTNHFOMVHX-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- -1 sodium acetate Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F16/04—Acyclic compounds
- C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
본 발명은 불용성 폴리비닐 알콜(PVA) 필름의 제조 방법에 관한 것으로서, The present invention relates to a method for producing an insoluble polyvinyl alcohol (PVA) film,
(i) 아크릴계 수지를 표면 코팅한 후 건조로를 통과시켜 이형지를 제조하는 단계;(i) surface-coating the acrylic resin and then passing the drying furnace to prepare a release paper;
(ii) 5°C 내지 15°C의 냉수를 사용하는 반응조에 15% 내지 25%중량비의 폴리비닐 알콜을 투입하여 이형지 표면위에 분산시키는 단계; (ii) adding 15% to 25% by weight of polyvinyl alcohol in a reaction tank using 5 ° C to 15 ° C cold water and dispersing it on the surface of the release paper;
(iii 상기 반응조에 유기산 또는 무기산을 1% 내지 25%의 중량비로 투입하여 용해반응 시키는 단계; (iii) dissolving the organic acid or inorganic acid in the reaction tank at a weight ratio of 1% to 25%;
(iv) 촉매를 사용하여 반응을 종결시킨 후 레진을 완성하는 단계 (iv) terminating the reaction using a catalyst to complete the resin
(v) 완성된 레진을 소정의 형태로 압출하는 성형하는 단계를 포함하는 것을 특징으로 하는 불용성 폴리비닐 알콜(PVA) 필름 제조 방법(v) a method of producing an insoluble polyvinyl alcohol (PVA) film, comprising the step of extruding the finished resin into a predetermined form.
및 이 제조방법에 의해 생산된 불용성 폴리비닐 알콜 필름에 관한 것이다. And an insoluble polyvinyl alcohol film produced by this production method.
폴리비닐알콜 필름, 환경친화적 Polyvinyl Alcohol Film, Environmentally Friendly
Description
본 발명은 폴리비닐알콜계 중합체 및 이의 제조방법에 관한 것이다. 보다 상세하게는 본 발명은 환경친화적인 폴리비닐알콜 중합체 제조방법에 관한 것이다. The present invention relates to a polyvinyl alcohol polymer and a preparation method thereof. More specifically, the present invention relates to a method for producing environmentally friendly polyvinyl alcohol polymer.
대표적인 수용성 고분자인 폴리비닐알콜계 중합체(이하, PVA라고 약칭하는 경우가 있다)는 수용성인 것에 추가하여, 강도 특성 및 막 제조성의 점에서 우수하며 이의 특성을 살리고, 통상적인 비닐론 섬유 또는 고강력 비닐론 섬유의 원료로서 또는 섬유가공재, 종이용 코팅재, 종이용 내부첨가제, 접착제, 유화안정제, 필름, 부티랄 수지, 화장품, 의약품 및 세라믹 결합제 등의 용도로 광범위하게 사용되고 있다. Polyvinyl alcohol-based polymer (hereinafter sometimes referred to as PVA), which is a representative water-soluble polymer, is excellent in strength properties and film manufacturability in addition to water-soluble, and utilizes its properties. It is widely used as a raw material of fibers or for textile processing materials, coating materials for paper, internal additives for paper, adhesives, emulsion stabilizers, films, butyral resins, cosmetics, pharmaceuticals and ceramic binders.
PVA를 적용하고자 하는 용도에 따라서는 저온수에 대한 용해성이 낮으며 고온수에 빠르게 용해된다는 성질을 갖는 PVA가 요구되는 경우가 있다. Depending on the intended use of the PVA, there is a case where a PVA having low solubility in low temperature water and rapidly dissolving in high temperature water is required.
통상적인 PVA는 수용액 형태로 사용되지만, 종이 등의 기재 위에 고전단 속도하에 도포할 때에 도포액의 점도가 상승하여, 도포액이 선 모양으로 되거나 도포액이 비산하는 등의 문제가 생기는 점으로부터 PVA의 입자직경을 작게 하여, 수성 슬러리의 형태로 사용한다는 검토가 수행되고 있다. 그러나 시멘트와 같은 무기물을 초조(抄造)법에 의해 성형하도록 하는 경우에 PVA를 수성 슬러리의 형태로 사용하면 PVA의 일부가 수중으로 용출되어, 성형물 중에서 제품 수율이 저하되거나 배수에 PVA가 유출되는 등의 문제가 생기는 점으로부터 저온수에 대한 용해성이 낮은 PVA가 요구되고 있다. Although conventional PVA is used in the form of an aqueous solution, the viscosity of the coating liquid increases when the coating liquid is applied on a substrate such as paper at high shear speed, which causes problems such as the coating liquid becoming linear or the coating liquid scattering. Examination has been carried out to reduce the particle diameter of the resin and to use it in the form of an aqueous slurry. However, in the case of forming an inorganic material such as cement by an evaporation method, when PVA is used in the form of an aqueous slurry, a part of the PVA is eluted in water, and the yield of the product in the molded product is lowered or the PVA is leaked to the drainage. In view of the problem of PVA, low solubility in low temperature water is required.
통상적으로 PVA는 폴리비닐에스테르계 중합체(이하, PVE라고 약칭하는 경우가 있다)를 염기성 촉매의 존재하에 알콜과 에스테르 교환반응시킴으로써 제조된다. 종래부터 공지되어 있는 PVA의 제조방법을 열거하면 하기와 같다. Usually, PVA is produced by transesterifying a polyvinyl ester polymer (hereinafter sometimes referred to as PVE) with an alcohol in the presence of a basic catalyst. It is as follows when the manufacturing method of PVA conventionally known is enumerated.
미국 특허 제2,642,419호 명세서에는 농도 24 내지 40중량%의 PVE의 메탄올 용액과 수산화나트륨의 메탄올 용액과의 혼합물을 연속적으로 벨트 컨베이어 위에 공급하여, 메타노리시스 반응에 의해 수득되는 겔상물을 분쇄 및 건조하는 것에 의한 PVA 분말의 제조방법(소위 벨트식 비누화법)에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말은 저온에서도 물에 용해되므로 PVA 분말의 표면만이 용해되어 응집하여, 괴상화한다. 따라서 연속 용해장치 등을 사용하여 물에 용해시키는 데 적합하지 않다. 또한, 본 방법에 따라 수득되는 PVA 분말은 이를 제조할 때에 사용하는 메탄올 및 메타노리시스 반응에 의해 생성되는 카복실산에스테르 등의 휘발성 유기 화합물 및 아세트산나트륨 등의 불휘발성 화합물을 상당량 함유하고 있다. PVA 분말에 함유되는 휘발성 유기 화합물이 많으면 PVA 분말을 취급할 때에 작업장 환경이 저하되며, 다시 PVA 수용액의 폐수처리가 필요해진다. 또한, 아세트산나트륨 등의 불휘발성 화합물이 PVA 분말에 함유되어 있는 경우에는 PVA 분말을 전기부품, 전자부품, 세라믹 결합제 등의 용도에 사용하는 경우에 절연불량 등의 문제가 생길 염려가 있다. US Pat. No. 2,642,419 discloses a mixture of a methanol solution of PVE in a concentration of 24 to 40 wt. The manufacturing method (so-called belt saponification method) of PVA powder by doing is disclosed. Since the PVA powder obtained by this method is soluble in water even at low temperatures, only the surface of the PVA powder is dissolved, aggregated, and agglomerated. Therefore, it is not suitable for dissolving in water using a continuous dissolving device or the like. In addition, the PVA powder obtained by the present method contains a considerable amount of volatile organic compounds such as carboxylic acid esters produced by methanol and metanosis reaction and nonvolatile compounds such as sodium acetate, which are used in producing them. If there are many volatile organic compounds contained in PVA powder, the workplace environment will fall when handling PVA powder, and wastewater treatment of PVA aqueous solution is needed again. In addition, when non-volatile compounds such as sodium acetate are contained in the PVA powder, problems such as poor insulation may occur when the PVA powder is used for applications such as electric parts, electronic parts, ceramic binders, and the like.
일본 특허공보 제(소)40-3700호에는 PVE를 알콜과 에스테르 교환반응시킬 때에 이의 반응계에 PVE의 메탄올 용액을 단속적으로 공급하는 PVA 분말의 제조방법에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말은 온수 또는 열수에 용해시키려고 해도 멍울이 생겨 균일한 수용액이 수득되지 않는 점으로부터 저온의 물에 투입한 다음, 물의 온도를 서서히 승온하는 것으로 물에 용해시키는 방법이 채용되고 있으며 용해에 장시간을 요한다는 문제가 있다. 또한 이러한 PVA 분말은 미세 분말의 비율이 많은 점으로부터 개봉할 때에 미세 분말이 비산되기 쉽다는 문제가 있다. Japanese Patent Publication No. 40-3700 discloses a method for producing PVA powder in which a methanol solution of PVE is intermittently supplied to a reaction system thereof when a PVE is transesterified with an alcohol. The PVA powder obtained by this method is added to low-temperature water from the point that lumps are generated even when trying to dissolve in hot water or hot water, and a uniform aqueous solution is not obtained, and then the temperature of the water is gradually raised to dissolve it in water. There is a problem that it takes a long time to dissolve. In addition, such PVA powder has a problem that the fine powder is likely to be scattered when opened due to the high proportion of the fine powder.
일본 특허공보 제(소)45-33191호에는 PVE를 알콜과 에스테르 교환반응시킬 때에 PVE의 메탄올 용액을 반응 혼합물 중의 가용성 중합체의 농도가 1중량%를 초과하지 않도록 하는 비율로 연속적으로 공급하여, 반응 혼합물로부터 PVA 슬러리를 연속적으로 회수하는 PVA 분말의 제조방법에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말에 대해서도 특허문헌 2에 관해 말한 것과 동일한 문제점이 지적된다. In Japanese Patent Publication No. 45-33191, when a PVE is transesterified with an alcohol, a methanol solution of PVE is continuously supplied at a rate such that the concentration of the soluble polymer in the reaction mixture does not exceed 1% by weight. A method for producing a PVA powder for continuously recovering a PVA slurry from a mixture is disclosed. The same problem as said about patent document 2 is also pointed out about the PVA powder obtained by this method.
일본 특허공보 제(소)46-9826호에는 비누화도 97 내지 98.5몰%의 PVA의 메틸 아세테이트. 메탄올 혼합용매의 슬러리에 비누화도 10 내지 40몰%의 부분 비누화 PVA의 메틸 아세테이트·메탄올 혼합용매 및 비누화 촉매의 메탄올 용액을 반응 혼합물 중의 가용성 중합체의 농도가 1중량%를 초과하지 않도록 하는 비율로 연속적으로 공급하는 동시에 반응 혼합물로부터 PVA 슬러리를 연속적으로 인출하여 탈액 및 건조하는 PVA 분말의 제조방법에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말에 대해서도 특허문헌 2에 관해서 기재된 것과 동일한 문제점이 지적된다. Japanese Patent Publication No. 46-9826 describes methyl acetate of PVA having a degree of saponification of 97 to 98.5 mol%. Methanol solution of methyl acetate-methanol mixed solvent and saponification catalyst of partially saponified PVA having a degree of saponification of 10-40 mol% in a slurry of methanol mixed solvent was continuously used at a ratio such that the concentration of soluble polymer in the reaction mixture did not exceed 1% by weight. Disclosed is a method for producing PVA powder in which the PVA slurry is continuously withdrawn from the reaction mixture while being fed into the solution to be liquefied and dried. The same problem as that described with respect to patent document 2 is also pointed out about the PVA powder obtained by this method.
물에 용해시킬 때에 생기는 괴상화 또는 멍울의 문제의 해결을 목적하는 PVA 분말의 제조방법이 제안되어 있다. A method for producing PVA powder has been proposed for the purpose of solving the problem of agglomeration or lumps produced when dissolved in water.
일본 특허공보 제(소)54-7311호에는 비누화도 93 내지 100몰%의 PVA를 메탄올, 물 등의 혼합용매 속에서 50℃ 이상의 온도로 가열하는 것에 의한 냉수에서의 용해성이 감소된 PVA 분말의 제조방법에 관해서 개시되어 있다. 그러나, 수득되는 PVA 분말은 고온수에 대한 용해성이 개선되어 있다고는 말하기 어렵다. 또한, 본 방법은 일단 제조된 PVA를 가열처리하므로 공정이 번잡해지고, 이를 위한 장치를 별도로 필요로 할 뿐만 아니라 에너지 효율도 낮다. Japanese Patent Publication No. 54-7311 discloses a PVA powder having reduced solubility in cold water by heating PVA having a saponification degree of 93 to 100 mol% to a temperature of 50 ° C or higher in a mixed solvent such as methanol and water. A manufacturing method is disclosed. However, it is difficult to say that the obtained PVA powder has improved solubility in hot water. In addition, the method heats the PVA once produced, which makes the process complicated, and requires a separate device for this, and also has low energy efficiency.
일본 공개특허공보 제2002-53616호에는 특정한 아조계 중합개시제를 저온으로 유지하면서 공급 라인을 통하여 아세트산비닐의 중합계에 도입하여, 아세트산비닐의 중합에 의해 수득되는 폴리아세트산비닐을 비누화하는 것에 의한 물에 대한 용해성이 개선된 PVA의 제조방법이 개시되어 있다. 본 방법에 따르면 결정성이 높은 PVA를 수득할 수 있지만, 저온에서 용해되기 어려우며 고온에서 빠르게 용해하는 PVA를 수득할 수 없다. 또한, 이러한 PVA는 건조에 의해 휘발성 유기 화합물의 함유량을 감소시키는 것이 곤란하며, 휘발성 유기 화합물이 잔존하면 작업환경의 악화를 초래한다. 또한, 본 방법에서는 중합촉매의 공급 라인을 저온으로 유지하기 위해 온도관리를 충분하게 실시하는 것이 필요하다. Japanese Laid-Open Patent Publication No. 2002-53616 discloses water by introducing a polyacetate obtained by polymerization of vinyl acetate by introducing a specific azo polymerization initiator into a polymerization system of vinyl acetate through a supply line while maintaining a low temperature. A method for preparing PVA with improved solubility in water is disclosed. According to this method, PVA having high crystallinity can be obtained, but PVA which is difficult to dissolve at low temperature and rapidly dissolves at high temperature cannot be obtained. In addition, it is difficult for such PVA to reduce the content of volatile organic compounds by drying, and deterioration of the working environment occurs when the volatile organic compounds remain. Moreover, in this method, it is necessary to perform sufficient temperature control in order to keep the supply line of a polymerization catalyst at low temperature.
일본 공개특허공보 제2000-265026호에는 입자직경 500 내지 1000μm의 입자를 20중량% 이상 함유하는 용해성이 우수한 PVA 분말이 개시되어 있다. 특허문헌 7에 제안되어 있는 PVA 분말은 저온수에서 용해할 때에 멍울로 되기 어렵다는 성질이 있지만, 입자직경이 크므로 용해에 장시간을 요하며, 실용성이 결핍된다. Japanese Laid-Open Patent Publication No. 2000-265026 discloses a PVA powder having excellent solubility containing 20% by weight or more of particles having a particle diameter of 500 to 1000 µm. PVA powder proposed in Patent Literature 7 has a property of hardly becoming vacant when dissolved in low temperature water. However, since the particle diameter is large, it takes a long time to dissolve and lacks practicality.
일본 공개특허공보 제(평)8-301936호에는 공지된 방법에 수득된 PVA를 140℃의 온도에서 무용매로 2시간 동안 가열하는 방법이 개시되어 있다. 본 방법에 따르면 PVA 분말의 용해특성의 온도 의존성은 커지지만, 특허문헌 5에 관해서 기재된 바와 동일하게 일단 제조한 PVA를 가열처리하므로 공정이 번잡해지며 또한, 이를 위한 장치를 별도로 필요로 할 뿐만 아니라 에너지 효율도 낮다. Japanese Laid-Open Patent Publication No. Hei 8-301936 discloses a method of heating PVA obtained in a known method for 2 hours with no solvent at a temperature of 140 ° C. According to this method, the temperature dependence of the dissolution characteristics of the PVA powder is increased, but the process is complicated by heat treatment of the PVA once prepared as described with respect to Patent Document 5, and not only requires a separate device for this. Energy efficiency is also low.
물에 대한 용해성이 개선된 PVA의 제조방법에 대해서도 제안되어 있다. A method for producing PVA with improved solubility in water has also been proposed.
일본 공개특허공보 제(평)9-316272호에는 비누화도 20 내지 60몰%의 부분 비누화 PVA와 PVE의 혼합 용액을 비누화로 처리하는 것에 의한 다공성의 PVA 분말의 제조방법이 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말은 저온수에 대한 용해성이 억제되어 있다는 점에서는 개선되어 있지만, 물의 온도를 상승시킬 때에 용해성의 점에서 또한 개선의 여지가 있다. 또한, 본 방법에서는 부분 비누화 PVA를 사용하므로 PVE의 예비적인 비누화 공정이 필요해진다. Japanese Laid-Open Patent Publication No. Hei 9-316272 discloses a method for producing porous PVA powder by treating a mixed solution of partially saponified PVA and PVE having a saponification degree of 20 to 60 mol% by saponification. Although the PVA powder obtained by the present method is improved in that the solubility in low temperature water is suppressed, there is room for improvement in terms of solubility when raising the temperature of water. In addition, the present method uses partially saponified PVA, which requires a preliminary saponification process of PVE.
일본 공개특허공보 제(평)8-188619호에는 PVE를 당해 PVE, PVA 및 알콜의 어느 것에도 용해되지 않는 유동 파라핀 등의 분산매 중에 분산시켜 비누화하는 것에 의한 PVA 미립자의 제조방법이 개시되어 있다. 본 방법에 따라 수득되는 PVA 미립자는 저온수에 대한 용해성이 억제되어 있다는 점에서는 개선되어 있지만, 다공성이 아니므로 PVA 중에 포함되는 휘발성 유기 화합물을 제거하는 것이 곤란하다는 문제가 있다. 또한, 본 방법에서는 폴리비닐피롤리돈 등의 분산제를 사용하는 것이 필요하며, 이들을 PVA 중에서 제거하기 위해서는 번잡한 공정이 필요하다. Japanese Laid-Open Patent Publication No. Hei 8-188619 discloses a method for producing PVA fine particles by dispersing PVE in a dispersion medium such as liquid paraffin that is not dissolved in any of the PVE, PVA, and alcohol. Although the PVA fine particles obtained by the present method have been improved in that the solubility in low temperature water is suppressed, there is a problem that it is difficult to remove volatile organic compounds contained in PVA because they are not porous. Moreover, in this method, it is necessary to use dispersing agents, such as polyvinylpyrrolidone, and a complicated process is needed in order to remove these in PVA.
저온수에 대한 용해성이 낮은 것으로 계분(멍울)상태로 되기 어려우며 또한 고온수에 빠르게 용해한다는 특성을 갖는 PVA가 강력하게 요청되고 있다. 과거에 저온수에 대한 용해성이 억제되어 있는 PVA가 제안되어 있지만, 작은 온도변화로 물에 대한 용해특성이 충분하게 크게 변화되는 PVA는 아직 수득되고 있지 않다. 또한, 종래에는 저온수에 대한 용해성을 억제하기 위해서 여분의 공정 또는 조작을 필요로 하고 있다. There is a strong demand for PVA, which has low solubility in low temperature water, which is difficult to become powdery, and which quickly dissolves in high temperature water. In the past, PVA in which solubility in low temperature water is suppressed has been proposed, but PVA whose solubility in water is sufficiently largely changed due to a small temperature change has not been obtained. In addition, conventionally, an extra process or operation is required in order to suppress solubility in low temperature water.
종래 기술에 있어서 문제점은 필름이 수용성이이서 공기 중에 노출시 변형이 쉽게 일어나서 사용용도가 제한되었다. 뿐만 아니라 불용성 폴리비닐알코올을 만들기 위해선 포름 알데하이드와 같은 촉매 또는 방부제를 사용하여야 하므로 환경에 유해한 영향을 끼치며 결과적으로 폴리비닐알코올의 큰 특징인 생분해 특성을 저하시켜 기존 플라스틱의 단점을 극복하지 못하는 문제가 있었다.The problem with the prior art is that the film is water soluble so that deformation occurs easily when exposed to air, thereby limiting its use. In addition, in order to make insoluble polyvinyl alcohol, it is necessary to use a catalyst or preservative such as formaldehyde, which has a detrimental effect on the environment and consequently deteriorates the biodegradation characteristics, which is a characteristic of polyvinyl alcohol, and does not overcome the disadvantages of conventional plastics. there was.
본 발명은 상기와 같은 문제점을 해결하고자, 폴리비닐 알코올을 생산하는 단계에 있어서 빙초산 또는 황산을 사용하여 환경오염을 최소화하는 불용성 폴리비닐 알코올 필름의 제조방법 및 그 제조방법에 의해 생산된 폴리비닐 알코올 필름을 제공하는 것을 목적으로 한다.The present invention to solve the above problems, in the step of producing polyvinyl alcohol using a glacial acetic acid or sulfuric acid production method of insoluble polyvinyl alcohol film to minimize environmental pollution and polyvinyl alcohol produced by the method It is an object to provide a film.
본 발명은 포름 알데히드를 사용하지 않는 불용성 폴리비닐 알콜(PVA) 필름제조방법 및 이에 의해 생산된 폴리비닐 알콜 필름을 제공한다.The present invention provides a process for producing an insoluble polyvinyl alcohol (PVA) film without using formaldehyde and a polyvinyl alcohol film produced thereby.
원지위에 제올라이트 코팅을 하고 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 표면 코팅한 후 건조 하여 이형지를 제조하는 단계;Preparing a release paper by zeolite coating on a base material and surface-coating a resin containing an acrylic resin with a spin coating machine, followed by drying;
상기 제조된 이형지를 냉수를 포함하고 있는 반응조에 삽입하고, 폴리비닐알콜이 반응조의 반응액의 15 -25중량%가 되도록 투입하는 단계;Inserting the prepared release paper into a reaction vessel containing cold water, and injecting the polyvinyl alcohol to be 15-25 wt% of the reaction solution of the reaction vessel;
빙초산 또는 황산을 반응조 반응액의 1 내지 25 중량%가 되도록 투입시킨 후 반응조의 온도를 서서히 올려서 용해시키는 단계;Adding glacial acetic acid or sulfuric acid to 1 to 25% by weight of the reaction tank reaction solution and gradually raising the temperature of the reaction tank to dissolve it;
용해 반응시킨 후 냉각시킨 후에 촉매를 이용하여 반응을 서서히 종결시킨 후 레진을 형성하는 단계; 및After the dissolution reaction and cooling, slowly terminating the reaction using a catalyst to form a resin; And
형성된 레진을 소정의 형태로 압출하는 성형과정을 포함하는 것을 특징으로 하는 불용성 폴리비닐 알콜 필름 제조방법을 제공한다.It provides a method for producing an insoluble polyvinyl alcohol film, characterized in that it comprises a molding process of extruding the formed resin into a predetermined form.
상기 아크릴계 레진을 포함한 수지는 고투명 아크릴로 계 레진 23% 내지 27%를 함유한 수지를 사용하며 보다 바람직하게는 고투명 아크릴계 레진 25%를 함유한 수지를 사용하는 것이 바람직하다. 보다 상세하게는 아크릴 수지 250g: 메틸 에틸 케톤(Methyl ethyl Ketone; mEK) 400g: 키실렌 200g : 톨루엔 150g의 조성비를 가지는 아크릴계 레진을 이용하는 것이 바람직하다. As the resin containing the acrylic resin, a resin containing 23% to 27% of high transparency acrylic resin is used, and more preferably, a resin containing 25% of high transparency acrylic resin is used. More specifically, it is preferable to use acrylic resin having a composition ratio of 250 g of acrylic resin: 400 g of methyl ethyl ketone (mEK): 200 g of xylene: 150 g of toluene.
상기 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 표면 코팅한 후 건조단계는 100°C로 건조 통과시키는 것이 바람직하다. After surface-coating the resin containing the acrylic resin with a spin coating machine, the drying step is preferably passed through to dry at 100 ° C.
상기 냉수의 온도는 5°C 내지 15°C의 냉수를 사용하는 것이 레진이 엉기는 것을 방지 할 수 있다. The temperature of the cold water may be 5 ° C to 15 ° C cold water to prevent the resin from tangling.
상기 용해 반응은 반응조의 온도를 서서히 올려서 반응조의 온도가 100℃가 되도록 상승시켜 3 내지 6시간 동안 용해시키는 것이 바람직하다. In the dissolution reaction, the temperature of the reaction tank is gradually raised to raise the temperature of the reaction vessel to 100 ° C, and then dissolved for 3 to 6 hours.
상기 냉각후 사용되는 촉매는 바조 56ws(듀퐁)를 이용하는 것이 바람직하다. It is preferable to use Bajo 56ws (Dupont) as the catalyst used after the cooling.
본 발명은 상기 방법을 이용하여 생산되어진 불용성 폴리비닐 알콜 필름을 제공한다. The present invention provides an insoluble polyvinyl alcohol film produced using the above method.
이 하 본 발명에 따른 바람직한 실시예를 상세히 설명한다. 그러나 본 발명이 하기 실시예로 제한되어지는 것은 아니다. Hereinafter, a preferred embodiment according to the present invention will be described in detail. However, the present invention is not limited to the following examples.
<실시예 1> 불용성 폴리비닐알콜 필름의 제조Example 1 Preparation of Insoluble Polyvinyl Alcohol Film
평량 145g/m 이상 원지위에 제올라이트 코팅을 10 미크론 코팅하고 고투명 아크릴 수지 250g: 메틸 에틸 케톤(Methyl ethyl Ketone; mEK) 400g: 키실렌 200g : 톨루엔 150g의 조성비를 가지는 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 25 미크론으로 표면 코팅한 후 약 5m 내지 30 m의 건조로에서 100°C로 건조 통과시켜서 이형지를 제조한다. 상기 제조된 이형지를 10℃의 냉수를 포함하고 있는 반응조에 삽입하고, 폴리비닐알콜이 반응조의 반응액의 15 -25중량%가 되도록 투입한다. 빙초산 또는 황산을 반응조 반응액의 1 내지 25 중량%가 되도록 투입시킨 후 반응조의 온도를 서서히 올려서 반응조의 온도가 100℃가 되도록 상승시켜 3 내지 6시간 동안 용해 반응시킨 후 80℃로 냉각시킨 후에 촉매(vazo 56ws, 듀퐁)를 이용하여 반응을 서서히 종결시켠 후 레진을 형성한다. 상기 형성된 레진을 소정의 형태로 압출 성형하여 불용성 폴리비닐 알콜 필름을 제조한다. 10 microns of zeolite coating on basis weight of 145g / m or more, and high transparency acrylic resin 250g: methyl ethyl ketone (mEK) 400g: xylene 200g: acrylic resin having a composition ratio of 150g toluene Release paper is prepared by surface coating 25 microns with a coating machine and then passing through dry at 100 ° C. in a drying furnace of about 5 m to 30 m. The release paper prepared above was inserted into a reaction vessel containing cold water at 10 ° C., and polyvinyl alcohol was added so as to be 15-25 wt% of the reaction liquid of the reaction vessel. After adding glacial acetic acid or sulfuric acid to 1 to 25% by weight of the reaction tank reaction solution, the temperature of the reaction tank is gradually raised to raise the temperature of the reaction tank to 100 ° C, dissolved and reacted for 3 to 6 hours, and then cooled to 80 ° C. (vazo 56ws, DuPont) is used to slowly terminate the reaction and form a resin. The resin thus formed is extrusion molded into a predetermined form to prepare an insoluble polyvinyl alcohol film.
본 발명의 폴리비닐알코올 필름제조를 위한 구체적 성분비는 표 1에 나타내었다.Specific component ratios for producing the polyvinyl alcohol film of the present invention are shown in Table 1.
[표1] 본 발명의 폴리비닐알코올 필름 조성비Table 1 Composition ratio of polyvinyl alcohol film of the present invention
본 발명에 의한 폴리비닐 알코올 필름의 제조방법 및 그 제조방법에 의해 생산된 폴피비닐 알코올 필름은 그 생산과정에 있어서 포름알데히드 대신에 빙초산 또는 황산을 사용하여 환경오염을 최소화 하는 불용성 폴리비닐 알코올 필름 및 그 제조방법을 제공한다. The method for producing a polyvinyl alcohol film according to the present invention and the polpyvinyl alcohol film produced by the method are insoluble polyvinyl alcohol films which minimize environmental pollution by using glacial acetic acid or sulfuric acid instead of formaldehyde in the production process and It provides a manufacturing method.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050105436A KR100744763B1 (en) | 2005-11-04 | 2005-11-04 | Process for the Producing Release Paper with Insoulble Polyvinyl Alcohol Films |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050105436A KR100744763B1 (en) | 2005-11-04 | 2005-11-04 | Process for the Producing Release Paper with Insoulble Polyvinyl Alcohol Films |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20070048396A true KR20070048396A (en) | 2007-05-09 |
| KR100744763B1 KR100744763B1 (en) | 2007-08-01 |
Family
ID=38272853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020050105436A KR100744763B1 (en) | 2005-11-04 | 2005-11-04 | Process for the Producing Release Paper with Insoulble Polyvinyl Alcohol Films |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100744763B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101879816B1 (en) * | 2016-05-09 | 2018-07-18 | 주식회사 에스케이씨에스 | Release paper and its manufacturing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5740508A (en) | 1980-08-21 | 1982-03-06 | Nippon Synthetic Chem Ind Co Ltd:The | Production of polyvinyl alcohol resin containing acetoacetic ester groups |
| JPH0790154B2 (en) | 1985-01-11 | 1995-10-04 | 日東電工株式会社 | Method for producing aromatic polysulfone composite semipermeable membrane |
| JP2511836B2 (en) * | 1991-04-08 | 1996-07-03 | 鐘紡株式会社 | Method for producing sponge sheet and porous body |
| FR2831172A1 (en) * | 2001-10-19 | 2003-04-25 | Inergy Automotive Systems Man | Hollow thermoplastic body, e.g. vehicle fuel tank, has a surface coating of polyvinyl alcohol with very low permeability due to chemical crosslinking and-or a protective layer |
-
2005
- 2005-11-04 KR KR1020050105436A patent/KR100744763B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101879816B1 (en) * | 2016-05-09 | 2018-07-18 | 주식회사 에스케이씨에스 | Release paper and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100744763B1 (en) | 2007-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3590498B2 (en) | Saponified ethylene-vinyl ester copolymer composition and co-extruded multilayer molded article using the same | |
| US4492783A (en) | Binder for obtaining a ceramic molded green body | |
| CN1626557B (en) | Polyvinyl alcohol based polymer and method of manufacturing the same | |
| JP5793577B2 (en) | Polyvinyl acetal fine particles for aqueous dispersions | |
| JP2004285144A (en) | Aqueous emulsion | |
| KR20220100871A (en) | A polyvinyl alcohol resin film, a method for discriminating a polyvinyl alcohol resin film, and a method for producing a polyvinyl alcohol resin film | |
| CN110172245B (en) | Graphene modified nylon 66 composite material and preparation method thereof | |
| US8664313B2 (en) | Method for producing aqueous ethylene/vinyl alcohol based copolymer dispersion | |
| KR100744763B1 (en) | Process for the Producing Release Paper with Insoulble Polyvinyl Alcohol Films | |
| JP4132467B2 (en) | Production method of vinyl alcohol polymer | |
| KR100744764B1 (en) | Release Paper Formed with Polyvinyl Alcohol and Polyvinyl Pyrrolidone Films Containing Proteins and Methods of Preparation Thereof | |
| TWI697355B (en) | Metal dispersion having enhanced stability | |
| JP2007269880A (en) | Manufacturing method of polyvinyl acetal composition | |
| CN103951919A (en) | Polyvinyl alcohol composite master batch and preparation method thereof | |
| JPS59128266A (en) | Manufacture of ceramic formed body | |
| JP2002301715A (en) | Method for manufacturing polyvinyl alcohol based resin pellet | |
| JP7001405B2 (en) | Polyvinyl alcohol resin and its manufacturing method | |
| CN108659424B (en) | Water-soluble granulation method of modified polyvinyl alcohol | |
| TW202136328A (en) | Polyvinyl alcohol resin, production method for polyvinyl alcohol resin, dispersant, and suspension polymerization dispersant | |
| CN110885510B (en) | Water dispersion system plasticized PVC resin and preparation method thereof | |
| CN104341296A (en) | Grafting modified ultraviolet crosslinking polyolefin waterproof film and preparation method thereof | |
| JPS6411647B2 (en) | ||
| JP3244197B2 (en) | Melt molding method for polyvinyl alcohol resin | |
| CN118420928A (en) | Ionic liquid modified polyvinyl alcohol gel and preparation method and application thereof | |
| CN112063051A (en) | Modified graphene plastic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20120824 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20130709 Year of fee payment: 7 |
|
| LAPS | Lapse due to unpaid annual fee |