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WO2017110599A1 - Support d'impression, procédé de fabrication d'un support d'impression et imprimés - Google Patents

Support d'impression, procédé de fabrication d'un support d'impression et imprimés Download PDF

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Publication number
WO2017110599A1
WO2017110599A1 PCT/JP2016/087130 JP2016087130W WO2017110599A1 WO 2017110599 A1 WO2017110599 A1 WO 2017110599A1 JP 2016087130 W JP2016087130 W JP 2016087130W WO 2017110599 A1 WO2017110599 A1 WO 2017110599A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
printing
ink
printing medium
acidic
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2016/087130
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English (en)
Japanese (ja)
Inventor
高広 座間
卓哉 五十嵐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yupo Corp
Original Assignee
Yupo Corp
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 Yupo Corp filed Critical Yupo Corp
Priority to JP2017558053A priority Critical patent/JP6824904B2/ja
Publication of WO2017110599A1 publication Critical patent/WO2017110599A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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 print medium, a method of manufacturing the print medium, and a printed matter. Specifically, the present invention has few surface streaks, and when performing general printing using an ultraviolet curable ink, it has excellent ink adhesion after storage under a high temperature and high humidity environment, and an ultraviolet curable ink is used.
  • the present invention relates to a print medium which is excellent in print quality and water adhesion after storage in a high temperature and high humidity environment when ink jet recording is performed.
  • the present invention also relates to a method for producing the print medium and printed matter using the print medium.
  • various data may be recorded on a printing medium using ink, and a printed matter such as a quote for goods, a bill for price, a price tag, etc. may be created.
  • fixed form data such as ground patterns and ruled lines are recorded on the same print medium by general printing (plate printing) such as offset printing or seal printing using oxidation polymerization type ink or ultraviolet curing type ink
  • Fine characters such as product names and amounts
  • variable data such as barcodes
  • print media are required to have excellent printability in both general printing and information recording systems.
  • the print medium used in the field of business form printing is also given the printability for recording variable data such as product names and bar codes by the information recording method Preferably. It is known to devise the composition of a resin layer provided on the surface of a support as a method of improving the printability of a print medium (see Patent Documents 1 to 4).
  • Patent Document 1 discloses that the print medium provided with the resin layer containing the nitrogen-containing polymer compound on the surface of the support is subjected to a high temperature and high humidity environment for a long time. It has been pointed out that the degree of moisture absorption of the resin layer to be the printing surface of the ink becomes high, and the printed material placed in a high temperature and high humidity environment for a long time can be easily peeled off when the printing surface is peeled off with an adhesive tape. Thus, in general printing, it is required that the ink adhesion to the printing medium be high after storage in a high temperature and high humidity environment.
  • the printability required is different depending on the recording method.
  • high definition, high speed printing, and price reduction of an ink jet printer which is one of recording apparatuses used for an information recording method have been advanced. Therefore, in recent years, there has been an increasing demand for performing recording of variable data using an inkjet recording method among information recording methods.
  • Such an inkjet recording method is required to have high print quality at a point with little ink bleeding and water-resistant adhesion when the printed matter after printing is exposed to moisture.
  • a method has been proposed in which the water-resistant adhesion of the ink jet recording system is improved by using an ultraviolet curable ink instead of an aqueous ink.
  • An object of the present invention is to provide a print medium which is excellent in print quality and water-resistant adhesion after storage in a high temperature and high humidity environment when ink jet recording used is performed.
  • a resin layer containing a cationic polyurethane resin (a), an ethyleneimine resin (b) and an acidic pH adjuster (c) is provided on at least one surface of a support containing a thermoplastic resin as a main component. It has been found that a print medium that can solve the above problems can be provided, and the present invention has been completed.
  • Patent Document 1 describes a printing medium suitable for a thermal transfer recording method among information recording methods. Specifically, a printing and thermal transfer image receiving film is described in which a coating layer comprising the following components (A) and (B) is provided on the surface of a support comprising a thermoplastic resin film.
  • Patent Document 1 discloses a thermal transfer film, particularly a fusion thermal transfer film, which is excellent in the transferability, adhesion and water-resistant adhesion of the ink in a high temperature and high humidity environment in such a configuration as described above. It has been described to provide a thermoplastic resin film which is excellent in transferability, adhesion and water-resistant adhesion of the ink in various printing methods. However, when the inventors of the present invention performed inkjet recording using a UV curable ink using a thermal transfer image receiving film using the cationic polyolefin resin described in Patent Document 1, ink bleeding occurs in the printed matter, and printing is performed. It has been found that there is a problem that the quality is poor and the readability of fine characters and barcodes is poor.
  • Patent Document 2 describes a composition for a printing medium containing (a) a cationic urethane resin, (b) an olefin copolymer emulsion, and (c) an ethyleneimine resin. Further, Patent Document 2 describes a print medium provided with a coating layer containing the above composition for a print medium on at least one surface of a support. Patent Document 2 describes that such a configuration provides a print medium having excellent printability in both of the plate printing method and the plateless printing method.
  • the present inventors examined the physical properties before printing of the printing medium which does not contain the acidic pH adjuster (c) described in Patent Document 2, there is a problem that the surface of the printing medium has many surface streaks such as coated streaks. It turned out that there is a point.
  • Patent Document 3 discloses a recording medium having an ink receiving layer containing alumina hydrate and a binder on a support, wherein the surface of the ink receiving layer is formed of a plurality of films containing cationic polyurethane.
  • a recording medium is described which is coated with a film, the average major axis of the plurality of films is 0.03 ⁇ m or more and less than 1.00 ⁇ m, and the coverage of the surface of the ink receiving layer by the partial film is 10% or more and less than 70%.
  • Patent Document 3 it is described that such a configuration provides a recording medium having excellent surface gloss, scratch resistance and color developability while maintaining excellent ink absorbency of the ink receiving layer. There is.
  • the recording medium described in Patent Document 3 is a dedicated printing medium specialized for the inkjet recording method using an aqueous ink, which needs to increase the ink absorbability of the ink receiving layer.
  • the ink absorbency of the ink receiving layer is not very important.
  • the configuration in which the surface of the ink receiving layer described in Patent Document 3 is partially coated with a film does not contribute to the improvement of printability when using a UV curable ink.
  • Patent Document 4 discloses a polyurethane resin (A) containing a compound obtained by quaternizing a tertiary amino group of a chain extender having a tertiary amino group in the molecule and a polycarbonate polyol as a component unit and a carbon-carbon double A laminate is obtained by applying a coating solution containing a polyurethane resin (B) having a bond, a cationic high molecular weight antistatic agent (C) and an oxazoline compound (D) and then drying it on at least one side. Polyester films are described. According to Patent Document 4, it is described to provide a polyester film having a coating layer in which the antistatic property and the easy adhesion property are compatible at a high level with such a configuration.
  • the recording medium containing neither the acidic pH adjuster (c) nor the ethyleneimine resin (b) described in Patent Document 4 has many surface streaks such as coated streaks on the surface of the printing medium, and uses UV curable ink. It has been found that there is also a problem in that there are many surface streaks such as coating streaks on the surface of the printing medium when ink jet recording is performed.
  • the present invention which is a specific means for solving the above problems, and preferred embodiments of the present invention are as follows.
  • a printing medium having a resin layer containing a cationic polyurethane resin (a), an ethyleneimine resin (b) and an acidic pH adjuster (c).
  • the resin layer preferably has a solid content of 0.01 g / m 2 to 5 g / m 2 .
  • the printing medium described in [1] or [2] is preferably such that the acidic pH adjuster (c) is solid at 20 ° C. and 1 atm.
  • the resin layer is preferably a coated layer formed from a coating liquid.
  • At least one surface of a support containing a thermoplastic resin as a main component A method for producing a printing medium, comprising the steps of applying a coating liquid containing a cationic polyurethane resin (a), an ethyleneimine resin (b) and an acidic pH adjuster (c) to form a resin layer.
  • the pH of the coating liquid is preferably 1.0 to 7.4.
  • a printed matter comprising an ultraviolet-curable ink on the resin layer of the print medium according to any one of [1] to [6].
  • the ink adhesion is excellent after storage in a high temperature and high humidity environment, and inkjet recording using the ultraviolet curable ink
  • the printing medium which is excellent in print quality and water resistance adhesion after storage in a high temperature and high humidity environment can be provided.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the printing medium of the present invention is a resin containing a cationic polyurethane resin (a), an ethyleneimine resin (b) and an acidic pH adjuster (c) on at least one surface of a support containing a thermoplastic resin as a main component.
  • a printing medium having a layer With such a configuration, the printing medium of the present invention has few surface streaks, and when performing general printing using an ultraviolet curable ink, it has excellent ink adhesion after storage in a high temperature and high humidity environment, and ultraviolet curing When ink jet recording using a mold ink is performed, the print quality and the water-resistant adhesion after storage under a high temperature and high humidity environment are excellent.
  • Including ethyleneimine resin (b) in the resin layer is expected to contribute to the improvement of the ink adhesion after storage under high temperature and high humidity environment when general printing using UV curable ink is performed .
  • Including the acidic pH adjuster (c) in the resin layer is expected to contribute to the improvement of surface streaks after storage in a high temperature and high humidity environment.
  • the printing medium of the present invention is a printing medium adapted to a general printing method such as offset printing and seal printing using an ultraviolet curable ink and to inkjet recording using an ultraviolet curable ink.
  • the printing medium of the present invention is preferably adapted to information recording methods such as a thermal transfer recording method, an electrophotographic method, and an ink jet recording method.
  • a printing medium is printing paper.
  • the printing medium may be other than printing paper (for example, a poster, a calendar, a map, a tag, a label, a sticker, etc.). In the following, details of preferred embodiments of the printing medium of the present invention are described.
  • the support contains a thermoplastic resin as a main component.
  • the main component of the support means a component contained at 50% by mass or more of the total mass of the support.
  • the support preferably contains 70% by mass or more of the thermoplastic resin, and more preferably 80% by mass or more.
  • thermoplastic resin used for the support is not particularly limited.
  • ethylene resins such as high density polyethylene and medium density polyethylene, polyolefin resins such as propylene resin, polymethyl-1-pentene, ethylene-cyclic olefin copolymer; polyamides such as nylon-6, nylon-6, 6
  • Thermoplastic resins such as polyethylene terephthalate and copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, aliphatic polyester such as polybutylene succinate and polylactic acid, etc. polycarbonate, atactic polystyrene, syndiotactic polystyrene, etc.
  • thermoplastic resins in view of water adhesion, chemical resistance, cost and the like, it is preferable to use a polyolefin resin or a polyester resin, and it is more preferable to use a polyolefin resin.
  • a propylene-based resin from the viewpoint of easily imparting an appropriate rigidity (toughness) to a printing medium.
  • a propylene-based resin a propylene homopolymer or a copolymer of propylene as a main component and an ⁇ -olefin such as ethylene, 1-butene, 1-hexene, 1-heptene or 4-methyl-1-pentene Can be used.
  • the stereoregularity is not particularly limited, and it is possible to use isotactic or syndiotactic and those showing various degrees of stereoregularity.
  • the copolymer may be a binary system or a multicomponent system of ternary system or more, and may be a random copolymer or a block copolymer. It is preferable to use 2 to 25% by mass of a resin having a melting point lower than that of a propylene homopolymer as the propylene-based resin. As such low melting point resin, high density or low density polyethylene can be exemplified.
  • thermoplastic resin used for a support body 1 type may be selected from said thermoplastic resins, and may be used independently, and 2 or more types may be selected and combined and used.
  • 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, if necessary.
  • the support may contain an inorganic fine powder.
  • the support contains an inorganic fine powder
  • the support can be whitened and opacified, and further concealability can be imparted, and the print can be easily viewed as a print medium, or the print strike-through (from the back side) 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 them, 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 upon stretching.
  • the surface treatment agent of inorganic fine powder includes, for example, resin acids, fatty acids, organic acids, sulfuric acid ester type anionic surfactants, sulfonic acid type anionic surfactants, petroleum resin acids, sodium, potassium and ammonium of these. Salts or fatty acid esters thereof, resin acid esters, waxes, paraffins, etc. are preferred, and nonionic surfactants, diene polymers, titanate coupling agents, silane coupling agents, phosphoric acid coupling agents, non 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, and a sulfonate type anion interface
  • the activator examples include alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, paraffin sulfonic acid, ⁇ -olefin sulfonic acid, alkyl sulfo succinic acid and the like or 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, hexenoic acid, oleic acid, linoleic acid, linolenic acid, and eleostearin.
  • An acid etc. are mentioned.
  • Examples of the organic acid include maleic acid and sorbic acid.
  • Examples of the diene-based polymer include polybutadiene and isoprene.
  • Examples of the nonionic surfactant include polyethylene glycol ester surfactants. Alumina, silica etc. are mentioned as an inactive inorganic oxide. These surface treatment agents can be used alone or in combination of two or more.
  • the method described in can be used.
  • the support may contain an organic filler. Also when the support contains an organic filler, the support can be whitened and opaque, and the print can be easily viewed as a print medium.
  • a resin for example, 120 to 300 ° C. whose melting point or glass transition point is higher than the melting point or glass transition point of the main thermoplastic resin constituting the support can be preferably used.
  • polyethylene terephthalate polyethylene naphthalate, polybutylene terephthalate, polyamide, polycarbonate, polystyrene, cyclic olefin homopolymer, ethylene- A cyclic olefin copolymer, polyethylene sulfide, polyimide, polymethacrylate, polyethyl ether ketone, polyphenylene sulfide, melamine resin and the like
  • polyethylene terephthalate polyethylene naphthalate
  • polybutylene terephthalate polyamide
  • polycarbonate polystyrene
  • cyclic olefin homopolymer ethylene- A cyclic olefin copolymer
  • polyethylene sulfide polyimide
  • polymethacrylate polyethyl ether ketone
  • polyphenylene sulfide polymelamine resin and the like
  • a propylene-based resin which is a main thermoplastic resin constituting the support, and are incompatible with the propylene-based resin, so that they can form pores during stretching. Preferred because it is good.
  • the support one type may be selected from inorganic fine powders or organic fillers and used alone, or two or more types may be selected and used in combination. When using in combination of 2 or more types, you may mix and use an inorganic fine powder and an organic filler.
  • the support preferably contains 5 to 75% by mass, more preferably 8 to 65% by mass, of the fine powder or the filler as a total amount. It is more preferable to contain 55 mass%. If the content of these components in the support is 5% by mass or more, desired pores are easily obtained, and it tends to be easy to achieve opacity of the printing medium. On the other hand, if the content is 75% by mass or less, the strength of the support tends to be unlikely to decrease.
  • 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, 0 More preferably, it is in the range of 1 to 1.3 ⁇ m. If fine powder or filler having an average particle size or an average dispersed particle size of 0.05 ⁇ m or more is used, pores tend to be obtained by stretch forming, and it tends to be easy to achieve opacity of the printing medium. The use of fine powder or filler having an average particle size or an average dispersed particle size of 15 ⁇ m or less tends to enhance the strength of the support.
  • the average particle size of the inorganic fine powder to be used and the average dispersed particle size of the organic filler are measured by using a particle measuring apparatus, for example, a laser diffraction particle measuring apparatus "Microtrac" (trade name of Microtrack Bell Co., Ltd.). Observation of particle size corresponding to 50% (cumulative 50% particle size), primary particle size observation with a scanning electron microscope (in the present invention, the average value of 100 particles is regarded as the average particle size), conversion from specific surface area (the present invention The specific surface area can be determined, for example, by using a powder specific surface area measuring device SS-100 manufactured by Shimadzu Corporation.
  • heat inhibitor such as a steric hindrance phenolic antioxidant, phosphorus antioxidant, or amine antioxidant within the range of usually 0.001 to 1% by mass.
  • a heat inhibitor such as a steric hindrance phenolic antioxidant, phosphorus antioxidant, or amine antioxidant
  • a light stabilizer When a light stabilizer is added, a sterically hindered amine light stabilizer, a benzotriazole light stabilizer, a benzophenone light stabilizer, a sulfur light stabilizer, etc. are usually used in the range of 0.001 to 1% by mass. can do.
  • the dispersant is used, for example, to disperse the inorganic fine powder.
  • silane coupling agents higher fatty acids such as oleic acid and stearic acid, metal soaps, polyacrylic acids, polymethacrylic acids and salts thereof are usually used in the range of 0.01 to 4% by mass. be able to.
  • the method of molding the support is not particularly limited.
  • the support can be formed by appropriately selecting from among various known methods. For example, cast molding, calendar molding, rolling molding, inflation molding, thermoplasticity that extrudes a molten thermoplastic resin composition into a sheet form using a single-layer or multilayer T-die or I-die connected to a screw-type extruder It can be molded using a method of casting or calendering a mixture of a resin and an organic solvent or oil and removing the solvent or oil.
  • the molten thermoplastic resin composition can also be extruded and laminated onto a substrate of paper or a thermoplastic resin film.
  • the support in particular, the thermoplastic resin film layer on the surface of the support
  • the support may be unstretched or stretched. Stretching can be performed by any of various methods commonly used. As specific examples, longitudinal stretching using circumferential speed difference of rolls, transverse stretching using a tenter oven, rolling, combination of a tenter oven and a linear motor, or simultaneous biaxial stretching by a combination of a tenter and a pantograph, etc. Can.
  • the stretching temperature is higher than the glass transition temperature of the thermoplastic resin to be used, and in the case of the crystalline resin, thermoplastic resin having the glass transition temperature of the non-crystalline portion to the melting point of the crystalline portion It can be carried out within the known temperature range suitable for the resin.
  • the stretching temperature is preferably a temperature 2 to 60 ° C. lower than the melting point of the thermoplastic resin used, and 152 to 164 ° C. when the resin is a propylene homopolymer (melting point 155 to 167 ° C.) It is preferable to set the temperature to 110 to 120 ° C. when the melting point is 121 to 134 ° C., and to 104 to 115 ° C. when the polyethylene terephthalate (melting point 246 to 252 ° C.).
  • the stretching speed is preferably 20 to 350 m / min.
  • stretching is not specifically limited, Considers the characteristic etc. of the thermoplastic resin to be used, and determines it suitably.
  • a propylene homopolymer or copolymer thereof as the thermoplastic resin
  • it is about 1.2 to 12 times, preferably 2 to 10 times, when stretching in one direction, and in the case of biaxial stretching,
  • the area magnification is 1.5 to 60 times, preferably 10 to 50 times.
  • another thermoplastic resin is used, 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, in the case of biaxial stretching.
  • it is 4 to 12 times.
  • the support may be a single layer or may have a laminated structure.
  • An example is given for the method of producing a single layer support.
  • a single-layer support including a polyolefin resin film is 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 inorganic fine powder. It can be prepared by uniaxially or biaxially stretching at a temperature lower than the melting point of the base resin (preferably a temperature lower than 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 a layer containing a polyolefin resin film is a resin film composed of a resin composition containing 40 to 100% by mass of a polyolefin resin and 60 to 0% by mass of inorganic fine powder.
  • the film is longitudinally stretched at a temperature lower than the melting point of the resin (preferably a temperature lower than 3 to 60 ° C.), and contains 25 to 100% by mass of a polyolefin resin and 75 to 0% by mass of inorganic fine powder on at least one side of the drawn film. It can prepare by laminating
  • the laminated film may be stretched in the lateral direction at a temperature lower than the melting point of the polyolefin resin (preferably at a temperature lower than 3 to 60 ° C.) to stretch the resin layer laminated on the stretched film in the lateral direction.
  • a temperature lower than the melting point of the polyolefin resin preferably at a temperature lower than 3 to 60 ° C.
  • the example of the support body which has a polyolefin resin film on both surfaces of natural pulp paper is shown.
  • Hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), or a mixture thereof is refined, and a slurry containing a dry strength agent, a wet strength agent, a sizing agent, a filler, etc.
  • 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 extrusion laminated on both sides of this substrate to form a support, and a support having the above single layer structure or laminated structure.
  • a resin film described as a body may be bonded to form a support.
  • the thickness of the support is preferably in the range of 30 to 500 ⁇ m, more preferably in the range of 40 to 400 ⁇ m, and still more preferably in the range of 50 to 300 ⁇ m, for the purpose of using as a printing medium.
  • the support in particular, the thermoplastic resin film layer on the surface of the support
  • the support may be stretched as described above.
  • a thermoplastic resin film containing an inorganic fine powder or an organic filler is stretched, a porous resin stretched film having many fine pores inside can be obtained.
  • Such a porous resin stretched film is suitable as a support of a printing medium from the viewpoint of lightness, opacity and the like.
  • the stretched support preferably has a density in the range of 0.65 to 1.2 g / cm 3 , and in the range of 0.7 to 1 g / cm 3 from the viewpoint of easy handling. More preferable.
  • the stretched support preferably has a porosity of 5 to 60%, more preferably 10 to 50%, as measured by the following method.
  • the porosity in each layer of the support is cut while cooling so as not to crush the pores of the support to form a cross-section in the thickness direction (observation surface), which is attached to the observation sample table, and gold is attached to the observation surface.
  • the vacancies of each layer are observed at an arbitrary magnification that is easy to observe by vapor deposition and using a scanning electron microscope, and the observed area is taken as image data, and the image is image processed to obtain the area ratio of the vacancies. This is determined as the porosity.
  • the opacity is preferably 50% or more, and more preferably 60% or more.
  • the print can be easily viewed when used as a printing medium, and when used as a label sheet, the bar code printing is affected by the background and a reading error occurs.
  • the whiteness of the similarly stretched support is preferably 80% or more, more preferably 90% or more. Such whiteness can contribute to the sharpness of the printed matter.
  • corona discharge treatment generally used as surface oxidation treatment, flame treatment, plasma treatment, glow discharge treatment, ozone treatment, etc. may be used alone or in combination. It is preferred to use. 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 ⁇ minute / m 2 ), and 1,200 to 10,800 J / m 2 (20 to 180 W ⁇ minute It is more preferable to carry out at / m 2 ).
  • flame treatment it is preferably carried out at 8,000 to 200,000 J / m 2 , more preferably 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 a cationic polyurethane resin (a), an ethyleneimine resin (b) and an acidic pH adjuster (c).
  • the resin layer is preferably a coated 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.
  • (Cationic polyurethane resin (a)) By using a cationic polyurethane resin (a) in the resin layer, it contributes to the improvement of print quality and water adhesion resistance after storage under high temperature and high humidity environment when ink jet recording using an ultraviolet curable ink is performed. can do. Although this mechanism is unknown, this effect can be read from the comparison between the example described later and the comparative example. In addition, it is expected that the improvement of the printing quality and the water-resistant adhesion after storage in a high temperature and high humidity environment also has a correlation with the balance of hydrophilic hydrophobicity of the urethane resin.
  • the cationic polyurethane resin (a) used for the said resin layer can form the coating layer excellent in adhesiveness with a support body.
  • the cationic polyurethane resin (a) used for the resin layer can form the resin layer rich in elasticity due to urethane bond, and adheres to the ink by following the volume shrinkage at the time of curing of the ultraviolet curing ink. Can be enhanced.
  • the cationic polyurethane resin (a) is cationic, it is highly miscible with the ethyleneimine resin (b). Therefore, in the resin layer of the structure of this invention, it becomes difficult to aggregate cationic polyurethane resin (a) and ethyleneimine resin (b), and it becomes difficult to produce the surface streak before printing.
  • the cationic polyurethane resin preferably has a structural unit represented by the following formula (1) in the molecule.
  • R 1 represents an alkylene group which may contain an aliphatic cyclic structure, a residue of a dihydric phenol, or a polyoxyalkylene group
  • R 2 and R 3 are each other
  • R 4 represents a hydrogen atom or an organic residue of a quaternizing agent introduced by a quaternization reaction
  • X - represents an anionic group. Represents counter ion
  • the structural unit represented by the formula (1) is obtained by introducing a cationic hydrophilic group into the urethane resin skeleton, and is obtained by reacting a compound having two epoxy groups in one molecule with a secondary amine.
  • a tertiary amino group-containing polyol can be obtained by reacting with a polyisocyanate.
  • the compound shown, for example by following formula (2) is mentioned.
  • R 1 represents an aliphatic cyclic structure that may contain an alkylene group, residue of dihydric phenols, or a polyoxyalkylene group.
  • R 1 is an alkylene group which may contain an aliphatic cyclic structure
  • specific examples of the compound represented by the above formula include ethanediol-1,2-diglycidyl ether, propanediol -1,2-diglycidyl ether, propanediol-1,3-diglycidyl ether, butanediol-1,4-diglycidyl ether, pentanediol-1,5-diglycidyl ether, 3-methyl-pentanediol-1 3,5-diglycidyl ether, neopentyl glycol-diglycidyl ether, hexanediol-1,6-diglycidyl ether, polybutadiene-diglycidyl ether, cyclohexane-1,4-diglycidyl ether, 2,2-bis (4- Hydroxycyclohexyl) -propane (hydrogenated bisphenol A And diglycidy
  • R 1 is a residue of a dihydric phenol
  • specific examples of the compound represented by the above formula include resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 2,2-bis Diglycidyl ether of 4-hydroxyphenyl) -propane (bisphenol A), diglycidyl ether of isomer mixture of dihydroxydiphenylmethane (bisphenol F), diglycidyl ether of 4, 4-dihydroxy-3-3'-dimethyldiphenylpropane, Diglycidyl ether of 4,4-dihydroxydiphenylcyclohexane, diglycidyl ether of 4,4-dihydroxydiphenyl, diglycidyl ether of 4,4-dihydroxydibenzophenone, diglyl of bis (4-hydroxyphenyl) -1,1-ethane Di-glycidyl ether of di-zyl ether, bis (4-hydroxyphenyl) -1,1-
  • R 1 is a polyoxyalkylene group
  • specific examples of the compound represented by the above formula include diethylene glycol-diglycidyl ether, dipropylene glycol-diglycidyl ether, and the number of repeating units of oxyalkylene.
  • Polyoxyalkylene glycol-diglycidyl ether of 3 to 60 for example, polyoxyethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether, diglycidyl ether of ethylene oxide-propylene oxide copolymer, polyoxytetraethylene Glycol-diglycidyl ether etc. may be mentioned.
  • secondary amines known compounds can be used, but branched or straight-chain aliphatic secondary amines are preferable in terms of the ease of reaction control. Specific examples of those usable as such secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, di-sec-butylamine, and di-sec-butylamine.
  • -N-pentylamine di-n-peptylamine, di-n-octylamine, diisooctylamine, dinonylamine, diisononylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, Di-n-pentadecylamine, di-n-octadecylamine, di-n-nonadecylamine, di-n-eicosylamine and the like.
  • aliphatic secondary amine having a carbon number in the range of 2 to 18 is more preferable, and the aliphatic secondary amine having a carbon number in the range of 3 to 8 is further preferable because it can reduce steric hindrance.
  • polyisocyanate examples include organic polyisocyanates used in the production of urethane resins such as aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
  • the cationic polyurethane resin (a) is preferably in the form of an emulsion.
  • the cationic polyurethane resin (a) is easy to apply when a coating liquid to be described later is prepared to reduce surface streaks before printing, and from the viewpoint of enhancing the water-resistant adhesion of the obtained resin layer, an aqueous medium It is more preferable that the emulsion is dispersed in the medium and not redissolved after drying.
  • the average dispersed particle diameter of the cationic polyurethane resin (a) emulsion can be, for example, 0.005 to 0.10 ⁇ m, preferably 0.005 to 0.05 ⁇ m. .
  • the average dispersed particle size of the emulsion corresponds to 50% of the cumulative particle size (cumulative 50% particle size) as measured by a particle measuring device, for example, a laser diffraction particle measuring device "Microtrac" (trade name of Microtrack Bell Co., Ltd.). Diameter), observation of primary particle diameter by scanning electron microscope (for example, average value of 100 particles), conversion from specific surface area (for example, powder specific surface area measurement device SS-100 manufactured by Shimadzu Corporation) Specific surface area can be determined by The minimum film-forming temperature of the cationic polyurethane resin (a) is preferably 0 to 40 ° C., more preferably 0 to 5 ° C.
  • an emulsion of the cationic urethane resin (a) can be obtained using a known method such as acetone method, prepolymer mixing method, ketimine method, hot melt dispersion method and the like.
  • a known method such as acetone method, prepolymer mixing method, ketimine method, hot melt dispersion method and the like.
  • the cationic polyurethane resin emulsion for example, Superflex 600, 610, 620, 650 (trade name) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Hydran CP-7030, 7050, 7060 (manufactured by DIC Co., Ltd.) Name), Neo Stickers made by Nikka Chemical Co., Ltd., etc. are commercially available and can be used.
  • the ethyleneimine resin (b) has high affinity to the ultraviolet curable ink, and thus can improve the ink adhesion to the ultraviolet curable ink.
  • Examples of the ethyleneimine resin (b) include polyethyleneimine, poly (ethyleneimine-urea), and ethyleneimine adduct of polyamine polyamide, or alkyl modified products thereof, cycloalkyl modified products, aryl modified products, allyl modified products And aralkyl modified products, benzyl modified products, cyclopentyl modified products, modified products, aliphatic cyclic hydrocarbon modified products, and hydroxides thereof. These can be used alone or in combination of two or more.
  • a modified product obtained by modifying an ethyleneimine adduct of polyethyleneimine or polyamine polyamide with a modifier such as alkyl halide having 1 to 24 carbon atoms, alkenyl halide, cycloalkyl halide or benzyl halide is preferable. It is preferable from the viewpoint of improving the adhesion of Specific examples of the halide used as a modifier include methyl chloride, methyl bromide, n-butyl chloride, lauryl chloride, stearyl iodide, oleyl chloride, cyclohexyl chloride, benzyl chloride, allyl chloride, cyclopentyl chloride and the like .
  • Epomin P-1000 (trade name) manufactured by Nippon Shokubai Co., Ltd.
  • Polymin SK (trade name) manufactured by BASF Corp.
  • Saftmer AC- manufactured by Mitsubishi Chemical Corp. 72 (brand name) etc.
  • the cationic polyurethane resin (a) suitably used in the present invention is designed to have high water adhesion after drying and is an emulsion having a small average particle size, so it tends to aggregate in a coating liquid. It has the nature. In general, when the absolute value of the surface potential (referred to as zeta potential or electrokinetic potential) of nano-sized particles is 20 mV or more, the electric double layer is difficult to be broken and the dispersibility of the particles is considered to be good. Ru.
  • the zeta potential of the cationic polyurethane resin (a) it is preferable to set the zeta potential of the cationic polyurethane resin (a) to 20 mV or more in the state of a coating liquid in which the acidic pH adjuster (c) is added to the aqueous dispersion of the cationic polyurethane resin (a) And 30 mV or more are more preferable.
  • the dispersibility of the cationic polyurethane resin is improved, aggregation is less likely to occur during mixing with the ethyleneimine resin (b), and a coating liquid which is less likely to be aggregated or thickened is obtained.
  • the resin layer there is a tendency for the resin layer to be easily coated, to be reduced in foreign matter, and reduced in surface streaks before printing.
  • the zeta potential of the cationic polyurethane resin in the coating liquid state is preferably 80 mV or less, more preferably 70 mV or less, and particularly preferably 60 mV or less. This tends to improve the water-resistant adhesion of the resin layer or to reduce the adverse effect of the addition of the acidic pH adjuster (c) or the cationic polyurethane resin (a).
  • the acidic pH adjuster (c) needs to be acidic.
  • the acidic pH adjuster (c) preferably has a pKa as a free acid of ⁇ 0.2 to 6.8, and more preferably 0.5 to 6.0. It is preferred that the acids having two or more pKa have all the pKa in the above range.
  • the pH of the coating liquid for forming the resin layer is preferably 1.0 to 7.4, more preferably 3.0 to 7.2, by adding the acidic pH adjuster (c). Preferably, 4.0 to 6.5 is particularly preferred.
  • a base may be added to adjust the pH of the coating liquid and the zeta potential of the cationic polyurethane resin (a) in the state of the coating liquid in the above range. It can.
  • a base which can be used sodium hydroxide, potassium hydroxide, ammonia etc. are mentioned.
  • the ethyleneimine resin (b) also functions as a base.
  • a base such as ammonia.
  • the acidic pH adjuster (c) moves in the resin layer and exudes on the resin layer surface. It is difficult to cause transfer failure of the printing ink due to migration. In particular, the tendency for migration to hardly occur in plate printing is remarkable. In addition, when migration does not easily occur, the ink-jet ink tends to be difficult to repel.
  • the acidic pH adjuster (c) is preferably in a solid state at 20 ° C. and 1 atm, more preferably in a solid state at 40 ° C. and 1 atm, and particularly preferably in a solid state at 60 ° C. and 1 atm. preferable.
  • the acidic pH adjuster (c) is solid under normal use conditions and can prevent migration over time, so there is a tendency not to inhibit ink transferability after long-term storage of the print medium.
  • the acidic pH adjuster (c) may be in a gaseous state at 20 ° C. and 1 atm, and examples of the gaseous acidic pH adjuster (c) include hydrochloric acid.
  • the concentration in the resin layer after drying is preferably 100 ppm or less, and 50 ppm or less, in order to prevent migration over time. Is more preferable, and 30 ppm or less is more preferable.
  • the acidic pH adjuster (c) is a monovalent aliphatic carboxylic acid having 9 to 18 carbon atoms, a divalent or higher aliphatic carboxylic acid having 3 to 12 carbon atoms, an aromatic carboxylic acid, It is preferable from the viewpoint of easy preparation of a coating liquid having the above-mentioned properties to contain one or more acids selected from boric acid and phosphoric acid.
  • the acidic pH adjuster (c) is selected from monovalent aliphatic carboxylic acids having 9 to 18 carbon atoms, aliphatic carboxylic acids having 2 to 12 carbon atoms, aromatic carboxylic acids, boric acids and phosphoric acids. It may be an acid consisting of one or more selected residues.
  • the “residue consisting of residues” of an acid refers to the remaining part from which an ion releasable from an acid is released.
  • the carboxylic acid having 2 to 12 carbon atoms having a carbon number of 3 to 12 include hydroxycarboxylic acids having a carbon number of 3 to 8 and having 2 to 8 carbon atoms. It is one.
  • the aromatic carboxylic acids include aromatic hydroxycarboxylic acids.
  • Boric acids include orthoboric acid and metaboric acid.
  • the phosphoric acids include orthophosphoric acid, metaphosphoric acid and polyphosphoric acid.
  • the acidic pH adjuster (c) is selected from a monovalent aliphatic carboxylic acid having 9 to 18 carbon atoms, a divalent or higher aliphatic carboxylic acid having 3 to 12 carbon atoms, an aromatic carboxylic acid and a phosphoric acid It is more preferable to contain the above acids, and it is particularly preferable to contain one or more acids selected from aliphatic carboxylic acids having 2 to 12 carbon atoms or more, aromatic carboxylic acids and phosphoric acids.
  • orthoboric acid, orthophosphoric acid, metaphosphoric acid, citric acid, itaconic acid, tartaric acid, L-lactic acid, malic acid are more preferable, and citric acid, itaconic acid, tartaric acid, L-lactic acid, apple Acids are particularly preferred, and citric acid is more particularly preferred.
  • the compounding quantity ratio as solid content after drying of each component in the said resin layer contains 1-60 mass parts of ethyleneimine resin (b) with respect to 100 mass parts of cationic polyurethane resin (a). And 1 to 40 parts by mass is more preferable, and 10 to 20 parts by mass is particularly preferable.
  • the acidic pH adjuster (c) is preferably contained in 0.01 to 5 parts by mass with respect to 100 parts by mass of the cationic polyurethane resin (a). It is more preferable to include parts by mass. It is still more preferable to adjust and coat pH of a coating liquid by the above-mentioned preferable range by this. If the amount ratio of each component in the resin layer is within this range, high print quality and water-resistant adhesion of printed matter can be obtained in various printing methods and information recording methods.
  • the resin layer does not deviate from the purport of the present invention as to the crosslinking agent (d), the antistatic agent (e), the antifoaming agent, other auxiliary agents, etc., as needed to improve coating suitability and printability. It can be included in the range.
  • the resin layer may contain a crosslinking agent (d).
  • the crosslinking agent (d) is preferably a substance which reacts with the ethyleneimine resin (b) to crosslink.
  • a crosslinking agent (d) is a water-soluble substance.
  • the crosslinking agent (d) is a bifunctional substance or a polymer-based substance.
  • a crosslinking agent (d) is a low molecular weight substance more than trifunctional.
  • 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 resins, isocyanate resins, formalin resins and oxazoline resins.
  • bisphenol A-epichlorohydrin resin epichlorohydrin resin of polyamine polyamide, aliphatic epoxy resin, epoxy novolac resin, alicyclic epoxy resin, brominated epoxy resin are preferable, epichlorohydrin adduct of polyamine polyamide, or monofunctional to polyfunctional.
  • glycidyl esters of glycidyl esters are more preferred.
  • epichlorohydrin adducts of polyamine polyamides are particularly preferable because they are multifunctional and can obtain highly flexible coating films and are water soluble.
  • the crosslinking agent (d) is preferably contained in an amount of 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, as solid content, with respect to 100 parts by mass of the cationic polyurethane resin (a).
  • the resin layer may contain an antistatic agent (e).
  • an antistatic agent e
  • the antistatic agent (e) is preferably a polymer-type antistatic agent which is unlikely to leak to the surface of the resin layer under long-term storage and cause a decrease in ink adhesion.
  • the antistatic agent (e) cationic type, anionic type, amphoteric type, nonionic type, etc. can be used, but aggregation is possible even when mixed with cationic polyurethane resin (a) or ethyleneimine resin (b).
  • the cationic type or the nonionic type is preferred, and the cationic type capable of obtaining high antistatic properties with a small amount of addition is more preferred.
  • the cationic type includes those having an ammonium salt structure or a phosphonium salt structure.
  • alkali metal salts such as sulfonic acid, phosphoric acid and carboxylic acid, for example, alkali metal salts such as acrylic acid, methacrylic acid and maleic anhydride (for example, lithium salt, sodium salt, potassium salt etc. And the like) having a structure in the molecular structure.
  • the amphoteric type contains both the above-mentioned cationic type and anionic type structures in the same molecule, and examples thereof include betaine type.
  • nonionic type examples include ethylene oxide polymers having an alkylene oxide structure, and polymers having an ethylene oxide polymerization component in a molecular chain.
  • polymeric antistatic agents having boron in the molecular structure can also be mentioned as an example.
  • nitrogen-containing polymeric antistatic agents that are cationic and polymeric are preferable, and tertiary nitrogen or quaternary nitrogen-containing acrylic resins are more preferable.
  • the resin layer is preferably a coating layer formed by applying a coating solution.
  • the coating liquid for forming the coating layer is homogeneous in a solvent such as water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene, or xylene because the process control is easy.
  • Solution or dispersion and used as a solution or dispersion. Above all, in terms of safety and odor, it is more preferable to use any of the above components as a water-soluble or water-dispersible substance in the form of an aqueous solution or aqueous dispersion.
  • the aqueous solution may contain alcohols compatible with water and ketones as a co-solvent. 0.1 mass% or more is preferable, and, as for 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 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 , and more preferably 0.01 g / m 2 to 5 g / m 2 . 0.05 g / m 2 to 3 g / m 2 is particularly preferred.
  • 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 preferably at least the lower limit value of the preferable range in order to practically express the adhesion of the ultraviolet curable ink. It is preferable that the solid content (coating amount) of the resin layer is equal to or less than the upper limit value of the preferable range from the viewpoint of reducing material cost by preventing adhesion force due to cohesive failure of the resin layer.
  • the 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, inkjet recording, thermal transfer recording, pressure-sensitive transfer recording, and electrophotographic recording. It is possible to use an approach. From the viewpoint of fineness of printing, gravure printing, an inkjet recording method, and electrophotographic recording method are preferable from the viewpoint of being able to cope with small lots, letter press printing and flexo printing.
  • an inkjet recording method (so-called UV inkjet 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, on at least one surface of a support containing a thermoplastic resin as a main component, a cationic polyurethane resin (a), an ethyleneimine resin (b) and an acidic pH adjuster (c) And the step of applying a coating liquid containing the above to form a resin layer.
  • the resin layer is preferably a coated layer formed from a coating liquid. It is technical to specify the structure of the resin layer because the condition of the surface streaks before printing of the printing medium differs depending on the pH and the zeta potential in the state of the coating liquid and the addition of the acidic pH adjuster (c).
  • a resin layer is formed by coating a coating liquid containing a cationic polyurethane resin (a), an ethyleneimine resin (b) and an acidic pH adjuster (c) on at least one surface of a support.
  • the zeta potential of the cationic polyurethane resin (a) in the state of the coating liquid is preferably 20 mV or more, and more preferably 20 mV to 70 mV.
  • the pH of the coating solution is preferably 1.0 to 7.4, and more preferably 3.0 to 7.2.
  • a further preferable range of the zeta potential of the cationic polyurethane resin (a) in the state of the coating liquid and the pH of the coating liquid in the method of producing a printing medium of the present invention is the description of the printing medium of the present invention It is the same as the preferred range.
  • the formation of the resin layer is preferably performed by applying a coating liquid to at least one surface of the outermost layer of the support. From the viewpoint of antistatic performance, it is preferable to coat the coating liquid on both surfaces of the support.
  • the coating step may be carried out in conjunction with the substrate molding in the molding line of the substrate, or may be carried out in a separate line using an already molded substrate.
  • coating may be performed before an extending process, and coating may be performed after an extending process. Before or after the coating process, if necessary, the excess solvent may be removed through a drying process using an oven or the like.
  • a general coating apparatus can be used to apply the coating liquid to the support, and the solid content (coating amount) after drying, the viscosity of the coating liquid, and the solid of the chemical in the coating liquid Appropriately selected according to the concentration and so on.
  • 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, a spray coater and the like.
  • a roll coater, a bar coater, a size press coater, a gravure coater and a spray coater are preferably used in a preferable embodiment of the compounding ratio of the cationic polyurethane resin (a), the ethyleneimine resin (b) and the acidic pH adjuster (c). It is preferable to use, and it is more preferable to use a roll coater, a size press coater, and a gravure coater.
  • the printed matter of the present invention has an ultraviolet curable ink on the resin layer of the printing medium of the present invention.
  • a solution or dispersion containing any coloring agent can be used.
  • the solution or dispersion containing the colorant is called “ink” or "ink”.
  • the ink used for these printings is preferably a UV curable ink from the viewpoint of ink adhesion (fixing ability) and abrasion resistance.
  • the ultraviolet curable ink is solidified by ultraviolet irradiation.
  • the UV irradiation method is not particularly limited as long as the UV 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 .
  • an ultraviolet curable ink Well-known ultraviolet curable ink can be used.
  • the ultraviolet curable ink preferably contains a colorant and a compound having at least a diluent and a radically polymerizable group having two or more functional groups.
  • Materials used for the ultraviolet curable ink include the materials described in [0016] to [0097] of JP-A No. 2004-526016 (especially aliphatic urethane acrylates), and [0010] to JP-A No. 2002-080767.
  • Materials described in [0062] (especially anionic aqueous polyurethane compounds), materials described in [0004] to [0026] of JP 2010-530922 A (especially chlorinated polyolefins excellent in adhesion to polyolefin-based films) Etc. can be preferably used.
  • the contents of these publications are incorporated herein by reference.
  • As the UV curable ink one further containing acryloyl morpholine as a diluent can be preferably used.
  • Production Example 1 The support of Production Example 1 was produced by the following method. (1) 81 mass% of a propylene homopolymer (melting point 164 ° C.) having a MFR (melt flow rate) of 0.8 g / 10 min, 16 mass of heavy calcium carbonate having 3 mass% of high density polyethylene and an average particle diameter of 1.5 ⁇ m % Of the resin composition (A) was kneaded with an extruder set at a temperature of 270 ° C., extruded into a sheet, and cooled by a cooling device to obtain a non-oriented sheet.
  • a propylene homopolymer melting point 164 ° C.
  • MFR melt flow rate
  • this sheet was again heated to a temperature of 150 ° C., and then stretched 5 times in the longitudinal direction by using the circumferential speed difference of the roll group to obtain a longitudinally 5 ⁇ stretched film.
  • a resin composition (B) obtained by mixing 55 mass% of a propylene homopolymer having a MFR of 4 g / 10 min (melting point 164 ° C.) and 45 mass% of ground calcium carbonate having an average particle diameter of 1.5 ⁇ m is The mixture is kneaded with another two extruders set at a temperature of ° C. and extruded into a sheet, which is laminated on both sides of a 5-fold longitudinal stretched film obtained in the above step (1) to form a three-layer structure A laminated film was obtained.
  • the obtained laminated stretched film having a three-layer structure has uniaxially stretched / biaxially stretched / uniaxially stretched layers having a number of stretching axes of each layer (B layer / A layer / B layer), and a thickness of 80 ⁇ m (B layer / A layer / B) Layers each having a thickness of 15 ⁇ m / 50 ⁇ m / 15 ⁇ m, a density of 0.79 g / cm 3 , a porosity of 29%, an opacity of 90% and a whiteness of 95% .
  • the density, porosity, opacity and whiteness were measured by known methods.
  • a corona discharge treatment apparatus (trade name: HF400F, manufactured by Kasuga Electric Co., Ltd.), a 0.8 m long aluminum discharge electrode and a treater roll with a silicone film 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 the corona discharge treatment was performed at a line processing speed of 15 m / min and an applied energy density of 4,200 J / m 2 .
  • the obtained support was used as a support of Production Example 1.
  • the support of Production 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 applied to 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 a support of Production Example 2.
  • the support of Production Example 2 contains a thermoplastic resin as a main component.
  • the coating liquid of Production Example 101 was produced by the following method. 6% by mass of a cationic polyurethane resin aqueous dispersion (trade name: Superflex 650, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as a cationic polyurethane resin (a), and a polyethyleneimine as an ethyleneimine resin (b) (Brand name: Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd.) at a solid content of 0.8% by mass, and an acidic pH adjuster (c) with orthophosphoric acid at pH 5.5 and added I got a liquid. The obtained coating liquid was used as the coating liquid of Production Example 101.
  • the blend ratio (solid content concentration in water dispersion: wt%) of each of the production examples is shown in Table 2 below.
  • "o" described in the column of acidic pH adjuster (c) means that the pH of the coating liquid was adjusted using the corresponding type of acidic pH adjuster (c) .
  • the acidic pH adjuster (c) added to the coating liquid in each example was in the range of 0.5 to 3 parts by mass with respect to 100 parts by mass of the cationic polyurethane resin (a).
  • Example 1 The solid content after drying is 0.5 g (0.5 / m 2 ) per unit area (m 2 ) of the coating liquid of Production Example 101 on the surface on the corona discharge treatment side of the support of Production Example 1 It applied using the bar coater by the various coating amount (solid content). Next, the coated substrate was placed in an oven at 60 ° C., and the coating solution was dried to form a resin layer (coated layer), and finally wound up in a roll by a winder to obtain a printing medium . The obtained print medium was used as the print medium of Example 1.
  • Examples 2 to 11 and Comparative Examples 2 to 4 The materials described in Table 1 above are prepared at the compounding ratios described in Table 2 below, and adjusted to the pH described in Table 2 by adding an acidic pH adjuster (c), and Production Examples 102 to 111 and 113 to 115 coating solutions were produced.
  • the coating liquid of Production Example 104 was manufactured such that ammonia water was used in combination when adjusting the pH of the coating liquid with the acidic pH adjuster (c), and the pH of the coating liquid was 3.2.
  • the coating liquid of Production Example 107 was manufactured such that sodium hydroxide was used in combination when adjusting the pH of the coating liquid with the acidic pH adjuster (c), and the pH of the coating liquid was 7.0.
  • Examples 2 to 11 and Comparative Examples were carried out in the same manner as Example 1 except that the coating liquid described in Table 2 below was used as the coating liquid and the coating amount (solid content) described in Table 2 below was used. Two to four print media were obtained.
  • Comparative Example 1 A coating liquid of Production Example 112 was produced in the same manner as in Production Example 105 except that the acidic pH adjuster (c) was not added in production of the coating liquid of Production Example 105.
  • a printing medium of Comparative Example 1 was obtained in the same manner as Example 1, except that the coating liquid of Production Example 112 was used as the coating liquid and the coating amount (solid content) described in Table 2 below was used.
  • Example 12 A printing medium of Example 12 is obtained in the same manner as in Example 5 except that the coating liquid obtained in Production Example 105 of the coating liquid is applied to the surface of the support of Production Example 2 in Example 5. The
  • Solid content of resin layer The solid content (coating amount) of the resin layer of the printing medium of each Example and Comparative Example is described in Table 2 below.
  • the solid content of the resin layer of the printing medium of each 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 of the examples and the comparative examples matches the value obtained by calculation from the solid content of the coating liquid of each production example.
  • the print medium was cut to 10 cm ⁇ 10 cm and allowed to pass for 2 hours under an atmosphere of temperature 23 ° C. and relative humidity 50%. Thereafter, the surface resistivity of the printing medium on the resin layer side is in accordance with JIS K 6911: 1995, using an insulation meter (trade name: DSM-8103, manufactured by Toa Denpa Kogyo Co., Ltd.) and an electrode of the double ring method. It was measured. JIS is an abbreviation of Japanese Industrial Standards. The case where the measured surface resistivity is 1 ⁇ 10 13 ⁇ or more is judged to be not antistatic. When the measured surface resistivity is less than 1 ⁇ 10 13 ⁇ , the antistatic property is good, the paper feeding and discharging properties at the time of printing and printing are good, and it is suitable as a printing medium.
  • the printed surface is irradiated with ultraviolet light by passing it once at a speed of 10 m / min at a distance of 10 cm from the lamp
  • the printed matter was obtained by drying and solidifying the ink.
  • the light reflection density (Macbeth density) of the printed matter is measured with a Macbeth densitometer (made by Kormogen Inc. in the United States), and unevenness in the developed surface is visually observed, and the following 5 It evaluated at the stage.
  • 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 the unevenness is not noticeable 1: The optical density is less than 1.5, and the unevenness is noticeable
  • a cellophane tape (trade name: Cellotape (registered trademark) CT-18, manufactured by Nichiban Co., Ltd.) was attached to the printed surface of the printed matter obtained in the above evaluation of ink transferability, and after sufficiently adhering, the cellophane tape was peeled off quickly. . Subsequently, the ink adhesion was evaluated in five steps on the basis of the following criteria from the visual observation of the state of the printing surface after tape peeling.
  • Inkjet suitability (ink contact angle)
  • the print media of each example and comparative example were stored for 7 days under an atmosphere of temperature 40 ° C. and relative humidity 80%. After allowing the printing medium to age for 2 hours under an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, a portable contact angle meter PG-X + (manufactured by FIBRO system ab) and a UV curable ink for inkjet printing are used. The contact angle after seconds was measured. The contact angle was evaluated according to the following criteria. Since the print medium is less likely to cause ink bleeding as the contact angle of the ultraviolet curable ink is larger, print quality after storage in a high temperature and high humidity environment when ink jet recording using the ultraviolet curable ink is performed It becomes good. 3: 20 ° or more (good) 2: 15 ° or more and less than 20 ° (possible) Less than 1: 15 °
  • Print quality A UV curable ink jet printer (trade name “OceArizona 250 GT”, manufactured by Oce) and a UV curable ink for inkjet printing (trade name: VEST CURE 161 (ink), manufactured by T & K TOKA Co., Ltd.) were used for printing. . After 7 days of storage under the atmosphere of temperature 40 ° C. and relative humidity 80%, the print medium was aged for a further 3 days under the atmosphere of temperature 23 ° C. and relative humidity 50%. Then, 100% solid and characters (line width: 5 pt) were inkjet-printed on the surface of the resin layer of the printing medium using the above-mentioned printing machine.
  • the printing mediums of Examples 1 to 12 have few surface streaks and have excellent ink adhesion after storage under high temperature and high humidity environment when general printing using ultraviolet curing ink is performed. It was a printing medium excellent in print quality and water-resistant adhesion after storage in a high temperature and high humidity environment when ink jet recording using an ultraviolet curable ink was performed.
  • the print medium of Comparative Example 1 containing no acidic pH adjuster (c) as in WO 2014/087670 had many surface streaks.
  • the printing medium of Comparative Example 2 which does not contain the ethyleneimine resin (b) has poor ink adhesion after storage under a high temperature and high humidity environment when general printing using an ultraviolet curable ink is performed.
  • the print medium of Comparative Example 3 which does not contain the cationic urethane resin (a) is inferior in print quality and water adhesion after storage in a high temperature and high humidity environment when ink jet recording using an ultraviolet curable ink is performed. It was a thing.
  • the printing medium of Comparative Example 4 manufactured using a coating liquid having a mixing ratio similar to that of Japanese Patent Application Laid-Open No. 2002-113959 using a cationic polyolefin resin instead of the cationic urethane resin (a) is an ultraviolet curable resin.
  • the print quality after storage in a high temperature and high humidity environment was inferior. The following trends can be read from the relationship between the examples.
  • the print media of the other examples were particularly excellent in the ink transferability of general printing, as compared with the print media of Examples 10 and 11 using the acidic pH adjuster (c) which is liquid at 20 ° C. and 1 atm.
  • the acidic pH adjuster (c) and the base can be used in combination so that the pH of the coating liquid does not become too low. It shows that the print quality of is improved.
  • the zeta potential of the cationic urethane resin (a) in the coating solution is adjusted to 30 to 60 mV, the ink adhesion and background stain in general printing can be improved, and printing in inkjet printing can be performed. It shows that it is effective in the improvement of quality and water resistant adhesion.
  • the inclusion of the cationic polyurethane resin (a) and the ethyleneimine resin (b) in the printing medium of each Example and Comparative Example and in the resin layer can be confirmed by infrared absorption analysis (IR).
  • the inclusion of the acidic pH adjuster (c) in the printing medium of each Example and Comparative Example and in the resin layer can be confirmed by immersing the printing medium in water and extracting the acidic pH adjuster (c).
  • the printing medium of the present invention has few surface streaks, and when performing general printing using an ultraviolet curable ink, it has excellent ink adhesion after storage in a high temperature and high humidity environment, and an inkjet using an ultraviolet curable ink It is a printing medium which is excellent in print quality and water resistance after storage under high temperature and high humidity environment when recording is performed. Therefore, it is suitable as a print medium, a print medium for labels, and a print medium for on demand in applications where water resistance is required.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Laminated Bodies (AREA)
  • Ink Jet (AREA)

Abstract

L'invention concerne un support d'impression comprenant une résine polyuréthanne cationique (a), une résine éthylènimine (b), et un agent d'ajustement de pH acide (c) sur au moins une surface d'un corps de support contenant une résine thermoplastique comme composant principal. Le support d'impression présente peu de stries de surface, possède une excellente adhésion d'encre après stockage dans un environnement très humide quand l'impression générale est effectuée à l'aide d'une encre durcissable aux ultraviolets, et présente une excellente qualité d'impression et d'adhérence résistante à l'eau après stockage dans un environnement à humidité élevée lorsque l'enregistrement à jet d'encre est effectué à l'aide d'une encre durcissable aux ultraviolets. La présente invention concerne en outre un procédé de fabrication du substrat d'impression ainsi que des imprimés.
PCT/JP2016/087130 2015-12-21 2016-12-14 Support d'impression, procédé de fabrication d'un support d'impression et imprimés Ceased WO2017110599A1 (fr)

Priority Applications (1)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
JP2018150489A (ja) * 2017-03-15 2018-09-27 三洋化成工業株式会社 印刷インキ用バインダー及びこれを用いた印刷インキ
JP2019183100A (ja) * 2018-03-30 2019-10-24 株式会社日本触媒 易接着性基材
JP2024505993A (ja) * 2021-06-08 2024-02-08 Dic株式会社 カチオン性ウレタン樹脂組成物

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JP2004249564A (ja) * 2003-02-19 2004-09-09 Nippon Paper Industries Co Ltd インクジェット記録用キャストコート紙
JP2005212358A (ja) * 2004-01-30 2005-08-11 Fuji Photo Film Co Ltd インクジェット記録媒体
JP2009241530A (ja) * 2008-03-31 2009-10-22 Nippon Paper Industries Co Ltd インクジェット記録媒体の製造方法
JP2012006242A (ja) * 2010-06-24 2012-01-12 Seiko Epson Corp インクジェット用記録媒体
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

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JP2004249564A (ja) * 2003-02-19 2004-09-09 Nippon Paper Industries Co Ltd インクジェット記録用キャストコート紙
JP2005212358A (ja) * 2004-01-30 2005-08-11 Fuji Photo Film Co Ltd インクジェット記録媒体
JP2009241530A (ja) * 2008-03-31 2009-10-22 Nippon Paper Industries Co Ltd インクジェット記録媒体の製造方法
JP2012006242A (ja) * 2010-06-24 2012-01-12 Seiko Epson Corp インクジェット用記録媒体
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018150489A (ja) * 2017-03-15 2018-09-27 三洋化成工業株式会社 印刷インキ用バインダー及びこれを用いた印刷インキ
JP2019183100A (ja) * 2018-03-30 2019-10-24 株式会社日本触媒 易接着性基材
JP7257123B2 (ja) 2018-03-30 2023-04-13 株式会社日本触媒 易接着性基材
JP2024505993A (ja) * 2021-06-08 2024-02-08 Dic株式会社 カチオン性ウレタン樹脂組成物
JP7658448B2 (ja) 2021-06-08 2025-04-08 Dic株式会社 カチオン性ウレタン樹脂組成物

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