TW201630746A - Laminate, laminate with colored layer, production method for laminate, production method for laminate with colored layer, and ink recording method - Google Patents

Abstract

Provided are: a laminate that adheres strongly to a substrate and includes a primer layer that adheres strongly to both the substrate and a colored layer, and has low tackiness; a laminate with a colored layer; a production method for the laminate; a production method for the laminate with the colored layer; and an ink recording method. The laminate is provided with a substrate and a primer layer formed directly on the substrate or with another layer therebetween, wherein the primer layer is provided on the outermost layer of the laminate, and is obtained by curing a primer composition comprising a compound having an ethylenically unsaturated group. The compound comprising the ethylenically unsaturated group contains a component A, which is a phenoxyalkyl(meth)acrylate comprising an optionally substituted phenoxy group and a C1-5 alkylene group, etc. The arithmetic mean roughness Ra of the laminate surface on the primer layer side is at least 0.8 [mu]m.

Description

Laminated body, laminated body with colored layer, method of manufacturing laminated body, attached Method for manufacturing laminated body of colored layer, and ink recording method

The present invention relates to a laminate, and more particularly to a method for producing a laminate and a laminate, which is formed on a surface of a substrate and is used to enable an active energy ray-curable coloring liquid to be sprayed. The ink method or the like is attached and hardened.

In recent years, inkjet printing has been widely used because it can obtain a good image at a high speed and has a wide range of uses. However, ink is directly dropped onto an ink-absorbent recording medium such as plain paper (hereinafter sometimes referred to as a water-absorbent substrate) or a non-absorbent recording medium such as plastic by an ink jet printer (hereinafter sometimes When the colored layer is formed on the non-water-absorbent substrate, the fixability varies depending on the type of the substrate, and thus the adhesion between the substrate and the colored layer may be insufficient. Among the various substrates, when a non-absorbent substrate is used, in addition to problems such as bleeding of an image, there are problems such as peeling of an image formed on a non-absorbent substrate, abrasion property, and the like.

As means for improving the adhesion between the substrate and the coloring layer, corona treatment, flame treatment, etc. may be applied to the substrate, but the fact is that The site where the inkjet printing operation is performed is not prepared with equipment capable of performing these pre-processing.

In order to solve such a problem, it is known to provide a primer layer to which a tackiness is imparted between a substrate and a coloring layer. The adhesion to the colored layer can be improved by the tackiness of the primer layer.

However, the effect of improving the adhesion differs depending on the type of substrate used. If the substrate is a water-absorptive substrate, the solvent in the primer composition forming the primer layer penetrates, so that the adhesion is high. In addition, even if it is a non-absorbent base material, if it is a plastic base material, etc., the surface of the plastic base material can be melted and swelled minutely by the solvent etc. in the primer composition ( Solvent attack) to improve adhesion. However, when the substrate is a non-aqueous substrate and is a glass substrate, it is not expected to improve adhesion by solvent etching, and therefore it is necessary to improve adhesion by other actions. As a result, depending on the substrate used, the effect of improving the adhesion is different, so the primer composition for improving the adhesion is generally a different primer for each substrate used. Composition.

Using a component consisting of phenoxyethyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, and a bifunctional urethane (meth)acrylate in a certain ratio The primer liquid can form an undercoat layer (primer layer) which improves the adhesion to an absorbent substrate such as plain paper or a non-absorbent substrate such as plastic or glass (Patent Document 1). An undercoat layer (primer layer) formed of the primer liquid described in Patent Document 1, which does not require pretreatment of the substrate, and is thermosetting plastic, thermoplastic A variety of substrates such as a non-absorbent substrate such as a plastic, a ceramic, a glass, and a metal plate, and an absorbent substrate are excellent in adhesion.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-043894

The undercoat layer (primer layer) described in Patent Document 1 is an excellent undercoat layer (primer layer) capable of improving adhesion to a plurality of substrates. However, the undercoat layer (primer layer) described in Patent Document 1 has a feeling of resilience in order to improve adhesion, but when a color layer is formed on the undercoat layer (primer layer), the undercoat layer is formed. After a certain period of time after the colored layer, a phenomenon of stickiness (stickiness) appeared on the surface of the colored layer. Since the dust or the like in the air easily adheres due to the appearance of the stickiness, such an undercoat layer (primer layer) needs to be handled with care, which is not preferable.

This is caused by the following reasons: the primer liquid described in Patent Document 1 contains phenoxyethyl (meth)acrylate having a low curability, and a mass of 40% by mass or more and 80 mass is added to the composition. 5% or less of phenoxyethyl (meth)acrylate.

On the other hand, since the epoxy resin (meth) acrylate is imparted to the undercoat layer (primer layer), if it is set to less than 40 mass %, sufficient adhesion to the colored layer could not be obtained. Therefore, the characteristics as a primer layer are degraded.

Therefore, the adhesion of the primer layer and the tackiness are originally a trade-off relationship, and it is strongly desired to develop a laminate having an undercoat layer capable of having these characteristics.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a laminate in which a water-absorbent substrate such as plain paper or a non-water-absorbent substrate such as a plastic is used as a recording medium. Good sex and low stickiness.

In order to solve the above problems, the present inventors have repeatedly studied intensively, and as a result, it has been found that the above problem can be solved by forming a laminate having a phenoxyalkyl (meth)acrylate of 1% by mass or more and 30% by mass. The present invention has been completed by setting the arithmetic mean roughness Ra of the surface of the laminated body on the laminated side of the primer layer to 0.8 μm or less. Specifically, the present invention provides the technology described below.

(1) A laminate comprising a substrate and a primer layer formed on the substrate directly or via another layer, wherein the primer layer is provided on an outermost layer of the laminate; The primer layer is obtained by hardening a primer composition comprising a compound having an ethylenically unsaturated group, and the compound having an ethylenically unsaturated group, comprising at least a component A of the following components. And the D component, and the B component and/or the C component: the A component is a phenoxyalkyl (meth)acrylate having a phenoxy group and an alkylene group having 1 or more and 5 or less carbon atoms, and the phenoxy group. can a substituent; a component B is a (meth) acrylate having an alicyclic structure; a component C is a (meth) acrylate having an aromatic ring other than the component A; and the component D is the aforementioned component A. And a (meth)acrylate having a hydroxyl group other than the component B and the component C; and the total amount of the primer composition is 1% by mass or more and 30% by mass or less, and the B component is 30% by mass. % or more and 70% by mass or less, the C component is 1% by mass or more and 15% by mass or less, and the D component is 1% by mass or more and 30% by mass or less; and the surface of the laminated body on the laminated side of the primer layer is The arithmetic mean roughness Ra is 0.8 μm or more.

(2) The layered product according to the above aspect, wherein the compound having an ethylenically unsaturated group further contains an E component, that is, the component A, the component B, the component C, and the component D (a) The alkyl group is a monofunctional monomer having a Tg of -30 ° C or less, and the E component is 1% by mass or more and 10% by mass or less based on the total amount of the primer composition.

(3) The layered product according to the above aspect, wherein the compound having an ethylenically unsaturated group further comprises an F component, that is, the component A, the component B, the component D, and the component E. The polyfunctional aliphatic urethane acrylate oligomer other than the above, and the F component is 1% by mass or more and 20% by mass or less in the total amount of the primer composition.

(4) The layered product according to the above aspect, wherein the component B is a compound of two or more different Tg.

(5) The laminate according to the above aspect, wherein the laminate has a primer layer having a penetration of 17 or more and 30 or less according to Japanese Industrial Standard (JIS) K2207 at 25 °C.

(6) A layered body having a coloring layer, further comprising a coloring agent on the surface of the layered body on the layer side of the primer layer of the layered body according to any one of (1) to (5) The color layer.

(7) A primer composition for forming the laminate according to any one of (1) to (5).

(8) A primer composition for inkjet, which is used for forming the laminate according to any one of (1) to (5).

(9) A method for producing a laminate comprising the steps of: applying a primer solution to apply a primer solution directly or via another layer to a substrate; and, a primer layer forming step, Applying an active energy ray to the undercoat liquid applied directly or on the substrate via the other layer, and curing the primer composition contained in the primer liquid to form a primer layer on the outermost layer; Here, as the compound having an ethylenically unsaturated group contained in the primer composition, the primer liquid contains at least a component having a phenoxy group and an alkylene group having 1 or more and 5 or less carbon atoms (A) The phenoxyalkyl acrylate is also the component A, which is 1% by mass or more and 30% by mass or less based on the total amount of the primer composition, and the phenoxy group may have a substituent; The acrylate is a component B, which is 30% by mass or more and 70% by mass or less based on the total amount of the primer composition; and the (meth) acrylate having an aromatic ring other than the component A is a C component. 1% by mass or more and 15% by mass or less in the total amount of the primer composition; and, the aforementioned A The (meth) acrylate having a hydroxyl group other than the component B, and the component C, that is, the component D, is 1% by mass or more and 30% by mass or less based on the total amount of the primer composition; and the primer The arithmetic mean roughness Ra of the surface of the laminated body on the laminated side of the layer is 0.8 μm or more.

(10) A method for producing a laminate having a colored layer, comprising the step of: a coloring liquid coating step, after the primer layer forming step of the method for producing a layered product according to (9), Applying a coloring liquid on a primer layer on a laminate side of the primer layer, the coloring liquid containing a coloring agent and a compound having an ethylenically unsaturated group; and a colored layer forming step for the aforementioned coated layer The coloring liquid irradiates the active energy ray to cure the composition contained in the coloring liquid to form a colored layer.

(11) An ink recording method comprising the step of applying a primer solution to a method in which the arithmetic mean roughness of the laminated side surface of the primer layer is 0.8 μm or more after the primer composition is cured. Applying the primer liquid directly or via another layer to the substrate; and, a primer layer forming step of irradiating the primer liquid coated on the substrate directly or via another layer An energy line for hardening the primer composition contained in the primer liquid to form a primer layer; wherein, as a compound having an ethylenically unsaturated group contained in the primer composition, the primer liquid contains at least The following component: a phenoxyalkyl (meth)acrylate having a phenoxy group and an alkylene group having 1 or more and 5 or less carbon atoms, that is, the component A, which is 1% by mass based on the total amount of the primer composition. Above 30% by mass, the phenoxy group may have a substituent; the (meth) acrylate having an alicyclic structure, that is, the component B, is 30% by mass or more and 70% by mass in the total amount of the primer composition. In the following, the (meth) acrylate having an aromatic ring other than the component A, that is, the component C, is 1% by mass or more and 15% by mass or less based on the total amount of the primer composition; The (meth) acrylate having a hydroxyl group other than the component B and the component C is a component D, and is 1% by mass or more and 30% by mass or less based on the total amount of the primer composition.

(12) The ink recording method according to (11), wherein the ink recording method comprises the step of: a coloring liquid coating step of coating the coloring liquid on the bottom formed by the aforementioned primer layer forming step a layered side of the lacquer layer, the coloring liquid containing a coloring agent and a compound having an ethylenically unsaturated group; and a colored layer forming step of irradiating the coloring liquid after the coating onto the active energy ray to make the composition contained in the coloring liquid The object hardens to form a colored layer.

According to the present invention, since the laminate of the substrate and the specific primer layer formed on the substrate is provided, the adhesion to the colored layer is excellent, and the feeling of stickiness can be reduced, so that an excellent laminate can be provided. It makes dust and the like in the air difficult to adhere, and thus is easy to handle.

Hereinafter, the specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.

[layered body]

The laminate of the present embodiment includes a substrate and a primer layer which is formed on the substrate directly or via another layer. The following is explained. In addition, the laminated body of this embodiment is a laminated body which has a primer layer in the outermost layer unless otherwise specified.

[substrate]

As the substrate is different, the effect of improving the adhesion is different. Therefore, the primer composition for improving the adhesion generally uses different primer compositions depending on the substrate to be used. However, the base material which can be used in the laminated body of the present embodiment is not particularly limited, and a base material composed of an organic material or a base material composed of an inorganic material can be used. As the substrate composed of an organic material, for example, a rubber-based substrate and a plastic-based substrate can be used. Examples of the rubber-based substrate include acrylonitrile/butadiene/styrene rubber (ABS), thermoplastic polyurethane (TPU), natural rubber (NR), and 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), fluororubber (FKM), styrene Thermoplastic elastomer, olefin-based thermoplastic elastomer, ester-based thermoplastic elastomer, urethane-based thermoplastic elastomer, amide-based A thermoplastic substrate, a polyvinyl chloride (PVC)-based thermoplastic elastomer, a fluorothermoplastic elastomer, and a rubber-based substrate obtained by mixing two or more kinds of these rubber-based substrates.

Examples of the plastic base material include polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile/butadiene/styrene (ABS), and propylene. Nitrile/styrene (AS), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), polyamine ( PA), polyacetal (POM), polycarbonate (PC), polyphenylene ether (PPE (modified polyoxyxylene (PPO))), polybutylene terephthalate (PBT), ultra high molecular weight Polyethylene (U-PE), polyvinylidene fluoride (PVDF), polyfluorene (PSF), polyether oxime (PES), polyphenylene sulfide (PPS), polyacrylate (PAR), polyamidoxime Amine (PAI), polyether quinone imine (PEI), polyetheretherketone (PEEK), polyimine (PI), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), phenol resin (PF) Urea resin (UF), melamine resin (MF), unsaturated polyester (UP) epoxy resin (EP), polyurethane (PUR), and two or more of these plastic substrates are mixed. The plastic substrate obtained.

Examples of the substrate 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 obtained by mixing two or more kinds of these metals, and plating of these metals. Materials and so on. Examples of the glass-based substrate include silicate glass (also A glass containing quartz glass and a component other than citrate as a main component.

The primer layer used in the laminate of the present embodiment is optimized in the concentration and type of the compound having an ethylenically unsaturated group used for forming the laminate layer. Therefore, the primer layer can be formed into a substrate regardless of the type of the substrate. A high adhesion primer layer.

[primer layer]

The primer layer is formed on the substrate directly or via another layer, and is provided on the outermost layer of the laminate to improve the adhesion to the colored layer. Forming on the substrate directly or through other layers means that the primer composition is directly cured on the substrate to form a primer layer; and the other layer is used to make the substrate The lacquer composition is hardened to form a primer layer which is formed by coating other resin or metal or the like. The primer layer used in the laminate of the present embodiment is formed by curing a compound having an ethylenically unsaturated group. Further, the compound having an ethylenically unsaturated group contains at least an A component, a D component, and a B component and/or a C component among the following components: the component A is a carbon atom number of 1 or more and 5 or less (methyl group). a phenoxyalkyl acrylate which is 1% by mass or more and 30% by mass or less based on the total amount of the entire primer composition; and a B component which is an alicyclic structure (meth) acrylate other than the above A component. It is 30% by mass or more and 70% by mass or less based on the total amount of all the primer compositions; and the C component is a (meth) acrylate having an aromatic ring other than the above-mentioned A component and the above B component. The total amount of the total primer composition is 1% by mass or more and 15% by mass or less; and the D component is the aforementioned A component and the aforementioned B component. The (meth) acrylate having a hydroxyl group other than the above-mentioned component C is 1% by mass or more and 30% by mass or less based on the total amount of all the primer compositions.

Further, if necessary, the component E may be an A component, a B component, a C component, or an alkyl (meth)acrylate other than the D component, and the E component is a monofunctional monomer having a Tg of -30 ° C or less. In the total amount of all the primer compositions, it is 1% by mass or more and 10% by mass or less; and the F component is a polyfunctional aliphatic uric acid other than the A component, the B component, the C component, the D component, and the E component. The ester acrylate oligomer is 1% by mass or more and 20% by mass or less based on the total amount of all the primer compositions.

The primer layer used in the laminate of the present embodiment is, for example, a primer liquid containing a primer composition applied onto the surface of a substrate, and then irradiated with an active energy ray or the like, whereby the primer composition has The compound of the ethylenically unsaturated group is formed by hardening, and the primer composition contains a compound having an ethylenically unsaturated group.

Further, in the laminated body of the present embodiment, the arithmetic mean roughness Ra of the surface of the laminated body on the laminated side of the primer layer is 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. By setting the arithmetic mean roughness Ra within such a large range, the surface area in which the primer layer is in contact with the coloring layer becomes large. Therefore, the adhesion of the primer layer and the coloring layer can be improved. In addition, the arithmetic mean roughness Ra in this specification is a value measured based on the arithmetic mean roughness (Ra) prescribed by the Japanese Industrial Standard (JIS) B0601 (1994).

The thickness of the primer layer used in the laminate of the present embodiment is preferably 5 μm or more and 20 μm or less, more preferably 6 μm or more and 15 μm or less, further preferably 7 μm or more and 10 μm or less, and further preferably 7 μm or more. 8.5μm or less. When the thickness of the primer layer is 5 μm or more and 20 μm or less, the adhesion to the colored layer can be improved, and the primer layer is less likely to be cracked or damaged. The thickness of the primer layer can be controlled by the amount of coating of the primer liquid applied to the substrate. Further, in the present embodiment, the thickness of the primer layer means the distance between the substrate and the highest vertex of the primer layer. The thickness of the primer layer can be measured by using, for example, P-16 manufactured by KLA-Tencor Corporation, and the measurement is performed by using a needle pressure of 1 mg and a measurement length of 1.7 mm. Specifically, when the primer layer is partially laminated in a dot shape instead of the entire surface of the laminate body, that is, when the surface of the substrate layer is exposed, the exposed portion of the substrate can be included in the measured length. The method is used for the measurement, and the value at this time is used as the thickness of the primer layer, and when the surface of the substrate is covered by the primer layer and is not exposed, the primer layer may be first ground or the like to make the substrate The surface was exposed, and the exposed surface was measured to be included in the measurement length, and the value at this time was used as the thickness of the primer layer.

The coating amount of the primer liquid applied to the substrate is preferably 0.1 mg/cm ² or more and 1.2 mg/cm ² or less, more preferably 0.2 mg/cm ² or more and 1.0 mg/cm ² or less. It is preferably 0.3 mg/cm ² or more and 0.8 mg/cm ² or less. By setting the coating amount of the undercoat liquid to 0.1 mg/cm ² or more and 1.2 mg/cm ² or less, the adhesion between the primer layer and the coloring layer can be improved.

The glass transition temperature (Tg) of the primer layer used in the laminate of the present embodiment is preferably 5 ° C or more and 35 ° C or less, more preferably 10 ° C or more and 30 ° C or less. By setting the glass transition temperature (Tg) of the primer layer to 5 ° C or more and 35 ° C or less, the primer layer can have better adhesion (rebonding property) and adhesion. The glass transition temperature (Tg) of the primer layer can be adjusted by selecting a compound having an ethylenically unsaturated group described later. Further, the above glass transition temperature (Tg) can be determined by using a differential scanning calorimeter (DSC) according to JIS K7121 and from the change point of the specific heat of the binder resin.

The penetration degree at 25 ° C of the primer layer used in the laminate of the present embodiment is preferably 17 or more and 30 or less, more preferably 19 or more and 29 or less, and most preferably 20 or more and 26 or less. The penetration degree is calculated in accordance with JIS K2207, and the distance is 1 when the needle is inserted into the sample at 1/10 mm. By setting the penetration to such a range, in addition to lower tackiness and higher adhesion, it is possible to obtain appropriate flexibility of the primer layer. Therefore, even in a low-temperature or high-temperature environment, the primer layer can be kept soft, so that the primer layer can be prevented from being broken.

The peel strength between the substrate and the primer layer can be evaluated, for example, by the American Society for Testing and Materials (ASTM) D3359, by adhesion evaluation of the adhesive tape after cross-cutting. For example, the hardened coating film is cross-cut into 100 grids at intervals of 1 mm, and a cellophane adhesive tape is adhered to the cross-cut portion, and then the cellophane is 90 degrees. Adhesive tape peeled off. As long as the degree of peeling is less than 5%, the adhesion between the substrate and the primer layer is considered to be sufficient. The peeling strength of the primer layer can be adjusted by selecting a compound having an ethylenically unsaturated group described later.

<Compounds having an ethylenically unsaturated group>

The primer layer of the present embodiment is formed by curing a primer composition containing a compound having an ethylenically unsaturated group. The primer composition means a solid component which is contained in a primer liquid such as a compound having an ethylenically unsaturated group, a photopolymerization initiator, or a photopolymerization inhibitor contained in the primer liquid, excluding the solution component The composition of the whole. The compound having an ethylenically unsaturated group contains at least a specific amount of the component A, the component D, and the component B and/or the component C. Further, a specific amount of the E component or the F component may be contained as needed.

<<A component>>

The component A refers to a phenoxyalkyl (meth)acrylate having 1 or more and 5 or less carbon atoms. The phenoxyalkyl (meth)acrylate can exhibit an effect of improving adhesion to a non-absorbent substrate such as polycarbonate after curing. From the viewpoint of tackiness, a phenoxyalkyl (meth)acrylate having a low back tack is preferred. From this viewpoint, the phenoxyalkyl (meth)acrylate is blended so as to be contained in an amount of 1% by mass or more and 30% by mass or less based on the total amount of the primer composition, preferably at the bottom. The blending is carried out in such a manner that the total amount of the lacquer composition is 3% by mass or more and 28% by mass or less, and it is preferable to carry out the blending in such a manner that the total amount of the primer composition is 5% by mass or more and 20% by mass or less. Hehe. Further, the phenoxyalkyl (meth)acrylate may be phenoxyethyl (meth)acrylate or a (meth) propylene having a substituent. Acid phenoxyethyl ester or phenoxyethyl (meth)acrylate obtained by modification.

Specific examples thereof include phenoxyethyl (meth)acrylate, EO-modified phenoxyethyl (meth)acrylate, PO-modified phenoxyethyl (meth)acrylate, and methyl benzene acrylate. Oxyethyl ester, nonylphenoxyethyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, hydroxyphenoxyethyl (meth)acrylate, (meth)acrylic acid Methylphenoxyethyl ester and the like. Here, "EO modification" means a block structure having an ethylene oxide unit (-CH ₂ -CH ₂ -O-), and "PO modification" means having a propylene oxide unit (-CH ₂ -CH(CH _{3 )} Block structure of -O-).

<<B component>>

The component B refers to a (meth) acrylate having an alicyclic structure. Since it has an alicyclic structure, for example, a rubber-based substrate or a plastic-based substrate is likely to intrude into the surface thereof, and has an effect of improving adhesion to the substrate after curing. The (meth) acrylate having an alicyclic structure may, for example, be a (meth) acrylate having an alicyclic structure such as a monofunctional monomer. The component B is contained in an amount of 30% by mass or more and 70% by mass or less, preferably 35% by mass or more and 60% by mass or less, based on the total amount of the primer composition, from the viewpoint of the adhesion of the substrate or the colored layer. It is preferable to contain 43% by mass or more and 55% by mass or less.

Examples of the component B include, for example, a monofunctional monomer (tri)butylcyclohexyl (meth)acrylate, isobornyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl acrylate, tetrahydrofuran methyl acrylate, Dicyclopentenyloxyethyl acrylate, dimethylol-tricyclodecane diacrylate, 1-adamantyl acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, and the like. Among them, 4-tributylcyclohexyl (meth)acrylate and isobornyl acrylate are preferably used in terms of ease of production.

Examples of the component B include cyclohexane dimethanol diacrylate of a bifunctional monomer, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, and dimethylol tricyclohexane. Decane dimethacrylate, tricyclodecane dimethanol diacrylate, and the like.

Further, the component B is preferably two or more compounds and their Tg are different. By including two or more kinds of compounds having different Tgs, in addition to low tackiness and high adhesion, the primer layer can be obtained with appropriate flexibility. Therefore, even when the temperature is low or high, the primer layer can be kept soft, so that the primer layer can be prevented from being broken. The two or more kinds of compounds preferably have a Tg difference from each other to 20 ° C or higher, more preferably a temperature difference of 40 ° C or higher.

<<C component>>

The component C refers to a (meth) acrylate having an aromatic ring other than the component A. Since it has an aromatic ring structure, for example, a rubber-based substrate or a plastic-based substrate is likely to intrude into the surface thereof, and has an effect of improving adhesion to the substrate after curing. From the viewpoint of the adhesion of the substrate or the colored layer, the component C is contained in an amount of 1% by mass or more and 15% by mass or less, preferably 3% by mass or more and 13% by mass or less, based on the total amount of the primer composition. Preferably, it is contained in an amount of 7 mass% or more and 12 mass% or less.

Examples of the component C include benzyl (meth)acrylate, tolyloxyethyl (meth)acrylate, and tolyl (meth)acrylate. Propyl ester, tolyloxy polyethylene glycol (meth) acrylate, tolyloxy polypropylene glycol (meth) acrylate, phthalic acid (meth) propylene methoxyethyl ester, phthalic acid (A Acryloxyethyl hydroxy ester, (meth) propylene methoxy propyl phthalate, neopentyl glycol benzyl ester (meth) acrylate, phenyl (meth) acrylate, (A) Acrylphenyl acrylate, o-phenylphenyl (meth)acrylate, m-phenylphenyl (meth)acrylate, p-phenylphenyl (meth)acrylate, etc. Base) acrylic. Among them, benzyl acrylate is particularly preferred from the viewpoint of curing speed and the like.

<<D component>>

The D component refers to a (meth) acrylate having a hydroxyl group other than the A component, the B component, and the C component. Since the D component has a hydroxyl group, it forms a hydrogen bond with respect to the base material which consists of an inorganic material, such as a metal base material, and has the function which improves the adhesiveness with a base material after hardening. The D component is contained in the total amount of the primer composition in an amount of 1% by mass or more and 30% by mass or less, preferably 5% by mass or more and 20% by mass or less, from the viewpoint of the adhesion of the substrate or the colored layer. Preferably, it is contained in an amount of 7 mass% or more and 15 mass% or less.

Examples of the component D include 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, and phthalic acid. 2-propenyloxyethyl-2-hydroxyethyl ester, 2-propenyloxyethyl phosphate, 2-hydroxy-3-propenyloxypropyl methacrylate, and the like. Among them, 2-hydroxy-3-phenoxypropyl (meth)acrylate is particularly preferred.

In addition, in the component D, a compound having a carboxyl group forms a hydrogen bond with respect to a base material composed of an inorganic material such as a metal base material. Therefore, it is expected that the adhesion to the base material composed of the inorganic material is improved. However, a compound having a carboxyl group may adversely affect the ink jet print head, and thus it is not preferable when the undercoat liquid is applied by an ink jet method. Therefore, from the viewpoint of adversely affecting the ink jet print head, the D component is preferably a (meth) acrylate having no carboxyl group, and is other than the A component, the B component, and the C component. A (meth) acrylate having a hydroxyl group.

<<E component>>

The E component is an alkyl (meth)acrylate other than the A component, the B component, the C component, and the D component, and the E component is a monofunctional monomer having a Tg of -30 ° C or less. Since the Tg is -30 ° C or lower, even after the compound having an ethylenically unsaturated group is cured, it has a certain degree of tackiness. The component E preferably has a Tg of -40 ° C or less, and preferably has a Tg of -50 ° C or less. The adhesion between the primer layer and the substrate and the adhesion between the primer layer and the colored layer can be improved by the feeling of back adhesion. Further, even in a low-temperature or high-temperature environment, the primer layer can be kept soft, so that the primer layer can be prevented from being broken. The component E is contained in an amount of 1% by mass or more and 10% by mass or less based on the total amount of the primer composition. Further, it is preferably contained in an amount of 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 the component E include tridecyl acrylate, dodecyl acrylate, and tetraethylene glycol diacrylate. Among them, it is particularly preferable to use tridecyl acrylate.

<<F component>>

The F component refers to a polyfunctional aliphatic urethane (meth) acrylate oligomer other than the A component, the B component, the C component, the D component, and the E component. The F component is an oligomer which exhibits tackiness after hardening and has an effect of improving adhesion. The F component preferably contains a bifunctional aliphatic urethane (meth) acrylate oligomer. Further, the F component is preferably contained in an amount of 1% by mass or more and 20% by mass or less, and more preferably 7% by mass or more and 15% by mass or less, based on the total amount of the primer composition.

As the F component, it can be obtained, for example, by esterifying a polyurethane oligomer with (meth)acrylic acid, which is a polyether polyether A reaction is obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate.

The polyfunctional aliphatic urethane (meth) acrylate which is commercially available is a bifunctional or trifunctional or higher functional functional urethane (meth) acrylate which is conventionally known. For example, the product name "Purple UV-3000B" manufactured by Nippon Synthetic Chemical Co., Ltd., (hereinafter the title is omitted) "UV-3200B", "UV-3201B", "UV-3310B", "UV-3500B" "UV-3520TL", "UV-3700B", "UV-6100B", "UV-6640B", "UV-2000B", "UV-2250EA", "UV-2750B"; manufactured by East Asia Synthetics Co., Ltd. The product name "ARONIX M1100", (hereinafter, the title is omitted) "M1200", "M1600"; the product name "EBECRYL 230" manufactured by Daicel-Cytec Co., Ltd., (hereinafter the title is omitted) "244", " 245", "270", "284", "285", "8401", "9270"; the trade names "CN961E75", "CN961H81", "CN962", "CN963", "" sold by Sartomer Company CN963A80, CN863B80, CN963E75, CN963E80, CN963J85, CN964, CN964E75, CN964A85, CN965, CN965A80, CN966A80, CN966J75, CN968 , "CN980", "CN981", "CN982", "CN983", "CN996", "CN9001", "CN9002", "CN9788", "CN9893", etc.

The undercoat liquid used in the present embodiment may have an adverse effect on the ink jet print head depending on the material of the print head, and the (meth) acrylate having a carboxyl group may be adversely affected by the primer. The total amount of the particles is 5% by mass or less, more preferably 1% by mass or less, and most preferably, the (meth) acrylate having a carboxyl group is not contained at all. Thereby, the primer liquid can be widely used regardless of the material of the print head.

<Photopolymerization initiator>

When the undercoat layer used in the layered body of the present embodiment is formed, a photopolymerization initiator may be used as needed. The photopolymerization initiator which can be used for forming an undercoat layer is an initiator capable of undergoing polymerization of a compound having an ethylenically unsaturated group by receiving an active energy ray such as an electron beam, an ultraviolet ray or an infrared ray and generating a radical. . As the photopolymerization initiator, fluorenylphosphine oxide, α-hydroxyketone, α-aminoalkylphenone, decyl ester or the like can be used. As the aforementioned fluorenylphosphine oxide, bis(2,4,6-trimethylbenzylhydrazine can be exemplified -Phenyl-phosphine oxide (trade name: IRGACURE 819, manufactured by BASF Corporation), bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphenyl oxide Phosphine, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (trade name: DAIDO UV-CURE APO, manufactured by Datong Chemical Co., Ltd.), etc.; among them, preferably 2, 4, 6-three Methyl benzhydryl-diphenyl-phosphine oxide (trade name: DAIDO UV-CURE APO)

As the α-hydroxyketone, 1-hydroxy-cyclohexyl-phenyl ketone (trade name: IRGACURE 184, manufactured by BASF Corporation), 2-hydroxy-1-{4-[4-(2-hydroxy-2-) is preferred. Methyl-propenyl)-benzyl]-phenyl}-2-methyl-propan-1-one (trade name: IRGACURE 127, manufactured by BASF Corporation), 2-hydroxy-4'-hydroxyethoxy group- 2-methylpropiophenone (trade name: IRGACURE 2959, manufactured by BASF Corporation), oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone] (commodity) Name: Esacure one, manufactured by Lamberti SpA). As the α-aminoalkylphenone, 2-benzyl-2-dimethylamino-1-(4-(N-morpholinylphenyl)-1-butanone is preferred (trade name: IRGACURE 369, manufactured by BASF). Further, as the oxime ester, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(O-ethenylhydrazine) is preferred.

The DAIDO UV-CURE APO and IRGACURE 127 are less likely to cause polymerization inhibition by oxygen, and therefore are particularly effective for the curability of a film formed by inkjet. Moreover, the above-mentioned DAIDO UV-CURE APO, IRGACURE 2959 and IRGACURE 369 have excellent internal hardenability, and therefore are in a thick film. The hardenability is particularly effective. DAIDO UV-CURE APO is capable of reacting with high sensitivity to active energy lines. Further, by using fluorenylphosphine oxide, α-hydroxyketone, and α-aminoalkylphenone in combination, both the film and the thick film can be excellent in curability, and can be highly sensitive to the active energy ray. Harden for a short time. The amount of the photopolymerization initiator to be added is preferably 3% by mass or more and 15% by mass or less based on the total amount of the entire primer composition, and the curability can be further maintained within this range.

<additive>

In the primer composition, in addition to the aforementioned components, various additives such as a plasticizer, a non-inductive resin, a solvent, a surface conditioner, an ultraviolet ray inhibitor, a photostabilizer, and an antioxidant may be blended. Further, a colored material may be added as needed, and for example, organic/inorganic fine particles, cerium oxide, titanium oxide, aluminum paste, mica, pearl pigment or the like may be blended. Further, as the material of the printing head is different, the compound having a carboxyl group may adversely affect the printing head. Therefore, the total amount of the primer composition is preferably 5% by mass or less, and further preferably 1 Below 5% by mass, it is most preferred that the compound having a carboxyl group is not contained at all. Thereby, the primer liquid can be widely used regardless of the material of the print head.

The primer composition can be prepared, for example, by preparing a primer liquid containing the above-mentioned blended component, and dispersing it using a general disperser such as a sand mill. The primer liquid is preferably filtered by a filter having a pore diameter of 3 μm or less, and more preferably filtered by a filter having a pore diameter of 1 μm or less.

[Manufacturing method of laminated body]

The laminate of the present embodiment can be produced by, for example, a step of applying a primer liquid onto a substrate directly or via another layer, the primer solution comprising a compound for an ethylenically unsaturated group; a primer layer forming step of irradiating an active energy ray to a primer liquid applied to a substrate directly or via another layer to form a primer contained in the primer liquid The material hardens to form a primer layer.

<Bottom coating solution step>

The primer coating step refers to a step of applying a primer liquid onto a substrate directly or via another layer, the primer solution comprising a primer composition. Further, a photopolymerization initiator may be contained in the primer liquid as needed. The method of applying the primer liquid to the substrate directly or via another layer is not particularly limited, and it is preferably one or more selected from the following methods: spray coating, coating. Machine method, inkjet method, gravure method, flexography method, and the like. Further, the primer liquid can also be applied by a coating device attached to a paper machine. Among these coating methods, the inkjet method can apply only a required amount of the primer liquid, and by adjusting the coating amount of the inkjet primer liquid, the primer layer can be adjusted after the primer composition is hardened. The arithmetic mean roughness Ra of the surface of the laminated body on the side is therefore more preferable. According to the above method, the coating method is applied to the substrate directly or via another layer, and then hardened by irradiation with an active energy ray or the like, whereby the substrate can be coated. In the place where the cloth (or printing, etc.) is colored, a primer layer is formed in advance.

<Paste layer forming step>

The primer layer forming step refers to a step of irradiating the primer liquid coated on the substrate directly or via another layer with an active energy ray to harden the primer composition contained in the primer liquid. To form a primer layer. The primer layer is formed on the surface so that the arithmetic mean roughness Ra of the surface on the side of the primer layer is 0.8 μm or more, and is preferably formed on the surface so as to be 1.0 μm or more. Preferably, it is formed on the surface so as to be 1.2 μm or more. As 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, a sunlight, and an LED (Light Emitting Diode) lamp can be used. When curing by an electron beam, it is generally cured by an electron beam having an energy of 300 eV or less, and can be instantaneously cured by an irradiation amount of 1 to 5 Mrad.

In particular, the phenoxyalkyl (meth)acrylate having a carbon number of 1 or more and 5 or less in the compound having an ethylenically unsaturated group used in the present embodiment is 1 mass in the total amount of all the primer compositions. % or more and 30% by mass or less, and the content is lower than that of the past primer layer as described in Patent Document 1. Therefore, even a low-output light source such as an LED lamp can obtain sufficient hardenability without a high-output light source such as a metal halide lamp. Therefore, the laminate having the primer layer on the outermost layer of the present embodiment is particularly excellent from the viewpoint of productivity.

[Ink recording method]

The ink recording method of the present embodiment includes, in addition to the primer coating step and the primer layer forming step, a coloring liquid coating step of applying a coloring liquid to the primer layer forming step. To form the bottom On the laminated side of the lacquer layer, the coloring liquid contains a coloring agent as a composition and a compound having an ethylenically unsaturated group; and a colored layer forming step of irradiating the colored liquid of the coating with an active energy ray to be contained in the coloring liquid The composition hardens to form a colored layer.

<Coloring liquid coating step>

The coloring liquid coating step refers to a step of applying a coloring liquid on the laminated side of the primer layer formed by the primer layer forming step. As the coloring liquid, a conventionally known coloring liquid can be used, and for example, an active energy ray-curable coloring liquid containing a coloring agent, a compound having an ethylenically unsaturated group, and, if necessary, a photopolymerization initiator can be used.

As the compound having an ethylenically unsaturated group, a conventionally known compound having an ethylenically unsaturated group, for example, a component B and/or a component C can be used, and it is preferred to use a component B and/or a component to be used for the primer. A compound having the same C component. The component B and/or the component C exhibits affinity with the cured component of the component B and/or the component C contained in the primer solution, that is, the primer layer, thereby improving the adhesion and adhesion of the colored layer. . Further, in the compound containing an ethylenically unsaturated group, it is preferred to contain 60% by mass or more and 95% by mass or less of the monofunctional monomer in the compound containing all of the ethylenically unsaturated groups. Further, it may further contain 10% by mass or more and 35% by mass or less (preferably 15% by mass or more and 30% by mass or less) of the A component, or 1% by mass or more and 10% by mass or less (preferably 3). F component of % by mass or more and 7% by mass or less.

<<Coloring agent>>

As the coloring agent, an inorganic pigment or an organic pigment which is generally used in the past oily ink composition can be used. As the pigment, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, titanium oxide, pearl pigment, aluminum, chromium oxide, viridian, titanium cobalt green, ultramarine blue can be used. ), Prussian blue, cobalt blue, pyrrolepyrrolopyrone, hydrazine, benzimidazolone, anthrapyrimidine, azo pigment, phthalocyanine pigment, isoporphyrin Ketone pigment, two (dioxazine) is a pigment, a threne pigment, an anthraquinone pigment, a perinone pigment, a thioindigo pigment, a quinophthalone pigment, a metal complex pigment, and the like.

The volume average particle diameter of the primary particles of the pigment is preferably a fine pigment having a measured value of laser light having an average particle diameter of 50 nm or more and 200 nm or less as measured by laser scattering. When the average particle diameter of the pigment is 50 nm or more, the particle diameter is large, whereby the light resistance can be improved, and when it is 200 nm or less, the dispersion can be stably maintained, and pigment precipitation can be suppressed. In addition, the content of the coloring agent 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 still more preferably 1% by mass or more and 10% by mass or less based on the coloring liquid. the following.

<<Dispersant>>

Preferably, a dispersing agent is blended in the coloring liquid, and as the dispersing agent, a polymer dispersing agent is preferably used. The polymer dispersant is, for example, a polymer dispersant in which the main chain is a polyester-based, polyacryl-based or polyaminocarboxylic acid. It is composed of an ester system, a polyamine system, a polycaprolactone system or the like, and has a polar group such as an amine group, a carboxyl group, a thiol group or a hydroxyl group as a branched chain; a polyester-based dispersant is preferred, and examples thereof include: "SOLSPERSE32000", "SOLSPERSE20000", "SOLSPERSE24000", "SOLSPERSE71000" manufactured by Lubrizol Corporation; "AJISPER PB821" and "AJISPER PB822" manufactured by Ajinomoto Fine-Techno Co., Inc. The amount of the dispersant to be added 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, based on 1 part by mass of the coloring agent. It is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less.

<<Other ingredients>>

As other components blended into the coloring liquid, various additives such as a plasticizer, a surface conditioner, an ultraviolet ray inhibitor, a light stabilizer, and an antioxidant may be contained.

<<Mixing coloring liquid>>

The coloring liquid which can be used in the present invention can be prepared by, for example, using a general dispersing machine such as a sand mill to uniformly disperse the coloring agent together with the compound having an ethylenically unsaturated group and a dispersing agent. While a dispersion liquid is obtained, a compound having an ethylenically unsaturated group, and optionally a photopolymerization initiator are added to the dispersion, and uniformly mixed. It is preferred to prepare a concentrate of a high concentration of a coloring agent in advance and to dilute it with a compound having an ethylenically unsaturated group, even if it is divided by a general dispersing machine. It is also possible to disperse sufficiently, and it is possible to prepare a coloring liquid excellent in stability. The coloring liquid is preferably filtered by a filter having a pore diameter of 3 μm or less, and more preferably filtered by a filter having a pore diameter of 1 μm or less.

<<Coating coloring liquid>>

When the coloring liquid is applied, for example, in order to improve the discharge property, a printer having an ink jet recording method in which a temperature rising mechanism is incorporated in a printing head can be used. In this case, the viscosity at 40 ° C is preferably 5 mPa ‧ or more and 20 mPa ‧ s or less. When the viscosity is 5 mPa ‧ or more, it is confirmed that the followability of the discharge is improved in the high-frequency print head; when the viscosity is 20 mPa ‧ or less, the mechanism for lowering the viscosity by heating is assembled on the print head It can lift the spit out, spit out more stably, and is easier to spit out. By mixing the pigments of yellow, cyan, magenta, and black, etc., into the coloring liquid, respectively, the ink is supplied to the printing head of the ink jet recording type printer, and can be discharged to the primer by the printing head. On the floor.

<Colored layer forming step>

The colored layer forming step is a step of irradiating a colored liquid coated on the surface of the primer layer with an active energy ray to cure the composition contained in the colored liquid to form a colored layer. For example, first, the yellow coloring liquid is adhered to the primer layer by an inkjet recording method, and then the active energy ray is irradiated to rapidly cure the adhered yellow coloring liquid. Then, the cyan coloring liquid is adhered to the primer layer in the same manner, and then the active energy ray is irradiated to cure the adhered cyan coloring liquid, and then, in the same manner, the magenta coloring liquid and the black coloring liquid are sequentially attached to each other. Irradiation activity on the primer layer Measure the wires to harden these colorants. Further, as the light source of the active energy ray, the same light source as the primer layer forming step can be used.

[Manufacturing method of laminated body with colored layer and laminated body with colored layer]

By the coloring coating step and the coloring layer forming step, for example, in the layered body of the present embodiment, a layered body with a colored layer having a colored layer on the primer layer can be produced. In the laminated body with the colored layer, the adhesion between the colored layer and the primer layer adhered to the colored layer is high, and the tackiness on the colored layer is also low. Therefore, it is possible to form an excellent laminated body with a colored layer, the colored layer is not easily peeled off, and the feeling of back tack is low, so dust or the like in the air is less likely to adhere and is easy to handle.

Further, in the primer coating step and the primer layer forming step included in the method for producing a layered product of the present embodiment, the steps of the coloring liquid coating step and the coloring layer forming step are sequentially performed, and the steps are sequentially performed. Therefore, the adhesion between the primer layer and the coloring layer can be further improved, which is preferable.

[surface protection layer]

In order to further improve the durability of the laminated body with the colored layer of the present embodiment, a surface protective layer may be further provided on the surface of the colored layer as needed. The surface protective layer can be formed by using an aqueous or oily overcoating agent known in the past, or by using a coating agent other than a composition containing active energy ray hardenability.

For example, the overcoating agent is the same composition as the composition excluding the coloring agent in the coloring liquid used to form the coloring layer, and is provided by the overcoating agent When the surface protective layer is formed, since the colored layer and the surface protective layer have the same composition, the adhesion of these layers becomes very high, which is preferable.

As the coating method of the overcoating agent, for example, a conventionally known printing method can be used. For example, various methods such as a film printing method, a gravure printing method, a screen printing method, an inkjet printing method, a spray coating method, a brush printing method, and the like can be used. Among them, from the viewpoint of being able to correspond to a small batch and a plurality of items, an inkjet method is preferred.

[Examples]

The present invention will be further specifically described by the following examples and comparative examples, but the present invention is not limited at all to the following examples.

(mixing the primer solution)

Component A: 2-phenoxyethyl acrylate (functional number: 1, molecular weight: 192, molecular weight / functional group number: 192, viscosity: 15 mPa ‧ , Tg: 5 ° C)

Component B 1: isobornyl acrylate (functional number: 1, molecular weight: 208, molecular weight / functional group number: 208, viscosity: 9 mPa ‧ , Tg: 94 ° C)

Component B 2: 4-tert-butylcyclohexyl acrylate (functional number: 1, molecular weight: 210, molecular weight / functional group number: 210, viscosity: 9 mPa ‧ , Tg: 34 ° C)

Component C: benzyl acrylate (number of functional groups: 1, molecular weight: 162, molecular weight / functional group number: 162, viscosity: 8 mPa ‧ s, Tg: 6 ° C)

Component D: 2-hydroxy-3-phenoxypropyl acrylate (functional number: 1, molecular weight: 222, molecular weight / functional group number: 222, viscosity: 150 to 200 mPa‧s, Tg: 17 ° C)

Component E: tridecyl acrylate (functional number: 1, molecular weight: 254, molecular weight / functional group number: 254, viscosity: 7 mPa ‧ s, Tg: -55 ° C)

F component: aliphatic urethane acrylate oligomer (functional number: 2, viscosity: 4240 mPa ‧ s)

Component G: 2-ethylhexyl acrylate (2-(methyl-2-ethyl-1,3-dioxocyclopentan-4-yl) acrylate), functional group number: 1, molecular weight: 184, molecular weight / functional group number: 184, Tg: -20 ° C)

Photopolymerization initiator 1: 2,4,6-trimethylbenzylindenyl-diphenyl-phosphine oxide

Photopolymerization initiator 2: oligomeric [2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propane]

Polymerization inhibitor: thiophene (phenothiazine, dibenzothiazide (thiodiphenylamine))

The primer liquids 1 to 5 were prepared so that the above components were in the following Table 1.

[Table 1]

(mixing coloring liquid)

As a compound having an ethylenically unsaturated group containing a component B and/or a component C, 4-tert-butylcyclohexyl acrylate is used (number of functional groups: 1, molecular weight: 210, molecular weight/functional group number: 210, viscosity: 9 mPa) ‧ s, Tg: 34 ° C), as a component having another ethylenically unsaturated group, phenoxyethyl acrylate, a bifunctional aliphatic urethane acrylate component, and N-vinyl caprolactone were used.

As the photopolymerization initiator, Photopolymerization Initiator 1 and the following photopolymerization initiator 3 were used. Photopolymerization initiator 3: 1-hydroxy-cyclohexyl-phenyl-one.

As the colorant M, PR122 (magenta pigment) was used.

As a polymerization inhibitor, use thiophene (dibenzothiazide) ).

As the dispersing agent, an amine group-containing polymer compound is used.

The coloring liquid was prepared so that the above components were in the following Table 2.

[Glass Adhesion Test]

The glass adhesion test was carried out in order to investigate the relationship between the arithmetic mean roughness Ra of the surface of the laminate on the build-up side of the primer layer and the tackiness and the adhesion to the colored layer.

(manufacturing laminate)

The laminate is produced by the following method: by the inkjet method (trade name: UJF3042, manufactured by MIMAKI ENGINEERING CO., LTD., on-demand piezo head), as shown in Table 1. The primer liquid 2 is applied onto a substrate (glass), and then irradiated with UV (LED-UV method) to cure the primer composition contained in the applied primer liquid to form a primer layer.

Further, the printing conditions carried out by the ink jet method are such that the primer printing density is 5 to 100%, the resolution is 720 × 1200 dpi (dots per inch, dots per inch), and 16 pass (inkjet stroke). number).

Thereafter, the arithmetic mean roughness Ra of the surface of the laminated body on the laminated side of the primer layer of the laminate was measured. In the measurement, the P-16 manufactured by KLA-Tencor Corporation was used as the height difference/surface roughness fine shape measuring device, and the arithmetic mean roughness Ra of any five places was measured by setting the needle pressure to 1 mg and the measurement length to 1.7 mm. Then find the average value (labeled Ra in Table 3).

(layered colored layer)

By the inkjet method (trade name: UJF3042, manufactured by MIMAKI ENGINEERING CO., LTD., a piezoelectric nozzle is required), the coloring liquid prepared as shown in Table 2 was applied so that the thickness after hardening became 20 μm. The primer layer of the laminate is then irradiated with UV (LED-UV method) to cure the colored liquid after coating to laminate the colored layer.

(adhesion evaluation)

The adhesion evaluation is carried out in accordance with ASTM D3359. The hardened coating film was cross-cut into 100 grids at intervals of 1 mm, and a cellophane adhesive tape was adhered to the cross-cut portion. Then, the coating film and the cellophane adhesive tape were sufficiently adhered to each other, and then the cellophane adhesive tape was peeled off at 90 degrees, and the degree of adhesion of the coating film to the substrate at this time was judged. The evaluation results are shown in Table 3 (labeled as adhesion in Table 3). Furthermore, the evaluation criteria are as follows.

5B: The degree of peeling is from 0% to less than 2%.

4B: The degree of peeling is 2% or more but less than 5%.

3B: The degree of peeling is 5% or more but less than 15%.

2B: The degree of peeling is 15% or more.

(back viscosity assessment)

The tackiness of the colored layer on the primer layer and the primer layer is carried out by finger touch. Specifically, a laminate sample (hereinafter, only referred to as a laminate) in which a colored layer is not laminated, and a laminate sample in which a colored layer is laminated (hereinafter, only a laminate having a colored layer) is placed at room temperature. And touching the primer layer laminated on the outermost layer of the laminate (the adhesion of the primer layer in Table 3) with a finger, and the colored layer laminated on the outermost layer of the laminate with the colored layer (in In Table 3, the color layer is marked as tacky, to confirm the presence or absence of stickiness. The tackiness is for one day after the production of the laminate and the laminate with the colored layer (marked as just after fabrication in Table 3), and after the laminate and the laminate with the colored layer are formed. (Marked in Table 3 as just after one day), and evaluated separately. The results of the evaluation are shown in Table 3.

The evaluation criteria are as follows. Further, in the laminates of Comparative Examples 1 to 3 and the laminate having the colored layer, the degree of peeling in the adhesion evaluation was more than 15%, so that the tackiness after one day after the production of the laminate was not carried out. Evaluation.

◎: There is almost no stickiness when touched with a finger.

○: A slight stickiness is felt by contact with a finger, but it is within a substantially allowable range.

△: When contacted with a finger, it is sticky and exceeds a substantially allowable range.

×: When contacted with a finger, the viscosity is high.

As is clear from Table 3, in the laminates of Examples 1 to 4, the arithmetic mean roughness Ra of the surface of the laminate on the laminate side of the primer layer of the laminate was more than 0.8 μm, compared with the laminates of Comparative Examples 1 to 3. It is a laminate with a high tackiness of the primer layer, a tackiness of the colored layer, and a high adhesion to the colored layer. Further, it is understood that the laminate of Examples 1 to 4 and the laminate having the colored layer are an excellent laminate which remains low even after one day after the laminate and the laminate having the colored layer are formed. The tackiness is such that dust or the like in the air is less likely to adhere and is easy to handle.

[Each substrate adhesion test]

In order to investigate the relationship between the composition of the primer composition contained in the primer liquid, the tackiness, and the adhesion to the coloring layer, each substrate adhesion test was carried out. In addition, each substrate is made of untreated PET, fusible PET (COSMOSHINE A4300 manufactured by Toyobo Co., Ltd.), and acrylic (three ACRYLITE EX) manufactured by Lingliyang Co., Ltd., aluminum plate, SUS plate (stainless steel, SUS304), glass (slide), TPU (thermoplastic polyurethane), SBR (styrene/butadiene rubber).

(layered colored layer)

The undercoat liquids 1 to 5 were applied to the substrate shown in Table 5 in the same manner as the above-mentioned glass adhesion test to laminate a primer layer (printing machine: manufactured by MIMAKI ENGINEERING CO., LTD.). UJF3042, primer printing density: 20%, resolution: 720 × 1200 dpi, arithmetic mean roughness Ra of the surface of the laminated body of the primer layer on the laminated side: 1.29 μm). In addition, in Comparative Example 6, since the LED lamp was not cured, the metal halide lamp (GS SYSTEM manufactured by GS Yuasa Corporation, the cumulative light amount was 118 mJ/cm ² and the peak illuminance was 591 mW/cm ² ) was irradiated. hardening.

(Penetration)

The penetration was measured in accordance with JIS K2207 at 25 °C. Specifically, a laminate sample having a thickness of 5 mm was prepared, and the sample was placed in a thermostat bath at 25 ° C for 30 minutes or longer. Further, the placed sample and the needle are placed on an asphalt penetrometer to measure the penetration. The load set to the needle was a load of 200 g for 60 seconds to measure the distance in which the needle was inserted into the sample (labeled as the primer layer penetration in Table 4). The results of the measurements are shown in Table 4. In addition, the penetration degree is a value obtained by setting this time to 1 when the distance in which the needle is inserted into the sample is 1/10 mm.

(back viscosity assessment)

The viscous evaluation is carried out by finger touch. Specifically, the laminate was placed at room temperature, and the coating film was touched with a finger to confirm the presence or absence of stickiness. The evaluation results (labeled as tackiness in Table 4) are shown in Table 4. Furthermore, the evaluation criteria are as follows.

◎: There is almost no stickiness when touched with a finger.

○: A slight stickiness is felt by contact with a finger, but it is within a substantially allowable range.

△: When contacted with a finger, it is sticky and exceeds a substantially allowable range.

×: When contacted with a finger, the viscosity is high.

[Glass transition temperature (Tg)]

The glass transition temperature (Tg) is determined by using a differential scanning calorimeter (DSC) according to JIS K7121 and from the change point of the specific heat of the binder resin. The evaluation results (labeled as the primer layer Tg in Table 4) are shown in Table 4.

(adhesion evaluation)

The adhesion evaluation is carried out in accordance with ASTM D3359. The hardened coating film was cross-cut into 100 grids at intervals of 1 mm, and a cellophane adhesive tape was adhered to the cross-cut portion. Then, the coating film and the cellophane adhesive tape were sufficiently adhered to each other, and then the cellophane adhesive tape was peeled off at 90 degrees, and the degree of adhesion of the coating film to the substrate at this time was judged. The evaluation results are shown in Table 5. Furthermore, the evaluation criteria are as follows.

5B: The degree of peeling is from 0% to less than 2%.

4B: The degree of peeling is 2% or more but less than 5%.

3B: The degree of peeling is 5% or more but less than 15%.

2B: The degree of peeling is 15% or more.

As is apparent from Tables 4 and 5, the laminates of Examples 5 and 6 were produced by hardening a primer composition containing a specific content of a compound having an ethylenically unsaturated group, and Example 5 The layered body of 6, is an excellent laminate having the following two properties which have a trade-off relationship: lower tackiness and higher adhesion in each substrate.

Further, in the primer liquid 5 used in Comparative Example 6, since the content ratio of the component A was high, the primer layer could not be cured when the LED lamp was irradiated, and it was necessary to have a high-output light source such as a metal halide lamp. A primer layer is formed. On the other hand, the primers 1 used in Examples 5 and 6 2, since the content of the component A is lower than that of the primer liquid 5, sufficient curability can be obtained even with a low-output light source such as an LED lamp. Therefore, it is understood that the laminate having the primer layer of the present invention is particularly excellent from the viewpoint of productivity.

Claims (12)

A laminate comprising a substrate and a primer layer formed on the substrate directly or via another layer, wherein the primer layer is provided on an outermost layer of the laminate; the primer The layer is obtained by hardening a primer composition comprising a compound having an ethylenically unsaturated group, and the compound having an ethylenically unsaturated group, comprising at least a component A and a component D of the following components. And component B and/or component C: component A is a phenoxyalkyl (meth)acrylate having a phenoxy group and an alkylene group having 1 or more and 5 or less carbon atoms, and the phenoxy group may have a substitution. The component B is a (meth) acrylate having an alicyclic structure; the component C is a (meth) acrylate having an aromatic ring other than the component A; and the component D is the aforementioned component A, the aforementioned a (meth) acrylate having a hydroxyl group other than the component B and the component C; the total amount of the primer composition is 1% by mass or more and 30% by mass or less, and the B component is 30% by mass or more. 70% by mass or less, the aforementioned C component is 1% by mass. And the 15% by mass or less, the component D is more than 1 mass% to 30 mass%; and, an arithmetic average surface laminate laminated side of the primer layer The roughness Ra is 0.8 μm or more. The layered product according to claim 1, wherein the compound having an ethylenically unsaturated group further contains an E component, that is, the component A, the component B, the component C, and the (meth)acrylic acid other than the component D. The E-component is a monofunctional monomer having a Tg of -30 ° C or less, and the E component is 1% by mass or more and 10% by mass or less based on the total amount of the primer composition. The laminate according to claim 1 or 2, wherein the compound having an ethylenically unsaturated group further contains an F component, that is, the A component, the component B, the component D, and the polyfunctional fat other than the component E. The urethane acrylate oligomer; and the F component is 1% by mass or more and 20% by mass or less based on the total amount of the primer composition. The laminate according to claim 1 or 2, wherein the component B is a compound of two or more different Tg. The laminate according to claim 1 or 2, wherein the laminate has a primer layer having a penetration of 17 or more and 30 or less according to Japanese Industrial Standard (JIS) K2207 at 25 °C. A laminate having a colored layer, which is a product of the laminate side of the primer layer of the laminate according to any one of claims 1 to 5 Further, a coloring layer containing a coloring agent is further provided on the surface of the layer. A primer composition for forming the laminate according to any one of claims 1 to 5. An inkjet primer composition for forming the laminate according to any one of claims 1 to 5. A method for producing a laminate comprising the steps of: a primer coating step of applying a primer solution directly or via another layer to a substrate; and a primer layer forming step, which is directly Or applying an active energy ray to the primer liquid coated on the substrate via another layer, and curing the primer composition contained in the primer liquid to form a primer layer on the outermost layer; a compound having an ethylenically unsaturated group contained in the primer composition, the primer liquid comprising at least the following component: (meth)acrylic acid having a phenoxy group and an alkylene group having 1 or more and 5 or less carbon atoms The phenoxyalkyl ester is also the component A, which is 1% by mass or more and 30% by mass or less based on the total amount of the primer composition, and the phenoxy group may have a substituent; the (meth) acrylate having an alicyclic structure In other words, the component B is 30% by mass or more and 70% by mass or less based on the total amount of the primer composition; and the (meth) acrylate having an aromatic ring other than the component A, that is, the component C, which is in the primer 1% by mass or more and 15% by mass or less of the total amount of the composition; and the aforementioned A component, before (Meth) acrylate having a hydroxyl group is the D component other than the B component and the C component, in which the primer The total amount of the composition is 1% by mass or more and 30% by mass or less, and the arithmetic mean roughness Ra of the surface of the laminated body on the laminated side of the primer layer is 0.8 μm or more. A method for producing a laminate having a colored layer, after the primer layer forming step of the method for producing a laminate according to claim 9, further comprising the step of: a coloring liquid coating step of coloring The liquid is applied onto the primer layer on the build side of the primer layer, the coloring liquid containing a colorant and a compound having an ethylenically unsaturated group; and a colored layer forming step of irradiating the coated colored liquid The active energy ray hardens the composition contained in the coloring liquid to form a colored layer. An ink recording method comprising the steps of: a primer coating step of directly or after the hardening of the primer composition, the arithmetic mean roughness of the laminated side surface of the primer layer is 0.8 μm or more Applying a primer liquid to the substrate through another layer; and a primer layer forming step of irradiating the active energy ray to the primer liquid coated on the substrate directly or via another layer, The primer composition contained in the primer liquid is cured to form a primer layer; wherein, as a compound having an ethylenically unsaturated group contained in the primer composition, the primer liquid contains at least the following components : (meth)acrylic acid phenoxy group having a phenoxy group and an alkylene group having 1 or more and 5 or less carbon atoms The alkyl ester is also the component A, which is 1% by mass or more and 30% by mass or less based on the total amount of the primer composition, and the phenoxy group may have a substituent; the (meth) acrylate having an alicyclic structure is also B. The component is 30% by mass or more and 70% by mass or less based on the total amount of the primer composition; and the (meth) acrylate having an aromatic ring other than the component A is a component C, which is in the total amount of the primer composition. The amount is 1% by mass or more and 15% by mass or less; and the (meth) acrylate having a hydroxyl group other than the A component, the B component, and the C component is the D component, and the total amount of the primer composition is The amount is 1% by mass or more and 30% by mass or less. The ink recording method according to claim 11, wherein the ink recording method comprises the step of: a coloring liquid coating step of coating the coloring liquid on the primer layer formed by the aforementioned primer layer forming step. The coloring liquid contains a coloring agent and a compound having an ethylenically unsaturated group, and a colored layer forming step of irradiating the coloring liquid after the coating onto the active energy ray to harden the composition contained in the coloring liquid. To form a colored layer.