KR20140139566A - Polyurethane resin composition for printing ink binder - Google Patents

Polyurethane resin composition for printing ink binder Download PDF

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KR20140139566A
KR20140139566A KR1020147029220A KR20147029220A KR20140139566A KR 20140139566 A KR20140139566 A KR 20140139566A KR 1020147029220 A KR1020147029220 A KR 1020147029220A KR 20147029220 A KR20147029220 A KR 20147029220A KR 20140139566 A KR20140139566 A KR 20140139566A
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South Korea
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polyurethane resin
printing ink
alcohol
ink
solvent
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KR1020147029220A
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Korean (ko)
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KR101588234B1 (en
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토모코 나카가와
모토이 시타카
미치히사 코푸지
타케후미 노무라
유고 하타노
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토요잉크Sc홀딩스주식회사
도요잉크주식회사
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
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    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D11/00—Inks
    • C09D11/02—Printing inks
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

톨릴렌디이소시아네이트를 포함하는 폴리이소시아네이트와 고분자 폴리올을 반응시켜 이루어지는 말단에 이소시아네이트기를 갖는 우레탄 프리폴리머에, 추가로, 유기 디아민 및 알칸올아민을 반응시켜, [NCO(전체)]/[OH] 및 [NCO(TDI)]/[OH], 폴리우레탄 수지의 수산기가, 유기 디아민과 알칸올아민의 비율을 제어한 폴리우레탄 수지, 그리고 에스테르계 용제와 알코올을 포함하는 혼합용제를 포함하는 폴리우레탄 수지 조성물을 제공한다.[NCO (total)] / [OH] and [NCO (total)] are obtained by reacting an urethane prepolymer having an isocyanate group at the terminal and a polyol, (TDI)] / [OH], a polyurethane resin in which the hydroxyl groups of the polyurethane resin are controlled in proportions of organic diamine and alkanolamine, and a mixed solvent containing an ester solvent and alcohol to provide.

Description

인쇄 잉크 바인더용 폴리우레탄 수지 조성물{POLYURETHANE RESIN COMPOSITION FOR PRINTING INK BINDER}TECHNICAL FIELD [0001] The present invention relates to a polyurethane resin composition for a printing ink binder,

본 발명은, 폴리우레탄 수지 조성물 및 인쇄 잉크 조성물에 관한 것이다.The present invention relates to a polyurethane resin composition and a printing ink composition.

종래부터, 인쇄 잉크에서 사용되는 용제로는, 톨루엔 및 자일렌 등 비교적 용해력이 강한 방향족계의 용제, 및 메틸에틸케톤 및 메틸이소부틸케톤 등의 케톤계의 용제를 들 수 있다. 그러나 최근, 세계적 환경보전 및 법규제면으로부터, 인쇄 잉크 업계에도, 환경과제에 대한 배려가 요구되고 있다. 이에, 이들 방향족계 용제 및 케톤계 용제를 배제한, 에스테르/알코올 용제계를 이용하는 인쇄 잉크가 요망되고 있다. 이에 따라, 에스테르/알코올 용제계의 인쇄 잉크의 연구개발이 행해지고 있다. 그러나, 에스테르/알코올 용제계는, 방향족계 및 케톤계의 용제와 비교할 때, 용해력이 낮아 인쇄적성이 나빴다. 또한, 에스테르/알코올 용제의 용해력을 높이면, 내알코올블리드성이나 내블로킹성 등의 다른 물성이 부족하여, 여전히 과제가 많았다.
Heretofore, examples of the solvent used in printing inks include aromatic solvents having relatively high solubility such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. In recent years, however, consideration has also been given to the printing ink industry from environmental preservation and regulatory aspects. Accordingly, a printing ink using an ester / alcohol solvent system in which these aromatic solvents and ketone solvents are excluded is desired. Accordingly, research and development of an ester / alcohol solvent-based printing ink have been carried out. However, ester / alcohol solvent systems have poor solubility and poor printability when compared with aromatic and ketone solvents. Further, if the solubility of the ester / alcohol solvent is increased, the other properties such as alcohol-alcohol bleed resistance and blocking resistance are insufficient, and there are still many problems.

예를 들어, 일본특허공개 H9-316156 공보에는, 디페닐메탄디이소시아네이트를 사용한 폴리우레탄 수지 조성물 및 인쇄 잉크 조성물이, 각종 플라스틱 필름에 대하여, 우수한 접착성을 갖는 것이 개시되어 있다. 그러나, 이들 조성물은, 인쇄적성의 확보를 위하여, 배제가 요구되고 있는 메틸에틸케톤을 포함한다. 또한, [NCO]/[OH]비가 낮아서, 내블로킹성에도 과제가 있다.
For example, Japanese Patent Application Laid-Open No. H9-316156 discloses that a polyurethane resin composition and a printing ink composition using diphenylmethane diisocyanate have excellent adhesiveness to various plastic films. However, these compositions contain methyl ethyl ketone, which is required to be excreted, in order to secure printability. In addition, the [NCO] / [OH] ratio is low and there is a problem in blocking resistance.

또한, 일본특허공개 2003-221539 공보에는, 잉크에 에스테르/알코올 용제계를 함유하고, 에스테르/알코올 용제계에 대한 용해성을 높이는 검토가 개시되어 있다. 그러나, 잉크 중에 하이드록시카르본산이 첨가되어 있으므로, 잔류용제의 문제가 발생하고, 또한, 내수성 및 내알코올블리드성이 부족하다.Japanese Patent Application Laid-Open No. 2003-221539 discloses an ink containing an ester / alcohol solvent system and enhancing solubility in an ester / alcohol solvent system. However, since the hydroxycarboxylic acid is added to the ink, a problem of the residual solvent occurs, and the water resistance and the alcoholic-alcohol bleeding property are insufficient.

일본특허공개 H9-316156 공보Japanese Patent Application Laid-Open No. H9-316156 일본특허공개 2003-221539 공보Japanese Patent Application Laid-Open No. 2003-221539

본 발명은, 톨루엔 및 자일렌 등의 방향족 유기용제, 및 메틸에틸케톤 및 메틸이소부틸케톤 등의 케톤계 유기용제를 배제한 인쇄 잉크 조성물을 제공하는 것을 목적으로 한다. 또한, 본 발명은, 에스테르/알코올 용제계를 함유하고, 우수한 먹날림성(fogging) 등의 인쇄적성을 가지며, 또한 여러가지 플라스틱 필름에 대하여 우수한 접착성, 내블로킹성, 내알코올블리드성 및 라미네이트 물성 등의 인쇄물성도 겸비하는 인쇄 잉크 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a printing ink composition in which aromatic organic solvents such as toluene and xylene, and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone are excluded. The present invention also provides an ink composition for inkjet recording which contains an ester / alcohol solvent system and has excellent printability such as fogging, and is also excellent in adhesion, blocking resistance, alcohol-alcohol bleeding property and laminate property And also to provide a printing ink composition which combines printability of the printing ink.

본 발명자들은, 상기 상황을 감안하여 예의 검토를 거듭한 결과, 톨릴렌디이소시아네이트를 포함하는 폴리이소시아네이트, 그리고 반응정지제로 알칸올아민을 사용하고, 또한 합성 파라미터를 제어한 폴리우레탄 수지를 이용함으로써, 비교적 용해력이 약한 에스테르/알코올 용제계를 이용하여도, 우수한 인쇄적성과 인쇄물성의 양립을 달성하는 인쇄 잉크 조성물의 설계를 가능하게 하는 것을 발견하여, 본 발명을 완성하였다.
The inventors of the present invention have made intensive investigations in view of the above circumstances. As a result, they have found that by using a polyisocyanate containing tolylene diisocyanate and an alkanolamine as a reaction terminator and by using a polyurethane resin whose synthesis parameters are controlled, It is possible to design a printing ink composition capable of achieving both good printability and print property both by using an ester / alcohol solvent system having weak solubility, and the present invention has been completed.

본 발명의 제1의 실시형태는, 톨릴렌디이소시아네이트를 포함하는 폴리이소시아네이트와 고분자 폴리올을 반응시켜 이루어지는, 말단에 이소시아네이트기를 갖는 우레탄 프리폴리머를, 유기 디아민 및 알칸올아민과 반응시켜 이루어지는 폴리우레탄 수지, 그리고 혼합용제를 포함하는 폴리우레탄 수지 조성물로서,A first embodiment of the present invention is a polyurethane resin obtained by reacting a urethane prepolymer having an isocyanate group at the terminal thereof with an organic diamine and an alkanolamine, which is obtained by reacting a polyisocyanate containing tolylene diisocyanate with a high molecular polyol, A polyurethane resin composition comprising a mixed solvent,

하기의 (A)~(F)인 것을 특징으로 하는 폴리우레탄 수지 조성물에 관한 것이다.The present invention relates to a polyurethane resin composition characterized by the following (A) to (F).

(A) 폴리이소시아네이트의 전체 이소시아네이트기와 고분자 폴리올의 수산기와의 반응에 있어서의 몰비[NCO(전체)]/[OH]가, 1.8~2.3이다.(NCO (total)) / [OH] in the reaction between the entire isocyanate group of the polyisocyanate (A) and the hydroxyl group of the high molecular polyol is 1.8 to 2.3.

(B) 톨릴렌디이소시아네이트의 이소시아네이트기와 고분자 폴리올의 수산기와의 반응에 있어서의 몰비[NCO(TDI)]/[OH]가, 1.0~2.1이다.(B) the molar ratio [NCO (TDI)] / [OH] in the reaction of the isocyanate group of tolylene diisocyanate with the hydroxyl group of the high molecular polyol is 1.0 to 2.1.

(C) 폴리우레탄 수지의 수산기가가 1.0~10.0mgKOH/g이다.(C) the hydroxyl value of the polyurethane resin is 1.0 to 10.0 mg KOH / g.

(D) 유기 디아민의 몰수 d1과 알칸올아민의 몰수 d2의 몰비 d1/d2가, 3~25이다.(D) the molar ratio d1 / d2 of the number of moles d1 of the organic diamine to the number of moles d2 of the alkanolamine is 3 to 25. [

(E) 혼합용제가, 에스테르계 용제와 알코올계 용제를 포함한다.(E) the mixed solvent includes an ester solvent and an alcohol solvent.

(F) 고분자 폴리올이, 폴리에스테르디올과 폴리에테르디올로 이루어진다.
(F) The polymer polyol is composed of a polyester diol and a polyether diol.

다음에, 제2의 실시형태는, 고분자 폴리올 중에, 상기 폴리에스테르디올이 20~80중량%, 상기 폴리에테르디올 80~20중량%인 것을 특징으로 하는 폴리우레탄 수지 조성물에 관한 것이다.
Next, the second embodiment relates to a polyurethane resin composition characterized in that the polyester diol is 20 to 80% by weight and the polyether diol is 80 to 20% by weight in the high molecular polyol.

나아가, 제3의 실시형태는, 제1 또는 제2의 실시형태의 폴리우레탄 수지 조성물을 함유하는 것을 특징으로 하는 인쇄 잉크 조성물에 관한 것이다.Further, the third embodiment relates to a printing ink composition comprising the polyurethane resin composition of the first or second embodiment.

본 실시형태에 따르면, 에스테르/알코올 용제계를 이용하여도, 우수한 인쇄적성 및 우수한 인쇄물성을 보유하는 인쇄 잉크 조성물을 제공하는 것을 가능하게 한다.According to this embodiment, it becomes possible to provide a printing ink composition having excellent printability and excellent printing property even by using an ester / alcohol solvent system.

이하, 인쇄 잉크 바인더용 폴리우레탄 수지 조성물에 대하여 설명한다. 폴리우레탄 수지는, 톨릴렌디이소시아네이트를 포함하는 폴리이소시아네이트와 고분자 폴리올을 반응시켜 이루어지는, 말단에 이소시아네이트기를 갖는 우레탄 프리폴리머에, 쇄연장제로서 유기 디아민, 반응정지제로서 알칸올아민을 반응시켜 얻어진다.
Hereinafter, the polyurethane resin composition for a printing ink binder will be described. The polyurethane resin is obtained by reacting an urethane prepolymer having an isocyanate group at the terminal thereof with an organic diamine as a chain extender and an alkanolamine as a reaction terminator, which are obtained by reacting a polyisocyanate containing tolylene diisocyanate and a high molecular polyol.

인쇄 잉크 바인더에 이용하는 폴리우레탄 수지에 있어서, 에스테르/알코올 용제에 대한 용해력과, 각종 플라스틱 필름에 대한 각종 인쇄물성의 양립을 고려하는 경우, 중요한 인자가 되는 것이, 우레탄 결합, 우레아 결합의 하드세그먼트를 형성하는 폴리이소시아네이트이다.
In consideration of compatibility between the solubility in ester / alcohol solvents and various printing properties for various plastic films in a polyurethane resin used in a printing ink binder, it is preferable that urethane bonds and urea bond hard segments Lt; / RTI >

본 실시형태에 있어서, 폴리우레탄 수지에서 이용하는 폴리이소시아네이트는, 톨릴렌디이소시아네이트를 포함한다(이하, TDI라고 표기되는 경우도 있다.). 톨릴렌디이소시아네이트는, 2,4-톨릴렌디이소시아네이트 또는, 2,6-톨릴렌디이소시아네이트가 바람직하고, 이들의 혼합물일 수도 있다.
In the present embodiment, the polyisocyanate used in the polyurethane resin includes tolylene diisocyanate (hereinafter sometimes referred to as TDI). The tolylene diisocyanate is preferably 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate, or a mixture thereof.

톨릴렌디이소시아네이트는 분자 내에 방향족환을 1개 가지므로, 지방족 이소시아네이트 및 지환족 이소시아네이트와 비교할 때, 알코올에 대한 내성이 보다 높다. 한편, 방향족환을 2개 갖는 방향족 이소시아네이트인 디페닐메탄디이소시아네이트와 비교할 때, 톨릴렌디이소시아네이트는 방향족환이 1개이므로, 에스테르/알코올 용제계에 대한 용해력이 높다. 따라서, 톨릴렌디이소시아네이트는 에스테르/알코올 용제계의 인쇄 잉크 조성물에 있어서, 먹날림성 등의 인쇄적성과 내알코올블리드성의 균형을 갖기 쉽다.
Since tolylene diisocyanate has one aromatic ring in the molecule, it is more resistant to alcohol than aliphatic isocyanate and alicyclic isocyanate. On the other hand, when compared with diphenylmethane diisocyanate, which is an aromatic isocyanate having two aromatic rings, the tolylene diisocyanate has a high aromatic hydrocarbon / ester solvent ratio because it has one aromatic ring. Therefore, in the printing ink composition of the ester / alcohol solvent system, the tolylene diisocyanate tends to have a balance of printing suitability such as ink-repellency and alcoholic-alcohol bleedability.

본 실시형태에 있어서, 우레탄 프리폴리머를 합성할 때, 전체 폴리이소시아네이트의 전체 이소시아네이트기와 고분자 폴리올의 수산기의 몰비율인 [NCO(전체)]/[OH]가, 1.8~2.3의 범위에 있다. [NCO(전체)]/[OH]가 1.8 이상이면, 하드세그먼트 결합수가 충분하여, 내블로킹성, 내알코올블리드성이 우수하다. 2.3 이하이면, 먹날림성이 우수하고, 또한 하드세그먼트 결합수가 적당하므로 접착성, EL 라미네이트 강도가 우수하다.
In the present embodiment, when the urethane prepolymer is synthesized, the molar ratio [NCO (total)] / [OH] of the total isocyanate group of the total polyisocyanate to the hydroxyl group of the polymer polyol is in the range of 1.8 to 2.3. When [NCO (total)] / [OH] is 1.8 or more, the number of hard segment bonds is sufficient and the blocking resistance and alcohol-alcohol bleeding resistance are excellent. When the ratio is 2.3 or less, excellent water repellency is obtained, and the number of hard segment bonds is moderate, so that the adhesive property and the EL laminate strength are excellent.

본 실시형태에 있어서, 톨릴렌디이소시아네이트의 이소시아네이트기와 고분자 폴리올의 수산기와의 반응에 있어서의 몰비율인 [NCO(TDI)]/[OH]는, 1.0~2.1의 범위에 있다. 일반적으로 방향족 이소시아네이트는, 지방족 이소시아네이트나 지환족 이소시아네이트와 비교할 때, 수산기나 아미노기의 반응속도가 빠르다. 따라서, [NCO(TDI)]/[OH]가 2.1 이하이면, 반응속도가 적당하므로 균일한 폴리우레탄 수지를 합성할 수 있다. 나아가, 분자 내의 방향족환 농도가 적당하므로 먹날림성이 우수하다. 또한, [NCO(TDI)]/[OH]가 1.0 이상이면 내알코올블리드성이 우수하다.
In the present embodiment, the molar ratio [NCO (TDI)] / [OH] in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the high molecular polyol is in the range of 1.0 to 2.1. In general, the aromatic isocyanate has a faster reaction rate of a hydroxyl group or an amino group than an aliphatic isocyanate or an alicyclic isocyanate. Therefore, when [NCO (TDI)] / [OH] is 2.1 or less, a uniform polyurethane resin can be synthesized because the reaction rate is appropriate. Furthermore, since the concentration of aromatic rings in the molecule is appropriate, it is excellent in water repellency. Further, when [NCO (TDI)] / [OH] is 1.0 or more, the alcohol has excellent bleedability.

한편, 상기 [NCO(전체)]/[OH] 및 [NCO(TDI)]/[OH]를 만족하는 범위라면, 톨릴렌디이소시아네이트 이외에 다른 폴리이소시아네이트를 병용할 수도 있다. 다른 폴리이소시아네이트로는, 폴리우레탄 수지의 제조에 일반적으로 이용되는 각종 공지의 지방족 이소시아네이트, 지환족 이소시아네이트를 들 수 있다. 예를 들어, 부탄-1,4-디이소시아네이트, 헥사메틸렌디이소시아네이트, 이소프로필렌디이소시아네이트, 메틸렌디이소시아네이트, 2,2,4-트리메틸헥사메틸렌디이소시아네이트, 리신디이소시아네이트, 시클로헥산-1,4-디이소시아네이트, 이소포론디이소시아네이트, 디메릴디이소시아네이트, 디시클로헥실메탄-4,4'-디이소시아네이트, 1,3-비스(이소시아네이트메틸)시클로헥산, 메틸시클로헥산디이소시아네이트, 노보난디이소시아네이트, 및 다이머산의 카르복실기를 이소시아네이트기로 전환된 다이머 디이소시아네이트 등을 들 수 있다. 다른 폴리이소시아네이트 중에서도, 이소시아네이트기의 반응속도 및 여러가지 물성의 관점으로부터 이소포론디이소시아네이트가 바람직하다.
On the other hand, polyisocyanates other than tolylene diisocyanate may be used in combination as long as [NCO (total)] / [OH] and [NCO (TDI)] / [OH] Examples of other polyisocyanates include various known aliphatic isocyanates and alicyclic isocyanates generally used in the production of polyurethane resins. Examples thereof include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane- Diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, norbornadiisocyanate, And dimer diisocyanate in which the carboxyl group of an acid is converted to an isocyanate group. Among other polyisocyanates, isophorone diisocyanate is preferable from the viewpoints of the reaction rate of isocyanate groups and various physical properties.

또한, 전체 이소시아네이트기의 몰수 중의 90~100%가 톨릴렌디이소시아네이트, 및 10~0%가 이소포론디이소시아네이트인 경우, 내알코올블리드성이 특히 우수하다. 또한, 마찬가지로 전체 이소시아네이트기의 몰수 중의 50~75%가 톨릴렌디이소시아네이트, 및 50~25%가 이소포론디이소시아네이트인 경우로서, 인쇄 잉크 조성물 중의 용제가, 35%중량 이상의 알코올계 용제를 함유하는 경우에는, 먹날림성이 특히 우수하다. 한편, 인쇄 잉크 조성물에 포함되는 혼합용제의 상세에 대해서는 후술한다.
Further, when alcohol is 90 to 100% of the total number of moles of isocyanate group is tolylene diisocyanate, and when 10 to 0% is isophorone diisocyanate, alcohol-alcohol bleeding is particularly excellent. Likewise, when 50 to 75% of the total number of moles of isocyanate group is tolylene diisocyanate and 50 to 25% is isophorone diisocyanate, and when the solvent in the printing ink composition contains an alcohol solvent of 35% by weight or more Is particularly excellent in the water repellency. Details of the mixed solvent contained in the printing ink composition will be described later.

나아가, 에스테르/알코올 용제계에서의 먹날림성 등의 인쇄적성과, 내알코올블리드성의 균형을 잡기 위해 중요한 인자로서, 폴리우레탄 수지의 수산기가가 있다. 본 실시형태에 있어서, 폴리우레탄 수지의 수산기가는 1.0~10.0mgKOH/g이다. 수산기가가 1.0mgKOH/g 이상이면, 접착성, EL 라미네이트 강도가 우수하고, 또한 용해성도 현저하게 양호하므로 먹날림성이 우수하다. 수산기가가 10.0mgKOH/g 이하이면, 내알코올블리드성이 우수하다.
Furthermore, there is a hydroxyl group of the polyurethane resin as an important factor for balancing the printability such as the ink-repellency in the ester / alcohol solvent system and the alcoholic-bleedability. In the present embodiment, the hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g. When the hydroxyl value is 1.0 mgKOH / g or more, the adhesive property and the EL laminate strength are excellent, and the solubility is also remarkably good, so that the water repellency is excellent. When the hydroxyl value is 10.0 mgKOH / g or less, the alcohol-alcohol bleeding property is excellent.

본 실시형태에 있어서의 쇄연장제로서의 유기 디아민은, 예를 들어, 에틸렌디아민, 프로필렌디아민, 헥사메틸렌디아민, 이소포론디아민, 디시클로헥실메탄-4,4'-디아민 등 이외에, 2-하이드록시에틸에틸렌디아민, 2-하이드록시에틸프로필디아민, 2-하이드록시에틸프로필렌디아민, 디-2-하이드록시에틸에틸렌디아민, 디-2-하이드록시에틸렌디아민, 디-2-하이드록시에틸프로필렌디아민, 2-하이드록시프로필에틸렌디아민, 디-2-하이드록시프로필에틸렌디아민, 디-2-하이드록시프로필에틸렌디아민 등 분자 내에 수산기를 갖는 아민류를 들 수 있다. 이들 쇄연장제는 단독으로, 또는 2종 이상을 혼합하여 이용할 수 있다. 그 중에서도, 특히 이소포론디아민이 바람직하다.
Examples of the organic diamine as the chain extender in the present embodiment include, for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxyethylpropylenediamine, 2-hydroxyethylethylenediamine, And amines having a hydroxyl group in the molecule such as hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine. These chain extenders may be used alone or in combination of two or more. Among them, isophoronediamine is particularly preferable.

본 실시형태에 있어서, 폴리우레탄 수지의 유기 디아민의 몰수 d1과, 알칸올아민의 몰수 d2의 몰비 d1/d2는, 3~25이다. d1/d2가 3 이상이면, 내알코올블리드성이 우수하고, 또한 폴리우레탄 수지의 중량평균분자량이 크므로 내블로킹성도 현저하게 양호하다. d1/d2가 25 이하이면, 접착성, EL 라미네이트 강도가 우수하고, 또한 용해성도 현저하게 양호하므로 먹날림성이 우수하다.
In the present embodiment, the molar ratio d1 / d2 of the molar number d1 of the organic diamine of the polyurethane resin to the molar number d2 of the alkanolamine is 3 to 25. [ When d1 / d2 is 3 or more, the alcohol-alcohol bleeding property is excellent, and the weight average molecular weight of the polyurethane resin is large, and the blocking resistance is also remarkably good. When d1 / d2 is 25 or less, the adhesive property and the EL laminate strength are excellent, and the solubility is also remarkably good, so that the water repellency is excellent.

한편, 반응정지제인 알칸올아민의 사용량이 많아지면, 얻어지는 폴리우레탄 수지의 중량평균분자량은 낮아진다. 또한, 알칸올아민에는 수산기가 포함되어 있으므로, 알칸올아민의 사용량이 많아지면, 수산기가는 커진다. 알칸올아민으로는, 예를 들어, 모노에탄올아민, 디에탄올아민 등을 들 수 있다. 이들은 단독으로, 또는 2종 이상을 혼합하여 이용할 수 있다. 그 중에서도, 특히 모노에탄올아민이 바람직하다.
On the other hand, when the amount of the alkanolamine as the reaction terminator is increased, the weight average molecular weight of the obtained polyurethane resin is lowered. Further, since the alkanolamine contains a hydroxyl group, the hydroxyl group becomes larger when the amount of the alkanolamine is increased. Examples of the alkanolamine include monoethanolamine, diethanolamine and the like. These may be used alone or in combination of two or more. Of these, monoethanolamine is particularly preferable.

고분자 폴리올로는 각종 공지의 폴리에스테르폴리올, 및 폴리에테르폴리올 등을 이용한다. 각각 1종 또는 2종 이상을 병용할 수도 있다. 폴리에스테르폴리올로는, 예를 들어, 에틸렌글리콜, 1,2-프로판디올, 1,3-프로판디올, 2메틸-1,3프로판디올, 2에틸-2부틸-1,3프로판디올, 1,3-부탄디올, 1,4-부탄디올, 네오펜틸글리콜, 펜탄디올, 3-메틸-1,5펜탄디올, 헥산디올, 옥탄디올, 1,4-부틴디올, 1,4-부틸렌디올, 디에틸렌글리콜, 트리에틸렌글리콜, 디프로필렌글리콜, 글리세린, 트리메틸올프로판, 트리메틸올에탄, 1,2,6-헥산트리올, 1,2,4-부탄트리올, 솔비톨, 펜타에리스리톨 등의 포화 또는 불포화의 저분자 폴리올류와, 아디프산, 프탈산, 이소프탈산, 테레프탈산, 말레산, 푸마르산, 석신산, 옥살산, 말론산, 글루타르산, 피멜린산, 수베린산, 아젤라산, 세바스산, 트리멜리트산, 피로멜리트산 등의 다가 카르본산 혹은 이들 무수물을 탈수축합 또는 중합시켜 얻어지는 폴리에스테르폴리올류,As the high molecular polyol, various known polyester polyols, polyether polyols and the like are used. One or more of them may be used in combination. Examples of the polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl- Butanediol, 1,4-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5 pentanediol, hexanediol, Saturated or unsaturated compounds such as glycols, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaerythritol; The present invention relates to a process for producing a polyol which comprises reacting a low-molecular polyol with at least one member selected from the group consisting of adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, , Pyromellitic acid and the like, or polyester polyols obtained by dehydration condensation or polymerization of these anhydrides,

환상 에스테르 화합물, 예를 들어 폴리카프로락톤, 폴리발레로락톤, 폴리(β-메틸-γ-발레로락톤) 등의 락톤류를 개환중합하여 얻어지는 폴리에스테르폴리올류 등을 들 수 있다. 폴리에테르폴리올로는, 예를 들어, 산화메틸렌, 산화에틸렌, 산화프로필렌, 테트라하이드로퓨란 등의 중합체 또는 공중합체를 들 수 있다. 폴리에스테르폴리올에 있어서도, 폴리에테르폴리올에 있어서도 분지구조를 갖는 것이 특히 바람직하다.
And polyester polyols obtained by ring-opening polymerization of lactones such as cyclic ester compounds, for example, polycaprolactone, polyvalerolactone and poly (beta -methyl- gamma -valerolactone). The polyether polyol includes, for example, polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran. It is particularly preferable that the polyether polyol has a branched structure both in the polyester polyol and in the polyether polyol.

고분자 폴리올로서, 폴리에스테르디올이 20~80중량%, 및 폴리에테르디올 80~20중량%의 범위에 있는 것이 바람직하다. 폴리에스테르디올이 80중량% 이하이면 먹날림성이 우수하다. 폴리에테르디올이 80중량% 이하이면, 내블로킹성이 우수하다.
As the polymer polyol, it is preferable that the polyester diol is in the range of 20 to 80% by weight, and the polyether diol is in the range of 80 to 20% by weight. When the content of the polyester diol is 80% by weight or less, the polyolefin is excellent in bleeding resistance. When the polyether diol is 80% by weight or less, the blocking resistance is excellent.

본 실시형태에 있어서의 폴리우레탄 수지의 아민가는 2.0~7.0mgKOH/g이 바람직하고, 보다 바람직하게는 3.0~6.0mgKOH/g이다. 아민가가 2.0mgKOH/g보다 이상이면, 먹날림성, 접착성 및 EL 라미네이트 강도가 우수하고, 7.0mgKOH/g 이하이면 내블로킹성이 우수하다.
The amine value of the polyurethane resin in the present embodiment is preferably 2.0 to 7.0 mgKOH / g, and more preferably 3.0 to 6.0 mgKOH / g. When the amine value is not less than 2.0 mgKOH / g, the water repellency, the adhesion and the EL laminate strength are excellent, and when it is 7.0 mgKOH / g or less, the blocking resistance is excellent.

본 실시형태에 있어서의 폴리우레탄 수지의 중량평균분자량은 10000~70000이 바람직하고, 보다 바람직하게는 15000~60000이다. 중량평균분자량이 10000 이상이면 내블로킹성이 우수하고, 또한 내열성이 양호하므로 EL 라미네이트 강도도 우수하다. 중량평균분자량이 70000 이하이면, 먹날림성, 접착성 및 EL 라미네이트 강도가 우수하다.
The weight average molecular weight of the polyurethane resin in the present embodiment is preferably from 10,000 to 700,000, more preferably from 15,000 to 60,000. When the weight average molecular weight is 10,000 or more, the blockability is excellent and the heat resistance is excellent, so that the EL laminate strength is also excellent. When the weight-average molecular weight is 70,000 or less, excellent water repellency, adhesive property and EL laminate strength are obtained.

본 실시형태에 있어서의 폴리우레탄 수지의 합성은, 이하의 프리폴리머법으로 제조할 수 있다.The synthesis of the polyurethane resin in the present embodiment can be produced by the following prepolymer method.

1) 고분자 폴리올과 톨릴렌디이소시아네이트를 포함하는 폴리이소시아네이트를, 10~100℃의 온도에서 반응시켜, 말단에 이소시아네이트기를 갖는 프리폴리머를 제조한다. 상기 반응시에, 필요에 따라 이소시아네이트기에 대하여 불활성인 용매를 이용할 수도 있다. 또한, 필요에 따라, 우레탄화 촉매를 이용할 수도 있다.1) A polyisocyanate containing a polymer polyol and tolylene diisocyanate is reacted at a temperature of 10 to 100 ° C to prepare a prepolymer having an isocyanate group at the terminal. In the above reaction, a solvent which is inert to the isocyanate group may be used if necessary. If necessary, a urethanation catalyst may also be used.

2) 이어서, 이 프리폴리머에 쇄연장제로서 유기 디아민, 반응정지제로서 알칸올아민을 10~80℃에서 반응시켜 폴리우레탄 수지를 얻는다.
2) Then, the prepolymer is reacted with an organic diamine as a chain extender and an alkanolamine as a reaction terminator at 10 to 80 ° C to obtain a polyurethane resin.

본 실시형태의 폴리우레탄 수지 조성물에 사용되는 용제는, 에스테르계 용제와 알코올계 용제의 혼합용제를 포함한다. 이들 용제로는, 이하와 같은, 공지의 용제를 사용하는 것이 바람직하다.The solvent used in the polyurethane resin composition of the present embodiment includes a mixed solvent of an ester solvent and an alcohol solvent. As these solvents, it is preferable to use the following known solvents.

에스테르계 용제로는, 예를 들어, 아세트산에틸, 아세트산n-프로필, 아세트산이소프로필, 아세트산이소부틸, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트 등을 들 수 있다.Examples of the ester-based solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like.

알코올계 용제로는, 메탄올, 에탄올, n-프로판올, 이소프로판올, n-부탄올, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노메틸에테르 등을 들 수 있다.
Examples of the alcohol-based solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether and propylene glycol monomethyl ether.

우레탄화 반응에는 촉매를 이용할 수도 있다. 사용가능한 촉매로는, 예를 들어, 트리에틸아민, 디메틸아닐린 등의 3급아민계의 촉매; 주석, 아연 등의 금속계의 촉매 등을 들 수 있다. 이들 촉매는 통상 폴리올에 대하여 0.001~1몰%의 범위에서 사용된다.
A catalyst may be used for the urethanization reaction. Examples of usable catalysts include tertiary amine catalysts such as triethylamine and dimethylaniline; Tin and zinc, and the like. These catalysts are usually used in the range of 0.001 to 1 mol% based on the polyol.

반응정지제인 알칸올아민과, 쇄연장제인 유기 디아민은 함께 사용하여 쇄연장 반응을 행할 수도 있다. 혹은, 쇄연장제에 의해, 어느 정도, 쇄연장 반응을 행한 후에, 반응정지제를 단독으로 첨가하여 반응을 정지할 수도 있다.
The chain extension reaction may be carried out using an alkanolamine as a reaction terminator and an organic diamine as a chain extender together. Alternatively, after the chain extension reaction is performed to some extent by the chain extender, the reaction may be stopped by adding the reaction terminator alone.

본 실시형태의 인쇄 잉크 조성물에는, 착색제로서 무기계 착색제 및 유기계 착색제를 사용할 수 있다. 백색착색제에는, 무기계 착색제인 산화티탄을 사용할 수 있으며, 안료표면이 염기성인 것이 보다 바람직하다. 무기계 착색제로서, 백색착색제 이외에는, 카본블랙, 알루미늄, 마이카(운모) 등의 안료를 들 수 있다. 알루미늄은 분말 또는 페이스트상이지만, 취급성 및 안전성의 면에서 페이스트상으로 사용하는 것이 바람직하고, 리핑(leafing) 또는 논리핑(non-leafing)을 사용할 것인지는 휘도감 및 농도의 점으로부터 적당히 선택된다. 한편, 유기계 착색제로는, 일반 잉크, 도료, 및 기록제 등에 사용되고 있는 유기안료 및 유기염료를 들 수 있다. 예를 들어, 아조계, 프탈로시아닌계, 안트라퀴논계, 페릴렌계, 페리논계, 퀴나크리돈계, 티오인디고계, 디옥사진계, 이소인돌리논계, 퀴노프탈론계, 아조메틴아조계, 디케토(ジクト)피롤로피롤계, 이소인돌린계 등을 들 수 있다.
In the printing ink composition of the present embodiment, an inorganic colorant and an organic colorant may be used as the colorant. As the white colorant, titanium oxide which is an inorganic colorant can be used, and it is more preferable that the pigment surface is basic. Examples of the inorganic colorant include pigments such as carbon black, aluminum, and mica (mica) other than the white colorant. Although aluminum is in powder or paste form, it is preferably used in paste form in view of handleability and safety, and whether to use leafing or non-leafing is suitably selected from the viewpoint of brightness and concentration. On the other hand, organic-based coloring agents include organic pigments and organic dyes used in general inks, paints, and recording agents. For example, there may be mentioned azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine, diketo ) Pyrrolopyrrole-based, isoindoline-based, and the like.

착색제는, 인쇄 잉크의 농도·착색력을 확보하기에 충분한 양, 즉 인쇄 잉크의 총중량에 대하여 1~50중량%의 비율로 포함되는 것이 바람직하다. 또한, 이들 착색제는 단독으로, 또는 2종 이상을 병용하여 이용할 수 있다.
The colorant is preferably contained in an amount sufficient to ensure the concentration / coloring power of the printing ink, that is, in a proportion of 1 to 50% by weight based on the total weight of the printing ink. These coloring agents may be used alone or in combination of two or more.

본 실시형태의 인쇄 잉크 조성물은, 수지 및 착색제 등을, 유기용제 중에 용해 및/또는 분산함으로써 제조할 수 있다. 구체적으로는, 안료와 폴리우레탄 수지 조성물과 필요에 따라 다른 화합물을 유기용제에 분산시킨 안료분산체를 제조하고, 얻어진 안료분산체에, 다시 폴리우레탄 수지 조성물과 유기용제와 필요에 따라 다른 화합물을 배합함으로써, 잉크를 제조할 수 있다.
The printing ink composition of the present embodiment can be produced by dissolving and / or dispersing a resin and a coloring agent in an organic solvent. Specifically, a pigment dispersion in which a pigment, a polyurethane resin composition and, if necessary, another compound are dispersed in an organic solvent is prepared, and a polyurethane resin composition, an organic solvent, and other compounds By mixing, the ink can be produced.

폴리우레탄 수지에 의해 안료를 유기용제에 안정적으로 분산시키는데, 더욱 안정적으로 분산시키려면 분산제를 병용할 수도 있다. 분산제로는, 음이온성, 비이온성, 양(陽)이온성, 쌍이온성 등의 계면활성제를 사용할 수 있다. 분산제는, 잉크의 보존안정성의 관점으로부터, 잉크의 총중량에 대하여 0.05중량% 이상, 또한, 라미네이트 적성의 관점으로부터, 5중량% 이하로 잉크 중에 포함되는 것이 바람직하다. 나아가, 0.1~2중량%의 범위로 포함되는 것이 보다 바람직하다.
The pigment is stably dispersed in an organic solvent by a polyurethane resin, and a dispersant may be used in combination in order to more stably disperse the pigment. As the dispersing agent, surfactants such as anionic, nonionic, positive ionic, and pionic can be used. From the viewpoint of the storage stability of the ink, it is preferable that the dispersing agent is contained in the ink at not less than 0.05% by weight based on the total weight of the ink and not more than 5% by weight from the viewpoint of laminate suitability. Further, it is more preferable that it is contained in the range of 0.1 to 2% by weight.

안료분산체에 있어서의 안료의 입도분포는, 분산기의 분쇄 미디어의 사이즈, 분쇄 미디어의 충전율, 분산처리시간, 안료분산체의 토출속도, 안료분산체의 점도 등을 적당히 조절함으로써, 조정할 수 있다. 분산기로는 일반적으로 사용되는, 예를 들어, 롤러 밀, 볼 밀, 페블 밀, 아트리토(attritor), 샌드 밀 등을 이용할 수 있다.
The particle size distribution of the pigment in the pigment dispersion can be adjusted by appropriately adjusting the size of the pulverizing medium of the dispersing machine, the filling rate of the pulverizing medium, the dispersion processing time, the discharge speed of the pigment dispersion, and the viscosity of the pigment dispersion. As the dispersing machine, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill or the like which is generally used can be used.

본 실시형태의 인쇄 잉크 조성물에 사용되는 용제는, 에스테르계 용제와 알코올계 용제의 혼합용제이다. 에스테르계 용제, 및 알코올계 용제로는, 공지의 용제를 사용하는 것이 바람직하고, 구체예는 상기 서술한 바와 같다.
The solvent used in the printing ink composition of the present embodiment is a mixed solvent of an ester solvent and an alcohol solvent. As the ester type solvent and the alcohol type solvent, it is preferable to use a known solvent, and specific examples are as described above.

잉크 중에 기포나 예기치 않게 조대입자 등이 포함되는 경우에는, 인쇄물의 품질을 저하시키므로, 여과 등에 의해 제거하는 것이 바람직하다. 여과기는 종래 공지의 것을 사용할 수 있다.
When bubbles or unexpected coarse particles are contained in the ink, it is preferable to remove the ink by filtration or the like because it lowers the quality of the printed matter. As the filter, conventionally known ones can be used.

상기 방법으로 제조된 잉크의 점도는, 안료의 침강을 방지하고, 적당히 분산시키는 관점으로부터 10mPa·s 이상, 잉크제조시나 인쇄시의 작업성 효율의 관점으로부터 1000mPa·s 이하의 범위인 것이 바람직하다. 한편, 상기 점도는 Tokimec, Inc.제 B형 점도계로 25℃에서 측정된 점도이다.
The viscosity of the ink prepared by the above method is preferably in the range of 10 mPa · s or more from the viewpoint of preventing the sedimentation of the pigment and dispersing it appropriately, and in the range of 1000 mPa · s or less from the viewpoint of ink- On the other hand, the viscosity is a viscosity measured at 25 캜 by Tokimec, Inc. B type viscometer.

인쇄 잉크 조성물은, 그라비어 인쇄, 플렉소 인쇄 등의 이미 알려진 인쇄방식으로 이용할 수 있다. 예를 들어, 그라비어 인쇄에 이용하는 경우에는, 그라비어 인쇄에 적합한 점도 및 농도까지 희석용제로 희석되고, 단독으로 또는 혼합되어 각 인쇄유닛에 공급된다. 바람직하게는, 그라비어 인쇄이다.
The printing ink composition can be used in a known printing method such as gravure printing, flexographic printing and the like. For example, in the case of using for gravure printing, the mixture is diluted with a diluting solvent to a viscosity and a concentration suitable for gravure printing, and supplied to each printing unit singly or in combination. Preferably, it is gravure printing.

인쇄 잉크 조성물을 적용할 수 있는 기재로는, 예를 들어, 폴리에틸렌, 폴리프로필렌 등의 폴리올레핀, 폴리에틸렌테레프탈레이트, 폴리카보네이트, 폴리유산 등의 폴리에스테르, 폴리스티렌, AS 수지, ABS 수지 등의 폴리스티렌계 수지, 나일론, 폴리아미드, 폴리염화비닐, 폴리염화비닐리덴, 셀로판, 종이, 알루미늄 등, 혹은 이들의 복합재료로 이루어진 필름상 혹은 시트상의 것을 들 수 있다. 상기 인쇄방식을 이용하여 기재에 인쇄 잉크 조성물을 도포하고, 오븐에 의한 건조에 의해 정착시킴으로써, 인쇄물을 얻을 수 있다. 기재는, 금속산화물 등을 표면에 증착하는 증착 코팅처리 및/또는 폴리비닐알코올 등을 코팅하는 코팅처리가 이루어져 있을 수도 있다. 또한 기재에 코로나 처리 등의 표면처리가 이루어져 있을 수도 있다.
Examples of the substrate to which the printing ink composition can be applied include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin , Nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum and the like, or a composite material thereof. A printed material can be obtained by applying a printing ink composition to a substrate using the above printing method and fixing it by drying with an oven. The base material may be subjected to a vapor deposition coating process for depositing a metal oxide or the like on the surface and / or a coating process for coating polyvinyl alcohol or the like. Further, the substrate may be subjected to surface treatment such as corona treatment.

인쇄물에, 라미네이트 가공을 실시하여 에이징하면, 라미네이트 적층체가 얻어진다. 라미네이트 가공법으로는,When the printed matter is subjected to lamination and aging, a laminate laminate is obtained. As a lamination method,

1) 얻어진 인쇄물의 인쇄면에, 필요에 따라 앵커코팅제를 도포 후, 용융 수지를 적층하는 압출 라미네이트법,1) an extrusion lamination method in which an anchor coating agent is applied to the printed surface of the obtained print, if necessary, and then a molten resin is laminated,

2) 접착제를 도포 후, 필요에 따라 건조시키고, 플라스틱 필름을 적층하는 드라이 라미네이트법 등을 들 수 있다.2) a dry lamination method in which an adhesive is applied, then dried if necessary, and a plastic film is laminated.

용융 수지로는, 예를 들어, 저밀도 폴리에틸렌, 폴리프로필렌, 에틸렌-아세트산비닐 공중합체 등을 사용할 수 있다. 접착제로는, 예를 들어, 이민계, 이소시아네이트계, 폴리부타디엔계, 티타네이트계 등을 들 수 있다.
As the molten resin, for example, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like can be used. Examples of the adhesive include an imine-based, isocyanate-based, polybutadiene-based, and titanate-based adhesive.

실시예
Example

이하, 실시예를 들어 본 발명의 실시형태를 상세하게 설명하는데, 본 발명은 이들 실시예로 한정되는 것은 아니다. 이하, 「부」 및 「%」는, 특별한 주석이 없는 경우, 각각 「중량부」 및 「중량%」를 나타낸다.
Hereinafter, embodiments of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, " parts " and "%" indicate " parts by weight " and "% by weight "

한편, 수산기가는, 수지 중의 수산기를 과잉 아세틸화 시약으로 아세틸화하고, 잔존하는 산을 알칼리로 역적정(逆適定)하여 산출한 수지 1g 중의 수산기량을, 수산화칼륨의 mg수로 환산한 값으로서, JIS K0070에 따라 행한 값이다. 아민가는, 수지 1g 중에 함유하는 아미노기를 중화하는데 필요한 염산의 당량과 동량인 수산화칼륨의 mg수이다. 산가는, 수지 1g 중에 함유하는 산기를 중화하는데 필요한 수산화칼륨의 mg수이고, 측정방법은 이미 알려진 방법이면 되는데, 일반적으로는 JIS K0070(1996년)에 준거하여 이루어진다. 분자량은 GPC(겔 퍼미에이션 크로마토그래피) 장치를 이용하여 분자량 분포를 측정하고, 폴리스티렌 환산 분자량으로서 구하였다. 아민가의 측정방법은, 하기와 같다.
On the other hand, the hydroxyl value is obtained by acetylating the hydroxyl group in the resin with an excess acetylating reagent, and calculating the amount of hydroxyl groups in 1 g of the resin calculated by reversely titrating the remaining acid with alkali to the number of mg of potassium hydroxide And is a value made in accordance with JIS K0070. Amine is the number of mg of potassium hydroxide which is the same as the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid group contained in 1 g of the resin. The measurement method may be any known method, and is generally performed in accordance with JIS K0070 (1996). The molecular weight was determined by measuring the molecular weight distribution using a GPC (Gel Permeation Chromatography) apparatus and calculating the molecular weight in terms of polystyrene. The measurement method of amine value is as follows.

[아민가의 측정방법][Measurement method of amine value]

시료를 0.5~2g 정칭한다. (시료량:Sg) 정칭한 시료에 중성 에탄올(BDG 중성) 30mL를 첨가하여 용해시킨다. 얻어진 용액에 지시약으로서 브로모페놀블루를 첨가하고, 0.2mol/L 에탄올성 염산용액(역가:f)으로 적정(滴定)을 행한다. 용액의 색이, 녹색에서 황색 사이의 색으로 변한 점을 종점으로 하고, 이때의 적정량(AmL)을 이용하여 다음 (식 1)으로부터 아민가를 구하였다.
0.5 to 2 g of the sample is determined. (Sample amount: Sg) 30 ml of neutral ethanol (BDG neutral) is added to the sample to be dissolved. Bromophenol blue is added as an indicator to the obtained solution, and titration is performed with a 0.2 mol / L ethanolic hydrochloric acid solution (activity: f). The amine value was determined from the following formula (1) using the appropriate amount (AmL) at the point where the color of the solution changed from green to yellow.

계산식 1Equation 1

아민가=(A×f×0.2×56.108)/S [mgKOH/g]
Amine value = (A x f x 0.2 x 56.108) / S [mg KOH / g]

[합성예 1][Synthesis Example 1]

교반기, 온도계, 환류냉각기 및 질소가스 도입관을 구비한 4구 플라스크에, 분자량 2000의 PPA2000(수산기가 56.1mgKOH/g) 111.99부, 분자량 1000의 PPG1000(수산기가 112.2mgKOH/g) 111.99부, 톨릴렌디이소시아네이트 52.65부, 2-에틸헥산산주석(II) 0.03부, 아세트산에틸 82.5부를 투입하고, 질소기류하에 90℃에서 3시간 반응시켜, 말단 이소시아네이트 프리폴리머의 용액 359.16부를 얻었다. 이어서 이소포론디아민 21.74부, 모노에탄올아민 1.64부, 이소프로필알코올 290부, 아세트산에틸 327.47부를 혼합한 것에, 얻어진 말단 이소시아네이트 프리폴리머의 용제용액 359.16부를 실온에서 서서히 첨가하고, 다음에 50℃에서 1시간 반응시켜, 고형분 30.0%, 중량평균분자량 30000, 아민가 4.0mgKOH/g의 폴리우레탄 수지 조성물(PU01)을 얻었다.
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introducing tube, 111.99 parts of PPA2000 (molecular weight of 56.1 mgKOH / g) having a molecular weight of 2000, 111.99 parts of PPG1000 having a molecular weight of 1000 (112.2 mgKOH / g of a hydroxyl group) (52.65 parts), tin (II) 2-ethylhexanoate (0.03 parts) and ethyl acetate (82.5 parts) were charged and reacted at 90 占 폚 for 3 hours under a nitrogen stream to obtain 359.16 parts of a solution of a terminal isocyanate prepolymer. Subsequently, 359.16 parts of the solvent solution of the obtained terminal isocyanate prepolymer was slowly added to the mixed solution of 21.74 parts of isophorone diamine, 1.64 parts of monoethanolamine, 290 parts of isopropyl alcohol and 327.47 parts of ethyl acetate, and then the mixture was reacted at 50 DEG C for 1 hour To obtain a polyurethane resin composition (PU01) having a solid content of 30.0%, a weight average molecular weight of 30,000, and an amine value of 4.0 mgKOH / g.

[합성예 2~26][Synthesis Examples 2 to 26]

표 1~3의 투입비로, 합성예 1과 동일한 조작으로, 폴리우레탄 수지 조성물(PU02~PU26)을 얻었다.
Polyurethane resin compositions (PU02 to PU26) were obtained in the same manner as in Synthesis Example 1, at the charging ratios shown in Tables 1 to 3.

[실시예 1][Example 1]

산화티탄(TITONE R45M Sakai Chemical Industry Co., Ltd.제) 30.00부, 폴리우레탄 수지 조성물(PU01) 10.00부, 아세트산에틸/이소프로필알코올 혼합용제(중량비 70/30) 10.00부를 교반혼합하여 샌드 밀로 연육(練肉)하였다. 다시, 폴리우레탄 수지 조성물(PU01) 40.00부, 아세트산에틸/이소프로필알코올 혼합용제(중량비 70/30) 10.00부를 첨가하여 교반혼합하여, 백색 인쇄 잉크 조성물(W01)을 얻었다. 다시, 이 백색 인쇄 잉크 조성물 100.00부에, 중량비로 아세트산에틸/이소프로필알코올=85/15의 희석용제 1, 또는 아세트산에틸/이소프로필알코올=50/50의 희석용제 2를, 각각 40.00부 혼합하여, 평가용 백색 희석 인쇄 잉크 1 및 백색 희석 인쇄 잉크 2로 하였다.
, 10.00 parts of a titanium oxide (TITONE R45M manufactured by Sakai Chemical Industry Co., Ltd.), 10.00 parts of a polyurethane resin composition (PU01) and 10.00 parts of an ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) (Kneaded). 40.00 parts of a polyurethane resin composition (PU01) and 10.00 parts of an ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) were added and stirred to obtain a white printing ink composition (W01). To 100.00 parts of this white printing ink composition, 40.00 parts of a diluting solvent 1 of ethyl acetate / isopropyl alcohol = 85/15 or a diluting solvent 2 of ethyl acetate / isopropyl alcohol = 50/50 were mixed in a weight ratio , White dilution printing ink 1 for evaluation and white dilution printing ink 2.

[실시예 2~18][비교예 1~8][Examples 2 to 18] [Comparative Examples 1 to 8]

폴리우레탄 수지 조성물(PU01)을 각각 폴리우레탄 수지 조성물(PU02)~(PU26)로 변경한 것을 제외하고는, 실시예 1과 동일한 조작으로, 백색 인쇄 잉크 조성물(W02~26)을 얻었다. 한편, 각각의 인쇄 잉크 조성물에 이용하는 폴리우레탄 수지 조성물은 표 4~6과 같았다. 또한, 실시예 1과 동일한 조작으로, 얻어진 백색 인쇄 잉크 조성물 100.00부에, 중량비로 아세트산에틸/이소프로필알코올=85/15의 희석용제 1, 또는 아세트산에틸/이소프로필알코올=50/50의 희석용제 2를, 각각 40.00부 혼합하여, 평가용 백색 희석 인쇄 잉크 1 및 백색 희석 인쇄 잉크 2로 하였다.
White printing ink compositions (W02 to 26) were obtained in the same manner as in Example 1 except that the polyurethane resin composition (PU01) was changed to the polyurethane resin compositions (PU02) to (PU26), respectively. On the other hand, the polyurethane resin compositions used for the respective printing ink compositions were as shown in Tables 4 to 6. In the same manner as in Example 1, 100.00 parts of the obtained white printing ink composition was mixed with a diluting solvent 1 of ethyl acetate / isopropyl alcohol = 85/15, or a diluting solvent of ethyl acetate / isopropyl alcohol = 2 were each mixed at 40.00 parts to prepare a white dilution printing ink for evaluation 1 and a white dilution printing ink 2 for evaluation.

한편 합성예 및 실시예에 있어서 하기의 원료를 이용하였다.On the other hand, the following raw materials were used in Synthesis Examples and Examples.

PPA2000: 폴리(1,2-프로필렌아디페이트)디올 (수평균분자량 2000)PPA2000: poly (1,2-propylene adipate) diol (number average molecular weight 2000)

NPG2000: 폴리(네오펜틸아디페이트)디올 (수평균분자량 2000)NPG2000: poly (neopentyl adipate) diol (number average molecular weight 2000)

PMPA2000: 폴리(3-메틸-1,5-펜탄아디페이트)디올 (수평균분자량 2000)PMPA2000: poly (3-methyl-1,5-pentanadipate) diol (number average molecular weight 2000)

PPG1000: 폴리(1,2-프로필렌글리콜) (수평균분자량 1000)PPG1000: poly (1,2-propylene glycol) (number average molecular weight 1000)

TDI: 톨릴렌디이소시아네이트TDI: tolylene diisocyanate

IPDI: 이소포론디이소시아네이트IPDI: isophorone diisocyanate

MDI: 디페닐메탄디이소시아네이트MDI: diphenylmethane diisocyanate

IPDA: 이소포론디아민IPDA: isophorone diamine

MEA: 모노에탄올아민MEA: Monoethanolamine

DEA: 디에탄올아민DEA: diethanolamine

DBA: 디-n-부틸아민DBA: di-n-butylamine

IPA: 이소프로필알코올IPA: Isopropyl alcohol

HDA: 헥사메틸렌디아민HDA: hexamethylenediamine

AEA: 2-하이드록시에틸에틸렌디아민
AEA: 2-hydroxyethylethylenediamine

[먹날림성][Spillability]

NBR(니트릴부타디엔고무)제의 고무경도 80Hs의 압동(壓胴), 인선(刃先)의 두께가 60μm(모재의 두께 40μm, 편측 세라믹층의 두께 10μm)인 세라믹 도금 닥터블레이드, Toyo Prepress Co., Ltd.제의 크롬경도 1050Hv의 전자조각판(스타일러스 각도 120도, 200선/inch)의 Fuji Kikai Kogyo Co., Ltd.제 그라비어 인쇄기에, 백색 희석 인쇄 잉크 1 또는 백색 희석 인쇄 잉크 2를 세팅하였다. 다음에, 닥터압(ドクタ-壓) 2kg/cm2, 100m/분의 회전속도로 공전을 60분 행한 후, 편면 코로나 처리 OPP 필름 「PYLEN P-2161(Toyobo Co., Ltd.제)」의 코로나 처리면에, 인쇄속도 100m/분, 인압(印壓;인쇄압) 2kg/cm2로 인쇄하고, 60℃의 열풍으로 건조하여, 인쇄물을 얻었다. 이 인쇄물을 흑색 종이 위에 붙여, 여백부분(비화상부)에 부착된 잉크의 양을 이하의 기준으로 육안 평가하였다.A ceramic plate doctor blade made of NBR (nitrile butadiene rubber) having a rubber hardness of 80 Hs and a thickness of 60 占 퐉 (base material thickness: 40 占 퐉, thickness of one side ceramic layer: 10 占 퐉); Toyo Prepress Co., A white dilution printing ink 1 or a white dilution printing ink 2 was set on a gravure printing machine manufactured by Fuji Kikai Kogyo Co., Ltd. with a chrome hardness of 1050 Hv (stylus angle of 120 degrees, 200 lines / inch) . Thereafter, revolution was performed for 60 minutes at a doctor pressure (doctor-pressure) of 2 kg / cm 2 at a rotation speed of 100 m / min, and then the single-sided corona-treated OPP film "PYLEN P-2161 (manufactured by Toyobo Co., Ltd.) The corona-treated surface was printed at a printing speed of 100 m / min and a pressure of 2 kg / cm 2 and dried with hot air at 60 캜 to obtain a printed product. The printed matter was stuck on a black paper, and the amount of ink adhering to the blank portion (non-formed portion) was visually evaluated based on the following criteria.

◎ : 비화상부에 잉크의 전이가 전혀 보이지 않았다.&Amp; cir &: No ink transition was observed at the non-image portion.

○ : 비화상부에 잉크의 전이가 약간 보였다.○: The transition of the ink was slightly visible on the non-image area.

○△ : 비화상부의 소면적에 잉크의 전이가 보였다. 이 이상 실용레벨이다.?: The ink was transferred to a small area of the non-image area. This is the ideal practical level.

△ : 비화상부의 대면적에 잉크의 전이가 보였다.?: Transition of ink was observed in a large area of the non-developed area.

△× : 비화상부의 거의 전체면에 잉크의 전이가 보였다.DELTA x: Transition of ink was observed on almost the entire surface of the non-image portion.

(△와 ×의 중간정도의 전이량이다)(A transition amount intermediate between? And X)

× : 비화상부 전체면에 잉크의 전이가 보였다.
X: Transition of ink was observed on the entire surface of the non-image portion.

[내블로킹성][My blocking ability]

백색 희석 인쇄 잉크 1을, 판심(版深) 35μm 그라비어판을 구비한 그라비어 교정기에 의한 코로나 처리 OPP 필름(TAIKO FOR FUTAMURA #20)에 인쇄하여 40~50℃에서 건조하고, 인쇄물을 얻었다. 이 인쇄물을 4cm×4cm로 샘플링하고, 이 샘플의 인쇄면과 동일한 크기의 미인쇄필름의 비처리면을 함께, 50℃ 12시간, 10kgf의 가압을 행하고, 샘플을 박리했을 때의, 탈잉크(インキ取られ; ink removal or ink taken-off)(잉크의 전이) 및 저항감을 관찰하였다.The white diluted printing ink 1 was printed on a corona-treated OPP film (TAIKO FOR FUTAMURA # 20) with a gravure calibrator equipped with a 35 μm gravure plate and dried at 40 to 50 ° C to obtain a printed product. The printed matter was sampled at 4 cm x 4 cm and untreated surfaces of unprinted films of the same size as those of the sample were pressed together at 50 ° C for 12 hours under a pressure of 10 kgf to remove the sample Ink removal or ink taken-off (ink transfer) and resistance were observed.

◎ : 인쇄물로부터 잉크의 전이가 전혀 보이지 않았으며, 박리시 저항감도 없었다.&Amp; cir & & cir & & cir & & cir &

○ : 인쇄물로부터 잉크의 전이가 전혀 보이지 않았으나, 박리시 저항감이 있었다.?: No ink transfer from the printed material was observed at all, but there was a resistance to peeling.

○△: 인쇄물로부터 잉크의 전이가 보였으나, 면적으로 했을 때 10% 미만이었다.?: The ink was transferred from the printed matter, but the area was less than 10%.

이 이상 실용레벨이다.This is the ideal practical level.

△ : 인쇄물로부터 잉크의 전이가, 10% 이상 50% 미만의 면적에서 보였다.?: Transition of ink from printed matter was observed in an area of 10% or more and less than 50%.

× : 인쇄물로부터 잉크의 전이가, 50% 이상의 면적에서 보였다.
X: Transition of ink from printed matter was observed in an area of 50% or more.

[접착성][Adhesiveness]

내블로킹성 시험에서 얻은 인쇄물에 셀로판테이프(Nichiban Co., Ltd.제, 폭 12mm)를 붙이고, 엄지손가락으로 5회 강하게 문지른 후, 셀로판테이프를 서서히 떼어내고, 도중에 급격히 떼어내어 잉크 피막의 박리 정도를 조사하였다.A cellophane tape (made by Nichiban Co., Ltd., 12 mm in width) was attached to the printed matter obtained in the blocking resistance test and rubbed strongly with the thumb five times. Then, the cellophane tape was gradually removed and rapidly peeled off to remove the ink film Respectively.

◎ : 천천히 떼어내어도, 급격히 떼어내어도, 전혀 잉크의 박리가 보이지 않았다.◎: Even if peeling off slowly, peeling off ink was not observed at all even if peeling off suddenly.

○ : 천천히 떼어내어도 전혀 잉크의 박리는 보이지 않으나, 급격히 떼어내면 잉크의 박리가 20% 미만의 면적에서 보였다. 이 이상 실용레벨이다.A: The ink was not peeled off even if it was slowly peeled off, but the peeling of the ink was observed in an area of less than 20% when the peeled off rapidly. This is the ideal practical level.

△ : 천천히 떼어내어도 잉크의 박리는 보이지 않으나, 급격히 떼어내면 잉크의 박리가 20% 이상의 면적에서 보였다.?: The ink did not peel off even if it was slowly peeled off, but the peeling of the ink was observed in an area of 20% or more when the peeled off rapidly.

△×: 천천히 떼어내어도 50% 정도까지의 면적의 잉크의 박리가 보였다.&Amp; cir & & tilde & • & cir & & tilde &

× : 천천히 떼어내어도 대부분의 잉크의 박리가 보였다.
×: Most of the ink was peeled off even if it was slowly peeled off.

[내알코올블리드성][Alcohol bleedability]

백색 희석 인쇄 잉크 1을, 판심 35μm 그라비어판을 구비한 그라비어 교정기에 의해, 코로나 처리 OPP 필름(TAIKO FOR FUTAMURA #20)에 인쇄하여, 40~50℃에서 건조하고, 이어서 인라인으로 이소프로필알코올을 도공, 40~50℃에서 건조하고, 블리드 자국의 흔적 등 외관을 관찰하였다.The white diluted printing ink 1 was printed on a corona-treated OPP film (TAIKO FOR FUTAMURA # 20) with a gravure calibrator equipped with a corrugated 35-μm gravure plate, dried at 40 to 50 ° C and then coated with isopropyl alcohol in-line , Dried at 40 to 50 ° C, and the appearance such as traces of bleeding marks was observed.

◎ : 인쇄물에 외관불량의 발생은 없었다.&Amp; cir &: No bad appearance occurred in printed matter.

○ : 인쇄물에 약간 얼룩이 보였다. 이 이상 실용레벨이다.○: The printed matter was slightly stained. This is the ideal practical level.

△ : 인쇄물에 연하게 블리드 자국이 보였다.B: bleeding marks were seen on the print.

× : 인쇄물에 명확하게 블리드 자국이 보였다.
X: The bleeding marks clearly appeared on the printed matter.

[EL 라미네이트 강도][EL Laminate Strength]

먹날림성 시험의 인쇄조건으로, 백색 희석 인쇄 잉크 1을, 기재의 코로나 처리면에 인쇄하여, 인쇄물을 얻었다. 여기서 이용한 기재는, 편면 코로나 처리에서 두께 20μm의 폴리프로필렌(이하, OPP라 한다.) 필름 「PYLEN P-2161(Toyobo Co., Ltd.제)」, 및 편면 코로나 처리에서 두께 12μm의 폴리에틸렌테레프탈레이트(이하, PET로 한다.) 필름 「Toyobo Co., Ltd. 에스테르 필름 E5100(Toyobo Co., Ltd.제)」이다. 다음에, 인쇄면 상에, 폴리에틸렌이민계 앵커코팅제 「Oribain EL-420」(Toyo-Morton, Ltd.제, 상품명)을 도포하였다. 다시, 도포면 상에 실런트로서 저밀도 폴리에틸렌 「Novatec LC600」(Japan polychem Corporation제, 상품명)의 용융온도를 315℃에서 압출하여, 라미네이트 가공물을 얻었다. 즉, (Extrusion laminate(EL))에 의해, 라미네이트 가공물을 얻었다. 저밀도 폴리에틸렌의 용융온도는, 압출 라미네이트기의 T다이 바로 밑에 있어서의 온도를 접촉식 온도계(Anritsu Meter Co., Ltd.제 HL-100)로 측정하였다. 이 라미네이트 가공물에 있어서의 잉크부를 너비 15mm로 재단하고, 잉크면과 용융 수지층의 층간에서 박리시킨 후, 박리강도를 INTESCO Co., Ltd.제 201 만능 인장 시험기로 박리강도의 측정을 행하였다. 한편, OPP를 이용한 라미네이트 가공물(OPP/이민 구성)에서는 1.0N/15mm 이상, PET를 이용한 라미네이트 가공물(PET/이민 구성)에서는 1.5N/15mm 이상을 실용레벨로 한다.
As a printing condition of the ink bleeding test, the white diluted printing ink 1 was printed on the corona-treated side of the substrate to obtain a printed matter. PYLEN P-2161 (manufactured by Toyobo Co., Ltd.) having a thickness of 20 占 퐉 in a single-sided corona treatment and polyethyleneterephthalate (Hereinafter referred to as PET) film "Toyobo Co., Ltd." Ester film E5100 (manufactured by Toyobo Co., Ltd.) ". Next, a polyethylene imine anchor coating agent " Oribain EL-420 " (trade name, manufactured by Toyo-Morton, Ltd.) was applied on the printing surface. Again, the melt temperature of low density polyethylene "Novatec LC600" (trade name, manufactured by Japan Polychem Corporation) as a sealant was extruded at 315 ° C to obtain a laminate workpiece. Namely, by extrusion laminate (EL), a laminate workpiece was obtained. The melting temperature of the low density polyethylene was measured with a contact type thermometer (HL-100 manufactured by Anritsu Meter Co., Ltd.) under the T die of the extruded laminate machine. The ink portion of the laminated workpiece was cut to a width of 15 mm and peeled off between the ink surface and the molten resin layer. The peel strength was measured by a 201 universal tensile tester manufactured by INTESCO Co., Ltd. On the other hand, a practical level is set to 1.0 N / 15 mm or more for a laminated workpiece (OPP / imine composition) using OPP and 1.5 N / 15 mm or more for a laminated workpiece using PET (PET / imine composition).

평가결과를 표 4~6에 정리한다. 실시예 1~18의 인쇄 잉크는, 비교예 1~8의 인쇄 잉크 조성물과 비교할 때, 에스테르/알코올 용제계에 있어서 우수한 먹날림성 등의 인쇄적성을 나타내고, 또한 내블로킹성, 접착성, 내알코올블리드성, 나아가 라미네이트 적성 등의 인쇄물성을 확보할 수 있는, 인쇄 잉크 조성물을 제공할 수 있다.The evaluation results are summarized in Tables 4-6. The printing inks of Examples 1 to 18 exhibited excellent printability such as ink-repellency in the ester / alcohol solvent system as compared with the printing ink compositions of Comparative Examples 1 to 8, and exhibited excellent blocking resistance, It is possible to provide a printing ink composition capable of ensuring printing property such as alcohol bleeding property and further laminate suitability.

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Figure pct00006

Claims (3)

톨릴렌디이소시아네이트를 포함하는 폴리이소시아네이트와 고분자 폴리올을 반응시켜 이루어지는 말단에 이소시아네이트기를 갖는 우레탄 프리폴리머를, 유기 디아민 및 알칸올아민과 반응시켜 이루어지는 폴리우레탄 수지,
그리고 혼합용제를 포함하는 폴리우레탄 수지 조성물에 있어서,
하기의 (A)~(F)인 것을 특징으로 하는 폴리우레탄 수지 조성물.
(A) 폴리이소시아네이트의 전체 이소시아네이트기와 고분자 폴리올의 수산기와의 반응에 있어서의 몰비[NCO(전체)]/[OH]가, 1.8~2.3이다.
(B) 톨릴렌디이소시아네이트의 이소시아네이트기와 고분자 폴리올의 수산기와의 반응에 있어서의 몰비[NCO(TDI)]/[OH]가, 1.0~2.1이다.
(C) 폴리우레탄 수지의 수산기가가 1.0~10.0mgKOH/g이다.
(D) 유기 디아민의 몰수 d1과 알칸올아민의 몰수 d2의 몰비 d1/d2가, 3~25이다.
(E) 혼합용제가, 에스테르계 용제와 알코올계 용제를 포함한다.
(F) 고분자 폴리올이, 폴리에스테르디올과 폴리에테르디올로 이루어진다.
A polyurethane resin obtained by reacting a polyisocyanate containing a tolylene diisocyanate with a high molecular polyol and reacting a urethane prepolymer having an isocyanate group at the terminal thereof with an organic diamine and an alkanolamine,
In a polyurethane resin composition containing a mixed solvent,
The polyurethane resin composition according to any one of (A) to (F) below.
(NCO (total)) / [OH] in the reaction between the entire isocyanate group of the polyisocyanate (A) and the hydroxyl group of the high molecular polyol is 1.8 to 2.3.
(B) the molar ratio [NCO (TDI)] / [OH] in the reaction of the isocyanate group of tolylene diisocyanate with the hydroxyl group of the high molecular polyol is 1.0 to 2.1.
(C) the hydroxyl value of the polyurethane resin is 1.0 to 10.0 mg KOH / g.
(D) the molar ratio d1 / d2 of the number of moles d1 of the organic diamine to the number of moles d2 of the alkanolamine is 3 to 25. [
(E) the mixed solvent includes an ester solvent and an alcohol solvent.
(F) The polymer polyol is composed of a polyester diol and a polyether diol.
제1항에 있어서,
고분자 폴리올 중, 상기 폴리에스테르디올이 20~80중량%, 상기 폴리에테르디올이 80~20중량%인 것을 특징으로 하는 폴리우레탄 수지 조성물.
The method according to claim 1,
Wherein the polyester diol is 20 to 80% by weight and the polyether diol is 80 to 20% by weight in the polymer polyol.
제1항 또는 제2항에 기재된 폴리우레탄 수지 조성물을 함유하는 것을 특징으로 하는 인쇄 잉크 조성물.A printing ink composition comprising the polyurethane resin composition according to claim 1 or 2.
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