KR101223952B1 - Manufacturing method of cellulose film and cellulose film using the sane - Google Patents

Manufacturing method of cellulose film and cellulose film using the sane Download PDF

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KR101223952B1
KR101223952B1 KR1020110086461A KR20110086461A KR101223952B1 KR 101223952 B1 KR101223952 B1 KR 101223952B1 KR 1020110086461 A KR1020110086461 A KR 1020110086461A KR 20110086461 A KR20110086461 A KR 20110086461A KR 101223952 B1 KR101223952 B1 KR 101223952B1
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cellulose
film
alcohol
weight
solution
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KR1020110086461A
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Korean (ko)
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신은주
이양헌
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동아대학교 산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Moulding By Coating Moulds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

PURPOSE: A manufacturing method of a cellulose film is provided to restrain excessive swelling phenomenon by reducing affinity with N-methylmorpholine-N-oxide, thereby obtaining a cellulose film with a uniform shape. CONSTITUTION: A manufacturing method of a cellulose film comprises: a step of manufacturing a cellulose solution by dissolving 4-6 parts by weight of cellulose based on 100 parts by weight of N-methylmorpholine-N-oxide; a casting step of spreading the cellulose solution on a planar glass at 80-100 °C to mold a film shape; and a solidification step of soaking the planar glass in an alcohol-based solidification solution at 20-25 °C. [Reference numerals] (S1) Cellulose solution manufacturing step; (S2) Casting step; (S3) Solidification step

Description

셀룰로오스 필름의 제조방법 및 이 방법에 의해 제조된 셀룰로오스 필름{MANUFACTURING METHOD OF CELLULOSE FILM AND CELLULOSE FILM USING THE SANE}Manufacturing method of cellulose film and cellulose film manufactured by this method {MANUFACTURING METHOD OF CELLULOSE FILM AND CELLULOSE FILM USING THE SANE}

본 발명은 셀룰로오스 필름의 제조방법 및 이 방법에 의해 제조된 셀룰로오스 필름에 관한 것으로, 구체적으로는 물을 대신하여 알코올계 용제를 응고액으로 사용함으로써, 균일한 형태의 셀롤로오스 필름을 제조할 수 있도록 하는 셀룰로오스 필름의 제조방법 및 이 방법에 의해 제조된 셀룰로오스 필름에 관한 것이다.
The present invention relates to a method for producing a cellulose film and a cellulose film prepared by the method. Specifically, by using an alcohol-based solvent as a coagulating solution in place of water, a uniform cellulose film can be produced. It relates to a method for producing a cellulose film and a cellulose film produced by the method.

일반적으로 셀룰로오스(cellulose)는 고등식물 세포벽의 주성분이며, 목질부의 대부분을 차지하는 다당류로써 섬유소(纖維素)라고도 한다. 상기와 같은 셀룰로오스는 자연계에서 석탄에 이어 다량으로 존재하는 유기화합물로, 가장 보편적이고 오래된 산업 원료 중 하나이며, 화학 약품에 대한 저항성도 강하고 미생물에도 침식당하지 않기 때문에 종이나 방직용 섬유로 널리 이용되고 있다.
In general, cellulose (cellulose) is the main component of the cell wall of higher plants, and is a polysaccharide that occupies most of the wood part, also called fibrin. The cellulose is an organic compound that exists in a large amount after natural coal, and is one of the most common and old industrial raw materials, and is widely used as a paper or textile fiber because it is resistant to chemicals and is not eroded by microorganisms. have.

관련 선행기술로써, 대한민국 공개특허공보 제10-2002-0080821호, 제10-2003-0079053호, 제10-2003-0083984호, 제10-2008-0111953호, 제10-2010-0001572호 및 대한민국 등록특허공보 제10-0575388호 등에는 상기와 같은 셀룰로오스를 이용하여 섬유를 제조하는 방법이 다양하게 공개되어 있다.
As related prior arts, Korean Patent Publication Nos. 10-2002-0080821, 10-2003-0079053, 10-2003-0083984, 10-2008-0111953, 10-2010-0001572, and Korea Korean Patent Publication No. 10-0575388 discloses various methods for producing fibers using cellulose as described above.

상기 선행기술들을 살펴보면, 셀룰로오스를 이용한 섬유의 제조시, 용매로써 NMMO(N-methylmorpholine-N-oxide)가 사용되고, 응고액으로써 물이 사용됨을 알 수 있다.Looking at the prior art, it can be seen that in the preparation of fibers using cellulose, NMMO (N-methylmorpholine-N-oxide) is used as a solvent, and water is used as a coagulation solution.

상기 NMMO는 셀룰로오스를 직접 용해시킬 수 있는 용매로써 1969년도부터 셀룰로오스의 용매로 사용되기 시작하였으며, 물을 응고액으로 한 건습식 방사법으로 셀룰로오스 섬유률 제조하는 기술은 1980년도에 영국의 courtaulds사에서 을 개발되어 현재까지 널리 이용되고 있다.
NMMO is a solvent capable of directly dissolving cellulose, and has been used as a solvent for cellulose since 1969. The technique for producing cellulose fiber by dry-wet spinning method using water coagulation liquid was developed by courtaulds of England in 1980. It is developed and widely used to date.

하지만, 셀룰로오스 섬유가 아닌, 셀룰로오스 필름의 제조시, 물을 응고액으로 적용할 경우에는 응고과정에서 필름 내부에 큰 기공이 생길 뿐만 아니라, 균일한 형태의 필름을 얻기 어려운 문제점이 있었다.However, in the manufacture of cellulose films, not cellulose fibers, when water is applied as a coagulation solution, not only large pores are generated inside the film during the coagulation process, but also it is difficult to obtain a uniform film.

그 이유는 물을 응고액으로 사용함에 따라 필름의 내,외간의 응고속도 차이로 인해 기공이 생기며, 물과 NMMO와의 친화력이 높아 과도한 팽윤 현상이 발생하기 때문이다.
The reason is that as water is used as the coagulation solution, pores are generated due to the difference in the coagulation speed between the inside and outside of the film, and the high affinity between water and NMMO causes excessive swelling.

즉, 종래와 같이 물을 응고액으로 사용할 경우, 셀룰로오스 섬유를 제조할 수는 있으나, 셀룰로오스 필름을 제조하는데는 한계가 있었다.
That is, when water is used as a coagulation liquid as in the prior art, cellulose fibers can be produced, but there is a limit in producing a cellulose film.

(특허 문헌 1) : 대한민국 공개특허공보 제10-2002-0080821호 "셀룰로오스 섬유의 제조방법"(Patent Document 1) Republic of Korea Patent Publication No. 10-2002-0080821 "Method for producing cellulose fiber" (특허 문헌 2) : 대한민국 공개특허공보 제10-2003-0079053호 "셀룰로오즈 섬유 및 그 제조 방법"(Patent Document 2) Republic of Korea Patent Publication No. 10-2003-0079053 "Cellulose fibers and a method of manufacturing the same" (특허 문헌 3) : 대한민국 공개특허공보 제10-2003-0083984호 "셀룰로오즈 섬유 및 그 제조 방법"(Patent Document 3) Korean Unexamined Patent Publication No. 10-2003-0083984 "Cellulose Fibers and a Manufacturing Method Thereof" (특허 문헌 4) : 대한민국 공개특허공보 제10-2008-0111953호 "고균질 셀룰로오스 용액 및 이로 부터 제조된 섬유"(Patent Document 4) Republic of Korea Patent Publication No. 10-2008-0111953 "Highly homogeneous cellulose solution and fibers produced therefrom" (특허 문헌 5) : 대한민국 공개특허공보 제10-2010-0001572호 "셀룰로오스계 섬유 및 그 제조방법"(Patent Document 5) Republic of Korea Patent Publication No. 10-2010-0001572 "Cellulose-based fiber and its manufacturing method" (특허 문헌 6) : 대한민국 등록특허공보 제10-0575388호 "셀룰로오스계 복합섬유, 그 제조방법 및 이를 포함하는 타이어 코드"(Patent Document 6) Republic of Korea Patent Publication No. 10-0575388 "Cellulose-based composite fiber, its manufacturing method and tire cord comprising the same"

상술한 바와 같은 문제점을 해결하기 위한 본 발명은, 물을 대신하여 알코올계 용제를 응고액으로 사용함으로써, NMMO와의 친화력을 낮춰 과도한 팽윤 현상을 억제할 수 있으며, 이로 인해 균일한 형태의 셀롤로오스 필름을 제조할 수 있도록 함을 과제로 한다.
The present invention for solving the problems described above, by using an alcohol solvent as a coagulant in place of water, it is possible to reduce the affinity with NMMO to suppress excessive swelling phenomenon, thereby uniform cellulose Let it be a subject to be able to manufacture a film.

아울러, 상기 알콜계 용제에 소량의 물을 첨가, 조절함으로써, 고밀도 셀롤로오스 필름에서부터 기공도가 큰 다공성 셀룰로오스 필름에 이르기까지 다양한 종류의 필름을 제조할 수 있도록 함을 다른 과제로 한다.
In addition, by adding and adjusting a small amount of water to the alcohol-based solvent, another object of the present invention is to be able to produce a variety of films ranging from a high density cellulose film to a porous cellulose film having a large porosity.

또한, 필름 캐스팅(casting)공정에서 나이프 에지(knife edge)법을 적용함으로써, 0.01 ~ 0.03mm 두께의 얇은 필름의 제조가 가능하도록 함을 또 다른 과제로 한다.
In addition, by applying the knife edge (knife edge) method in the film casting (casting) process, to make another thin film of 0.01 ~ 0.03mm thickness is another problem.

본 발명은 셀룰로오스 필름의 제조방법에 있어서, NMMO(N-methylmorpholine-N-oxide) 100 중량부에 대하여, 셀룰로오스 4 ~ 6 중량부를 용해시켜 셀룰로오스 용액을 제조하는 셀룰로오스 용액 제조단계(S1); The present invention provides a method for producing a cellulose film, the cellulose solution manufacturing step of preparing a cellulose solution by dissolving 4 to 6 parts by weight of cellulose relative to 100 parts by weight of NMMO (N-methylmorpholine-N-oxide) (S1);

상기 제조된 셀룰로오스 용액을 80 ~ 100℃로 예열된 평면유리에 나이프(knife)로 펼쳐 필름형태로 성형하는 캐스팅 단계(S2); 및 Casting the prepared cellulose solution into a flat film preheated to 80 to 100 ° C. with a knife to form a film (S2); And

상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 20 ~ 25℃의 알콜계 응고액에 침지시켜 응고시키는 응고단계(S3);를 포함하여 구성되는 셀룰로오스 필름의 제조방법 및 이 방법에 의해 제조된 셀룰로오스 필름을 과제의 해결 수단으로 한다.
A solidification step (S3) of immersing the flat glass having the cellulose solution unfolded on the upper surface thereof in an alcoholic coagulant solution at 20 to 25 ° C. (S3); The solution is to solve the problem.

한편, 상기 알콜계 응고액은, 메틸알콜, 에틸알콜 또는 부틸알콜 중에서 1 종 이상을 선택,병용하여 사용할 수 있다.
On the other hand, the alcohol-based coagulant can be used by selecting one or more of methyl alcohol, ethyl alcohol or butyl alcohol in combination.

또한, 상기 알콜계 응고액은, 메틸알콜, 에틸알콜 또는 부틸알콜 중에서 1 종 이상을 선택, 병용한 알콜계 응고액 80 ~ 90 중량%와 물 10 ~ 20 중량%를 혼합한 것을 사용할 수도 있다.
The alcohol-based coagulant may be a mixture of 80 to 90% by weight of alcohol-based coagulant and 10 to 20% by weight of water.

한편, 상기 NMMO는, 1수화물(NMMOㆍ1H2O) 상태로 농축시킨 것을 사용하는 것이 바람직하다.
On the other hand, the NMMO is, it is preferable to use the concentrated state monohydrate (NMMO and 1H 2 O).

본 발명에 의하면, 물을 대신하여 알코올계 용제를 응고액으로 사용함으로써, NMMO와의 친화력을 낮춰 과도한 팽윤 현상을 억제할 수 있고, 이로 인해 균일한 형태의 셀롤로오스 필름을 제조할 수 있으며, 아울러, 상기 알콜계 용제에 소량의 물을 첨가, 조절함으로써, 고밀도 셀롤로오스 필름에서부터 기공도가 큰 다공성 셀룰로오스 필름에 이르기까지 다양한 종류의 필름을 제조할 수 있을 뿐만 아니라 필름 캐스팅(casting)공정에서 나이프 에지(knife edge)법을 적용함으로써, 0.01 ~ 0.03mm 두께의 얇은 필름의 제조가 가능하도록 하는 효과가 있다.
According to the present invention, by using an alcohol-based solvent as a coagulant instead of water, the affinity with NMMO can be lowered to suppress excessive swelling, thereby producing a uniform cellulose film. By adding and adjusting a small amount of water to the alcoholic solvent, various types of films can be manufactured, ranging from high density cellulose films to porous cellulose films having large porosities, as well as knives in the film casting process. By applying the edge (knife edge) method, there is an effect to enable the production of a thin film of 0.01 ~ 0.03mm thickness.

도 1은 본 발명의 일 실시예에 따른 셀룰로오스 필름의 제조방법의 흐름도.
도 2는 본 발명의 실시예 및 비교예에 따른 셀룰로오스 필름의 형태 사진
도 3 및 4는 본 발명의 실시예 및 비교예에 따른 셀룰로오스 필름의 SEM 사진1 is a flow chart of a manufacturing method of a cellulose film according to an embodiment of the present invention.
Figure 2 is a photograph of the shape of the cellulose film according to the Examples and Comparative Examples of the present invention
3 and 4 are SEM pictures of the cellulose film according to the Examples and Comparative Examples of the present invention

상기의 효과를 달성하기 위한 본 발명은 셀룰로오스 필름의 제조방법 및 이 방법에 의해 제조된 셀룰로오스 필름에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.
The present invention for achieving the above effect relates to a method for producing a cellulose film and a cellulose film produced by the method, and only parts necessary for understanding the technical configuration of the present invention are described, and the description of the other parts is described in the present invention. It should be noted that it will be omitted so as not to distract the subject matter.

이하, 본 발명에 따른 셀룰로오스 필름의 제조방법을 상세히 설명하면 다음과 같다.
Hereinafter, the manufacturing method of the cellulose film according to the present invention will be described in detail.

본 발명은 셀룰로오스 필름의 제조방법에 있어서,The present invention is a method for producing a cellulose film,

NMMO(N-methylmorpholine-N-oxide) 100 중량부에 대하여, 셀룰로오스 4 ~ 6 중량부를 용해시켜 셀룰로오스 용액을 제조하는 셀룰로오스 용액 제조단계(S1);A cellulose solution preparing step (S1) of dissolving 4 to 6 parts by weight of cellulose to 100 parts by weight of NMMO (N-methylmorpholine-N-oxide) to prepare a cellulose solution;

상기 제조된 셀룰로오스 용액을 80 ~ 100℃로 예열된 평면유리에 나이프(knife)로 펼쳐 필름형태로 성형하는 캐스팅 단계(S2); 및 Casting the prepared cellulose solution into a flat film preheated to 80 to 100 ° C. with a knife to form a film (S2); And

상부면에 셀룰로오스 용액이 펼쳐진 평면유리를 20 ~ 25℃의 알콜계 응고액에 침지시켜 응고시키는 응고단계(S3);를 포함하여 구성된다.
It comprises a; solidification step (S3) to immerse the flat glass, the cellulose solution is spread on the upper surface in the alcohol-based coagulation solution of 20 ~ 25 ℃.

상기 셀룰로오스 용액 제조 단계(S1)에서 사용되는 NMMO는, 셀룰로오스를 용해시키기 위한 용매로써, 셀룰로오스가 1수화물(NMMOㆍ1H2O)에 가장 쉽게 되는 것을 고려하여, 통상 2.5수화물(NMMOㆍ2.5H2O) 상태로 판매되는 NMMO를 1수화물(NMMOㆍ1H2O)로 농축시켜 사용하는 것이 바람직하다.The NMMO used in the cellulose solution preparation step (S1) is a solvent for dissolving cellulose, and is generally 2.5 hydrate (NMMO · 2.5H 2 ) in consideration that cellulose is most easily in monohydrate (NMMO · 1H 2 O). It is preferable to concentrate NMMO sold in O) state into monohydrate (NMMO.1H 2 O).

한편, 상기 2.5수화물 상태의 NMMO를 1수화물로 농축시키기 위해 다양한 방법을 적용할 수 있으나, 본 발명에서는 일 실시예로써, NMMO 수용액 100 중량부에 대하여, 항산화제를 2 중량부 혼합한 후, 90℃를 유지시킨 상태에서 12시간 농축시켜 1수화물 상태의 NMMO를 제조하였다.
On the other hand, various methods may be applied to concentrate the NMMO in the 2.5-hydrate state to monohydrate, but in one embodiment of the present invention, with respect to 100 parts by weight of NMMO aqueous solution, after mixing 2 parts by weight of antioxidant, 90 NMMO in monohydrate was prepared by concentrating for 12 hours while maintaining the temperature.

아울러, 상기 셀룰로오스 용액 제조 단계(S1)에서 사용되는 셀롤로오스는 100% 셀롤로오스 펄프를 사용하며, NMMO 100 중량부에 대하여, 셀룰로오스 4 ~ 6 중량부를 용해시켜 셀롤로오스 용액을 제조하는데, 상기 셀룰로오스의 함량이 4 중량부 미만일 경우, 필름으로의 성형시 셀룰로오스의 고유 물성을 발현하지 못할 우려가 있으며, 6 중량부를 초과할 경우, 셀룰로오스 중 일부가 미용해될 우려가 있다.In addition, the cellulose used in the cellulose solution manufacturing step (S1) is 100% cellulose pulp, and based on 100 parts by weight of NMMO, by dissolving 4 to 6 parts by weight of cellulose to prepare a cellulose solution, When the content of the cellulose is less than 4 parts by weight, there is a fear that the intrinsic physical properties of the cellulose when forming into a film may not be expressed, and when more than 6 parts by weight, some of the cellulose may be undissolved.

이때, 상기 셀룰로오스의 용해 시, 별도의 냉각장치를 부착하여 온도를 조절함으로써, 상기 NMMO를 1수화물 상태로 계속 유지시키는 것이 바람직하다.
At this time, when dissolving the cellulose, by attaching a separate cooling device to adjust the temperature, it is preferable to keep the NMMO in the monohydrate state.

상기 캐스팅 단계(S2)는, 상기 제조된 셀룰로오스 용액을 필름형태로 성형하는 단계로써, 상기와 같이 나이프(knife)를 이용하여 몰드에 펼쳐 성형하는 나이프 에지(knife edge)법을 사용함으로써, 두께 0.01mm ~ 0.03mm의 필름을 제조할 수 있게 된다.The casting step (S2) is a step of forming the prepared cellulose solution in the form of a film, by using a knife edge (knife edge) method of spreading the mold by using a knife (knife) as described above, thickness 0.01 It is possible to produce a film of mm ~ 0.03mm.

이때, 몰드를 이루는 상기 평면유리는 셀룰로오스 용액의 두께조절 등 성형 용이성을 고려하여 80 ~ 100℃로 예열되도록 하는 것이 바람직하다.
At this time, the flat glass forming the mold is preferably to be preheated to 80 ~ 100 ℃ in consideration of the ease of molding, such as the thickness control of the cellulose solution.

상기 응고단계(S3)는, 상기 필름형태로 성형된 셀룰로오스 용액을 응고시키는 단계로써, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 응고액에 침지하여 응고시키는데, 응고효율을 고려하여 실온(20 ~ 25℃) 상태의 알콜계 응고액에 침지시켜 응고시킨다.The solidification step (S3) is a step of solidifying the cellulose solution formed in the form of the film, and solidified by immersing the flat glass on which the cellulose solution is spread on the top surface by dipping into a coagulation liquid, considering the coagulation efficiency at room temperature (20 ~ It is immersed in the alcohol-based coagulating solution of 25 ℃) solidification.

여기서, 사용되는 상기 알콜계 응고액은 메틸알콜, 에틸알콜 또는 부틸알콜 중에서 1 종 이상을 선택,병용하여 사용할 수 있으며, 또한, 메틸알콜, 에틸알콜 또는 부틸알콜 중에서 1 종 이상을 선택, 병용한 알콜계 응고액 80 ~ 90 중량%와 물 10 ~ 20 중량%를 혼합한 것을 사용할 수도 있다.Here, the alcohol-based coagulant to be used may be used in combination of one or more selected from methyl alcohol, ethyl alcohol or butyl alcohol, and at least one of methyl alcohol, ethyl alcohol or butyl alcohol may be used in combination. It is also possible to use a mixture of 80% to 90% by weight of alcohol-based coagulant and 10% to 20% by weight of water.

즉, 물보다 분자량이 크고 NMMO와의 친화력이 낮은 알콜계 응고액을 사용함으로써, 필름의 과도한 팽윤 현상을 억제할 수 있으며, 이로 인해 균일한 형태의 셀롤로오스 필름을 제조할 수 있을 뿐만 아니라 소량의 물을 첨가, 조절하여 응고속도를 함으로써, 고밀도 셀롤로오스 필름에서부터 기공도가 큰 다공성 셀룰로오스 필름에 이르기까지 다양한 종류의 필름을 제조할 수 있게 된다.In other words, by using an alcohol-based coagulant having a higher molecular weight than water and a low affinity with NMMO, it is possible to suppress excessive swelling of the film, thereby producing a uniform form of a cellulose film as well as a small amount of By adding and adjusting water to increase the solidification rate, various kinds of films can be manufactured, ranging from high density cellulose films to porous cellulose films having high porosity.

한편, 상기 알콜계 응고액은 응고가 진행되는 동안 1시간 간격으로 새로운 알콜계 응고액으로 교환해주는 것이 바람직하며, 응고가 완료된 셀롤로오스 필름은 증류수로 세척한 후, 실온에서 자연 건조한다.
On the other hand, the alcohol-based coagulant is preferably exchanged with a new alcohol-based coagulant at an interval of 1 hour while the coagulation is in progress, the completed cellulose film is washed with distilled water, and then naturally dried at room temperature.

이하 본 발명의 구성을 실시예를 통해 상세히 설명하면 다음과 같으며, 본 발명의 구성은 반드시 하기의 실시예에 의해서만 한정되는 것은 아니다.
Hereinafter, the configuration of the present invention will be described in detail with reference to the following Examples, the configuration of the present invention is not necessarily limited to the following examples.

1. 셀롤로오스 필름의 제조
1. Preparation of Cellulose Film

(실시예 1)(Example 1)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 메틸알콜을 사용하였다.
In this case, methyl alcohol was used as the alcohol-based coagulant.

(실시예 2)(Example 2)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 메틸알콜 90 중량%에 물 10 중량%를 혼합하여 사용하였다.
In this case, the alcohol-based coagulant was used by mixing 10% by weight of water with 90% by weight of methyl alcohol.

(실시예 3)(Example 3)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 메틸알콜 80 중량%에 물 20 중량%를 혼합하여 사용하였다.
At this time, the alcohol-based coagulant was used by mixing 20% by weight of water with 80% by weight of methyl alcohol.

(실시예 4)(Example 4)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 에틸알콜을 사용하였다.
At this time, ethyl alcohol was used as the alcohol-based coagulant.

(실시예 5)(Example 5)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 에틸알콜 90 중량%에 물 10 중량%를 혼합하여 사용하였다.
In this case, the alcohol-based coagulant was used by mixing 10% by weight of water with 90% by weight of ethyl alcohol.

(실시예 6)(Example 6)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 에틸알콜 80 중량%에 물 20 중량%를 혼합하여 사용하였다.
In this case, the alcohol-based coagulant was used by mixing 20% by weight of water with 80% by weight of ethyl alcohol.

(실시예 7)(Example 7)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 부틸알콜을 사용하였다.
In this case, butyl alcohol was used as the alcohol-based coagulant.

(실시예 8)(Example 8)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 부틸알콜 90 중량%에 물 10 중량%를 혼합하여 사용하였다.
At this time, the alcohol-based coagulant was used by mixing 10% by weight of water with 90% by weight of butyl alcohol.

(실시예 9)(Example 9)

1수화물(NMMOㆍ1H2O) 상태로 농축시킨 NMMO 100 중량부에 대하여, 100% 셀룰로오스 펄프 5 중량부를 용해시켜 셀룰로오스 용액을 제조하고, 상기 제조된 셀룰로오스 용액을 90℃로 예열된 평면유리에 나이프로 펼쳐 0.03mm 두께의 필름형태로 성형하고, 상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 23℃의 알콜계 응고액에 침지시켜 필름을 응고시킨 후, 세척, 건조하여 셀롤로오스 필름을 제조하였다.To 100 parts by weight of NMMO concentrated in monohydrate (NMMO.1H 2 O), 5 parts by weight of 100% cellulose pulp was dissolved to prepare a cellulose solution, and the prepared cellulose solution was knives in flat glass preheated to 90 ° C. Unfolded into a film shape of 0.03mm thick, cellulose solution on the top surface of the flat glass is immersed in the alcohol-based coagulation solution at 23 ℃ solidified film, washed, dried to prepare a cellulose film. .

이때, 상기 알콜계 응고액은, 부틸알콜 80 중량%에 물 20 중량%를 혼합하여 사용하였다.
At this time, the alcohol-based coagulant was used by mixing 20% by weight of water with 80% by weight of butyl alcohol.

(비교예 1)(Comparative Example 1)

실시예 1과 동일한 방법으로 셀롤로오스 필름을 제조하되, 알콜계 응고액이 아닌, 물 100 중량%를 응고액으로 사용하였다.
A cellulose film was prepared in the same manner as in Example 1, except that 100% by weight of water was used as the coagulant, not an alcoholic coagulant.

2. 셀롤로오스 필름의 분석2. Analysis of Cellulose Films

필름 형태 사진 촬영: 필름의 전체 형태를 살펴보기 위하여 일반 사진기로 촬영하였다.Film-type photographing: A general camera was photographed to examine the overall form of the film.

주사전자현미경(Scanning Electron Microscope: SEM) 사진 촬영: 필름의 내부 및 표면 상태를 알아보기 위하여, 필름을 액체질소로 얼린 후 절단한 단면과 표면을 백금으로 진공 증착 한 후, 단면은 2000배, 표면은 1000배의 배율로 주사전자현미경(FE-SEM: JSM 6700F Jeol, Japan)으로 확대 촬영하였다.
Scanning Electron Microscope (SEM) Photographing: In order to examine the internal and surface condition of the film, the film was frozen with liquid nitrogen, and the cut section and the surface were vacuum deposited with platinum, and then the cross section was 2000 times. Was photographed with a scanning electron microscope (FE-SEM: JSM 6700F Jeol, Japan) at a magnification of 1000 times.

알콜계 응고액을 단독으로 사용한 실시예 1, 4, 7과, 알콜계 응고액에 물을 첨가한 실시예 2, 3, 5, 6, 8, 9 및 물을 단독으로 사용한 비교예 1에 따른 셀룰로오스 필름의 주사전자현미경(scanning electron microscope:SEM)으로 촬영하여 그 결과를 도 3, 4(본 발명의 실시예 및 비교예에 따른 셀룰로오스 필름의 SEM사진)에 나타내었다.
Examples 1, 4, 7 using alcohol-based coagulants alone, and Examples 2, 3, 5, 6, 8, 9, in which water was added to alcohol-based coagulants, and Comparative Example 1 using water alone Scanning electron microscope (SEM) of the cellulose film was taken and the results are shown in FIGS. 3 and 4 (SEM photographs of the cellulose film according to the Examples and Comparative Examples of the present invention).

즉, 도 3, 4에 도시된 바와 같이, 실시예 1 내지 9에 따른 셀룰로오스 필름의 경우, 균일한 형태를 가짐을 알 수 있었다.That is, as shown in Figures 3 and 4, in the case of the cellulose film according to Examples 1 to 9, it can be seen that it has a uniform form.

아울러, 실시예 1, 4, 7의 경우에는 고밀도의 셀룰로오스 필름을 획득할 수 있었으며, 실시예 2, 3, 5, 6, 8, 9에서는 물의 첨가량에 따라 기공도를 조절할 수 있었음을 알 수 있다.In addition, in the case of Examples 1, 4, 7, it was possible to obtain a high density cellulose film, and in Examples 2, 3, 5, 6, 8, 9 it can be seen that the porosity was adjusted according to the amount of water added. .

한편, 비교예1의 경우, 과도한 팽윤에 의해 불균일한 형태 및 큰 기공이 형성되어 필름으로써 사용할 수 없음을 알 수 있었다.
On the other hand, in the case of Comparative Example 1, it was found that a non-uniform form and large pores were formed due to excessive swelling and thus could not be used as a film.

상기에서 설명 드린 바와 같이 본 발명에 따른 셀룰로오스 필름의 제조방법 및 이 방법에 의해 제조된 셀룰로오스 필름은 상기의 실시예를 통해 그 우수성이 입증되었지만 본 발명은 상기의 구성에 의해서만 반드시 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능하다.
As described above, the manufacturing method of the cellulose film according to the present invention and the cellulose film prepared by the method have been proved excellent in the above examples, but the present invention is not necessarily limited only to the above configuration. Various substitutions, modifications, and changes may be made without departing from the spirit of the present invention.

S1 : 셀룰로오스 용액 제조단계
S2 : 캐스팅 단계
S3 : 응고단계S1: cellulose solution manufacturing step
S2: casting step
S3: solidification stage

Claims (5)

셀룰로오스 필름의 제조방법에 있어서,
NMMO(N-methylmorpholine-N-oxide) 100 중량부에 대하여, 셀룰로오스 4 ~ 6 중량부를 용해시켜 셀룰로오스 용액을 제조하는 셀룰로오스 용액 제조단계(S1);
상기 제조된 셀룰로오스 용액을 80 ~ 100℃로 예열된 평면유리에 나이프(knife)로 펼쳐 필름형태로 성형하는 캐스팅 단계(S2); 및
상부면에 셀룰로오스 용액이 펼쳐진 상기 평면유리를 20 ~ 25℃의 알콜계 응고액에 침지시켜 응고시키는 응고단계(S3);를 포함하여 구성되는 것을 특징으로 하는 셀룰로오스 필름의 제조방법
In the manufacturing method of a cellulose film,
A cellulose solution preparing step (S1) of dissolving 4 to 6 parts by weight of cellulose to 100 parts by weight of NMMO (N-methylmorpholine-N-oxide) to prepare a cellulose solution;
Casting the prepared cellulose solution into a flat film preheated to 80 to 100 ° C. with a knife to form a film (S2); And
A solidification step (S3) of immersing the flat glass having the cellulose solution unfolded on the upper surface thereof in an alcoholic coagulant solution at 20-25 ° C .;
제 1항에 있어서,
상기 알콜계 응고액은,
메틸알콜, 에틸알콜 또는 부틸알콜 중에서 1 종 이상을 선택,병용하여 사용하는 것을 특징으로 하는 셀룰로오스 필름의 제조방법
The method of claim 1,
The alcohol-based coagulation liquid,
Method for producing a cellulose film, characterized in that at least one selected from methyl alcohol, ethyl alcohol or butyl alcohol, used in combination
제 1항에 있어서,
상기 알콜계 응고액은,
메틸알콜, 에틸알콜 또는 부틸알콜 중에서 1 종 이상을 선택, 병용한 알콜계 응고액 80 ~ 90 중량%와 물 10 ~ 20 중량%를 혼합한 것을 사용하는 것을 특징으로 하는 셀룰로오스 필름의 제조방법
The method of claim 1,
The alcohol-based coagulation liquid,
Method for producing a cellulose film, characterized in that at least one selected from methyl alcohol, ethyl alcohol or butyl alcohol, mixed with 80 to 90% by weight of alcohol-based coagulant and 10 to 20% by weight of water
제 1항에 있어서,
상기 NMMO는,
1수화물(NMMOㆍ1H2O) 상태로 농축시킨 것을 사용하는 것을 특징으로 하는 셀룰로오스 필름의 제조방법
The method of claim 1,
The NMMO,
Method for producing a cellulose film, characterized in that concentrated to the monohydrate (NMMO.1H 2 O) state
제 1항 내지 제 4항 중 어느 한 항에 따른 제조방법에 의해 제조된 셀룰로오스 필름
Cellulose film prepared by the manufacturing method according to any one of claims 1 to 4.
KR1020110086461A 2011-08-29 2011-08-29 Manufacturing method of cellulose film and cellulose film using the sane KR101223952B1 (en)

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JPH1052630A (en) 1996-05-15 1998-02-24 Akzo Nobel Nv Manufacture of stable and storage cellulose dialysis membrane and cellulose dialysis membrane
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KR20220151458A (en) * 2021-05-06 2022-11-15 군산대학교산학협력단 Method for preparing biodegradable plastic from Ulva sp. and biodegradable plastic prepared by the same
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