JP6006865B2 - Ink for inkjet printer and printed matter - Google Patents
Ink for inkjet printer and printed matter Download PDFInfo
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- JP6006865B2 JP6006865B2 JP2015508166A JP2015508166A JP6006865B2 JP 6006865 B2 JP6006865 B2 JP 6006865B2 JP 2015508166 A JP2015508166 A JP 2015508166A JP 2015508166 A JP2015508166 A JP 2015508166A JP 6006865 B2 JP6006865 B2 JP 6006865B2
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
Description
本発明は、インクジェットプリンタに使用されるインク及び印字物に関する。 The present invention relates to ink and printed matter used in an ink jet printer.
ポリオレフィン樹脂などで構成された表面の活性が極めて乏しい基板にマーキング（印字、印刷）をする場合、基板と印字した塗膜との密着性が低いために、印字した塗膜が、その表面に他の物体が接触し、擦れること等によって容易に剥離する場合がある。 When marking (printing, printing) on a substrate composed of polyolefin resin or the like that has a very poor surface activity, the printed coating is not on the surface because the adhesion between the substrate and the printed coating is low. May come off easily when the object touches and rubs.
特許文献１には、インクの基板密着性を向上させることを目的として、塩素化ポリプロピレンを添加したインクが開示されている。 Patent Document 1 discloses an ink added with chlorinated polypropylene for the purpose of improving the substrate adhesion of the ink.
特許文献１のインクでは、印字物とポリオレフィン基板との密着性を向上することができる一方で、塩素化ポリプロピレンの添加量が多く、インクジェットプリンタ装置中の金属製接液部材が腐食し易いという課題がある。 In the ink of Patent Document 1, while the adhesion between the printed matter and the polyolefin substrate can be improved, the amount of the chlorinated polypropylene added is large, and the metal wetted member in the ink jet printer apparatus is easily corroded. There is.
本発明の目的は、印字物とポリオレフィン樹脂基板との密着性の向上と、装置負荷軽減とを両立することにある。 An object of the present invention is to achieve both improvement in adhesion between a printed matter and a polyolefin resin substrate and reduction in apparatus load.
本発明は、着色剤、複数種の樹脂、及び添加剤を含み、ポリオレフィン樹脂の基板に形成された印字物において、樹脂のうち少なくとも一種類を塩素系樹脂とし、印字物における塩素系樹脂の濃度は、空気と印字物との界面である空気界面近傍部よりも、基板と印字物との界面である印字基板界面近傍部の方が高いことを特徴とする。 The present invention includes a colorant, a plurality of types of resins, and an additive, and in a printed matter formed on a polyolefin resin substrate, at least one of the resins is a chlorine-based resin, and the concentration of the chlorine-based resin in the printed matter Is characterized in that the vicinity of the printed substrate interface, which is the interface between the substrate and the printed matter, is higher than the vicinity of the air interface, which is the interface between the air and the printed matter.
また、本発明は、着色剤、樹脂、及び溶剤を含むインクジェットプリンタ用インクにおいて、樹脂として塩素系樹脂を用い、溶剤が主溶剤及び副溶剤から構成され、主溶剤の２０℃における蒸気圧が９．０ｋＰａ以上であり、副溶剤の２０℃における蒸気圧が０．６〜２．０ｋＰａであることを特徴とする。 In addition, the present invention provides an inkjet printer ink that includes a colorant, a resin, and a solvent. A chlorine resin is used as the resin, the solvent is composed of a main solvent and a sub-solvent, and the vapor pressure of the main solvent at 20 ° C. is 9 0.0 kPa or more, and the vapor pressure at 20 ° C. of the auxiliary solvent is 0.6 to 2.0 kPa.
本発明によれば、印字物とポリオレフィン樹脂基板との密着性の向上と、装置負荷軽減とを両立することができる。 According to the present invention, it is possible to achieve both improvement in adhesion between the printed matter and the polyolefin resin substrate and reduction in apparatus load.
本明細書においては、インクが被印字基材に着弾し、インクに含まれる溶剤が蒸発することにより形成されたものを「印字物」と称する。印字物は、一般に、ドット状の塗膜又はその集合体であるが、形状はドットに限定されるものではない。また、被印字基材と、その表面に付着した印字物とを含むものを「印字済み部材」と称することにする。 In the present specification, a product formed by ink landing on a substrate to be printed and evaporation of a solvent contained in the ink is referred to as “printed matter”. The printed matter is generally a dot-like coating film or an aggregate thereof, but the shape is not limited to dots. In addition, a member including a substrate to be printed and printed matter attached to the surface thereof is referred to as a “printed member”.
本発明は、ポリオレフィン樹脂基板に形成された印字物に含まれる塩素系樹脂を基板近傍に偏在させる。即ち、空気と印字物との界面（空気界面近傍部）よりも、基板と印字物との界面（印字基板界面近傍部）の方が塩素系樹脂の濃度が高くなっている。これにより、インクに添加する塩素系樹脂の量を抑えるとともに、基板に対する高い密着性を得ることができる。 In the present invention, a chlorinated resin contained in a printed matter formed on a polyolefin resin substrate is unevenly distributed in the vicinity of the substrate. That is, the chlorine-based resin concentration is higher at the interface between the substrate and the printed matter (near the printed substrate interface) than at the interface between the air and the printed matter (near the air interface). Thereby, while suppressing the quantity of the chlorine-type resin added to an ink, the high adhesiveness with respect to a board | substrate can be acquired.
上記の印字物構造を実現するため、インクに蒸発速度の遅い有機溶剤を加えることにより、乾燥速度を抑制させる。本発明は、インクジェットプリンタ用のインクとして必要な速乾性を維持するため、蒸発速度の速い有機溶剤をベースにしつつ、蒸発速度の遅い有機溶剤も混ぜる。これにより、インクが基材に着弾した後インクが空気界面から乾燥する際、基板との親和性が最も高い塩素系樹脂が基板に選択的に付着する時間を確保でき、基板近傍への偏在を促進できる。 In order to realize the above-described printed matter structure, the drying rate is suppressed by adding an organic solvent having a slow evaporation rate to the ink. In the present invention, an organic solvent having a low evaporation rate is mixed while an organic solvent having a high evaporation rate is used as a base in order to maintain the quick drying property required for ink for an ink jet printer. As a result, when the ink is dried from the air interface after the ink has landed on the base material, it is possible to secure time for the chlorine-based resin having the highest affinity with the substrate to selectively adhere to the substrate, and uneven distribution near the substrate is prevented. Can promote.
以下、本発明の実施形態を説明する。以下に述べる実施形態は、本発明を具体化した一例に過ぎず、本発明の技術的範囲を限定するものではない。 Embodiments of the present invention will be described below. Embodiment described below is only an example which actualized this invention, and does not limit the technical scope of this invention.
１．インクの構成材料
インクは、樹脂、着色剤及び溶剤を含む。これらをオーバーヘッドスターラー等により撹拌混合し溶解した後、孔径０．２５〜１０μｍのフィルタにて濾過することによりインクジェットプリンタ用インクを得た。1. Ink Constituent Materials The ink contains a resin, a colorant, and a solvent. These were stirred and mixed with an overhead stirrer or the like and dissolved, and then filtered through a filter having a pore size of 0.25 to 10 μm to obtain an ink for an ink jet printer.
（１）樹脂
樹脂としては、塩素系樹脂の他、アクリル樹脂、スチレン−アクリル樹脂若しくはポリエステル樹脂が用いられる。これらの樹脂は、単独で用いてもよいし、２種以上混合して用いてもよい。これらの樹脂は、溶剤として用いる２−ブタノン又はアセトンに対して可溶である必要がある。ここでいう塩素系樹脂は、塩素化ポリプロピレン、塩素化ポリエチレン、ポリ塩化ビニル及びポリ塩化酢酸ビニルを含む。アクリル樹脂は、アクリル酸、アクリル酸エステル、メタクリル酸又はメタクリル酸エステルから合成される単重合体樹脂及びこれらの共重合体樹脂を含む。スチレン−アクリル樹脂は、スチレン−アクリル共重合体樹脂及びスチレン−メタクリル共重合体樹脂を含む。ポリエステル樹脂は、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリプロピレンテレフタレート、ポリプロピレンイソフタレート、ポリブチレンテレフタレート及びポリブチレンイソフタレートを含む。(1) Resin As the resin, an acrylic resin, a styrene-acrylic resin, or a polyester resin is used in addition to a chlorine-based resin. These resins may be used alone or in combination of two or more. These resins must be soluble in 2-butanone or acetone used as a solvent. The chlorinated resin here includes chlorinated polypropylene, chlorinated polyethylene, polyvinyl chloride, and polyvinyl chloride acetate. The acrylic resin includes a homopolymer resin synthesized from acrylic acid, acrylic acid ester, methacrylic acid or methacrylic acid ester, and a copolymer resin thereof. Styrene-acrylic resins include styrene-acrylic copolymer resins and styrene-methacrylic copolymer resins. Polyester resins include polyethylene terephthalate, polyethylene isophthalate, polypropylene terephthalate, polypropylene isophthalate, polybutylene terephthalate and polybutylene isophthalate.
塩素系樹脂は、塩素化ポリプロピレンが好ましい。他の塩素を含む樹脂と比較して、ポリオレフィン基材との親和性が高く、かつ、溶剤への溶解性が高いためである。また、樹脂に占める塩素化ポリプロピレン樹脂の割合は、６〜２１質量％であることが好ましい。６質量％未満の場合、基板との充分な密着性が得られず、２１質量％以上の場合、金属部材の腐食リスクが増大するためである。 The chlorinated resin is preferably chlorinated polypropylene. This is because the affinity with the polyolefin substrate is high and the solubility in a solvent is high as compared with other chlorine-containing resins. Moreover, it is preferable that the ratio of the chlorinated polypropylene resin to resin is 6-21 mass%. If it is less than 6% by mass, sufficient adhesion to the substrate cannot be obtained, and if it is 21% by mass or more, the risk of corrosion of the metal member increases.
（２）着色剤
着色剤は、溶剤に溶解する材料であれば特に限定は無い。着色剤の例としては、具体的にはVALIFAST(R) Yellow 3150, VALIFAST(R) Yellow 3170, VALIFAST(R) Yellow 4120, VALIFAST(R) Yellow 4121, VALIFAST(R) Orange 2210, VALIFAST(R) Orange 3209, VALIFAST(R) Red 1306, VALIFAST(R) Red 2320, VALIFAST(R) Red 3311, VALIFAST(R) Red 3312, VALIFAST(R) Pink 2310N, VALIFAST(R) Brown 3402, VALIFAST(R) Blue 1605, VALIFAST(R) Blue 1621, VALIFAST(R) Blue 2620, VALIFAST(R) Blue 2627, VALIFAST(R) Blue 2670, VALIFAST(R) Black 1807, VALIFAST(R) Black 3804, VALIFAST(R) Black 3810, VALIFAST(R) Black 3820, VALIFAST(R) Black 3830, VALIFAST(R) Black 3840, VALIFAST(R) Black 3866, VALIFAST(R) Black 3870（以上、オリヱント化学工業（株）製）、Orasol(R) Yellow 152, Neptun(R) Yellow 078, Orasol(R) Orange 247, Orasol(R) Orange RG, Orasol(R) Brown 322, Orasol(R) Brown 324, Orasol(R) Brown 326, Orasol(R) Red 330, Orasol(R) Red 385, Orasol(R) Red 363, Orasol(R) Red BL, Orasol(R) Pink 478, Orasol(R) Blue 825, Orasol(R) Blue GL, Neptun(R) Blue 755, Orasol(R) Black X55, Orasol(R) Black X45（以上、BASF製）、Savinyl Yellow RLS, Savinyl Red 3BLS, Savinyl Pink 6BLS, Savinyl Blue GLS, Savinyl Black RLSN（以上、Clariant製）、Solvent Yellow 25, 88, 89, Solvent Orange 11, 99, Solvent Brown 42, 43, 44, Solvent Red 122, 135, 127, 130, 233, Solvent Blue 67, 70, Solvent Black 27, 28, 29等が挙げられる。(2) Colorant The colorant is not particularly limited as long as it is a material that dissolves in a solvent. Examples of colorants are VALIFAST (R) Yellow 3150, VALIFAST (R) Yellow 3170, VALIFAST (R) Yellow 4120, VALIFAST (R) Yellow 4121, VALIFAST (R) Orange 2210, VALIFAST (R) Orange 3209, VALIFAST (R) Red 1306, VALIFAST (R) Red 2320, VALIFAST (R) Red 3311, VALIFAST (R) Red 3312, VALIFAST (R) Pink 2310N, VALIFAST (R) Brown 3402, VALIFAST (R) Blue 1605, VALIFAST (R) Blue 1621, VALIFAST (R) Blue 2620, VALIFAST (R) Blue 2627, VALIFAST (R) Blue 2670, VALIFAST (R) Black 1807, VALIFAST (R) Black 3804, VALIFAST (R) Black 3810 , VALIFAST (R) Black 3820, VALIFAST (R) Black 3830, VALIFAST (R) Black 3840, VALIFAST (R) Black 3866, VALIFAST (R) Black 3870 (above, manufactured by Orient Chemical Industries), Orasol (R ) Yellow 152, Neptun (R) Yellow 078, Orasol (R) Orange 247, Orasol (R) Orange RG, Orasol (R) Brown 322, Orasol (R) Brown 324, Orasol (R) Brown 326, Orasol (R) Red 330, Orasol (R) Red 385, Orasol (R) Red 363, Orasol (R) Red BL, Orasol (R) Pink 478, Orasol (R) Blue 825, Orasol (R) Blue GL, Neptun (R) Blue 755, Ora sol (R) Black X55, Orasol (R) Black X45 (above, BASF), Savinyl Yellow RLS, Savinyl Red 3BLS, Savinyl Pink 6BLS, Savinyl Blue GLS, Savinyl Black RLSN (above, made by Clariant), Solvent Yellow 25, 88, 89, Solvent Orange 11, 99, Solvent Brown 42, 43, 44, Solvent Red 122, 135, 127, 130, 233, Solvent Blue 67, 70, Solvent Black 27, 28, 29 and the like.
（３）溶剤
インクの溶剤は、主溶剤と副溶剤とから構成されている。主溶剤には、２０℃における蒸気圧が９．０ｋＰａ以上の有機溶剤を用いる。樹脂の溶解性の観点から、アセトン又は２−ブタノンを用いることが好ましい。これらを混合してもよい。副溶剤には、２０℃における蒸気圧が０．６〜２．０ｋＰａである有機溶剤を用いる。樹脂の溶解性の観点から、アルコール若しくは脂肪酸エステルを単独又は２種以上混合して用いることが好ましい。(3) Solvent The solvent of the ink is composed of a main solvent and an auxiliary solvent. As the main solvent, an organic solvent having a vapor pressure at 20 ° C. of 9.0 kPa or more is used. From the viewpoint of the solubility of the resin, it is preferable to use acetone or 2-butanone. These may be mixed. As the auxiliary solvent, an organic solvent having a vapor pressure at 20 ° C. of 0.6 to 2.0 kPa is used. From the viewpoint of the solubility of the resin, it is preferable to use an alcohol or a fatty acid ester alone or in combination of two or more.
要件を満たすアルコールには、１−ブタノール、２−ブタノール及び１−プロパノールが含まれる。脂肪酸エステルとしては、酢酸ブチル、酢酸イソブチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル及び酪酸エチルが好ましい。副溶剤の蒸気圧が０．６ｋＰａ未満ではインク速乾性が失われ、２．０ｋＰａより高いと塩素化ポリプロピレン樹脂の充分な基板偏在が得られない。また、溶剤に占める副溶剤の割合は５〜２０質量％であることが好ましい。５質量％未満では、乾燥抑制効果が得られず、結果として塩素化ポリプロピレンが充分に基板へ偏在しない。一方、２０質量％より多い場合は、インクの速乾性が失われる。 Alcohols that meet the requirements include 1-butanol, 2-butanol and 1-propanol. As the fatty acid ester, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, methyl butyrate and ethyl butyrate are preferable. If the vapor pressure of the secondary solvent is less than 0.6 kPa, the ink quick drying property is lost, and if it is higher than 2.0 kPa, sufficient substrate uneven distribution of the chlorinated polypropylene resin cannot be obtained. Moreover, it is preferable that the ratio of the subsolvent to a solvent is 5-20 mass%. If it is less than 5% by mass, the drying inhibiting effect cannot be obtained, and as a result, the chlorinated polypropylene is not sufficiently unevenly distributed on the substrate. On the other hand, when the content is more than 20% by mass, the quick drying property of the ink is lost.
（４）添加剤
インク及び印字物の諸物性を調整するために添加剤を加えても良い。例えば、帯電制御方式のインクジェットプリンタ等で使用する場合は、インク液の導電率を調整するために導電剤を加えても良い。また、印字物の形状を平滑化させ、視認性を向上させるためシリコーン系添加剤を加えても良い。(4) Additive Additives may be added to adjust various physical properties of the ink and printed matter. For example, when used in a charge control type ink jet printer or the like, a conductive agent may be added to adjust the conductivity of the ink liquid. Further, a silicone-based additive may be added to smooth the shape of the printed matter and improve the visibility.
２．インクジェットプリンタ
上記のインクは、公知のインクジェットプリンタで使用することができる。このようなインクジェットプリンタとしては、例えば、帯電制御方式、ドロップ・オン・デマンド方式等のプリンタが挙げられる。因みに、凹凸のある面への高速印字においては、インク液滴の飛翔距離を長くとれる帯電制御方式が適している。2. Inkjet printer The ink described above can be used in a known inkjet printer. As such an ink jet printer, for example, a charge control system, a drop-on-demand system, or the like can be cited. Incidentally, in high-speed printing on uneven surfaces, a charge control method that can increase the flying distance of ink droplets is suitable.
３．基板
基板材料は、ポリプロピレン、ポリエチレンなどのポリオレフィン樹脂を用いる。ポリオレフィン樹脂はインクに含まれる樹脂と化学構造が似ているため、引き合う分子間力が大きくなる。そのため、インクに含まれる樹脂と基板との親和性が高くなり、印字物中の樹脂を基板側により偏在させることができる。インクを印字する基板の形状は平滑であっても凹凸があっても良い。3. Substrate The substrate material is a polyolefin resin such as polypropylene or polyethylene. Since the polyolefin resin has a chemical structure similar to that of the resin contained in the ink, the attracting intermolecular force increases. Therefore, the affinity between the resin contained in the ink and the substrate is increased, and the resin in the printed matter can be unevenly distributed on the substrate side. The shape of the substrate on which the ink is printed may be smooth or uneven.
７５ｇの２−ブタノン（主溶剤）に、副溶剤として２−ブタノールを４ｇ、樹脂として平均分子量約１０，０００のスチレンアクリル樹脂を１５．０ｇ、平均分子量約１０，０００の塩素化ポリプロピレンを１ｇ、染料としてsolvent black 34を５．０ｇ加え、撹拌して溶解した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本実施例のインクを調製した。 75 g of 2-butanone (main solvent), 4 g of 2-butanol as an auxiliary solvent, 15.0 g of a styrene acrylic resin having an average molecular weight of about 10,000 as a resin, 1 g of chlorinated polypropylene having an average molecular weight of about 10,000, 5.0 g of solvent black 34 was added as a dye and dissolved by stirring. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, the ink of this example was prepared.
調製したインクを帯電制御方式のインクジェットプリンタで吐出し、ポリプロピレン基板にドット状の塗膜を形成した。以下の実施例及び比較例でもポリプロピレン基板を用いた。例示していないが、ポリエチレンなどの他のポリオレフィン樹脂でも、ポリプロピレンと同様の傾向であった。 The prepared ink was discharged by a charge control type ink jet printer to form a dot-like coating film on a polypropylene substrate. Polypropylene substrates were also used in the following examples and comparative examples. Although not illustrated, other polyolefin resins such as polyethylene have the same tendency as polypropylene.
印字後４８時間経過した塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 When the coating film which had passed 48 hours after printing was observed, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、塗膜を断面加工し、塗膜の空気界面近傍部及び塗膜のポリプロピレン基板界面近傍部をエネルギー分散型Ｘ線分析法で元素分析した。本明細書においては、空気界面近傍部は、塗膜の表面から深さ２００ｎｍまでの領域とし、基板界面近傍部は、基板と塗膜との接触面（界面）から深さ２００ｎｍまでの領域とした。 Moreover, the coating film was processed into a cross section, and elemental analysis was performed by an energy dispersive X-ray analysis method in the vicinity of the air interface of the coating film and in the vicinity of the polypropylene substrate interface of the coating film. In this specification, the vicinity of the air interface is a region from the surface of the coating film to a depth of 200 nm, and the vicinity of the substrate interface is a region from the contact surface (interface) between the substrate and the coating film to a depth of 200 nm. did.
図１は、基板及び印字物の断面ＳＥＭ画像並びに印字物の膜厚方向における塩素濃度分布を示したものである。図中、右側が断面ＳＥＭ画像であり、左側が塩素濃度分布のグラフである。 FIG. 1 shows a cross-sectional SEM image of a substrate and a printed matter, and a chlorine concentration distribution in the film thickness direction of the printed matter. In the figure, the right side is a cross-sectional SEM image, and the left side is a graph of chlorine concentration distribution.
断面ＳＥＭ画像には、ポリプロピレン基板１０１及びその上に形成された印字物１００が示してある。
The cross-sectional SEM image shows the
左側のグラフにおいて、縦軸は右側のポリプロピレン基板１０１の表面を基準とする膜厚方向の距離を、横軸は塩素濃度をとっている。塩素濃度は、塩素化ポリプロピレンの分布に対応している。
In the left graph, the vertical axis represents the distance in the film thickness direction based on the surface of the
グラフから、基板界面近傍部における塩素化ポリプロピレン濃度は、空気界面近傍部と比較して約１．５倍高いことがわかる。 From the graph, it can be seen that the chlorinated polypropylene concentration in the vicinity of the substrate interface is about 1.5 times higher than that in the vicinity of the air interface.
副溶剤を酢酸ブチルとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本実施例のインクを調製した。 An ink was prepared in the same manner as in Example 1 except that the secondary solvent was butyl acetate. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, the ink of this example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
副溶剤を１−ブタノールとし、染料をsolvent black 29としたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本実施例のインクを調製した。 An ink was prepared in the same manner as in Example 1 except that 1-butanol was used as the auxiliary solvent and solvent black 29 was used as the dye. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, the ink of this example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
染料をsolvent black 29とし、主溶剤の２−ブタノンを６４ｇ、副溶剤の２−ブタノールを１６ｇとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本実施例のインクを調製した。 An ink was prepared in the same manner as in Example 1 except that the dye was solvent black 29, the main solvent 2-butanone was 64 g, and the sub-solvent 2-butanol was 16 g. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, the ink of this example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
染料をsolvent black 29とし、樹脂を分子量約５０，０００のアクリル酸エステル樹脂としたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本実施例のインクを調製した。 An ink was prepared in the same manner as in Example 1 except that the dye was solvent black 29 and the resin was an acrylic ester resin having a molecular weight of about 50,000. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, the ink of this example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
樹脂を分子量約１０，０００のポリエチレンテレフタレート樹脂としたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本実施例のインクを調製した。 An ink was prepared in the same manner as in Example 1 except that the resin was a polyethylene terephthalate resin having a molecular weight of about 10,000. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, the ink of this example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
塩素化ポリプロピレン添加量を４ｇとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本実施例のインクを調製した。 An ink was prepared in the same manner as in Example 1 except that the amount of chlorinated polypropylene added was 4 g. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, the ink of this example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
（比較例１）
副溶剤をメチルイソブチルケトンとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本比較例のインクを調製した。(Comparative Example 1)
An ink was prepared in the same manner as in Example 1, except that methyl isobutyl ketone was used as the auxiliary solvent. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, an ink of this comparative example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍未満であった。 Moreover, when the interface vicinity part of the coating film was elementally analyzed like Example 1, the chlorinated polypropylene density | concentration in a board | substrate interface vicinity part was less than 1.5 time compared with the air interface vicinity part.
（比較例２）
副溶剤をエチルセロソルブとし、染料をsolvent black 29としたこと以外は、実施例１と同様にしてインクを調製した。得られた液を０．５μｍ孔径のポリプロピレン製フィルタで濾過した。こうして本比較例のインクを調製した。(Comparative Example 2)
An ink was prepared in the same manner as in Example 1 except that the secondary solvent was ethyl cellosolve and the dye was solvent black 29. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, an ink of this comparative example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
（比較例３）
染料をsolvent black 29とし、副溶剤の２−ブタノールを用いず、主溶剤の２−ブタノンの添加量を８０ｇとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本比較例のインクを調製した。(Comparative Example 3)
An ink was prepared in the same manner as in Example 1 except that the dye was solvent black 29, the secondary solvent 2-butanol was not used, and the addition amount of the main solvent 2-butanone was 80 g. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, an ink of this comparative example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍未満であった。 Moreover, when the interface vicinity part of the coating film was elementally analyzed like Example 1, the chlorinated polypropylene density | concentration in a board | substrate interface vicinity part was less than 1.5 time compared with the air interface vicinity part.
（比較例４）
副溶剤の２−ブタノールの添加量を２ｇとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本比較例のインクを調製した。(Comparative Example 4)
An ink was prepared in the same manner as in Example 1 except that the amount of the auxiliary solvent 2-butanol added was 2 g. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, an ink of this comparative example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍未満であった。 Moreover, when the interface vicinity part of the coating film was elementally analyzed like Example 1, the chlorinated polypropylene density | concentration in a board | substrate interface vicinity part was less than 1.5 time compared with the air interface vicinity part.
（比較例５）
実施例１とは、主溶剤及び副溶剤の添加量が異なるインクを調製した。２−ブタノンを５６ｇ、２−ブタノールを２４ｇ添加し、溶解した。得られた液を孔径０．５μｍのポリプロピレン製フィルタで濾過した。こうして本比較例のインクを調製した。(Comparative Example 5)
An ink having a different amount of the main solvent and the sub-solvent from that of Example 1 was prepared. 56 g of 2-butanone and 24 g of 2-butanol were added and dissolved. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, an ink of this comparative example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
（比較例６）
染料をsolvent black 29とし、塩素化ポリプロピレン添加量を０．５ｇとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を０．５μｍ孔径のポリプロピレン製フィルタで濾過した。こうして本比較例のインクを調製した。(Comparative Example 6)
An ink was prepared in the same manner as in Example 1 except that the dye was solvent black 29 and the addition amount of chlorinated polypropylene was 0.5 g. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, an ink of this comparative example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍未満であった。 Moreover, when the interface vicinity part of the coating film was elementally analyzed like Example 1, the chlorinated polypropylene density | concentration in a board | substrate interface vicinity part was less than 1.5 time compared with the air interface vicinity part.
（比較例７）
染料をsolvent black 29とし、塩素化ポリプロピレン添加量を５ｇとしたこと以外は、実施例１と同様にしてインクを調製した。得られた液を０．５μｍ孔径のポリプロピレン製フィルタで濾過した。こうして本比較例のインクを調製した。(Comparative Example 7)
An ink was prepared in the same manner as in Example 1 except that the dye was solvent black 29 and the addition amount of chlorinated polypropylene was 5 g. The obtained liquid was filtered through a polypropylene filter having a pore size of 0.5 μm. Thus, an ink of this comparative example was prepared.
調製したインクについて、実施例１と同様に塗膜を観察したところ、直径３８０μｍ、平均膜厚１．３μｍであった。 For the prepared ink, the coating film was observed in the same manner as in Example 1. As a result, the diameter was 380 μm and the average film thickness was 1.3 μm.
また、実施例１と同様に塗膜の界面近傍部を元素分析したところ、基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して１．５倍高かった。 Moreover, when the elemental analysis of the interface vicinity part of the coating film was carried out similarly to Example 1, the chlorinated polypropylene density | concentration in the board | substrate interface vicinity part was 1.5 times higher compared with the air interface vicinity part.
以下、塗膜の特性に関する試験結果について説明する。 Hereinafter, the test result regarding the characteristic of a coating film is demonstrated.
実施例１〜７、比較例１〜７で調製したインクを帯電制御方式のインクジェットプリンタで吐出し、ポリプロピレン基板にドット状の塗膜の集合体を形成した。印字後２４時間経過したドット状の塗膜の集合体に対して、消しゴムを使って加重０．３ＭＰａでドット状の塗膜の集合体を２５回擦る耐擦性試験を実施した。この試験の後、塗膜の剥離の有無を確認し、下記の基準で密着性を評価した。 The inks prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were discharged by a charge control type ink jet printer to form an aggregate of dot-like coating films on a polypropylene substrate. A rub resistance test in which the dot-like film aggregate was rubbed 25 times with a weight of 0.3 MPa using an eraser was applied to the dot-like film aggregate 24 hours after printing. After this test, the presence or absence of peeling of the coating film was confirmed, and the adhesion was evaluated according to the following criteria.
これらの評価結果は、表１及び２に示してある。○印は剥離ほぼ無し、△印はやや剥離あり、×印は剥離が多いことを示す。 These evaluation results are shown in Tables 1 and 2. ○ indicates almost no peeling, Δ indicates somewhat peeling, and X indicates that there is much peeling.
以上より、塩素化ポリプロピレンの樹脂中割合を６質量％以上、２０℃における蒸気圧が０．６〜２．０ｋＰａである副溶剤の溶剤中割合を５〜２０質量％としたインクによって形成した塗膜は耐擦性が高いことが示された。 As mentioned above, the coating formed with the ink which made the ratio in the solvent of the sub-solvent whose vapor | steam pressure in 20 degreeC of the chlorinated polypropylene in the resin 6 mass% or more and 20 degreeC is 0.6-2.0 kPa was 5-20 mass%. The film was shown to be highly scratch resistant.
実施例１〜７、比較例１〜７の塗膜中での塩素化ポリプロピレンの偏在性についての評価結果も、表１及び２に示してある。塗膜の基板界面近傍部における塩素化ポリプロピレン濃度が空気界面近傍部と比較して○印は１．５倍以上、×印は１．５倍未満であることを示す。 Tables 1 and 2 also show the evaluation results on the uneven distribution of chlorinated polypropylene in the coating films of Examples 1 to 7 and Comparative Examples 1 to 7. It shows that the chlorinated polypropylene concentration in the vicinity of the substrate interface of the coating film is 1.5 times or more and the x mark is less than 1.5 times compared with the vicinity of the air interface.
以上より、塩素化ポリプロピレンの樹脂中割合が６質量％以上で、２０℃における蒸気圧が２．０ｋＰａ以下である副溶剤の溶剤中割合が５質量％以上のとき、塩素化ポリプロピレンが基板に偏在することが示された。 From the above, when the proportion of the chlorinated polypropylene in the resin is 6% by mass or more and the vapor pressure at 20 ° C. is 2.0 kPa or less, and the proportion in the solvent of the secondary solvent is 5% by mass or more, the chlorinated polypropylene is unevenly distributed on the substrate. Was shown to do.
実施例１〜７、比較例１〜７のインク５０ｇに直径１０ｍｍのＳＵＳ３０４製ボール１０個を投入し、６０℃環境下で１００時間放置した後、インクからボールを取り出し、２−ブタノンで洗浄後、ボール表面の腐食の有無を確認した。 Ten balls made of SUS304 having a diameter of 10 mm were put into 50 g of the inks of Examples 1 to 7 and Comparative Examples 1 to 7, and left for 100 hours in an environment of 60 ° C., then the balls were taken out from the ink and washed with 2-butanone. The presence or absence of corrosion on the ball surface was confirmed.
評価結果を表１及び２に示す。○印は腐食なし、×印は腐食ありを示す。 The evaluation results are shown in Tables 1 and 2. ○ indicates no corrosion, and x indicates corrosion.
以上より、塩素化ポリプロピレンの樹脂中割合を２１質量％以下としたインクは高温環境下で金属を腐食させないことが示された。 From the above, it was shown that the ink in which the proportion of the chlorinated polypropylene in the resin is 21% by mass or less does not corrode the metal in a high temperature environment.
１００：印字物、１０１：ポリプロピレン基板。 100: Printed matter, 101: Polypropylene substrate.
Claims (2)
前記樹脂が塩素化ポリプロピレンを含み、
前記溶剤が主溶剤及び副溶剤から構成され、
前記主溶剤の２０℃における蒸気圧が９．０ｋＰａ以上であり、
前記副溶剤の２０℃における蒸気圧が０．６〜２．０ｋＰａであり、
前記主溶剤が２−ブタノン又はアセトンを含み、
前記副溶剤がアルコール又は脂肪酸エステルを含み、
前記副溶剤の前記溶剤中の割合が５〜２０質量％であり、
前記塩素化ポリプロピレンの前記樹脂中の割合が６〜２１．１質量％であることを特徴とするインクジェットプリンタ用インク。 In an inkjet printer ink containing a colorant, a resin, and a solvent,
The resin comprises chlorinated polypropylene;
The solvent is composed of a main solvent and a sub-solvent,
The vapor pressure of the main solvent at 20 ° C. is 9.0 kPa or more,
The vapor pressure of the secondary solvent at 20 ° C. is 0.6 to 2.0 kPa,
The main solvent comprises 2-butanone or acetone;
The co-solvent comprises an alcohol or a fatty acid ester,
The ratio of the secondary solvent in the solvent is 5 to 20% by mass,
An ink for an ink jet printer, wherein a ratio of the chlorinated polypropylene in the resin is 6 to 21.1% by mass.
前記主溶剤が２−ブタノンを含み、
前記副溶剤がブタノール又は酢酸ブチルを含むことを特徴とするインクジェットプリンタ用インク。 In claim 1 ,
The main solvent comprises 2-butanone;
An ink for an ink jet printer, wherein the co-solvent contains butanol or butyl acetate.
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Citations (7)
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|---|---|---|---|---|
| JPH10195356A (en) * | 1997-01-08 | 1998-07-28 | Dainippon Toryo Co Ltd | Ink composition for use in jet printing |
| US20030152753A1 (en) * | 2000-06-09 | 2003-08-14 | 3M Innovative Properties Company | Materials and methods for creating waterproof, durable aqueous inkjet receptive media |
| JP2005060716A (en) * | 2003-06-12 | 2005-03-10 | Hitachi Maxell Ltd | Oil pigment ink composition |
| WO2007072910A1 (en) * | 2005-12-22 | 2007-06-28 | Sakata Inx Corp. | Process for producing ink jet recorded matter and ink jet recorded matter produced by said process |
| JP2011016964A (en) * | 2009-07-10 | 2011-01-27 | Sakata Corp | Continuous inkjet ink composition |
| JP2012072236A (en) * | 2010-09-28 | 2012-04-12 | Kishu Giken Kogyo Kk | Inkjet ink |
| JP2012131885A (en) * | 2010-12-21 | 2012-07-12 | Tokyo Printing Ink Mfg Co Ltd | Ink composition for laser recording, laminate for recording, and recorded matter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10195356A (en) * | 1997-01-08 | 1998-07-28 | Dainippon Toryo Co Ltd | Ink composition for use in jet printing |
| US20030152753A1 (en) * | 2000-06-09 | 2003-08-14 | 3M Innovative Properties Company | Materials and methods for creating waterproof, durable aqueous inkjet receptive media |
| JP2005060716A (en) * | 2003-06-12 | 2005-03-10 | Hitachi Maxell Ltd | Oil pigment ink composition |
| WO2007072910A1 (en) * | 2005-12-22 | 2007-06-28 | Sakata Inx Corp. | Process for producing ink jet recorded matter and ink jet recorded matter produced by said process |
| JP2011016964A (en) * | 2009-07-10 | 2011-01-27 | Sakata Corp | Continuous inkjet ink composition |
| JP2012072236A (en) * | 2010-09-28 | 2012-04-12 | Kishu Giken Kogyo Kk | Inkjet ink |
| JP2012131885A (en) * | 2010-12-21 | 2012-07-12 | Tokyo Printing Ink Mfg Co Ltd | Ink composition for laser recording, laminate for recording, and recorded matter |
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| CN105102554B (en) | 2018-10-02 |
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