Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
• • 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
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

• the present invention relates to a laminate, and more particularly, to a laminate for forming an active energy ray-curable coloring liquid on a substrate surface and curing it by an inkjet method or the like, a method for manufacturing the laminate, and the like.
• inkjet printing is becoming popular as a suitable printing method because good images can be obtained at high speed and its application is wide.
• an ink jet printer for ink-absorbing recording media such as plain paper (hereinafter sometimes referred to as a water-absorbing substrate) or an ink non-water-absorbing recording medium such as plastic (hereinafter also referred to as a non-water-absorbing substrate).
• a water-absorbing substrate plain paper
• an ink non-water-absorbing recording medium such as plastic
• the fixability varies depending on the type of the substrate, and thus the adhesion between the substrate and the colored layer may be insufficient.
• problems such as peeling of images formed on the non-absorbing substrate, scratching, etc. in addition to problems such as image bleeding. It was.
• the base material As a means to improve the adhesion between the base material and the colored layer, it is possible to subject the base material to corona treatment, flame treatment, etc., but equipment to perform these pretreatments at the site where actual ink jet printing operations are performed Is not in place.
• a primer layer imparting a tack feeling between the base material and the colored layer.
• the tackiness of the primer layer can improve the adhesion to the colored layer.
• the effect of improving the adhesion varies depending on the type of base material used. If the base material is a water-absorbing base material, the solvent in the primer composition forming the primer layer penetrates, so that the adhesion is high. Further, even if the base material is a non-water-absorbing base material, if the base material is a plastic base material, the surface of the plastic base material is caused by minute melting, swelling, etc. with a solvent in the primer composition (hereinafter referred to as a solvent attack). The adhesion can be improved.
• the base material is a non-water-absorbing base material such as a glass base material
• action which improves adhesiveness changes with the base materials to be used, it is common to use a different primer composition for improving adhesiveness for every base material to be used.
• the undercoat solution using a fixed proportion of three components consisting of phenoxyethyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, and bifunctional urethane (meth) acrylate is an absorbent substrate such as plain paper, or plastic or glass
• an undercoat layer (primer layer) that improves the adhesion to a non-absorbent substrate such as (Patent Document 1).
• the undercoat layer (primer layer) formed by the undercoat liquid described in Patent Document 1 does not require any pretreatment on the base material, and is made of a thermosetting plastic, a thermoplastic plastic, a ceramic, glass, a metal plate, or the like. Adhesiveness to various substrates such as a non-absorbent substrate and an absorbent substrate is excellent.
• the undercoat layer (primer layer) described in Patent Document 1 is an excellent undercoat layer (primer layer) that can improve adhesion to various types of substrates.
• the undercoat layer (primer layer) described in Patent Document 1 has a tackiness to improve adhesion, but is formed when a colored layer is formed on the above-described undercoat layer (primer layer). After a certain period of time, a tackiness (adhesion feeling) emerged on the surface of the colored layer.
• Such an under-tacking layer (primer layer) is not preferable in that it needs to be handled with care because dust or the like in the air tends to be attached due to the tactile sensation that appears.
• the undercoating liquid described in Patent Document 1 contains phenoxyethyl (meth) acrylate, which has a slow curing property, and phenoxyethyl (meth) acrylate is contained in the composition in an amount of 40% by mass to 80% by mass. This is because it is added in a large amount as follows.
• the present invention has been made in view of the above circumstances, and when using a water-absorbing substrate such as plain paper or a non-water-absorbing substrate such as plastic as a recording medium, it has good adhesion to the colored layer. It aims at providing the laminated body with low property and tackiness.
• the present inventors have conducted intensive research.
• the phenoxyalkyl (meth) acrylate content is 1% by mass or more and 30% by mass or less
• the arithmetic average roughness of the surface of the laminate on the primer layer lamination side is as follows.
• the present inventors have found that the above-mentioned problems can be solved by using a laminate having a thickness Ra of 0.8 ⁇ m or more, and have completed the present invention.
• the present invention provides the following.
• a laminate including a substrate and a primer layer formed directly or via another layer on the substrate, wherein the primer layer is provided on the outermost layer of the laminate.
• the primer layer is obtained by curing a primer composition containing a compound having an ethylenically unsaturated group, and as the compound having an ethylenically unsaturated group, component A): a phenoxy group which may have a substituent A phenoxyalkyl (meth) acrylate having an alkylene group having 1 to 5 carbon atoms, B component): (meth) acrylate having an alicyclic structure, C component): aromatic other than A component) (Meth) acrylate having a ring, component D): (meth) acrylate having a hydroxyl group other than component A), component B) and component C)), and component D ), B component) and / or C component), and in the total amount of the primer composition, the A component) is 1% by mass to 30% by mass, and the B component) is 30% by
• the C component is 1% by mass or more and 15% by mass or less
• the D component is 1% by mass or more and 30% by mass or less
• the arithmetic average roughness Ra of the surface of the laminate on the primer layer lamination side is 0.
• component E) a monofunctional monomer having a Tg of ⁇ 30 ° C. or less, component A), component B), component C), and component D
• the laminate according to (1), which contains an alkyl (meth) acrylate other than), and the E component) in the total amount of the primer composition is 1% by mass or more and 10% by mass or less.
• a laminate with a colored layer in which a color layer containing a colorant is further provided on the surface of the laminate on the primer layer laminate side of the laminate according to any one of (1) to (5).
• a primer composition for forming the laminate according to any one of (1) to (5) is a primer composition for forming the laminate according to any one of (1) to (5).
• a compound having an ethylenically unsaturated group contained in the primer composition at least a phenoxy group having an optionally substituted phenoxy group and an alkylene group having 1 to 5 carbon atoms
• a component which is a meth) acrylate is 1% by mass to 30% by mass in the total amount of the primer composition
• a B component which is a (meth) acrylate having an alicyclic structure is 30% by mass to 70% by mass in the total amount of the primer composition.
• the component C) which is a (meth) acrylate having an aromatic ring other than the component A) is 1% by mass to 15% by mass in the total amount of the primer composition, the component A), the component B) and the component C.
• An undercoat liquid application step of applying directly or via another layer on the substrate, and irradiating active energy rays to the undercoat liquid applied directly or via the other layer on the substrate to the undercoat liquid A primer layer forming step of curing a primer composition contained therein to form a primer layer on the outermost layer, and a laminate having an arithmetic average roughness Ra of 0.8 ⁇ m or more on the surface of the laminate on the primer layer laminate side Manufacturing method.
• a coloring liquid further containing a colorant and a compound having an ethylenically unsaturated group is added to the lamination side of the primer layer.
• a compound having an ethylenically unsaturated group contained in the primer composition at least a phenoxy group having an optionally substituted phenoxy group and an alkylene group having 1 to 5 carbon atoms
• a component which is a meth) acrylate is 1% by mass to 30% by mass in the total amount of the primer composition
• a B component which is a (meth) acrylate having an alicyclic structure is 30% by mass to 70% by mass in the total amount of the primer composition.
• the component C) which is a (meth) acrylate having an aromatic ring other than the component A) is 1% by mass to 15% by mass in the total amount of the primer composition, the component A), the component B) and the component C.
• An ink recording method comprising:
• the laminate including the base material and the predetermined primer layer formed on the base material has excellent adhesion to the colored layer, and can reduce the tackiness, so that the air
• An excellent laminate that is easy to handle can be provided because it is difficult for dust and the like to adhere to the inside.
• the laminate of the present embodiment includes a base material and a primer layer formed on the base material directly or via another layer. This will be described below.
• the laminated body of this embodiment means the laminated body with which the outermost layer was equipped with the primer layer unless there is particular description.
• the base material that can be used in the laminate of the present embodiment is not particularly limited, and a base material made of an organic material and a base material made of an inorganic material can be used.
• a base material made of an organic material for example, a rubber base material and a plastic base material can be used.
• rubber base materials include acrylonitrile / butadiene / styrene rubber (ABS), thermoplastic polyurethane (TPU), natural rubber (NR), styrene / butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber ( BR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), butyl rubber (isobutylene-isoprene rubber (IIR)), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), urethane rubber (U) , Silicone rubber (Si rubber), fluoro rubber (FKM), styrene thermoplastic elastomer, olefin thermoplastic elastomer, ester thermoplastic elastomer, urethane thermoplastic elastomer, amide thermoplastic elastomer, PVC thermoplastic Elastomer, fluorine thermoplastic elastomers
• plastic base materials include polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene (AS), polymethyl meta Acrylic (PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), polyamide (PA), polyacetal (POM), polycarbonate (PC), polyphenylene ether (PPE (modified PPO)), Polybutylene terephthalate (PBT), ultrahigh molecular weight polyethylene (U-PE), polyvinylidene fluoride (PVDF), polysulfone (PSF), polyethersulfone (PES), polyphenylenesulfur Id (PPS), Polyarylate (PAR), Polyamideimide (PAI), Polyetherimide (PEI), Polyetheretherketone (PEEK), Polyimide (PI
• Examples of the base material made of an inorganic material include a metal base material and a glass base material.
• Examples of the metal base material include steel, stainless steel, aluminum, nickel, magnesium, copper, zinc, tin, titanium, an alloy material in which two or more of these are mixed, and a material obtained by plating them.
• Examples of the glass-based substrate include silicate glass (including quartz glass), and glass mainly containing other than silicate.
• the primer layer used in the laminate of the present embodiment is optimized for the concentration and type of the compound having an ethylenically unsaturated group used for the formation thereof, the primer layer can be used with any substrate. High adhesion can be achieved.
• the primer layer is formed directly on the substrate or via another layer, and is provided on the outermost layer of the laminate to improve the adhesion with the colored layer.
• Forming directly or via other layers on the substrate means that the primer composition is cured directly on the substrate to form a primer layer, or that the substrate is coated with other resins or metals, etc.
• the primer composition is cured through another layer formed by the step of forming a primer layer.
• the primer layer used in the laminate of this embodiment is formed by curing a compound having an ethylenically unsaturated group.
• B component) (Meth) acrylate having an alicyclic structure other than A component) is 30% by mass to 70% by mass in the total amount of all primer compositions
• the (meth) acrylate having a ring has a hydroxyl group other than 1% by mass to 15% by mass in the total amount of the primer composition (component D): component A), component B) and component C) (meth).
• the acrylate contains at least component A), component D), component B) and / or component C) in the total amount of the primer composition of 1% by mass to 30% by mass.
• alkyl (meth) acrylates other than E component) monofunctional monomer having Tg of ⁇ 30 ° C. or less and other than A component), B component), C component), and D component
• E component monofunctional monomer having Tg of ⁇ 30 ° C. or less and other than A component), B component), C component), and D component
• F component): A component), B component), C component), D component), and E component) in the total composition 1 mass% or more and 20 mass% or less may be contained in the composition whole quantity.
• the primer layer used in the laminate of the present embodiment is irradiated with active energy rays after applying an undercoat liquid containing a primer composition containing a compound having an ethylenically unsaturated group to the surface of the substrate.
• the compound having an ethylenically unsaturated group as the primer composition is cured and formed.
• the arithmetic average roughness Ra of the laminate surface on the primer layer laminate side is 0.8 ⁇ m or more, preferably 1.0 ⁇ m or more, more preferably 1.2 ⁇ m or more. .
• arithmetic mean roughness Ra in this specification is a value measured based on arithmetic mean roughness (Ra) prescribed
• the thickness of the primer layer used in the laminate of the present embodiment is preferably 5 ⁇ m or more and 20 ⁇ m or less, more preferably 6 ⁇ m or more and 15 ⁇ m or less, further preferably 7 ⁇ m or more and 10 ⁇ m or less, and 7 ⁇ m or more and 8. More preferably, it is 5 ⁇ m or less. It is preferable that the thickness of the primer layer be 5 ⁇ m or more and 20 ⁇ m or less because the adhesion with the colored layer is improved and the primer layer is less likely to be cracked or scratched.
• the thickness of the primer layer can be controlled by the amount of the undercoat liquid applied onto the substrate.
• the thickness of a primer layer means the distance of a base material and the maximum vertex of a primer layer.
• the thickness of the primer layer can be calculated as a value when measured with a needle pressure of 1 mg and a measurement length of 1.7 mm using, for example, P-16 manufactured by tencor. Specifically, when the primer layer is partially laminated in the form of dots instead of the entire surface of the laminate, that is, when the surface of the substrate layer is exposed, the exposed portion of the substrate becomes the measurement length.
• the value when measured to be included is the thickness of the primer layer, and if the surface of the base material is not covered and exposed by the primer layer, the surface of the base material is exposed by scraping the primer layer, etc.
• the value obtained by measuring the exposed surface to be included in the measurement length can be calculated as the thickness of the primer layer.
• the coating amount of the undercoat liquid onto a substrate is that it 0.1 mg / cm 2 or more 1.2 mg / cm 2 or less is preferable, 0.2 mg / cm 2 or more 1.0 mg / cm 2 or less More preferably, it is more preferably 0.3 mg / cm 2 or more and 0.8 mg / cm 2 or less. It may be preferred adhesion between the primer layer and the colored layer by the coating amount of the undercoat liquid and 0.1 mg / cm 2 or more 1.2 mg / cm 2 or less.
• the glass transition temperature (Tg) of the primer layer used in the laminate of the present embodiment is preferably 5 ° C. or higher and 35 ° C. or lower, and more preferably 10 ° C. or higher and 30 ° C. or lower.
• the primer layer can have preferable adhesiveness (tackiness) and adhesion.
• the glass transition temperature (Tg) of the primer layer can be prepared by selecting a compound having an ethylenically unsaturated group, which will be described later.
• the said glass transition temperature (Tg) can be calculated
• the penetration calculated as 1 when the distance that the needle has entered the sample is 1/10 mm is 17 to 30 Preferably, it is 19 or more and 29 or less, more preferably 20 or more and 26 or less.
• the primer layer can be provided with appropriate flexibility. Therefore, since the primer layer can be kept soft even in a low temperature or high temperature environment, cracking of the primer layer can be suppressed.
• the peel strength between the base material and the primer layer can be evaluated by, for example, evaluation of adhesive tape adhesion after cross-cutting according to ASTM D3359.
• the cured coating film is cross-cut into 100 squares at 1 mm intervals, a cellophane adhesive tape is attached to the cross-cut portion, and then the cellophane adhesive tape is peeled off at 90 degrees. If the degree of peeling is less than 5%, the adhesion between the substrate and the primer layer can be considered sufficient.
• the peel strength of the primer layer can be prepared by selecting a compound having an ethylenically unsaturated group, which will be described later.
• the primer layer of this embodiment is formed by curing a primer composition containing a compound having an ethylenically unsaturated group.
• the primer composition means the entire solid composition excluding the solvent component contained in the undercoat liquid, such as a compound having an ethylenically unsaturated group, a photopolymerization initiator, or a photopolymerization inhibitor contained in the undercoat liquid.
• the compound having an ethylenically unsaturated group includes at least a predetermined amount of component A), component D), component B) and / or component C). If necessary, a predetermined amount of E component) or F component) may be included.
• a component is a phenoxyalkyl (meth) acrylate having 1 to 5 carbon atoms. Phenoxyethyl (meth) acrylate exhibits an effect of improving adhesion to a non-absorbent substrate such as polycarbonate after curing. From the viewpoint of tackiness, those with low tackiness are preferred. From this point of view, phenoxyethyl (meth) acrylate is contained in the total amount of the primer composition in an amount of 1% by mass to 30% by mass, preferably 3% by mass to 28% by mass, and most preferably 5% by mass to 20% by mass. Blend as follows. The phenoxyethyl (meth) acrylate may be phenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate containing a substituent, or each modified one.
• EO modified means having a block structure of ethylene oxide units (—CH 2 —CH 2 —O—)
• PO modified means propylene oxide units (—CH 2 —CH (CH 3 ) -O-).
• (B component) is (meth) acrylate which has an alicyclic structure. Since it has an alicyclic structure, for example, the surface of a rubber-based substrate or a plastic-based substrate is likely to be eroded, and the adhesiveness with the substrate is improved after curing.
• Examples of the (meth) acrylate having an alicyclic structure include (meth) acrylate having an alicyclic structure which is a monofunctional monomer.
• Component B) from the viewpoint of adhesion of the base material and the colored layer is 30% by mass to 70% by mass, preferably 35% by mass to 60% by mass, and most preferably 43% by mass to 55% in the total amount of the primer composition. It is contained in mass% or less.
• B component is, for example, a monofunctional monomer such as tertiary butyl cyclohexyl (meth) acrylate, isobornyl acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyloxyethyl acrylate Dimethylol-tricyclodecane diacrylate, 1-adamantyl acrylate, cyclohexyl acrylate, 3-3-5-trimethylcyclohexanol acrylate, and the like.
• 4-tertiary butyl cyclohexyl (meth) acrylate and isobornyl acrylate are preferably used because of their ease of production.
• B component includes bifunctional monomers such as cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane dimethacrylate, tricyclodecane dimethanol diacrylate, etc. Can do.
• B component is a 2 or more types compound, Comprising: Tg differs, respectively.
• Tg differs, respectively.
• the two or more compounds preferably have Tg of 20 ° C. or more apart from each other, more preferably 40 ° C. or more.
• C component is a (meth) acrylate having an aromatic ring other than A component). Since it has an aromatic ring structure, for example, the surface of a rubber-based substrate or a plastic-based substrate is likely to be eroded, and the adhesiveness to the substrate is improved after curing. From the viewpoint of adhesion of the base material and the colored layer, component C) is 1% by mass to 15% by mass, preferably 3% by mass to 13% by mass, and most preferably 7% by mass to 12% in the total amount of the primer composition. It is contained in mass% or less.
• component (C) examples include benzyl (meth) acrylate, triloxyethyl (meth) acrylate, triloxypropyl (meth) acrylate, triloxypolyethylene glycol (meth) acrylate, triloxypolypropylene glycol (meth) acrylate, (meth) ) Acryloyloxyethyl phthalate, (meth) acryloyloxyethyl hydroxyphthalate, (meth) acryloyloxypropyl phthalate, neopentyl glycol benzoate (meth) acrylate, phenyl (meth) acrylate, p-cumylphenyl (meth) acrylate, o -Aromatic monofunctional (meth) acrylates such as phenylphenyl (meth) acrylate, m-phenylphenyl (meth) acrylate, p-phenylphenyl (meth) acrylate,
• D component is a (meth) acrylate having a hydroxyl group other than A component), B component) and C component). Since component D) has a hydroxyl group, it has a function of forming a hydrogen bond with a substrate made of an inorganic material such as a metal-based substrate and improving adhesion with the substrate after curing. From the viewpoint of adhesion of the base material and the colored layer, component D) is 1% by mass to 30% by mass, preferably 5% by mass to 20% by mass, and most preferably 7% by mass to 15% in the total amount of the primer composition. It is contained in mass% or less.
• component D) examples include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl -Phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-hydroxy-3-acryloyloxypropyl methacrylate and the like.
• 2-hydroxy-3-phenoxypropyl (meth) acrylate is particularly preferably used.
• a compound having a carboxyl group also forms a hydrogen bond with a base material made of an inorganic material such as a metal-based base material. Therefore, an improvement in adhesion to a base material made of an inorganic material can be expected. it can.
• the D component) is a (meth) acrylate having no carboxyl group, and has a hydroxyl group other than the A component), the B component) and the C component). A (meth) acrylate is preferred.
• E component is a monofunctional monomer having a Tg of ⁇ 30 ° C. or lower, and is an alkyl (meth) acrylate other than A component), B component), C component), and D component). Since Tg is ⁇ 30 ° C. or lower, it has a certain degree of tackiness even after curing of the compound having an ethylenically unsaturated group.
• the component (E) preferably has a Tg of ⁇ 40 ° C. or less, and most preferably has a Tg of ⁇ 50 ° C. or less. The tackiness improves adhesion between the primer layer and the base material, and the primer layer and the colored layer.
• E component is contained in the total amount of the primer composition in an amount of 1% by mass to 10% by mass.
• the content is preferably 2% by mass or more and 7% by mass or less, and most preferably 3% by mass or more and 6% by mass or less.
• Examples of (E component) include tridecyl acrylate, lauryl acrylate, tetraethylene glycol diacrylate, and the like. Among these, it is particularly preferable to use tridecyl acrylate.
• F component is a polyfunctional aliphatic urethane (meth) acrylate oligomer other than A component), B component), C component), D component), and E component).
• F component) is an oligomer having an action of exhibiting tackiness after curing and improving adhesion.
• F component) preferably contains a bifunctional aliphatic urethane (meth) acrylate oligomer.
• (F component) can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol with polyisocyanate with (meth) acrylic acid.
• the polyfunctional aliphatic urethane (meth) acrylate that can be obtained on the market may be a conventionally known bifunctional or trifunctional or higher functional aliphatic urethane (meth) acrylate, for example, manufactured by Nippon Synthetic Chemical Co., Ltd.
• Product name “purple light UV-3000B” hereinafter abbreviated) “UV-3200B”, “UV-3201B”, “UV-3310B”, “UV-3500B”, “UV-3520TL”, “ “UV-3700B”, “UV-6100B”, “UV-6640B”, “UV-2000B”, “UV-2250EA”, “UV-2750B”; trade name “Aronix M1100” manufactured by Toagosei Co., Ltd.
• the undercoat liquid used in this embodiment may have an adverse effect on the inkjet printer head due to the carboxyl group-containing (meth) acrylate, and is therefore 5% by mass or less based on the total amount of the primer composition. Is preferable, and it is more preferable that it is 1 mass% or less, and it is most preferable not to contain it at all. By doing so, it can be used widely regardless of the material of the printer head.
• a photopolymerization initiator For the formation of the primer layer used in the laminate of the present embodiment, a photopolymerization initiator can be used as necessary.
• the photopolymerization initiator that can be used for forming the primer layer receives an active energy ray such as an electron beam, ultraviolet ray, or infrared ray, generates a radical, and becomes an initiator for polymerization of a compound having an ethylenically unsaturated group. It can be.
• an active energy ray such as an electron beam, ultraviolet ray, or infrared ray
• the photopolymerization initiator acylphosphine oxide, ⁇ -hydroxyketone, ⁇ -aminoalkylphenone, oxime ester, and the like can be used.
• acylphosphine oxide examples include bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide (Irgacure 819, manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl.
• -Pentylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAIDO UV-CURE APO: manufactured by Daido Kasei Co., Ltd.) and the like are exemplified, among them 2,4,6-trimethyl Benzoyl-diphenyl-phosphine oxide (DAIDO UV-CURE APO) is preferred.
• ⁇ -hydroxyketone examples include 1-hydroxy-cyclohexyl phenyl ketone (Irgacure 184, manufactured by BASF), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -Phenyl ⁇ -2-methyl-propan-1-one (Irgacure 127, manufactured by BASF), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (Irgacure 2959, manufactured by BASF), oligo [2 -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] (Esacure one, Lamberti) is preferred.
• Irgacure 184 1-hydroxy-cyclohexyl phenyl ketone
• ⁇ -aminoalkylphenone 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369, manufactured by BASF) is preferable.
• the oxime ester is preferably 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime).
• the above-mentioned DAIDO UV-CURE APO and Irgacure 127 are particularly effective for the curability of a thin film formed by ink jet because they are less likely to inhibit polymerization by oxygen.
• the above-mentioned DAIDO UV-CURE APO, Irgacure 2959, and Irgacure 369 are particularly effective for curing with a thick film because they have excellent internal curability.
• DAIDO UV-CURE APO reacts with active energy rays with high sensitivity.
• acylphosphine oxide ⁇ -hydroxyketone
• ⁇ -aminoalkylphenone it has excellent curability for both thin and thick films, and is highly sensitive to active energy rays and cures in a short time. Can be made.
• the addition amount of the photopolymerization initiator is preferably 3% by mass or more and 15% by mass or less based on the total amount of all the primer compositions, and the curability can be maintained by being within this range.
• the primer composition may contain various additives such as a plasticizer, a non-radioactive resin, a solvent, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, and an antioxidant.
• a coloring material as needed, for example, organic / inorganic fine particles, silica, titanium oxide, an aluminum paste, mica, a pearl pigment, etc. can be mix
• the compound having a carboxyl group may adversely affect the printer head, and therefore it is preferably 5% by mass or less and preferably 1% by mass or less in the total amount of the primer composition. More preferably, it is most preferable not to contain at all. By doing so, it can be used widely regardless of the material of the printer head.
• the primer composition can be prepared by, for example, preparing an undercoat liquid containing the above-described blending components and dispersing it using a normal dispersing machine such as a sand mill.
• the undercoat liquid is preferably filtered through a filter having a pore size of 3 ⁇ m or less, more preferably 1 ⁇ m or less.
• the laminate of the present embodiment includes, for example, an undercoat liquid application step in which an undercoat liquid containing a compound having an ethylenically unsaturated group is applied directly on the substrate or via another layer, and directly or on the substrate.
• the primer layer can be manufactured by irradiating an undercoat liquid applied through another layer with an active energy ray and curing the primer composition contained in the undercoat liquid to form a primer layer. .
• the undercoat liquid application step is a step of applying the undercoat liquid containing the primer composition directly on the substrate or through another layer.
• the undercoat liquid may contain a photopolymerization initiator as necessary.
• the method for applying the undercoat liquid directly on the substrate or through another layer is not particularly limited, but in practice one or two selected from a spray method, a coater method, an ink jet method, a gravure method, a flexo method, etc. It is preferable that it is a seed or more.
• the undercoat liquid can also be applied with a coating apparatus attached to the paper machine.
• the ink jet method can apply only the required amount of the undercoat liquid, and by adjusting the amount of the ink jet undercoat liquid applied, the arithmetic average of the surface of the laminate on the primer layer lamination side after the primer composition is cured Since roughness Ra can be adjusted, it is more preferable.
• the primer layer forming step is a step of forming a primer layer by irradiating an active energy ray to an undercoat liquid applied directly on a substrate or via another layer to cure a primer composition contained in the undercoat liquid. It is.
• the primer layer is formed on the surface so that the arithmetic average roughness Ra of the surface on the primer lamination side is 0.8 ⁇ m or more, preferably 1.0 ⁇ m or more, more preferably 1.2 ⁇ m or more.
• the light source of the active energy ray for example, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, sunlight, an LED (Light Emitting Diode) lamp, or the like can be used.
• a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, sunlight, an LED (Light Emitting Diode) lamp, or the like can be used.
• curing with an electron beam curing is usually performed with an electron beam having an energy of 300 eV or less, but it is also possible to cure instantaneously with an irradiation dose of 1 to 5 Mrad.
• the phenoxyalkyl (meth) acrylate having 1 to 5 carbon atoms which is a compound having an ethylenically unsaturated group used in the present embodiment, is 1% by mass to 30% by mass in the total amount of all primer compositions.
• its content is low. For this reason, sufficient curability can be obtained even if it is not a high output light source such as a metal halide lamp but a low output light source such as an LED lamp. Therefore, the laminate in which the primer layer of the present embodiment is provided as the outermost layer is particularly excellent from the viewpoint of productivity.
• a colorant and an ethylenically unsaturated compound are formed as a composition on the side of the primer layer formed by the primer layer forming step.
• a coloring liquid application process is a process of apply
• a conventionally known coloring liquid can be used.
• active energy ray-curable coloring including a coloring agent, a compound having an ethylenically unsaturated group, and a photopolymerization initiator as necessary.
• a liquid can be used.
• the compound having an ethylenically unsaturated group a conventionally known compound having an ethylenically unsaturated group can be used.
• component B) and / or component C is component B used in the undercoat liquid) and It is preferable to use the same as the C component.
• the B component) and / or C component exhibits affinity with the primer layer, which is a cured product of the B component) and / or C component contained in the undercoat liquid, and improves the fixability and adhesion of the colored layer.
• the compound containing an ethylenically unsaturated group contains 60 to 95 mass% of monofunctional monomers in the compound containing all the ethylenically unsaturated groups.
• the A component is 10% by mass to 35% by mass (preferably 15% by mass to 30% by mass)
• the F component is 1% by mass to 10% by mass (preferably 3% by mass to 7% by mass). (Mass% or less) may be contained.
• colorant inorganic pigments or organic pigments usually used in conventional oil-based ink compositions can be used. Carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, titanium oxide, pearl pigments, aluminum, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, di Ketopyrrolopyrrole, anthraquinone, benzimidazolone, anthrapyrimidine, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, dioxazine pigment, selenium pigment, perylene pigment, perinone pigment, thioindigo A pigment, a quinophthalone pigment, a metal complex pigment, or the like can be used.
• the volume average particle diameter of the primary pigment particles is preferably a fine pigment having an average particle diameter of 50 nm to 200 nm as measured by laser scattering.
• the average particle diameter of the pigment is 50 nm or more, the light resistance is improved by increasing the particle diameter.
• the average particle diameter is 200 nm or less, the dispersion is stably maintained and precipitation of the pigment can be suppressed.
• the content of the colorant is preferably 0.5% by mass or more and 25% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and further preferably 1% by mass or more and 10% by mass in the coloring liquid. It is as follows.
• dispersant it is preferable to add a dispersant to the coloring liquid, and it is preferable to use a polymer dispersant as the dispersant.
• the polymer dispersant for example, the main chain is made of polyester, polyacryl, polyurethane, polyamine, polycaprolactone, etc., and the side chain is a polar group such as amino group, carboxyl group, sulfone group, hydroxyl group, etc.
• a polyester-based dispersant such as “SOLSPERSE 32000”, “SOLSPERSE 20000”, “SOLSPERSE 24000”, “SOLSPERSE 71000” manufactured by Lubrizol, “Ajispur PB821”, “Ajispar PB822” manufactured by Ajinomoto Fine-Techno Co., Ltd. Illustrated.
• the addition amount of the dispersant is preferably 0.03 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass or less as a solid content with respect to 1 part by mass of the colorant.
• they are 0.1 mass% or more and 30 mass% or less, More preferably, they are 0.5 mass% or more and 20 mass% or less.
• additives such as a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, and an antioxidant can be contained.
• the coloring liquid that can be used in the present invention is obtained by, for example, dispersing the coloring agent well with a compound having an ethylenically unsaturated group and a dispersing agent using a normal dispersing machine such as a sand mill to obtain a dispersion. It can prepare by adding the compound which has an ethylenically unsaturated group to a liquid, and a photoinitiator as needed, and mixing uniformly. It is preferable to prepare a concentrated solution with a high concentration of colorant in advance and dilute with a compound having an ethylenically unsaturated group.
• a colored liquid is prepared.
• the coloring liquid is preferably filtered through a filter having a pore size of 3 ⁇ m or less, more preferably 1 ⁇ m or less.
• the viscosity at 40 ° C. is preferably 5 mPa ⁇ s or more and 20 mPa ⁇ s or less.
• the viscosity is 5 mPa ⁇ s or more
• improvement in the followability of the discharge is recognized in the high-frequency head, and when it is 20 mPa ⁇ s or less, the discharge itself is improved by incorporating a mechanism for reducing the viscosity by heating into the head.
• the discharge becomes stable and the discharge becomes easy. Yellow, cyan, magenta, black pigments and the like are blended in the colored liquid, respectively, so that they can be supplied to the printer head of the ink jet recording printer and discharged from the printer head onto the primer layer.
• the colored layer forming step is a step of forming a colored layer by irradiating an active energy ray to the colored liquid applied on the surface of the primer layer to cure the composition contained in the colored liquid.
• the yellow coloring liquid is first deposited on the primer layer by an ink jet recording method, and then the active energy ray is irradiated to quickly cure the deposited yellow coloring liquid.
• the cyan coloring liquid is similarly deposited on the primer layer, and then the applied cyan coloring liquid is cured by irradiating active energy rays, and then the magenta coloring liquid and the black coloring liquid in the same order. After adhering to the primer layer, these colored liquids are cured by irradiating active energy rays.
• the light source similar to a primer layer formation process can be utilized.
• the laminated body with a colored layer in which the colored layer is provided on the primer layer can be produced by, for example, passing through the colored liquid coating process and the colored layer forming process on the laminated body of the present embodiment.
• the laminate with a colored layer has high adhesion between the colored layer and the primer layer in close contact with the colored layer, and also has low tackiness on the colored layer. Therefore, since the colored layer is difficult to peel off and the tackiness is low, it is possible to obtain an excellent laminate with a colored layer that is difficult to handle dust in the air and is easy to handle.
• the primer layer and This is preferable because the adhesion to the colored layer can be further improved.
• a surface protective layer may be further provided on the surface of the colored layer as necessary.
• the surface protective layer may be formed by using a conventionally known aqueous or oily overcoat agent, or by using an overcoat agent containing a composition such as active energy ray curability. May be.
• the surface protective layer is formed with an overcoat agent having the same composition as that obtained by removing the colorant from the color liquid in which the colored layer is formed
• the colored layer and the surface protective layer have the same composition. This is preferable because the adhesion is extremely high.
• a conventionally known printing method can be used.
• various methods such as an offset printing method, a gravure printing method, a screen printing, an ink jet printing, a spray method, and a brush coating method can be used.
• the ink jet method is preferable in that it can cope with a wide variety of small lots.
• B component) 1 Isobornyl acrylate (functional group number: 1, molecular weight: 208, molecular weight / functional group number: 208, viscosity: 9 mPa ⁇ s, Tg: 94 ° C.)
• Component B 4t-butylcyclohexyl acrylate (functional group number: 1, molecular weight: 210, molecular weight / functional group number: 210, viscosity: 9 mPa ⁇ s, Tg: 34 ° C.)
• D component 2-hydroxy-3-phenoxypropyl acrylate (functional group number: 1, molecular weight: 222, molecular weight / functional group number: 222, viscosity: 150 to 200 mPa ⁇ s, Tg: 17 ° C.)
• Tridecyl acrylate (functional group number: 1, molecular weight: 254, molecular weight / functional group number: 254, viscosity: 7 mPa ⁇ s, Tg: ⁇ 55 ° C.)
• G component 2-ethylhexyl acrylate ((2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, functional group number 1, molecular weight 184, molecular weight / functional group number 184, Tg:- 20 ° C)
• Photopolymerization initiator 1 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
• Photopolymerization initiator 2 oligo [2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanone]
• Undercoating liquids 1 to 5 were prepared so that the above components were as shown in Table 1 below.
• photopolymerization initiator 1 As the photopolymerization initiator component, photopolymerization initiator 1 and the following photopolymerization initiator 3 were used. Photoinitiator 3: 1-hydroxy-cyclohexyl-phenyl-ketone.
• PR122 magenta pigment was used as the colorant M.
• phenothiazine thiodiphenylamine
• An amine group-containing polymer compound was used as a dispersant.
• a colored liquid was prepared so that the above components were as shown in Table 2 below.
• Glass adhesion test In order to investigate the relationship between the arithmetic average roughness Ra on the surface of the laminate on the primer layer lamination side, tackiness, and adhesion between the colored layers, a glass adhesion test was conducted.
• the ink jet printing conditions were such that the primer print density was 5 to 100% and the resolution was 720 ⁇ 1200 dpi and 16 pass.
• the arithmetic average roughness Ra of the surface of the laminate on the primer layer lamination side in the laminate was measured.
• the measurement is carried out using a P-16 made by tencor as a step / surface roughness fine shape measuring device, and measuring an arithmetic average roughness Ra at any five locations with a needle pressure of 1 mg and a measurement length of 1.7 mm. The value was determined (indicated as Ra in Table 3).
• the adhesion evaluation was performed according to ASTM D3359.
• the cured coating film is cross-cut into 100 squares at 1 mm intervals, and a cellophane adhesive tape is applied to the cross-cut portion. Then, after the coating film and the cellophane adhesive tape were sufficiently adhered, it was judged from the degree of adhesion of the coating film to the substrate when the cellophane adhesive tape was peeled off at 90 degrees.
• the evaluation results are shown in Table 3 (indicated as adhesion in Table 3).
• the evaluation criteria are as follows. 5B: The degree of peeling is 0% to less than 2%. 4B: The degree of peeling is 2% or more and less than 5%. 3B: The degree of peeling is 5% or more and less than 15%. 2B: The degree of peeling is 15% or more.
• the tackiness of the primer layer and the colored layer on the primer layer was determined by a finger touch method. Specifically, a laminate sample in which a colored layer is not laminated (hereinafter simply referred to as a laminate) and a laminate sample with a colored layer in which a colored layer is laminated (hereinafter simply referred to as a laminate with a colored layer). Is placed at room temperature, and the primer layer (indicated as primer layer tackiness in Table 3) laminated on the outermost layer of the laminate and the colored layer (colored in Table 3) laminated on the outermost layer of the laminate with the colored layer The presence of stickiness was confirmed by touching with a finger.
• a laminate sample in which a colored layer is not laminated hereinafter simply referred to as a laminate
• a laminate sample with a colored layer in which a colored layer is laminated hereinafter simply referred to as a laminate with a colored layer
• the tackiness is expressed immediately after the production of the laminate and the laminate with the colored layer (indicated as “immediately after production” in Table 3) and after one day after the production of the laminate and the laminate with the colored layer (in Table 3, “after one day has elapsed) ).
• the evaluation results are shown in Table 3.
• the evaluation criteria are as follows. For the laminates of Comparative Examples 1 to 3 and the laminate with the colored layer, the degree of peeling exceeded 15% in the adhesion evaluation, and therefore, the tackiness evaluation after 1 day from the production of the laminate was not performed. .
• X Stickiness is large when touched with a finger.
• the laminates according to Examples 1 to 4 in which the arithmetic average roughness Ra of the laminate surface on the primer layer lamination side of the laminate exceeds 0.8 ⁇ m are the laminates according to Comparative Examples 1 to 3.
• the laminate has high primer layer tackiness, colored layer tackiness, and high adhesion to the colored layer.
• the laminated body and the laminated body with the colored layer according to Examples 1 to 4 maintain low tackiness even after one day has passed since the laminated body and the laminated body with the colored layer are formed, and are attached with dust in the air. It can be seen that it is an excellent laminate that is difficult to handle.
• each substrate adhesion test In order to investigate the relationship between the composition of the primer composition contained in the undercoat liquid, tackiness, and adhesion with the colored layer, each substrate adhesion test was conducted.
• each base material is untreated PET, easily welded PET (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.), acrylic (acrylic light EX manufactured by Mitsubishi Rayon Co., Ltd.), aluminum plate, SUS plate (stainless steel, SUS304), glass (slide glass) ), TPU (thermoplastic polyurethane), and SBR (styrene-butadiene rubber).
• undercoat liquids 1 to 5 were applied onto the substrate shown in Table 5 and a primer layer was laminated (printer: UJF3042, manufactured by Mimaki Engineering Co., Ltd., primer printing density: 20%, resolution: 720 ⁇ 1200 dpi, arithmetic average roughness Ra of the laminate surface on the primer layer lamination side: 1.29 ⁇ m).
• the comparative example 6 was not cured by the irradiation of the LED lamp, it was cured by irradiating a metahalhalide (GS SYSTEM manufactured by GS Yuasa Co., Ltd., integrated light amount 118 mJ / cm 2 , peak illuminance 591 mW / cm 2 ). .
• the penetration was measured according to JIS K2207 at 25 ° C. Specifically, a laminate sample having a thickness of 5 mm was prepared, and the sample was left in a constant temperature bath at 25 ° C. for 30 minutes or more. Then, the left sample and the penetration needle were set on an asphalt penetration meter, and the penetration was measured. The load of the needle was set at a load of 200 g for 60 seconds, and the distance at which the needle entered the sample was measured (indicated as primer layer penetration in Table 4). Table 4 shows the measurement results. The penetration is a value obtained by setting 1 when the distance that the needle has entered the sample is 1/10 mm.
• the tackiness evaluation was performed by the finger touch method. Specifically, the laminate was placed at room temperature, and the coating film was touched with a finger to check for stickiness.
• the evaluation results (shown as tackiness in Table 4) are shown in Table 4.
• the evaluation criteria are as follows. A: Stickiness is hardly felt even when touched with a finger. ⁇ : Some stickiness is felt even when touched by a finger, but it is substantially within an allowable range. (Triangle
• Glass transition temperature (Tg) The glass transition temperature (Tg) was determined from the change point of the specific heat of the binder resin using a differential scanning calorimeter (DSC) according to JIS K7121. The evaluation results (indicated as primer layer Tg in Table 4) are shown in Table 4.
• the adhesion evaluation was performed according to ASTM D3359.
• the cured coating film is cross-cut into 100 squares at 1 mm intervals, and a cellophane adhesive tape is applied to the cross-cut portion. Then, after the coating film and the cellophane adhesive tape were sufficiently adhered, it was judged from the degree of adhesion of the coating film to the substrate when the cellophane adhesive tape was peeled off at 90 degrees.
• the evaluation results are shown in Table 5.
• the evaluation criteria are as follows. 5B: The degree of peeling is 0% to less than 2%. 4B: The degree of peeling is 2% or more and less than 5%. 3B: The degree of peeling is 5% or more and less than 15%. 2B: The degree of peeling is 15% or more.
• the primer layer cannot be cured by the irradiation of the LED lamp, and must be a high output light source such as a metal halide lamp. Thus, a primer layer cannot be formed.
• the undercoat liquids 1 and 2 used in Examples 5 and 6 have a smaller content ratio of component A) than the undercoat liquid 5, sufficient curability is obtained even with a low output light source such as an LED lamp. Can be obtained. Therefore, it turns out that the laminated body provided with the primer layer of this invention is especially excellent also from a viewpoint of productivity.

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