KR100365814B1 - Composition for absorbing aqueous ink and drawing film using the same - Google Patents
Composition for absorbing aqueous ink and drawing film using the same Download PDFInfo
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- KR100365814B1 KR100365814B1 KR1019960063838A KR19960063838A KR100365814B1 KR 100365814 B1 KR100365814 B1 KR 100365814B1 KR 1019960063838 A KR1019960063838 A KR 1019960063838A KR 19960063838 A KR19960063838 A KR 19960063838A KR 100365814 B1 KR100365814 B1 KR 100365814B1
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract
Description
본 발명은 수성잉크 흡수용 수지 조성물 및 이를 이용한 제도용 필름에 관한 것으로, 보다 상세하게는 수성잉크를 기록매체로 하는 출력장치에 적용할 수 있는 수성잉크 흡수용 수지 조성물 및 제도용 필름에 관한 것이다.The present invention relates to an aqueous ink absorbing resin composition and a drawing film using the same, and more particularly, to an aqueous ink absorbing resin composition and a drawing film applicable to an output device using an aqueous ink as a recording medium. .
제도용 필름은 제도용 종이에 비해 기계적 강도, 치수안정성, 내후성, 필기성 등이 우수하여 항공, 조선, 자동차, 건설, 전자 등 산업분야의 설계제도용으로 많이 사용되고 있으며, 일반적으로 플라스틱 필름(지지체, 베이스), 고분자 수지, 무기입자 등으로 구성된다.Drafting film has better mechanical strength, dimensional stability, weather resistance, and writing ability than drafting paper, so it is widely used for design system in aviation, shipbuilding, automobile, construction, electronics, etc. , Base), polymer resin, inorganic particles and the like.
이러한 종래 제도용 필름으로는 플라스틱 필름의 표면에 아크릴 수지 혹은 폴리우레탄 수지에 산화규소 입자 등을 분산시켜 매트층을 형성한 것이 있으며, 근래에는 매트층에 셀룰로오스, 폴리비닐피롤리돈, PVA, 젤라틴, 알부민 등의 친수성 수지를 사용하여 수성잉크층을 형성한 것이 많이 사용되고 있다.Such conventional drafting films are formed by dispersing silicon oxide particles in an acrylic resin or a polyurethane resin on the surface of a plastic film to form a mat layer. In recent years, cellulose, polyvinylpyrrolidone, PVA, and gelatin are formed on the mat layer. The thing which formed the aqueous ink layer using hydrophilic resins, such as and albumin, is used a lot.
그러나, 이러한 제도용 필름은 출력후 수성잉크의 초기흡수성이 불량하고 건조속도가 느린 단점이 있으며, 특히 친수성 수지를 사용하여 내수성에 문제가 있다.However, such a drawing film has a disadvantage in that the initial absorption of the aqueous ink after output is poor and the drying speed is slow, in particular, there is a problem in water resistance using a hydrophilic resin.
한편 컴퓨터용 출력장치로 도트, 잉크젯, 열전사, 레이저 플로터 등 다양한 출력장치가 개발되고, 특히 인쇄매체로 수성잉크를 채택한 출력장치가 우수한 성능과 저렴한 가격으로 급속히 성장하고 있으며, 최근 제도용 플로터 분야에도 잉크젯 출력장치가 적용되어 일반화되는 추세에 있다. 따라서 보다 수성잉크의 초기 흡수성이 우수하고 건조속도가 빠른 제도용 필름의 개발이 요구되고 있다.In the meantime, various output devices such as dot, inkjet, thermal transfer, and laser plotter have been developed as computer output devices. Especially, the output device adopting water-based ink as a print medium is growing rapidly with excellent performance and low price. In addition, the inkjet output device is being applied to the general trend. Therefore, there is a demand for the development of a drafting film having a better initial absorption of aqueous ink and a faster drying speed.
본 발명의 목적은 초기 흡수성과 건조속도가 빠르고 해상도가 양호할 뿐만 아니라 내수성이 우수한 수성잉크 흡수용 수지 조성물을 제공하는 데에 있다.An object of the present invention is to provide a resin composition for absorbing aqueous ink having not only good initial water absorption and fast drying speed, but also good water resistance.
또한 본 발명의 다른 목적은 상기 수성잉크 흡수용 수지 조성물을 이용한 제도용 필름을 제공하는 데에 있다.Another object of the present invention is to provide a film for drafting using the resin composition for absorbing aqueous ink.
상기 본 발명의 목적을 달성하기 위한 수성잉크 흡수용 수지 조성물은, (A)메타크릴산, 아크릴산에스테그, 하이드록시메타크릴레이트 및 다음 식1로 표시되는 알킬메타크릴레이트를 공중합시킨 유리전이점 30∼100℃, 중량평균분자량 30,000~200,000인 비닐계공중합체와, (B)산화규소미립자가 40∼80 : 20∼60의 중량비로 함유된 데에 그 특징이 있다.Aqueous ink absorption resin composition for achieving the object of the present invention, the glass transition point copolymerized with (A) methacrylic acid, acrylic acid ester, hydroxy methacrylate and alkyl methacrylate represented by the following formula (1) It is characterized by containing a vinyl copolymer having a weight average molecular weight of 30,000 to 200,000 at 30 to 100 ° C. and (B) silicon oxide fine particles at a weight ratio of 40 to 80:20 to 60.
[식1][Equation 1]
상기 식1에서, R1은 탄소수 1∼10인 알킬기이다.In Formula 1, R 1 is an alkyl group having 1 to 10 carbon atoms.
또한 제도용 필름을 프라스틱 지지체(이하, 베이스라 한다) 상에 상기 수성 잉크 흡수용 수지 조성물이 5∼100㎛ 두께로 도포되어 흡수층을 형성한 데에 그 특징이 있다.In addition, the film for drawing is applied on a plastic support (hereinafter referred to as a base), and the aqueous ink absorption resin composition is applied to a thickness of 5 to 100 µm to form an absorbing layer.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명의 (A)비닐계공중합체는 수성잉크의 흡수를 가능하게 하는 메타크릴산, 하이드록시메타크릴레이트와, 베이스와의 밀착력을 부여할 뿐만 아니라 표면 특성을 건조하게 하고 블로킹 방지 및 잉크분사노즐의 마찰에 의한 표면 긁힘을 방지하는 아크릴산에스테르 및 식1로 표시되는 알킬메타크릴레이트로 구성되며, 또한 상기 공중합 재료 이외의 공지 화합물을 특성이 악화되지 않는 범위내에서 사용할 수도 있다.The vinyl copolymer (A) of the present invention not only provides adhesion between methacrylic acid and hydroxy methacrylate, which allows the absorption of aqueous ink, and the base, but also makes surface properties dry, prevents blocking, and ink spraying. It consists of acrylic ester which prevents surface scratching by the friction of a nozzle, and alkyl methacrylate represented by Formula 1, and can also use well-known compounds other than the said copolymerization material in the range which a characteristic does not deteriorate.
아크릴산에스테르로는 아크릴산메틸, 아크릴산에틸, 아크릴산프로필, 아크릴산이소프로필, 아크릴산부틸, 아크릴산이소부틸, 아크릴산-tert-부틸, 아크릴산펜틸, 아크릴산헥실, 아크릴산헵틸, 아크릴산옥틸, 아크릴산-2-에틸헥실, 아크릴산노닐, 아크릴산운데실, 아크릴산도데실, 아크릴산스테아릴, 아크릴산페닐, 아크릴산시클로헥실, 아크릴산-2-페녹시에틸과 같은 탄소수 1∼20인 알킬기 등을 갖는 것을 사용한다.As the acrylic ester, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate and acrylic acid Those having an alkyl group having 1 to 20 carbon atoms such as nonyl, undecyl acrylate, dodecyl acrylate, stearyl acrylate, phenyl acrylate, cyclohexyl acrylate, and 2-phenoxy ethyl acrylate are used.
식1로 표시되는 알킬메타크릴레이트로는 메틸메타크릴레이트, 프로필메타크릴레이트, 이소프로필메타크릴레이트, 부틸메타크릴레이트, 이소부틸메타크릴레이트 등이 있으며, 이것을 단독 또는 2종 이상을 조합하여 사용할 수도 있다.Alkyl methacrylate represented by Formula 1 includes methyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, and the like, alone or in combination of two or more thereof. Can also be used.
(A)비닐계공중합체(총량 100중량부)는 아크릴산 5∼30중량부, 아크릴산에스테르 5∼30중량부, 하이드록시메타크릴레이트 20∼60중량부, 좋기로는 20∼50중량부, 알킬메타크릴레이트 10∼60중량부, 좋기로는 20∼50중량부로 구성되는 것이 바람직하다. 이 비율의 범위를 벗어나면 수성잉크의 흡수성이 저하되거나 내수성, 베이스와의 밀착력 및 마찰특성 등이 저하된다.(A) Vinyl copolymer (100 parts by weight in total) is 5 to 30 parts by weight of acrylic acid, 5 to 30 parts by weight of acrylate ester, 20 to 60 parts by weight of hydroxy methacrylate, preferably 20 to 50 parts by weight, alkyl The methacrylate is preferably composed of 10 to 60 parts by weight, preferably 20 to 50 parts by weight. Outside the range of this ratio, the water absorbency of the aqueous ink is lowered, or the water resistance, adhesion to the base and friction characteristics are lowered.
또한 (A)비닐계공중합체는 Tg 30∼100℃이고, 중량평균분자량 30,000∼200,000, 바람직하게는 50,000∼120,000 인 것을 사용한다. Tg가 30℃ 미만이면 표면특성이 건조하지 못하고 잉크분사노즐에 의한 표면 긁힘이 일어날 수 있으며, Tg가 100℃ 이상이면 베이스와의 밀착력이 저하될 수 있다. 또한 중량평균분자량이 상기 범위를 벗어나면 수성잉크의 초기 흡수성, 건조속도 및 내수성이 저하될 수 있다.The vinyl copolymer (A) has a Tg of 30 to 100 ° C and a weight average molecular weight of 30,000 to 200,000, preferably 50,000 to 120,000. If the Tg is less than 30 ° C., the surface characteristics may not be dried, and surface scratches may occur due to the ink jetting nozzle. If the Tg is more than 100 ° C., the adhesion to the base may be reduced. In addition, when the weight average molecular weight is out of the above range, the initial absorbency, drying rate and water resistance of the aqueous ink may decrease.
(B)산화규소 미립자는 수성잉크의 초기 흡수와 확산을 가속화시키고 표면 촉감을 건조하게 개선시켜 인쇄시의 잉크의 원할한 공급을 위해 첨가한다. 이는 평균 입경이 5.0㎛ 이하인 것과 그 이상인 것을 40∼80 : 20∼60의 중량비로, 바람직하게는 50∼70 : 30∼50의 중량비로 혼합하여 사용하는 것이 좋다. 평균입경이 5.0㎛이하인 산화규소 미립자는 수성잉크 흡착층내에 미세한 모세관을 형성하여 내부로의 잉크확산을 가속화시키고, 평균입경 5.0㎛ 이상인 산화규소 미립자는 수성잉크 흡착층 표면을 조도화(마찰계수 저하)시켜 표면특성을 향상시킨다. 산화규소 미립자 총량 100중량부에 대하여 평균입경 5.0㎛ 이상인 것을 20중량부 이하로 사용하면 초기 잉크 흡수성이 저하되고 60중량부 이상으로 사용하면 수성잉크의 퍼짐성에의해 해상도가 저하된다.(B) Silicon oxide fine particles are added for a smooth supply of ink in printing by accelerating the initial absorption and diffusion of the aqueous ink and improving the surface feel dry. It is good to mix and use the thing whose average particle diameter is 5.0 micrometers or less by the weight ratio of 40-80: 20-60, Preferably it is 50-70: 30-50. Silicon oxide fine particles having an average particle diameter of 5.0 μm or less form a fine capillary tube in the aqueous ink adsorption layer to accelerate the diffusion of ink into the inside, and silicon oxide fine particles having an average particle diameter of 5.0 μm or more roughen the surface of the aqueous ink adsorption layer (reduced friction coefficient) To improve the surface properties. When 20 parts by weight or less of an average particle diameter of 5.0 µm or more is used with respect to 100 parts by weight of the total amount of silicon oxide fine particles, the initial ink absorbency decreases, and when used in more than 60 parts by weight, the resolution decreases due to the spreadability of the aqueous ink.
본 발명의 수성잉크 흡수용 수지 조성물에는 대전방지제, 형광증백제, 계면활성제, 분산제 등을 더 첨가하여 조성하여도 된다.The resin composition for absorbing aqueous ink of the present invention may further contain an antistatic agent, a fluorescent brightener, a surfactant, a dispersant, and the like.
본 발명의 수성잉크 흡수용 수지 조성물을 제조함에 있어서 사용될 수 있는 용제로는, 톨루엔, 메틸에틸케톤, 아세톤, 메틸이소부틸케톤, 메틸셀로솔브, 에틸셀로솔브, 클로로포름, 염화메틸렌, 메틸알콜, 에틸알콜, N-메틸-2-피롤리돈 등이 있다.Solvents that can be used in the preparation of the aqueous ink absorption resin composition of the present invention include toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, methyl alcohol , Ethyl alcohol, N-methyl-2-pyrrolidone and the like.
또한 베이스로 사용될 수 있는 플라스틱 필름으로는 폴리에스테르, 폴리카보네이트, 폴리아미드, 폴리올레핀, 폴리염화비닐, 셀룰로오즈트리아세테이트 등이 있다. 이 중에 치수안정성, 내열성 및 내후성이 우수한 폴리에스테르 필름을 사용하는 것이 좋다. 폴리에스테르 필름은 이축연신 폴리에틸렌테레프탈레이트 필름으로서 사용목적에 따라 차이가 있지만 15∼200㎛ 두께의 것을 사용하며, 수성잉크 흡수층과의 접착력을 향상시키기 위하여 표면에 코로나 처리 혹은 폴리에스테르 공중합체를 전처리한 필름을 사용하는 것이 좋다.Plastic films that can also be used as the base include polyesters, polycarbonates, polyamides, polyolefins, polyvinyl chloride, cellulose triacetate and the like. It is preferable to use the polyester film excellent in dimensional stability, heat resistance, and weather resistance among these. The polyester film is biaxially stretched polyethylene terephthalate film, which varies depending on the purpose of use, but has a thickness of 15 to 200 μm, and is pretreated with a corona treatment or polyester copolymer on the surface to improve adhesion to the aqueous ink absorbing layer. It is better to use a film.
본 발명에 따른 수성잉크 흡수용 수지 조성물 및 이를 사용한 제도용 필름의 제조방법을 간단히 설명한다.The manufacturing method of the aqueous ink absorption resin composition and the drafting film using the same according to the present invention will be briefly described.
먼저 초음파, 고속교반기, 볼밀, 롤밀, 샌드밀 등의 분산수단을 사용하여 적당한 용제에 산화규소 미립자를 분산시킨 후 비닐계공중합체 수지를 용해시켜 수성 잉크 흡수용 조성물(코팅액)을 제조한다.First, dispersing silicon oxide fine particles in a suitable solvent using a dispersing means such as an ultrasonic wave, a high speed stirrer, a ball mill, a roll mill, a sand mill, and then dissolve a vinyl copolymer resin to prepare an aqueous ink absorption composition (coating solution).
이 조성물을 베이스의 한면 혹은 양면에 메이어바코터(Mayer Bar Coater),그라비아롤코터, 리버스롤코터, 에어나이프(Air knife) 등을 사용하여 5∼100㎛의 두께로 도포 코팅하고 100∼200℃에서 1∼10분간 건조시켜 제도용 필름을 만든다.This composition is coated on one or both sides of the base using a Mayer Bar Coater, a gravure roll coater, a reverse roll coater, an air knife, etc. to a thickness of 5 to 100 탆 and 100 to 200 캜. It is dried for 1 to 10 minutes in to make a drawing film.
이하 실시예를 통해 본 발명을 상세히 설명한다.The present invention will be described in detail through the following examples.
비닐계공중합체의 제조Preparation of Vinyl Copolymer
에틸알콜/테트라하이드로퓨란(중량비 7/3)의 혼합물(이하, 혼합물A라 한다) 200g을 500㎖ 플라스크에 넣고 가열하여 80℃로 승온시킨 후, 메타크릴산 24g, 메틸아크릴레이트 20g, 하이드록시 메타크릴레이트 80g, 메틸메타크릴레이트 76g, 아조비스이소부틸니트릴 1g을 첨가하고 80℃를 유지하면서 3시간 동안 반응시켰다. 다음 테트라하이드로퓨란 20g 및 아조비스이소부틸니트릴 1.5g을 가하여 5시간 보온하고 냉각하였다. 이렇게 얻은 비닐계공중합체(화합물)은 중량평균분자량 65,000, 유리전이점 60℃, 고형분 함량 48.8% 이었다.200 g of ethyl alcohol / tetrahydrofuran (weight ratio 7/3) (hereinafter referred to as mixture A) were put into a 500 ml flask and heated to 80 ° C. Then, 24 g of methacrylic acid, 20 g of methyl acrylate and hydroxy 80 g of methacrylate, 76 g of methyl methacrylate, and 1 g of azobisisobutylnitrile were added and reacted for 3 hours while maintaining the temperature at 80 ° C. Next, 20 g of tetrahydrofuran and 1.5 g of azobisisobutylnitrile were added thereto, and the mixture was kept warm for 5 hours and cooled. The vinyl copolymer (compound) thus obtained had a weight average molecular weight of 65,000, a glass transition point of 60 ° C., and a solid content of 48.8%.
실시예 1Example 1
메타크릴산/메타아크릴레이트/하이드록시메타크릴레이트/메틸메타크릴레이트(l7/10/40/38 중량비, Tg 60℃, 중량평균분자량 65,000)로 조성된 것 24g, 산화규소 입자 평균입경이 3.5㎛인 것 4.8g, 평균입경이 7.0㎛인 것 3.2g, 메틸알콜 44g 및 N-메틸-2-피롤리돈 24g을 혼합하여 완전히 분산시켰다.Composition composed of methacrylic acid / methacrylate / hydroxy methacrylate / methyl methacrylate (l7 / 10/40/38 weight ratio, Tg 60 ℃, weight average molecular weight 65,000) 24g, silicon oxide particles average particle size 3.5 4.8 g of µm, 3.2 g of 7.0 µm of average particle diameter, 44 g of methyl alcohol and 24 g of N-methyl-2-pyrrolidone were mixed and completely dispersed.
다음 이 분산액을 두께 75㎛의 이축연신 폴리에틸렌테레프탈레이트 필름에 메이어바 #30으로 도포하여 건조시켰다. 건조 후 흡수층의 두께는 12㎛ 이었다.Next, this dispersion was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 75 μm with Mayer # 30, and dried. The thickness of the absorber layer after drying was 12 µm.
실시예2~4, 비교예 1~2Examples 2-4, Comparative Examples 1-2
다음 표1과 같은 조성으로 실시예1의 방법으로 제도용 필름을 제조하였다.Next, the drawing film was manufactured by the method of Example 1 with the composition as shown in Table 1.
[표1]Table 1
상기 실시예 및 비교예에서 제조한 수성잉크 흡착층을 갖는 제도용 필름을 아래와 같은 방법으로 시험 평가하였으며, 그 결과는 표2와 같다.The drafting film having the aqueous ink adsorption layer prepared in Examples and Comparative Examples was tested and evaluated in the following manner, and the results are shown in Table 2.
수성잉크의 초기 흡수성: 잉크젯플로터(Hewlett Packard사 Designjet 750C)로 출력한 직후 깨끗한 A4용지를 덮어서 골고루 문지른 후 묻어나는 정도를 평가.Initial Absorbency of Water-based Inks: Immediately after printing on an inkjet plotter (Designjet 750C from Hewlett Packard), cover the clean A4 paper and rub it evenly to evaluate the degree of bleeding.
수성잉크의 건조속도: 잉크젯플로터로 출력한 후 잉크가 완전히 건조되는데 소요되는 시간 측정.Drying speed of aqueous ink: Determination of the time it takes for the ink to dry completely after printing to an inkjet plotter.
수성잉크 접착력: 잉크젯플로터로 출력후 스카치테이프를 붙인 후 박리.Water-based ink adhesion: Printed with an ink jet plotter, peeled off after scotch tape is applied.
막강도(연필강도): 연필경도 측정기(일본 TOYO SEIKI 사 제품)의 시료면에 45°각도로 연필를 장착하고 200g의 하중을 가한 후 일정속도로 시료판을 이동시키면서 시료판의 막파괴에 따라 연필경도로 표시.Membrane strength (pencil strength): A pencil is placed on the sample surface of a pencil hardness tester (manufactured by TOYO SEIKI, Japan) at a 45 ° angle, and the sample is moved at a constant speed while applying a 200g load. Displayed as longitude.
[표2][Table 2]
상기 표2에서 ◎은 우수, O은 양호, X은 불량을 뜻한다.In Table 2, ◎ is excellent, O is good, X means bad.
상기 표2에서 확인할 수 있듯이, 본 발명에 의한 것이 종래 것에 비해 수성 잉크의 초기흡수성, 건조속도, 베이스와의 접착력이 우수하다.As can be seen in Table 2, the present invention has superior initial absorbency, drying speed, and adhesion to the base of the aqueous ink compared with the conventional one.
이상에서 상세히 설명한 바와 같이, 본 발명에 따른 수성잉크 흡수용 수지 조성물은 잉크의 초기 흡습성, 내수성 및 베이스와의 접착력이 우수하여 고해상도와 다양한 색상을 갖는 패턴을 만들 수 있다.As described in detail above, the aqueous ink absorption resin composition according to the present invention is excellent in the initial hygroscopicity, water resistance and adhesion to the base of the ink can make a pattern having a high resolution and various colors.
Claims (4)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62278081A (en) * | 1986-05-26 | 1987-12-02 | Mitsubishi Paper Mills Ltd | Ink jet recording medium |
| JPH0551469A (en) * | 1991-08-23 | 1993-03-02 | Toray Ind Inc | Recording sheet |
| KR930023169A (en) * | 1992-05-26 | 1993-12-18 | 엔니오 펠리노 | Non-drop forming film or plate composed of acrylic polymer, and method for producing same |
| JPH06279605A (en) * | 1993-03-24 | 1994-10-04 | Toray Ind Inc | Film for printing-recording |
| KR970010598A (en) * | 1995-08-30 | 1997-03-27 | 코다마 슈니치로 | Cap of container |
| KR0178064B1 (en) * | 1993-05-24 | 1999-04-01 | 최준식 | Recording film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62278081A (en) * | 1986-05-26 | 1987-12-02 | Mitsubishi Paper Mills Ltd | Ink jet recording medium |
| JPH0551469A (en) * | 1991-08-23 | 1993-03-02 | Toray Ind Inc | Recording sheet |
| KR930023169A (en) * | 1992-05-26 | 1993-12-18 | 엔니오 펠리노 | Non-drop forming film or plate composed of acrylic polymer, and method for producing same |
| JPH06279605A (en) * | 1993-03-24 | 1994-10-04 | Toray Ind Inc | Film for printing-recording |
| KR0178064B1 (en) * | 1993-05-24 | 1999-04-01 | 최준식 | Recording film |
| KR970010598A (en) * | 1995-08-30 | 1997-03-27 | 코다마 슈니치로 | Cap of container |
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