JP5327563B2 - INKJET INK RECORDING MEDIUM, INKJET PRINTED MATERIAL AND ITS MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to an ink jet recording medium that enables ink jet printing even on a plastic substrate. More specifically, the ink jet ink has excellent adhesion between the ink jet ink and the plastic substrate, and the printed surface does not peel off after printing. The present invention relates to an ink recording medium and printed matter thereof.

  In recent years, with the progress of multimedia technology, ink jet printers have become widespread regardless of business use and consumer use. Inkjet printers have many features such as being easy to make multicolor images and large images, printing on uneven surfaces as well as smooth surfaces, and enabling on-demand printing. Have.

  The ink-jet recording material using paper as a support has a problem that the appearance is deteriorated due to occurrence of a phenomenon called cockling in which the support is waved when touched with water or tearing. In order to solve such a problem, it has been proposed to use an ink jet recording medium having a plastic film itself as a support and an ink receiving layer thereon, and to perform printing (for example, Patent Document 1). ~ 4). Such a medium is excellent in water resistance and can be used as an outdoor advertisement, a poster, a label, wallpaper, or the like. However, the surface of the plastic film has poor adhesion to the ink-jet ink, and a layer usually called an anchor layer, primer layer, undercoat layer, adhesive layer, etc. is formed on the film surface, and polyurethane, polyacryl, etc. The step of providing an ink receiving layer containing as a main component was essential. Such a surface treatment process not only leads to an increase in cost, but also requires a lot of time for production because the number of processes increases. Furthermore, when the surface treatment is performed by application of a paint containing a solvent, a step for removing the contained solvent is required, and when the solvent is an organic solvent, the burden on the environment is increased. On the other hand, there has also been reported an ink jet recording medium in which micropores are provided on the film surface instead of applying an ink receiving agent, and the micropores are fixed by absorbing ink (see, for example, Patent Document 5). However, since the stretching process is necessary and the micropores diffusely reflect light, the use is usually limited depending on the field where the film is white and transparency is required.

Japanese Patent Laid-Open No. 10-119428 JP 2001-150612 A Japanese Patent Laid-Open No. 2002-103802 JP 2007-130780 A JP 2001-181424 A

  The problem of the present invention has been made in view of the above problems, and has good adhesion with ink without performing the surface treatment and stretching process essential when using a conventional plastic film as a base material. An object of the present invention is to provide a recording medium for ink-jet ink that does not cause problems such as peeling after ink-jet printing, and a printed matter thereof.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a layer (A1) containing a polyolefin resin (a1) as a main component and a layer (A2) containing an acid-modified olefin resin (a2). The present invention has been completed by finding that the above-mentioned problems can be solved by using a multilayer film in which the above and others are laminated as an inkjet recording medium.

  That is, in the present invention, the layer (A1) containing the polyolefin resin (a1) as a main component and the layer (A2) containing the acid-modified olefin resin (a2) are in the order of (A1) / (A2). The present invention provides a recording medium for ink-jet ink characterized by being laminated, a printed matter obtained by performing ink-jet printing on a layer (A2) of the recording medium, and a method for producing them.

  The ink-jet printed matter obtained by the present invention can be easily obtained by directly performing ink-jet printing on a multilayer film. The design can be easily changed by selecting the layer structure of the multilayer film according to the target performance (transparency, rigidity, workability, etc.) and application (packaging material, poster, label, etc.). Excellent. The printed matter obtained has good adhesion between the ink and the multilayer film, so that even if it is stored for a long time, the printed part does not peel off. A bag shape or the like is also possible.

  The plastic film functioning as a support for the inkjet printed matter of the present invention has at least a layer (A1) mainly comprising a polyolefin resin (a1) and a layer (A2) containing an acid-modified olefin resin (a2). Is. This layer (A2) functions not only as a support but also as an easy adhesion layer with ink. In the present invention, “main component” means that the specific resin is contained in an amount of 80% by mass or more based on the total amount of the resin composition forming the layer, and preferably 85% by mass. The above is a specific resin. Further, in the present invention, “containing” means that the specific resin is contained in an amount of 1% by mass or more with respect to the total amount of the resin composition forming the layer, and preferably 20% by mass or more. Say that it is a specific resin.

  The opposite side of the printing surface of the inkjet printed material of the present invention is a layer (A1) mainly composed of a polyolefin resin (a1). Examples of the polyolefin-based resin (a1) that can be used here include homopolymers or copolymers of α-olefins having 2 to 6 carbon atoms. The copolymerization type may be a block copolymer or a random copolymer. Further, as the polyolefin-based resin (a1), it is preferable to use a resin having a melting point of 110 ° C. or more from the viewpoint of maintaining the appearance during molding after recording and suppressing the warpage of the film itself.

  As the polyolefin resin (a1), for example, any of those known as polypropylene resin, polyethylene resin and the like can be used. For example, as a polypropylene resin, a propylene homopolymer, a propylene-ethylene copolymer, a propylene-butene-1 copolymer, a propylene-ethylene-butene-1 copolymer, an ethylene-propylene block copolymer, a metallocene catalyst And polypropylene. These may be used alone or in combination of two or more. When the inkjet ink recording medium before inkjet printing is rolled up and stored for a long period of time, it is preferable to use a crystalline propylene resin from the viewpoint of preventing blocking. In addition, in this application, crystallinity means having a peak of 0.5 J / g or more in the range of 95-250 degreeC in DSC (differential scanning calorimetry).

The polypropylene resin has a melt flow rate (hereinafter referred to as “230 ° C. MFR”; a value measured at 230 ° C. and 21.18 N in accordance with JIS K7210: 1999) of 0.5 to 30. Those having a melting point of 120 to 165 ° C. at 0.0 g / 10 min are preferred, and more preferably those having an MFR of 230 ° C. of 2.0 to 15.0 g / 10 min and a melting point of 125 to 162 ° C. . If the MFR and the melting point are in this range, the film shrinkage is small even when the printed matter is subjected to thermoforming, etc., so that the appearance of the printed surface can be maintained and the warp of the medium itself is not generated, and the coextrusion multilayer The film formability when a film is formed is also improved. It is preferable that density is 0.890~0.910g / cm ^3, more preferably 0.895~0.905g / cm ^3.

  In particular, when a propylene-ethylene block copolymer is used for the layer (A1), the surface is modified into a satin finish, and the generation of wrinkles when winding the multilayer film into a roll can be suppressed. Blocking when stored in roll form can be reduced. Here, the propylene-ethylene block copolymer is a resin obtained by block polymerization of propylene and ethylene. For example, propylene obtained by polymerizing ethylene or ethylene and propylene in the presence of a propylene homopolymer. -An ethylene block copolymer etc. are mentioned.

  Further, when a mixed resin of crystalline propylene resin and ethylene / propylene rubber (hereinafter referred to as “EPR”) is used for the layer (A1), the surface of the layer (A1) can be easily modified into a satin finish. Can do. As the crystalline propylene-based resin used at this time, a highly versatile propylene homopolymer is preferable. On the other hand, as the EPR used at this time, those having a weight average molecular weight in the range of 400,000 to 1,000,000 are preferable in that irregularities are formed on the film surface and the surface can be modified into a satin finish, A range is more preferable. In addition, the EPR content in the mixed resin is preferably in the range of 5 to 35% by mass in that the film surface can be uniformly modified into a satin finish. The MFR (230 ° C.) of the mixed resin of the crystalline propylene polymer and EPR is preferably in the range of 0.5 to 15 g / 10 minutes from the viewpoint of easy extrusion. In addition, the weight average molecular weight of the EPR was obtained by calculating a component extracted from the mixed resin by a cross fractionation method at 40 ° C. using orthodichlorobenzene as a solvent by GPC (gel permeation chromatography). It is. The content of EPR in the mixed resin is obtained from the amount of EPR extracted by cross-fractionation at 40 ° C. using orthodichlorobenzene as a solvent.

  The method for producing the mixed resin of the crystalline propylene-based resin and EPR is not particularly limited. As a specific example, for example, a propylene homopolymer and ethylene / propylene rubber are separately mixed using a Ziegler type catalyst. After producing by a combination method, a slurry polymerization method, a gas phase polymerization method, etc., a propylene homopolymer is produced in the first stage by a method of mixing both with a mixer or a two-stage polymerization method, and then the second stage. And a method of generating EPR in the presence of this polymer.

  The Ziegler-type catalyst is a so-called Ziegler-Natta catalyst, and is obtained by supporting a transition metal compound such as a titanium-containing compound or a transition metal compound on a support such as a magnesium compound. The combination with the promoter of an organometallic compound is mentioned.

Examples of the polyethylene resin include medium density polyethylene (MDPE) and high density polyethylene (HDPE), and the density is preferably 0.92 to 0.97 g / cm ³ . When the density is within this range, the film has an appropriate rigidity and improves film formability and extrusion suitability. Moreover, it is preferable that it is 2-20 g / 10min, and, as for MFR (190 degreeC, 21.18N) of a polyethylene-type resin, it is more preferable that it is 3-10 g / 10min. When the MFR is within this range, the extrudability of the film is improved, the generation of wrinkles that are likely to occur when the multilayer film is rolled up can be suppressed, and the roll-out property from the roll is excellent. Furthermore, these polyethylene resins preferably have a melting point of 110 to 135 ° C, more preferably a melting point of 115 to 130 ° C. When the melting point is within this range, the film shrinks little even when heated by molding after printing, etc., so that the appearance of the recording surface can be maintained, and warping of the film itself can be suppressed. These may be used alone or in combination of two or more.

  As a layer (A1) which has polyolefin resin (a1) as a main component, it may be a single layer or may have a multilayer structure of two or more layers. From the viewpoint of more excellent rigidity and heat resistance and excellent workability when the printed material is secondarily processed, a film having a single layer or a multilayer structure mainly composed of a polypropylene resin is preferable. For example, when a printed material is used as a package, the outermost layer on the surface opposite to the printed surface is 1-butene having 1-butene and propylene as essential components as described in JP-A-2006-213065. By using a heat seal layer containing a copolymer and a copolymer containing propylene and ethylene as essential components, an easily openable bag can be obtained. Similarly, when used as a lid, it can be easily opened by adopting a multilayer structure as described in JP-A-2004-75181 and JP-A-2008-80543. It is. Furthermore, when a cyclic polyolefin resin as described in JP 2010-234660 A is used as one layer in a multilayer structure, it is possible to obtain a printed material having easy tearability, depending on the use of the printed material. It is preferable to employ various multilayer configurations.

  Moreover, it can also be set as the inkjet printed material (label) which can be affixed on a signboard, a vehicle, etc. by providing an adhesive layer on a layer (A1) [surface opposite to layer (A2) mentioned later]. The type of the adhesive is not particularly limited. For example, natural rubber, synthetic rubber, acrylic, urethane, vinyl ether, silicone, amide and styrene adhesive, styrene elastomer, olefin elastomer Etc. For the purpose of controlling the adhesive properties, etc., the pressure-sensitive adhesive layer may include, for example, terpene resins such as α-pinene, β-pinene polymer, diterpene polymer, α-pinene / phenol copolymer, fat Appropriate tackifiers such as aromatic resins, aromatic resins, aliphatic / aromatic copolymer systems, other rosin resins, coumarone indene resins, (alkyl) phenol resins and xylene resins Can be blended. Among these, when laminating a layer (A1) and a layer (A2) to be described later by a coextrusion method, a method of simultaneously laminating an adhesive layer on the layer (A1) opposite to the layer (A2) by coextrusion Is preferable in the manufacturing cycle.

  The layer (A2) in the present invention is a layer containing the acid-modified olefin resin (a2) as an essential component. Although the olefin component which is the main component of the acid-modified polyolefin resin (a2) is not particularly limited, it has 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene and the like. Alkenes are preferred and mixtures of these may be used. Among these, alkene having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene is more preferable, ethylene and propylene are further preferable, and ethylene is most preferable. Moreover, the acid-modified polyolefin resin (a2) needs to contain a (meth) acrylic acid ester component. (Meth) acrylic acid ester components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. In view of easy availability and adhesiveness, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hexyl acrylate are more preferable, and methyl acrylate and ethyl acrylate are more preferable. The (meth) acrylic acid ester component may be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization. (Graft modification) and the like. (Note that “(meth) acrylic acid˜” means “acrylic acid˜ or methacrylic acid˜”). Specifically, for example, ethylene- (meth) acrylic acid ester copolymers include Elvalloy ( Product name: Mitsui-DuPont Polychemical Co., Ltd.), Aklift (trade name: Sumitomo Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.

  Further, the acid-modified polyolefin resin (a2) may be acid-modified with an unsaturated carboxylic acid component. Examples of unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. The unsaturated carboxylic acid component may be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization (grafting). Modification). Specifically, examples of the ethylene-acrylic acid copolymer include Nucrel (trade name: Mitsui / DuPont Polychemical Co., Ltd.). Examples of the ethylene- (meth) acrylic acid ester-maleic anhydride copolymer include bondine (trade name: manufactured by Tokyo Materials Co., Ltd.). These may be used alone or in combination of two or more.

  The acid modification rate of the acid-modified olefin resin (a2) includes adhesion to inkjet ink, blocking in the case of winding and storing a multilayer film, suppression of appearance defects such as wrinkles after printing, etc. From the point of being excellent in balance, it is preferable to use 0.5 to 40%, more preferably 0.5 to 35%, and particularly preferably 0.5 to 30%.

  In the layer (A2) in the present invention, in addition to the acid-modified olefin resin (a2), other resins may be used in combination. In particular, it is preferable to use a polyolefin-based resin in combination because it is mixed with the acid-modified olefin-based resin (a2) and can be easily coextruded with the layer (A1). At this time, the acid-modified olefin resin (a2) is preferably contained in an amount of 20 parts by mass or more, particularly preferably 50 parts by mass or more in 100 parts by mass of the resin component forming the layer (A2).

  As the polyolefin resin, any of those exemplified for the polyolefin resin (a1) used for the layer (A1) can be suitably used. At this time, the polyolefin resin used in the layer (A1) and the layer (A2) may be the same or different. The polyolefin resin used in the layer (A2) may be a single resin or a mixture of plural kinds.

  In each of the layers (A1) and (A2), an antifogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, and an ultraviolet absorber are added as necessary. Components such as a colorant and a colorant can be added within a range not impairing the object of the present invention. In particular, the surface friction coefficient is preferably 1.5 or less, more preferably 1.0 or less in order to impart processing suitability when forming a film or packaging suitability when a printed material is used as a packaging material. It is preferable to add a lubricant, an antiblocking agent or an antistatic agent to the resin layer corresponding to the layer as appropriate.

  The total thickness of each of the layers (A1) and (A2) can be set as appropriate according to the use of the printed matter. For example, when the packaging material (bag or lid material) is used, the thickness is 20 to 50 μm. In the case of labels and posters, it is preferably in the range of 70 to 1000 μm. Further, the ratio of the thickness of the layer (A2) to the total thickness of the layers (A1) and (A2) is preferably in the range of 5 to 40% from the viewpoint of ensuring adhesion with the inkjet ink described later. The thickness of the layer (A2) is preferably in the range of 2 to 30 μm.

  The method for laminating the layer (A1) and the layer (A2) is preferably a coextrusion laminating method in which the layer (A1) and the layer (A2) are laminated adjacently. After laminating layers (A1) and (A2) in a molten state by various coextrusion methods such as coextrusion multi-layer die method, feed block method, etc., which are melt-extruded using an extruder of more than one table, inflation, T-die A method of processing into a long wound film by a method such as a chill roll method is preferable, and a coextrusion method using a T die is more preferable.

  Further, it is desirable that the surface of the layer (A2) is continuously subjected to surface treatment using corona discharge or plasma discharge under heating or in an inert gas atmosphere during the production of the multilayer film.

  The printed matter obtained by the present invention is obtained by inkjet printing on the multilayer film obtained above.

(Inkjet ink)
The inkjet ink used in the present invention is not particularly limited, and various inks can be used. Ink-jet inks include water-based inks using water or a mixed solvent of water and water-soluble organic solvents as the main solvent, non-aqueous (oil-based) inks using organic solvents as the main solvent, or UV curable inks that do not use these solvents Although inks and the like are known, the film used in the present invention may be an oil-based ink having good adhesion to a plastic film, a UV curable ink, or a water-based ink that usually causes problems such as repellency. It can be used without any problem because of its excellent adhesion.

(Color material)
As the coloring material used in these ink jet inks, pigments and dyes are usually used, but it is preferable to use pigments from the viewpoint of durability of printed matter. Examples of the dye include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, and various dyes that are usually used in inkjet recording. . In addition, as pigments, inorganic pigments such as barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, carbon black, anthraquinone pigments, perylene pigments, disazo pigments, phthalocyanine pigments, isoindoline pigments And dioxazine pigments, quinacridone pigments, perinone pigments, and benzimidazolone pigments. These can be used alone or in combination.

  In general-purpose color printing, black ink, cyan ink, magenta ink, and yellow ink using black pigment, cyan pigment, magenta pigment, and yellow pigment are used.

  As the black pigment, it is preferable to use furnace black, lamp black, acetylene black, channel black and other carbon black, titanium black, etc. which have excellent light resistance and high hiding power.

Furthermore, among the representative organic pigments of cyan, magenta, and yellow, which are the three primary colors, pigments that can be suitably used in the present invention are exemplified below.
Examples of cyan pigments include C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, and the like.

  Examples of magenta pigments include C.I. I. Pigment red 5, C.I. I. Pigment red 7, C.I. I. Pigment red 12, C.I. I. Pigment red 48, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 112, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 146, C.I. I. Pigment red 168, C.I. I. Pigment red 184, C.I. I. Pigment red 202, C.I. I. Pigment bio red 19, and the like.

  Examples of yellow pigments include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, and the like.

  As for the particle diameter of the pigment, the primary particle diameter is preferably in the range of 1 to 500 nm, and more preferably in the range of 20 to 200 nm. The particle diameter of the pigment after being dispersed in the medium is preferably in the range of 10 to 300 nm, and more preferably in the range of 50 to 150 nm. The primary particle diameter of the pigment can be measured by an electron microscope, a gas or solute adsorption method, an air flow method, an X-ray small angle scattering method, and the like. The pigment particle diameter after dispersion can be measured by a centrifugal sedimentation method, a laser diffraction method (light scattering method), an ESA method, a capillary method, an electron microscope method, or the like.

(Water-based ink)
The water used in the water-based ink is preferably pure water or ultrapure water that has undergone a purification process such as ion exchange or distillation. Examples of the water-soluble organic solvent include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-methoxy Examples include alcohols such as ethanol; ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; and amides such as dimethylformamide and N-methylpyrrolidone. Among these, it is preferable to use a compound selected from the group consisting of a ketone having 3 to 6 carbon atoms and an alcohol having 1 to 5 carbon atoms.

  The water-based ink is obtained by dispersing the coloring material such as the pigment in the water or a mixed solvent of water and a water-soluble organic solvent. Usually, the pigment is dispersed using a dispersing resin. Examples of the stirring / dispersing device for dispersing the pigment include various types such as an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a bead mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disper mat, an SC mill, and a nanomizer. A disperser can be used. A binder resin can also be used for the purpose of film formation and film adhesion. The dispersing resin and binder resin may be the same or several types may be used in combination. In general, water-soluble or water-dispersible urethane resins, acrylic resins, polyester resins and the like are used. If necessary, it is prepared by adding a drying inhibitor, a penetrant, a surfactant or other additives. It can also be prepared by preparing a high-concentration pigment dispersion (mill base) in advance and then appropriately diluting and adding additives.

(Oil-based ink)
The oil-based ink is preferably used based on a solvent having a high boiling point in order to prevent clogging of the head. Nonpolar solvents include long chain fatty acid esters, vegetable oil esters, higher fatty acids, vegetable oils, hydrocarbons, higher alcohols, and the like. Examples of highly polar solvents include lower alcohols, glycols, glycol ethers, glycol esters, lower alcohol esters, pyrrolidones and the like.

  Non-polar solvents include, for example, methyl oleate, ethyl oleate, isopropyl oleate, isobutyl oleate, methyl linoleate, isobutyl linoleate, ethyl linoleate, soy oil methyl, soy oil isobutyl, linseed oil butyl, large Bean oil, linseed oil, castor oil, Nippon Oil Corporation “Nisseki Naphthezol H, No. 0 Solvent H, Isosol 300, Isosol 400, AF-5, AF-6, AF-7”, Exxon Mobil “Exxol D80, Exxol D110, Exxol D130, Exxol D140 "(all trade names), isomyristyl alcohol, isopalmityl alcohol, isostearyl alcohol, oleyl alcohol, isononanoic acid, isomyristic acid, hexadecanoic acid, isopalmitic acid, oleic acid Phosphate, and isostearic acid.

  Examples of the highly polar solvent include ethylene glycol, diethylene glycol, glycerin, xylitol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, tetra Examples include ethylene glycol dimethyl ether, propylene glycol monomethyl ether monoacetate, dipropylene glycol monomethyl ether, isopropyl acetate, pyrrolidone, and N-methylpyrrolidone.

  In the case where quick drying is important, more volatile solvents, for example, alkyl alcohols such as ethanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; Esters such as ethyl acetate; amides such as dimethylformamide and dimethylacetamide; ethers such as dioxane and tetrahydrofuran can be mixed with the above solvents or used alone.

  Further, in consideration of safety in recent years, suitable solvents for so-called eco solvent ink not containing cyclohexanone include, for example, cyclic esters such as γ-butyrolactone, dioxane, trioxane, furan, tetrahydrofuran, methyltetrahydrofuran, methylfuran, tetrahydro. Cyclic ethers such as pyran and furflate, butyl formate, isoamyl formate, isobutyl formate, hexyl formate, butyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, pentyl acetate, ethyl propionate, propyl propionate, isopropyl propionate, Butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, methyl isobutyrate, diethyl malonate, diethyl oxalate, ethyl lactate, butyl lactate, malo Dimethyl acid is a chain ester having 5 to 7 carbon atoms, diethyl ketone, methyl isoamyl ketone, methyl isobutyl ketone, methyl propyl ketone, methyl butyl ketone, methyl pentyl ketone, ethyl propyl ketone, ethyl butyl ketone, dipropyl ketone, diisopropyl Examples include ketones, chain ketones such as t-butyl methyl ketone, methyl isopropyl ketone, acetyl ketone, and acetonitrile acetone. These solvents can be used alone or in combination.

  Similar to the water-based ink, the oil-based ink is obtained by dispersing a coloring material such as the pigment in an organic solvent. Even in the case of oil-based inks, the pigment is usually dispersed using a dispersing resin. As the stirring / dispersing device for dispersing the pigment, the same device as the water-based ink can be used. A binder resin can also be used for the purpose of film formation and film adhesion. The dispersing resin and binder resin may be the same or several types may be used in combination. In general, oil-soluble urethane resin, acrylic resin, polyester resin, vinyl chloride resin, vinyl acetate resin and the like are used.

  Moreover, stabilizers, such as antioxidant and a ultraviolet absorber, surfactant, binder resin, etc. can be added as needed. Examples of such antioxidants include BHA (2,3-butyl-4-oxyanisole), BIT (2,6-di-tert-butyl-P-cresol), etc .; benzophenone series, benzotriazole series as ultraviolet absorbers As the surfactant, any of anionic, cationic amphoteric and nonionic compounds can be used.

  Specific examples of the resin that can be used as the binder resin include acrylic resins, styrene acrylic resins, rosin-modified resins, phenol resins, terpene resins, polyester resins, polyamide resins, and epoxy resins.

(UV curable ink)
Since the UV curable ink cures the printed film with ultraviolet rays or the like, an ultraviolet curable compound or a photopolymerization initiator is used. Any of these compounds can be used, but if the viscosity is too high, there is a possibility that the ejection properties may be hindered. Therefore, it is preferable to appropriately select a low-viscosity ultraviolet curable compound. There are a radical polymerization type and a cationic polymerization type depending on the reaction mechanism. In order to obtain an ink having a fast curing and drying rate, it is preferable to use a compound having an ethylenic double bond such as (meth) acrylate as the ultraviolet curable compound.

  Specific examples of the compound having an ethylenic double bond include a monofunctional monomer having one ethylenic double bond and a polyfunctional monomer having two or more ethylenic double bonds. Can be used in combination. Further, it is preferable to contain a (meth) acrylate oligomer or a trifunctional or higher polyfunctional acrylate, but these have a high viscosity, and in particular, the (meth) acrylate oligomer has a higher viscosity than the monomer. It is preferable to use in the range of 2 to 20% by mass with respect to the total amount of compounds having a bond.

  Examples of the monofunctional monomer include methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, (Meth) acrylate having a substituent such as glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl, vinyl caprolactam, vinyl pyrrolidone, N-vinylformamide and the like It is done. Two or more of these can be used in combination.

  Examples of the polyfunctional monomer include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neo Di (meth) acrylates such as pentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, bisphenol Di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of diol A, diol of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane Or di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of tri (meth) acrylate, bisphenol A , Dipentaerythritol poly (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, ethylene oxide-modified alkyl phosphoric acid (meth) acrylate, and the like. Two or more of these can be used in combination.

  As said (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, etc. are mentioned, It can also use in combination of 2 or more types.

  Examples of the photopolymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are preferably used, and Other molecular cleavage types include 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. may be used in combination, and hydrogen extraction light Polymerization initiators such as benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide and the like can be used in combination.

  For the above photopolymerization initiator, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N An amine that does not cause an addition reaction with the polymerizable component, such as dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone, can also be used in combination. Of course, it is preferable to select and use the photopolymerization initiator and the sensitizer that are excellent in solubility in the ultraviolet curable compound and do not inhibit the ultraviolet transmittance.

  Ink jet inks contain a polymerization inhibitor such as hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salt in the ink in order to increase the storage stability of the ink. You may add in the range of the mass%.

  Further, a dispersant may be preferably used for the purpose of enhancing the dispersion stability of the pigment. Examples of the dispersant include Ajimoto PB821, PB822, and PB817 manufactured by Ajinomoto Fine-Techno Co., Ltd., Solspers 24000GR, 32000, 33000, and 39000 manufactured by Abyssia, and Disparon DA-703-50, DA-705, and DA-725 manufactured by Enomoto Kasei Co., Ltd. However, it is not limited to these. The amount of the dispersant used is preferably in the range of 10 to 80% by mass, particularly preferably in the range of 20 to 60% by mass with respect to the pigment. When the amount used is less than 10% by mass, the dispersion stability tends to be insufficient, and when it exceeds 80% by mass, the viscosity of the ink tends to increase, and the ejection stability tends to decrease.

  In addition, non-reactive resins such as acrylic resin, epoxy resin, terpene phenol resin, rosin ester, etc. can be blended for the purpose of imparting adhesiveness to the recording medium.

  The UV curable ink contains, for example, a pigment and an ultraviolet curable compound, and the pigment is dispersed by using a stirring / dispersing device such as a bead mill, in which a polymer dispersant and a resin are added as necessary. Then, it can prepare by adding a photoinitiator and also adding additives, such as a surface tension adjuster, if necessary, and stirring and melt | dissolving. It can also be prepared by preparing a high-concentration pigment dispersion (mill base) in advance and then appropriately diluting and adding additives.

  The printing method is preferably ink jet printing, but printing may be performed by other printing methods such as offset printing, letterpress printing, gravure printing, silk screen printing, or a combination of these two or more printing methods. It doesn't matter.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these. In the examples, “part” and “%” are based on mass unless otherwise specified.

[Evaluation of ink coating suitability]
The solvent type ink and the UV curable ink were applied to an A4 size film with a bar coater (No. 6), and the number of repellings was measured visually.
○: No repelling.
X: There are one or more repels.

[Evaluation of heat resistance of film]
After printing, the appearance of the film when dried at 90 ° C. for 1 minute was visually evaluated.
○: Almost no defects in appearance such as kinks, wrinkles and film deformation.
Δ: Appearance defects such as slight kinks, wrinkles and film deformation are observed.
X: Appearance defects such as significant kinks, wrinkles, and film deformation are observed.

[Evaluation of printability]
It was visually evaluated whether or not stable ink transfer (printing) was performed on the (A2) surface of the recording medium.
○: Printed satisfactorily with no prints or no printable parts.
×: Printing is faint or there are parts that cannot be printed, and there is a printing defect.

[Evaluation of ink adhesion after printing]
A cellophane tape (manufactured by Nichiban) peel test was conducted and visually evaluated.
○: No peeling.
X: There is peeling.

[Preparation example of solvent-based ink 1]
Cyan pigment Fastogen Blue TGR (CI Pigment Blue 15: 3, manufactured by DIC Corporation) 20 parts, Dispersant Azisper PB821 (Ajinomoto Fine Techno Co., Ltd.) 6 parts, Diethylene glycol diethyl ether 74 parts, together with zirconia beads, polyethylene The mixture was placed in a container and shaken with a paint conditioner for 2 hours to obtain a cyan pigment dispersion A having a pigment concentration of 20%. 12.5 parts of this dispersion A, 6.5 parts of resin VROH (manufactured by Dow Chemical Japan Co., Ltd.), 0.5 part of Eposizer W100EL (manufactured by DIC Corporation), 0.5 part of KF54 (manufactured by Shin-Etsu Silicone Co., Ltd.) Parts, 46 parts of diethylene glycol diethyl ether, 15 parts of dipropylene glycol monomethyl ether and 20 parts of γ-butyrolactone were heated to 60 ° C. while stirring. After uniformly dissolving and mixing, the solution was cooled to room temperature and filtered through a 1.2 μm membrane filter to prepare solvent-based ink 1. Using this ink 1, the ink coating suitability was evaluated.

[Preparation example of solvent-based ink 2]
Preparation of Solvent Ink 1 Solvent ink 2 was prepared in the same manner as the preparation of ink 1 except that the solvent was 41 parts ethylene glycol monobutyl ether acetate and 40 parts cyclohexane. Using this ink, the applicability of the ink was evaluated.

[Preparation example of UV curable ink]
As the UV curable ink, a commercially available cyan ink (Mimaki Engineering Co., Ltd., UFJ-605C) was used, and ink coating suitability was evaluated.

  Regarding the preparation of printed matter using solvent-based ink, the inkjet printing machine “VJ-1608HSJ” (manufactured by Muto Kogyo Co., Ltd.) and “Ramiles III: PJ-1634NX” (Muto Kogyo Co., Ltd.) are used for the (A2) side of the recording medium Inkjet printing was carried out using Regarding the preparation of the printed matter using the UV curable ink, inkjet printing was performed on the (A2) surface of the recording medium using an inkjet printer “UFJ-605C” (Mimaki Engineering Co., Ltd.).

Example 1
As the resin for the resin layer (A1), homopolypropylene [MFR: 10 g / 10 min (230 ° C., 21.18 N), melting point: 163 ° C .; hereinafter referred to as “HOPP”] was used. As the resin for the resin layer (A2), ethylene- (meth) methyl acrylate copolymer (density: 0.940 g / cm ³ , MA content 18%; hereinafter referred to as “MA1”) was used. Each of these resins is supplied to an extruder for a resin layer (A1) (caliber 50 mm) and an extruder for a resin layer (A2) (caliber 50 mm) and melted at 200 to 250 ° C. Co-extruded multilayer film manufacturing apparatus (feed block and T-die temperature: 250 ° C.) having T die / chill roll method and co-melt extrusion are carried out, and the layer structure of the film is (A1) / (A2) A two-layered coextruded multilayer film having a thickness of 96 μm / 24 μm (total 120 μm) was obtained. After the corona discharge treatment was applied to the surface of the (A2) layer of the support so that the wetting tension was 40 mN / m, the printed matter of Example 1 was produced by printing using the ink obtained in the preparation example. did.

Example 2
An ink-jet printed material was produced in the same manner as in Example 1 except that the thickness of each layer of the layer structure (A1) / (A2) of the film of Example 1 was 56 μm / 14 μm (total 70 μm).

Example 3
An ink jet printed matter was produced in the same manner as in Example 1 except that the thickness of each layer of the layer constitution (A1) / (A2) of the film of Example 1 was 24 μm / 6 μm (total 30 μm).

Example 4
The acid-modified olefin resin of the resin layer (A2) of Example 1 was replaced with an ethylene-methyl acrylate copolymer (MA content 12%, density: 0.933 g / cm ³ ; hereinafter referred to as “MA2”). An ink-jet printed material was produced in the same manner as in Example 1 except that.

Example 5
The acid-modified olefin resin of the resin layer (A2) of Example 1 is an ethylene-methyl acrylate-maleic anhydride copolymer [density: 1.00 g / cm ³ , copolymer content: 15%; hereinafter referred to as “MA3”. An inkjet printed material was produced in the same manner as in Example 1 except that the description was replaced.

Example 6
50% of resin MA1 for resin layer (A2) of Example 1 and propylene-ethylene copolymer [density: 0.900 g / cm ³ , MFR: 7-9 g / 10 min (230 ° C., 21.18 N), Melting point: 150 ° C .; hereinafter referred to as “COPP”] An ink-jet print was prepared in the same manner as in Example 1 except that the composition was replaced with 50%.

Example 7
An ink jet print was produced in the same manner as in Example 1 except that the resin MA1 for the resin layer (A2) of Example 1 was replaced with a blend of 20% and COPP of 80%.

Example 8
The HOPP of the resin layer (A1) of Example 6 is made of high-density polyethylene [density: 0.963 g / cm ³ , MFR: 7 g / 10 min (190 ° C., 21.18 N), melting point 130 ° C .; hereinafter referred to as “HDPE”. An ink-jet printed material was produced in the same manner as in Example 6 except that the description was replaced.

Example 9
HOPP of the resin layer (A1) of Example 6 was changed to medium density polyethylene [density: 0.934 g / cm ³ , MFR: 5.3 g / 10 min (190 ° C., 21.18 N), melting point 119 ° C .; Inkjet printed matter was produced in the same manner as in Example 6 except that the above was replaced.

Example 10
Example 1 except that the acrylic acid-modified resin of Example 1 was replaced with an ethylene- (meth) acrylic acid copolymer [density: 0.940 g / cm ³ , acid modification rate 12%; hereinafter referred to as “MA4”] In the same manner as in Example 1, an inkjet printed material was produced.

Example 11
An ink jet print was produced in the same manner as in Example 1 except that the thickness of each layer of the layer structure (A1) / (A2) of Example 1 was 114 μm / 6 μm (total 120 μm).

Example 12
An ink jet printed matter was produced in the same manner as in Example 1 except that the thickness of each layer of the layer structure (A1) / (A2) of the film of Example 1 was 90 μm / 30 μm (total 120 μm).

Comparative Example 1
An ink jet print was produced in the same manner as in Example 1 except that the acid-modified olefin resin in the resin layer (A2) of Example 1 was replaced with COPP.

Comparative Example 2
An inkjet printed material was produced in the same manner as in Example 1 except that the acid-modified olefin resin in the resin layer (A2) of Example 1 was replaced with HDPE.

  The evaluation results for the printed matter obtained above are shown in Tables 1-2.

  The inkjet printed matter of the present invention can be used for various purposes such as outdoor advertisements (posters, banners, etc.), labels, wallpaper, packaging films, postcards, OHP sheets, jet paper, lottery tickets, forms, and the like.

Claims (9)

A layer (A1) mainly composed of a polyolefin-based resin (a1);
Denaturation rate a 0.5 to 40% of the denatured polyolefin resin pre Symbol denatured polyolefin resin, and olefin component is an alkene having 2 to 6 carbon atoms, (meth) acrylic acid ester component or a layer composed of a copolymer der ging olefin resin with an unsaturated carboxylic acid component (a2),
Or, pre SL consists denatured olefin resin and (a2) a polyolefin-based resin, into 100 parts by mass of the resin component to form a layer, and the pre-Symbol denatured olefin resin (a2) is contained more than 20 parts by weight A layer (A2) comprising a resin composition;
A method for producing an ink-jet printed matter, comprising performing ink-jet printing on a surface of a layer (A2) of a multilayer film in which is laminated. The method for producing an inkjet printed matter according to claim 1, wherein the polyolefin resin (a1) has a melting point of 110 ° C. or higher. The method for producing an inkjet printed matter according to any one of claims 1 to 2, wherein the layer (A1) and the layer (A2) are laminated by a coextrusion lamination method. The layer which consists of the said modified olefin resin (a2) and polyolefin resin, and consists of a resin composition which contained 20 mass parts or more of the said modified olefin resin (a2) in 100 mass parts of resin components which form a layer. The polyolefin resin used in (A2) is
It is a polypropylene resin or a polyethylene resin, The manufacturing method of the inkjet printed material of any one of Claims 1-3. The polypropylene resin is a propylene homopolymer, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer, ethylene-propylene block copolymer or metallocene catalyst-based polypropylene. The method for producing an inkjet printed matter according to claim 4, wherein the polyethylene resin is medium density polyethylene or high density polyethylene. A layer (A1) mainly composed of a polyolefin-based resin (a1);
Denaturation rate a 0.5 to 40% of the denatured polyolefin resin pre Symbol denatured polyolefin resin, and olefin component is an alkene having 2 to 6 carbon atoms, (meth) acrylic acid ester component or a layer composed of a copolymer der ging olefin resin with an unsaturated carboxylic acid component (a2),
Or, pre SL consists denatured olefin resin and (a2) a polyolefin-based resin, into 100 parts by mass of the resin component to form a layer, and the pre-Symbol denatured olefin resin (a2) is contained more than 20 parts by weight The layer (A2) made of the resin composition is laminated, and the ratio of the layer (A2) to the total thickness of the layer (A1) and the layer (A2) is 5 to 40%, and the layer ( A2) A recording medium for ink-jet ink, which performs ink-jet printing on the surface. The layer which consists of the said modified olefin resin (a2) and polyolefin resin, and consists of a resin composition which contained 20 mass parts or more of the said modified olefin resin (a2) in 100 mass parts of resin components which form a layer. The polyolefin resin used in (A2) is
The recording medium for inkjet ink according to claim 6, which is a polypropylene resin or a polyethylene resin. The polypropylene resin is a propylene homopolymer, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer, ethylene-propylene block copolymer or metallocene catalyst-based polypropylene. The ink-jet ink recording medium according to claim 7, wherein the polyethylene resin is medium density polyethylene or high density polyethylene. An ink-jet printed matter obtained by ink-jet printing on the surface (A2) of the recording medium for ink-jet ink according to any one of claims 6 to 8 .