KR100358600B1 - Process for preparing polyamide mat film - Google Patents

Process for preparing polyamide mat film Download PDF

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KR100358600B1
KR100358600B1 KR1019950039333A KR19950039333A KR100358600B1 KR 100358600 B1 KR100358600 B1 KR 100358600B1 KR 1019950039333 A KR1019950039333 A KR 1019950039333A KR 19950039333 A KR19950039333 A KR 19950039333A KR 100358600 B1 KR100358600 B1 KR 100358600B1
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film
polyamide
weight
parts
average particle
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KR970027157A (en
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문경철
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주식회사 코오롱
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • 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)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

PURPOSE: Provided is a process for preparing polyamide mat film having improved mat property and writing-erasing capability with a pencil and a drawing ink adequate, which can be used as packaging materials including industrial packaging, food packaging and book covering. CONSTITUTION: The process for preparing polyamide mat film by using the resin polymerized with aliphatic diamines, dicarbonic acids and caprolactam, comprises the steps of blending 80 to 10 parts by weight of polyamide chips containing 1 to 5 wt% of SiO2 having average particle diameter of 1 to 10 micrometers and 20 to 90 parts by weights of polyamide chips containing no inorganic particles, and extruding them. The polyamide film obtained by the process has improved haze, light transmission and writing-erasing capability.

Description

폴리아미드 매트 필름의 제조방법Method for producing polyamide matte film

본 발명은 나일론 매트 필름의 제조방법에 관한 것으로, 연필 및 제도잉크에 필기성 및 소거성이 있으면서, 포장재로서 산업용 및 각종 스낵류 등의 식품포장이나 책표지, 쇼핑백 적층용 등에 사용될 수 있는 나일론 매트필름의 제조방법에 관한 것이다.The present invention relates to a method for producing a nylon matte film, which has a writing and erasing property on pencils and drafting inks, and can be used as a packaging material for food packaging, book covers, shopping bags, etc. It relates to a manufacturing method of.

종래, 합성수지에 필기성을 부여하기 위하여, 모래분사(Sand blust)법이나 엠보스(emboss)법 등에 의해 표면을 조면화(粗面化)하는 방법과 CaCO3, SiO2, TiO2등과 같은 무기 및 유기입자인 매트제를 지지필름상에 도포하는 방법, 그리고 유기용제에 의한 표면 에칭(etching)법 등이 알려져 있다.Conventionally, in order to give handwriting property to synthetic resins, a method of roughening the surface by sand spraying, embossing, etc., and inorganic materials such as CaCO 3 , SiO 2 , TiO 2, and the like And a method of applying a mat agent, which is an organic particle, onto a support film, and a method of surface etching with an organic solvent.

그러나 상기 방법중 모래분사법은 연필에 대한 필기성은 우수하나 수성잉크에 대한 필기성이 부족하고 투사기 마모 및 불균일한 조면화층이 형성되며, 에칭법은 필름의 조면화 정도가 약하여 필기성이 부족하고 인체에 유해한 유기용제를 사용해야 하는 문제점이 있으며, 매트제를 도포하는 방법은 매트층이 후가공이나 제품 사용시 지지필름으로부터 박리될 우려가 있을 뿐 아니라, 특히 고온다습한 조건하에서 매트필름을 서로 겹쳐둔 채로 방치하면 매트필름이 주위의 수분을 흡수하게 되어 블로킹(Blocking)현상이 발생되는 문제점 등이 있었다.However, the sand spray method of the above method is excellent in writing to pencil, but lacks in writing to water-based ink, and wear of a projector and a non-uniform roughening layer are formed, and etching method is insufficient to roughen the film. In addition, there is a problem in that it is necessary to use organic solvents that are harmful to the human body, and the method of applying the mat agent may not only cause the mat layer to be peeled off from the support film during post-processing or use of the product, but also in that the mat film is stacked If left unattended, the matte film absorbs the surrounding moisture and has a problem of blocking.

또한 무광택성이 부족하여 태양광이나 전등 아래서 포장의 내용을 관찰하거나 필름이 적충되어 있는 책을 볼 때 필름 표면의 광택때문에 무늬나 문자의 형태를 정확하게 파악하기 어려울 뿐만 아니라 눈에 상당한 피로감을 주는 등 문제점이 있어 포장재로서 사용하기에는 부적당한 점이 있었다.In addition, the lack of matte properties makes it difficult to accurately identify patterns and text shapes due to the gloss of the film when observing the contents of the package under sunlight or electric light, or when reading a book with film on it. There was a problem that it was unsuitable for use as a packaging material.

본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위하여 안출된 것으로, 필름 내부의 SiO2입자의 분포 밀도가 증가하면 빛의 투과성이 저하되므로 필름의 흐림도(Haze)가 증가하며 SiO2입자를 배합한 중합체 혼합물로부터 제조된 필름 표면에 만들어진 요철에 의하여 연필 및 제도잉크에 대한 필기성을 나타내면서 동시에 포장재로서도 사용할 수 있는 폴리아미드 매트필름의 제조방법에 관한 것이다.The present invention has been made to solve the problems of the prior art as described above, the increase in the distribution density of the SiO 2 particles in the film increases the transmittance of light, so the haze of the film increases and the SiO 2 particles The present invention relates to a method for producing a polyamide matte film that can be used as a packaging material while exhibiting writeability to pencils and drawing inks by irregularities made on the film surface prepared from the blended polymer mixture.

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

먼저 지방족 또는 방향족 디아민, 디카르본산, 카프로락탐 등으로 부터 중합되는 폴리아미드에 평균입경이 1∼10㎛이고 흡유량이 100ml/100g~200ml/100g인 실리카와 200ml/100g∼300ml/100g인 실리카를 1:5∼5:1 중량비로 혼합하여 1∼5중량%되도록 첨가한다.First, a polyamide polymerized from aliphatic or aromatic diamine, dicarboxylic acid, caprolactam and the like is silica having an average particle diameter of 1 to 10 µm and oil absorption of 100 ml / 100 g to 200 ml / 100 g and silica of 200 ml / 100 g to 300 ml / 100 g. The mixture is added in an amount of 1 to 5% by weight, mixed at a weight ratio of 1: 5 to 5: 1.

흡유량이 낮은 실리카를 많이 사용하면 제도 잉크에 대한 필기성이 불량하고 소량 첨가하면 제도잉크에 대한 소거성이 나쁘게 된다.When a large amount of low oil absorption silica is used, the writing ability for the drawing ink is poor, and when a small amount is added, the erasing ability for the drawing ink is bad.

입자의 평균 입경이 1㎛미만이면 필름 형성후 요철 형성이 작아서 필기성이 불량해지고 10㎛를 초과하는 경우에는 조대입자의 존재확률이 높아져 필름 성형시 파단이 증가될 수 있다.If the average particle diameter of the particles is less than 1㎛ the uneven formation after forming the film is poor because the poor writeability, if the exceeding 10㎛ may increase the probability of the presence of coarse particles may increase the fracture when forming the film.

더욱 바람직하게는 5∼10㎛이 적합하다.More preferably, 5-10 micrometers is suitable.

첨가량에 있어서는 1 중량% 미만일 경우 그 첨가량이 너무 적어 충분한 무광택성을 부여할 수 없으며 5 중량%를 초과할 경우에는 입자의 응집 확률이 높아지고 필름강도 저하 현상이 발생하여 필름 성형시 파단이 많이 발생하게 된다.If the amount is less than 1% by weight, the added amount is too small to provide sufficient matteness. If the amount is more than 5% by weight, the probability of agglomeration of particles increases and film strength decreases, causing a lot of breakage during film forming. do.

상기 방법에 의해 SiO2를 함유한 폴리아미드 칩 80∼10 중량%와 무기 입자를 합유하지 않은 폴리아미드 수지 20∼90 중량%를 블렌딩(blending)하여 260℃로 용융하고 환상다이로 압출하여 수냉한 후, 미연신 시트를 만들고 이를 튜블라 방식 동시 이축연신으로 연신하여 필름을 제조하고 이 연신 필름을 열처리 및 오븐에서 140∼120℃ 범위로 열고정을 한 다음 필름을 제조한다.By the above method, 80 to 10% by weight of polyamide chips containing SiO 2 and 20 to 90% by weight of polyamide resins not containing inorganic particles are blended, melted to 260 ° C, extruded into an annular die, and cooled by water. Thereafter, an unstretched sheet is made and stretched in a tubular simultaneous biaxial stretching to prepare a film, and the stretched film is heat-set and heat-set in the range of 140 to 120 ° C. in an oven to prepare a film.

블렌딩시 기존 첨가제의 분산성 및 블렌딩 시간에 대한 영향은 없으며 블렌딩 비가 낮을 경우 SiO2입자의 분산성이 감소할 가능성이 커지며 블렌딩 비가 높을 경우는 슬립(Slip)성 증가로 와인더(Winder)에 폼(form)빠짐 현상이 나타날 수 있다.When blending, there is no influence on the dispersibility and blending time of the existing additives. If the blending ratio is low, the dispersibility of SiO 2 particles is likely to decrease. The form may be missing.

블렌딩 비는 20∼90%범위가 가능하며 더욱 좋기로는 40∼60% 이다.Blending ratios can range from 20 to 90%, more preferably 40 to 60%.

상기 제조방법에 의하여 제조된 무광택 필름은 흐림도(Haze)가 65% 이상이고 표면의 광택도가 40% 이하이며 전광선 투과율이 90% 이상인 필름으로서 각종 식품포장재, 책표지, 쇼핑백용에 사용시 강열한 빛 아래서도 포장물의 무늬나 문자가 선명하게 보이며 눈의 피로감을 덜어줄 뿐 아니라 포장물에 고급스러움을 더해주는 장점이 있다.Matte film produced by the above manufacturing method has a haze of 65% or more, the gloss of the surface of 40% or less, the total light transmittance of 90% or more as a film used in various food packaging materials, book covers, shopping bags intense light The patterns and letters on the package can be seen clearly from below, which not only reduces eye fatigue but also adds luxury to the package.

이하, 본 발명을 실시예를 통하여 더욱 구체적으로 설명하겠는바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

실시예에 언급된 물성치는 다음 방법에 의해서 측정되었다.The physical properties mentioned in the examples were measured by the following method.

1)흐림도(Haze)%1) Haze%

JIS-K 6714로 측정.Measured by JIS-K 6714.

2)광택도(%)2) Glossiness (%)

ASTM D 2457에 표시된 입사각, 광을 받아들이는 각 모두 60°의 측정법에 의해 측정.The angle of incidence indicated in ASTM D 2457 and the angle of accepting light were all measured by a 60 ° measurement method.

3)전광선 투과율(%)3) Total light transmittance (%)

JIS-K 6714로 측정.Measured by JIS-K 6714.

4)필기성 및 소거성 시험 : 2H 연필로 필기한 후 육안으로 판별.4) Handwriting and Erasability Test: After writing with 2H pencil, visually discriminated.

5)블로킹 형상 JIS-K 6842에 의거 시험.5) Blocking shape Tested according to JIS-K 6842.

실시예 1)Example 1

흡유량이 100g당 100∼200㎖인 실리카와 200∼300㎖인 실리카를 1:1 중량비로 혼합한 평균입경 1㎛인 SiO2입자를ε-카프로락탐에 대해서 5중량% 첨가하여 중합한 나일론 칩 30중량부와 통상의 나일론 칩 70중량부를 혼합하여 260℃에서 용융하고 환상 다이로 압출하여 수냉한 후, 미연신 시트를 만들고 이를 튜블라 방식 동시 이축연신으로 종 .횡 3.0배 연신하여 필름을 제조하고, 이 연신필름을 열처리 롤 및 오븐에서 140∼120℃ 범위로 열고정을 한 다음 완성된 필름을 제조하였다.Nylon chip polymerized by adding 5 wt% of ε -caprolactam to SiO 2 particles having an average particle diameter of 1 μm in which oil absorption amount was mixed with 100 to 200 ml of silica and 200 to 300 ml of silica in a 1: 1 weight ratio. After mixing the parts by weight and 70 parts by weight of conventional nylon chips, melted at 260 ℃, extruded into an annular die and cooled by water, to make an unstretched sheet and stretch it longitudinally and horizontally 3.0 times in a tubular method simultaneous biaxial stretching to prepare a film , The stretched film was heat-set in the range of 140 to 120 ° C. in a heat treatment roll and an oven to prepare a finished film.

실시예2)Example 2

평균입경 5㎛인 SiO2를 3중량% 사용한 것을 제외하고는 실시예1과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 1 except that 3 wt% of SiO 2 having an average particle diameter of 5 μm was used.

실시예3)Example 3

평균입경 5㎛인 SiO2가 5중량%함유된 나일론 70중량부와 통상의 나일론 칩 30중량부를 사용한 것을 제외하고는 실시예1과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that 70 parts by weight of 5 wt% of SiO 2 having an average particle diameter of 5 μm and 30 parts by weight of a normal nylon chip were used.

실시예4)Example 4

평균입경 10㎛인 SiO2를 1중량% 사용한 것을 제외하고는 실시예3과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 3 except that 1 wt% of SiO 2 having an average particle diameter of 10 μm was used.

실시예5)Example 5

평균입경 10㎛인 SiO2가 3중량% 함유된 나일론 칩 50중량부와 통상의 나일론 칩 50중량부를 사용한 것을 제외하고는 실시예1과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that 50 parts by weight of nylon chips containing 3 wt% of SiO 2 having an average particle diameter of 50 μm and 50 parts by weight of ordinary nylon chips were used.

비교예1)Comparative Example 1)

평균입경 0.5㎛인 SiO2를 0.5중량% 사용한 것을 제외하고는 실시예 1과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 1 except that 0.5 wt% of SiO 2 having an average particle diameter of 0.5 μm was used.

비교예2)Comparative Example 2)

평균입경 1㎛인 SiO2를 0.5중량% 사용한 것을 제외하고는 실시예1과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 1 except that 0.5 wt% of SiO 2 having an average particle diameter of 1 μm was used.

비교예3)Comparative Example 3)

평균입경 l5㎛인 SiO2를 0.1중량% 사용한 것을 제외하고는 실시예3과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 3 except that 0.1 wt% of SiO 2 having an average particle diameter of 5 μm was used.

비교예4)Comparative Example 4)

평균입경 l5㎛인 SiO2를 7중량% 사용한 것을 제외하고는 실시예3과 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 3, except that 7 wt% of SiO 2 having an average particle diameter of 5 μm was used.

비교예5)Comparative Example 5)

평균입경 0.1㎛인 SiO2를 8중량% 사용한 것을 제외하고는 실시예5와 동일하게 실시하여 필름을 제조하였다.A film was prepared in the same manner as in Example 5 except that 8 wt% of SiO 2 having an average particle diameter of 0.1 μm was used.

(표-1)Table-1

Claims (1)

본 발명은 지방족 디아민, 디카르본산, 카프로락탐으로 중합되는 수지로 폴리아미드6 매트 필름을 제조함에 있어서, 평균입경이 1∼10㎛인 SiO2를 1∼5wt% 함유한 폴리아미드 칩 80∼10중량부와 무기입자가 함유되지 않은 폴리아미드 칩 20∼90중량부 블랜딩(blending)하여 압출, 제작하는 것을 특징으로 하는 폴리아미드6 매트필름의 제조방법.The present invention relates to a polyamide chip containing from 1 to 5 wt% of SiO 2 having an average particle diameter of 1 to 10 µm in preparing a polyamide 6 mat film from a resin polymerized with aliphatic diamine, dicarboxylic acid, and caprolactam. 20 to 90 parts by weight of a polyamide chip containing no parts by weight and no inorganic particles is blended and extruded to produce a polyamide 6 mat film.
KR1019950039333A 1995-11-02 1995-11-02 Process for preparing polyamide mat film KR100358600B1 (en)

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KR20150116500A (en) * 2014-04-07 2015-10-16 주식회사 효성 polyamide matte film consists of multi-layer structure having improved printing property and method for preparing the same

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KR20030033624A (en) * 2001-10-24 2003-05-01 주식회사 효성 Polyamide Composition And Film Using Masterbatch And Preparation Thereof

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US3763082A (en) * 1972-05-31 1973-10-02 Milprint Inc Nylon packaging film with thermally developable slip
JPH01275659A (en) * 1988-04-28 1989-11-06 Du Pont Mitsui Polychem Co Ltd Packaging polyamide film
JPH02133434A (en) * 1988-11-14 1990-05-22 Asahi Chem Ind Co Ltd Highly slippery polyamide film and its production
JPH0335059A (en) * 1989-06-30 1991-02-15 Hitachi Chem Co Ltd Paste composition and semiconductor device using the same
JPH0532892A (en) * 1991-07-31 1993-02-09 Hitachi Chem Co Ltd Paste composition and semiconductor device made therefrom
KR960022832A (en) * 1994-12-12 1996-07-18 이웅열 Polyamide film composition
KR960022840A (en) * 1994-12-22 1996-07-18 이웅열 Process for producing polyamide film

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US3763082A (en) * 1972-05-31 1973-10-02 Milprint Inc Nylon packaging film with thermally developable slip
JPH01275659A (en) * 1988-04-28 1989-11-06 Du Pont Mitsui Polychem Co Ltd Packaging polyamide film
JPH02133434A (en) * 1988-11-14 1990-05-22 Asahi Chem Ind Co Ltd Highly slippery polyamide film and its production
JPH0335059A (en) * 1989-06-30 1991-02-15 Hitachi Chem Co Ltd Paste composition and semiconductor device using the same
JPH0532892A (en) * 1991-07-31 1993-02-09 Hitachi Chem Co Ltd Paste composition and semiconductor device made therefrom
KR960022832A (en) * 1994-12-12 1996-07-18 이웅열 Polyamide film composition
KR960022840A (en) * 1994-12-22 1996-07-18 이웅열 Process for producing polyamide film

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Publication number Priority date Publication date Assignee Title
KR20150116500A (en) * 2014-04-07 2015-10-16 주식회사 효성 polyamide matte film consists of multi-layer structure having improved printing property and method for preparing the same
KR101629078B1 (en) 2014-04-07 2016-06-10 주식회사 효성 polyamide matte film consists of multi-layer structure having improved printing property and method for preparing the same

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