JP2013107276A - Recording medium for aqueous ink-jet ink, and aqueous ink-jet printed material and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording medium for aqueous ink-jet ink which has satisfactory adhesion with aqueous ink and does not cause problems such as peeling after printing without performing surface treatment or stretching process requisite when using the conventional plastic film as base material, and to provide a printed material of the recording medium.SOLUTION: A production method of the aqueous ink-jet printed material is characterized in that on the treated surface of a single layer or a multilayer film which has a layer consisting primarily of a cyclic polyolefin resin and in which the degree of surface treatment is 40 mN/m or more, the printing is performed according to an ink-jet recording method by using the aqueous ink which includes at least color material, a resin having a polar radical, and water or water-soluble organic solvent, and has a surface tension at 25°C in the range of 15 to 30 mN/m and a viscosity of 5 mPa s or less. Also, the printed material is obtained by the method.

Description

  The present invention relates to a water-based inkjet recording medium that enables inkjet recording even on a plastic substrate. Specifically, the adhesion between the water-based inkjet ink and the plastic substrate is excellent, and the printed surface is peeled off after printing. The present invention relates to a non-aqueous inkjet 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. Ink jet printing using water-based inks, which are less likely to cause problems in terms of environment and safety than oil-based inks, has recently become the mainstream.

  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 object of the present invention has been made in view of the above problems, and has good adhesion to water-based ink without performing a surface treatment or stretching process essential when using a conventional plastic film as a substrate. Another object of the present invention is to provide an aqueous inkjet recording medium and printed matter thereof that do not cause problems such as peeling after inkjet printing.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using, as an ink jet recording medium, a plastic film having a surface layer composed mainly of a cyclic polyolefin resin. The headline and the present invention were completed.

  That is, the present invention is a monolayer or multilayer film having a layer (A) mainly composed of a cyclic polyolefin-based resin (a1), wherein the surface of the layer (A) is treated to 40 mN / m or more. There are provided a recording medium for water-based inkjet ink, a printed matter obtained by performing inkjet printing using a water-based ink on a treated surface of the recording medium, and a production method thereof.

  The aqueous inkjet printed matter obtained by the present invention can be easily obtained by directly performing inkjet printing on a single layer or 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 water-based ink and the multilayer film, so that even if it is stored for a long period of time, the printed part will not peel off. It is also possible to form a bag.

  The plastic film functioning as a support for the aqueous inkjet printed matter of the present invention is a single layer or multilayer film (I) having at least a layer (A) mainly composed of a cyclic polyolefin resin (a1). This layer (A) functions not only as a support but also as an easy adhesion layer with water-based ink. In the present invention, “main component” means that the specific resin is contained in an amount of 50% by mass or more, preferably 55% by mass or more, based on the total amount of the resin composition forming the layer. Is a specific resin.

  Examples of the cyclic polyolefin resin (a1) include a norbornene polymer, a vinyl alicyclic hydrocarbon polymer, and a cyclic conjugated diene polymer. Among these, norbornene-based polymers are preferable. The norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter, referred to as “COP”). , “COC”). Furthermore, COP and COC hydrogenates are particularly preferred. The weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.

  The norbornene polymer and the norbornene monomer used as a raw material are alicyclic monomers having a norbornene ring. Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidene tetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenyl norbornene, methoxycarbonyl norbornene, methoxycarbonyl And tetracyclododecene. These norbornene monomers may be used alone or in combination of two or more.

  The norbornene-based copolymer is a copolymer of the norbornene-based monomer and an olefin copolymerizable with the norbornene-based monomer, and examples of such olefin include the number of carbon atoms such as ethylene, propylene, and 1-butene. Examples thereof include olefins having 2 to 20; cycloolefins such as cyclobutene, cyclopentene, and cyclohexene; and non-conjugated dienes such as 1,4-hexadiene. These olefins can be used alone or in combination of two or more.

  As a commercial product that can be used as the cyclic polyolefin resin (a1), examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and norbornene. Examples of the system copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by Polyplastics Co., Ltd., and the like.

  As described above, the content of the cyclic polyolefin resin (a1) with respect to the resin component forming the resin layer (A) easily increases the degree of surface treatment of the resulting single layer or multilayer film (recording medium) (I). From the viewpoint of adhesion to the water-based ink-jet ink, it is essential that the content is 50% by mass or more. If the content is lower than this, it is difficult to obtain a film having the intended performance. Particularly preferred is 80% by mass or more.

  Moreover, it is preferable that the glass transition point (Tg) of the said cyclic polyolefin resin (a1) is 60 degreeC or more from a viewpoint of the rigidity of the film (I) obtained. As will be described later, when a multilayer film (I) in which other resin layers (B) are laminated in order to develop further easy peel properties, it is possible to manufacture by a coextrusion lamination method, From the viewpoint of easy availability of raw materials, Tg is preferably 200 ° C. or lower. The temperature is particularly preferably 70 ° C to 180 ° C. As the cyclic polyolefin resin (a1) having such Tg, the content ratio of the norbornene monomer is preferably in the range of 30 to 90% by mass, more preferably 40 to 90% by mass, and still more preferably. It is 50-85 mass%. If the content ratio is within this range, the rigidity and processing stability of the film are improved. In addition, the glass transition point and melting | fusing point in this invention are measured by differential scanning calorimetry (DSC).

  On the other hand, norbornene copolymers with a high glass transition point (Tg) have low tensile strength, are extremely easy to break, and may tear easily. In view of this balance, it is also preferable to blend a high Tg product and a low Tg product having a glass transition point of less than 100 ° C. In addition, from the viewpoint of packaging mechanical properties (from the viewpoint that wrinkles and shrinkage do not occur on the sealing surface during bag making and article filling, and pinholes do not occur from the heat seal part), a resin mainly composed of a polyolefin resin (b) as described later It is preferable to make it the multilayer film which laminated | stacked the layer (B).

  In particular, the rigidity is too high and tearing or tearing easily due to dropping during transportation, or the sealing start temperature when used as a package becomes too high, or improvement in strength maintenance (hot tackiness) immediately after heat sealing, By blending COC having a Tg of less than 100 ° C., the falling bag strength and the packaging machine suitability can be improved. It is also effective to blend a polyolefin resin (a2), acid-modified olefin resin (a3), which does not contain a cyclic structure, which is compatible with COC, or a rubber elastomer resin having a low melting point and a low Tg. .

  Examples of the polyolefin resin (a2) that can be used in combination with the cyclic polyolefin resin (a1) in the resin layer (A) include a homopolymer or copolymer of an α-olefin having 2 to 6 carbon atoms. The copolymerization type may be a block copolymer or a random copolymer. Examples of the polyolefin resin (a2) include a polyethylene resin (a2-1) and a polypropylene resin (a2-2).

As said polyethylene-type resin (a2-1), the high heat-sealing intensity | strength at the time of using as a packaging material is expressed easily, pinhole-proof property, and the interlayer at the time of laminating | stacking the resin layer (B) mentioned later for the maintenance of strength, preferably has a density of 0.900~0.950g / cm ^3, more preferably at a density of 0.905~0.945g / cm ^3.

  Examples of the polyethylene resin (a2-1) include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE), and ethylene-vinyl acetate copolymer (EVA). ) And the like, and may be used alone or in admixture of two or more. Among these, VLDPE, LDPE, LLDPE, and MLDPE are preferable because of a good balance of sealing properties, rigidity, and adhesion to ink.

  The LDPE may be a branched low density polyethylene obtained by a high pressure radical polymerization method, and is preferably a branched low density polyethylene obtained by homopolymerizing ethylene by a high pressure radical polymerization method.

  As LLDPE and MLDPE, an ethylene monomer as a main component and a comonomer such as butene-1, hexene-1, octene-1, and 4-methylpentene are produced by a low-pressure radical polymerization method using a single site catalyst. -Copolymerized olefin. As a comonomer content rate in LLDPE, it is preferable that it is the range of 0.5-20 mol%, and it is more preferable that it is the range of 1-18 mol%.

  Examples of the single-site catalyst include various single-site catalysts such as metallocene catalyst systems such as combinations of metallocene compounds of Group IV or V transition metals and organoaluminum compounds and / or ionic compounds. In addition, the single-site catalyst has a uniform active site, so the molecular weight distribution of the resulting resin is sharper than a multi-site catalyst with a non-uniform active site. This is preferable because a resin having physical properties excellent in stability of sealing strength and anti-blocking property can be obtained.

As described above, the density of the polyethylene resin (a2-1) is preferably 0.900 to 0.950 g / cm ³ . If the density is within this range, it has moderate rigidity, excellent mechanical strength such as heat seal strength and pinhole resistance, and film film formability and extrusion suitability are improved. Moreover, it is preferable that melting | fusing point is generally the range of 60-130 degreeC, and 70-125 degreeC is more preferable. If melting | fusing point is this range, the process stability and the extrusion processability at the time of using it mixed with the said cyclic polyolefin resin (a1) will improve. Moreover, it is preferable that it is 2-20 g / 10min, and, as for MFR (190 degreeC, 21.18N) of the said polyethylene-type resin (a2-1), it is more preferable that it is 3-10 g / 10min. When the MFR is within this range, the extrusion moldability of the film is improved.

  Since such polyethylene resin (a2-1) has good compatibility with the cyclic polyolefin resin (a1), transparency as a film can be maintained. Moreover, without using an adhesive resin or the like, the interlayer adhesion strength between the resin layer (A) and the resin layer (B) described later can be maintained, and since it has flexibility, the pinhole resistance is also good. . Furthermore, when improving pinhole resistance, it is preferable to use LLDPE and MLDPE.

  Examples of the polypropylene resin (a2-2) include propylene homopolymer, propylene / α-olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene- An ethylene-butene-1 copolymer, a metallocene catalyst type polypropylene, etc. are mentioned. These may be used alone or in combination. A propylene-α-olefin random copolymer is desirable, and a propylene / α-olefin random polymer polymerized using a metallocene catalyst is particularly preferable. When these polypropylene resins are used, the heat resistance of the film is improved and the softening temperature can be increased, so that steam such as boiling at 100 ° C. or lower, hot filling, or retort sterilization at 100 ° C. or higher is used. -It can also be used as a packaging material with excellent high-pressure heat sterilization characteristics.

  In addition, these polypropylene resins (a2-2) preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 min and a melting point of 110 to 165 ° C., more preferably MFR ( 230 ° C.) is 2.0 to 15.0 g / 10 min, and the melting point is 115 to 162 ° C. If MFR and melting | fusing point are this range, there will be little shrinkage | contraction of the film at the time of heat sealing, and also the film-forming property of a film will improve.

  Further, examples of the resin that can be used in combination with the cyclic polyolefin resin (a1) include an acid-modified olefin resin (a3). When the acid-modified olefin resin (a3) is used in combination, the adhesion with the aqueous inkjet ink is further improved, and the long-term storage stability as a printed matter is improved.

  The olefin component which is the main component of the acid-modified olefin resin (a3) is not particularly limited, but 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 thereof 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 (a3) 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. From the viewpoint of easy availability and ink adhesion, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hexyl acrylate are more preferable, and methyl acrylate and ethyl acrylate are more preferable. 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. (In addition, "(meth) acrylic acid ~" means "acrylic acid ~ or methacrylic acid ~".) Specifically, as an ethylene- (meth) acrylic acid ester copolymer, for example, 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.

  The acid-modified polyolefin resin (a3) 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.

  As the acid modification rate of the acid-modified olefin resin (a3), adhesion with aqueous inkjet ink, blocking when the film (I) is wound and stored, and appearance defects such as wrinkles after printing, etc. From the viewpoint of excellent balance such as suppression, it is preferable to use 0.5 to 40%, more preferably 0.5 to 35%, and particularly preferably 0.5 to 30%.

  In addition, as described above, when the printed matter of the present invention is used as a packaging material, the cyclic polyolefin resin (a1) is used as a main component in order to improve heat sealability and to provide easy opening. Further, a multilayer film (I) obtained by further laminating a resin layer (B) containing a polyolefin-based resin (b) as a main component on the resin layer (A) to be formed can be used.

  After water-based inkjet printing on the multilayer film (I), when this is used as a lid material, etc., it is brought into close contact with the outermost layer of the container, and is bonded by applying a temperature to a desired site for one purpose. However, the polyolefin-based resin (b) and the polyethylene-based resin (b1) can be easily developed from the viewpoint of easy opening due to cohesive failure or interfacial peeling when further peeled. It is preferable that it is a mixture with a polypropylene resin (b2).

Examples of the polyethylene resin (b1) include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE), and ethylene-vinyl acetate copolymer (EVA). ), Ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-) EA-MAH), ethylene-acrylic acid copolymers (EAA), ethylene-based copolymers such as ethylene-methacrylic acid copolymer (EMAA); and ethylene-acrylic acid copolymer ionomers, ethylene-methacrylic acid Examples include ionomers of copolymers. Among these, the density is 0.91 from the viewpoints of compatibility when used in combination with the polypropylene resin (b2) described later, ease of cohesive failure, and surface appearance after peeling. low density polyethylene ~0.93g / cm ^3, or density is preferably used high-density polyethylene 0.94~0.96g / cm ^3. Furthermore, the melt flow rate (190 ° C., 21.18 N) is preferably 1 g / 10 min or more from the viewpoint of film formability.

  Examples of the polypropylene resin (b2) include propylene homopolymer, propylene-α-olefin copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, and propylene-ethylene-butene-1. A copolymer, a metallocene catalyst type | system | group polypropylene, etc. are mentioned. These may be used alone or in combination. An ethylene-propylene random copolymer from the viewpoint of easy opening when the resulting multilayer film (I) is used as a packaging material and easy adjustment of the sealing strength. It is preferable to use ethylene-propylene-butene-1 terpolymer or ethylene-propylene copolymer polymerized using a single site catalyst.

  Further, these polypropylene resins (b2) preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 minutes and a melting point of 120 to 165 ° C., more preferably MFR (230 ° C. ) Is 2.0 to 15.0 g / 10 min and the melting point is 125 to 162 ° C. If MFR and melting | fusing point are this range, there will be little shrinkage | contraction of the film at the time of sealing, and also the film-forming property of a film will improve.

  Furthermore, as a use ratio of the polyethylene resin (b1) and the polypropylene resin (b2), the mass ratio represented by (b1) / (b2) is in the range of 10-40 / 60-90. However, it is preferable from the point which can express easily openability, and it is especially preferable that it is the range of 15-30 / 70-85.

  In addition, in the resin layer (B), from the viewpoint of further facilitating easy opening and adjusting the sealing strength, other olefin resins such as polybutene resins and the above-mentioned cyclic polyolefin resins are used in combination. May be. At this time, the total mass of the polyethylene resin (b1) and the polypropylene resin (b2) is contained in the resin component in the resin layer (B) at 85% by mass or more from the viewpoint of not impairing easy opening. It is preferable.

  In the multilayer film (I), the resin layer (B) may be a single layer or a multilayer of two or more layers. In particular, from the viewpoint of maintaining the rigidity of the film, it is preferable to laminate two or more layers. As an intermediate layer between the resin layer (A) and the outermost layer, a polypropylene resin or a direct resin synthesized using a metallocene catalyst may be used. The use of chain low density polyethylene is preferable from the viewpoint of maintaining the mechanical strength of the film.

  In particular, when a propylene-ethylene block copolymer is used for the outermost layer on the opposite side of the resin layer (A), the surface is modified into a satin finish, and the film (I) having a multilayer structure is wound into a roll. Generation of wrinkles can be suppressed, and blocking when stored in a roll 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.

  If a mixed resin of crystalline propylene resin and ethylene / propylene rubber (hereinafter referred to as “EPR”) is used for the outermost layer on the opposite side of the resin layer (A), the surface 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.

  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 an intermediate 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, by providing an adhesive layer on the resin layer (B) on the surface opposite to the treatment layer of the layer (A), or on the surface opposite to the resin layer (A) in the case of a multi-layer film, it can be used on signs, vehicles, It can also be set as the water-based inkjet printed matter (label) which can be affixed. 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. The pressure-sensitive adhesive layer is formed by coextrusion of the pressure-sensitive adhesive layer at the same time when the resin layer (A) is extruded or when the resin layer (B) is laminated by coextrusion. The method is preferred for the production cycle.

  For each of the layers (A) and (B), an anti-fogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, and an ultraviolet absorber, if necessary. Components such as a colorant and a colorant can be added within a range that does not impair 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 (A) and (B) can be set as appropriate according to the use of the printed material. For example, in the case of a packaging material (bag or lid material), 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 (B) to the total thickness of the layers (A) and (B) is preferably in the range of 5 to 40% from the viewpoint of ensuring adhesion with the aqueous ink described later. The thickness of the layer (A) is preferably in the range of 2 to 30 μm.

  The method for laminating the layer (A) and the layer (B) is preferably a coextrusion laminating method in which the layer (A) and the layer (B) are laminated adjacently. After laminating layers (A) and (B) in a molten state by various coextrusion methods such as a coextrusion multi-layer die method and a feed block method, which are melt-extruded using an extruder of a table or higher, 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.

  In the present invention, it is essential to treat the surface of the resin layer (A) of the single-layer or multilayer film (I) to 40 mN / m or more. Although it does not specifically limit as a processing method, It is desirable to surface-treat the surface of a layer (A) continuously using a corona discharge or a plasma discharge etc. under the atmosphere of heating or an inert gas.

The method of corona treatment is not particularly limited. For example, JP-B-39-12838, JP-A-47-19824, JP-A-48-28067, and JP-A-52-42114. It can be performed by the processing method described in the above. As the corona discharge treatment apparatus, a solid state corona treatment machine manufactured by Pillar, a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used. The treatment can be performed at normal pressure in air. The discharge frequency during the treatment is 5 kV to 40 kV, more preferably 10 kV to 30 kV, and the waveform is preferably an alternating sine wave. The gap transparent lance between the electrode and the dielectric roll is 0.1 mm to 10 mm, more preferably 1.0 mm to 2.0 mm. The discharge is processed above a dielectric support roller provided in the discharge zone, and the treatment amount is 0.34 kV · A · min / m ^{2 to} 0.4 kV · A · min / m ² , more preferably 0.344 kV. A · min / m ^{2 to} 0.38 kV · A · min / m ² .

  In the present invention, since the resin layer (A) of the film (I) contains the cyclic polyolefin resin (a) at 50% by mass or more, the degree of treatment in such corona treatment does not have a cyclic structure. This is better than when polyolefin resin is treated. The degree of treatment can be determined, for example, by measuring the surface tension with a wetting reagent. When the film (I) is used, it can be easily set to 40 mN / m or more, and 50 mN / m. It can also be done above. It is presumed that such a high degree of corona treatment contributes to the development of adhesion with the water-based inkjet ink and suppresses peeling of the printed surface. On the other hand, when the same corona treatment is performed with a normal polypropylene film, it can only be about 38 mN / m, and the polyester film is about 45 mN / m, and the deterioration with time is large, and the degree of surface treatment is high over a long period of time. It is difficult to maintain. The surface of the film (I) is very little deteriorated with time after corona treatment, and it can be stored for several months as the film (I) and then subjected to water-based inkjet printing. It is the feature in I).

  The aqueous inkjet printed matter obtained by the present invention is obtained by aqueous inkjet printing on the treated surface of the monolayer or multilayer film (I) obtained above.

(Water-based ink)
The water-based ink used in the present invention comprises a coloring material, a resin having a polar group, and water or a water-soluble organic solvent, and has a surface tension at 25 ° C. in the range of 15 mN / m to 30 mN / m, The water-based ink has a viscosity of 5 mPa · s or less.

(Color material)
As the coloring material used in the water-based ink, a pigment or a dye is usually used, but it is preferable to use a pigment 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 various methods, for example, centrifugal sedimentation method, laser diffraction method (light scattering method), ESA method, capillary method, electron microscope method and the like.

(Resin having a polar group)
Resins having polar groups used in the present invention include, for example, proteins such as glue, gelatin, casein and albumin; natural rubbers such as gum arabic and tragacanth; glucosides such as saponin; alginic acid and propylene glycol alginate ester, alginic acid Alginic acid derivatives such as triethanolamine and ammonium alginate; natural polymers such as cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and ethylhydroxyethylcellulose; polyvinyl alcohols; polyvinylpyrrolidones; polyacrylic acid and acrylic acid-acrylonitrile Polymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, acrylic acid-acrylic Acrylic resin such as alkyl ester copolymer; styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer Styrene-acrylic acid resin such as styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer; styrene-maleic acid; styrene-maleic anhydride; vinylnaphthalene-acrylic acid copolymer; vinylnaphthalene- Maleic acid copolymer: Acetic acid such as vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate maleate ester copolymer, vinyl acetate crotonic acid copolymer, vinyl acetate acrylic acid copolymer, etc. Synthetic materials such as vinyl copolymers and their salts Child, and the like.

  Among these, a polymer compound having a carboxyl group (preferably in the form of a salt) (for example, the above styrene-acrylic acid resin, styrene-maleic acid, styrene-maleic anhydride, vinylnaphthalene-acrylic acid copolymer). Polymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate acrylic acid copolymer), copolymer of monomer having hydrophobic group and monomer having hydrophilic group, and hydrophobic group and hydrophilic group Polymers consisting of monomers with a combination of alkali metal, diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol , Morpholine, etc. Preferred salts of. These copolymers preferably have a weight average molecular weight of 3,000 to 300,000, more preferably 10,000 to 250,000.

  It is also preferable to use an aqueous dispersion in which the polymer is dispersed in water in the form of fine particles. These aqueous dispersions can be obtained by appropriately neutralizing a synthetic polymer containing the acid monomer such as acrylic acid or methacrylic acid. The content of the acid monomer is preferably 1% by weight to 15% by weight of the total monomer, and can provide an ink-jet ink that is relatively stable over a relatively long period of time and resistant to aggregation.

  These fine particles may be crosslinked. For example, it is possible to obtain fine particles having a crosslinked structure by using 0.1% by mass to 3% by mass of all monomers as a bifunctional or higher functional crosslinkable monomer. Since the crosslinkable monomer may cause gelation if used in a large amount, it is preferable to use it so that it does not exceed 3% by weight.

  Preferred examples of such an aqueous dispersion include, for example, a synthetic polymer using styrene, (meth) acrylate having 1 to 8 carbon atoms, ethylene glycol di (meth) acrylate, (meth) acrylic acid, and the like as appropriate. An aqueous dispersion obtained by neutralization is mentioned.

  The molecular weight of the resin having a polar group is preferably in the range of 10,000 to 2,000,000, more preferably in the range of 20,000 to 250,000, in terms of weight average molecular weight. When the weight average molecular weight is lower than 20,000, the storage stability of the ink may be deteriorated. If it is higher than 250,000, ink ejection properties are affected, and clogging or the like may easily occur. The glass transition temperature is preferably in the range of −20 ° C. to + 30 ° C. The particle diameter of the fine particles is in the range of 20 nm to 500 nm, more preferably in the range of 100 nm to 300 nm, and an ink having no problem in ejection property can be obtained.

  Here, the particle size 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. Preferable is measurement by Microtrac UPA using a dynamic light scattering method.

(Water or water-soluble organic solvent)
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 Alcohols such as ethanol; ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; dimethylformamide, N-methylpyrrolidone, 2-pyrrolidone, LEG-1, glycerol, diethylene glycol, trimethylolpropane And / or the like can be used.

(Surfactant or low surface tension organic solvent)
In order to appropriately adjust the surface tension, a surfactant or a low surface tension organic solvent can be added to the water-based ink. The surfactant is not particularly limited, and examples include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, anionic surfactants are included. Agents and nonionic surfactants are preferred.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol ether. Sulfate salts and sulfonates of the above, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples include dodecylbenzene sulfonate, isopropyl naphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfate. , And the like salts.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Polyethylene glycol polypropylene glycol block copolymer, alkylphenol etoxy Among these, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid Esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and alkylphenol ethoxylates are preferred.

  Other surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. Biosurfactants such as spicrispolic acid, rhamnolipid, lysolecithin and the like can also be used.

  These surfactants can be used alone or in combination of two or more. In consideration of the dissolution stability of the surfactant, the HLB is preferably in the range of 7-20.

  As commercially available fluorosurfactants, Novec FC-4430, FC-4432 (above, manufactured by Sumitomo 3M), Zonyl FSO-100, FSN-100, FS-300, FSO (above, manufactured by DuPont), Ftop EF- 122A, EF-351, 352801, 802 (Gemco), MegaFuck F-470, F-1405, F474, F-444 (DIC), Surflon S-111, S-112, S-113, S121, S131 , S132, S-141, S-145 (manufactured by Asahi Glass), footage series (manufactured by Neos), Fluorad FC series (manufactured by Minnesota Mining and Manufacturing Company), Monflor (Imperial) (Chemical Industry) Kobetto (Licowet) VPF series (manufactured by Farubeberuke Hoechst), and the like.

  Examples of the silicon-based surfactant include KF-351A, KF-642, Olphine PD-501, Olphine PD-502, Olphine PD-570 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK347, BYK348 (manufactured by BYK Japan).

  The polyoxyethylene alkyl ether activators include BT series (Nikko Chemicals), Nonipol series (Sanyo Kasei), D-, P-series (Takemoto Yushi), EMALEX DAPE series (Nippon Emulsion), Pegnol series (Toho) Chemical industry). An example of the polyethylene glycol alkyl ester system is peganol (Toho Chemical Industries).

  Examples of acetylene glycol surfactants include Olphine E1010, STG, Y (manufactured by Nissin Chemical Co., Ltd.), Surfynol 104, 82, 420, 440, 465, 485, TG (manufactured by Air Products and Chemicals Inc.). Can be mentioned.

  A low surface tension organic solvent can also be used. For example, as glycol ether compounds, diethylene glycol mono (C 1-8 alkyl) ether, triethylene glycol mono (C 1-8 alkyl) ether, propylene glycol mono (C 1-6 alkyl) ether, di Mention may be made of propylene glycol mono (C1-6 alkyl) ethers, which can be used as one or a mixture of two or more.

  Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Ether, diethylene glycol mono-iso-propyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, diethylene glycol monoheptyl ether, diethylene glycol monooctyl ether, triethylene glycol Cole monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, triethylene glycol monoheptyl ether, triethylene glycol monooctyl Tityl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono-iso-propyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopentyl ether, propylene glycol Mono hex Ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-iso-propyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl An ether etc. can be mentioned.

  Glycol ethers and surfactants can be used to adjust the surface tension of the ink. Specifically, the ink can be appropriately added so that the surface tension of the ink is 15 mN / m to 30 mN / m or less, and the addition amount of the surfactant is preferably in the range of about 0.1 to 10% by mass with respect to the ink composition. More preferably, it is 0.3-2 mass%. The surface tension is more preferably in the range of 16 to 28, and most preferably in the range of 18 to 25.

(Wetting agent)
Furthermore, a wetting agent can be similarly added to the water-based ink for the purpose of preventing the ink from drying. The content of the wetting agent in the ink for the purpose of preventing drying is preferably 3 to 50% by mass. The wetting agent is not particularly limited, but a wetting agent that is miscible with water and can prevent clogging of an inkjet printer head is preferable. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,2-butane Diol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, 1, Diol compounds such as 2-heptanediol, 1,2-nonanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-nonanediol, 1,2-octanediol 1,4-butanediol, 1,3-butanediol, mesoerythritol, pentaerythritol, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, and nitrogen-containing heterocyclic compounds such as ε-caprolactam. Among them, the inclusion of propylene glycol and 1,3-butyl glycol has safety and excellent effects in ink drying properties and ejection performance.

(Penetration agent)
Further, a penetrant can be added to the water-based ink for the purpose of improving the permeability to a film as a recording medium and adjusting the dot diameter on the recording medium. Examples of the penetrant include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether. The penetrant content in the ink is preferably 0.01 to 10% by mass.

  In addition, antiseptics, viscosity modifiers, pH adjusters, chelating agents, plasticizers, antioxidants, ultraviolet absorbers, and the like can be added as necessary.

(Production method)
The method for producing the water-based ink used in the present invention is not limited at all. A coloring material such as the pigment, a resin having the polar group, water or a water-soluble organic solvent, and an additive such as a surfactant as necessary may be charged and dispersed to form a water-based ink. A water-based ink may be prepared by preparing a mill base having a high concentration of coloring material and diluting and appropriately adding additives. In the following, a method for forming the latter mill base and making it a water-based ink will be described.

As a manufacturing method of the mill base,
(1) A method of preparing an aqueous pigment dispersion by adding a coloring material to an aqueous medium containing a pigment dispersant and water and then dispersing the coloring material in the aqueous medium using a stirring / dispersing device.
(2) The coloring material and the pigment dispersant are kneaded using a kneader such as two rolls or a mixer, and the obtained kneaded material is added to an aqueous medium containing water, and the mixture is aqueous using a stirring / dispersing device. A method for preparing a pigment dispersion.
(3) After adding a coloring material to a solution obtained by dissolving a pigment dispersant in an organic solvent having compatibility with water such as methyl ethyl ketone and tetrahydrofuran, the white pigment is organically mixed using a stirring / dispersing device. A method of preparing an aqueous pigment dispersion by dispersing in a solution and then emulsifying by phase inversion using an aqueous medium, and then distilling off the organic solvent.
Etc.

  Examples of the agitation / dispersing device include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer. May be used alone, or two or more kinds of apparatuses may be used in combination.

  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]
A water-based ink was applied to an A4 size film with a bar coater (No. 6), and the number of repels was visually measured.
○: 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 (A) 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 water-based ink]
As the water-based ink, a commercially available cyan ink (manufactured by Hured Packard, HP DESIGNJET L25500) was used, and ink coating suitability was evaluated. As a result of measuring the surface tension of the ink at a temperature of 25 ° C. by a platinum plate method using a surface tension meter (manufactured by Kyowa Interface Science: CBVP-A3), it was 18.2 mN / m. Similarly, the result of measuring the viscosity at 25 ° C. using a viscometer (manufactured by Toa DKK: TVE-25L) was 3.22 mPa · s.

  Regarding the adjustment of the printed matter using water-based ink, inkjet printing was performed on the (A2) surface of the recording medium using an inkjet printer “HP DESIGNJET L25500” (manufactured by Hured Packard).

Example 1
Example 1
(A) As a resin for the layer, a ring-opening polymer of a norbornene-based monomer [“Apel APL6015T” manufactured by Mitsui Chemicals, MFR: 10 g / 10 min (260 ° C., 21.18 N), glass transition point: 145 ° C .; "COC (1)". ] 20 parts and a ring-opening polymer of a norbornene-based monomer [“Apel APL8008T” manufactured by Mitsui Chemicals, MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition point: 70 ° C .; 3) ". A resin mixture of 80 parts was used. This resin is supplied to an extruder for layer (A) (caliber: 50 mm) and melted at 200 to 230 ° C., and the melted resin is co-extruded multilayer film manufacturing apparatus (feed) having a feed block. Block and T die temperature: 250 ° C.), and melt extrusion is performed to obtain a film having a single layer configuration of (A) and a total layer thickness of 70 μm. ) Corona treatment was applied to the layer surface. The surface tension with a wetting reagent (Wako Pure Chemical Industries, Ltd., mixed liquid for wet tension test) was 45 mN / m.

Example 2
(A) As the layer resin, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. In the same manner as in Example 1, after obtaining a film having a single layer configuration of (A) and a thickness of all layers of 30 μm, the surface of the (A) layer was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m.

Example 3
(A) 60 parts of COC (1) and 30 parts of COC (3) and linear medium density polyethylene [density: 0.930 g / cm ³ , melting point 125 ° C., MFR: 5 g / 10 min (190] Hereinafter referred to as “LMDPE”. A resin mixture with 10 parts was used. After performing melt extrusion in the same manner as in Example 1 to obtain a film having a single layer configuration of (A) and a total thickness of 30 μm, (A) the surface of the layer was subjected to corona treatment. gave. The surface tension by the wetting reagent was 45 mN / m.

Example 4
(A) Propylene-α-olefin random copolymer polymerized using 60 parts of COC (1) and 30 parts of COC (3) and a metallocene catalyst as the layer resin [density: 0.900 g / cm ³ , melting point 135 ° C., MFR: 4 g / 10 min (230 ° C., 21.18 N); hereinafter referred to as “MRCP”. ) 10 parts resin mixture was used. After performing melt extrusion in the same manner as in Example 1 to obtain a film having a single layer configuration of (A) and a total thickness of 20 μm, (A) the surface of the layer is subjected to corona treatment. gave. The surface tension by the wetting reagent was 45 mN / m.

Example 5
(A) As the layer resin, a resin mixture of 40 parts of COC (1), 40 parts of COC (3) and 20 parts of LMDPE was used. After melt extrusion was performed in the same manner as in Example 1 to obtain a film having a single layer configuration of (A) and a total thickness of 50 μm, (A) the surface of the layer was subjected to corona treatment. gave. The surface tension by the wetting reagent was 45 mN / m.

Example 6
(A) As a layer resin, a ring-opening polymer of norbornene-based monomer [“Appel AP6013T” manufactured by Mitsui Chemicals, MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition temperature: 125 ° C .; "COC (2)". ] 60 parts and high density polyethylene [density: 0.960 g / cm ³ , melting point 128 ° C., MFR: 10 g / 10 minutes (190 ° C., 21.18 N); hereinafter referred to as “HDPE”. 40 parts of the resin mixture was used. After performing melt extrusion in the same manner as in Example 1 to obtain a film having a single layer structure of (A) and a total thickness of 40 μm, (A) the surface of the layer is subjected to corona treatment. gave. The surface tension by the wetting reagent was 43 mN / m.

Example 7
(A) As a resin for the layer, a resin mixture of 70 parts COC (1) and 10 parts COC (3), 10 parts LMDPE and 10 parts MRCP was used. In addition, MRCP was used as the resin for the resin layer (B). These resins are supplied to (A) layer extruder (50 mm diameter) and (B) layer extruder (50 mm diameter) and melted at 200 to 230 ° C., and the molten resin is fed with a T having a feed block. Co-extrusion extrusion is performed by supplying each to a die-chill roll co-extrusion multilayer film production apparatus (feed block and T-die temperature: 250 ° C.), and the film layer structure is (A) / (B) = 20 μm / 20 μm. Thus, a coextruded multilayer film having a total thickness of 40 μm was obtained. The surface of the layer (A) was subjected to corona treatment. The surface tension by the wetting reagent was 40 mN / m.

Example 8
(A) As the layer resin, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. MRCP was used as the resin for the intermediate layer (B), and a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used as the resin for the outermost layer. These resins were supplied to (A) layer extruder (50 mm diameter), (B) layer extruder (50 mm diameter), and (C) layer extruder (50 mm diameter) and melted at 230 to 250 ° C. Then, the melted resin is supplied to a T-die / chill roll co-extrusion multi-layer film production apparatus (feed block and T-die temperature: 250 ° C.) having a feed block, and co-melt extrusion is performed to form a layer structure of the film. (A) / (B) / (C) = 10 μm / 30 μm / 10 μm, and a coextruded multilayer film having a total thickness of 50 μm was obtained. In the same manner as in Example 1, corona treatment was performed on one surface. The surface tension by the wetting reagent was 42 mN / m.

Example 9
(A) A resin mixture of 40 parts of COC (1) and 60 parts of COC (3) was used as the layer resin. Using LMDPE as the resin for the layer (B) and further using a resin mixture of 40 parts of COC (1) and 60 parts of COC (3) as the resin for the outermost layer, the layer thickness of the film is 10 μm / 30 μm / A coextruded multilayer film was obtained in the same manner as in Example 8 so as to be 10 μm (total 50 μm), and then one surface was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.

Example 10
(A) 70 parts of COC (1) as the resin for the layer and ethylene- (meth) acrylate methyl copolymer as the acid-modified olefin-based resin fat [density: 0.940 g / cm ³ , MA content 18%; Hereinafter referred to as “MA1”] 30 parts of the resin mixture was used. As the resin for the layer (B), a resin mixture of 80 parts of LMDPE and 20 parts of COC (3) was used. Further, as the resin for the outermost layer, Example 8 was used by using a resin mixture of 70 parts of COC (1), 20 parts of LMDPE and 10 parts of HDPE so that the thickness of the film layer was 20 μm / 30 μm / 20 μm (total 70 μm). In the same manner as described above, a coextruded multilayer film was obtained, and then the surface of the layer (A) was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.

Example 11
(A) 60 parts of COC (1) and 20 parts of COC (3) as the resin for the layer and ethylene-methyl acrylate-maleic anhydride copolymer [density: 1.00 g / cm as the acid-modified olefin resin fat ^3. Copolymer content 15%; hereinafter referred to as “MA2”] 20 parts of resin mixture were used. A resin mixture of 80 parts of MRCP and 20 parts of COC (3) was used as the resin for the layer (B). Furthermore, as the resin for the outermost layer, using a resin mixture of 70 parts of COC (3) and 30 parts of LMDPE, the same as in Example 8 so that the thickness of the film layer is 20 μm / 30 μm / 20 μm (total 70 μm). After obtaining the coextruded multilayer film, the surface of the layer (A) was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.

Example 12
(A) As the layer resin, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. As the resin for the layer (B), a resin mixture of 50 parts of LMDPE and 50 parts of MRCP was used. Furthermore, as the resin for the outermost layer, a resin mixture of 20 parts of COC (1), 60 parts of COC (2) and 20 parts of LMDPE is used so that the thickness of the film layer becomes 20 μm / 30 μm / 20 μm (total 70 μm). Then, after obtaining a coextruded multilayer film in the same manner as in Example 8, the surface of the layer (A) was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.

Comparative Example 1
(A) Homopropylene [density: 0.900 g / cm ³ , melting point 160 ° C., MFR: 7 g / 10 min (230 ° C., 21.18 N)]; hereinafter referred to as “HOPP”. ), A 30 μm monolayer film was obtained, and then one surface was subjected to corona treatment. The surface tension by the wetting reagent was 43 mN / m.

Comparative Example 2
(A) As a resin for layers, linear low density polyethylene [density: 0.905 g / cm ³ , melting point 90 ° C., MFR: 5 g / 10 min (190 ° C., 21.18 N); hereinafter referred to as “LLDPE”. ] To obtain a 30 μm monolayer film, and then subjected to corona treatment on one surface. The surface tension by the wetting reagent was 40 mN / m.

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

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

Claims (9)

On the treated surface of a single layer or multilayer film (I) having a layer (A) mainly composed of a cyclic polyolefin resin (a1) and having a surface treatment degree of 40 mN / m or more,
It comprises at least a colorant, a resin having a polar group, and water or a water-soluble organic solvent, has a surface tension at 25 ° C. in the range of 15 mN / m to 30 mN / m, and a viscosity of 5 mPa · s or less. A method for producing a water-based inkjet printed matter, wherein printing is performed by an inkjet recording method using the water-based ink. The method for producing an aqueous inkjet printed matter according to claim 1, wherein the cyclic olefin-based resin (a1) is a norbornene-based polymer. The method for producing an aqueous inkjet printed matter according to claim 1 or 2, wherein the resin layer (A) further contains a polyolefin resin (a2) and / or an acid-modified olefin resin (a3). The method for producing an aqueous inkjet printed matter according to any one of claims 1 to 3, wherein the film (I) is a multilayer film further having a resin layer (B) mainly composed of a polyolefin resin (b). The method for producing an aqueous inkjet printed matter according to claim 4, wherein the polyolefin resin (b) is a mixture of a polyethylene resin (b1) and a polypropylene resin (b2). The method for producing an aqueous inkjet printed matter according to claim 1, wherein the aqueous ink contains a surfactant or a low surface tension organic solvent. The method for producing an aqueous inkjet printed matter according to claim 1, wherein printing is performed while heating the film (I), or the film (I) after printing is heated. A layer (A) containing a cyclic polyolefin resin (a1) as a main component and a layer (B) containing a polyolefin resin (b) are laminated, and the total of the layer (A) and the layer (B). A recording medium for an aqueous inkjet ink, wherein the ratio of the layer (B) to the thickness is 5 to 70%, and the surface of the layer (A) is 40 mN / m or more. A water-based inkjet printed matter, wherein the surface of the recording medium for water-based inkjet ink according to claim 8 is inkjet-printed using a water-based ink.