WO2017110600A1 - Support d'impression, procédé de fabrication de support d'impression, et matériel imprimé - Google Patents

Support d'impression, procédé de fabrication de support d'impression, et matériel imprimé Download PDF

Info

Publication number
WO2017110600A1
WO2017110600A1 PCT/JP2016/087131 JP2016087131W WO2017110600A1 WO 2017110600 A1 WO2017110600 A1 WO 2017110600A1 JP 2016087131 W JP2016087131 W JP 2016087131W WO 2017110600 A1 WO2017110600 A1 WO 2017110600A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
printing medium
printing
ink
basic
Prior art date
Application number
PCT/JP2016/087131
Other languages
English (en)
Japanese (ja)
Inventor
高広 座間
卓哉 五十嵐
Original Assignee
株式会社ユポ・コーポレーション
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ユポ・コーポレーション filed Critical 株式会社ユポ・コーポレーション
Publication of WO2017110600A1 publication Critical patent/WO2017110600A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings

Definitions

  • the present invention relates to a printing medium, a printing medium manufacturing method, and a printed matter.
  • the present invention uses an anionic resin, has few surface streaks, and performs ink transfer and ink adhesion after storage in a high-temperature and high-humidity environment when performing general printing using an ultraviolet curable ink.
  • the present invention relates to a printing medium having excellent water resistance and excellent water-resistant adhesion after being stored in a high-temperature and high-humidity environment when ink-jet recording is performed using an ultraviolet curable ink.
  • the present invention also relates to a method for producing the print medium and a printed matter using the print medium.
  • print medium In the printing field, various types of data are recorded on a printing medium using ink, and printed materials such as product quotations, price bills, and price tags may be created.
  • standard data such as background patterns and ruled line frames on the same print medium is recorded by general printing (plate printing) such as offset printing or seal printing using oxidative polymerization type ink or ultraviolet curable ink, Fine characters such as product names and prices, and variable data such as barcodes were recorded by an information recording method (printless printing) such as a thermal transfer recording method or an electrophotographic recording method. Therefore, the print medium is required to have excellent printability in both general printing and information recording methods.
  • printing media used in the field of business form printing include ink transferability for recording variable data such as product names and barcodes in an information recording method in addition to printability for multicolor printing in normal printing. It is preferable that printability such as ink adhesion is also imparted.
  • a method for improving the printability of a print medium it is known to devise the composition of a resin layer provided on the surface of a support (see Patent Documents 1 to 3).
  • General printing media and label paper are given printing suitability and processing suitability such as surface strength and ink setting properties as necessary.
  • processing suitability such as surface strength and ink setting properties
  • the transferability and adhesion of ink and toner to record variable data such as product names and barcodes by the information recording method Suitability such as (fixing property) is also given.
  • JP 2002-113959 A WO2014 / 087670 JP 2011-116125 A JP 2002-080767 A
  • Patent Document 1 discloses that a primer layer coated with a water-soluble primer of a nitrogen-containing polymer compound absorbs moisture in a high-temperature and high-humidity environment. It has been pointed out that the ink transfer is hindered by the fact that it has the property and contains a large amount of moisture, and it becomes difficult to transfer the ink. Further, Patent Document 1 discloses that a printing medium provided with a resin layer containing a nitrogen-containing polymer compound on the surface of a support has a moisture absorption of the resin layer that becomes an ink printing surface when left in a high temperature and high humidity environment for a long time.
  • the ink is easily peeled off when the printed surface is peeled off with an adhesive tape in a high-temperature and high-humidity environment for a long time.
  • Patent Documents 2 and 3 disclose ink jet recording paper using an aqueous cationic polyurethane resin.
  • Patent Documents 1 to 3 a cationic resin is used for the coating layer of the printing medium. From the viewpoint of mastering materials suitable for various printing conditions, it has been required to use an anionic resin for the coating layer of the printing medium instead of the cationic resin. However, there have been few known examples in which an anionic resin is used for the coating layer of the printing medium and both the printing suitability for general printing and inkjet recording is compatible.
  • an anionic polyurethane resin may be used for an ink composition.
  • Patent Document 4 discloses that an aqueous compound having a carboxyl group neutralized with a basic compound and a group having an unsaturated double bond in the molecule is used as an active energy ray-curable component in the ink.
  • an active energy ray-curable water-based ink composition for ink jet recording can be obtained which is excellent in abrasion resistance, water resistance and the like, has less odor and skin irritation, and has excellent ejection stability.
  • the problem to be solved by the present invention is that the ink transferability and ink after storage in a high-temperature and high-humidity environment when an anionic resin is used, surface printing is small, and general printing is performed using an ultraviolet curable ink It is an object of the present invention to provide a printing medium that has excellent adhesion and water resistance after storage in a high-temperature and high-humidity environment when inkjet recording is performed using an ultraviolet curable ink.
  • an anionic polyurethane resin (a), a nonionic or anionic binder resin (b), and a basic pH adjuster (c) are contained on at least one surface of a support containing a thermoplastic resin as a main component. It has been found that having a resin layer can provide a print medium that can solve the above-mentioned problems, and the present invention has been completed.
  • the present invention which is a specific means for solving the above problems, and preferred embodiments of the present invention are as follows.
  • a support containing a thermoplastic resin as a main component Having a resin layer containing an anionic polyurethane resin (a), a nonionic or anionic binder resin (b) and a basic pH adjuster (c);
  • the resin layer preferably has a solid content of 0.01 g / m 2 to 5 g / m 2 .
  • the basic pH adjuster (c) is preferably in a gas state or a solid state at 20 ° C. and 1 atm.
  • the basic pH adjuster (c) includes a base having a pKa of 9.9 to 13.0 as a free base. preferable.
  • the basic pH adjuster (c) is an alkylamine having 1 or 2 carbon atoms, triethanolamine, and a side chain has carbon atoms.
  • the resin layer is preferably a coating layer formed from a coating solution.
  • the basic pH adjuster (c) contains a free base and a pKa of 9.9 to 13.0.
  • the pH of the coating liquid is preferably 6.5 to 13.0.
  • an anionic resin is used, there are few surface streaks, and excellent in ink transferability and ink adhesion after storage in a high temperature and high humidity environment when performing general printing using an ultraviolet curable ink.
  • ink jet recording using an ultraviolet curable ink it is possible to provide a printing medium having excellent water resistance adhesion after storage in a high temperature and high humidity environment.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the printing medium of the present invention has an anionic polyurethane resin (a), a nonionic or anionic binder resin (b) and a basic pH adjuster (on the surface of at least one surface of a support containing a thermoplastic resin as a main component.
  • the basic pH adjuster (c) contains a free base and a pKa of 9.5 to 13.0, the water-resistant adhesion after storage in a high-temperature and high-humidity environment when ink jet recording is performed. Excellent.
  • the printing medium of the present invention uses an anionic resin, has few surface streaks, and performs ink transfer after storage in a high-temperature and high-humidity environment when performing general printing using an ultraviolet curable ink.
  • it is excellent in water resistance and ink adhesion, and is excellent in water adhesion after storage in a high-temperature and high-humidity environment when ink jet recording using an ultraviolet curable ink is performed.
  • the inclusion of an anionic polyurethane resin (a) in the resin layer is expected to contribute to the improvement of ink transferability after storage in a high temperature and high humidity environment when general printing using an ultraviolet curable ink is performed. .
  • the print medium of the present invention is a print medium suitable for general printing methods such as offset printing and seal printing using ultraviolet curable ink and ink jet recording using ultraviolet curable ink.
  • the print medium of the present invention is preferably adapted to an information recording system such as a thermal transfer recording system, an electrophotographic system, and an ink jet recording system.
  • the printing medium of the present invention is suitable for various printing methods using ultraviolet curable ink, and is particularly preferably a printing medium having excellent printing quality in ink jet recording and excellent water resistance of printing and images. . Further, it is more preferable that the print medium has high print quality in terms of less ink bleeding in ink jet recording.
  • the print medium is preferably printing paper. However, the printing medium may be other than printing paper (for example, a poster, calendar, map, tag, label, sticker, etc.).
  • details of preferred embodiments of the print medium of the present invention will be described.
  • the support includes a thermoplastic resin as a main component.
  • the main component of the support means a component contained in an amount of 50% by mass or more of the total mass of the support.
  • the support preferably contains 70% by mass or more, more preferably 80% by mass or more of the thermoplastic resin.
  • thermoplastic resin used for the support is not particularly limited.
  • polyolefin resins such as ethylene resins such as high density polyethylene and medium density polyethylene, propylene resins, polymethyl-1-pentene, and ethylene-cycloolefin copolymers; polyamides such as nylon-6 and nylon-6,6 Resin: Polyethylene terephthalate and its copolymer, Polyethylene naphthalate, Polybutylene terephthalate, Polybutylene succinate, Polyester of aliphatic polyester such as polylactic acid; Polycarbonate, Atactic polystyrene, Syndiotactic polystyrene, etc.
  • thermoplastic resins can be mentioned.
  • Propylene resins include propylene homopolymers and copolymers of propylene as a main component and ⁇ -olefins such as ethylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene. Can be used.
  • the stereoregularity is not particularly limited, and isotactic or syndiotactic and those showing various degrees of stereoregularity can be used.
  • the copolymer may be a binary system or a ternary or higher multi-element system, and may be a random copolymer or a block copolymer.
  • the propylene resin is preferably used by blending 2 to 25% by mass of a resin having a melting point lower than that of the propylene homopolymer. Examples of such a resin having a low melting point include high-density or low-density polyethylene.
  • thermoplastic resin used for the support one of the above thermoplastic resins may be selected and used alone, or two or more may be selected and used in combination. If necessary, an inorganic fine powder, an organic filler, a heat stabilizer (antioxidant), a light stabilizer, a dispersant, a lubricant and the like can be added to the thermoplastic resin used for the support.
  • the support may include an inorganic fine powder.
  • the support contains an inorganic fine powder, the support can be whitened, opaque, and further concealed, making it easy to visually recognize printing as a print medium, It is possible to prevent see-through).
  • the inorganic fine powder include heavy calcium carbonate, light calcium carbonate, calcined clay, talc, diatomaceous earth, titanium oxide, barium sulfate, alumina, silica, zinc oxide, magnesium oxide, diatomaceous earth and the like.
  • the surface treatment goods by the various surface treatment agent of the said inorganic fine powder can also be illustrated. Among these, heavy calcium carbonate, precipitated calcium carbonate and their surface-treated products, clay, and diatomaceous earth are preferable because they are inexpensive and have good pore forming properties during stretching.
  • Examples of surface treatment agents for inorganic fine powders include resin acids, fatty acids, organic acids, sulfate ester type anionic surfactants, sulfonic acid type anionic surfactants, petroleum resin acids, sodium, potassium, ammonium, and the like. Salts or fatty acid esters thereof, resin acid esters, waxes, paraffins and the like are preferable.
  • Nonionic surfactants, diene polymers, titanate coupling agents, silane coupling agents, phosphoric acid coupling agents, Active inorganic oxides are also preferred.
  • sulfate ester type anionic surfactant examples include long chain alcohol sulfate ester, polyoxyethylene alkyl ether sulfate ester, sulfated oil and the like or salts thereof such as sodium and potassium.
  • activator examples include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, paraffin sulfonic acid, ⁇ -olefin sulfonic acid, alkyl sulfosuccinic acid and the like, and salts thereof such as sodium and potassium.
  • Examples of the fatty acid include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, ariaic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid.
  • An acid etc. are mentioned.
  • Examples of the organic acid include maleic acid and sorbic acid.
  • Examples of the diene polymer include polybutadiene and isoprene.
  • Examples of the nonionic surfactant include a polyethylene glycol ester type surfactant.
  • Examples of the inert inorganic oxide include alumina and silica. These surface treatment agents can be used alone or in combination of two or more.
  • Examples of surface treatment methods for inorganic fine powders using these surface treatment agents include, for example, JP-A-5-43815, JP-A-5-139728, JP-A-7-300568, and JP-A-10-176079.
  • the support may contain an organic filler. Even when the support includes an organic filler, the support can be whitened and opaque, and printing can be easily viewed as a printing medium.
  • an organic filler a resin having a melting point or glass transition point higher than that of the main thermoplastic resin constituting the support (eg, 120 to 300 ° C.) can be preferably used.
  • the organic filler when a propylene resin is used as the main thermoplastic resin constituting the support polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyamide, polycarbonate, polystyrene, cyclic olefin homopolymer, ethylene- Examples thereof include cyclic olefin copolymers, polyethylene sulfide, polyimide, polymethacrylate, polyethyl ether ketone, polyphenylene sulfide, and melamine resin. These have a higher melting point or glass transition temperature than the propylene resin, which is the main thermoplastic resin constituting the support, and are incompatible with the propylene resin. Is preferable because it is good.
  • the support one kind selected from inorganic fine powder or organic filler may be used alone, or two or more kinds may be selected and used in combination.
  • the support preferably contains 5 to 75% by mass, more preferably 8 to 65% by mass of the fine powder or filler. More preferably, 55% by mass is contained. If the content of these in the support is 5% by mass or more, the desired pores are easily obtained and the printing medium tends to be opaque. Conversely, if it is 75 mass% or less, there exists a tendency for the intensity
  • the average particle size of the inorganic fine powder used and the average dispersed particle size of the organic filler are preferably in the range of 0.01 to 15 ⁇ m, more preferably in the range of 0.05 to 1.5 ⁇ m. More preferably, it is in the range of 1 to 1.3 ⁇ m. If a fine powder or filler having an average particle diameter or an average dispersed particle diameter of 0.05 ⁇ m or more is used, pores are likely to be obtained by stretch molding, and the printing medium tends to be opaque. Further, if a fine powder or filler having an average particle diameter or an average dispersed particle diameter of 15 ⁇ m or less is used, the strength of the support tends to be increased.
  • the average particle size of the inorganic fine powder used and the average dispersed particle size of the organic filler are cumulative values measured by a particle measuring device such as a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Microtrack Bell Co., Ltd.). 50% particle diameter (cumulative 50% particle diameter), observation of primary particle diameter with a scanning electron microscope (in the present invention, the average value of 100 particles is an average particle diameter), conversion from specific surface area (the present invention Then, the specific surface area was measured using a powder specific surface area measuring device SS-100 manufactured by Shimadzu Corporation).
  • a particle measuring device such as a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Microtrack Bell Co., Ltd.). 50% particle diameter (cumulative 50% particle diameter), observation of primary particle diameter with a scanning electron microscope (in the present invention, the average value of 100 particles is an average particle diameter), conversion from specific surface area (the present invention Then, the specific surface area was measured using a powder specific surface area measuring device
  • heat stabilizers such as sterically hindered phenolic antioxidants, phosphorus antioxidants, amine antioxidants, etc., usually in the range of 0.001 to 1% by mass. Can do.
  • a light stabilizer When a light stabilizer is added, sterically hindered amine light stabilizers, benzotriazole light stabilizers, benzophenone light stabilizers, sulfur light stabilizers, etc. are usually used within a range of 0.001 to 1% by mass. can do.
  • the dispersant is used, for example, for the purpose of dispersing the inorganic fine powder.
  • silane coupling agents higher fatty acids such as oleic acid and stearic acid, metal soaps, polyacrylic acid, polymethacrylic acid and salts thereof are usually used in the range of 0.01 to 4% by mass. be able to.
  • the method for forming the support is not particularly limited.
  • the support can be molded by appropriately selecting from various known methods. For example, cast molding, calender molding, rolling molding, inflation molding, thermoplasticity that extrudes a molten thermoplastic resin composition into a sheet using a single-layer or multilayer T-die or I-die connected to a screw-type extruder A mixture of a resin, an organic solvent, and an oil can be cast or calendered and then molded using a method of removing the solvent or oil.
  • the molten thermoplastic resin composition can also be extruded and laminated on the base material of paper or a thermoplastic resin film.
  • the support may be unstretched or stretched. Stretching can be performed by any of a variety of commonly used methods. Specific examples include longitudinal stretching using the difference in peripheral speed between rolls, transverse stretching using a tenter oven, rolling, a combination of a tenter oven and a linear motor, or simultaneous biaxial stretching using a combination of a tenter and a pantograph. Can do.
  • the stretching temperature is higher than the glass transition temperature of the thermoplastic resin used, and in the case of a crystalline resin, the thermoplasticity is higher than the glass transition temperature of the amorphous portion to the melting point of the crystalline portion. It can be performed within a known temperature range suitable for the resin. Specifically, the stretching temperature is preferably 2 to 60 ° C. lower than the melting point of the thermoplastic resin to be used.
  • the resin is a propylene homopolymer (melting point 155 to 167 ° C.), 152 to 164 ° C., high density polyethylene ( When the melting point is 121 to 134 ° C., it is preferably 110 to 120 ° C., and when polyethylene terephthalate (melting point 246 to 252 ° C.) is used, it is preferably 104 to 115 ° C.
  • the stretching speed is preferably 20 to 350 m / min.
  • the stretching ratio at the time of the stretching is not particularly limited, and is appropriately determined in consideration of the characteristics of the thermoplastic resin used.
  • a propylene homopolymer or a copolymer thereof is used as the thermoplastic resin, it is about 1.2 to 12 times, preferably 2 to 10 times when stretched in one direction, and biaxially stretched.
  • the area magnification is 1.5 to 60 times, preferably 10 to 50 times.
  • it is 1.2 to 10 times, preferably 2 to 5 times when stretched in one direction, and 1.5 to 20 times in area magnification when biaxially stretched. Preferably 4 to 12 times.
  • the support may be a single layer or a layered structure.
  • An example is shown about the manufacturing method of a single layer support.
  • a single-layer support including a polyolefin resin film includes a resin film comprising a resin composition containing 40 to 99.5% by mass of a polyolefin resin and 60 to 0.5% by mass of an inorganic fine powder. It can be prepared by stretching in a uniaxial or biaxial direction at a temperature lower than the melting point of the resin (preferably a temperature lower by 3 to 60 ° C.).
  • An example is shown about the manufacturing method of the support body which has a laminated structure.
  • a support having a laminated structure of layers containing a polyolefin resin film is a resin film comprising a resin composition containing 40 to 100% by mass of a polyolefin resin and 60 to 0% by mass of an inorganic fine powder. Stretched in the machine direction at a temperature lower than the melting point of the resin (preferably a temperature lower by 3 to 60 ° C.), and contains 25 to 100% by mass of polyolefin resin and 75 to 0% by mass of inorganic fine powder on at least one side of the stretched film. It can prepare by laminating
  • the laminated film may be stretched in the transverse direction at a temperature lower than the melting point of the polyolefin resin (preferably a temperature lower by 3 to 60 ° C.), and the resin layer laminated on the stretched film may be stretched in the transverse direction.
  • a temperature lower than the melting point of the polyolefin resin preferably a temperature lower by 3 to 60 ° C.
  • the resin layer laminated on the stretched film may be stretched in the transverse direction.
  • the example of the support body which has a polyolefin resin film on both surfaces of natural pulp paper is shown. Beating hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), or a mixture thereof, and papermaking a slurry containing a dry paper strength enhancer, wet paper strength enhancer, sizing agent, filler, etc.
  • Paper having an amount of 50 to 200 g / m 2 and a density adjusted to 0.90 to 1.15 g / cm 3 can be used as a base material.
  • a resin composition containing 40 to 80% by mass of a polyolefin resin and 20 to 60% by mass of an inorganic fine powder may be extruded and laminated on both sides of the base material to form a support, or a support having the above single-layer structure or laminated structure. It is good also as a support body by bonding the resin film demonstrated as a body.
  • the support For the purpose of use as a printing medium, the support preferably has a thickness in the range of 30 to 500 ⁇ m, more preferably in the range of 40 to 400 ⁇ m, and further preferably in the range of 50 to 300 ⁇ m. preferable.
  • the support (particularly the thermoplastic resin film layer on the support surface) may be stretched as described above. If a thermoplastic resin film containing an inorganic fine powder or an organic filler is stretched, a stretched porous resin film having a large number of fine pores inside can be obtained.
  • Such a stretched porous resin film is suitable as a support for a printing medium from the viewpoints of lightness and opacity. From the viewpoint of ease of handling, the stretched support preferably has a density in the range of 0.65 to 1.2 g / cm 3 , and preferably in the range of 0.7 to 1 g / cm 3. More preferred.
  • the stretched support preferably has a porosity measured by the following method in the range of 5 to 60%, more preferably in the range of 10 to 50%.
  • the porosity of each layer of the support is cut while cooling so as not to crush the holes of the support, creating a cross section in the thickness direction (observation surface), pasting it on the observation sample stage, and applying gold to the observation surface Evaporate and observe the vacancies in each layer at an arbitrary magnification that is easy to observe using a scanning electron microscope, capture the observed area as image data, and image-process the image to determine the vacancy area ratio. This is determined as the porosity.
  • the physical properties of the stretched support are preferably 50% or more, more preferably 60% or more. If the opacity of the support is 50% or more, printing is easy to see when used as a printing medium, and when used as label paper, barcode printing is affected by the background and reading errors occur. There is almost no fear.
  • the stretched support preferably has a whiteness of 80% or more, more preferably 90% or more. Such whiteness can contribute to the sharpness of the printed matter.
  • corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, ozone treatment, etc. which are generally used as surface oxidation treatment, are used alone or in combination. It is preferable to use it. Among these, corona discharge treatment and flame treatment are preferable, and corona discharge treatment is more preferable.
  • the treatment amount is preferably 600 to 12,000 J / m 2 (10 to 200 W ⁇ min / m 2 ), and 1,200 to 10,800 J / m 2 (20 to 180 W ⁇ min). / M 2 ) is more preferable.
  • frame processing it is preferably performed at 8,000 to 200,000 J / m 2 , and more preferably at 20,000 to 100,000 J / m 2 .
  • the resin layer used in the present invention is located on at least one surface of the support and contains an anionic polyurethane resin (a), a nonionic or anionic binder resin (b), and a basic pH adjuster (c). .
  • the resin layer is preferably a coating layer.
  • the resin layer may be a layer formed by a method other than coating.
  • the print medium may have the resin layer only on one surface of the support, or may have the resin layer on both surfaces of the support.
  • anionic polyurethane resin (a) By using the anionic polyurethane resin (a) for the resin layer, it is possible to contribute to improvement of water resistance after storage in a high-temperature and high-humidity environment when ink-jet recording using an ultraviolet curable ink is performed. it can. Although this mechanism is unclear, this effect can be read from a comparison of examples, reference examples, and comparative examples described later. Note that the improvement in print quality and water-resistant adhesion after storage in a high-temperature and high-humidity environment is expected to have a correlation with the balance of hydrophilicity and hydrophobicity of the urethane resin.
  • the anionic polyurethane resin (a) used for the resin layer can form a coating layer having excellent adhesion to the support.
  • the anionic polyurethane resin (a) can form a coating layer rich in elasticity due to urethane bonds, and can improve ink adhesion by following volume shrinkage at the time of curing of ultraviolet curable ink. .
  • anionic polyurethane resin (a) is anionic, it is rich in miscibility with nonionic or anionic binder resin (b). Therefore, the anionic polyurethane resin (a) and the nonionic or anionic binder resin (b) are less likely to aggregate in the resin layer having the configuration of the present invention, and surface streaking before printing is less likely to occur.
  • the anionic polyurethane resin (a) in the present invention is an anionic group (for example, a carboxyl group, a sulfonic acid group and a salt thereof) in the main chain and / or side chain of a urethane resin based on a polyol and a polyisocyanate compound. It means a urethane resin having a functional group or the like.
  • examples of the “polyol” used for forming the anionic polyurethane resin (a) include polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polyolefin polyol, polyacrylate polyol and castor oil derivative. .
  • polyester polyol examples include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, poly- ⁇ - Caprolactone diol, poly-3-methylpentane adipate, 1,6-hexanediol and dimer acid polycondensate, 1,6-hexanediol, adipic acid and dimer acid copolycondensate, nonanediol and dimer acid polycondensate Examples include condensates, polycondensates of ethylene glycol and dimer acid, and copolycondensates of ethylene glycol, adipic acid and dimer acid.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymer and block copolymer of ethylene oxide and propylene oxide, random copolymer and block of ethylene oxide and butylene oxide A copolymer can be illustrated.
  • polycarbonate polyol examples include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly-1,4-cyclohexane dimethylene carbonate diol, and polyhexamethylene-1,4-cyclohexane dimethylene carbonate diol.
  • polybutadiene polyol examples include a polyol composed of a homopolymer having a polybutadiene skeleton (1,2 adduct and 1,4 adduct), a polyol composed of a polybutadiene copolymer obtained by polymerizing butadiene, styrene and acrylonitrile, and the like.
  • hydrogenated product examples can be given.
  • polyolefin polyol include a polyhydroxy polymer.
  • polyacrylate ester polyol for example, an acrylic polyol obtained by copolymerizing an acrylic monomer such as hydroxyethyl methacrylate (HEMA) with an acrylic ester, methacrylic ester, styrene or the like, a polyacrylic ester polyol, and Examples thereof include polymethacrylate polyols.
  • the “castor oil derivative” include refined castor oil, dehydrated castor oil, polymerized dehydrated castor oil, and castor oil polyol. These polyols can be used alone or in combination.
  • anionic urethane resin (a) it is preferable to use a compound having two or more functional groups having active hydrogen capable of reacting with the isocyanate group of the isocyanate compound and having an anionic group.
  • anionic groups include functional groups in the form of carboxyl groups, sulfonic acid groups, and salts thereof.
  • Examples of the “compound having an anionic group” include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl)- Examples include sulfonic acid group-containing compounds such as 2-aminoethylsulfonic acid, and carboxyl group-containing compounds such as 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolvaleric acid.
  • the compounds having an anionic group can be used alone or in combination.
  • the “anionic polyurethane resin emulsion” is a combination of the above-mentioned polyol, polyisocyanate compound and compound having an anionic group as appropriate, using other monomers, a chain extender, a catalyst, etc. as necessary, using conventional methods.
  • the anionic urethane resin (a) can be synthesized by reacting the above-mentioned polyol, polyisocyanate compound and compound having an anion group in the presence of a hydrophilic volatile solvent such as acetone, methyl ethyl ketone, isopropanol and the like. .
  • the anionic polyurethane resin (a) preferably has an emulsion form.
  • An anionic polyurethane resin (a) is an aqueous medium from the viewpoint of facilitating coating when the coating liquid described later is prepared, reducing surface streaks before printing, and enhancing the water-resistant adhesion of the obtained resin layer. More preferably, it is in the form of an emulsion dispersed therein and is not redissolved after drying. Further, from the viewpoint of enhancing the transparency of the resin layer, the average particle diameter of the anionic polyurethane resin (a) emulsion can be, for example, 0.01 to 1 ⁇ m, and preferably 0.05 to 0.5 ⁇ m.
  • the average dispersed particle size of the emulsion is 50% of the cumulative particle size measured by a particle measuring device such as a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Microtrack Bell Co., Ltd.). Diameter), observation of primary particle diameter with a scanning electron microscope (for example, average value of 100 particles), conversion from specific surface area (for example, a powder specific surface area measuring device SS-100 manufactured by Shimadzu Corporation) The specific surface area can be measured).
  • a particle measuring device such as a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Microtrack Bell Co., Ltd.). Diameter), observation of primary particle diameter with a scanning electron microscope (for example, average value of 100 particles), conversion from specific surface area (for example, a powder specific surface area measuring device SS-100 manufactured by Shimadzu Corporation) The specific surface area can be measured).
  • an emulsion of the anionic urethane resin (a) can be obtained by using a known method such as an acetone method, a prepolymer mixing method, a ketimine method, or a hot melt dispersion method.
  • a known method such as an acetone method, a prepolymer mixing method, a ketimine method, or a hot melt dispersion method.
  • an emulsion of an anionic polyurethane resin (a) for example, Hydran AP20 (trade name, Hydran is a registered trademark), which is a sulfonic acid group-containing anionic polyurethane resin aqueous dispersion manufactured by Dainippon Ink and Chemicals, Inc.
  • Hydran AP40F (trade name) which is an aqueous dispersion of anionic polyurethane resin containing carboxylic acid groups, manufactured by Dainippon Ink & Chemicals, Inc., Superflex 150 (tradename) and Superflex 500M from Daiichi Kogyo Seiyaku Co., Ltd.
  • Nonionic or anionic binder resin (b) Since the nonionic or anionic binder resin (b) used in the resin layer has a strong affinity with the ultraviolet curable ink, the ink adhesion with the ultraviolet curable ink can be improved. In addition, the nonionic or anionic binder resin (b) used for the resin layer improves water adhesion after storage in a high-temperature and high-humidity environment when inkjet recording is performed using an ultraviolet curable ink. Can contribute. Although this mechanism is unclear, this effect can be read from a comparison of examples, reference examples, and comparative examples described later.
  • the nonionic or anionic binder resin (b) used for the resin layer is preferably capable of enhancing the adhesion to various supports.
  • nonionic or anionic binder resin (b) include acid-modified polyolefin resins, acid-modified ethylene / acrylic acid copolymers, acid-modified ethylene / ethyl acrylate copolymers, acid-modified LLDPE (Linear).
  • Low density Polyethylene acid-modified VLDPE (Very Low Density Polyethylene), ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, butadiene, styrene / butadiene copolymer, Examples thereof include an isobutylene / maleic anhydride copolymer, a carboxylic acid-modified polyester, a hydroxyl group-modified polyolefin resin, and a hydroxyl group-modified polyester resin. These can be used in the form of an emulsion or an aqueous solution, and can be used alone or in combination.
  • VLDPE Very Low Density Polyethylene
  • anionic binder resins are preferable, and acid-modified polyolefin resins, acid-modified ethylene / acrylic acid copolymers, acid-modified ethylene / ethyl acrylate copolymers, acid-modified LLDPE, and acid-modified VLDPE are more preferable.
  • a modified polyolefin resin is particularly preferred.
  • nonionic or anionic binder resin (b) include EL-452 (trade name) manufactured by Toyo Morton Co., Ltd., A-3804 (trade name) manufactured by Asahi Kasei Latex, and Kuraray Co., Ltd.
  • Arrow Base SB-1010 and Arrow Base SB-1030 are commercially available and can be used. .
  • the anionic polyurethane resin (a) suitably used in the present invention is designed to have high water resistance after drying, and has a property of being easily aggregated in a solution because it is an emulsion having a small average particle size. .
  • the absolute value of the surface potential (zeta potential) of nano-sized particles is 20 mV or more, the electric double layer is hardly broken and the dispersibility of the particles is good.
  • the zeta potential of the anionic polyurethane resin (a) is preferably set to ⁇ 20 mV or less in the state where the basic pH adjuster (c) is added to the aqueous dispersion of the anionic polyurethane resin (a).
  • the zeta potential of the anionic polyurethane resin is preferably ⁇ 70 mV or more, and more preferably ⁇ 60 mV or more.
  • the basic pH adjuster (c) preferably has a pKa as a free base of 7.5 to 13.0, more preferably 8.0 to 13.0, and preferably 9.5 to 13. It is particularly preferably 0, more particularly preferably 9.9 to 13.0, and even more particularly preferably 9.9 to 12.0.
  • the pH in the state of the coating solution is preferably 6.5 to 13.0, more preferably 6.5 to 10.5, and particularly preferably 7.5 to 9.5. preferable.
  • the pH of the coating liquid is not more than the upper limit of the above preferable range, the zeta potential of the anionic polyurethane resin (a) in the state of the coating liquid is decreased (the absolute value of the zeta potential is increased) and controlled to a preferable range. And the anionic polyurethane resin (a) is less likely to aggregate.
  • the pH in the state of the coating solution can be adjusted to the above range by adding an acid.
  • Usable acids include hydrochloric acid, sulfuric acid, carbonic acid, acetic acid and the like. Further, if the basic pH adjuster (c) is in a solid state or a gas state under normal use conditions, the basic pH adjuster (c) moves in the resin layer and oozes out on the surface of the resin layer. Inferior transfer of printing ink due to migration (migration) is unlikely to occur. In particular, the tendency for migration to hardly occur in plate printing is remarkable. Further, if migration is difficult to occur, it tends to be difficult to repel inkjet ink.
  • the basic pH adjuster (c) is preferably in a gas state or a solid state at 20 ° C. and 1 atmosphere, more preferably in a gas state or a solid state at 40 ° C.
  • the basic pH adjuster (c) is a solid under normal use conditions, and migration with time can be prevented, so that there is a tendency not to inhibit the ink transferability after long-term storage of the print medium.
  • the concentration in the coating layer after drying is preferably 100 ppm or less in order to prevent migration over time, and is 50 ppm or less. More preferably, it is more preferably 30 ppm or less.
  • basic pH adjusters (c) that are in a solid state at 20 ° C. and 1 atm those having no deliquescence are more preferable.
  • the basic pH adjuster (c) is composed of ammonia, an alkylamine having 1 or 2 carbon atoms, diethanolamine, triethanolamine, a side chain having 4 to 4 carbon atoms or a phenyl group. It preferably contains one or more bases selected from tertiary ammonium, tertiary sulfonium, secondary iodonium hydroxide, guanidine, amino acids having an isoelectric point of 7.5 or more, polyvinylamine, and polyallylamine.
  • the basic pH adjuster (c) is an alkylamine having 1 or 2 carbon atoms, triethanolamine, a quaternary ammonium whose side chain is an alkyl group having 1 to 4 carbon atoms or a phenyl group, It is more preferable to include one or more bases selected from tertiary sulfonium, secondary iodonium hydroxide, guanidine, amino acids having an isoelectric point of 9.5 or more, polyvinylamine, and polyallylamine.
  • Examples of the basic pH adjuster (c) that is in a gaseous state at 20 ° C. and 1 atm include ammonia, alkylamines having 1 or 2 carbon atoms, and diethanolamine.
  • ammonia is preferable.
  • alkylamines having 1 or 2 carbon atoms are also preferred.
  • a basic pH adjuster (c) that is in a solid state at 20 ° C. and 1 atm triethanolamine, quaternary ammonium, tertiary sulfonium whose side chain is an alkyl group having 1 to 4 carbon atoms or a phenyl group
  • examples include secondary iodonium hydroxide, guanidine, amino acids having an isoelectric point of 7.5 or more, polyvinylamine, and polyallylamine.
  • an amino acid having an isoelectric point of 7.5 or more an amino acid having an isoelectric point of 9.5 or more is preferable.
  • tetraethylammonium hydroxide guanidine
  • polyvinylamine polyallylamine
  • those obtained by neutralizing some of them with acid, arginine, histidine, and lysine are preferable.
  • the blending ratio of each component in the resin layer as a solid content after drying is 1 to 40 parts by mass of the nonionic or anionic binder resin (b) with respect to 100 parts by mass of the anionic polyurethane resin (a). It is preferable to include 10 to 20 parts by mass.
  • the basic pH adjuster (c) is preferably contained in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the anionic polyurethane resin (a). It is more preferable to include 3 parts by mass.
  • the amount ratio of each component in the resin layer is within this range, high printing quality and water-resistant adhesion of printed matter can be obtained in various printing methods and information recording methods.
  • the resin layer does not contradict the gist of the present invention with a crosslinking agent (d), an antistatic agent (e), an antifoaming agent, other auxiliary agents, etc. as necessary to improve coating suitability and printability. Can be included in a range.
  • the coating layer of the present invention may contain a crosslinking agent (d).
  • the crosslinking agent (d) is preferably a substance that crosslinks by reacting with the nonionic or anionic binder resin (b).
  • a crosslinking agent (d) is a water-soluble substance.
  • the cross-linking agent (d) is preferably a bifunctional substance or a polymer substance.
  • the crosslinking agent (d) is a trimolecular or higher functional low molecular substance in order to give the resin layer water resistance adhesion and wear resistance.
  • a bifunctional substance and a trifunctional or higher functional substance may be used in combination as the crosslinking agent (d).
  • the crosslinking agent (d) include epoxy-based, carbodiimide-based, isocyanate-based, formalin-based, and oxazoline-based crosslinking agents. Among these, an epoxy system, a carbodiimide system, and an oxazoline system are preferable.
  • the crosslinking agent (d) is preferably contained in an amount of 3 to 20 parts by mass, more preferably 10 to 20 parts by mass, based on 100 parts by mass of the anionic polyurethane resin (a) as a solid content.
  • the resin layer may contain an antistatic agent (e).
  • an antistatic agent e
  • the antistatic agent (e) is preferably a polymer-type antistatic agent that oozes out on the surface of the resin layer under long-term storage and hardly causes a decrease in ink adhesion.
  • the antistatic agent (e) anion type, amphoteric type, nonionic type and the like can be used.
  • Anionic types include alkali metal salts such as sulfonic acid, phosphoric acid and carboxylic acid, for example, alkali metal salts such as fatty acid having 1 to 12 carbon atoms, acrylic acid, methacrylic acid and (anhydrous) maleic acid (lithium salt, sodium salt). Salt, potassium salt, etc.) having a structure in the molecular structure.
  • the amphoteric type contains both the cation type and the anion type structures in the same molecule, and examples thereof include a betaine type.
  • Nonionic types include fatty acid amides, ethylene oxide polymers having an alkylene oxide structure, and polymers having an ethylene oxide polymerization component in the molecular chain.
  • a polymer type antistatic agent having boron in the molecular structure can be given as an example.
  • polyoxyalkylene ether phosphates that are anionic and polymer are preferable, and tertiary nitrogen or quaternary nitrogen-containing acrylic resins are more preferable.
  • the resin layer is preferably a coating layer formed by coating a coating solution. Since the coating liquid for forming the coating layer is easy to manage the process, the above components are homogeneous in a solvent such as water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene, or xylene. It is preferable to use it as a solution or dispersion by dissolving or dispersing in the solution.
  • a solvent such as water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene, or xylene. It is preferable to use it as a solution or dispersion by dissolving or dispersing in the solution.
  • any of the above components as a water-soluble or water-dispersible substance in the form of an aqueous solution or an aqueous dispersion.
  • the aqueous solution may contain alcohols and ketones compatible with water as a cosolvent. 0.1 mass% or more is preferable and, as for the solid content concentration in the coating liquid which forms a resin layer, 0.2 mass% or more is more preferable. 20 mass% or less is preferable and, as for the solid content concentration in the coating liquid which forms a resin layer, 10 mass% or less is more preferable.
  • the resin layer preferably has a solid content of 0.01 g / m 2 to 7 g / m 2 , more preferably 0.01 g / m 2 to 5 g / m 2 , 0.05 g / m 2 to 3 g / m 2 is particularly preferable.
  • the solid content of the resin layer in this specification means the solid content after drying per one side.
  • the solid content (coating amount) of the resin layer is not less than the lower limit of the preferred range.
  • the solid content (coating amount) of the resin layer is preferably not more than the upper limit of the preferred range from the viewpoint of preventing the adhesion due to cohesive failure of the resin layer and reducing the material cost.
  • Printing on the printing medium of the present invention can be performed by various known methods such as offset printing, gravure printing, flexographic printing, letter press printing, screen printing, ink jet recording method, thermal transfer recording method, pressure-sensitive transfer recording method, and electrophotographic recording method. It is possible to use a technique. From the viewpoint of fineness of printing, gravure printing, ink jet recording system, and electrophotographic recording system are preferable, and letter press printing and flexographic printing are preferable from the viewpoint of being able to handle small lots.
  • an inkjet recording method using an ultraviolet curable ink among the inkjet recording methods Is preferably used.
  • the method for producing a printing medium of the present invention comprises an anionic polyurethane resin (a), a nonionic or anionic binder resin (b) and a basic pH on at least one surface of a support containing a thermoplastic resin as a main component. It includes a step of forming a resin layer by coating (also referred to as coating) a coating liquid containing the adjusting agent (c).
  • the basic pH adjuster (c) contains a free base and a pKa of 9.5 to 13.0, the water-resistant adhesion after storage in a high-temperature and high-humidity environment when ink jet recording is performed. Excellent.
  • the resin layer is preferably a coating layer formed from a coating liquid.
  • the state of the surface streaks before printing of the printing medium differs, so it is technical to specify the structure of the resin layer Implicating work that is impossible or specific in nature.
  • a crosslinking agent is added to the coating solution, it is technically impossible to specify the structure in which the resin component crosslinks, or it involves an operation that is almost impractical to specify. Therefore, it is also preferable that one of the preferred embodiments of the print medium of the present invention is described in a product-by-process claim.
  • a coating liquid containing an anionic polyurethane resin (a), a nonionic or anionic binder resin (b) and a basic pH adjuster (c) is applied to at least one surface of the support.
  • a resin layer is formed.
  • the anionic polyurethane resin (a) in the state of the coating liquid preferably has a zeta potential of ⁇ 70 mV to ⁇ 20 mV.
  • the pH of the coating liquid is preferably 6.5 to 13.0, and more preferably 6.5 to 10.5.
  • the resin layer is preferably formed by applying a coating solution to at least one surface of the outermost layer of the support. From the viewpoint of antistatic performance, it is preferable to apply a coating solution on both surfaces of the support.
  • the coating process may be performed in combination with support molding in a support molding line, or may be performed in a separate line using an already molded support.
  • the coating may be performed before the stretching step or may be performed after the stretching step. You may remove an excess solvent through the drying process using oven etc. before or after the coating process as needed.
  • a general coating apparatus can be used to apply the coating liquid to the support.
  • the solid content after drying (coating amount), the viscosity of the coating liquid, and the solids of the chemical in the coating liquid It chooses suitably according to a partial concentration etc.
  • the coating apparatus include a roll coater, a blade coater, a bar coater, an air knife coater, a size press coater, a gravure coater, a die coater, a lip coater, and a spray coater.
  • a roll coater in a preferred embodiment of the blending ratio of the anionic polyurethane resin (a), the nonionic or anionic binder resin (b) and the basic pH adjuster (c), a roll coater, a bar coater, a size press coater, a gravure It is preferable to use a coater or a spray coater, and it is more preferable to use a roll coater, a size press coater, or a gravure coater.
  • the printed matter of the present invention has an ultraviolet curable ink on the resin layer of the print medium of the present invention.
  • a solution or dispersion containing an arbitrary colorant can be used.
  • a solution or dispersion containing a colorant is referred to as “ink” or “ink”.
  • “ink” is used for plate printing performed using a plate, and “ink” is used for plateless printing such as printer output without using a plate.
  • “ink” and “ink” will be described as “ink” without any particular distinction.
  • the ink used for these printings is preferably an ultraviolet curable ink from the viewpoint of ink adhesion (fixability) and scratch resistance. When printing with ultraviolet curable ink, the ultraviolet curable ink is solidified by ultraviolet irradiation.
  • the ultraviolet irradiation method is not particularly limited as long as the ultraviolet curable ink is cured.
  • a metal halide lamp 200 to 400 nm
  • a low pressure mercury lamp 180 to 250 nm
  • a high pressure mercury lamp 250 to 365 nm
  • a black light 350 ⁇ 360nm
  • the ultraviolet rays irradiated from UV-LED lamp 355 ⁇ 375nm
  • 300 ⁇ 3000mJ / cm 2 is preferably exemplified by irradiating such that the dose of 400 ⁇ 1000mJ / cm 2 .
  • the ultraviolet curable ink is not particularly limited, and a known ultraviolet curable ink can be used.
  • the ultraviolet curable ink preferably includes at least a diluent, a compound having a bifunctional or higher functional radical polymerizable group, and a colorant.
  • materials used for the ultraviolet curable ink materials described in [0016] to [0097] of JP-T-2004-526016 (particularly aliphatic urethane acrylate), and [0010] to [0010] of JP-A-2002-080767 are disclosed.
  • Materials described in [0062] (especially anionic aqueous polyurethane compounds), materials described in JP-A-2010-530922 [0004] to [0026] (especially chlorinated polyolefin excellent in adhesion to polyolefin film) Etc. can be preferably used.
  • the contents of these publications are incorporated herein by reference.
  • an ink further containing acryloylmorpholine as a diluent can be preferably used.
  • inkjet recording using ultraviolet curable ink if ink droplets flow between the time when ink droplets land on the outermost layer of the print medium and solidify by ultraviolet irradiation, the image blurs or the line drawing becomes thicker.
  • the print quality image quality
  • the pH of the coating liquid for forming the resin layer is 3.0 or more. If the pH of the surface of the resin layer of the printing medium is equal to or higher than the lower limit of the pH of the preferred coating liquid, the ink droplets are deformed so that the ink droplets are repelled and the line drawing is less likely to fade. Since the pigment in the inside is less likely to aggregate to form a metallic gloss film, the print quality can be improved.
  • Production Example 1 The support of Production Example 1 was produced by the following method. (1) MFR (melt flow rate) 0.8 g / 10 min propylene homopolymer (melting point 164 ° C.) 81% by mass, high density polyethylene 3% by mass and heavy calcium carbonate 16 ⁇ m in average particle size of 1.5 ⁇ m % Of the resin composition (A) mixed with% was kneaded in an extruder set at a temperature of 270 ° C., then extruded into a sheet, and further cooled by a cooling device to obtain an unstretched sheet.
  • MFR melt flow rate
  • the number of stretching axes of each layer (B layer / A layer / B layer) is uniaxial stretching / biaxial stretching / uniaxial stretching, and the thickness is 80 ⁇ m (B layer / A layer / B The thickness of each layer was 15 ⁇ m / 50 ⁇ m / 15 ⁇ m), the density was 0.79 g / cm 3 , the porosity was 29%, the opacity was 90%, and the whiteness was 95%. . Density, porosity, opacity and whiteness were measured by known methods.
  • a corona discharge treatment device (trade name: HF400F, manufactured by Kasuga Electric Co., Ltd.), a 0.8 m long aluminum discharge electrode and a treater roll on one surface of a laminated stretched film having a three-layer structure.
  • the gap between the discharge electrode and the treater roll was 5 mm, and a corona discharge treatment was performed at a line treatment speed of 15 m / min and an applied energy density of 4,200 J / m 2 .
  • the obtained support was used as the support in Production Example 1.
  • the support body of the manufacture example 1 contains a thermoplastic resin as a main component.
  • Production Example 2 The support of Production Example 2 was produced by the following method. The same corona discharge treatment as in Production Example 1 was performed on one side of a commercially available polyester film (trade name “Lumirror E20”, manufactured by Toray Industries, Inc., thickness 100 ⁇ m). The obtained support was used as the support in Production Example 2.
  • the support body of the manufacture example 2 contains a thermoplastic resin as a main component.
  • the coating liquid of Production Example 101 was produced by the following method.
  • Table 2 below shows the blending ratio of the coating liquid of each production example (solid content concentration wt% in the aqueous dispersion).
  • “ ⁇ ” described in the column of basic pH adjuster (c) means that the pH of the coating solution was adjusted using the corresponding type of basic pH adjuster (c). means.
  • the basic pH adjuster (c) added to the coating solution in each example, reference example and comparative example was 0.5 to 3 parts by mass with respect to 100 parts by mass of the anionic polyurethane resin (a). It was a range.
  • Comparative Example 1 The materials listed in Table 1 above were prepared at the blending ratios listed in Table 2 below, and the coating liquid of Production Example 111 was produced. A printing medium of Comparative Example 1 was obtained in the same manner as Reference Example 1 except that the coating liquid of Production Example 111 was used as the coating liquid and the coating amount (solid content) shown in Table 2 below was used.
  • Example 11 In Example 4, the printing medium of Example 11 was obtained in the same manner as in Example 4 except that the coating liquid obtained in Manufacturing Example 104 of the coating liquid was applied to the surface of the support in Manufacturing Example 2. It was.
  • Solid content of resin layer The solid content (coating amount) of the resin layer of the printing media of each Example, Reference Example and Comparative Example is shown in Table 2 below.
  • the solid content of the resin layer of the printing medium of each example, reference example and comparative example can be measured by peeling the resin layer.
  • the solid content of the resin layer of the printing medium of each Example, Reference Example, and Comparative Example coincides with the value calculated from the solid content of the coating liquid of each Production Example.
  • the print medium was cut into 10 cm ⁇ 10 cm and allowed to pass for 2 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the surface resistivity on the resin layer side of the print medium is based on JIS K 6911: 1995, using an insulation meter (trade name: DSM-8103, manufactured by Toa Denpa Kogyo Co., Ltd.) and a double ring method electrode. It was measured. JIS is an abbreviation for Japan Industrial Standards. When the measured surface resistivity is 1 ⁇ 10 13 ⁇ or more, it is determined that there is no antistatic property. When the measured surface resistivity is less than 1 ⁇ 10 13 ⁇ , the antistatic property is good, the paper feeding and discharging properties during printing and printing are good, and it is suitable as a printing medium.
  • Example 5 (2) General printability (blank yellowing) The print medium was stored in an atmosphere of 40 ° C. and 80% relative humidity for 7 days, and then the presence or absence of yellowing was evaluated by visual observation. In Example 5, yellowing occurred at the paper edge of the printing medium of Example 5 that is printing paper.
  • Optical density is 2.0 or more (good) 4: Optical density is 1.7 or more and less than 2.0 (possible) 3: Optical density is 1.5 or more and less than 1.7 (possible) 2: The optical density is less than 1.5, but unevenness is not noticeable (impossible) 1: Optical density is less than 1.5, and unevenness is conspicuous (impossible)
  • Ink adhesion A cellophane tape (trade name: Cellotape (registered trademark) CT-18, manufactured by Nichiban Co., Ltd.) was applied to the printed surface of the printed matter obtained by the above-described evaluation of ink transferability. . Next, from the visual observation of the state of the printed surface after peeling the tape, the ink adhesion was evaluated in five stages according to the following criteria. 5: Ink does not peel at all (good) 4: A small portion of ink peeled off (possible) 3: The peeled portion was less than 25% (possible) 2: The peeled portion was 25% or more and less than 50% (impossible) 1: The peeled portion was 50% or more (impossible)
  • Inkjet suitability for printing, an ultraviolet curable inkjet printer (trade name “OceArizona250GT”, manufactured by Oce) and an ultraviolet curable inkjet printing ink (trade name: Best Cure 161 (black), manufactured by T & K TOKA) were used. .
  • the print medium after storage for 7 days in an atmosphere of 40 ° C. and 80% relative humidity was aged for another 3 days in an atmosphere of 23 ° C. and 50% relative humidity. Thereafter, 100% solid and characters (ruled line thickness: 5 pt) were printed on the surface of the resin layer of the printing medium using the above-described printing machine. After printing, the characters were visually observed and observed with a magnifying glass, and the print quality was evaluated from the ink bleeding according to the following criteria.
  • the printing media of Reference Examples 1, 2 and 6, and Examples 3 to 5 and 7 to 11 were made of anionic resin, had few surface streaks, and were subjected to general printing using ultraviolet curable ink. Excellent ink transfer and ink adhesion after storage in a high temperature and high humidity environment, and water resistance adhesion after storage in a high temperature and high humidity environment when ink-jet recording using UV curable ink is performed. It was an excellent print medium.
  • the printing media of Examples 3 to 5 and 7 to 11 containing the basic pH adjuster (c) as a free base and a base having a pKa of 9.5 to 13.0 are the same as those of Reference Examples 1, 2, and 6.
  • the coating liquid used in each Example to which the basic pH adjuster (c) was added was an anionic urethane resin (in the coating liquid) compared to Comparative Example 1 in which the basic pH adjuster (c) was not added.
  • the absolute value of the zeta potential in a) was increased.
  • the printing medium of Comparative Example 1 not containing the basic pH adjuster (c) had many surface streaks.
  • the printing medium of Comparative Example 2 that does not contain the nonionic or anionic binder resin (b) has ink adhesion after storage in a high-temperature and high-humidity environment when performing general printing using an ultraviolet curable ink. Inferior, when performing ink jet recording using an ultraviolet curable ink, the water adhesion after storage in a high temperature and high humidity environment was also poor.
  • the print medium of Comparative Example 3 that does not contain an anionic urethane resin (a) has poor ink transferability after storage in a high-temperature and high-humidity environment when general printing using an ultraviolet curable ink is performed. It was.
  • Reference Example 1 in which the solid content (coating amount) of the resin layer is preferable is that the ink adhesion of general printing and the print quality of inkjet are high. It was good.
  • the addition of the antistatic agent decreased the surface resistivity and exhibited antistatic properties (Example 3).
  • B1 which is an acid-modified nonionic or anionic binder resin (b), easily reacts with a carbodiimide crosslinking agent (Examples 3 to 5), and other nonionic or anionic binder resins (b) were used.
  • Example 3 to 5 the water-resistant adhesion of the ink-jet printed material was improved (Examples 3 to 5).
  • the basic pH adjusters (c) the gas state type (Reference Example 1) and the solid state type (Reference Examples 2 and 6, Examples 3 to 5, In the case of using 8 to 11), the ink adhesion in general printing was higher than in the case of using the liquid state type (Example 7) at room temperature.
  • the basic pH adjusting agent (c) having a pKa in an appropriate range was added, no blank yellowing was observed on the printing medium after storage for 7 days in an atmosphere at a temperature of 40 ° C. and a relative humidity of 80% ( Reference Examples 1, 2, 6 and Examples 3, 4, 7 to 11).
  • IR infrared absorption analysis
  • the anionic polyurethane resin (a) is contained in the printing medium of each example, reference example and comparative example and in the resin layer.
  • the nonionic or anionic binder resin (b) is contained in the printing media of each Example, Reference Example and Comparative Example.
  • the basic pH adjuster (c) is contained in the printing medium of each example, reference example and comparative example and in the resin layer.
  • the basic pH adjuster (c) is extracted by immersing the printing medium in water. Can be confirmed.
  • the printing medium of the present invention uses an anionic resin, has few surface streaks, and has excellent ink transferability and ink adhesion after storage in a high-temperature and high-humidity environment when performing general printing using an ultraviolet curable ink. It excels in water-resistant adhesion after storage in a high-temperature and high-humidity environment when performing ink jet recording using an ultraviolet curable ink. Therefore, it is suitable as a print medium, a label print medium, and an on-demand print medium in applications requiring water resistance.

Abstract

La présente invention concerne un support d'impression ayant une couche de résine qui contient une résine de polyuréthane anionique (a), une résine de liant non-ionique ou anionique (b) et un agent de réglage du pH basique (c) sur au moins une surface d'un corps de support contenant une résine thermoplastique comme composant principal, l'agent de réglage du pH basique (c) contenant une base ayant un pKa de 9,5-13,0 en tant que base libre. Le support d'impression présente peu de traînées en surface, présente une excellente aptitude au transfert de l'encre et une excellente adhérence de l'encre après stockage dans un environnement à haute température et forte humidité lorsqu'une impression générale est réalisée à l'aide d'une encre durcissable aux ultraviolets et présente une excellente adhérence résistant à l'eau après stockage dans un environnement à haute température et forte humidité lorsque l'impression à jet d'encre est réalisée à l'aide d'une encre durcissable aux ultraviolets.
PCT/JP2016/087131 2015-12-21 2016-12-14 Support d'impression, procédé de fabrication de support d'impression, et matériel imprimé WO2017110600A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015249027 2015-12-21
JP2015-249027 2015-12-21

Publications (1)

Publication Number Publication Date
WO2017110600A1 true WO2017110600A1 (fr) 2017-06-29

Family

ID=59090258

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/087131 WO2017110600A1 (fr) 2015-12-21 2016-12-14 Support d'impression, procédé de fabrication de support d'impression, et matériel imprimé

Country Status (1)

Country Link
WO (1) WO2017110600A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113978074A (zh) * 2021-10-22 2022-01-28 索菲亚家居股份有限公司 一种亚克力饰面板及其制备方法与应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0999635A (ja) * 1995-10-09 1997-04-15 Konica Corp インクジェット記録用シート
JPH09104160A (ja) * 1995-10-11 1997-04-22 Konica Corp インクジェット記録用シート
JP2002317116A (ja) * 2001-02-16 2002-10-31 Dainippon Ink & Chem Inc 水性樹脂組成物及びそれを用いた被記録材
JP2010052369A (ja) * 2008-08-29 2010-03-11 Fujifilm Corp インクジェット記録媒体及びインクジェット記録媒体の製造方法
JP2011152803A (ja) * 2003-11-20 2011-08-11 Canon Inc インクジェット記録方法およびインクジェット記録装置
WO2014087670A1 (fr) * 2012-12-07 2014-06-12 株式会社ユポ・コーポレーション Composition d'agent d'impression et agent d'impression
WO2015072331A1 (fr) * 2013-11-15 2015-05-21 株式会社ユポ・コーポレーション Film de résine thermoplastique, récipient creux moulé à étiquette fixée, film adhésif, étiquette, et film à utiliser en impression

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0999635A (ja) * 1995-10-09 1997-04-15 Konica Corp インクジェット記録用シート
JPH09104160A (ja) * 1995-10-11 1997-04-22 Konica Corp インクジェット記録用シート
JP2002317116A (ja) * 2001-02-16 2002-10-31 Dainippon Ink & Chem Inc 水性樹脂組成物及びそれを用いた被記録材
JP2011152803A (ja) * 2003-11-20 2011-08-11 Canon Inc インクジェット記録方法およびインクジェット記録装置
JP2010052369A (ja) * 2008-08-29 2010-03-11 Fujifilm Corp インクジェット記録媒体及びインクジェット記録媒体の製造方法
WO2014087670A1 (fr) * 2012-12-07 2014-06-12 株式会社ユポ・コーポレーション Composition d'agent d'impression et agent d'impression
WO2015072331A1 (fr) * 2013-11-15 2015-05-21 株式会社ユポ・コーポレーション Film de résine thermoplastique, récipient creux moulé à étiquette fixée, film adhésif, étiquette, et film à utiliser en impression

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113978074A (zh) * 2021-10-22 2022-01-28 索菲亚家居股份有限公司 一种亚克力饰面板及其制备方法与应用
CN113978074B (zh) * 2021-10-22 2023-11-21 索菲亚家居股份有限公司 一种亚克力饰面板及其制备方法与应用

Similar Documents

Publication Publication Date Title
US6562451B2 (en) Coated film
JP6625081B2 (ja) 熱可塑性樹脂フィルム、ラベル付き中空成型容器、粘着フィルム及びラベル
JP2008213199A (ja) 熱収縮性積層フィルム、熱収縮性積層フィルムの製造方法、容器、容器の製造方法
JP2006247963A (ja) インクジェット記録用シート
CN106457865B (zh) 用于印刷的纤维素纳米晶体涂层介质
JP6310232B2 (ja) 熱可塑性樹脂フィルム及び粘着シート並びに熱転写用画像受容シート
JP6824904B2 (ja) 印刷媒体、印刷媒体の製造方法および印刷物
WO2017110600A1 (fr) Support d'impression, procédé de fabrication de support d'impression, et matériel imprimé
JP2001225422A (ja) コーテッドフィルム
JP6411825B2 (ja) 記録用紙、および該記録用紙を用いたラベル
JP3225148B2 (ja) インクジェット記録シート
JP3878580B2 (ja) インクジェット記録用シート
JP5141796B2 (ja) インクジェット印刷物及びその製造方法
JP2001034004A (ja) 電子写真用ラベル用紙
JPH06143798A (ja) 記録シート
JP2004181935A (ja) インクジェット記録用シート
JPH1178223A (ja) 印刷用シート
JPH0867064A (ja) 記録シート
JP2023088871A (ja) 塗工液、塗工層及び印刷用紙
JPH11192778A (ja) 記録シート
JP3638043B2 (ja) 記録シート
JPH0952460A (ja) 熱転写受像体
JP2020049835A (ja) インクジェット記録材料
JPH07246782A (ja) 熱転写受像体
JPH10151848A (ja) バックプリントフィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16878491

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16878491

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP