JP2021084088A - Production method for laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminate having both adhesiveness and coating film fastness, obtaining a laminate with good quality, and having good productivity. SOLUTION: This method is a method of manufacturing a laminate by a multi-pass method by a manufacturing means which is provided with a ejection means and an irradiation means and can be scanned, and a first ink and a second ink are landed on a base material to activate energy. When the first step of irradiating the line and the second step of landing the second ink and irradiating the active energy ray are included and the scanning of the manufacturing means is a scan, the first step is one scan. The first cured product formed by the first step has a coverage ratio of 50% or more with respect to the substrate. The second cured product formed by the second step has a coverage ratio of 80% or more with respect to the first cured product. [Selection diagram] Fig. 1

Description

The present invention relates to a method for producing a laminate.

Conventionally, active energy ray-curable inks such as UV (ultraviolet) and EB (electron beam) have been supplied and used for offsets, silk screens, topcoat agents, etc., but cost reduction by simplifying the drying process and In recent years, the amount used has been increasing due to merits such as reduction of the volatilization amount of the solvent as an environmental measure. Recently, as industrial applications, the applications for decorative printing and coating using inkjet are increasing due to its on-demand properties.

However, in terms of inkjet suitability, there is generally a trade-off relationship between coating film fastness and adhesion, and inkjet ink coating films alone often cannot meet market demands. Therefore, it is necessary to separately apply a coating or a laminate, but if it is a separate process, the productivity will decrease. In addition, productivity can be maintained by providing an in-line inkjet drawing process and a coating process, but a large device that connects the processes corresponding to each layer is required, which has a great advantage of on-demand performance. It cannot be applied to small inkjet devices.

There is a means to achieve both adhesion and coating film fastness by forming multiple layers with an inkjet device such as a serial printer and separating the functions, but since it is necessary to print each layer individually, the production speed is significantly reduced. .. Further, in each layer, delamination may occur due to poor adhesion at the interface between the layers.

Patent Document 1 reports that good print quality and adhesion can be obtained by controlling the contact angle of each layer with respect to the substrate in overprinting of an active energy ray-curable ink composition. However, in order to form each layer, it is necessary to eject ink and irradiate with UV, which significantly reduces the production rate. In addition, the compatibility between the film fastness and the adhesion is insufficient.

In Patent Document 2, an ultraviolet curable material (liquid B) is ejected on the liquid surface of an ultraviolet curable resin liquid (liquid A) by an inkjet method, and the liquids A and B are irradiated with active energy rays to form an image (layer). A method has been proposed to make it. However, although the layer is formed, the purpose is to spread the image pattern thinly on the surface, and it is difficult to impart the function of coating film fastness because the upper layer film thickness is thin.

In Patent Document 3, a multi-pass inkjet printer is used to inject a base color ink and irradiate ultraviolet rays for each pass, and a top coat that injects base color inks and color inks and irradiates ultraviolet rays. It has been proposed to print by process. According to Patent Document 3, the printing time can be shortened without impairing the curability and adhesiveness. However, in Patent Document 3, although the base color UV curable ink is printed separately in the undercoating step and the topcoating step, it is still not possible to satisfy the adhesion to the base material, the adhesion between layers, and the toughness of the coating film. Insufficient. Further, in the prior art, when the number of layers for imparting fastness is increased for the reason of improving the fastness of the coating film, the colors appear to be mixed and the quality is inferior.

As described above, in the prior art, further improvement is required in the method for producing a laminate having both adhesion and coating film fastness, obtaining a laminate with good quality, and having good productivity. ..

Therefore, an object of the present invention is to provide a method for producing a laminate having both adhesion and coating film fastness, obtaining a laminate with good quality, and having good productivity.

In order to solve the above problems, the method for producing a laminate of the present invention comprises a discharge means for discharging a first active energy ray-curable composition and a second active energy ray-curable composition, and an active energy ray. A method for producing a laminate, which comprises an irradiation means for irradiating and can scan from one side to the other side or from the other side to one side of the base material by a multi-pass method. ,
The first active energy ray-curable composition is landed on the substrate, and then the second active energy ray-curable composition is landed on the first active energy ray-curable composition. The first step of forming the first cured product by irradiating with active energy rays, and
A second step of landing the second active energy ray-curable composition on the base material and irradiating the base material with the active energy rays to form a second cured product.
While the discharging means discharges at least one of the first active energy ray-curable composition and the second active energy ray-curable composition, the manufacturing means from one side to the other side of the base material. When one scan is to scan in one direction or the manufacturing means reciprocates from one side to the other side of the base material and then to one side, the first step is within one scan. It is performed once, and the second step is performed once in one scan.
In one or more passes, in each pass, the first step is first performed once, the first step is performed, and then the second step is performed once or multiple times.
The first cured product has a covering area ratio of 50% or more with respect to the base material.
The second cured product is characterized in that the coverage area ratio with respect to the first cured product is 80% or more.

According to the present invention, it is possible to provide a method for producing a laminate having both adhesion and coating film fastness, obtaining a laminate with good quality, and having good productivity.

It is the schematic for demonstrating an example of the manufacturing method of the laminated body in this invention. It is another schematic diagram for demonstrating an example of the manufacturing method of the laminated body in this invention. It is the schematic for demonstrating an example of a multipath system.

Hereinafter, a method for producing a laminate according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments shown below, and can be modified within the range conceivable by those skilled in the art, such as other embodiments, additions, modifications, and deletions. However, as long as the action and effect of the present invention are exhibited, it is included in the scope of the present invention.

(Manufacturing method of laminated body and image forming apparatus)
The method for producing a laminate of the present invention includes a discharge means for discharging a first active energy ray-curable composition and a second active energy ray-curable composition, and an irradiation means for irradiating the active energy rays. Moreover, it is a manufacturing method of a laminated body in which a laminated body is manufactured by a multi-pass method by a manufacturing means capable of scanning from one side to the other side or from the other side to one side of a base material.
The first active energy ray-curable composition is landed on the substrate, and then the second active energy ray-curable composition is landed on the first active energy ray-curable composition. The first step of forming the first cured product by irradiating with active energy rays, and
A second step of landing the second active energy ray-curable composition on the base material and irradiating the base material with the active energy rays to form a second cured product.
While the discharging means discharges at least one of the first active energy ray-curable composition and the second active energy ray-curable composition, the manufacturing means from one side to the other side of the base material. When one scan is to scan in one direction or the manufacturing means reciprocates from one side to the other side of the base material and then to one side, the first step is within one scan. It is performed once, and the second step is performed once in one scan.
In one or more passes, in each pass, the first step is first performed once, the first step is performed, and then the second step is performed once or multiple times.
The first cured product has a covering area ratio of 50% or more with respect to the base material.
The second cured product is characterized in that the coverage area ratio with respect to the first cured product is 80% or more.

Hereinafter, the first active energy ray-curable composition and the second active energy ray-curable composition may be referred to as, for example, a first ink, a second ink, and the like. Further, when the two are described without distinction, they may be simply referred to as an active energy ray-curable composition, and in addition to this, they may be simply referred to as ink.

In the present embodiment, the base material is provided with a discharge means for discharging the first active energy ray-curable composition and the second active energy ray-curable composition, and an irradiation means for irradiating the active energy rays. The laminate is manufactured by a manufacturing means that can scan from one side to the other or from the other side to one side.

Examples of the ejection means include a head unit having an inkjet head and the like. Examples of the irradiation means include UV irradiation means for irradiating UV (ultraviolet rays) as active energy rays. Examples of the manufacturing means include a carriage and the like.

The figures for explaining the manufacturing method of the laminated body of this embodiment are shown in FIGS. 1 and 2. 1 and 2 are views schematically showing a main part of an image forming apparatus for carrying out the present embodiment, and the image forming apparatus of the present embodiment has a first head 25 and a second head 26. The carriage 28 (manufacturing means) having the irradiation means 27 is provided. The means having the first head 25 and the second head 26 is a head unit 24 (discharging means).

FIG. 1 is a diagram for explaining a first step, and FIG. 2 is a diagram for explaining a second step. In FIG. 1, the first ink 22a is ejected by the first head 25 and lands on the base material 21. After that, the second ink 23a is ejected by the second head 26 and landed on the first ink 22. Next, the activation energy ray 27a is irradiated by the irradiation means 27, whereby the first cured product 31 is formed.

In FIG. 2, the second ink 23a is ejected by the second head 26 and landed on the base material 21. In the example shown here, the second ink 23a lands on the first cured product 31. Next, the activation energy ray 27a is irradiated by the irradiation means 27, whereby the second cured product 32 is formed. Although not shown, the second step may be repeated with respect to FIG.

In FIGS. 1 and 2, the carriage 28 has a first head 25 and a second head 26 arranged therein, includes an irradiation means 27, and scans in the arrow A direction (main scanning direction). While the carriage 28 is scanned in the main scanning direction, the first ink 22a is ejected from the first head 25, and the second ink 23a is ejected from the second head 26, landing on the substrate 21 and then landing on the substrate 21. The activation energy ray is irradiated by the irradiation means 27. In this way, the ink is cured and laminated to produce a laminate.

As a method for manufacturing the laminate of the present embodiment, a serial that moves the head to eject ink onto the base material with respect to a base material that moves intermittently according to the width of the ejection means, for example, the head width of the inkjet head. It can be applied to the method. The direction in which the base material moves is referred to as a sub-scanning direction. In this embodiment, the main scanning direction and the sub scanning direction are orthogonal to each other.

In the present embodiment, the laminate is manufactured by a multipath method in which a plurality of scans are performed. The multi-pass method is an image-forming method included in the serial method, and as compared with the single-pass method, the effect on image quality due to poor ejection is small, so that a buffer can be provided for ejection stability. Further, the multi-pass method is characterized in that the boundary streaks for each scan become inconspicuous and the image quality is superior such as high resolution.

In the single-pass method, when the layer is formed according to the head width, the layer is formed in one scan, whereas in the multi-pass method, the same layer is formed by dividing it into a plurality of scans. The number of divisions may be referred to as the number of passes. The total amount of ink (g / m ² ) ejected when forming the layer is the same for both the single-pass method and the multi-pass method.

Scanning means that the carriage (manufacturing means) moves while the head unit (discharging means) ejects ink. Further, in the present embodiment, the manufacturing means scans in one direction from one side to the other of the base material while the ejection means ejects at least one of the first ink and the second ink. One scan is that the manufacturing means reciprocates from one side of the base material to the other side and then to one side.

In the present embodiment, the first step is performed once in one scan, and the second step is performed once in one scan. The scanning direction is not particularly limited and can be changed as appropriate. The scanning direction of the first step and the scanning direction of the second step may be the same or different.

Further, unidirectional printing may be performed in which the ejection means discharges only when the manufacturing means is scanned from one side of the base material to the other side, or when the manufacturing means is scanned from one side of the base material to the other side. Bidirectional printing may be performed in which the ejection is performed by the ejection means and the ejection is performed by the ejection means when scanning from the other side to one side. In the examples shown in FIGS. 1 and 2, the irradiation means 27 is shown only on the downstream side of the discharge means with respect to the main scanning direction, but the present invention is not limited to this, and the irradiation means 27 is on the upstream side of the discharge means. It may also be provided. When bidirectional printing is performed, it is preferable that the irradiation means 27 are provided on the upstream side and the downstream side.

In the first step, it is preferable, but not limited to, the first ink 22a and the second ink 23a are ejected when scanning from one side to the other side of the base material. For example, when scanning from one side of the base material to the other side, the first ink 22a is ejected, and when scanning from the other side of the base material to the unidirectional side, the second ink 23a is ejected. , Irradiation with active energy rays may be performed. Even in this case, the first step is performed once in one scan.

In the multi-pass method, the total amount of ink to be ejected is divided according to the number of passes, and layers are stacked while moving either the head or the base material for each pass in the sub-scanning direction by the amount divided with respect to the head width. By doing so, the target layer is formed. For example, if the ink droplet size per drop is fixed and the dot density of 600 dpi x 600 dpi is laminated in two passes, the dot density is half of 600 dpi x 600 dpi for each half of the head width in each pass. Ink is ejected.

In forming the layer, it is not always necessary to eject ink in all the passes for the set number of passes. For example, in the case of a 4-pass condition, ink is ejected in only 2 passes to form a layer. You may.

A schematic diagram for explaining an example of the multipath method is shown in FIG. FIG. 3 (A) shows the case of 2 passes, and FIG. 3 (B) shows the case of 4 passes. For example, the path is divided into a to b and a to d with respect to the head width w in the sub-scanning direction. The path from which the cured product is formed is not particularly limited and can be changed as appropriate.

As a method for producing the laminate, in the conventional method in the multipath method, each composition is discharged separately to produce the laminate. For example, the first layer formed in the first pass is a layer made of white ink, and the second layer formed in the second pass is made of color ink. Laminate while curing with a wire.

In this case, it is conceivable to achieve both adhesion and coating film fastness by giving the layer made of white ink a function of adhesion and the layer made of color ink having a function of coating film fastness. However, in the conventional method, since each layer is formed of different inks, delamination is likely to occur and the adhesion is likely to be lowered. In addition, since layers made of different inks are laminated one by one, the productivity is greatly reduced.

On the other hand, in the present embodiment, by adopting the above configuration and the following configuration, both adhesion and coating film fastness are compatible, a laminate with good quality can be obtained, and good productivity is obtained. A method for producing a laminate can be provided.

In the first step of the present embodiment, since the first ink and the second ink are ejected and the active energy rays are irradiated in one scan, good productivity can be obtained. On the other hand, in the conventional example, when the laminate containing the first cured product and the second cured product in the present embodiment is produced, the ink is ejected and cured for each layer, so that the productivity is inferior.

Further, in the first step of the present embodiment, the second ink is landed in a state where the first ink is not cured, and the first ink and the second ink are cured at the same time by irradiating with active energy rays. I'm letting you. As a result, the layer made of the first ink and the layer made of the second ink are engaged with each other, and while having hardness, it can be made difficult to peel off. Therefore, the adhesion between layers can be improved.

The first cured product obtained by the first step has a coverage ratio of the first ink to the base material of 50% or more. Since the first ink forms the lower layer of the laminate, it is preferable to impart the function of adhesion, and when the coverage area ratio is 50% or more, the adhesion to the substrate is improved. If the coverage area ratio is less than 50%, adhesion to the substrate cannot be obtained. Further, the coverage area ratio of the first cured product is preferably 70% or more, and in this case, the adhesion to the base material is further improved.

Further, in the second step, the second ink is landed on the first cured product formed in the first step. In this case, since the second ink, which is the same ink, is further landed on the layer made of the second ink to form a layer, good interlayer adhesion can be obtained. Thereby, the peeling between the first cured product and the second cured product can be further reduced. Further, since the second ink is landed on the first cured product that has already been irradiated with the active energy rays, when, for example, a color ink is used as the second ink, color bleeding is suppressed and the quality is good. A laminate is obtained.

In the present embodiment, in one or a plurality of passes, the first step is performed once in each pass, the first step is performed, and then the second step is performed once or a plurality of times. In this case, since the layer made of the first ink is not formed after the first step, color mixing can be prevented and the quality can be improved. When a layer made of the first ink is formed on the layer made of the second ink, such as when a layer made of the first ink is formed after performing the first step, color mixing occurs. As a result, the density of the ink decreases and the color tone becomes blurred.

The second cured product obtained by the second step has a coverage area ratio of the second ink with respect to the first cured product of 80% or more. Since the second ink forms the upper layer of the laminate, it is preferable to impart the function of coating film toughness, and when the coating area ratio is 80% or more, the function of coating film toughness is improved, for example. The hardness of the laminate is improved. If the coverage area ratio is less than 80%, the coating film fastness cannot be obtained and the hardness of the laminate deteriorates. The coverage area ratio of the second cured product is preferably 95% or more. In this case, the coating film fastness of the laminate is improved, and for example, the hardness is improved.

The number of times the second step is performed in one pass is not particularly limited and can be changed as appropriate. When the number of passes in the multipath method is an integer n, the total number of times of the second step in one pass is preferably n-1. In this case, the total amount of ink ejected is the same as or equivalent to that of the single-pass method, and the laminate aimed at by the single-pass method is superior in adhesion, coating film fastness, and quality to the laminate obtained thereby. A laminate is obtained. As for the total number of times, for example, in the case of 2 passes, the second step is preferably performed once in one pass, and in the case of 4 passes, the second step is preferably performed 3 times in one pass. .. The reason why it is set to "-1" is that it is considered that the first step is performed once.

When the second step is performed a plurality of times in one pass, each second cured product obtained in each second step may satisfy the covering area ratio within the above range. It is not limited. A plurality of second cured products may be regarded as one second cured product, and the cured products may satisfy the above-mentioned coverage ratio.

The appropriate amount of the first ink and the second ink per drop is not particularly limited, but is preferably 4 ng to 30 ng, for example. In this case, discharge stability can be ensured.

The number of passes can be changed as appropriate. In the multi-pass method, since the amount of ink required to form the laminate is divided and ejected, a buffer can be provided for ejection stability, and the influence on image quality due to defective ejection that is not ejected from the nozzle is reduced. can do. This effect becomes more pronounced as the number of passes increases, but as the number of passes increases, the productivity for producing the laminate decreases. Further, if the number of passes is excessively increased, the amount of the first ink ejected in the first pass decreases according to the number of passes, so that the covering area with respect to the substrate is reduced and the adhesion may be lowered. is there.

Therefore, in the present embodiment, it is preferable to use two passes, and in this case, the advantage of the multi-pass method that the influence of defective ejection on the image quality can be reduced can be further improved. Further, in the present embodiment, since the coverage area ratio of the first ink to the base material is high, high adhesion is exhibited in the case of 2 passes, and it is possible to achieve both robustness at a higher level.

The laminate obtained by the present embodiment includes not only those printed on a smooth surface such as ordinary paper or resin film, but also those printed on a surface to be printed having irregularities, and various types such as metal and ceramic. It also includes those printed on the surface to be printed, which is made of a material. Further, by superimposing two-dimensional images, it is possible to form a partially three-dimensional image (an image composed of two-dimensional and three-dimensional) or a three-dimensional object.

In the present embodiment, the image forming apparatus used for manufacturing the laminate includes a discharge means for discharging the active energy ray-curable composition and an irradiation means for irradiating the active energy ray, and is a base material. It is provided with manufacturing means capable of scanning from one side to the other side or from the other side to one side. In addition to this, a storage unit for accommodating the active energy ray-curable composition, a supply unit for supplying the active energy ray-curable composition, and the like may be provided.

The discharge means is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

As the active energy rays, in addition to ultraviolet rays, those capable of imparting energy necessary for advancing the polymerization reaction of polymerizable components in the composition such as electron beams, α rays, β rays, γ rays, and X-rays. It suffices, and is not particularly limited. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

The ejection means may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism for cooling the base material to about room temperature by contact or non-contact may be provided.

Examples of the storage portion of the active energy ray-curable composition include an inkjet ink storage container. The inkjet ink container means a container in which an active energy ray-curable composition is contained, and can be used for various purposes. For example, when the active energy ray-curable composition is used for ink, the container containing the ink can be used as an ink cartridge or an ink bottle, whereby in operations such as ink transfer and ink replacement. , It is not necessary to touch the ink directly, and it is possible to prevent the fingers and clothes from getting dirty. In addition, it is possible to prevent foreign substances such as dust from being mixed into the ink. The shape, size, material, etc. of the container itself may be suitable for the intended use and usage, and is not particularly limited, but the material is a light-shielding material that does not transmit light, or the container blocks light. It is desirable that it is covered with a sex sheet or the like.

The base material is not particularly limited, and examples thereof include paper, film, ceramics, glass, metal, and composite materials thereof, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or double-sided printing is also possible. Not limited to those used as general recording media, cardboard, building materials such as wallpaper and floor materials, cloth for clothing such as concrete and T-shirts, textiles, leather and the like can be appropriately used.

(Active energy ray-curable composition)
In the present embodiment, a laminate is produced using the first active energy ray-curable composition and the second active energy ray-curable composition. The first active energy ray-curable composition and the second active energy ray-curable composition are distinguished by differences in materials, physical properties, and the like. In the present embodiment, the first active energy ray-curable composition and the second active energy ray-curable composition are used as, for example, inks and inkjet inks.

Similar to the above, hereinafter, the first active energy ray-curable composition and the second active energy ray-curable composition may be referred to as, for example, a first ink and a second ink. Further, when the two are described without distinction, they may be simply referred to as an active energy ray-curable composition, and in addition to this, they may be simply referred to as ink.

The material composition of the first active energy ray-curable composition (first ink) and the second active energy ray-curable composition (second ink) is not particularly limited and may be appropriately changed. It is possible. For example, a polymerizable compound, a surfactant and the like can be mentioned, and in addition, a polymerization initiator, a coloring material, a polymerization inhibitor, a diluting solvent, other known components and the like can be mentioned. Since the polymerizable compound and the surfactant have a great influence on the physical properties of the obtained laminate, it is preferable that there are no major restrictions.

<Polymerizable compound>
Examples of the polymerizable compound include monomers. The monomer is a compound that undergoes a polymerization reaction by an active energy ray (ultraviolet ray, electron beam, etc.) or an active species generated by the active energy ray and is cured, and is a polyfunctional monomer or a monofunctional monomer depending on the number of functional groups. Monomer can be mentioned. The polymerizable compound may include a polymerizable oligomer, a polymerizable polymer (macromonomer), and the like.

There are no restrictions on the type of monomer for each ink, but as the first active energy ray-curable composition (first ink), since it is located in the lower layer of the laminate, it imparts an adhesion function. Is preferable. Further, the first ink preferably contains a large amount of monofunctional monomer, and preferably contains 50% by mass or more of the monofunctional monomer in the first ink.

Since the second active energy ray-curable composition (second ink) is located on the upper layer of the laminate, it is preferable to impart the function of coating film fastness. The second ink preferably contains a polyfunctional monomer. When the second ink contains a polyfunctional monomer, the first ink also preferably contains a polyfunctional monomer, and the content of the polyfunctional monomer in the first ink is the content of the polyfunctional monomer in the second ink. It is preferably less than the content. That is, it is preferable that the content of the polyfunctional monomer in the first ink <the content of the polyfunctional monomer in the second ink, and in this case, the polyfunctional monomer is excessively contained in the first ink. It is possible to suppress the curing shrinkage that occurs in the above, and it is possible to prevent a decrease in adhesion due to the curing shrinkage.

The content of the polyfunctional monomer in the second ink is preferably 10% by mass or more, and more preferably 25% by mass or more. In this case, the hardness of the laminated body can be improved.

The polyfunctional monomer refers to a bifunctional monomer, a trifunctional monomer, or a monomer having a higher number of functional groups.
The polyfunctional monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Neopentyl glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane, and trimethylolpropane di (meth) acrylate. Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, bisphenol A propylene oxide (PO) adduct di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, bisphenol A ethylene oxide (EO) adduct di (meth) acrylate ) Acrylate, EO-modified pentaerythritol trimethylolpropane (meth) acrylate, PO-modified pentaerythritol trimethylolpropane (meth) acrylate, EO-modified pentaerythritol tetra (meth) acrylate, PO-modified pentaerythritol tetra (meth) acrylate, EO-modified dipentaerythritol tetra (meth) acrylate Meta) acrylate, PO-modified dimethylolethanetetra (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolmethanetetra (meth) acrylate, PO-modified Tetramethylolmethane Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) Acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, bis (4- (meth) acryloxipolyethoxyphenyl) propane, diallylphthalate, triallyl trimellitate, 1,6-hexanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (hydroxypivalate) Meta) Acrylate, Tetra Methylolmethane tri (meth) acrylate, dimethylol tricyclodecandi (meth) acrylate, modified glycerin tri (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, modified bisphenol A di (meth) acrylate, caprolactone. Modified Dipentaerythritol Hexa (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate Tolylene Urethane Prepolymer, Pentaerythritol Tri (Meta) Acrylate Hexamethylene Diisocyanate Urethane Prepolymer, Ditrimethylol Propane Examples thereof include tetra (meth) acrylate, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymer, urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate oligomer, polyether acrylate oligomer, and silicone acrylate oligomer. These may be used alone or in combination of two or more.

The monofunctional monomer refers to a monomer having one functional group.
The monofunctional monomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine, dimethylaminopropylacrylamide, isobornyl (meth) acrylate, and adamantyl (meth). ) Acrylate, 2-methyl-2-adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 3,3,5-trimethylcyclohexane (Meta) acrylate, t-butyl methacrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Examples thereof include hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, phenoxyethyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, and cyclic trimethylolpropaneformal acrylate. These may be used alone or in combination of two or more.

<Surfactant>
The surfactant has an effect of suppressing mixing of the compositions of the first ink and the second ink when the first ink and the second ink are layered with a liquid. In any of the inks, it is preferable to add a small amount as needed, and it is preferable that at least the second ink contains a surfactant, and it is preferable that the ink contains 0.01% by mass to 1% by mass. When it is 1% by mass or less, it is possible to suppress deterioration of antifouling property and ejection stability in inkjet when an excessive amount of surfactant is contained. Further, when it is 0.01% by mass or more, the above effect can be exhibited.
As the surfactant, known components can be used, and one type may be used alone or two or more types may be used in combination.

<Polymerization initiator>
The active energy ray-curable composition in the present embodiment may contain a polymerization initiator. The polymerization initiator may be one that can generate active species such as radicals and cations by the energy of the active energy ray and initiate the polymerization of the polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used alone or in combination of two or more, and among them, a radical polymerization initiator is used. Is preferable. Further, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the ink in order to obtain a sufficient curing rate.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and the like. Examples thereof include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Further, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited, but for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, N, Amine compounds such as N-dimethylbenzylamine and 4,4'-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

<Color material>
The active energy ray-curable composition in the present embodiment may contain a coloring material. As the coloring material, various pigments and dyes that impart black, white, magenta, cyan, yellow, green, orange, glossy colors such as gold and silver, and the like can be used according to the purpose and required characteristics. The content of the coloring material may be appropriately determined in consideration of the desired color density, dispersibility in the inkjet ink, etc., and is not particularly limited, but is 0. It is preferably 1 to 20% by mass. The active energy ray-curable composition in the present embodiment may be colorless and transparent without containing a coloring material, and in that case, for example, it is suitable as an overcoat layer for protecting an image.

The type of ink is not particularly limited and can be changed as appropriate. The addition of the coloring material is optional for the combination of the first ink and the second ink in the present embodiment, but since the second ink is landed on the upper layer, the dots of the droplets are arranged in high definition. It is preferable to make it easy, and it is preferable to use a color ink for drawing containing a color material or a clear ink containing no color material. Further, the first ink used as the base is preferably white ink or clear ink.

As the pigment, an inorganic pigment or an organic pigment can be used, and one type may be used alone or two or more types may be used in combination.
As the inorganic pigment, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments and quinophthalones. Polycyclic pigments such as pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing lake (basic dye type lake, acidic dye type lake), nitro pigment, nitroso pigment, aniline black, Daylight fluorescent pigments can be mentioned.
In addition, a dispersant may be further contained in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used, and one type may be used alone or two or more types may be used in combination.

<Organic solvent>
The active energy ray-curable composition in the present embodiment may contain an organic solvent, but it is preferable not to contain it if possible. If the composition does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further enhanced, and it is possible to prevent environmental pollution. .. The "organic solvent" means, for example, a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. is there. Further, "not containing" the organic solvent means that it is substantially not contained, and it is preferably less than 0.1% by mass.

<Other ingredients>
The active energy ray-curable composition in the present embodiment may contain other known components, if necessary. The other components are not particularly limited, but are, for example, conventionally known polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration promoters, wetting agents (moisturizing agents), fixing agents, and viscosity stabilizers. , Antifungal agents, preservatives, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like.

<Preparation of active energy ray-curable composition>
The active energy ray-curable composition in the present embodiment can be prepared by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like are ball milled. , Kitty mill, disc mill, pin mill, dyno mill, etc., and disperse to prepare a pigment dispersion liquid, and further add a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. to the pigment dispersion liquid. It can be prepared by mixing.

<Viscosity>
The viscosity of the active energy ray-curable composition in the present embodiment may be appropriately adjusted according to the application and the application means, and is not particularly limited. For example, a discharge means for discharging the composition from a nozzle is applied. In some cases, the viscosity in the range of 20 ° C. to 65 ° C., preferably the viscosity at 25 ° C. is preferably 3 to 40 mPa · s, more preferably 5 to 15 mPa · s, and particularly preferably 6 to 12 mPa · s. Further, it is particularly preferable that the viscosity range is satisfied without containing the organic solvent. For the above viscosity, a cone rotor (1 ° 34'x R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Use>
The use of the active energy ray-curable composition in the present embodiment is not particularly limited as long as it is in a field in which an active energy ray-curable material is generally used, and can be appropriately selected depending on the intended purpose. For example, molding. Examples thereof include resins, paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, and various optical materials.
Further, the active energy ray-curable composition in the present embodiment is used as an ink to form not only two-dimensional characters and images and a design coating film on various substrates, but also a three-dimensional stereoscopic image (three-dimensional model). ) Can also be used as a three-dimensional modeling material.

It also includes a cured product obtained by curing an active energy ray-curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate. The molded product is, for example, a cured product or structure formed in the form of a sheet or a film, which has been subjected to molding processing such as heat stretching or punching. For example, automobiles, OA equipment, and electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, panels for operation units, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following, "part" means "parts by mass", and "%" means "% by mass".

(Examples 1 to 12 and Comparative Examples 1 to 5)
<Preparation of active energy ray-curable composition>
Based on the materials and contents (parts by mass) shown in Table 1, inks 1 to 11 (active energy ray-curable composition) used in Examples 1 to 12 and Comparative Examples 1 to 5 were prepared by a conventional method. The ink 11 had poor ejection properties and was not used for evaluation.

In Table 1, the trade names and manufacturing company names of the compounds used are as follows.

-Monomer-
・ ACMO: Acryloyl morpholine (manufactured by KJ Chemicals)
・ NVC: N-vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.)
-PEA: Phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
-CTFA: Cyclic trimethylolpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
-DPGDA: Dipropylene glycol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
-CN963: Aliphatic urethane acrylate (manufactured by Sartmer)

-Surfactant-
-Wet270: TEGO WET270 (manufactured by EVONIK)

-Color material-
・ PR122: Pigment Red 122

-Polymerization initiator-
-IrgTPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by LAMBERTI)

<Manufacturing method of laminated body>
[Examples 1, 2, 4 to 12 and Comparative Examples 1, 2]
For an inkjet ejection device in which a plurality of inkjet heads and a UV light source are mounted on a series of carriages as shown in FIGS. 1 and 2, MH5421 (manufactured by Ricoh) is used as the inkjet head and UV having a wavelength of 395 nm is used as the active energy ray irradiation device. -The LED light source was mounted, and the ink was set in the combinations shown in Tables 2 and 3. As the base material, a polycarbonate base material (manufactured by Mitsubishi Gas Chemical Company, Ltd., Iupiron NF-2000, thickness 0.5 mm, length width 100 mm, width 100 mm) was used. A laminate was produced by the above-mentioned inkjet ejection device by a 2-pass multipath method.
First, in the first scan, the first step is performed for the first pass. That is, the first ink was ejected onto the base material, then the second ink was ejected, and then UV irradiation was performed to form the first cured product. Next, in the second scan, the second step was performed on the first pass, and at the same time, the first step was performed on the second pass. As a result, a second cured product was formed in the first pass. In the second step, the second ink is ejected and UV irradiation is performed. Next, in the third scan, the second step was performed on the second pass, so that the second cured product was formed in the second pass. In this way, each laminated body was produced.

The output of the UV-LED light source with a wavelength of 395 nm is 4.5 W / cm ² , the moving speed of the carriage is 840 mm / sec, the distance from the head to the UV irradiator is 30 cm, and the amount of drops per ink drop is. It is shown in Table 2 and Table 3. Further, the dot density was set to be 600 dpi × 600 dpi.

[Example 3]
In the above example, the laminate was produced in the same manner except that the conditions were changed as shown in Table 2. In Example 3, a laminate was produced by a 4-pass multipath method.
First, the first scan and the second scan were performed in the same manner as described above. Next, in the third scan, the second step was performed on the first pass and the second pass, and the first step was performed on the third pass. Next, in the 4th scan, the 2nd step was performed for the 1st to 3rd passes, and the 1st step was performed in the 4th pass. In the next 5th scan, the second step was not performed in the first pass, but the second step was performed in the other pass. In the subsequent scans, as in the fifth scan, a path in which the second step is not performed and a path in which the second step is performed are mixed. In this way, a laminate was produced. In the third embodiment, the first step is performed once and the second step is performed three times in each pass.

[Comparative Example 3]
For an inkjet ejection device in which a plurality of inkjet heads and a UV light source are mounted on a series of carriages as shown in FIGS. 1 and 2, MH5421 (manufactured by Ricoh) is used as the inkjet head and UV having a wavelength of 395 nm is used as the active energy ray irradiation device. -The LED light source was mounted, and the ink was set in the combinations shown in Table 3. As the base material, a polycarbonate base material (manufactured by Mitsubishi Gas Chemical Company, Ltd., Iupiron NF-2000, thickness 0.5 mm, length width 100 mm, width 100 mm) was used. A laminate was produced by the above-mentioned inkjet ejection device by a 2-pass multipath method.
In Comparative Example 3, the first ink was laminated in 3 scans and 2 passes, and then the second ink was further laminated in 3 scans and 2 passes. UV irradiation is performed for each scan. As a result, a laminated body was produced.

The output of the UV-LED light source with a wavelength of 395 nm is 4.5 W / cm ² , the moving speed of the carriage is 840 mm / sec, the distance from the head to the UV irradiator is 30 cm, and the amount of drops per drop is 18 ng. The dot density was set to be 600 dpi × 600 dpi.

[Comparative Example 4]
For an inkjet ejection device in which a plurality of inkjet heads and a UV light source are mounted on a series of carriages as shown in FIGS. 1 and 2, MH5421 (manufactured by Ricoh) is used as the inkjet head and UV having a wavelength of 395 nm is used as the active energy ray irradiation device. -The LED light source was mounted, and the ink was set in the combinations shown in Table 3. As the base material, a polycarbonate base material (manufactured by Mitsubishi Gas Chemical Company, Ltd., Iupiron NF-2000, thickness 0.5 mm, length width 100 mm, width 100 mm) was used. A laminate was produced by the above-mentioned inkjet ejection device by a 2-pass multipath method.
First, in the first scan, the first ink and the second ink were ejected and UV irradiation was performed on the first pass and the second pass. Next, in the second scan as well, the first ink and the second ink were ejected and UV irradiation was performed on the first pass and the second pass in the same manner as in the first scan. As a result, a laminated body was produced.

[Comparative Example 5]
In Comparative Example 4, a laminate was produced in the same manner except that the conditions were changed as shown in Table 2. In Comparative Example 5, a laminate was produced by a 4-pass multipath method.
First, in the first scan, the first ink and the second ink were ejected and UV irradiation was performed on the first to fourth passes. Next, in the second to fourth scans as well, the first ink and the second ink were ejected and UV irradiation was performed on the first to fourth passes in the same manner as in the first scan. As a result, a laminated body was produced.

(Evaluation)
<Pencil hardness>
According to JIS K 5600 5-4, the scratch hardness (pencil method) test of the obtained laminate was carried out under a load of 750 g using a Cortec model KT-VF2391.

<Adhesion to PC (polycarbonate)>
Eleven cuts were made vertically and horizontally at 1 mm intervals on the obtained laminate using a cutter guide to make 100 grids. Nichiban cellophane tape (registered trademark) No. The frequency of exposure of the base material when 405 was strongly crimped to the grid portion and peeled off at once was confirmed. The evaluation criteria are as follows. In addition,% means the ratio of the number of bases which exposed base material to the total number of bases (100 pieces).

[Evaluation criteria]
〇: Base material exposure is less than 5% Δ: Base material exposure is 5% or more and less than 35% ×: Base material exposure is 35% or more

<Delamination>
Eleven cuts were made vertically and horizontally at 1 mm intervals on the obtained laminate using a cutter guide to make 100 grids. Nichiban cellophane tape (registered trademark) No. The 405 was strongly crimped to the grid portion, and peeling between layers was confirmed when the 405 was peeled off at once. The evaluation criteria are as follows. In addition,% means the ratio of the number of bases which peeled off between layers of a base material with respect to the total number of bases (100 pieces).

[Evaluation criteria]
〇: Delamination between layers is less than 5% Δ: Peeling between layers is 5% or more and less than 35% ×: Peeling between layers is 35% or more

<Covering area ratio>
The coverage area ratio of the first ink with respect to the substrate was measured in the range of 643 μm × 643 μm from the back surface of the substrate on which the laminate was produced, with respect to the obtained laminate using the Olympus laser microscope OLS4100. By binarizing the ink, the covering area of the first ink was calculated.

The coverage area ratio of the second ink on the surface of the laminate is binarized by measuring the range of 643 μm × 643 μm with respect to the surface of the obtained laminate using the Olympus laser microscope OLS4100. The coverage area ratio of the ink of 2 was calculated.

<Mixed color>
For an inkjet ejection device in which a plurality of inkjet heads and a UV light source are mounted on a series of carriages as shown in FIGS. 1 and 2, MH5421 (manufactured by Ricoh) is used as the inkjet head and UV having a wavelength of 395 nm is used as the active energy ray irradiation device. -The LED light source was mounted, and the inks shown in Tables 1 to 3 were set.
By ejecting the second ink onto a polycarbonate base material (manufactured by Mitsubishi Gas Chemical Company, Iupiron NF-2000, thickness 0.5 mm, vertical width 100 mm, horizontal width 100 mm) by the above inkjet ejection device, UV irradiation is performed. , A single layer film of the second ink was prepared. The output of the UV-LED light source with a wavelength of 395 nm is an illuminance of 4.5 W / cm ² , the moving speed of the carriage is 840 mm / sec, the distance from the head to the UV irradiator is 30 cm, the amount of drops per drop is 18 ng, and dots. The density was set to be 600 dpi × 600 dpi.
The OD (Optical Density) value of the monolayer film prepared under the above conditions was measured using a spectrophotometric densitometer X-Rite Model 939 (manufactured by Video Jet X-Rite). Using this OD value as a reference for each ink shown in Tables 1 to 3, the OD value on the surface of the obtained laminate is measured, and the color mixing is performed from the rate of change of the measured OD value with respect to the reference OD value. I confirmed the degree.

In Example 9, since clear ink was used as the second ink, the following evaluation was performed. First, a monolayer film was prepared with the first ink on the polycarbonate base material, a black sheet was placed on the back surface of the polycarbonate base material, and the OD value was measured. This is used as the reference OD value. Next, the OD value of the surface of the laminate produced by the above method for producing the laminate was measured, and the rate of change of the measured OD value with respect to the reference OD value was determined.

[Evaluation criteria]
〇: Change rate of OD value is less than 10% Δ: Change rate of OD value is 10% or more and less than 20% ×: Change rate of OD value is 20% or more

As shown in Tables 2 and 3, adhesion is exhibited under the condition that the first ink covers 50% or more of the base material, but if it is less than 50%, the adhesion decreases. .. Further, under the condition that the first ink covers 80% or more of the base material, the adhesion is further improved.
Under the condition that the surface of the cured product is covered with 80% or more of the second ink, the pencil hardness is as high as F or more, and under the condition that the surface of the cured product is sufficiently adhered to the PC and 95% or more is covered. , Pencil hardness is H and the hardness is further improved. This is because when the adhesion is lowered, the cured product is peeled off from the base material before the surface of the cured product is scratched, resulting in a pencil hardness lower than the original hardness of the cured product surface.

The method for producing the laminate in Comparative Example 3 can increase the ejection amount of the first ink and increase the covering area of the base material as compared with the production method of Example 1 and the like, but for each layer. Since the laminate is formed by UV irradiation, delamination is likely to occur.
The method for producing the laminate in Comparative Examples 4 and 5 is different from the method for producing the first ink and the second ink because a layer composed of the first ink and the second ink is formed for each scan. Color mixing of the inks of 2 is likely to occur. Further, in the same method, it becomes difficult to increase the coverage area ratio of the first ink to the base material and the coverage area ratio of the second ink on the surface of the laminate.

Further, in Examples 1 to 12, the production speed of the laminated body was faster than that of the conventional method (Comparative Example 3), and good productivity was obtained. In Comparative Example 3, the number of scans was larger than that in Example 1 and the like, and the time required to prepare the laminate was significantly increased.

21 Base material 22, 22a First ink 23, 23a Second ink 24 Head unit 25 First head 26 Second head 27 Irradiation means 28 Carriage 31 First cured product 32 Second cured product

JP-A-2010-138298 Japanese Patent No. 5990868 Japanese Unexamined Patent Publication No. 2016-36933

Claims (9)

A discharge means for discharging the first active energy ray-curable composition and the second active energy ray-curable composition, and an irradiation means for irradiating the active energy rays are provided, and one side to the other side of the base material is provided. A method for manufacturing a laminated body in which a laminated body is manufactured by a multi-pass method by a manufacturing means capable of scanning from one side to the other side.
The first active energy ray-curable composition is landed on the substrate, and then the second active energy ray-curable composition is landed on the first active energy ray-curable composition. The first step of forming the first cured product by irradiating with active energy rays, and
A second step of landing the second active energy ray-curable composition on the base material and irradiating the base material with the active energy rays to form a second cured product.
While the discharging means discharges at least one of the first active energy ray-curable composition and the second active energy ray-curable composition, the manufacturing means from one side to the other side of the base material. When one scan is to scan in one direction or the manufacturing means reciprocates from one side to the other side of the base material and then to one side, the first step is within one scan. It is performed once, and the second step is performed once in one scan.
In one or more passes, in each pass, the first step is first performed once, the first step is performed, and then the second step is performed once or multiple times.
The first cured product has a covering area ratio of 50% or more with respect to the base material.
The second cured product is a method for producing a laminated body, characterized in that the covering area ratio with respect to the first cured product is 80% or more. The method for manufacturing a laminate according to claim 1, wherein when the number of passes in the multipath method is an integer n, the total number of times of the second step in one pass is n-1. The method for producing a laminate according to claim 1 or 2, wherein the first cured product has a covering area ratio of 70% or more with respect to the base material. The method for producing a laminate according to any one of claims 1 to 3, wherein the second cured product has a covering area ratio of 95% or more with respect to the first cured product. The first active energy ray-curable composition and the second active energy ray-curable composition contain a polyfunctional monomer, and the content of the polyfunctional monomer in the first active energy ray-curable composition. The method for producing a laminate according to any one of claims 1 to 4, wherein is less than the content of the polyfunctional monomer in the second active energy ray-curable composition. The method for producing a laminate according to any one of claims 1 to 5, wherein the first active energy ray-curable composition contains 50% by mass or more of a monofunctional monomer. The method for producing a laminate according to any one of claims 1 to 6, wherein the second active energy ray-curable composition contains 0.01% by mass to 1% by mass of a surfactant. The first active energy ray-curable composition is a clear ink or a white ink, and the second active energy ray-curable composition is a color ink or a clear ink. 7. The method for producing a laminate according to any one of 7. The method for producing a laminate according to any one of claims 1 to 8, wherein the multi-pass method is two-pass.

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