WO2017199896A1 - Procédé de production de matériau d'impression - Google Patents

Procédé de production de matériau d'impression Download PDF

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Publication number
WO2017199896A1
WO2017199896A1 PCT/JP2017/018155 JP2017018155W WO2017199896A1 WO 2017199896 A1 WO2017199896 A1 WO 2017199896A1 JP 2017018155 W JP2017018155 W JP 2017018155W WO 2017199896 A1 WO2017199896 A1 WO 2017199896A1
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WO
WIPO (PCT)
Prior art keywords
ink
actinic ray
cationic polymerizable
ray curable
curable cationic
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PCT/JP2017/018155
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English (en)
Japanese (ja)
Inventor
佐藤　正樹
成寿 鈴木
大 平工
杉田　修一
Original Assignee
日新製鋼株式会社
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Priority claimed from JP2017094896A external-priority patent/JP2017206016A/ja
Application filed by 日新製鋼株式会社 filed Critical 日新製鋼株式会社
Publication of WO2017199896A1 publication Critical patent/WO2017199896A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements

Definitions

  • the present invention relates to a method for producing a printing material having an ink layer having excellent adhesion to an ink receiving layer that is a cured product of a resin composition.
  • printing materials are often used as interior and exterior wall materials for buildings.
  • the printing material is manufactured by applying a desired pattern to the surface of a base material processed into a desired shape by inkjet printing or the like.
  • a pattern is imparted to a printing material by ink jet printing, weather resistance, ink curability, ink adhesion on the substrate surface, and the like are important.
  • the printing material has a metal plate, an ink receiving layer disposed on the surface of the metal plate, and an ink layer disposed on the surface of the ink receiving layer.
  • a printing material is activated, for example, by irradiating actinic rays (for example, ultraviolet rays) after inkjet printing of actinic ray curable cationic polymerizable ink on the surface of a metal plate having an ink receiving layer disposed on the surface. It is produced by curing a photocurable cationic polymerizable ink.
  • the actinic ray curable cationic polymerizable ink contains a cationic polymerizable compound and a photopolymerization initiator.
  • actinic light is irradiated to the actinic ray curable cationic polymerizable ink printed on the surface of the ink receiving layer, the photopolymerization initiator is decomposed to become active species.
  • This active species then reacts with the cationic polymerizable compound to produce a new active species.
  • New active species are cationically polymerized with other cationically polymerizable compounds, and this reaction is repeated to polymerize and cure.
  • Patent Document 1 discloses an actinic ray curable cationic polymerizable ink having a cationic polymerizable compound, an oxetane compound and a photopolymerization initiator.
  • the actinic ray curable cationic polymerizable ink described in Patent Document 1 is excellent in curability by blending an oxetane compound, and is excellent in adhesion even at high humidity.
  • the printing material produced using the actinic ray curable cationic polymerizable ink described in Patent Document 1 has insufficient weather resistance.
  • Patent Document 2 discloses an actinic ray curable cationic polymerizable ink having a cationic polymerizable compound, a compound having a siloxane bond and an oxetanyl group, and a photopolymerization initiator.
  • the actinic ray curable cationic polymerizable ink described in Patent Document 2 is excellent in weather resistance by blending a compound having a siloxane bond, and is excellent in curability even at high humidity.
  • the present inventors tried to cure the actinic ray curable cationic polymerizable ink by lowering the humidity. As a result, even when the humidity was kept low, there were cases where the actinic ray curable cationic polymerizable ink was properly cured and cases where the actinic ray curable cationic polymerizable ink was not properly cured. From this, the present inventors considered that other elements were important in addition to humidity as conditions for curing the actinic ray curable cationic polymerizable ink.
  • the present invention has been made in view of such points, and an object of the present invention is to provide a method for producing a printing material capable of stably producing a printing material having excellent adhesion and curability of an ink layer.
  • the present inventors have found that the above-mentioned problems can be solved by bringing the absolute humidity and temperature during irradiation with actinic rays to the actinic ray curable cationic polymerizable ink within a predetermined range, Further studies were made to complete the present invention.
  • Applying the actinic ray curable cationic polymerizable ink on the receiving layer, irradiating and curing the actinic ray to form an ink layer, and the actinic ray curable cationic polymerizable ink comprises: Actinically polymerizable compound, 0.5 to 10.0% by mass of an epoxy group-containing silane coupling agent, 10 to 50% by mass of a hydroxyl group-containing oxetane compound, and a photopolymerization initiator, The absolute humidity VH (g / m 3 ) and temperature T (° C.) during irradiation with the actinic ray to cure the curable cationic polymerizable ink are expressed by
  • a printing material manufacturing method that satisfies the above. 6 ⁇ VH ⁇ 103 ⁇ T ⁇ 10 ⁇ VH-5 (1) 15 ⁇ T ⁇ 40 (2) [2] A step of measuring and adjusting the absolute humidity VH (g / m 3 ) and the temperature T (° C.) while irradiating the actinic ray to cure the actinic ray curable cationic polymerizable ink.
  • the ink layer is formed when the absolute humidity VH (g / m 3 ) during irradiation with the actinic ray for curing the actinic ray curable cationic polymerizable ink is 10 g / m 3 or more.
  • step of performing within 2 minutes after irradiating the actinic ray, heat treatment is started at a temperature of 50 ° C. or higher to further cure the actinic ray curable cationic polymerizable ink [1] or [2]
  • the manufacturing method of the printing material as described in 2.
  • the ink layer is formed when the absolute humidity VH (g / m 3 ) during irradiation with the actinic ray is 10 g / m 3 or more in order to cure the actinic ray curable cationic polymerizable ink.
  • step of, within 2 minutes after irradiating the actinic ray heat treatment is started at a temperature of 50 ° C. or higher and 145 ° C.
  • the present invention it is possible to provide a method for producing a printing material capable of stably producing a printing material having excellent adhesion and curability of the ink layer.
  • the printing material obtained by the manufacturing method of the printing material of this invention has a base material, the ink receiving layer arrange
  • the printing material may further have an overcoat layer disposed on the ink layer.
  • the printing material obtained by the method for producing a printing material of the present invention can be suitably used as a building material used as, for example, a building interior material and an outer wall material. Hereinafter, each component of the printing material will be described.
  • Base material The kind of base material is not specifically limited.
  • the substrate include a metal-based substrate (metal plate) and a ceramic-based substrate.
  • metal base materials include plated steel sheets such as hot-dip Zn-55% Al alloy-plated steel sheets, steel sheets such as ordinary steel sheets and stainless steel sheets, aluminum plates, and copper plates. These metal base materials may be embossed or drawn and subjected to uneven processing such as tile tone, brick tone, and wood grain. Furthermore, for the purpose of improving heat insulation and soundproofing, the back surface of the metal base material may be covered with aluminum laminated kraft paper using an inorganic material such as a resin foam or gypsum board as a core material.
  • Ceramic base materials include unglazed porcelain plates, glazed and fired porcelain plates, cement plates, and plate materials formed using cementitious materials and fiber materials. Moreover, you may give uneven
  • the base material may have a chemical conversion treatment film or an undercoat film formed on the surface thereof.
  • the chemical conversion film is formed on the entire surface of the base material, and improves coating film adhesion and corrosion resistance.
  • the kind of chemical conversion treatment which forms a chemical conversion treatment film is not specifically limited. Examples of the chemical conversion treatment include chromate treatment, chromium-free treatment, and phosphate treatment.
  • the adhesion amount of the chemical conversion coating is not particularly limited as long as it is within a range effective for improving coating film adhesion and corrosion resistance. For example, in the case of a chromate film, the adhesion amount may be adjusted so that the total Cr conversion adhesion amount is 5 to 100 mg / m 2 .
  • the Ti-Mo composite coating has a range of 10 to 500 mg / m 2
  • the fluoroacid-based coating has a fluorine equivalent or total metal element equivalent deposit of 3 to 100 mg / m 2.
  • the adhesion amount may be adjusted. In the case of a phosphate film, the adhesion amount may be adjusted so as to be 5 to 500 mg / m 2 .
  • the undercoat coating film is formed on the entire surface of the base material or the chemical conversion coating film, and improves the adhesion and corrosion resistance of the coating film.
  • the undercoating film is formed, for example, by applying an undercoating paint containing a resin to the surface of the base material or the chemical conversion film and drying (or curing).
  • the kind of resin contained in the undercoat paint is not particularly limited. Examples of resin types include polyester, epoxy resin, acrylic resin, and the like. Epoxy resins are particularly preferred because of their high polarity and good adhesion.
  • the thickness of the undercoat coating film is not particularly limited as long as the above function can be exhibited.
  • the film thickness of the undercoat coating film is, for example, about 5 ⁇ m.
  • the ink receiving layer is a layer for receiving the actinic ray curable cationic polymerizable ink disposed on the entire surface of the base material or the undercoat coating film.
  • the ink receiving layer includes a resin serving as a matrix.
  • the type of resin used as the matrix is not particularly limited.
  • the resin serving as the matrix include polyester, acrylic resin, polyvinylidene fluoride, polyurethane, epoxy resin, polyvinyl alcohol, and phenol resin.
  • the resin used as the matrix preferably contains polyester from the viewpoint of high weather resistance and adhesion to the actinic ray curable cationic polymerizable ink.
  • the resin used as the matrix does not form a porous ink receiving layer for water-based ink. This is because the porous ink-receiving layer may have poor water resistance and weather resistance, and is not suitable for applications such as building materials.
  • the polyester resin composition for forming the matrix contains, for example, polyester and melamine resin, contains polyester and urethane resin, or contains polyester, melamine resin and urethane resin. Moreover, the polyester resin composition which has polyester and a melamine resin further contains a catalyst and an amine.
  • a cured product (ink receiving layer) of such a resin composition has a high crosslinking density and is impermeable to actinic ray curable cationic polymerizable ink.
  • the ink receiving layer (cured product of the resin composition) is impermeable to the actinic ray curable cationic polymerizable ink because the cross section of the ink receiving layer and the ink layer can be measured with a microscope at a magnification of 100 to 200 times.
  • the ink receiving layer is impermeable, the interface between the ink receiving layer and the ink layer can be clearly identified.
  • the ink receiving layer is permeable, the interface between the ink receiving layer and the ink layer is unclear and difficult to distinguish.
  • the type of polyester is not particularly limited as long as it can cause a crosslinking reaction with melamine resin, urethane resin, or a combination thereof.
  • the number average molecular weight of the polyester is not particularly limited, but is preferably 5000 or more from the viewpoint of processability.
  • the hydroxyl value of the polyester is not particularly limited, but is preferably 40 mgKOH / g or less.
  • the glass transition point of the polyester is not particularly limited, but is preferably in the range of 0 to 70 ° C. When the glass transition point is less than 0 ° C., the hardness of the ink receiving layer may be insufficient. On the other hand, when the glass transition point is higher than 70 ° C., the workability may be reduced.
  • Melamine resin is a polyester cross-linking agent. Although the kind of melamine resin is not specifically limited, It is preferable that it is a methylated melamine resin.
  • the methylated melamine resin preferably has a methoxy group content in the functional groups in the molecule of 80 mol% or more.
  • the methylated melamine resin may be used alone or in combination with other melamine resins.
  • the catalyst promotes the reaction of melamine resin.
  • the catalyst include dodecylbenzenesulfonic acid, paratoluenesulfonic acid, and benzenesulfonic acid.
  • the blending amount of the catalyst is preferably in the range of 0.1 to 8.0% with respect to the resin solid content.
  • the amine neutralizes the catalytic reaction.
  • examples of the amine include triethylamine, dimethylethanolamine, dimethylaminoethanol, monoethanolamine, and isopropanolamine.
  • the compounding quantity of an amine is not specifically limited, It is preferable that it is the quantity of 50% or more of an equivalent with respect to an acid (catalyst).
  • Urethane resin is a polyester cross-linking agent.
  • aliphatic diisocyanate or alicyclic diisocyanate is preferable instead of aromatic diisocyanate from the viewpoint of enhancing weather resistance.
  • examples of the aliphatic diisocyanate and the alicyclic diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanomethyl) cyclohexane.
  • the urethane resin the aforementioned urethane resin may be used alone, or two or more kinds of urethane resins may be used in combination.
  • the arithmetic average roughness Ra of the ink receiving layer measured in accordance with JIS B B0601 is preferably in the range of 400 to 3000 nm.
  • the wetting and spreading property of the actinic ray curable cationic polymerizable ink on the surface of the ink receiving layer is good.
  • the method for forming fine irregularities on the surface of the ink receiving layer satisfying the condition of the arithmetic average roughness Ra is not particularly limited. Examples of such a method include a nanoimprint method and a shot peening method.
  • a mold provided with a texture (unevenness) that satisfies the arithmetic average roughness Ra and an ink receiving layer formed on a substrate are pressed while being heated.
  • the mold used in the nanoimprint method can be manufactured by using a known direct plate making or electronic engraving plate making.
  • an oxide-based abrasive is used in the shot peening method.
  • predetermined irregularities can be formed on the surface of the ink receiving layer by appropriately adjusting the particle diameter of the abrasive, the speed of the shot grains, the peening time, and the like.
  • the film thickness of the ink receiving layer is not particularly limited, but is preferably in the range of 10 to 40 ⁇ m. If the film thickness is less than 10 ⁇ m, the durability and concealment of the ink receiving layer may be insufficient. In addition, when the film thickness is more than 40 ⁇ m, the manufacturing cost increases and there is a risk of occurrence of cracks during baking. In addition, the surface of the ink receiving layer may have a cocoon skin shape and the appearance may be deteriorated.
  • the ink layer is disposed on the ink receiving layer.
  • the ink layer is disposed on the entire surface or a part of the ink receiving layer so that a desired image is formed on the surface of the ink receiving layer.
  • the ink layer is formed by inkjet printing the actinic ray curable cationic polymerizable ink on the surface of the ink receiving layer and irradiating the actinic ray to cure the actinic ray curable cationic polymerizable ink.
  • the actinic ray curable cationic polymerizable ink is preferably a cationic polymerization type UV ink that is cured by irradiation with ultraviolet rays (active rays).
  • the actinic ray curable cationic polymerizable ink contains a cationic polymerizable compound, an epoxy group-containing silane coupling agent, a hydroxyl group-containing oxetane compound, and a photopolymerization initiator.
  • the actinic ray curable cationic polymerizable ink may further contain a pigment and a dispersant.
  • the type of the cationic polymerizable compound is not particularly limited as long as it is a monomer capable of cationic polymerization.
  • the cationically polymerizable compound include oxetane compounds other than aromatic epoxides, alicyclic epoxides, aliphatic epoxides, and hydroxyl group-containing oxetane compounds.
  • aromatic epoxides include di- or polyglycidyl ethers of bisphenol A or alkylene oxide adducts thereof, di- or polyglycidyl ethers of hydrogenated bisphenol A or alkylene oxide adducts thereof, and novolak-type epoxy resins.
  • alicyclic epoxides examples include cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with an oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is included.
  • aliphatic epoxides include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, diglycidyl or adduct of alkylene oxide thereof.
  • polyglycidyl ether of polyhydric alcohol such as triglycidyl ether, diglycidyl ether of polyalkylene glycol such as polyethylene glycol or diglycidyl ether of alkylene oxide adduct thereof, polypropylene glycol or diglycidyl ether of alkylene oxide adduct thereof It is. Since the oxetane compound easily undergoes a growth reaction, it can be increased in molecular weight by cationic polymerization. Examples of the oxetane compound include known oxetane compounds described in JP-A Nos. 2001-220526 and 2001-310937.
  • the oxetane compound may be used alone, or a monofunctional oxetane compound containing one oxetane ring and a polyfunctional oxetane compound containing two or more oxetane rings may be used in combination.
  • the content of the cationic polymerizable compound in the actinic ray curable cationic polymerizable ink is preferably in the range of 60 to 95% by mass.
  • the cationically polymerizable compound is less than 60% by mass, there is a possibility that the curing component becomes too small to form an ink layer.
  • the amount of the cationically polymerizable compound is more than 95% by mass, the amount of the photopolymerization initiator added may be too small to sufficiently cure the ink layer.
  • the epoxy group-containing silane coupling agent improves the weather resistance of the ink layer by forming a siloxane bond with a cationically polymerizable compound or a hydroxyl group-containing oxetane compound.
  • the kind of epoxy group-containing silane coupling agent is not particularly limited.
  • Examples of the epoxy group-containing silane coupling agent include (3- (2,3 epoxypropoxy) propyl) trimethyltrimethoxysilane, 3-gridoxypropylmethoxysilane, and an epoxy-containing oligomer type silane coupling agent. These epoxy group-containing silane coupling agents may be produced by using known methods, or commercially available products may be used.
  • epoxy group-containing silane coupling agents examples include “KBM-303; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane”, “KBM-403; 3-glycid” manufactured by Shin-Etsu Chemical Co., Ltd. Xylpropyltrimethoxysilane ". Since the epoxy group-containing silane coupling agent has an epoxy group, the initiation reaction of cationic polymerization is likely to proceed.
  • the content of the epoxy group-containing silane coupling agent in the actinic ray curable cationic polymerizable ink is in the range of 0.5 to 10.0% by mass.
  • the epoxy group-containing silane coupling agent is less than 0.5% by mass, the siloxane bond is insufficient, and the weather resistance may be lowered.
  • the epoxy group-containing silane coupling agent exceeds 10.0% by mass, self-condensation may occur and adhesion to the ink receiving layer may be reduced.
  • the hydroxyl group-containing oxetane compound is a compound having one or more hydroxyl groups in the molecule.
  • the kind of hydroxyl group-containing oxetane compound is not particularly limited.
  • Examples of hydroxyl group-containing oxetane compounds include 3-ethyl-3-hydroxymethyloxetane.
  • the hydroxyl group-containing oxetane compound may be produced using a known method, or a commercially available product may be used.
  • Examples of commercially available hydroxyl group-containing oxetane compounds include “OXT-101; 3-ethyl-3-hydroxymethyloxetane” manufactured by Toa Gosei Co., Ltd. In such a hydroxyl group-containing oxetane compound, the initiation reaction is unlikely to proceed, but the polymerization reaction is likely to proceed.
  • the content of the hydroxyl group-containing oxetane compound in the actinic ray curable cationic polymerizable ink is in the range of 10 to 50% by mass.
  • the hydroxyl group-containing oxetane compound is less than 10% by mass, the proportion of the epoxy group-containing silane coupling agent in the actinic ray curable cationic polymerizable ink is increased, and the adhesion of the ink layer to the ink receiving layer is reduced. There is a fear.
  • the actinic ray curable cationic polymerizable ink may not be cured because it absorbs moisture in the air.
  • the photopolymerization initiator initiates cationic polymerization by irradiation with actinic rays.
  • the type of photopolymerization initiator is not particularly limited as long as cationic polymerization can be initiated by irradiation with actinic rays, but is preferably an onium salt that generates a Lewis acid by irradiation with actinic rays.
  • Examples of photopolymerization initiators include Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, and the like.
  • onium salts, and the cationic moiety comprising an aromatic diazonium, aromatic iodonium, or an aromatic sulfonium, anionic portion is BF 4 -, PF 6 -, SbF 6 -, or [BX 4] - (X is at least And an anionic moiety including a phenyl group substituted with two or more fluorine or trifluoromethyl groups.
  • the content of the photopolymerization initiator in the actinic ray curable cationic polymerizable ink is preferably in the range of 3 to 15% by mass.
  • the photopolymerization initiator is less than 3% by mass, a sufficient degree of polymerization cannot be obtained, so that an ink layer may not be formed.
  • the photopolymerization initiator is more than 15% by mass, the difference in the degree of cure between the surface layer and the deep layer of the ink layer increases, which may cause distortion and reduce the adhesion.
  • the type of pigment is not particularly limited as long as it is an organic pigment or an inorganic pigment.
  • organic pigments include nitroso, dyed lakes, azo lakes, insoluble azos, monoazos, disazos, condensed azos, benzimidazolones, phthalocyanines, anthraquinones, perylenes, quinacridones, dioxazines , Isoindolines, azomethines and pyrrolopyrroles.
  • inorganic pigments include oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, carbons (carbon black) and metals Contains flour.
  • the pigment is preferably blended in the actinic ray curable cationic polymerizable ink within a range of 0.5 to 20% by mass.
  • the pigment is less than 0.5% by mass, coloring may be insufficient and a desired image may not be formed.
  • the pigment is more than 20% by mass, the viscosity of the actinic ray curable cationic polymerizable ink becomes too high, and there is a risk of causing ejection failure from the inkjet head.
  • the dispersant makes each component of the actinic ray curable cationic polymerizable ink dispersed.
  • the dispersant any of a low molecular dispersant and a high molecular dispersant can be used.
  • the dispersant may be manufactured using a known method, or a commercially available product may be used. Examples of such commercially available dispersants include “Ajisper PB822” and “Ajisper PB821” (both are Ajinomoto Fine Techno Co., Ltd.).
  • FIG. 1 is a structural diagram showing an outline of a crosslinked siloxane oligomer.
  • the silane coupling agent generates a plurality of silanol groups by hydrolysis of a plurality of alkoxy groups on the silicon atom.
  • the silanol group forms a crosslinked siloxane oligomer by forming a double or triple siloxane bond using a strong acid generated from a photopolymerization initiator as an acid catalyst. Since this crosslinkable siloxane oligomer has a high cure shrinkage ratio, it can cause a decrease in the adhesion of the ink layer. Therefore, in order to improve the adhesion of the ink layer to the ink receiving layer, it is necessary to suppress the formation of this crosslinked siloxane oligomer.
  • the present inventors can suppress the formation of a crosslinked siloxane oligomer by a three-dimensional crosslinking reaction between silane coupling agents and improve the adhesion of the ink layer. I found it.
  • silane coupling agent An epoxy group capable of cationic polymerization is introduced into the molecular structure of the silane coupling agent.
  • a silane coupling agent becomes a part of cationic polymerization polymer chain. For this reason, it can suppress that a silane coupling agent adjoins by a hydrogen bond, and three-dimensionally crosslinks and forms a crosslinked siloxane oligomer.
  • the content of the epoxy group-containing silane coupling agent is 0.5 to 10% by mass, which is smaller than the content of the hydroxy group-containing oxetane, and the cationic polymerizable functional group introduced into the silane coupling agent is oxetane.
  • an epoxy compound that is a cationically polymerizable monomer has a property that the curing reaction starts quickly but the polymerization rate does not increase so much.
  • the oxetane compound, which is a cationic polymerization monomer has a characteristic that the initiation of curing is slow, but the curing rate is increased in the latter half of the reaction, and the polymerization rate is increased.
  • the ring has an inverse characteristic that the epoxy group is larger in the epoxy group than the oxetane ring and the basicity is larger in the oxetane ring than the epoxy group.
  • the epoxy group-containing silane coupling agent is introduced at the polymerization starting point of the cationic polymerization polymer by the above (1) to (3), the possibility that the silane coupling agent continuously undergoes cationic polymerization due to the properties of the epoxy group is Extremely low. This is also considered to suppress the formation of a crosslinked siloxane oligomer due to the proximity of the silane coupling agents.
  • the addition amount of the epoxy group-containing silane coupling agent exceeds 10% by mass, the silane coupling agents not introduced at the polymerization starting point of the cationic polymerization polymer are close to each other by a hydrogen bond to form a crosslinked siloxane oligomer. Since it may produce
  • the printing material of the present invention may further have an overcoat layer on the ink layer.
  • the type of overcoat paint for forming the overcoat layer is not particularly limited.
  • overcoat paints include organic solvent-type paints, water-based paints, and powder paints.
  • the kind of the resin component used for these paints is not particularly limited.
  • the resin component include acrylic resin, polyester, alkyd resin, silicone-modified acrylic resin, silicone-modified polyester, silicone resin, and fluororesin. These resin components may be used alone or in combination of two or more. Moreover, you may mix
  • the manufacturing method of the printing material according to the present invention includes a step of preparing a base material, a step of forming an ink receiving layer on the base material, and a step of forming an ink layer on the ink receiving layer. And having. Moreover, you may have the process of measuring and adjusting temperature and absolute humidity as needed, and the process of forming an overcoat layer on an ink layer.
  • the aforementioned metal base material or ceramic base material is prepared.
  • a chemical conversion treatment film can be formed by applying a chemical conversion treatment liquid on the surface of a base material, and making it dry.
  • the method for applying the chemical conversion liquid is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, an air spray method, an airless spray method, and a dip pulling method. What is necessary is just to set suitably the drying conditions of a chemical conversion liquid according to the composition of a chemical conversion liquid, etc.
  • the base material coated with the chemical conversion treatment solution is put into a drying oven without being washed with water, and heated so that the ultimate plate temperature is in the range of 80 to 250 ° C., thereby forming a uniform chemical conversion on the surface of the base material.
  • a treatment film can be formed.
  • an undercoat coating film can be formed by apply
  • the method for applying the undercoat paint the same method as the method for applying the chemical conversion treatment liquid can be used. What is necessary is just to set suitably the drying conditions of an under_coat_film according to the kind etc. of resin.
  • a uniform undercoat film can be formed on the surface of the chemical conversion film by heating so that the ultimate plate temperature is in the range of 150 to 250 ° C.
  • the ink receiving layer is formed by applying the above-mentioned resin composition to the surface of the base material (or chemical conversion coating or undercoat coating) and drying (or curing) it.
  • the application method of the resin composition is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, an air spray method, an airless spray method, and a dip pulling method.
  • the drying conditions for the resin composition are not particularly limited. For example, by drying the base material coated with the resin composition so that the ultimate plate temperature is in the range of 150 to 250 ° C., the ink receiving layer is formed on the surface of the base material (or chemical conversion coating or undercoat coating film). Can be formed.
  • irregularities having an arithmetic average roughness Ra measured in accordance with JIS B B0601 in the range of 400 to 3000 nm may be formed by a nanoimprint method or a shot peening method.
  • the above-mentioned actinic ray curable cationic polymerizable ink is ink jet printed on the surface of the ink receiving layer using an ink jet printer, and the integrated light quantity is 100 to 800 mJ / Actinic rays (for example, ultraviolet rays) are irradiated so as to be in the range of cm 2 to cure the actinic ray curable cationic polymerizable ink.
  • Actinic rays for example, ultraviolet rays
  • the actinic ray curable cationic polymerizable ink includes a cationic polymerizable compound, 0.5 to 10.0% by mass of an epoxy group-containing silane coupling agent, and 10 to 50% by mass of a hydroxyl group-containing oxetane.
  • the total amount of ultraviolet light can be measured using a UV illuminometer / light meter (UV-351-25; Oak Manufacturing Co., Ltd.) in a measurement wavelength range: 240 to 275 nm, a measurement wavelength center: 254 nm.
  • the present inventors examined environmental parameters for curing the actinic ray curable cationic polymerizable ink.
  • the present inventors have important relationships between the ambient absolute humidity and temperature when curing the actinic radiation curable cationic polymerizable ink. I found out.
  • the absolute humidity VH during irradiation of the actinic ray curable cationic polymerizable ink with actinic rays is used.
  • temperature T ° C.
  • the actinic ray curable cationic polymerizable ink may not be properly cured, and the actinic ray curable cationic polymerizable ink may not adhere to the ink receiving layer.
  • a method for controlling the absolute humidity VH (g / m 3 ) and the temperature T (° C.) to satisfy the expressions (1) and (2) is not particularly limited. It is preferable to control the absolute humidity and temperature (temperature) after enclosing the atmosphere in the region irradiated with actinic rays so that the atmosphere can be kept constant.
  • the air temperature may be controlled by an air conditioner.
  • the humidity control when the absolute humidity is high may be performed by dehumidifying with a dehumidifier.
  • the humidity control when the absolute humidity is low may be performed by humidifying with a humidifier.
  • the absolute humidity VH (g / m 3 ) during irradiation of the actinic ray to the actinic ray curable cationic polymerizable ink further satisfies the following formula (3). 4.2 ⁇ VH ⁇ 19.8 (3)
  • the actinic ray curable cationic polymerizable ink may be heated at a predetermined temperature after irradiation with actinic rays.
  • the actinic ray curable cationic polymerizable ink is easily polymerized by both actinic ray irradiation and heat treatment.
  • the absolute humidity upon irradiation with actinic rays is 10 g / m 3 or more, the ink may be insufficiently cured after irradiation with actinic rays, so heat treatment is performed after irradiation with actinic rays. Is preferred.
  • the interval from the end of the actinic ray irradiation to the start of the heat treatment is preferably within 2 minutes. More preferably, it is within minutes. If the interval between irradiation of actinic rays and heat treatment is more than 2 minutes, the ink layer absorbs moisture in the air and the reaction activity is lost, so that the ink layer may not be cured sufficiently even after heat treatment. is there.
  • the temperature of the heat processing after actinic ray irradiation is 50 degreeC or more.
  • the temperature of the heat treatment is lower than 50 ° C., the curing of the ink layer even if the heat treatment may be insufficient. Therefore, when actinic rays are irradiated under conditions where the absolute humidity is 10 g / m 3 or more, the temperature of the heat treatment is more preferably 60 ° C. or more, and further preferably 70 ° C. or more.
  • the metal base material has a larger coefficient of thermal expansion than the ceramic base material, when it is heated to 150 ° C. or higher, there is a possibility that a defect may occur in the product shape due to thermal strain. In particular, this problem is remarkable in an aluminum-based metal substrate.
  • ceramic base materials often contain bubbles or the like in the base material compared to metal base materials, so when heated to 150 ° C. or higher, the thermal conductivity becomes low and the temperature of the base material is unlikely to decrease.
  • the ink receiving layer is a resin composition, when it is kept at 150 ° C. or higher for a long time, there is a high possibility that problems such as a change in color tone and a decrease in adhesion occur due to thermal degradation.
  • the absolute humidity VH upon irradiation with actinic rays is in the range of 4.5 to 9.9 g / m 3 and heat treatment is performed after irradiation with actinic rays, the adhesion of the ink layer and the curability of the ink layer are further improved. (See Examples).
  • the temperature and absolute humidity of the environment for curing the actinic ray curable cationic polymerizable ink are measured, and the temperature and absolute humidity are expressed by the above formulas (1) and (2). Adjust to meet.
  • the air temperature may be controlled by an air conditioner.
  • the humidity control when the absolute humidity is high may be performed by dehumidifying with a dehumidifier.
  • the humidity control when the absolute humidity is low may be performed by humidifying with a humidifier.
  • the overcoat layer is formed.
  • the overcoat layer is formed by applying an overcoat paint to the surface of the ink layer and drying (or curing).
  • the method for applying the overcoat paint is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, an air spray method, an airless spray method, and a dip pulling method.
  • the drying conditions for the overcoat paint are not particularly limited.
  • the overcoat layer can be formed on the surface of the printing material by drying the printing material coated with the overcoat paint so that the ultimate plate temperature is in the range of 60 to 150 ° C.
  • the printing method of the present invention is characterized by using an actinic ray curable cationic polymerizable ink containing a predetermined amount of an epoxy group-containing silane coupling agent and a hydroxyl group-containing oxetane compound, and adjusting the absolute humidity and temperature.
  • Actinic light is irradiated in a controlled environment to cure the actinic ray curable cationic polymerizable ink.
  • VH absolute humidity
  • T temperature
  • the printing material produced by the method is excellent in the adhesion of the ink layer to the ink receiving layer while the actinic ray curable cationic polymerizable ink is appropriately cured.
  • Example 1 Preparation of printing material (1) Substrate As a coating original plate, a molten Zn-55% Al alloy plated steel plate having a plate thickness of 0.27 mm and a coating adhesion amount per side of 90 g / m 2 was prepared. A coating-type chromate treatment liquid (NRC300NS; Nippon Paint Co., Ltd.) was applied to the surface of the alkali degreased coating original plate to form a chemical conversion treatment film having a total chromium equivalent adhesion amount of 50 mg / m 2 .
  • NRC300NS Nippon Paint Co., Ltd.
  • a polyester primer coating (700P; Nippon Fine Coatings Co., Ltd.) is applied onto the chemical conversion film using a bar coater and baked at a final plate temperature of 215 ° C. to form an undercoat film having a dry film thickness of 5 ⁇ m. Formed.
  • the resin composition for forming the ink receiving layer is applied onto the undercoat film using a bar coater, and baked at a final plate temperature of 225 ° C. for 1 minute to obtain a dry film thickness.
  • a 20 ⁇ m ink receiving layer was formed.
  • the resin composition (white paint) consists of polyester (number average molecular weight 5000, glass transition temperature 30 ° C., hydroxyl value 28 mg KOH / g; DIC Corporation) and methylated melamine resin (Cymel 303; Mitsui Cytec Corporation) as a crosslinking agent. And a base resin obtained by mixing at 70:30 with a catalyst, an amine and a color pigment.
  • a catalyst 1% by mass of dodecylbenzenesulfonic acid was added to the resin solid content.
  • As an amine dimethylaminoethanol was added in an amount equivalent to 1.25 times as an amine equivalent to an acid equivalent of dodecylbenzenesulfonic acid.
  • As the color pigment titanium oxide (JR-603; Teika Co., Ltd.) having an average particle size of 0.28 ⁇ m was added in an amount of 45 mass% based on the resin solid content.
  • Actinic ray curable cationic polymerizable ink was prepared by mixing 18% by mass of a cationic photopolymerization initiator (CPI-100P; San Apro Co., Ltd.) with the pigment dispersion.
  • CPI-100P cationic photopolymerization initiator
  • Inkjet printing used an inkjet head having a nozzle diameter of 35 ⁇ m.
  • the head heating temperature during ink jet printing is 45 ° C.
  • the applied voltage is 11.5 V
  • the pulse width is 10.0 ⁇ s
  • the drive frequency is 3483 Hz
  • the ink droplet volume is 42 pl
  • the resolution is 360 dpi
  • the ink application amount is 8.4 g. It printed so that it might become / m ⁇ 2 > (amount that an ink layer should be formed without a gap).
  • UV irradiation For coating materials after inkjet printing, using a high-pressure mercury lamp (H bulb; Fusion UV Systems Japan Co., Ltd.), with a lamp output of 200 W / cm, integrated light amount: 600 mJ / cm 2 (infrared light meter) UV-351-25; measured by Oak Manufacturing Co., Ltd.). After inkjet printing, the ambient temperature (air temperature) and humidity of the coating material were adjusted as appropriate during irradiation with ultraviolet rays.
  • H bulb Fusion UV Systems Japan Co., Ltd.
  • the temperature was controlled using an air conditioner.
  • the humidity was controlled by dehumidifying with a desiccant dehumidifier (dry save (registered trademark) R-060BP type; Seibu Giken Co., Ltd.) or by humidifying with a PTC steam humidifier (Humidas; Yucan Co., Ltd.).
  • the temperature and humidity were measured using a humidity indicator HMI41 (Vaisala Co., Ltd.) equipped with a temperature / humidity probe HMP46.
  • UV ink layer was rubbed 100 times with 1 cm ⁇ 1 cm absorbent cotton containing 99% ethanol solution against the printing material, and the appearance of the UV ink layer was visually observed. It was evaluated by. If the appearance of the UV ink layer does not change, it is evaluated as “ ⁇ ”, and if it is glossy, it is evaluated as “ ⁇ ”. The UV ink layer dissolves to the substrate, and the exposed area of the substrate is 0%. Those exceeding 20% and less than 20% were evaluated as “ ⁇ ”, and those having a substrate exposure exceeding 20% were evaluated as “x”. If the evaluation of the adhesion of the UV ink layer is ⁇ or more, it is practical.
  • FIG. 2 is a graph in which the evaluation results in Table 1 are plotted, and is a graph showing the relationship between the absolute humidity VH and temperature T and the ink adhesion.
  • the relationship between absolute humidity VH and temperature T during irradiation with ultraviolet rays was T ⁇ 6 VH-103 or T> 10 VH-5.
  • the printing materials of 25 to 29 were inferior in either adhesion or curability.
  • the relationship between the absolute humidity VH and the temperature T during the irradiation with ultraviolet rays satisfies the conditions of 6VH ⁇ 103 ⁇ T ⁇ 10VH-5 and 15 ⁇ T ⁇ 40.
  • the adhesiveness and curability were within the practical range.
  • the absolute humidity VH during irradiation with ultraviolet rays was within the range of 4.2 ⁇ VH ⁇ 19.8, the adhesion and curability were good.
  • the absolute humidity VH during irradiation with ultraviolet rays is in the range of 4.5 ⁇ VH ⁇ 9.9, and no.
  • the printing materials of 2, 4, 6 to 8, 16, 19, and 24 had particularly good adhesion and curability.
  • Example 2 In Example 2, about 20 seconds after the end of irradiation with ultraviolet rays, an automatic discharge dryer (AT0-101 type; Tojo Thermal Co., Ltd.) was used for 5 minutes at a furnace temperature of 50 ° C. or 145 ° C. No. in Example 1 except that post-heating treatment was performed. In the same manner as the printing materials 1 to 4, 6 to 12, 14 to 19, and 21 to 29, no. 30 to 81 printing materials were obtained. Further, in the same manner as in Example 1, evaluation of the ink layer, evaluation of adhesion, evaluation of curability, and comprehensive evaluation were performed.
  • AT0-101 type Tojo Thermal Co., Ltd.
  • Table 2 shows the printing material No. when the post-heating temperature is 50 ° C. Absolute humidity, temperature, relative humidity and various evaluation results are shown.
  • Table 3 shows the printing material No. when the post-heating temperature is 145 ° C. Absolute humidity, temperature, relative humidity and various evaluation results are shown.
  • FIG. 3 is a graph in which the evaluation results in Table 2 are plotted
  • FIG. 4 is a graph in which the evaluation results in Table 3 are plotted.
  • 3 and 4 are graphs showing the relationship between the absolute humidity VH and temperature T and the ink adhesion.
  • the printing material with a post-heating treatment temperature of 70 ° C. has a better evaluation result than the printing material with a post-heating treatment temperature of 50 ° C. This is considered because the ink layer is cured without absorbing moisture in the air.
  • a comparison between a printing material with a post-heating treatment temperature of 70 ° C. and a printing material with a post-heating treatment temperature of 145 ° C. shows a large difference in evaluation results even when the post-heating treatment temperature exceeds 70 ° C. Was not seen.
  • the printing material heated to a temperature of 150 ° C. or higher after the post-heating treatment has a defective product shape due to thermal strain, or the adhesion of the ink layer is lowered.
  • the method for producing a printing material of the present invention can produce a printing material excellent in adhesion and curability of actinic ray curable cationic polymerizable ink.
  • the printing material produced by the method for producing a printing material of the present invention is excellent in the adhesion and curability of the cured product of the actinic ray curable cationic polymerizable ink, and is useful, for example, as an interior material and an outer wall material of a building. is there.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Architecture (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

Selon la présente invention, un substrat qui est un substrat métallique ou un substrat céramique est préparé. Une composition de résine est appliquée sur le substrat et une couche de réception d'encre est formée. Une encre polymérisable par voie cationique durcissable par rayonnement actif est appliquée sur la couche de réception d'encre et une couche d'encre est formée. L'encre polymérisable par voie cationique durcissable par rayonnement actif contient un composé polymérisable par voie cationique, de 0,5 à 10 % en masse d'un agent de couplage au silane contenant de l'époxy, de 10 à 50 % en masse d'un composé d'oxétane contenant un groupe hydroxyle, et un initiateur de photopolymérisation. L'humidité absolue VH (g/m3) et la température de l'air T (°C) tout en irradiant avec des rayons actifs afin de durcir l'encre polymérisable par voie cationique durcissable par rayonnement actif satisfont 6VH - 103 ≤ T ≤ 10VH - 5 et 15 ≤ T ≤ 40.
PCT/JP2017/018155 2016-05-16 2017-05-15 Procédé de production de matériau d'impression WO2017199896A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006037021A (ja) * 2004-07-29 2006-02-09 Toshiba Tec Corp インクジェットインク、印刷物、およびインクジェット印字方法
JP2008248071A (ja) * 2007-03-30 2008-10-16 Fujifilm Corp インクジェット記録用インクセット及びインクジェット記録方法
JP2011195731A (ja) * 2010-03-19 2011-10-06 Fujifilm Corp 硬化膜及び硬化膜の形成方法
JP2012116933A (ja) * 2010-11-30 2012-06-21 Seiko Epson Corp 紫外線硬化型インクジェット用インク組成物、記録物、及びインクジェット記録方法
WO2013190913A1 (fr) * 2012-06-19 2013-12-27 ナトコ 株式会社 Composition durcissable par rayons à énergie active, produit durci et son utilisation
WO2015053164A1 (fr) * 2013-10-07 2015-04-16 東京インキ株式会社 Encre à polymérisation photocationique pour impression au jet d'encre, son procédé de production, article imprimé et son procédé de production
WO2015092976A1 (fr) * 2013-12-18 2015-06-25 日新製鋼株式会社 Matériau d'impression
JP2016199034A (ja) * 2015-04-09 2016-12-01 日新製鋼株式会社 印刷材の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006037021A (ja) * 2004-07-29 2006-02-09 Toshiba Tec Corp インクジェットインク、印刷物、およびインクジェット印字方法
JP2008248071A (ja) * 2007-03-30 2008-10-16 Fujifilm Corp インクジェット記録用インクセット及びインクジェット記録方法
JP2011195731A (ja) * 2010-03-19 2011-10-06 Fujifilm Corp 硬化膜及び硬化膜の形成方法
JP2012116933A (ja) * 2010-11-30 2012-06-21 Seiko Epson Corp 紫外線硬化型インクジェット用インク組成物、記録物、及びインクジェット記録方法
WO2013190913A1 (fr) * 2012-06-19 2013-12-27 ナトコ 株式会社 Composition durcissable par rayons à énergie active, produit durci et son utilisation
WO2015053164A1 (fr) * 2013-10-07 2015-04-16 東京インキ株式会社 Encre à polymérisation photocationique pour impression au jet d'encre, son procédé de production, article imprimé et son procédé de production
WO2015092976A1 (fr) * 2013-12-18 2015-06-25 日新製鋼株式会社 Matériau d'impression
JP2016199034A (ja) * 2015-04-09 2016-12-01 日新製鋼株式会社 印刷材の製造方法

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