KR960002733B1 - Production of paper and paper board - Google Patents

Production of paper and paper board Download PDF

Info

Publication number
KR960002733B1
KR960002733B1 KR1019890003911A KR890003911A KR960002733B1 KR 960002733 B1 KR960002733 B1 KR 960002733B1 KR 1019890003911 A KR1019890003911 A KR 1019890003911A KR 890003911 A KR890003911 A KR 890003911A KR 960002733 B1 KR960002733 B1 KR 960002733B1
Authority
KR
South Korea
Prior art keywords
polymer
paper
molecular weight
suspension
low molecular
Prior art date
Application number
KR1019890003911A
Other languages
Korean (ko)
Other versions
KR890014836A (en
Inventor
그레함 랭글리 존
Original Assignee
얼라이드 콜로이즈 리미티드
제이. 테일러
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26293708&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=KR960002733(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from GB888807444A external-priority patent/GB8807444D0/en
Priority claimed from GB888815219A external-priority patent/GB8815219D0/en
Application filed by 얼라이드 콜로이즈 리미티드, 제이. 테일러 filed Critical 얼라이드 콜로이즈 리미티드
Publication of KR890014836A publication Critical patent/KR890014836A/en
Application granted granted Critical
Publication of KR960002733B1 publication Critical patent/KR960002733B1/en

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765—Addition of all compounds to the pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06—Controlling the addition
    • D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
    • D21H23/16—Addition before or during pulp beating or refining
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/08—Mechanical or thermomechanical pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers

Abstract

내용 없음.No content.

Description

종이와 판지의 제조방법Manufacturing method of paper and cardboard

본 발명은 종이와 판지의 제조방법에 관한 것이다.The present invention relates to a method for producing paper and cardboard.

일반적으로, 종이 또는 판지는, 진한 지료(紙料)를 만드는 공정과 이 진한 지료를 희석시켜서 묽은 지료로 만드는 공정, 이 묽은 지료를 여수(濾水)시켜서 초지(抄紙)로 만드는 공정 및 이 초지를 건조시키는 공정을 거쳐서 제조되어진다. 이때, 상기의 진한 지료는, 건조된 펄프에 물을 혼합하거나, 여수시킨 펄스를 통합밀(intergrated mill)에서 희석시키게 되면, 얻어질 수 있다.Generally, paper or paperboard is a process of making a thick paper, a process of diluting the thick paper into a thin paper, a process of making the thin paper by water and making it into paper, and this paper. It is prepared through a process of drying. At this time, the thick stock can be obtained by mixing water with dried pulp or diluting the filtered pulse in an integrated mill.

상기와 같은 공정 단계중 하나 또는 그 이상의 단계에서 여러 종류의 첨가제를 부여하여 공정 수행이나 최종 제품의 품질을 개선시키는 것은 기본적으로 사용되고 있는 방법이다 .Improving the performance of the process or the quality of the final product by adding various kinds of additives in one or more of the above process steps is basically a method used.

예를 들면, 진한 지료를 만들기 위한 펄프에 불순물이 섞여 있는 경우, 이를 제조하기 위한 통상의 방법에서는 여수성을 위해 펄프화 단계나 진한 지료의 제조 단계에서 백반이나 활석 또는 벤토나이트 등의 무기질 재료를 첨가시키고 있는 바, 이러한 처리는 피치(pitch)와 그 밖의 점착성 물질들로 인한 문제를 감소시키게 된다.For example, when the pulp for making a thick stock is mixed with impurities, a conventional method for preparing the same includes adding a mineral material such as alum, talc or bentonite in the pulping step or the preparation of the thick stock for freeness. This treatment reduces the problems caused by pitch and other sticky materials.

만일 최종 초지의 강도를 향상시킬 필요가 있을 경우에는, 여수시키고자 하는 지료에 양이온성 전분과 같은 건조 강력 수지를 포함시키는 것이 일반적이다.If it is necessary to improve the strength of the final papermaking, it is common to include a dry strong resin such as cationic starch in the stock to be filtered.

또한, 여수성 및/또는 보유성을 개선시키기 위해서 여수시키고자 하는 지료에 양이노성 폴리머를 함유시키는 것은 기본적인 실시 방법으로 알려져 있다. U.S. 특허 제4,388,150호에는 보유성을 개선시키기 위해서, 여수 단계 이전에 지료에다 양이온성 전분과 콜로이드성 규산을 첨가시키는 방법이 개시되어 있다. 이는 "Composil"라는 상표명으로 상품화되어져 있다.In addition, it is known as a basic practice to include a cationic polymer in the paper to be filtered in order to improve the filtrate and / or retention. U.S. Patent 4,388,150 discloses a method of adding cationic starch and colloidal silicic acid to a stock prior to the Yeosu step to improve its retention. It is commercialized under the trade name "Composil".

한편, EP 특허 제235893호에는 여수성, 보유성, 건조 및 형성 공정을 개선시키기 위한 방법으로서, 먼저 합성 양이온성 폴리머를 전단 단계 이전에 투입하고 벤토나이트를 전단 단계 이후에 투입하는 기술이 개시되어 있다. 이는 "Hydrocol"라는 상표명으로 상품화되어져 있다.On the other hand, EP Patent No. 223593 discloses a technique for introducing the synthetic cationic polymer prior to the shearing step and the bentonite after the shearing step as a method for improving the processability, retention, drying and formation. . It is commercialized under the trade name "Hydrocol".

그러나, 상기 방법은 비록 우수한 결과를 나타내긴 하지만, 어떤 지료, 예를들면 불순물이 섞인 지료를 개선시키기 위해서나 최종 제품이, 예컨대 신문용지나 판지인 경우에는, 별도의 룸(room)이 필요한 단점이 있다.However, although the method shows excellent results, a disadvantage is that a separate room is required to improve some stocks, for example, stocks containing impurities, or when the final product is, for example, newspaper or cardboard. have.

이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 기계 처리로 유도된 펄프가 적어도 25중량% 형성되어 있는 수용성의 셀룰로스 현탁액을 형성하고, 상기 현탁액을 세정, 혼합 및 펌핑 단계 중에서 선택된 하나 이상의 전단 단계를 거치게 하되 그 중 하나의 전단 단계를 거치기 이전에 분자량이 500,000 이상이고 고유 점도(I.V.)가 4dl/g 이상인 고분자량의 선형 합성 양이온성 폴리머인 주 폴리머를 첨가하고, 상기 전단 단계 이후에 벤토나이트를 첨가시킨 다음, 상기 현탁액을 여수시켜서 초지로 만들고, 이 초지를 건조시켜서 종이와 판지 제품을 제조하는데 있어서, 상기 주 폴리머를 첨가하기 이전에 상기 현탁액에 고유 점도(I.V.)가 2dl/g 이하인 저 분자량의 수용성 합성 양이온성 폴리머를 0.01% 내지 0.2%의 양으로 첨가하여 여수성을 개선시키는 것을 특징으로 하는 종이와 판지의 제조 방법인 것이다.The present invention forms a water-soluble cellulose suspension having at least 25% by weight of pulp derived from mechanical treatment and subjecting the suspension to at least one shearing step selected from washing, mixing and pumping steps, wherein one of the shearing steps is carried out. The main polymer, a high molecular weight linear synthetic cationic polymer having a molecular weight of at least 500,000 and an intrinsic viscosity (IV) of at least 4 dl / g, is added after the shearing step, bentonite is added, and then the suspension is filtered In the manufacture of paper and cardboard products by drying the paper, prior to the addition of the main polymer, a low molecular weight, water-soluble synthetic cationic polymer having an intrinsic viscosity (IV) of 2 dl / g or less is added in an amount of 0.01% to It is added to the amount of 0.2% to improve the freeness of the paper and cardboard manufacturing method characterized in that A.

이와 같은 본 발명의 제조방법을 더욱 상세히 설명하면 다음과 같다.If described in more detail the manufacturing method of the present invention as follows.

본 발명에서 주 폴리머를 첨가시키기 전에 묽은 지료에다 저분자량의 양이온성 폴리머를 함유시키게 되면, 전단 단계 이전에 주 폴리머를 첨가하고 전단단계 이후에 벤토나이트를 첨가하는 방법에 따라 얻어지는 공정 및 실시 특성을 향상시킬 수 있게 된다. 예컨대, 다른 조건들에 따라, 여수성을 개선시킬 수 있고, 피치와 그 밖의 점착성 물질로 인한 문제점을 감소시킬 수 있으며, 습식 및/또는 건식 강도, 이동성(runability), 린팅(linting), 불투명성 및 그 밖의 종이 품질을 개선시킬 수 있다.In the present invention, when the thin stock contains a low molecular weight cationic polymer before adding the main polymer, the process and the execution characteristics obtained by the method of adding the main polymer before the shearing step and the bentonite after the shearing step are improved. You can do it. For example, depending on other conditions, it is possible to improve the freeness, to reduce the problems caused by the pitch and other sticky materials, wet and / or dry strength, runability, linting, opacity and Other paper quality can be improved.

종래의 방법에 따라, 건조된 펄프나 통합 밀에서 여수된 펄프를 희석시켜서 수용성 셀룰로스 현탁액을 만들 수 있다.According to conventional methods, water-soluble cellulose suspensions can be made by diluting dried pulp or filtered pulp in an integrated mill.

여기서, 고유 점도(I.V.)는 인산나트륨을 사용해서 pH가 약 4로 완충된 1몰랄 NaCl에서 25℃용액의 현탁된 레벨 점도계를 이용하여 용액의 점도를 측정하는 기본적인 방법에 의하여 측정된 것이다.Here, the intrinsic viscosity (I.V.) is measured by the basic method of measuring the viscosity of a solution using a suspended level viscometer of a 25 ° C. solution in 1 molar NaCl buffered with sodium phosphate at a pH of about 4.

나머지 공정은 저 분자량을 첨가한 후에 "Hydrocol" 공정과 유사한 바, EP 특허 및 제235893호에서 실시한 바와같이, 전단 단계 중 하나의 단계 이전에 적어도 분자량이 500,000 이상이고 고유 점도(I.V.)가 4dl/g인 합성 양이온성 폴리머를 첨가하고 그 이후에 벤토나이트를 이용하는 방법을 적용시킨다. 즉, EP 특허 제235893호에 기술된 재질과 공정 조건들은 본 발명에 적용되어질 수 있으며, 주 폴리머를 첨가시키기 이전에 현탁액에 저 분자량의 폴리머를 함유시키는 형태로 변형하여도 된다.The rest of the process is similar to the "Hydrocol" process after the addition of a low molecular weight, as at EP patent and heading 23.525, at least 500,000 molecular weight and intrinsic viscosity (IV) of 4 dl / before one of the shearing steps. The synthetic cationic polymer, g, is added followed by the method using bentonite. That is, the materials and process conditions described in EP Patent No. 223593 can be applied to the present invention and may be modified to include low molecular weight polymers in the suspension prior to addition of the main polymer.

어떤 경우에는 EP 특허 제235893호에 제시된 것 보다 적은 양의 주 폴리머를 사용할 때, 예컨대, 300g/t 이하의 양, 즉, 50g/t(0.005%) 내지 250g/t, 특히 100g/t 이상일 때(지료의 건조 중량에 기초한 것이다), 본 발명에서는 보다 우수한 결과를 나타낼 수도 있다.In some cases, when using an amount of the main polymer less than that set forth in EP Patent 2235893, for example, an amount of 300 g / t or less, ie 50 g / t (0.005%) to 250 g / t, in particular 100 g / t or more (It is based on the dry weight of a stock.) In this invention, a more excellent result can also be shown.

저 분자량의 폴리머는, 진한 지료에 존재하도록 하여 이를 희석시켜서 묽은 지료를 형성시킬 수 있으며, 또는 묽은 지료에 첨가되어질 수도 있다. 예컨대, 일반적으로 진한 지료를 백수로 희석시켜 묽은 지료를 얻게 되는데, 이러한 백수로 희석시킬 때나 그 전 또는 그 직후에 저 분자량의 폴리머를 첨가시키고, 이 묽은 지료에 주 폴리머를 첨가시키는 것이 바람직하다.The low molecular weight polymer may be present in the thick stock and diluted to form a thin stock or may be added to the thin stock. For example, a thick stock is usually diluted with white water to obtain a thin stock. A low molecular weight polymer is added at or before or immediately after dilution with the white stock and the main polymer is added to the thin stock.

저 분자량의 폴리머는 고유 점도(I.V.)가 2dl/g 이하이며, 대체로 500,000 이하의 분자량을 갖게 된다. 분자량은 대체로 50,000 이상이 되며 경우에 따라서는 100,000 이상이다.Low molecular weight polymers have an intrinsic viscosity (I.V.) of 2 dl / g or less and generally have a molecular weight of 500,000 or less. The molecular weight is usually 50,000 or more and in some cases 100,000 or more.

상대적으로 낮은 분자량을 갖는 바람직한 폴리머로서는 폴리에틸렌이민이 있으며, 이러한 형태의 폴리머로는 "Polymin SK"라는 상품명으로 판매되고 있는 물질이 적당하다. 그 밖의 적당한 물질로서 폴리아민 및 폴리디시안디아미드-포름알데히드 폴리머 이외에도 디알릴디메틸암모늄클로라이드, 디알킬아미노알킬(메트) 아크릴레이트 및 디알킬아미노알킬(메트)아크릴아미드(산부가염 또는 사급암모늄염으로서)의 폴리머와 코폴리머등이 있다. 그리고, 양성 합성 폴리머도 사용될 수 있다.Preferred polymers having a relatively low molecular weight include polyethyleneimine, and a substance sold under the trade name "Polymin SK" is suitable for this type of polymer. Other suitable materials include diallyldimethylammonium chloride, dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides (as acid addition salts or quaternary ammonium salts) in addition to polyamines and polydiciandiamide-formaldehyde polymers. Polymers and copolymers. And amphoteric synthetic polymers can also be used.

본 발명에 따른 방법은, 상대적으로 상당량의 피치를 함유하거나 또는 높은 양이온 요구성을 갖는 조(祖)지료를 이용하는 것인 바, 예컨대, 보유성을 개선시키기 위하여 종래 방식에서 보유 보조제로서 사용되었던 Polymin SK(상표명)을 적어도 0.1% 필요로 하며, 이러한 지료는 기계 처리로 유도된 펄프를 적어도 25중량% 이상, 보통은 50중량% 이상을 함유한다. 여기서, 기계 처리로 유도된 펄프란 쇄목 펄프, 가압 재생 쇄목 펄프, 열기계 펄프, 화학-열기계 펄프 또는 그 밖에 고 수율의 기계 처리로 유출된 섬유등을 말한다.The process according to the invention is to use a crude feed containing a relatively significant amount of pitch or having a high cation demand, for example Polymin which has been used as a retention aid in the conventional manner to improve retention. At least 0.1% of SK ™ is required, and the stock contains at least 25% by weight, usually 50% by weight, of the pulp derived from the mechanical treatment. Herein, pulp induced by mechanical treatment refers to ground wood pulp, pressurized regenerated ground wood pulp, thermomechanical pulp, chemical-thermodynamic pulp, or other fibers that have been discharged by high yield mechanical treatment.

본 발명의 방법은, 상대적으로 미 가공된 펄프를 사용할 경우 지료를 신문용지의 제조에 사용할 때 특히 유용한 바, 충진제를 함유시키지 않거나 지료의 건조 중량을 기초로 하여 단지 0 내지 15%, 경우에 따라서는 0 내지 10%의 적은량의 충진제만이 함유된 지료를 사용하되 최종 종이 제품에서 충진제의 양이 30% 이상이 되도록 지료에 충진제를 함유시키게 되면 우수한 효과를 얻을 수 있게 된다.The process of the present invention is particularly useful when using a relatively unprocessed pulp when the stock is used in the production of newspaper paper, containing no fillers or only 0-15% based on the dry weight of the stock, in some cases. When using a paper containing only a small amount of filler of 0 to 10%, the filler is included in the paper so that the amount of filler in the final paper product is 30% or more, it is possible to obtain an excellent effect.

한편, 이 방법은 충진제를 포함하지 않거나 조금 포함하게 되는 미가공 펄프로부터 판지를 제조하는 방법에도 유용하다. 이 경우, 저분자량 폴리머의 선택적 또는 부가적인 특성, 즉 판지의 강도를 개선시킬 수 있는 바, 이를 위해서 폴리머로서 저 분자량의 수용성 합성 양이온성 건조 강력 수지가 사용될 수 있으며, 양성의 폴리머가 특히 적합하다.On the other hand, this method is also useful for producing cardboard from raw pulp that contains little or no filler. In this case, the selective or additional properties of the low molecular weight polymer, ie, the strength of the paperboard, can be improved, for which a low molecular weight, water-soluble synthetic cationic dry strong resin can be used, with a positive polymer being particularly suitable. .

저 분자량 폴리머의 사용량은 지료의 건조 중량을 기초로 0.01% 또는 0.05 내지 0.2% 범위에서 사용할 수 있고, 최적 조건은 통상적인 실험 조건에 의하여 찾아낼 수 있다. 저 분자량의 폴리머로 처리하기 이전에 펄프는 대체로 400g/t 이상의 양이온 요구성(주 양이온성 폴리머로 적정하여 측정됨)을 갖게 되며, 저 분자량의 폴리머는 주 폴리머를 첨가하기 이전에 지료에 첨가하거나 또는 지료에 앞서서 첨가하여, 묽은 지료의 양이온 요구성을 300g/t 이하로 감소시키도록 하는 양으로 함유시킨다.The amount of the low molecular weight polymer can be used in the range of 0.01% or 0.05 to 0.2% based on the dry weight of the stock, and the optimum conditions can be found by conventional experimental conditions. Prior to treatment with low molecular weight polymers, the pulp will generally have a cationic requirement (measured by titration with the main cationic polymer) of at least 400 g / t, and the low molecular weight polymer may be added to the stock prior to addition of the main polymer. Or added prior to the stock, in an amount to reduce the cation demand of the thin stock to 300 g / t or less.

본 발명의 공정은, 피치 및/또는 점착 물질을 제거하는데 유리하며, 불투명도 및 린팅 특성과 같은 종이의 품질을 개선시키고, 제조시 습식 강도 또는 이동성을 개선시키는 등, 실행 특성이 개선되었다. 더욱이, EP 특허 제235893호에 기술된 바와 같은 폴리머 없이 수행되는 공정에 비하여 제2의 폴리머를 부여함으로써 여수 특성 또한 개선되었다.The process of the present invention is advantageous for removing pitch and / or adhesive materials, and has improved performance characteristics, such as improving paper quality, such as opacity and lining properties, and improving wet strength or mobility in manufacturing. Moreover, the Yeosu properties were also improved by imparting a second polymer as compared to the process carried out without polymers as described in EP patent 2235893.

다음의 실시예에서, 폴리머 A는 아크릴아미드 75중량%와 메틸클로라이드로 4분체화된 디메틸아미노에틸 25중량%로 형성되어진 폴리머로서 고유 점도가 7dl/g이고, 폴리머 B는 상품명 Polyimine SK로 판매되는 변성폴리에틸렌아민이다.In the following examples, polymer A is a polymer formed from 75% by weight of acrylamide and 25% by weight of dimethylaminoethyl tetrased into methyl chloride, having an intrinsic viscosity of 7 dl / g, and polymer B sold under the trade name Polyimine SK. Modified polyethyleneamine.

[실시예 1]Example 1

0.5%의 고유 점도를 갖는 100%의 혼합된 폐물 지료를 제조하였다. 이 지료에 대한 여수성 시험을, Shopper Riegler 여수성 시험기를 이용하여 지료로부터 600㎖의 배수가 여수되는데 요구되는 시간을 측정하여서 실시하였다. 이때, 지료를 전단시킨 후에 여수성을 측정하였다.100% mixed waste stock was prepared having an inherent viscosity of 0.5%. The filing test for this stock was carried out using a Shopper Riegler filing tester, measuring the time required to drain 600 ml of drainage from the stock. At this time, the shearing property was measured after shearing the stock.

다른 시험들에서는, 벤토나이트를 전단 단계 이전에 첨가하고, 폴리머 A 및/또는 폴리머 B를 전단 단계 이후에 첨가하였다.In other tests, bentonite was added before the shear step and polymer A and / or polymer B were added after the shear step.

폴리머 A와 B 모두를 첨가할 경우, B를 A보다 상당히 먼저 첨가하였다. 시험결과는 다음 표 1에 나타내었다.When both polymers A and B were added, B was added considerably before A. The test results are shown in Table 1 below.

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

[실시예 2]Example 2

기계섬유 함량이 높으며, 특히 경점도가 0.1%인 50 : 50 쇄목 : 표백 클래프트 펄프의 지료를 이용하며, 상기 실시예1과 유사한 방법으로 실시하였다. 상기 실시예1의 방법에 따라 여수시간을 측정하여, 피치의 수를 세었다(Allen 방법을 이용, 입자 수/㎖). 그 결과를 다음 표2에 나타내었다.A high mechanical fiber content, in particular, 50: 50 crushed wood with a viscosity of 0.1%: bleached kraft pulp material was carried out in a similar manner to Example 1. The free water time was measured according to the method of Example 1, and the number of pitches was counted (number of particles / ml using the Allen method). The results are shown in Table 2 below.

[표 2]TABLE 2

Figure kpo00002
Figure kpo00002

이 실시예로부터, 양호한 여수성 및 보유성을 위해 요구되는 고분자량(고유점도 4이상)의 양이온성 보유 보조제의 양을 감소시키고, 또한 지료의 높은 양이온 요구성 특히 높은 피치수를 감소시키기 위한, 폴리에틸렌이민의 첨가량이, 예컨대, 0.01 내지 0.1%, 일반적으로는 0.02 내지 0.07% 정도인 것이 확인되었다.From this example, in order to reduce the amount of high molecular weight cationic retention aid required for good freeness and retention, and also to reduce the high cation demand of the stock, especially the high pitch number, It was confirmed that the addition amount of polyethyleneimine is, for example, about 0.01 to 0.1%, generally about 0.02 to 0.07%.

[실시예 3]Example 3

3%의 크래프트와 17%의 마그네피트, 38%의 열기계 펄프 및 42%의 쇄목을 기재로 하며 20%의 조악물(粗惡物)이 첨가되어 있는 지료를 이용하여 신문용지를 만들었다. 일부 시험에서는, 고분자량의 폴리머를 마지막 전단 단계 직전에 첨가하였으며, 또한 일부 시험에서는 벤토나이트를 마지막 전단 단계 이후에 첨가하였다. 저 분자량의 폴리머는 진한 지료를 희석시킨 후 곧바로 묽은 지료에 첨가하였다.Newspapers were made from a stock containing 3% kraft, 17% magnetite, 38% thermodynamic pulp, and 42% crushed wood and 20% crude material added. In some tests, high molecular weight polymer was added just before the last shear step, and in some tests bentonite was added after the last shear step. Low molecular weight polymers were added to the thin stock immediately after diluting the thick stock.

이들 시험에서, 저 분자량의 폴리머로는 약 20중량%의 아크릴아미드와 80중량%의 디알킬디메틸암모늄클로라이드로 형성된 고유 점도 dl/g의 용액 폴리머인 폴리머 K를 사용하였으며, 고분자량의 폴리머 L은 70%의 아크릴 아미드와 30%의 메틸클로라이드로 4분체화된 디메틸 아미노에틸 아크릴아미드 .V.8이고, 폴리머 M은 95% 아크릴아미드와 5% 메틸 클로라이드로 4분체화된 디메틸 아미노에틸 아크릴레이트 I.V.11로 형성된 것이다. 처리된 현탁액의 각 여수율을 측정하여, 최적의 여수 형태를 갖을 때의 최선의 결과와 함께 다음 표 3에 나타내었다.In these tests, polymer K, a solution polymer of intrinsic viscosity dl / g formed from about 20% by weight of acrylamide and 80% by weight of dialkyldimethylammonium chloride, was used as the low molecular weight polymer. Dimethyl aminoethyl acrylamide .V.8 quadriplexed with 70% acrylamide and 30% methyl chloride, Polymer M is dimethyl aminoethyl acrylate IV tetraparted with 95% acrylamide and 5% methyl chloride. 11 is formed. Each free rate of the treated suspension was measured and is shown in Table 3 below with the best results when having the best free form.

[표 3]TABLE 3

Figure kpo00003
Figure kpo00003

이들 결과들은 고분자량의 폴리머가 비교적 낮은 양이온성 부하를 가질때도 신문 용지의 제조시 전단 단계 직전에 고분자량의 양이온성 폴리머를 첨가하고 전단 단계 후에 벤토나이트를 첨가하는 것이 이점이 있음을 명백히 증명해 주고 있으며, 또한, 고분자량의 폴리머를 500,000 이상의 분자량을 가지는 저 분자량의 폴리머로 교체함으로써 유용한 결과를 얻을 수 있음을 보여 주고 있지만, 더 좋은 결과는 이들을 조합하여 사용할때 얻을 수 있다.These results clearly demonstrate the benefits of adding high molecular weight cationic polymers immediately before the shearing step and adding bentonite after the shearing step, even when high molecular weight polymers have relatively low cationic loading. In addition, it has been shown that useful results can be obtained by replacing high molecular weight polymers with low molecular weight polymers having a molecular weight of 500,000 or more, but better results can be obtained when using these in combination.

Claims (8)

기계 처리로 유도된 펄프가 적어도 25중량% 형성되어 있는 수용성의 셀룰로스 현탁액을 형성하고, 상기 현탁액을 세정, 혼합 및 펌핑 단계 중에서 선택된 하나 또는 그 이상의 전단 단계를 거치게 하되, 그 중 하나의 전단 단계를 거치기 이전에 상기 현탁액에다 고유 점도가 4dl/g 이상인 고분자량의 수용성 양이온성 폴리머인 주 폴리머를 적어도 50g/t 첨가하고, 상기 전단 단계 이후에는 벤토나이트를 첨가한 다음, 상기 현탁액을 여수시켜서 초지로 만들고, 이 초지를 건조시켜서 종이와 판지 제품을 제조하는데 있어서, 상기 주 폴리머를 첨가하기 이전에 상기 현탁액에 고유 점도가 2dl/g 이하인 저 분자량의 수용성 합성 양이온성 폴리머를 0.01% 내지 0.2%의 양으로 첨가하여 여수성을 개선시키는 것을 특징으로 하는 종이와 판지의 제조방법.Forming a water-soluble cellulose suspension having at least 25% by weight of mechanically derived pulp and subjecting the suspension to one or more shearing steps selected from washing, mixing and pumping steps, wherein one of the shearing steps At least 50 g / t of a main polymer, a high molecular weight, water-soluble cationic polymer having an intrinsic viscosity of at least 4 dl / g, is added to the suspension prior to passing, and after the shearing step, bentonite is added, and then the suspension is filtered to make paper. Drying the paper to produce paper and paperboard products, wherein the low molecular weight, water-soluble synthetic cationic polymer having an intrinsic viscosity of 2 dl / g or less in the suspension prior to addition of the main polymer in an amount of 0.01% to 0.2%. Method for producing paper and cardboard, characterized in that the addition to improve the freeness. 제1항에 있어서, 상기 셀룰로스 현탁액은 그 중에서 적어도 50중량%가 기계적으로 유도된 펄프로 부터 형성된 것임을 특징으로 하는 종이와 판지의 제조 방법.The method of claim 1, wherein the cellulose suspension is at least 50% by weight formed from mechanically derived pulp. 제1항에 있어서, 상기 제품은 신문용지인 것임을 특징으로 하는 종이와 판지의 제조방법.The method of claim 1, wherein the product is newspaper paper. 제1항에 있어서, 상기 저 분자량의 폴리머는 그 분자량이 100,000 내지 500,000인 것임을 특징으로 하는 종이와 판지의 제조 방법.The method of claim 1, wherein the low molecular weight polymer has a molecular weight of 100,000 to 500,000. 제1항에 있어서, 상기 저 분자량의 폴리머는 폴리에틸렌이민, 폴리아민, 폴리시안디아미드 포름알데이히드 폴리머, 양성 폴리머 그리고 디알릴 디메틸 암모늄 클로라이드, 디알킬아미노알킬(메트) 아크릴레이트 및 디알킬아미노알킬(메트) 아크릴아미드로부터 선택된 모노머의 폴리머 중에서 선택된 것임을 특징으로 하는 종이와 판지의 제조방법.The polymer of claim 1 wherein the low molecular weight polymer comprises polyethyleneimine, polyamine, polycyandiamide formaldehyde polymer, amphoteric polymer and diallyl dimethyl ammonium chloride, dialkylaminoalkyl (meth) acrylate and dialkylaminoalkyl ( Meth) a process for producing paper and paperboard, characterized in that it is selected from polymers of monomers selected from acrylamide. 제1항에 있어서, 상기 저 분자량의 폴리머가 첨가된 현탁액은, 상기 주 양이온성 폴리머에 대해 측정 되었을 때, 그 양이온 요구성이 적어도 400g/t이며, 상기 저 분자량 폴리머는 상기 양이온 요구성을 300g/t 이하로 감소시킬 수 있는 양으로 첨가시키는 것임을 특징으로 하는 종이와 판지의 제조방법.2. The suspension of claim 1 wherein the low molecular weight polymer is added has a cation requirement of at least 400 g / t as measured for the main cationic polymer and the low molecular weight polymer has a 300 g cation requirement. A method for producing paper and cardboard, characterized in that the addition in an amount that can be reduced to less than / t. 제1항에 있어서, 상기 종이와 판지를 형성하기 위하여 여수된 현탁액은 진한 지료를 희석하여 만들어진 묽은 지료이고, 상기 주 폴리머는 묽은 지료에 첨가되고 상기 저 분자량의 폴리머는 진한 지료에 존재하는 것을 특징을 하는 종이와 판지의 제조방법.The method of claim 1, wherein the suspension which is filtered to form paper and cardboard is a thin stock made by diluting a thick stock, the main polymer is added to a thin stock, and the low molecular weight polymer is present in the thick stock. Method of making paper and cardboard. 제1항에 있어서, 상기 종이와 판지를 형성하기 위하여 여수된 현탁액은 진한 지료를 희석하여 만들어진 묽은 지료이고, 상기 주 폴리머는 묽은 지료에 첨가되며, 상기 저 분자량의 폴리머는 묽은 지료에 첨가되는 것을 특징으로 하는 종이와 판지의 제조방법.The method according to claim 1, wherein the suspension filtered to form paper and paperboard is a thin stock made by diluting a thick stock, the main polymer is added to a thin stock, and the low molecular weight polymer is added to a thin stock. Method for producing paper and cardboard characterized in that.
KR1019890003911A 1988-03-28 1989-03-28 Production of paper and paper board KR960002733B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB888807444A GB8807444D0 (en) 1988-03-28 1988-03-28 Production of paper & paper board
GB8807444.8 1988-03-28
GB888815219A GB8815219D0 (en) 1988-06-27 1988-06-27 Production of paper & paper board
GB8815219.4 1988-06-27

Publications (2)

Publication Number Publication Date
KR890014836A KR890014836A (en) 1989-10-25
KR960002733B1 true KR960002733B1 (en) 1996-02-26

Family

ID=26293708

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019890003911A KR960002733B1 (en) 1988-03-28 1989-03-28 Production of paper and paper board

Country Status (9)

Country Link
EP (1) EP0335575B2 (en)
JP (2) JPH026683A (en)
KR (1) KR960002733B1 (en)
AU (1) AU613465B2 (en)
CA (1) CA1322435C (en)
DE (1) DE68905208T3 (en)
ES (1) ES2053980T5 (en)
FI (1) FI97307C (en)
NO (1) NO174724B (en)

Families Citing this family (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE9003954L (en) * 1990-12-11 1992-06-12 Eka Nobel Ab SET FOR MANUFACTURE OF SHEET OR SHAPE CELLULOSA FIBER CONTAINING PRODUCTS
US5126014A (en) * 1991-07-16 1992-06-30 Nalco Chemical Company Retention and drainage aid for alkaline fine papermaking process
US5221435A (en) * 1991-09-27 1993-06-22 Nalco Chemical Company Papermaking process
DE4311599A1 (en) * 1993-04-08 1994-10-13 Henkel Kgaa Process for controlling the settling of sticky contaminants from pulp suspensions
US5484834A (en) * 1993-11-04 1996-01-16 Nalco Canada Inc. Liquid slurry of bentonite
GB9410920D0 (en) * 1994-06-01 1994-07-20 Allied Colloids Ltd Manufacture of paper
US5810971A (en) * 1995-05-17 1998-09-22 Nalco Canada, Inc. Liquid slurry of bentonite
SE9502522D0 (en) * 1995-07-07 1995-07-07 Eka Nobel Ab A process for the production of paper
EP0760406A3 (en) * 1995-08-24 1997-09-17 Nalco Canada Inc Combination of poly (dadmac/acrylamide) and bentonite for deposition control in papermaking processes
US5840158A (en) * 1995-09-28 1998-11-24 Nalco Chemical Company Colloidal silica/polyelectrolyte blends for pulp and paper applications
US5620629A (en) * 1995-09-28 1997-04-15 Nalco Chemical Company Colloidal silica/polyelectrolyte blends for natural water clarification
CA2180371A1 (en) * 1996-02-13 1997-08-14 Brian Frederic Satterfield Production of filled paper and compositions for use in this
GB9603909D0 (en) 1996-02-23 1996-04-24 Allied Colloids Ltd Production of paper
DE19627553A1 (en) * 1996-07-09 1998-01-15 Basf Ag Process for the production of paper and cardboard
US6113741A (en) * 1996-12-06 2000-09-05 Eka Chemicals Ab Process for the production of paper
DE19654390A1 (en) * 1996-12-27 1998-07-02 Basf Ag Process for making paper
DE19715832A1 (en) 1997-04-16 1998-10-22 Basf Ag Process for the production of paper, cardboard and cardboard
US7306700B1 (en) 1998-04-27 2007-12-11 Akzo Nobel Nv Process for the production of paper
EP0953680A1 (en) * 1998-04-27 1999-11-03 Akzo Nobel N.V. A process for the production of paper
KR100403838B1 (en) 1998-04-27 2003-11-01 악조 노벨 엔.브이. A process for the production of paper
US6083997A (en) * 1998-07-28 2000-07-04 Nalco Chemical Company Preparation of anionic nanocomposites and their use as retention and drainage aids in papermaking
CN1231639C (en) * 1998-09-22 2005-12-14 卡尔贡公司 Silica-acid colloid blend in a microparticle system used in papermaking
TW527457B (en) 1999-11-08 2003-04-11 Ciba Spec Chem Water Treat Ltd Manufacture of paper and paperboard
WO2002025013A1 (en) 2000-09-20 2002-03-28 Akzo Nobel N.V. A process for the production of paper
MY140287A (en) 2000-10-16 2009-12-31 Ciba Spec Chem Water Treat Ltd Manufacture of paper and paperboard
JP3819731B2 (en) * 2000-11-30 2006-09-13 ハイモ株式会社 How to make neutral newsprint
DE20220979U1 (en) 2002-08-07 2004-10-14 Basf Ag Preparation of paper, pasteboard, or cardboard involving cutting of the paper pulp, addition of microparticles of cationic polymer, e.g. cationic polyamide, and a finely divided inorganic component after the last cutting step
GB0402469D0 (en) 2004-02-04 2004-03-10 Ciba Spec Chem Water Treat Ltd Production of a fermentation product
GB0402470D0 (en) 2004-02-04 2004-03-10 Ciba Spec Chem Water Treat Ltd Production of a fermentation product
JP4517662B2 (en) * 2004-02-10 2010-08-04 栗田工業株式会社 Paper and paperboard manufacturing method
DE102004044379B4 (en) 2004-09-10 2008-01-10 Basf Ag Process for the production of paper, paperboard and cardboard and use of a retention agent combination
DE102004058587A1 (en) 2004-12-03 2006-06-14 Basf Ag Process for the production of papers with high basis weights
DE102004063005A1 (en) 2004-12-22 2006-07-13 Basf Ag Process for the production of paper, cardboard and cardboard
US7955473B2 (en) 2004-12-22 2011-06-07 Akzo Nobel N.V. Process for the production of paper
US20060254464A1 (en) 2005-05-16 2006-11-16 Akzo Nobel N.V. Process for the production of paper
PT1969183E (en) 2005-12-30 2015-03-06 Akzo Nobel Nv A process for the production of paper
KR101506920B1 (en) * 2006-10-25 2015-03-30 시바 홀딩 인크 A process for improving paper strength
US7758934B2 (en) 2007-07-13 2010-07-20 Georgia-Pacific Consumer Products Lp Dual mode ink jet paper
JP5190877B2 (en) * 2008-04-04 2013-04-24 ハイモ株式会社 How to suppress paper defects
JP5584505B2 (en) * 2010-03-30 2014-09-03 日本製紙株式会社 Paper manufacturing method
US9404223B2 (en) 2012-02-01 2016-08-02 Basf Se Process for the manufacture of paper and paperboard
CN104145060B (en) 2012-03-01 2017-02-22 巴斯夫欧洲公司 Process for the manufacture of paper and paperboard
US10113270B2 (en) 2013-01-11 2018-10-30 Basf Se Process for the manufacture of paper and paperboard
JP6929899B2 (en) * 2018-06-15 2021-09-01 栗田工業株式会社 Manufacturing method of paper and paper board
WO2019239819A1 (en) * 2018-06-15 2019-12-19 栗田工業株式会社 Paper and paperboard production method

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5512868A (en) * 1978-07-12 1980-01-29 Mitsubishi Paper Mills Ltd Production of neutral paper
EP0017353B2 (en) * 1979-03-28 1992-04-29 Ciba Specialty Chemicals Water Treatments Limited Production of paper and paper board
DE3541163A1 (en) * 1985-11-21 1987-05-27 Basf Ag METHOD FOR PRODUCING PAPER AND CARDBOARD
GB8602121D0 (en) * 1986-01-29 1986-03-05 Allied Colloids Ltd Paper & paper board
US4795531A (en) * 1987-09-22 1989-01-03 Nalco Chemical Company Method for dewatering paper
JPH0192498A (en) * 1987-10-02 1989-04-11 Hokuetsu Paper Mills Ltd Production of neutral paper

Also Published As

Publication number Publication date
EP0335575A2 (en) 1989-10-04
JPH0529719B2 (en) 1993-05-06
EP0335575B1 (en) 1993-03-10
KR890014836A (en) 1989-10-25
NO891301L (en) 1989-09-29
ES2053980T3 (en) 1994-08-01
FI97307B (en) 1996-08-15
CA1322435C (en) 1993-09-28
JPH05239800A (en) 1993-09-17
ES2053980T5 (en) 2000-12-16
EP0335575A3 (en) 1990-12-12
FI97307C (en) 1997-11-11
FI891465A (en) 1989-09-29
AU3174989A (en) 1989-09-28
NO174724B (en) 1994-03-14
DE68905208T3 (en) 2001-02-15
FI891465A0 (en) 1989-03-28
DE68905208D1 (en) 1993-04-15
JPH026683A (en) 1990-01-10
DE68905208T2 (en) 1993-10-07
EP0335575B2 (en) 2000-08-23
AU613465B2 (en) 1991-08-01
NO891301D0 (en) 1989-03-28

Similar Documents

Publication Publication Date Title
KR960002733B1 (en) Production of paper and paper board
US5501774A (en) Production of filled paper
CA1168404A (en) Production of paper and board
US4969976A (en) Pulp dewatering process
AU2008213009B2 (en) Manufacture of paper or paperboard
CA2624998C (en) Method for the production of paper, cardboard and card
EP1792010B1 (en) Method for the production of paper, paperboard and cardboard
US5695609A (en) Process for producing paper
EP2334871B1 (en) Method for manufacturing paper, cardboard and paperboard using endo-beta-1,4 glucanases as dewatering means
EP0357574B1 (en) A process for the production of paper
JP2003512541A (en) Cation-modified polysaccharide
EP0255933A2 (en) Dry strength resin of amino/aldehyde acid colloid with acrylamide polymer, process for the production thereof and paper produced therefrom
CA2405649C (en) Papermaking furnish comprising solventless cationic polymer retention aid combined with phenolic resin and polyethylene oxide
EP0700473B2 (en) Process for producing paper
AU761303B2 (en) An acid colloid in a microparticle system used in papermaking
US6719881B1 (en) Acid colloid in a microparticle system used in papermaking
EP1047834A1 (en) Silica-acid colloid blend in a microparticle system used in papermaking
EP0203817A1 (en) Polymeric compositions
FI108060B (en) Production of filled paper
WO2005124020A1 (en) Method for manufacturing paper or similar

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
G160 Decision to publish patent application
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20100225

Year of fee payment: 15

EXPY Expiration of term