KR100454111B1 - Preparation method of nylon film by primary coating solution comprising aqueous urethane resin and aqueous aziridine curing agent, and drying, drawing to at least one direction and heat treating the coated one - Google Patents
Preparation method of nylon film by primary coating solution comprising aqueous urethane resin and aqueous aziridine curing agent, and drying, drawing to at least one direction and heat treating the coated one Download PDFInfo
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- KR100454111B1 KR100454111B1 KR1019970000634A KR19970000634A KR100454111B1 KR 100454111 B1 KR100454111 B1 KR 100454111B1 KR 1019970000634 A KR1019970000634 A KR 1019970000634A KR 19970000634 A KR19970000634 A KR 19970000634A KR 100454111 B1 KR100454111 B1 KR 100454111B1
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Abstract
Description
제 1 도는 나일론 필름의 제조 공정도이다.1 is a manufacturing process diagram of a nylon film.
*도면의 주요 부분에 대한 부호의 설명** Description of the symbols for the main parts of the drawings *
1. 칩 호포,2. 압출기,Chip hopper, 2. Extruder,
3. 환형다이,4. 냉각조,Annular die, 4. Cooling Tank,
5. 미연신 튜브,6. 그라비아코터,5. Unstretched tube, 6. Gravure Coater,
7. 적외선 히터가 설치된 건조부,8. 링 가열기,7. Drying unit with infrared heater, 8. Ring burner,
9. 연신필름,10. 열처리부9. Stretched film, 10. Heat treatment
본 발명은 이접착성(易接着性) 나일론 필름의 제조방법, 더 자세하게는 접착제 또는 인쇄잉크와 나일론 필름과의 접착력을 강화시켜 내수성, 내열성이 우수한 이접착성 나일론 필름의 제조방법에 관한 것이다.The present invention relates to a method for producing an easy-adhesive nylon film, and more particularly, to a method for producing an easy-adhesive nylon film having excellent water resistance and heat resistance by enhancing adhesion between an adhesive or printing ink and a nylon film.
일반적으로 나일론 필름은 뛰어난 기계적 성질과 열적 성질 및 가스 차단성이 우수해서 식품 포장용 재료로서 널리 사용되고 있는데, 특히 뛰어난 내마모성, 내충격성, 내굴곡피로성 및 내한성 등과 같이 포장재에 요구되는 실용 강도가 우수하여 파대 및 핀홀에 저항성이 크게 요구되는 액상 식품 포장 분야를 비롯해서 식품 포장용에 신뢰성이 매우 높다.In general, nylon film is widely used as a food packaging material because of its excellent mechanical properties, thermal properties, and gas barrier properties. In particular, nylon film has excellent practical strength required for packaging materials such as excellent wear resistance, impact resistance, bending fatigue resistance, and cold resistance. And it is very reliable for food packaging, including the liquid food packaging field that requires a great resistance to pinholes.
최근에는 젖은 면을 그대로 포장하는 특수 포장 용도로서 생면용 나일론필름이 많이 쓰임에 따라 강력한 내수성과 내열성을 필요로 한다.Recently, as a special packaging for packaging wet noodles as they are, raw nylon film is used a lot and needs strong water resistance and heat resistance.
그런데 실제적으로 나일론 필름은 식품 포장재의 표면 재료로서 이면에 인쇄를 하고 열봉함을 위한 라미네이트제를 합지하여 사용하는 경우가 대부분이다. 이때는 필름의 품질로서 기본적인 포장재의 실용 강도 이외에 인쇄 및 라미네이트 가공 적성이 요구된다. 특히 레토르트 제품에서는 라미네이트제와 기질의 필름을 합지, 제대한 후 내용물을 충진하여 진공 살균 포장하게 되고, 게다가 소비자들이 비등수로 레토르트 제품을 처리하므로 인쇄 및 라미네이트제와의 가공 적성이 우수해야 할 뿐만 아니라 강력한 내수성과 내열성이 필요하다. 만일 내수성과 내열성이 약할 경우 보일링이나 기타 가공 도중에 라미네이트제와 기질이 필름 사이에 박리가 쉽게 일어난다.By the way, in practice, nylon film is mostly used as a surface material of food packaging material printed on the back side and laminated with a laminate for heat sealing. At this time, in addition to the practical strength of the basic packaging material as the quality of the film, printing and laminate processing aptitudes are required. In particular, in retort products, the laminate and the film of the substrate are laminated and filled in the vacuum sterilization package after filling the contents, and in addition, the retort product is processed by boiling water, so that the aptitude for printing and laminating should be excellent. But strong water resistance and heat resistance are required. If the water resistance and heat resistance are weak, the laminate and the substrate easily peel off between the film during the boiling or other processing.
인쇄 및 라미네이트제와 가공적성 및 접착력을 향상시키기 위해서는 나일론 필름 제조 공정 후에 내수성과 내열성을 보유하고 있는 수지를 도포하여 피막을 형성시켜 주는 공정을 행하는데, 우레탄 수지나 아크릴 수지를 주로 사용하여 앙카코팅(Anchor Coating) 또는 프라이머리코팅(Primary Coating)과 같은 오프라인코팅(Off-Line coating)을 많이 행하고 있다.In order to improve processability and adhesion with printing and laminating agents, a process of forming a film by coating a resin having water resistance and heat resistance after the nylon film manufacturing process is carried out. There are many off-line coatings such as Anchor Coating or Primary Coating.
그러나 위와 같은 오프 라인 코팅 방법으로 코팅을 실시할 경우에는 나일론 필름 제조 공정 이외에 코팅공정을 한 단계 더 거쳐야 하기 때문에 원가의 부담 외에도 에너지의 낭비를 초래할 뿐만 아니라 1μm 이하의 박막을 균일하게 도포하기는 어렵다.However, when the coating is performed by the above-described off-line coating method, the coating process must be performed in addition to the nylon film manufacturing process, which leads to waste of energy in addition to the cost burden, and it is difficult to uniformly apply a thin film of 1 μm or less. .
본 발명자들은 꾸준한 연구와 실험을 한 결과 나일론 필름 제조공정 중에 복합코팅액을 도포할 경우 상기의 문제점을 개선할 수 있음을 알게 되었다.The present inventors have found that the above problems can be improved by applying the composite coating liquid during the nylon film manufacturing process as a result of steady research and experiment.
본 발명의 목적은 접착제 또는 인쇄잉크와 나일론 필름과의 접착력을 강화시켜 내열성과 내수성이 우수한 이접착성 나일론 필름의 제조방법을 제공하는데 있다.An object of the present invention is to provide a method for producing an easily adhesive nylon film having excellent heat resistance and water resistance by strengthening the adhesive force between the adhesive or the printing ink and the nylon film.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명은 나일론의 미연신 원단에 수성 우레탄수지, 수성 아지리딘 경화제를 함유하는 코팅액을 도포한후, 건조, 연신, 열처리를 하는 이접착성 나일론 필름의 제조방법에 관한 것으로서, 슬립성을 좋게 하기 위하여 SiO2미립자를 0.01~2 중량부 첨가할 수 있다.The present invention relates to a method for producing an easily-adhesive nylon film which is dried, stretched and heat treated after applying a coating solution containing an aqueous urethane resin and an aqueous aziridine curing agent to an unstretched fabric of nylon. In order to add 0.01 to 2 parts by weight of SiO 2 fine particles.
본 발명에서 사용하는 수성 우레탄 수지의 분자량은 10,000~200,000이 좋다. 분자량이 10,000 이하일 경우에는 내수성, 내용제성, 내마모성이 불량하며, 분자량이 200,000 이상일 경우에는 수용화가 어렵기 때문이다. 수성 이지리딘 경화제는 0.01~5 중량부를 첨가하는 것이 바람직하다.As for the molecular weight of the aqueous urethane resin used by this invention, 10,000-200,000 are good. This is because when the molecular weight is 10,000 or less, water resistance, solvent resistance, and abrasion resistance are poor, and when the molecular weight is 200,000 or more, it is difficult to receive water. It is preferable to add 0.01-5 weight part of aqueous irilidine hardening | curing agents.
상기 제조방법에서 도포되는 수지는 여러 종류가 있겠으나, 본 발명의 수성 우레탄 수지가 내열성과 내수성이 우수하여 레토르트용 제품에 적당할 뿐 아니라, 인쇄 잉크 또는 드라이라미네이션을 실시할 때 우레탄 프라이머리 코팅제와의 접착력이 좋으므로 바람직하다.There are many kinds of resin to be applied in the manufacturing method, but the aqueous urethane resin of the present invention is excellent in heat resistance and water resistance, suitable for retort products, and when the printing ink or dry lamination is carried out with a urethane primary coating agent Since the adhesive force of is good, it is preferable.
한편 드라이라미네이션 제품의 내열성과 내수성을 향상시키기 위해서는 프라이머리 코팅층이 열경화성 필름을 형성해야 좋은 물성을 가지게 되는 바, 본 발명에서는 관능기로서 카르복실기를 가지고 있는 수성 우레탄 수지를 선정하여 수성 아지리딘 경화제와 가교를 이루어 견고한 막을 형성하며, 후의 인쇄 잉크나 드라이라미네이션시의 접착제와 접착력을 강화시켜 준다.Meanwhile, in order to improve heat resistance and water resistance of the dry lamination product, the primary coating layer must have a thermosetting film to have good physical properties. In the present invention, an aqueous urethane resin having a carboxyl group as a functional group is selected to form an aqueous aziridine curing agent and a crosslinking agent. It forms a firm film and strengthens adhesives and adhesives in later printing inks or dry laminations.
카르복실기가 함유된 수성 우레탄 수지와 수성 아지리딘 경화제와의 반응은 하기 도식 1과 같다.The reaction between the aqueous urethane resin containing a carboxyl group and the aqueous aziridine curing agent is shown in Scheme 1 below.
[도식 1]Scheme 1
상기 화학 반응에서 형성된 -NH는 후의 우레탄형 결합제를 사용한 인쇄 잉크나 접착제의 -NCO와 반응하여 강한 화학결합을 형성하므로 내수성과 내열성이 더욱 강화될 수 있다.The -NH formed in the chemical reaction reacts with -NCO of a printing ink or an adhesive using a later urethane-type binder to form a strong chemical bond, thereby further enhancing water resistance and heat resistance.
또한 수성 수지의 레벨링성과 건조성을 극대화시키기 위하여 도면 1과 같이 건조부에 적외선 히터를 사용하여 견고한 피막 형성을 극대화하였다.In addition, in order to maximize the leveling and drying properties of the aqueous resin, as shown in FIG.
이접착성 나일론필름의 제조방법을 다시 한번 설명하면 도면 1에 나타낸 바와 같이, 다이(Die)에서 용융압출, 급냉각 고화하여 얻어진 미연신 원단에 그라비아 코터를 이용하여 수지를 코팅, 건조하고 연신함으로써 나일론과 코팅된 수지가 동시에 연신되어 박막의 프라이머리 코팅층이 나일론 필름 표면 위에서 형성되는 이접착성 나일론 필름이 제조된다.Referring to the method of manufacturing the easily-adhesive nylon film once again, as shown in Fig. 1, by using a gravure coater on the unstretched fabric obtained by melt-extruding and solidifying in a die, the resin is coated, dried and stretched. Nylon and coated resin are simultaneously drawn to produce an easily-adhesive nylon film in which a thin primary coating layer is formed on the nylon film surface.
이접착성 나일론 필름 표면위에 형성된 수지의 피막은 후의 인쇄공정이나 다른 필름과의 합지 공정시 온도가 40℃이상이 되면 나일론 필름에 코팅된 수지의 접착성이 회복되어 인쇄 잉크나, 접착제 코팅시 강한 결합력을 부여하여 주기 때문에 가공 후에 높은 내수성과 내열성을 나타내 준다.When the temperature of the resin film formed on the surface of the easily-adhesive nylon film is 40 ° C. or higher during the subsequent printing process or lamination process with other films, the adhesiveness of the resin coated on the nylon film is restored, which is strong when printing ink or adhesive coating. It gives high bonding and heat resistance after processing.
상기의 제조공정을 거쳐서 제조되는 이접착성 나일론 필름은 우레탄 수지나 아크릴 수지만을 이용하여 오프라인 코팅을 하는 정규 나일론 필름에 비교하여, 수성 우레탄 수지에 수성 아지리딘 경화제를 혼합하여 도포함으로써 접착제나 인쇄잉크와 나일론 필름과의 접착력을 강화시켜 내수성과 내열성이 보다 우수하다. 또한 환경 문제를 유발시킬 수 있는 고가의 유기용제를 사용하지 않고 수성수지를 사용함으로써 발화의 위험성이 줄어들 뿐 아니라 리사이클링 공정도 필요하지 않게 된다.The easily-adhesive nylon film produced through the above-described manufacturing process is compared with a regular nylon film which is coated offline using only urethane resin or acrylic resin, and is mixed with an aqueous aziridine curing agent and applied to an aqueous urethane resin to apply an adhesive or printing. Strengthen adhesion between ink and nylon film, so it is more water and heat resistant. In addition, the use of aqueous resins without the use of expensive organic solvents, which can cause environmental problems, reduces the risk of ignition and eliminates the need for a recycling process.
다음은 본 발명의 효과를 증명하기 위한 실시예이지만 본 발명이 여기에 한정되는 것은 아니다.The following is an example for demonstrating the effects of the present invention, but the present invention is not limited thereto.
[실시예 1]Example 1
아래의 조성으로 코팅액을 조액하여 하기의 실험을 실시하였다.The following experiment was performed by preparing a coating solution with the following composition.
호모믹서(Homomixer)를 이용하여 SiO2미립자 1 중량부를 증류수 90 중량부에 첨가한 후에 2,000 rpm 정도에서 1시간 교반을 실시하고 1시간 정도 방치한다. (이 액을 1액이라 칭한다)After adding 1 part by weight of SiO 2 fine particles to 90 parts by weight of distilled water using a homomixer, the mixture was stirred at about 2,000 rpm for 1 hour and left for about 1 hour. (We call this liquid one liquid)
이 1액에 분자량 30,000의 수성 우레탄 수지 10 중량부를 첨부하여 거품이 발생하지 않도록 주의하면서 교반기를 이용하여 1,000 rpm 정도에서 20분간 교반을 실시한 후 수성 아지리딘 경화제 2 중량부를 넣어 10분 교반하고 30분 정도 방치하여 조액을 완료한다.10 parts by weight of an aqueous urethane resin having a molecular weight of 30,000 was added to this 1 solution, and the mixture was stirred at about 1,000 rpm using a stirrer for 20 minutes while being careful not to generate bubbles. Then, 2 parts by weight of an aqueous aziridine curing agent was added and stirred for 10 minutes. Leave about to complete the liquid.
한편 관형상 다이(Die)으로 부터 나일론-6 레진(융점 270℃)을 용융 압출하여 급냉각 고화하여 얻어진 튜브 상의 미연신 원단에 그라비아 코터를 이용하여 조제된 조액을 1μm정도 도포(Dry Pick-up)한 후 80℃에서 적외선 히터가 설치된 건조부에서 건조하여, 가로세로 동시에 3×3배 2축 연신을 행하여 도포층이 0.1μm 정도 두께를 갖는 균일한 막을 얻을 수가 있었으며, 이 복함 필름을 열처리 공정을 거치게 한후 양끝 부분을 절단기로 절개하여 2개의 다른 코어에 감았다. 이때 제조된 나일론 필름의 두께는 25μm였다.Meanwhile, the crude liquid prepared by using a gravure coater was applied to the unstretched fabric on the tube obtained by melt extruding the nylon-6 resin (melting point 270 ° C) from the tubular die to solidify and quench it (Dry Pick-up) After drying at 80 ° C. in a drying unit equipped with an infrared heater, a 3 × 3 times biaxial stretching was carried out simultaneously in length and width to obtain a uniform film having a thickness of about 0.1 μm. After passing through the both ends were cut with a cutter and wound on two different cores. At this time, the thickness of the prepared nylon film was 25μm.
위에서 연신 후의 코팅된 피막의 균일성을 조사하기 위하여 부위 별 접촉각을 측정하여 표 1에 정리하였다.In order to investigate the uniformity of the coated film after stretching from above, the contact angle for each site was measured and summarized in Table 1.
또한 위의 공정을 거쳐 제조된 이접착 나일론 필름의 우레탄 결합제형 잉크와 라미네이트지와의 접착력을 조사하기 위하여 다음과 같은 실험을 실시하였다.In addition, the following experiments were carried out to investigate the adhesion between the urethane binder ink and the laminated paper of the easily-adhesive nylon film prepared through the above process.
이접착 나일론 필름에 2μm 두께로 백색과 적색의 잉크를 사용하여 인쇄를 행한 후에 적색은 50℃에서 백색은 80℃의 열풍 오븐에서 건조를 실시한 후 1일간 상온에서 숙성(aging)을 시키고, 다음과 같은 방법으로 드라이 라미네이션(Dry Lamination)을 실시하고 접착강도를 조사하여 표 2 에 정리하여 보았다.After printing using white and red ink with 2μm thickness on easy-adhesive nylon film, red is dried in hot air oven at 50 ℃ and 80 ℃ in aging at room temperature for 1 day. Dry Lamination was carried out in the same way and the adhesive strength was examined and summarized in Table 2.
드라이라미네이션의 접착제는 2액형 우레탄(도요모토사 adcote)을 사용하였으며 그라비아 코터를 이용하여 도포량을 5g/㎡으로 조정하여 80℃에서 30초간 건조한 후에 두께 50μm 폴리에틸렌 필름과 70℃에서 드라이라미네이션을 실시하였다.Dry lamination adhesive was used as two-component urethane (adapted by Toyomoto Co., Ltd.), and the coating amount was adjusted to 5 g /
이때에 접착제를 분산시킨 유기용제는 에틸 아세테이트를 사용하였으며, 고형분은 30%로 조절하였다.At this time, the organic solvent in which the adhesive was dispersed was used ethyl acetate, the solid content was adjusted to 30%.
또한 무지 부분의 박리강도를 조사하기 위하여 인쇄를 행하지 않은 부분을 위와 같은 방법으로 드라이라미네이션을 실시하여 박리강도를 표 2 에 , 기타 물성은 표 3 에 정리하였다.In addition, dry lamination was carried out in the same manner as above to investigate the peel strength of the plain portion, and the peel strength is summarized in Table 2 and other physical properties in Table 3.
- 조성 -- Furtherance -
우레탄 수지 : 10 중량부 (제네카)Urethane resin: 10 parts by weight (Geneca)
증류수 : 90 증량부Distilled water: 90 parts increase
아지리딘 경화제 : 2 중량부 (제네카)Aziridine hardener: 2 parts by weight (Geneca)
SiO2미립자 : 1 중량부SiO 2 fine particles: 1 part by weight
[실시예 2]Example 2
아래와 같은 조성을 실시예 1과 같은 방법으로 실험을 실시하여 결과를 표 1, 2, 3에 정리하였다.The experiment was carried out in the same manner as in Example 1, and the results are summarized in Tables 1, 2, and 3.
- 조성 -- Furtherance -
우레탄 수지 : 15 중량부 (DIC 화학)Urethane resin: 15 parts by weight (DIC Chemical)
증류수 : 80 증량부Distilled water: 80 parts by weight
아지리딘 경화제 : 3 중량부 (제네카)Aziridine hardener: 3 parts by weight (Geneca)
SiO2미립자 : 0.5 중량부SiO 2 fine particles: 0.5 parts by weight
[실시예 3]Example 3
아래와 같은 조성을 실시예 1과 같은 방법으로 실험을 실시하여 결과를 표 1, 2, 3에 정리하여 보았다.The following composition was carried out in the same manner as in Example 1, and the results were summarized in Tables 1, 2, and 3.
- 조성 -- Furtherance -
우레탄 수지 : 10 중량부 (다이이찌 화학)Urethane resin: 10 parts by weight (Daiichi Chemical)
증류수 : 100 증량부Distilled Water: 100 parts by weight
아지리딘 경화제 : 제네카Aziridine Hardener: Geneca
SiO2미립자 : 1 중량부SiO 2 fine particles: 1 part by weight
[실시예 4]Example 4
아래와 같은 조성을 실시예 1과 같은 방법으로 실험을 실시하여 결과를 표 1, 2, 3에 정리하여 보았다.The following composition was carried out in the same manner as in Example 1, and the results were summarized in Tables 1, 2, and 3.
- 조성 -- Furtherance -
우레탄 수지 : 9 중량부 (다께다 수지)Urethane resin: 9 parts by weight (resin)
증류수 : 100 증량부Distilled Water: 100 parts by weight
아지리딘 경화제 : 1 증량부Aziridine hardener: 1 portion
SiO2미립자 : 1 중량부SiO 2 fine particles: 1 part by weight
[비교예 1]Comparative Example 1
관형상 다이(Die)로 부터 나일론-6 레진(융점 270℃)을 용융 압출하여 급냉각 고화하여 얻어진 튜브형상의 미연신 원단을 가로세로 동시에 3×3 배로 2축 연신을 행하여, 열처리공정을 거친 후, 이 필름의 양끝 부분을 절단기로 절개하여, 2개의 다른 코어에 감았다. 이를 정규 나일론필름이라 칭하며 이의 물성표를 표 3 에 정리하여 보았다.Tube-shaped unstretched fabric obtained by melt extruding nylon-6 resin (melting point 270 ° C) from a tubular die and solidified by quenching was biaxially stretched 3 × 3 times at the same time in a vertical and horizontal manner, followed by a heat treatment process. Both ends of this film were cut with a cutter and wound around two different cores. This is called a regular nylon film and its physical properties are summarized in Table 3.
이 정규 나일론필름을 실시예 1의 방법으로 우레탄형 결합제의 적색 잉크와 백색 잉크를 그라비아 코터 2μm로 인쇄를 행한 후 라미네이트지와 실시예 1과 같은 방법을 드라이라미네이션을 실시하여, 박리강도를 측정하여 표 2 에 정리하였다.The regular nylon film was printed with the red ink and the white ink of the urethane binder by the method of Example 1 with a gravure coater 2μm, and then laminated with the laminate and the same method as in Example 1 to measure the peel strength. It summarized in Table 2.
[비교예 2]Comparative Example 2
SiO2미립자를 증류수에 첨가한 후에 호모믹서를 이용하여 2000 rpm 에서 1시간 정도 교반을 거친 후에 1시간 정도 방치한 후에, 이에 우레탄 수지를 넣은 후에 교반기를 이용하여 1000 rpm 정도에서 30분 교반한 후에 실시예 1과 같은 방법으로 실험을 실시하여 표 1, 2, 3에 정리하여 보았다.After adding SiO 2 fine particles to distilled water, after stirring for 1 hour at 2000 rpm using a homomixer, the mixture was left for about 1 hour, and after adding urethane resin thereto, the mixture was stirred at 1000 rpm for 30 minutes. The experiment was carried out in the same manner as in Example 1 and summarized in Tables 1, 2, and 3.
- 조성 -- Furtherance -
우레탄 수지 : 10 중량부 (제네카)Urethane resin: 10 parts by weight (Geneca)
증류수 : 90 중량부Distilled water: 90 parts by weight
SiO2미립자 : 1 중량부SiO 2 fine particles: 1 part by weight
[비교예 3]Comparative Example 3
아래의 조성을 비교예 2와 같은 방법으로 실험을 실시하여 표 1, 2, 3에 정리하여 보았다.The following compositions were tested in the same manner as in Comparative Example 2 and summarized in Tables 1, 2, and 3.
- 조성 -- Furtherance -
우레탄 수지 : 15 중량부 (DIC 화학)Urethane resin: 15 parts by weight (DIC Chemical)
증류수 : 80 중량부Distilled water: 80 parts by weight
SiO2미립자 : 0.5 중량부SiO 2 fine particles: 0.5 parts by weight
[표 1]TABLE 1
이접착성 나일론 필름의 접촉각 (필름 표면의 피막 균일성 나타냄)Contact angle of easy-adhesive nylon film (shows film uniformity on film surface)
[표 2]TABLE 2
비등수의 처리 전후의 드라이라미네이션 샘플의 박리강도Peel strength of dry lamination sample before and after boiling water treatment
단위 : (g.f/15mm)Unit: (g.f / 15mm)
* : 우레탄계 결합제를 사용한 잉크 도포 후에 드라이라미네이션 실시*: Dry lamination after ink application using urethane binder
** : 니트로 셀룰로오스계 결합제를 사용한 잉크 도포 후에 드라이라미네이션 실시**: Dry lamination after ink application using nitrocellulose binder
*** : 인쇄하지 않고 드라이라미네이션 실시***: Dry lamination without printing
[표 3]TABLE 3
나일론 필름의 기타 물성Other Properties of Nylon Film
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| JPS63288749A (en) * | 1987-05-21 | 1988-11-25 | Toyobo Co Ltd | Water-resistant adhesive biaxially drawn film |
| JPH023432A (en) * | 1988-06-17 | 1990-01-09 | Kohjin Co Ltd | Easily bondable film |
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| US5494960A (en) * | 1990-12-10 | 1996-02-27 | H.B. Fuller Licensing & Financing, Inc. | Aqueous polyurethane dispersions and adhesives based thereon |
| US5532058A (en) * | 1990-12-10 | 1996-07-02 | H. B. Fuller Licensing & Financing, Inc. | Dry-bonded film laminate employing polyurethane dispersion adhesives with improved crosslinkers |
| KR19980016222A (en) * | 1996-08-27 | 1998-05-25 | 구광시 | METHOD FOR PREPARING COMPOSITE TOTAL FILM FILM |
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|---|---|---|---|---|
| JPS55100127A (en) * | 1979-01-24 | 1980-07-30 | Unitika Ltd | Manufacture of polyamide film of improved slip property |
| JPS55164244A (en) * | 1979-06-08 | 1980-12-20 | Konishi Kk | Aqueous resin composition |
| JPS63288749A (en) * | 1987-05-21 | 1988-11-25 | Toyobo Co Ltd | Water-resistant adhesive biaxially drawn film |
| JPH023432A (en) * | 1988-06-17 | 1990-01-09 | Kohjin Co Ltd | Easily bondable film |
| US5494960A (en) * | 1990-12-10 | 1996-02-27 | H.B. Fuller Licensing & Financing, Inc. | Aqueous polyurethane dispersions and adhesives based thereon |
| US5532058A (en) * | 1990-12-10 | 1996-07-02 | H. B. Fuller Licensing & Financing, Inc. | Dry-bonded film laminate employing polyurethane dispersion adhesives with improved crosslinkers |
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| KR20160062777A (en) | 2014-11-25 | 2016-06-03 | (주)대성엘이디 | A light emitting diode module for attaching by magnet |
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