JP2018024810A - Active energy ray-curable ink composition, laminate prepared with ink composition, image forming method for forming image on base material, and method for producing printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable ink composition that prevents cracking of a cured film and reduces tackiness on the surface of the cured film even with a flexible base material used as a recording medium, and allows use of general-purpose base materials.SOLUTION: An active energy ray-curable ink composition contains a monofunctional monomer represented by formula (1), and a polyfunctional monomer represented by formula (2): R-CH=CR-COOR-O-CH=CH-R.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable ink composition mainly used as an inkjet ink, a laminate on which the ink composition is printed, and an image and / or an uneven image on a substrate using the ink composition. The present invention relates to an image forming method to be formed, and a method for producing a printed matter using the ink composition.

  2. Description of the Related Art Conventionally, active energy ray-curable ink compositions that are cured by ultraviolet rays, electron beams, or other active energy rays have been developed. Since the active energy ray-curable ink composition is quick-drying, ink bleeding can be prevented even when printing on a substrate that does not absorb or hardly absorbs ink, such as plastic, glass, and coated paper. The active energy ray-curable ink composition is composed of an active energy ray polymerizable monomer, a coloring material, and other additives.

  For example, an active energy ray-curable ink composition containing a predetermined amount of a compound having both a vinyl group and a (meth) acryl group in the molecule and a polymerizable compound having another specific structure is disclosed ( Patent Document 1).

  The active energy ray-curable ink composition of Patent Document 1 is an active energy ray-curable ink composition having a viscosity that is low enough to be used as an inkjet ink, and has excellent adhesion to PET and has an active energy ray. It is an active energy ray-curable ink composition that can suppress shrinkage of the cured film due to curing of the ink.

JP 2012-193260 A

  In recent years, an active energy ray-curable ink composition is sometimes used with a flexible base material having a deformable shape such as a vinyl chloride resin as a recording medium. However, since the polyfunctional monomer such as 2- (2-vinyloxyethoxy) ethyl acrylate used in Patent Document 1 does not have stretchability, the active energy ray-curable ink composition of Patent Document 1 is When a flexible base material is printed as a recording medium, the cured film formed on the base material is broken by bending the base material without stretching following the flexible base material. There is a problem of end.

  Even if the cured film has stretchability, if the surface of the cured film is tacky, the surface of the cured film is likely to adhere to dust, dust, mud, soot, pitch, etc. Therefore, there is a problem that the cured film adheres to the other substrate when the cured film comes into contact with the other substrate. In this specification, the term “tack” means that the surface of the cured film is sticky when touched with a finger. Thus, stretchability and tack in the cured film are in a trade-off relationship.

  Although the active energy ray-curable ink composition of Patent Document 1 has problems of adhesion and suppression of shrinkage of the cured film due to curing of the active energy ray, no study has been made on stretchability and tack in the cured film. Absent.

  The present invention has been made in view of the above circumstances, and an object thereof is to suppress cracking of a cured film even when a flexible base material is used as a recording medium. The present invention provides an active energy ray-curable ink composition that can be used and has low tack on the surface of a cured film and has a high versatility of a usable substrate.

  In order to solve the above-mentioned problems, the present inventor has conducted extensive research and found that it is an active energy ray-curable ink composition containing a monofunctional monomer and a polyfunctional monomer having a specific structure, each active energy ray. It has been found that the above problems can be solved by an active energy ray-curable ink composition in which the content ratio of the polymerizable monomer is adjusted, and the present invention has been completed. Specifically, the present invention provides the following.

(1) As an active energy ray polymerizable monomer, monomer A): a monofunctional monomer represented by the following general formula (1) and monomer B): a polyfunctional monomer represented by the following general formula (2) Containing, in the total amount of the active energy ray polymerizable monomer,
The total content of monofunctional monomers including the monomer A) is 45% by mass or more,
An active energy ray-curable ink composition in which the content of the monomer A) is 20% by mass or more based on the total amount of the monofunctional monomer.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、直鎖、分岐鎖又は環状の炭素数１以上１８以下のアルキル基又はフェニル基を示し、Ｒ^１とＲ^２とは結合して環を形成していてもよい。Ｒ^３は水素原子又は炭素数１以上４以下のアルキル基を示す。Ｒ^４は水素原子又は炭素数１以上４以下のアルキル基を示す。Ｒ^５は炭素数１以上５以下のアルキレン基を示す。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms or a phenyl group, and R ¹ and R ² are bonded to each other. R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents An alkylene group having 1 to 5 carbon atoms is shown.)

R ⁴ —CH═CR ¹ —COOR ² —O—CH═CH—R ³ (2)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent organic residue having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or a monovalent organic group having 1 to 11 carbon atoms. Represents an organic residue, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  (2) At least one monofunctional monomer selected from the group consisting of the monomer A), tetrahydrofurfuryl acrylate, trimethylolpropane formal acrylate, and 4-t-butylcyclohexyl acrylate in the total amount of the monofunctional monomer. The active energy ray-curable ink composition according to (1), wherein the content is 90% by mass or more.

  (3) The active energy ray-curable ink composition according to (1) or (2), wherein the viscosity at 25 ° C. measured based on JIS Z 8803: 2001 is 7.0 mPa · s or less.

  (4) The active energy ray-curable ink composition according to any one of (1) to (3), which is used as an inkjet ink.

  (5) The active energy ray-curable ink composition according to any one of (1) to (4) is formed on a vinyl chloride sheet having a thickness of 80 μm as a cured film having a thickness of 10 μm. When the cured film-forming substrate was subjected to a tensile test at 25 ° C. and a tensile speed of 10 mm / min as a dumbbell-shaped No. 6 type (JIS K6251-5) test piece, cracks in the cured film were observed. An active energy ray-curable ink composition having a cured film elongation at break of 50% or more.

  (6) A laminate in which an ink cured film layer that is a cured film of the active energy ray-curable ink composition according to any one of (1) to (5) is formed on a substrate.

  (7) An image forming method for forming an image and / or a concavo-convex image on a substrate using the active energy ray-curable ink composition according to any one of (1) to (5).

  (8) A method for producing a printed material, wherein an image and / or a concavo-convex image is formed on a substrate using the active energy ray-curable ink composition according to any one of (1) to (5).

  The active energy ray-curable ink composition of the present invention can suppress cracking of a cured film even when a flexible substrate is used as a recording medium, and can be applied to the surface of the cured film. This is an active energy ray-curable ink composition with a low tack and a versatile base material that can be used.

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

<Active energy ray-curable ink composition>
The active energy ray-curable ink composition of one embodiment of the present invention includes a monomer A) which is a monofunctional monomer represented by the following general formula (1), and a polyfunctional monomer represented by the following general formula (2) And an active energy ray-curable ink composition containing the monomer B).

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、直鎖、分岐鎖又は環状の炭素数１以上１８以下のアルキル基又はフェニル基を示し、Ｒ^１とＲ^２とは結合して環を形成していてもよい。Ｒ^３は水素原子又は炭素数１以上４以下のアルキル基を示す。Ｒ^４は水素原子又は炭素数１以上４以下のアルキル基を示す。Ｒ^５は炭素数１以上５以下のアルキレン基を示す。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms or a phenyl group, and R ¹ and R ² are bonded to each other. R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents An alkylene group having 1 to 5 carbon atoms is shown.)

R ⁴ —CH═CR ¹ —COOR ² —O—CH═CH—R ³ (2)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent organic residue having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or a monovalent organic group having 1 to 11 carbon atoms. Represents an organic residue, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  In the active energy ray-curable ink composition of the present invention, the total content of monofunctional monomers including monomer A) in the total amount of active energy ray polymerizable monomers is 45% by mass or more. Furthermore, the content of the monomer A) in the total amount of the monofunctional monomer is 20% by mass or more. By optimizing the content of the monofunctional monomer including the monomer A) in the total amount of the active energy ray polymerizable monomer and the content of the monomer A) in the total amount of the monofunctional monomer, the stretched film is imparted with stretchability. be able to. Therefore, even if it is a case where the base material which has flexibility is used as a recording medium, it can be set as the active energy ray hardening-type ink composition which can suppress the crack of a cured film.

  The monofunctional monomer represented by the general formula (1) and the polyfunctional monomer represented by the general formula (2) have a small odor, and the monofunctional monomer represented by the general formula (1) and the general formula ( The active energy ray-curable ink composition containing the polyfunctional monomer represented by 2) is excellent in that the viscosity does not increase.

  In the present specification, the low odor of the active energy ray-curable ink composition means that the active energy ray-curable ink composition itself has a low odor, and the active energy ray-curable ink composition has a low odor. The active energy ray curable ink composition, when forming an image on the substrate using the active energy ray curable ink composition, or using the active energy ray curable ink composition When manufacturing printed matter, it is possible for workers to concentrate on the work without worrying about odors, and even a worker with sensitive nose can work without a mask. There is a merit.

  It is not always easy to develop an active energy ray-curable ink composition having a low odor and a low viscosity and satisfying all physical properties necessary for the active energy ray-curable ink composition. For example, an active energy ray-polymerizable monomer having a high boiling point tends to be an active energy ray-polymerizable monomer having a low odor because it is hardly vaporized at room temperature. However, high-boiling active energy ray-polymerizable monomers often have high boiling points due to an increase in molecular force between active energy ray-polymerizable monomers due to an increase in molecular weight. Viscosity tends to increase. Therefore, the active energy ray-curable ink composition itself containing such an active energy ray-polymerizable monomer also has a high viscosity and is difficult to be ejected as an ink jet. In particular, when used as an inkjet ink, an active energy ray-curable ink composition having a low viscosity in a room temperature environment is desirable.

  Also, even if the active energy ray polymerizable monomer has a low odor and low viscosity, the glass transition point (Tg) is extremely low, and the curability of the cured film formed by the active energy ray polymerizable monomer is extremely inferior. There is also. Hereinafter, the “active energy ray-curable ink composition” has characteristics that the cured film formed by the active energy ray-polymerizable monomer has the curability of the “active energy ray-curable ink composition” or “ink” It may be referred to as “curability of the composition”.

  A monomer A) which is a monofunctional monomer represented by the general formula (1) and a monomer B) which is a polyfunctional monomer represented by the general formula (2), and each of the active energy ray polymerizable monomers With the active energy ray-curable ink composition of the present invention, the content ratio of which is adjusted, the active energy has low odor and low viscosity and can satisfy the physical properties required for an ink composition used as an ink jet ink. It is characterized in that it can be a linear curable ink composition.

  The viscosity at a measurement temperature of 25 ° C. measured based on JIS Z 8803: 2001 of the active energy ray-curable ink composition of the present invention is preferably 20 mPa · s or less, and preferably 10 mPa · s or less. More preferably, it is more preferably 7 mPa · s or less. When the viscosity is 20 mPa · s or less, the ejection stability in inkjet is improved.

  Hereinafter, the active energy ray polymerizable monomer contained in the active energy ray-curable ink composition of the present invention will be described.

(Monofunctional monomer)
[Monomer A): Monofunctional monomer represented by general formula (1)]
Monomer A) is a monofunctional monomer represented by the following general formula (1). By containing the monomer A), the curing by the active energy ray is affected, the curing speed is increased, and the curability of the ink composition can be improved. Further, by adjusting the content ratio between the monomer A) and the monomer B described later, a cured film having stretchability can be formed, so that it is formed by the active energy ray-curable ink composition of the present invention. The cured film is a cured film having both stretchability and curability. Furthermore, since the monofunctional monomer represented by the following general formula (1) has a low odor, the active energy having a large odor due to the monomer A) being contained in the active energy ray-curable ink composition. It is not a linear curable ink composition. Furthermore, since the monofunctional monomer represented by the following general formula (1) has a low viscosity, the viscosity of the active energy ray-curable ink composition is increased due to the inclusion of the monomer A). Absent. For this reason, the active energy ray-curable ink composition containing the monomer A) has a very high ejection stability in inkjet, and can be an active energy ray-curable ink composition preferable as an inkjet ink.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、直鎖、分岐鎖又は環状の炭素数１以上１８以下のアルキル基又はフェニル基を示し、Ｒ^１とＲ^２とは結合して環を形成していてもよい。Ｒ^３は水素原子又は炭素数１以上４以下のアルキル基を示す。Ｒ^４は水素原子又は炭素数１以上４以下のアルキル基を示す。Ｒ^５は炭素数１以上５以下のアルキレン基を示す。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms or a phenyl group, and R ¹ and R ² are bonded to each other. R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents An alkylene group having 1 to 5 carbon atoms is shown.)

R ¹ and R ² are each independently preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms or a phenyl group. R ³ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. R ⁵ is preferably an alkylene group having 1 to 3 carbon atoms.

  Examples of monomer A) include 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (2-methyl-2-isobutyl-1,3-dioxolan-4-yl) Examples thereof include, but are not limited to, methyl (meth) acrylate and (cyclohexanespiro-2- (1,3-dioxolan-4-yl)) methyl (meth) acrylate. Among the monomers A), (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate is most preferred from the viewpoint of low viscosity and extremely low odor.

  Further, the content of the monomer A) is preferably 20% by mass or more, more preferably 25% by mass or more, based on the total amount of the monofunctional monomer. When the content of the monomer A) is less than 20% by mass based on the total amount of the monofunctional monomer, the viscosity of the active energy ray-curable ink composition is increased and the ejection stability in the inkjet is lowered, or the active energy ray-curable type This is not preferable because the curability of the ink composition is lowered and tackiness occurs.

[Monofunctional monomer other than monomer A)
The active energy ray-curable ink composition of the present invention may contain a monofunctional monomer other than the monomer A). Monofunctional monomers other than monomer A) include, for example, benzyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, 4-t-butylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxy. Ethyl acrylate, γ-butyrolactone acrylate, cresol acrylate, trimethylolpropane formal acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2 -Acryloyloxypropyl phthalate, paracumylphenoxyethylene glycol acrylate, nonylphenoxy polyethylene glycol Rate, 1-adamantyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, 3-3-5-trimethylcyclohexanol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and various modifications such as alkoxy modification and caprolactone modification to these acrylates And monofunctional monomers having a cyclic structure such as (meth) acrylate, acryloylmorpholine, N-vinylcaprolactam, imide acrylate, isooctyl acrylate, tridecyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, stearyl Acrylate, isodecyl acrylate, caprolactone acrylate, methoxypolyethylene glycol acrylate, methoxypoly Acyclic monofunctional monomers such as propylene glycol acrylate, 2-methoxyethyl acrylate, ethyl carbitol acrylate, and 2-ethylhexyl acrylate can be exemplified.

  Further, since at least one monofunctional monomer selected from the group consisting of tetrahydrofurfuryl acrylate, trimethylolpropane formal acrylate and 4-t-butylcyclohexyl acrylate has a low odor, the active energy ray curing of the present invention It can be particularly preferably used for a type ink composition. Specifically, at least one monofunctional monomer selected from the group consisting of monomer A), tetrahydrofurfuryl acrylate, trimethylolpropane formal acrylate, and 4-t-butylcyclohexyl acrylate in the total amount of monofunctional monomers. The content of is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.

[Content ratio of monofunctional monomer]
The total content of monofunctional monomers contained in the active energy ray-curable ink composition of the present invention is 45% by mass or more and 45% by mass or more and 95% by mass or less in the total amount of the active energy ray polymerizable monomer. Preferably, it is 45 mass% or more and 90 mass% or less. When the total content of monofunctional monomers contained in the active energy ray-curable ink composition of the present invention is 45% by mass or more, stretchability can be imparted to the cured film.

  The active energy ray-curable ink composition of the present invention imparts stretchability to a cured film by adjusting the ratio of the total content of monofunctional monomers including monomer A) in the total amount of active energy ray polymerizable monomers. However, even when a flexible base material is used as a recording medium, it is characterized in that cracking of the cured film can be suppressed.

[Monomer B): Multifunctional monomer represented by general formula (2)]
Monomer B) is a polyfunctional monomer represented by the following general formula (2). By containing the monomer B), the curability of the active energy ray-curable ink composition can be improved. Further, by adjusting the content ratio of the monomer A) and the monomer B), a cured film having stretchability can be formed. Therefore, the curing formed by the active energy ray-curable ink composition of the present invention. The film becomes a cured film having both stretchability and curability. Also, the content ratio is adjusted. Since the polyfunctional monomer represented by the following general formula (2) has a low odor, the monomer B) is contained in the active energy ray-curable ink composition. It is not an active energy ray-curable ink composition having a large odor. Furthermore, since the monofunctional monomer represented by the following general formula (2) has a low viscosity, the viscosity of the active energy ray-curable ink composition is increased due to the inclusion of the monomer B). Absent. For this reason, the active energy ray-curable ink composition containing the monomer B) can be an active energy ray-curable ink composition that is preferable as an inkjet ink.

R ⁴ —CH═CR ¹ —COOR ² —O—CH═CH—R ³ (2)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent organic residue having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or a monovalent organic group having 1 to 11 carbon atoms. Represents an organic residue, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

In the general formula (2), the divalent organic residue represented by R ² is a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, which may be substituted, An optionally substituted alkylene group having 2 to 20 carbon atoms and an optionally substituted divalent aromatic group having 6 to 11 carbon atoms having an oxygen atom by at least one of an ether bond and an ester bond. Is preferred. Among these, an alkylene group having 2 to 6 carbon atoms, such as an ethylene group, an n-propylene group, an isopropylene group, and a butylene group, an oxyethylene group, an oxy n-propylene group, an oxyisopropylene group, and an oxybutylene group An alkylene group having 2 to 9 carbon atoms and having an oxygen atom due to an ether bond in the structure is suitably used.

In the general formula (2), the monovalent organic residue having 1 to 11 carbon atoms represented by R ³ is linear, branched or cyclic substituted having 1 to 10 carbon atoms. Suitable alkyl groups and optionally substituted aromatic groups having 6 to 11 carbon atoms are preferred. Among these, an alkyl group having 6 to 8 carbon atoms such as an alkyl group having 1 to 2 carbon atoms, such as a methyl group or an ethyl group, a phenyl group, and a benzyl group is preferably used.

  In the general formula (2), when each organic residue is an optionally substituted group, the substituent is divided into a group containing a carbon atom and a group not containing a carbon atom. First, when the substituent is a group containing a carbon atom, the carbon atom is counted in the carbon number of the organic residue. Examples of the group containing a carbon atom include, but are not limited to, a carboxyl group and an alkoxy group. Next, examples of the group not containing a carbon atom include, but are not limited to, a hydroxyl group and a halo group.

In the general formula (2), the hydrogen atom represented by R ⁴ or the monovalent organic residue having 1 to 4 carbon atoms is a hydrogen atom or a straight chain, branched or 1 to 4 carbon atoms Cyclic optionally substituted alkyl groups are preferred. Of these, hydrogen atoms are preferably used.

  Specific examples of the monomer B) represented by the general formula (2) include, for example, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and 1-methyl-2 (meth) acrylate. -Vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2- (meth) acrylate Vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, (Meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl, (meth) acrylic acid 2- (vinyloxyethoxy) Ethyl, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, (meth) acrylic acid 2- (vinyloxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxy) Ethoxyisopropoxy) ethyl, (meth) acrylic acid 2- (vinyloxy) Isopropoxyethoxy) ethyl, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyiso) (meth) acrylate Propoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) Isopropyl, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate , ( (Meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxy) ethyl, (meth) 2- (isopropenoxyethoxyethoxyethoxy) ethyl acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth ) Polyethylene glycol monovinyl ether acrylate, and polypropylene glycol monovinyl ether (meth) acrylate.

  Among those described above, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, ( (Meth) acrylic acid 4-vinyloxybutyl, (meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6-vinyloxyhexyl, (meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid p- Vinyloxymethylphenylmethyl, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate Is preferred.

  Among these, since it has a low viscosity, a high flash point, and excellent curability of the active energy ray polymerizable monomer, (meth) acrylic acid 2- (vinyloxyethoxy) ethyl is preferable, and further, the odor is small, And since it is excellent in reactivity and adhesiveness, (meth) acrylic acid 2- (vinyloxyethoxy) ethyl is more preferable.

  Examples of 2- (vinyloxyethoxy) ethyl (meth) acrylate include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate and 2- (1-vinyloxyethoxy) ethyl (meth) acrylate. Examples of 2- (vinyloxyethoxy) ethyl acrylate include 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (1-vinyloxyethoxy) ethyl acrylate. Monomer B) may be used alone or in combination of two or more.

  Further, the content of the monomer B) is preferably 5% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 25% by mass or less, based on the total amount of the active energy ray polymerizable monomer. Since the content of the monomer B) is 5% by mass or more and 30% by mass or less in the total amount of the active energy ray-polymerizable monomer, stretchability can be imparted to the cured film. Even when the recording medium is used, cracks in the cured film can be suppressed.

[Polyfunctional monomers other than Monomer B)
Further, in addition to the monomer B), another polyfunctional monomer (polyfunctional monomer other than the polyfunctional monomer represented by the general formula (2)) may be appropriately added as long as the object of the present invention can be achieved.

  For example, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, polyalkylene glycol diacrylate, alkoxylated bisphenol A diacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, tetraethylene glycol diacrylate, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, glycerin triacrylate, And their modified number, modified species, structural differences It can be mentioned the (meth) acrylate.

  In addition, as the polyfunctional monomer other than the polyfunctional monomer represented by the general formula (2), a polyfunctional monomer capable of maintaining the viscosity of the active energy ray-curable ink composition to the extent that the ejection stability in inkjet can be improved, and / or Alternatively, it is preferable to use a polyfunctional monomer that does not increase the odor of the active energy ray-curable ink composition. An increase in viscosity and / or an increase in odor of the active energy ray-curable ink composition can be suppressed. The content of the active energy ray polymerizable monomer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.

  In the present invention, a polymer component having no reactivity may be further contained. Examples of such polymer components include acrylic resins and cellulose acetate butyrate resins.

[Active energy ray polymerization initiator]
The active energy ray-curable ink composition may contain an active energy ray polymerization initiator as necessary. Active energy rays are energy rays that can trigger polymerization reactions such as radicals, cations, and anions. In addition to rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams Any of proton beam, neutron beam and the like may be used, but curing by ultraviolet irradiation is preferable from the viewpoints of curing speed, availability of an irradiation apparatus, price, and the like. The active energy ray polymerization initiator is not particularly limited as long as it accelerates the polymerization reaction of the compound having an ethylenically unsaturated double bond in the active energy ray-curable ink composition by irradiation with active energy rays, Conventionally known active energy ray polymerization initiators can be used. Specific examples of active energy ray polymerization initiators include, for example, aromatic ketones containing thioxanthone, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, aromatic onium salts, organic peroxides Thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

  The amount of the active energy ray polymerization initiator may be an amount capable of appropriately starting the polymerization reaction of the active energy ray polymerizable monomer, and is 1.0% by mass or more and 20.20% with respect to the entire active energy ray curable ink composition. The content is preferably 0% by mass or less, and more preferably 3.0% by mass or more and 20.0% by mass or less. In the present invention, the active energy ray polymerization initiator is not necessarily required. For example, when an electron beam is used as the active energy ray, the active energy ray polymerization initiator may not be used.

[Color material]
The active energy ray-curable ink composition of the present invention may contain a color material as necessary. By containing a color material, the cured film can be preferably used as a cured film for decoration. The coloring material may be any inorganic pigment or organic pigment that is usually used in conventional oil-based ink compositions, such as carbon black, cadmium red, molybdenum red, chrome yellow, and cadmium yellow. , Titanium yellow, titanium oxide, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, diketopyrrolopyrrole, anthraquinone, benzimidazolone, anthrapyrimidine, azo pigment, phthalocyanine pigment, quinacridone Pigment, isoindolinone pigment, dioxazine pigment, selenium pigment, perylene pigment, perinone pigment, thioindigo pigment, quinophthalone pigment, metal complex pigment, aluminum paste, silica, calcium carbonate, magnesium carbonate Beam, clay, precipitated barium sulfate, pearl pigments, and the like.

  A preferable dispersed particle diameter of the pigment of the active energy ray-curable ink composition is preferably 10 nm or more and 300 nm or less in terms of a volume average particle diameter by a laser scattering method. When the volume average particle size is 10 nm or more and 300 nm or less, light resistance can be maintained, dispersion can be stabilized, and pigment sedimentation or when inkjet ink is ejected by an inkjet recording apparatus. Therefore, it is possible to reduce the possibility of occurrence of head clogging or ejection bending, and thus a more preferable active energy ray-curable ink composition can be obtained.

  In the present invention, when a pigment is used, its content may be adjusted as appropriate. Although it varies depending on the type of pigment, the content of the pigment in the entire inkjet ink composition is 0.1% by mass or more and 20.0% by mass or less in the case of an organic pigment from the viewpoint of achieving both dispersibility and coloring power. Is preferable, and 0.2 mass% or more and 10 mass% or less are more preferable. Further, in the case of an inorganic pigment, 1.0% by mass or more and 40.0% by mass or less are preferable, and 5.0% by mass or more and 20.0% by mass or less are more preferable in terms of achieving both dispersibility and coloring power. .

[Dispersant]
The active energy ray-curable ink composition may contain a dispersant as necessary. Examples of the dispersant include a polymer dispersant. The main chain of this polymer dispersant is made of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and the polymer dispersant has amino groups, carboxyl groups, sulfone groups, hydroxyl groups, etc. as side chains. It is preferable to have a polar group or a salt thereof.

  A preferred polymer dispersant is a polyester-based dispersant. Specific examples thereof include “SOLPERSE 33000” and “SOLPERSE 32000” and “SOLPERSE 24000” manufactured by Lubrizol Japan; “Dispersbyk 168” manufactured by BYK Chemie; Etc.

[Surface conditioner]
The active energy ray-curable ink composition may further contain a surface conditioner. Although it does not specifically limit as a surface conditioning agent, As a specific example, "BYK-306", "BYK-333", "BYK-371", "BYK-377", and Evonik Degussa Japan by the Big Chemie company which have dimethylpolysiloxane are included. “TegoRad2010”, “TegoRad2100”, “TegoRad2200N”, “TegoRad2300”, and the like manufactured by the company are listed.

  The content of the surface conditioner is preferably 0.1% by mass or more and 5.0% by mass or less with respect to the total amount of the ink composition. By setting the content to 0.1% by mass or more and 5.0% by mass or less, the ink composition has preferable wettability with respect to the thermoplastic resin substrate and the like, and recording on the substrate (forms an image). In this case, the active energy ray-curable ink composition can be spread and spread without causing repellency, so that it can be a particularly preferable active energy ray-curable ink composition.

[Delustering agent]
The active energy ray-curable ink composition of the present invention may contain a matting agent, if necessary. As the matting agent, for example, various powders such as silica, alumina, calcium carbonate and the like can be used. Matting agents may be used alone or in combination of two or more.

[Other additives]
The active energy ray curable ink composition may contain various additives such as a plasticizer, a polymerization inhibitor, a light stabilizer, and an antioxidant as other additives. The solvent can be added within a range that achieves the object of the present application.

[viscosity]
The viscosity at 25 ° C. measured based on JIS 8803: 2001 of the active energy ray-curable ink composition is preferably 20.0 mPa · s or less, more preferably 10.0 mPa · s or less, More preferably, it is 7.0 mPa · s or less. By setting it to 20.0 mPa · s or less, preferable ejection stability can be maintained when ejecting using an inkjet apparatus. Here, preferable ejection stability means that printing can be performed normally without missing ink dots or ejection irregularities during continuous printing.

  In particular, the active energy ray-curable ink composition of the present invention is a monomer A) which is a monofunctional monomer represented by the general formula (1) and does not have high viscosity. Since the monomer B), which is a functional monomer, is contained as an active energy ray polymerizable monomer, an active energy ray curable ink composition having a low viscosity can be obtained.

  In addition, the surface tension of the active energy ray-curable ink composition of the present invention is such that the surface tension at 40 ° C. is 20 mN / m or more and 40 mN / m or less from the viewpoint of inkjet dischargeability and discharge stability. preferable.

<Method for producing active energy ray-curable ink composition>
The method for producing the active energy ray-curable ink composition of the present invention is not particularly limited, and a conventionally known method can be used. In addition, when using a granular color material, a granular matting agent, etc., use a disperser to disperse with an active energy ray polymerizable monomer, a dispersing agent, etc., and then, if necessary, an active energy ray polymerization initiator. The active energy ray-curable ink composition of the present invention can be obtained by adding a surface conditioner and the like, stirring uniformly, and further filtering through a filter.

<Method for producing laminate>
The laminate of the present invention is produced by printing the active energy ray-curable ink composition on a substrate, preferably by an ink jet method, and then curing with an active energy ray. The printing can be performed by a conventionally known method such as an offset printing method, a gravure printing method, a spray method, or a brush coating method, but an inkjet method is preferable in that it can cope with a wide variety of small lots. Moreover, when printing by an inkjet system, you may print in the state which heated the inkjet head, and may print with room temperature. Since the active energy ray-curable ink composition of the present invention contains the monomer A) and the monomer B) which are extremely low in viscosity even at room temperature, the low energy active energy ray is also used in the room temperature environment. A curable ink composition can be obtained. Therefore, it is possible to print on the substrate without heating the inkjet head.

  An image can be formed on the substrate using the active energy ray-curable ink composition. For example, an ink set of an active energy ray-curable ink composition containing color materials of various shades is prepared, and after printing by an ink jet method, the ink composition is cured to display various images on the substrate. Can be formed. An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an image on a substrate are also within the scope of the present invention. In the present specification, the term “image” means a decorative image that can be recognized through vision including letters, diagrams, figures, symbols, photographs, etc. composed of a single color or a plurality of colors. Also included are patterns made of stone, cloth, sand, geometric patterns, letters, etc.

[Base material]
The substrate is not particularly limited, and for example, any of a coated paper, a non-coated paper, an absorbent body such as a fabric, and a non-absorbent substrate can be used. Specifically, as non-coated paper, renewed paper, medium-quality paper, high-quality paper, and coated paper as coated paper, art paper, cast paper, lightweight coated paper, fine coated paper, fabric, etc. Examples of the body include cotton, synthetic fabric, silk, hemp, fabric, non-woven fabric, leather, etc. Examples of the non-absorbent substrate include polyester resin, polypropylene synthetic paper, vinyl chloride resin, polyimide resin, metal, metal Examples thereof include foil-coated paper, glass, synthetic rubber, and natural rubber. Further, the active energy ray-curable ink composition of the present invention is not limited to the case where a non-flexible base material such as metal is used as a recording medium, and the flexible base material is a recording medium. Even when it is used as, it is possible to effectively suppress cracking of the cured film due to bending of the flexible substrate. Note that “having flexibility” means that the radius of curvature is usually 1 m, preferably 50 cm, more preferably 30 cm, still more preferably 10 cm, particularly preferably 5 cm at room temperature. Say.

[Curing with active energy rays]
The active energy ray for forming the cured film (hereinafter sometimes referred to as “cured film”) obtained by curing the active energy ray-curable ink composition of the present invention has a wavelength range of 200 nm or more and 450 nm or less. The light in the wavelength range of 250 nm or more and 430 nm or less is more preferable. The light source is not particularly limited, and examples thereof include a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, sunlight, and an LED lamp. By using these light sources and irradiating active energy rays so that the integrated light quantity is 100 mJ / cm ² or more, preferably 200 mJ / cm ² or more, the ink composition can be cured instantaneously.

  The thickness of the cured film is preferably 1 μm or more and 100 μm or less. By setting the thickness to 1 μm or more, the color density of the cured film containing the coloring material is not decreased, and physical properties such as a decrease in design properties, decorativeness, adhesion, and extensibility are improved. By setting the thickness to 100 μm or less, the ink composition can be sufficiently cured in a shorter time when the ink composition is irradiated with active energy rays, which is more preferable.

  The cured film thickness was measured by applying the active energy ray-curable ink composition of the present invention to a PET film (A4300, manufactured by Toyobo Co., Ltd.) under the same coating conditions as the prepared cured film, and then obtaining the cured film. The film thickness can be measured with a micrometer. In this specification, the thickness of the cured film is 10 locations per sample, and the average value of these is the thickness (the average thickness). The same applies to the protective layer and primer described later.

[Curing film]
The cured film formed from the active energy ray-curable ink composition of the present invention can be used as a decorative layer as long as it contains a coloring material as described above, but it can be added without adding a coloring material. If it discharges on a decoration layer, this cured film itself can also be utilized as an overcoat layer which protects a cured film. Further, it can be used as a primer layer for improving the adhesion between the substrate surface and the cured film. An active energy ray-curable ink composition that forms such a cured film is also within the scope of the present invention.

  The active energy ray-curable ink composition of the present invention may be used to form a decorative layer, an overcoat layer, or a primer layer independently only with a cured film formed by the active energy ray-curable ink composition of the present invention. Or a combination of these layers. For example, the active energy ray-curable ink composition of the present invention in which a coloring material is added to the active energy ray-curable ink composition of the present invention to form a decorative layer, and no coloring material is added on the decorative layer. An overcoat layer can also be formed by discharging. Moreover, the cured film formed with the active energy ray-curable ink composition of the present invention can also be used in combination with a decorative layer, overcoat layer or primer layer formed with a conventionally known ink composition. For example, when the active energy ray-curable ink composition of the present invention is used as a decorative layer, an overcoat layer can be formed on the decorative layer using a conventionally known overcoat composition.

  When forming an overcoat layer or primer layer on a substrate, any method may be used to form these layers, for example, spray coating, towel, sponge, non-woven fabric, tissue-based coating, etc. , Dispenser, brush coating, gravure printing, flexographic printing, silk screen printing, ink jet, thermal transfer method, etc. may be used.

[Overcoat layer]
For the purpose of further improving the durability of the laminate, an overcoat layer comprising a conventionally known overcoat agent or the ink composition of the present invention is used as an overcoat agent on the surface of the cured film of the ink composition of the present invention. The overcoat layer formed by using may be further formed. The overcoat layer is not limited to being formed on the surface of the layer made of the cured film of the ink composition, but may be directly formed on the surface of the substrate, or may be formed on the surface of the substrate. You may form in the surface of the primer layer mentioned later.

  As the overcoat agent, the active energy ray-curable ink composition of the present invention can be preferably used. By using the active energy ray-curable ink composition of the present invention, excellent curability and stretchability can be realized. Furthermore, for example, when an overcoat layer is formed with an overcoat agent using the active energy ray-curable ink composition of the present invention on a cured film using the active energy ray-curable ink composition of the present invention, the curing is performed. Since the film and the overcoat layer have the same composition, their adhesion is extremely high. Therefore, it is particularly preferable to use the active energy ray-curable ink composition of the present invention as an overcoat agent for the cured film of the active energy ray-curable ink composition of the present invention.

  The thickness of the overcoat layer is preferably 1 μm or more and 100 μm or less. The thickness is preferably 1 μm or more because the cured film can be appropriately protected. Moreover, it is preferable for the thickness to be 100 μm or less because the drying time can be shortened to form an overcoat layer and the productivity can be improved.

  Further, when the overcoat layer is formed, the design properties are imparted to the overcoat layer by adjusting the conditions such as the discharge amount of the ink composition and the time from the discharge of the ink composition to the irradiation of the active energy ray. You can also. For example, it is also possible to form a three-dimensional and highly designed overcoat layer with irregularities by making the surface matt or glossy, or by making the surface film thickness non-uniform. Specifically, after discharging the ink composition, the surface can be made glossy by irradiating active energy rays after a predetermined time has elapsed, and the surface can be quickly irradiated by irradiating active energy rays after discharging. It can be matte. In addition, unevenness can be imparted by increasing / decreasing the discharge amount per time depending on the discharge location, and unevenness difference from other locations can be achieved by repeating the ejection of the ink composition and the irradiation of active energy rays at the same location. Can also be given. An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming an uneven image are also within the scope of the present invention. Such an overcoat layer is desirably formed by an ink jet method from the viewpoint of easy condition adjustment. The concavo-convex image is not necessarily limited to what is visually recognized, and includes, for example, a colorless cured film or a cured film having a single color or a plurality of colors, as long as it has a concavo-convex shape. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all by these description.

<Preparation of Ink Composition (Examples 1 to 12, Comparative Examples 1 to 5)>
Table 1 shows the parts by mass of the active energy ray polymerizable monomer, active energy ray polymerization initiator, photopolymerization initiator, polymer dispersant, and pigment of the ink composition in the total amount of the ink composition in Examples and Comparative Examples. Example) and Table 2 (comparative example).

  In Tables 1 and 2, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate is “MEDOL-10” (monofunctional having a heterocyclic structure) manufactured by Osaka Organic Chemical Industry. Monomer, corresponding to “Monomer A)”. ).

  In Tables 1 and 2, it is 2- (2-vinyloxyethoxy) ethyl acrylate (“VEEA-AI” manufactured by Nippon Shokubai Co., Ltd. (which is a polyfunctional monomer and corresponds to “Monomer B”)).

  In Tables 1 and 2, tetrahydrofurfuryl acrylate is “Biscoat # 150” (corresponding to a monofunctional monomer that is a monofunctional monomer and not “monomer A”) from Osaka Organic Chemical Industry.

  In Tables 1 and 2, 4- (1,1-dimethylethyl) cyclohexyl acrylate is “LAROMER TBCH” (corresponding to a monofunctional monomer that is a monofunctional monomer and not “monomer A”) manufactured by BASF. is there.

  In Table 2, “V-CAP (N-vinyl-ε-caprolactam)” corresponds to “V-CAP (RC)” (monofunctional monomer, which is a monofunctional monomer and not “monomer A”) manufactured by ISB Japan. ).

  In Table 2, PO-modified (× 2) neopentyl glycol diacrylate is “SR9003” (corresponding to a polyfunctional monomer that is a polyfunctional monomer and not “monomer B”) manufactured by Sartomer.

  In Table 2, IBXA (isobornyl acrylate) is “light acrylate IBXA” (corresponding to a monofunctional monomer that is a monofunctional monomer and not “monomer A”) manufactured by Kyoeisha Chemical.

  In Table 2, 2-phenoxyethyl acrylate is “Biscoat # 192” (corresponding to a monofunctional monomer that is a monofunctional monomer and not “monomer A”) manufactured by Osaka Organic Chemical Industry.

  In Tables 1 and 2, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is “IRGAQUA TPO” (photopolymerization initiator) manufactured by BASF.

  In Tables 1 and 2, “Solsperse 32000” means a polymer dispersant manufactured by Nippon Lubrizol.

  In Tables 1 and 2, carbon black is “NEROX5600” (pigment) manufactured by Evonik Degussa.

  In Table 2, “monomer A) / ink composition” means the content (mass%) of monomer A) in the total amount of the active energy ray-curable ink composition.

  In Table 2, “monofunctional monomer other than monomer A) / ink composition” means the content (mass%) of a monofunctional monomer other than monomer A) in the total amount of the active energy ray-curable ink composition. .

  In Table 2, “monofunctional monomer / ink composition” means the content (mass%) of the monofunctional monomer in the total amount of the active energy ray-curable ink composition.

  In Table 2, “monomer / ink composition” means the content (% by mass) of the active energy ray-polymerizable monomer in the total amount of the active energy ray-curable ink composition.

  In Table 2, “monofunctional monomer / monomer” means the content (mass%) of the monofunctional monomer in the total amount of the active energy ray polymerizable monomer.

  In Table 2, “monomer A) / monofunctional monomer” means the content (mass%) of monomer A) in the total amount of monofunctional monomer.

[Preparation of ink composition]
Each monomer material was mixed so that it might become a ratio shown in Table 1, Table 2, and it stirred at room temperature (20-25 degreeC) for 1 hour. Thereafter, it was confirmed that there was no undissolved residue. Then, it filtered using the membrane filter and prepared the ink composition of an Example and a comparative example.

<Viscosity measurement test>
The viscosity of the ink compositions of Examples and Comparative Examples was measured. Specifically, the viscosity was measured at 25 ° C. using a viscosity measurement tester (AMVn manufactured by Anton Paar) based on JIS Z 8803: 2001. The measurement results are shown in Tables 1 and 2.

<Odor test>
An odor test was performed on the ink compositions of Examples and Comparative Examples. Specifically, the ink composition was diluted with polyethylene glycol (ink composition: polyethylene glycol = 1: 1000), five subjects were smelled, and sensory evaluation was performed according to the following criteria. When the majority evaluation is 3, “○” is indicated. When the majority evaluation is 1 or 2, “X” is indicated (indicated in the table as “odor”). The measurement results are shown in Tables 1 and 2.
Evaluation 3: There is no odor.
Evaluation 2: There is a slight odor.
Evaluation 1: There is an unpleasant odor.

  [Manufacture of laminates]

A laminate was produced using vinyl chloride having a thickness of 80 μm as a base material. Each sample was produced on the surface of the base material by the inkjet method using the compositions constituting the cured films shown in Tables 1 and 2. Then, the ink composition is cured using a UV-LED lamp (wavelength 385 nm) under the conditions of an integrated light amount of 100 mJ / cm ² and a peak illuminance of 1500 mW / cm ² (both UV-V wavelength region (375 to 415 nm)). did. Measurement of the integrated light quantity and peak illuminance was performed using an ultraviolet light quantity meter UV Power Pack 2 (manufactured by EIT). This produced the cured film.

<Extension test>
About the laminated body of an Example and a comparative example, after producing a laminated body and using a test piece of dumbbell-shaped No. 6 form (JIS K6251-5) after one day, the range of elongation from 0% to 50% at 25 ° C It was confirmed whether or not the cured film was cracked when the laminate was stretched once at a strain rate of 100 mm / min. The elongation was calculated from (length of laminated body when crack of cured film occurred−original length of laminated body) / original length of laminated body × 100. Tables 1 and 2 show the elongation at the time when substantial cracking occurred. Here, the substantial crack means a crack in which a crack (crack) has progressed by 50% or more with respect to the length of the sample piece width.

<Curing test>
The curability was evaluated by rubbing the cured film with a cotton swab and checking for the presence or absence of color transfer. The results are shown in Tables 1 and 2. When no color transfer is observed with a cotton swab, “◎”, when there is almost no color transfer with a cotton swab, “○”, when color transfer is observed with a cotton swab, and substantially exceeds the allowable range Was “×”.

<Tack test>
Evaluation of tack was performed at room temperature.
The laminate was placed at room temperature, and the cured film was touched with a finger to check for stickiness. The results are shown in Tables 1 and 2. The case where there was no stickiness was designated as “◎”, the case where there was a little stickiness but was substantially within the allowable range was indicated as “◯”, and the case where the stickiness was strong and substantially exceeded the allowable range was indicated as “x”.

<Evaluation results>
From Tables 1 and 2, the active energy ray-curable ink compositions of the examples have low viscosity and low odor, and the stretchability of the cured film formed by the active energy ray-curable ink compositions of the examples, It turns out that it is excellent in sclerosis | hardenability and tackiness.

Claims (8)

As an active energy ray polymerizable monomer,
Monomer A): a monofunctional monomer represented by the following general formula (1),
Monomer B): a polyfunctional monomer represented by the following general formula (2),
In the total amount of the active energy ray polymerizable monomer,
The total content of monofunctional monomers including the monomer A) is 45% by mass or more,
In the total amount of the monofunctional monomer,
An active energy ray-curable ink composition having a content of the monomer A) of 20% by mass or more.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms or a phenyl group, and R ¹ and R ² are bonded to each other. R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents An alkylene group having 1 to 5 carbon atoms is shown.)
R ⁴ —CH═CR ¹ —COOR ² —O—CH═CH—R ³ (2)
(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent organic residue having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or a monovalent organic group having 1 to 11 carbon atoms. Represents an organic residue, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) In the total amount of the monofunctional monomer,
The content of at least one monofunctional monomer selected from the group consisting of the monomer A), tetrahydrofurfuryl acrylate, trimethylolpropane formal acrylate and 4-t-butylcyclohexyl acrylate is 90% by mass or more. 2. The active energy ray-curable ink composition according to 1.   The viscosity at 25 ° C. measured based on JIS Z 8803: 2001 is 7.0 mPa · s or less. The active energy ray-curable ink composition according to claim 1.   The active energy ray-curable ink composition according to claim 1, which is used as an inkjet ink.   The active energy ray-curable ink composition according to claim 1 is formed as a cured film having a thickness of 10 μm on a vinyl chloride sheet having a thickness of 80 μm, and the cured film is formed by forming the cured film. When a base material is subjected to a tensile test at 25 ° C. and a tensile speed of 10 mm / min as a test piece of dumbbell-shaped No. 6 (JIS K6251-5), the cured film breakage point at which the cured film breaks. An active energy ray-curable ink composition having an elongation percentage of 50% or more.   A laminate in which an ink cured film layer that is a cured film of the active energy ray-curable ink composition according to any one of claims 1 to 5 is formed on a substrate.   An image forming method for forming an image and / or a concavo-convex image on a substrate using the active energy ray-curable ink composition according to claim 1.   The manufacturing method of the printed matter which forms an image and / or an uneven | corrugated image on a base material using the active energy ray hardening-type ink composition in any one of Claim 1 to 5.