WO2018235748A1

WO2018235748A1 - Active energy ray-curable ink composition, layered body using said ink composition, image forming method for forming image on substrate, and method for producing printed article

Info

Publication number: WO2018235748A1
Application number: PCT/JP2018/023005
Authority: WO
Inventors: 森田　浩司; 克巳渡部; 公淳宇▲高▼
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2017-06-19
Filing date: 2018-06-15
Publication date: 2018-12-27
Also published as: JP2019001962A; JP6445624B1

Abstract

Provided is an active energy ray-curable ink composition which exhibits excellent adhesion to a substrate, even when the active energy ray-curable ink composition is coated onto the surface of a substrate which primarily exhibits a wetting tension no greater than a prescribed value. As active energy ray-polymerizable components, the active energy ray-curable ink composition at least contains the component A and the component B from among: a component A which is a bifunctional component represented by general formula (1) R4-CH=CR1-COOR2-O-CH=CH-R3 (In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a divalent organic residue having a carbon number of 2-20, inclusive, R3 represents a hydrogen atom or a monovalent organic residue having a carbon number of 1-11, inclusive, and R4 represents a hydrogen atom or an alkyl group having a carbon number of 1-4, inclusive); a component B which is a urethane(meth)acrylate component having a structure derived from an alkanediol; a component C which is a bifunctional component that does not contain the component A or the component B; and a component D which is a monofunctional component that does not contain the component B.

Description

Active energy ray curable ink composition, laminate using this ink composition, image forming method for forming an image on a substrate, and method for producing printed matter

The present invention relates to an active energy ray-curable ink composition, a laminate using the ink composition, an image forming method for forming an image on a substrate, and a method for producing a printed matter.

Conventionally, development of active energy ray curable ink compositions which are cured by ultraviolet light, electron beam or other active energy rays has been promoted. Since the active energy ray-curable ink composition is quick-drying, ink bleeding can be prevented even when printing on a substrate such as plastic, glass, coated paper, or the like that does not or hardly absorbs the ink. The active energy ray curable ink composition is composed of an active energy ray polymerizable component, a coloring material and other additives.

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

According to Patent Document 1, the active energy ray-curable ink composition described in Patent Document 1 is an active energy ray-curable ink composition which becomes highly reactive while having a low viscosity, and further, a predetermined functional It is an active energy ray-curable ink composition capable of imparting flexibility to the cured ink film layer by containing a radical aliphatic urethane (meth) acrylate.

Patent No. 6011600

In order to form an ink cured film layer which is a cured film of an active energy ray curable ink composition on the surface of a substrate used as a recording medium, adhesion between the substrate and the active energy ray curable ink composition Sex is required.

From the viewpoint of the present inventors, it has been found that the adhesion to the active energy ray curable ink composition may be lowered depending on the surface condition of the substrate. Specifically, when the active energy ray-curable ink composition is applied to the surface of a substrate having a wetting tension of less than a predetermined value, the adhesion between the active energy ray-curable ink composition and the substrate is reduced.

The present invention has been made in view of the above circumstances, and the object of the present invention is to apply an active energy ray curable ink composition to the surface of a substrate having a wetting tension of less than a predetermined value. An object of the present invention is to provide an active energy ray-curable ink composition which is excellent in adhesion to a substrate even if it is present.

The inventors of the present invention have conducted intensive studies to solve the above problems, and by optimizing the content of a predetermined active energy ray polymerizable component contained in the active energy ray curable ink composition, It has been found that the above problems can be solved, and the present invention has been completed. Specifically, the present invention provides the following.

(1) As an active energy ray polymerizable component,
Component A): a bifunctional component represented by the following general formula (1):
Component B): a urethane (meth) acrylate component having a structure derived from an alkanediol,
Component C): a bifunctional component which does not contain the component A) and the component B).
Component D): a monofunctional component which does not contain the component B)
And at least component A) and component B)
In the total amount of the active energy ray polymerizable component,
The total content of the component A) and the component C) is 88.0% by mass or more.
Content of said B component is 1.0 mass% or more and 9.0 mass% or less,
An active energy ray curable ink composition, wherein the content of the component D) is not more than 9.0% by mass.
R ⁴ -CH = CR ¹ -COOR ² -O-CH = CH-R ³ (1)
(Wherein, 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 1 to 11 carbon atoms. R ⁴ represents a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.

(2) The active energy ray-curable ink composition according to claim 1, which is used on a substrate surface having a wetting tension of 45.0 mN / m or less measured by a test method in accordance with JIS K 6768: 1999.

(3) The active energy ray curing according to (1) or (2), wherein the content of the component A) in the total amount of the component A) and the component C) is 70.0 mass% or more. Mold ink composition.

(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), wherein the carbon number of the alkanediol of the component B) is 1 or more and 6 or less.

(6) The active energy ray-curable ink composition according to any one of (1) to (5), which has a viscosity of 7 mPa · s or less measured at 40 ° C. based on DIN EN ISO 12058-1.

(7) A laminate, wherein an ink cured film layer which is a cured film of the active energy ray curable ink composition according to any one of (1) to (6) is formed on the substrate surface.

(8) The laminate according to (7), wherein the wet tension of the surface of the substrate measured by the test method in accordance with JIS K 6768: 1999 is 45.0 mN / m or less.

(9) An image forming method for forming an image and / or a concavo-convex image on the surface of a substrate using the active energy ray-curable ink composition according to any one of (1) to (6).

(10) The image forming method according to (9), wherein the wet tension of the surface of the substrate measured by the test method in accordance with JIS K 6768: 1999 is 45.0 mN / m or less.

The manufacturing method of the printed matter which forms an image and / or an uneven | corrugated image in the base-material surface using the active energy ray-curable ink composition in any one of (11) (1) to (6).

(12) The method for producing the printed matter according to (11), wherein the wet tension of the surface of the substrate measured by the test method in accordance with JIS K 6768: 1999 is 45.0 mN / m or less.

The active energy ray-curable ink composition of the present invention is excellent in adhesion to the substrate even when the active energy ray-curable ink composition is applied to the surface of the substrate having a wetting tension of a predetermined value or less. It is an active energy ray curable ink composition.

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

<Active energy ray curable ink composition>
An active energy ray-curable ink composition according to an embodiment of the present invention (hereinafter simply referred to as the active energy ray-curable ink composition of the present invention) has at least a difunctional group represented by the following general formula (1) It is an active energy ray curable ink composition containing A component which is a component, and B component which is a urethane (meth) acrylate. In the present specification, "(meth) acrylate" means both acrylate and methacrylate. Further, in the present specification, the “bifunctional component” is an active energy ray polymerizable component, which is a monomer having two ethylenically unsaturated groups (also referred to as an oligomer or a prepolymer depending on the molecular weight) Means).

R ⁴ -CH = CR ¹ -COOR ² -O-CH = CH-R ³ (1)
(Wherein, 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 1 to 11 carbon atoms. R ⁴ represents a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.

The active energy ray-curable ink composition of the present invention may also contain a bifunctional component C) which does not contain the component A) and the component B). Furthermore, you may include D component which is a monofunctional component which does not contain B component). And, the total content of the component A) and the component C) is 88.0% by mass or more in the total amount of the active energy ray polymerizable component. Furthermore, content of B component is 1.0 mass% or more and 9.0 mass% or less in whole quantity of an active energy ray polymeric component. In addition, it is preferable that content of A component) is 70.0 mass% or more in whole quantity of A component) and C component). Further, in the present specification, the “monofunctional component” is an active energy ray polymerizable component, which is a monomer having one ethylenically unsaturated group (a component also referred to as an oligomer or prepolymer depending on the molecular weight) Means).

Component B) may be a monofunctional component, a bifunctional component, or a trifunctional or higher component. The “difunctional component” which does not contain “component A) and component B) in component C) refers to“ component A) ”when component B) is a bifunctional component,“ component A)), and It means that it is "difunctional component other than B component)." When the component B) is not a bifunctional component, it means that the component C) is a "difunctional component other than the component A)". Similarly, “a monofunctional component not containing component B)” in component D) means a monofunctional component containing no component B) when component B) is a monofunctional component Means to be. When the component B) is not a monofunctional component, it means that the component D is a "monofunctional component".

Since a bifunctional component such as component A) has low odor and low viscosity, it has low odor and low content if it is an active energy ray curable ink composition containing component A) as an active energy ray polymerizable component. It is possible to make a viscous active energy ray curable ink composition.

However, in the view of the present inventors, when an active energy ray-curable ink composition containing a component A) and a urethane acrylate is applied to the surface of a substrate having a predetermined wetting tension or less, the active energy ray cures It has been found that the adhesion between the mold ink composition and the substrate may be reduced.

Therefore, in the active energy ray-curable ink composition of the present invention, the total content of component A) and component C), the content of component B), the content of component D), and the content of component A) The quantity and each are specified. In the past, there have been active energy ray-curable ink compositions containing a bifunctional component represented by the general formula (1) such as component A) and a urethane acrylate, but the surface is wet below a predetermined level The active energy ray-curable ink composition of the present invention, in which the type and content of the active energy ray polymerizable component are optimized for the purpose of improving the adhesion to the surface of the substrate which is tension, is a novel active energy It is a line-curable ink composition.

Specifically, the active energy ray-curable ink composition of the present invention is used on a substrate surface having a wetting tension of 45.0 mN / m or less, which is measured by a test method in accordance with JIS K 6768: 1999. Preferably, it is used for a substrate surface of 40.0 mN / m or less, more preferably for a substrate surface of 37.0 mN / m or less.

The wet tension measured by the test method in accordance with JIS K 6768: 1999 can be measured, for example, by using a mixture for wet tension test manufactured by Wako Pure Chemical Industries, Ltd.

Further, the bifunctional component represented by the general formula (1) has a low odor and a low viscosity. Therefore, the active energy ray-curable ink composition of the present invention containing the bifunctional component represented by the general formula (1) is excellent also in the point of low odor, low viscosity and high viscosity stability. Therefore, it is preferable that the active energy ray curable ink composition of the present invention be used as an inkjet ink in which the viscosity of the active energy ray curable ink composition needs to be strictly adjusted according to the specification of the nozzle and the like.

In the present specification, that the odor of the active energy ray curable ink composition is small means that the odor of the laminate is low, in which the ink cured film layer which is a cured film of the active energy ray curable ink composition is formed. If the laminate has a small odor, the active energy ray curable ink composition is used to form an image on a substrate, or the active energy ray curable ink composition is used to print When manufacturing a product, it is possible for workers to concentrate on the work without worrying about odors, and it is also possible for workers with a sensitive nose to work without a mask. is there.

The viscosity at a measurement temperature of 40 ° C. of the active energy ray-curable ink composition of the present invention varies depending on the specifications of the printing apparatus and the nozzles, but is preferably 20 mPa · s or less and 10 mPa · s or less Is more preferable, and 7 mPa · s or less is more preferable. When the viscosity is 20 mPa · s or less, the ejection stability in the inkjet is improved. The viscosity can be measured, for example, by means of a falling ball viscometer according to DIN EN ISO 12058-1.

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

[Component A): Bifunctional Component Represented by General Formula (1)]
A component) is a bifunctional component represented by following General formula (1). By containing the component A), the curability of the active energy ray-curable ink composition can be improved.

In General Formula (1), as a divalent organic residue represented by R ² , a linear, branched or cyclic optionally substituted alkylene group having 2 to 20 carbon atoms, in the structure And an optionally substituted alkylene group having 2 to 20 carbon atoms and an optionally substituted divalent aromatic group having 6 to 11 carbon atoms, each having an oxygen atom by at least one of an ether bond and an ester bond. It is suitable. Among these, alkylene groups having 2 to 6 carbon atoms, such as ethylene group, n-propylene group, isopropylene group, and butylene group, oxyethylene group, oxy n-propylene group, oxyisopropylene group, and oxybutylene group An alkylene group having 2 to 9 carbon atoms having an oxygen atom by an ether bond in a structure such as is preferably used.

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

In General Formula (1), when each organic residue is a group which may be substituted, the substituent is divided into the group containing a carbon atom, and the group which does not contain a carbon atom. First, when the substituent is a group containing a carbon atom, the carbon atom is counted in the number of carbon atoms 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 (1), as a hydrogen atom or a monovalent organic residue having 1 to 4 carbon atoms represented by R ⁴ , a hydrogen atom or a linear, branched or 1 to 4 carbon atom, Preferred is a cyclic optionally substituted alkyl group. Among these, a hydrogen atom is preferably used.

The total content of the active energy ray-curable ink composition of the present invention is 88.0% by mass or more based on the total amount of the active energy ray polymerizable component, and the total content of the component A) and the component C) is 90.0 mass % Or more is preferable, and 92.0% by mass or more is most preferable. When the total content of component A) and component C) is less than 88.0% by mass in the total amount of the active energy ray polymerizable component, the adhesion to the surface of the substrate having a predetermined wetting tension or less is descend.

In the active energy ray-curable ink composition of the present invention, the content of component A) is preferably 70.0% by mass or more based on the total amount of component A) and component C). When the content of the component A) is 70.0% by mass or more in the total amount of the component A) and the component C), the viscosity of the active energy ray-curable ink composition can be lowered. The content of component A) is preferably 80.0% by mass or more, more preferably 90.0% by mass or more, of the total amount of components A) and C), and 95.0%. It is more preferable that the content is at least% by mass.

Specific examples of the component A) represented by the general formula (1) include, for example, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and 1-methyl-2 (meth) acrylic acid -Vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, (Meth) acrylic acid 2-methyl-3-vinyloxypropyl, (meth) acrylic acid 1,1-dimethyl-2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxybutyl, (meth) acrylic acid 1-methyl-2- Vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, ( Ta) p-vinyloxymethylphenylmethyl acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenyl methyl (meth) acrylate, 2- (vinyloxyethoxy) (meth) acrylic acid Ethyl, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, (meth) acrylate 2- (vinyloxyisopropoxy) propyl, (meth) acrylate 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylate 2- (vinyloxyethoxyethoxy) ethyl, (meth) acrylate 2- (vinyloxy) Ethoxyisopropoxy) ethyl, (meth) acrylic acid 2- (vinyloxy) Sopropoxyethoxy) ethyl, (meth) acrylate 2- (vinyloxyisopropoxyisopropoxy) ethyl, (meth) acrylate 2- (vinyloxyethoxyethoxy) propyl, (meth) acrylate 2- (vinyloxyethoxyiso) Propoxy) propyl, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) (meth) acrylate Isopropyl, 2- (vinyloxyethoxyisopropoxy) isopropyl of (meth) acrylic acid, 2- (vinyloxyisopropoxyethoxy) isopropyl of (meth) acrylic acid, 2- (vinyloxyisopropoxyisopropoxy) isopropyl of (meth) acrylic acid , (M Ta) 2- (vinyloxyethoxyethoxyethoxy) ethyl acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) ethyl (meth) acrylate, (meth) 2- (Isopropenoxyethoxyethoxy) ethyl acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) And the like) acrylic acid polyethylene glycol monovinyl ether, and (meth) acrylic acid polypropylene glycol monovinyl ether. When these (meth) acrylates are contained as active energy ray polymerizable components, the content of these (meth) acrylates is preferably 90.0% by mass or more in the total amount of component A) 95. The content is more preferably 0% by mass or more, further preferably 99.0% by mass or more.

Among the above-mentioned, 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- Vinyloxymethylphenyl methyl, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate Is preferred.

Among these, 2- (vinyl) ethyl 2- (vinyloxyethoxy) acrylate is preferable because of its low viscosity, high flash point and excellent curability of the active energy ray polymerizable component, and the odor is small, In addition, 2- (vinyloxyethoxy) ethyl (meth) acrylate is more preferable because of its excellent reactivity and adhesion.

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. Component A) may be used alone or in combination of two or more.

[Component B]: Urethane (meth) acrylate component having a structure derived from an alkanediol
The active energy ray-curable ink composition of the present invention further contains a urethane (meth) acrylate component having a structure derived from alkanediol. The urethane (meth) acrylate has a main skeleton having a plurality of urethane groups (urethane bonds) obtained by the addition reaction of a polyol and a polyisocyanate (a portion connected with the plurality of urethane groups described above), and It is a compound in which a (meth) acrylic group is introduced at the terminal and / or side chain.

And this urethane (meth) acrylate is urethane (meth) acrylate which has a structure derived from alkanediol. The urethane (meth) acrylate which has a structure derived from alkanediol means that the above-mentioned "polyol" is urethane (meth) acrylate which became "alkanediol". That is, urethane (meth) acrylate having a structure derived from alkanediol means urethane (meth) acrylate containing a molecular chain derived from alkanediol.

The alkanediol may have a linear structure or one containing an alicyclic alkyl group in part of the structure, but preferably has a linear structure without a cyclic structure. Further, in the linear structure, the arrangement of the carbon element is preferably linear or branched, and more preferably linear.

The alkanediol is preferably an alkanediol having 1 to 6 carbon atoms, more preferably butanediol having 4 carbon atoms, and a linear 1,4-butanediol. Is more preferred.

The polyisocyanate in the urethane (meth) acrylate is not particularly limited, but is preferably, for example, one containing an alicyclic alkyl group in part of its structure. As such polyisocyanate, isophorone diisocyanate (IPDI) etc. can be mentioned, for example.

Component B) is an active energy ray polymerizable component, and is a monomer having an ethylenically unsaturated group (including a component also referred to as an oligomer or prepolymer depending on the molecular weight). The number of functional groups of the component B) is not particularly limited, but is preferably 2 or less. Component B) may be a monomer, or may be a component called an oligomer or prepolymer depending on the molecular weight, but a component called an oligomer or prepolymer having a molecular weight of 1000 or more Is preferred.

The urethane (meth) acrylate which has a structure derived from alkanediol can mention, for example, urethane (meth) acrylate which has isophorone diisocyanate (IPDI) / butanediol / hydroxyethyl acrylate as a structural component. When these urethane (meth) acrylates are contained as active energy ray polymerizable components, the content of these urethane (meth) acrylates is preferably 90.0% by mass or more in the total amount of the component B), It is more preferable that it is 95.0 mass% or more, and it is still more preferable that it is 99.0 mass% or more.

Content of B component is 1.0 mass% or more and 9.0 mass% or less in whole quantity of an active energy ray polymeric component. It can be set as the active energy ray hardening-type ink composition which is excellent in adhesiveness with a substrate as it is this content. If the amount is less than 1.0% by mass, the adhesion to the substrate is reduced. On the other hand, if it exceeds 8.0% by mass, adhesion to the substrate is lowered, and the viscosity of the active energy ray-curable ink composition is increased. The content of the component B) is preferably 2.0% by mass or more, and more preferably 3.0% by mass or more, in the total amount of the active energy ray polymerizable component. The content of the component B) is preferably 8.5% by mass or less, more preferably 8.0% by mass or less, based on the total amount of the active energy ray polymerizable component.

[Component C): Component A) and Component B), and a bifunctional component]
The active energy ray-curable ink composition of the present invention does not contain the component A) and the component B) as an optional component as long as the object of the present invention can be achieved. You may contain. Component C) contains component C) in an amount of 70.0% by mass or more based on the total amount of component A) and component C) in the total amount of component A) and component C). Is preferred. Making the viscosity of the active energy ray-curable ink composition low by containing component C) so as to be 70.0% by mass or more in the total amount of component A) and component C). it can.

As Component C), for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long -Chain aliphatic di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di Meta) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, di Cyclopentanyl di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di ( Meta) acrylate, methoxylated cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxy neopentyl glycol) adipate, biphenyl Phenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, Zinc di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, alkoxylated bisphenol A di (meth) acrylate and the like can be mentioned. When these bifunctional (meth) acrylates are contained as active energy ray polymerizable components, the content of these bifunctional (meth) acrylates is 90.0% by mass or more in the total amount of the component C). Preferably, the content is 95.0% by mass or more, and more preferably 99.0% by mass or more.

1,6-Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polyalkylene glycol di ( It is preferable that it is 1 or more types selected from the group which consists of a meta) acrylate and alkoxylated bisphenol A di (meth) acrylate.

[Component D): Monofunctional Component Containing Component B)]
The active energy ray-curable ink composition of the invention may contain, as an optional component, a component (D) as a monofunctional component which does not contain the component (B) as long as the object of the present invention can be achieved. However, the component D) contains the component D) such that the content of the monofunctional component is 9.0% by mass or less in the total amount of the active energy ray polymerizable component. When the content of the component D) is more than 9.0% by mass, the adhesion with the surface of the substrate having a wetting tension of a predetermined value or less is unfavorably lowered. The content of the component D) is preferably 8.0% by mass or less, more preferably 7.5% by mass or less, and more preferably 1.0% by mass or less in the total amount of the active energy ray polymerizable component. More preferably, it is 0.0% by mass.

Examples of monofunctional components include tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, n-decyl (meth) acrylate, benzyl (meth) Acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, ethyl carbitol (meth) ) Acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, -Butyl (meth) acrylate, isononyl (meth) acrylate, nonyl (meth) acrylate, methoxyethyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, acryloyl morpholine, N-acryloyloxyethyl hexahydrophthalimide, stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, 2,2,2- and trifluoroethyl (meth) acrylate, 2,2,3,3 -Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate and the like . In addition, when these monofunctional (meth) acrylates are contained as an active energy ray polymerizable component, the content of these monofunctional (meth) acrylates is 90.0 mass% or more in the total amount of D component). Preferably, the content is 95.0% by mass or more, and more preferably 99.0% by mass or more.

Among them, tetrahydrofurfuryl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable from the viewpoint of the adhesion between the active energy ray-curable ink composition and the substrate.

[Component of trifunctional or higher]
The active energy ray curable ink composition of the present invention may contain a trifunctional or higher functional component as an active energy ray polymerizable component as long as the effects of the present invention are not impaired. The total amount of the active energy ray polymerizable component is preferably 3.0% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.5% by mass or less. Further, in the present specification, the “trifunctional or higher component” is an active energy ray polymerizable component, and is a monomer having three or more ethylenic unsaturated groups (also called an oligomer or prepolymer depending on the molecular weight) Containing the ingredients)).

Examples of trifunctional or higher components include trimethylpropane triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, tetraethylene glycol diacrylate Acrylate, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, glycerin triacrylate, and (meth) acrylates having different modified numbers, modified species, and structural differences can be mentioned. When these (meth) acrylates are contained as active energy ray polymerizable components, the content of these (meth) acrylates is preferably 90.0% by mass or more in the total amount of trifunctional or higher components. It is more preferable that it is 95.0 mass% or more, and it is still more preferable that it is 99.0 mass% or more.

[Active energy ray polymerization initiator]
The active energy ray-curable ink composition of the present invention may contain an active energy ray polymerization initiator (hereinafter, may be simply referred to as a polymerization initiator) as necessary. The active energy ray is an energy ray that can trigger a polymerization reaction of a radical, cation, anion or the like, a light ray such as far ultraviolet ray, ultraviolet ray, near ultraviolet ray, infrared ray or the like, electromagnetic wave such as X ray or γ ray, electron beam, Although any of a proton beam, a neutron beam and the like may be used, in terms of curing speed, availability of an irradiation apparatus, cost and the like, curing by ultraviolet irradiation is preferable. The polymerization initiator is not particularly limited as long as it accelerates the polymerization reaction of the active energy ray polymerizable monomer in the active energy ray curable ink composition by irradiation of active energy rays, and a conventionally known polymerization initiator may be used. It can be used. Specific examples of the polymerization initiator include, for example, aromatic ketones including thioxanthone etc., α-aminoalkylphenones, α-hydroxy ketones, acyl phosphine 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 polymerization initiator according to the present invention may be an amount capable of appropriately initiating the polymerization reaction of the active energy ray polymerizable monomer, and is 1.0% by mass or more with respect to the entire active energy ray curable ink composition. Is preferably, and more preferably 3.0% by mass or more. Moreover, it is preferable that it is 20.0 mass% or less with respect to the whole active energy ray curable ink composition. In the present invention, the polymerization initiator is not necessarily essential. For example, when using an electron beam as an active energy ray, the polymerization initiator may not be used.

[Polymerization inhibitor]
The active energy ray-curable ink composition of the present invention may optionally contain a polymerization inhibitor. As the polymerization inhibitor, it is preferable to use a phenothiazines polymerization inhibitor and a nitrosamines polymerization inhibitor. By using a combination of a phenothiazines polymerization inhibitor and a nitrosamines polymerization inhibitor as a polymerization inhibitor, it is stable for a long period of time both in an oxygen-free atmosphere and in the presence of oxygen, and has excellent curability. An active energy ray-curable inkjet ink composition is obtained.

[Color material]
The active energy ray-curable ink composition of the present invention may contain a colorant, if necessary. By containing a coloring material, a cured film can be preferably used as a cured film for decoration. The coloring material may be any inorganic or organic pigment generally used in conventional ink compositions, for example, carbon black, cadmium red, molybdenum red, chromium yellow, cadmium yellow, Titanium yellow, titanium oxide, chromium oxide, bilizian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, diketopyrrolopyrrole, anthraquinone, benzimidazolone, anthrapyrimidine, azo based pigments, phthalocyanine based pigments, quinacridones Pigments, isoindolinone pigments, dioxazine pigments, Sureren pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, aluminum pastes, silica, calcium carbonate, magnesium carbonate Clay, precipitated barium sulfate, pearl pigments.

The preferable dispersed particle size of the pigment in the active energy ray-curable ink composition of the present invention is preferably 10 nm or more in volume average particle size by a laser scattering method. Further, in the active energy ray-curable ink composition of the present invention, a preferable dispersed particle size of the pigment is preferably 300 nm or less in volume average particle size by a laser scattering method. By setting the volume average particle diameter to 10 nm or more and 300 nm or less, or 10 nm or more and 300 nm or less, it becomes possible to maintain the light resistance, and the dispersion can be stabilized, and the sedimentation of the pigment and the inkjet recording device Since it is possible to reduce the possibility of the occurrence of head clogging and discharge bending when discharging the ink, it is possible to obtain a more preferable active energy ray curable ink composition.

In the present invention, when a pigment is used, its content may be adjusted appropriately. The content of the pigment in the total active energy ray-curable ink composition is preferably 0.1% by mass or more, in the case of an organic pigment, from the viewpoint of achieving both dispersibility and coloring power, though it varies depending on the type of pigment. 0.2 mass% or more is more preferable. In addition, in the case of an organic pigment, 20.0% by mass or less is preferable, and 10.0% by mass or less is more preferable in terms of achieving both dispersibility and coloring power. Moreover, in the case of an inorganic pigment, 1.0 mass% or more is preferable, and 5.0 mass% or more is more preferable, in terms of achieving both dispersibility and coloring power. Moreover, in the case of an inorganic pigment, 40.0 mass% or less is preferable, and 20.0 mass% or less is more preferable.

[Dispersing agent]
The active energy ray-curable ink composition of the present invention may optionally contain a dispersant. As a dispersing agent, a polymer dispersing agent is mentioned, for example. The main chain of this polymer dispersant is polyester type, polyacrylic type, polyurethane type, polyamine type, polycaprolactone type, etc., and the polymer dispersant is composed of amino group, carboxyl group, sulfone group, hydroxyl group etc. as a side chain. It is preferable to have a polar group of

As the polymer dispersant, "DISPERBYK-168", "DISPERBYK-2013", "DISPERBYK-2055", "DISPERBYK-2096", "DISPERBYK-2052", "DISPERBYK-2152", "DISPERBYK-2155", "DISPERBYK-2155", manufactured by BIC-Chemie Co., Ltd. “BYK-9076”, “BYK-9077”, “BYKJET-9142”, “BYKJET-9150”, “BYKJET-9151”, “BYKJET-9152”; BSF “Dispex Ultra FA 4420” Dispex Ultra FA 4425 "," Efka PX 4701 "," Efka PX 4731 "," Efka PX 4732 "," Efka PX 4733 "; "SOL SPERSE 3000", "SOL SPERSE 5000", "SOL Sparse 9000", "SOL Sparse 12000", "SOL Sparse 13240", "SOL Sparse 13940", "SOL Sparse 17000", "SOL Sparse 22000", "SOL Sparse 24000", manufactured by Brisol Corporation "Sors spars 26000", "Sors spars 28000", "Sors spars 32000", "Sors spars 33000", "Sors spars 36000", "Sors spars 39000", "Sors spars 41000", "Sors spars 71000"; "Disperon DA-375" "Disperon DA-234" "Disperon DA-550"; Ajinomoto Finetech "Aispar PB 821", "Aisper PB 822", "Aisper PB 824", "Aisper PB 881"; manufactured by Kyoeisha Chemical Co., Ltd., "Floren G-700", "Floren KDG-2400", "Floren GW-1500"; Evonik Degussa Examples include "TEGO Dispers 685" and "TEGO Dispers 690" manufactured by Japan.

[Surface modifier]
The active energy ray-curable ink composition of the present invention may further contain a surface conditioner. The surface conditioner is not particularly limited, but specific examples thereof include BYK-307, BYK-333, BYK-354, BYK-361N, and BYK-by BYK-Chemie having dimethylpolysiloxane. 377 "," BYK-378 "," BYK-3455 "," BYK-UV3500 "," BYK-UV3505 "," BYK-UV3510 "," BYK-UV3535 "," BYK-UV3570 "; Evonik Degussa Japan Co., Ltd. “TEGO Flow 425”, “TEGO Glide 100”, “TEGO Glide 110”, “TEGO Glide 130”, “TEGO Glide 432”, “TEGO Glide 435”, “TEGO Glide 440”, “TEGO Glide 450”, “TEGO Glide” G400, TEGO Twin 4000, TEGO Twin 4200, TEGO Wet 270, TEGO Rad 2010, TEGO Rad 2010, TEGO Rad 2 100, TEGO Rad 2 200 N, TEGO Rad 2 250, TEGO Rad 2 300, TEGO Rad 2 500 , "TEGO Rad 2700";"PolyflowKL-401","PolyflowKL-402","PolyflowKL-403","PolyflowKL-404" manufactured by Kyoeisha Chemical Co., Ltd .; .75 "," Polyflow No. 77 "," Polyflow No. 90 "," Polyflow No. 95 "," Polyflow No. 99C ";" TEGO W made by Evonik Degussa Japan " t500 "and the like.

The content of the surface control agent is preferably 0.1% by mass or more based on the total amount of the ink composition. The content of the surface control agent is preferably 5.0% by mass or less in the total amount of the ink composition. When the content is 0.1% by mass or more or 5.0% by mass or less, the ink composition has preferable wettability to the thermoplastic resin substrate and the like, and the image is recorded on the substrate (forming an image) Since the active energy ray-curable ink composition can wet and spread without causing repelling during the formation of the ink composition, the particularly preferable active energy ray-curable ink composition can be obtained.

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

[Other additives]
The active energy ray-curable ink composition of the present invention may further contain various additives such as a plasticizer, a light stabilizer, and an antioxidant as other additives. A solvent can also be added within the range which achieves the purpose of this application.

The surface tension of the active energy ray-curable ink composition of the present invention is preferably 20 mN / m or more at 40 ° C. from the viewpoint of the ink jettability and discharge stability. The surface tension at 40 ° C. is preferably 40 mN / m or less.

<Production method of printed matter>
In the present invention, the printed material (laminate) is produced by printing the above-mentioned active energy ray curable ink composition on a substrate, preferably by an inkjet method, and then curing the ink by using an active energy beam. Film layer) is performed. When printing is performed by the inkjet method, printing may be performed in a state where the inkjet head is heated, or printing may be performed at room temperature.

In addition, an image can be formed on a substrate using the active energy ray-curable ink composition of the present invention. For example, an ink set of an active energy ray-curable ink composition containing coloring materials of various colors is prepared, and printing is performed by an inkjet method, and then the ink composition is cured to form various images on a substrate. It 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, “image” refers to a decorative image that can be recognized through vision including characters, charts, figures, symbols, photographs, etc. consisting of a single color or a plurality of colors, for example, wood, Also included are patterns made of stone, grain, grain, geometric patterns, characters, etc.

[Base material]
The substrate is not particularly limited, and, for example, any of an absorbent body such as coated paper, non-coated paper, fabric and the like and non-absorbent substrate can be used. Specifically, non-coated paper includes new paper, medium-grade paper, high-quality paper, and coated paper includes coated paper, art paper, cast paper, lightweight coated paper, finely coated paper, fabrics, etc. Examples of the body include cotton, synthetic fiber fabric, silk, hemp, cloth, non-woven fabric, leather and the like, and non-absorptive substrates include polyester resins, polypropylene synthetic papers, vinyl chloride resins, polyimide resins, metals, metals Foil coated paper, glass, synthetic rubber, natural rubber and the like can be exemplified.

Among them, the active energy ray-curable ink composition of the present invention has a content of a predetermined active energy ray polymerizable component so as to improve adhesion to a substrate surface having a wetting tension mainly equal to or less than a predetermined value. Since it is an optimized active energy ray-curable ink composition, it can be said that it is a preferred method of use for a substrate surface having a wetting tension of a predetermined value or less.

Specifically, it is preferable that the suitable base material has a wetting tension of 45.0 mN / m or less, which is measured by a test method based on JIS K 6768: 1999, on its surface, and 40.0 mN / m or less Is more preferable, and 37.0 mN / m or less is more preferable.

In addition, the active energy ray-curable ink composition of the present invention is a substrate that contains a predetermined amount of fluorine atoms, which is difficult to maintain adhesion with conventional active energy ray-curable ink compositions. Can also be suitably used. For example, a base material formed of a resin composition containing a fluorine-based additive, a resin sheet coated or laminated with a coating solution containing a fluorine-based additive on the surface of a resin such as polyethylene terephthalate (PET), etc. be able to. In this case, the base material containing a predetermined amount of fluorine atoms is a group containing a fluorine atom of 0.01 atomic mass% or more, 0.05 atomic mass% or more, or 0.10 atomic mass% or more. The material can be illustrated. The content of fluorine atoms is preferably 5.0 atomic mass% or less, preferably 3.0 atomic mass% or less, and more preferably 1.0 atomic mass% or less. When the content of fluorine atoms is 5.0 atomic mass% or less, adhesion between the substrate and the active energy ray curable ink composition can be maintained. In addition, content of the fluorine atom in a base material calculates the quantity of the fluorine atom when the whole surface of the detected atom is set to 100, for example, using the fluorescent X ray (XRF) to measure a base material surface. can do. Fluorescent X-ray (XRF) refers to irradiation of a sample containing a certain atom (fluorine atom) with primary X-ray to generate fluorescent X-ray of the atom (fluorine atom), and the fluorescent X-ray of the atom (fluorine atom) This is a method of performing quantitative analysis of atoms (fluorine atoms) contained in a sample by measuring the intensity.

[Hardening by active energy ray]
The active energy ray for forming a cured film (hereinafter sometimes referred to as "cured film") obtained by curing the active energy ray-curable ink composition of the present invention is light in a wavelength range of 200 nm or more. Preferably, light in a wavelength range of 250 nm or more is more preferable. The light of the wavelength range at 450 nm or less is preferable, and the light of the wavelength range at 430 nm or less is more preferable for the active energy ray for forming a cured film. 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, an LED lamp and the like. With these light sources, integrated light quantity 100 mJ / cm ² or more, preferably by irradiation with an active energy ray to be 200 mJ / cm ² or more, it is possible to cure the ink composition instantaneously.

The thickness of the cured film is preferably 1 μm or more. Moreover, it is preferable that the thickness of a cured film is 100 micrometers or less. By setting the thickness to 1 μm or more, physical properties such as design property and decorativeness, adhesion, and extensibility are improved without decreasing the color density of the cured film containing the coloring material, it is more preferable. 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 an active energy ray, which is more preferable.

The method of measuring the thickness of the cured film was obtained 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 produced cured film. The thickness of the membrane can be measured by a micrometer. In addition, in this specification, thickness of a cured film is performed ten places per sample, and the average value of these is made thickness (average thickness). The same applies to the protective layer and the primer described later.

[Cured film]
This cured film can be used as a decorative layer as long as it contains a coloring material or the like as described above. Furthermore, the main cured film can also be used as an overcoat layer for protecting the cured film by discharging onto the decorative layer without adding a coloring material. Furthermore, it can be utilized also as a primer layer for improving the adhesiveness of both by forming between a base-material surface and a cured film. An active energy ray curable ink composition for forming such a cured film is also within the scope of the present invention.

In the active energy ray-curable ink composition of the present invention, the decorative layer, the overcoat layer or the primer layer may be independently formed only with the cured film formed by the active energy ray-curable ink composition of the present invention. It can also be formed by combining a plurality of these layers. For example, a coloring material or the like is added to the active energy ray-curable ink composition of the present invention to form a decorative layer, and the active energy ray-curable ink composition of the present invention on which the coloring material or the like is not added on the decorative layer The overcoat layer can also be formed by discharging. The cured film formed by the active energy ray-curable ink composition of the present invention can also be used in combination with a decorative layer, an overcoat layer or a primer layer formed by 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 also be formed on the decorative layer using a conventionally known overcoat composition.

When forming an overcoat layer or a primer layer on a base material, any method may be used as a method of forming these layers, for example, application using spray application, towel, sponge, non-woven fabric, tissue etc. , Dispenser, brush coating, gravure printing, flexographic printing, silk screen printing, ink jet, thermal transfer system, etc. may be used. When the overcoat layer is formed by discharging the active energy ray-curable ink composition of the present invention to which no coloring material or the like is added, it is preferable to form these layers by inkjet.

[Overcoat layer]
In order to further improve 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 in the ink composition of the present invention. An overcoat layer formed by using it may be further formed. The overcoat layer is not limited to the case where it is formed on the surface of the layer formed of the cured film of the ink composition, and may be formed directly on the surface of the substrate, or it is 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 on a cured film using the active energy ray-curable ink composition of the present invention by an overcoat agent using the active energy ray-curable ink composition of the present invention, the curing 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 a cured film in the active energy ray curable ink composition of the present invention.

The thickness of the overcoat layer is preferably 1 μm or more. It is preferable to set the thickness to 1 μm or more because the cured film can be appropriately protected. The thickness of the overcoat layer is preferably 100 μm or less. By setting the thickness to 100 μm or less, the drying time for forming the overcoat layer can be shortened and the productivity can be excellent, which is preferable.

In addition, when forming the overcoat layer, the design property is imparted to the overcoat layer by adjusting 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. It can also be done. For example, it is also possible to form a three-dimensional, high-designed overcoat layer having irregularities by making the surface matte or glossy or by making the surface film thickness uneven. Specifically, after the ink composition is discharged, the surface can be made to have a gross tone by irradiating the active energy ray after a predetermined time has elapsed, and after the ink composition is discharged, the surface can be irradiated quickly by the active energy ray. It can be matted. Further, asperity can also be imparted by increasing or decreasing the discharge amount at one time depending on the discharge location, and by repeating the discharge of the ink composition and the irradiation of the active energy ray at the same location, the difference in unevenness with other locations It can also be granted. An active energy ray-curable ink composition for forming such a cured film and an image forming method for forming a concavo-convex image are also within the scope of the present invention. In addition, it is desirable to form such an overcoat layer by an inkjet system from the point which conditions adjustment is easy. The concavo-convex image is not necessarily limited to what is recognized visually, and for example, it may be 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. .

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these descriptions.

Preparation of Ink Composition (Examples, Comparative Examples)>
The parts by mass of the active energy ray polymerizable monomer, polymerization inhibitor, polymerization initiator, surfactant, and pigment dispersion of the ink composition in the total amount of the ink composition in Examples and Comparative Examples are shown in Tables 1 to 3 .

[Preparation of Ink Composition]
Each material was mixed in the proportions shown in Tables 1 to 3 and stirred at room temperature (20 to 25 ° C.) for 1 hour. After that, it was confirmed that there was no melting residue. After that, filtration was performed using a membrane filter to prepare active energy ray-curable ink compositions of Examples and Comparative Examples. The numbers in Tables 1 to 3 are the numerical values of the respective components in the total amount of the active energy ray-curable ink composition. In Tables 4 and 5, based on the numerical values of each component in the total amount of the active energy ray-curable ink composition shown in Tables 1 to 3, "A component" in "the total amount of the active energy ray polymerizable component" And the total content of the component C), the content of the component B), the content of the component D) and the total amount of the component A) and the component C) The content of the component A) is described respectively.

In Tables 1 to 3, tetrahydrofurfuryl acrylate is Biscoat # 150 manufactured by Osaka Organic Chemical Industry Co., Ltd., which corresponds to a monofunctional component (component D).

In Tables 1 to 3, phenoxyethyl acrylate is SR339A manufactured by Sartomer and corresponds to a monofunctional component (component D).

In Tables 1 to 3, 2- (2-vinyloxyethoxy) ethyl acrylate is VEEA-AI manufactured by Nippon Shokuhin Co., Ltd. and is a bifunctional component (corresponding to the component A)).

In Tables 1 to 3, 1,6-hexanediol diacrylate is 1,6HX-A manufactured by Kyoeisha Chemical Co., Ltd. and corresponds to a bifunctional component (component C)).

In Tables 1 to 3, 1,9-nonanediol diacrylate is 1,9-ND-A manufactured by Kyoeisha Chemical Co., Ltd. and corresponds to a bifunctional component (component C)).

In Tables 1 to 3, neopentyl glycol diacrylate is ND-A manufactured by Kyoeisha Chemical Co., Ltd. and corresponds to a bifunctional component (component C)).

In Tables 1 to 3, dipentaerythritol polyacrylate is KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. and is a trifunctional or higher functional component.

In Tables 1 to 3, trimethylpropane triacrylate is Biscoat # 295 manufactured by Osaka Organic Chemical Industry Co., Ltd. and is a trifunctional or higher functional component.

In Tables 1 to 3, urethane (meth) acrylate A is a urethane acrylate oligomer (mass average molecular weight: 13000), and urethane (meth) having isophorone diisocyanate (IPDI) / butanediol / hydroxyethyl acrylate as a component. It is an acrylate. That is, it is a urethane (meth) acrylate component (corresponding to component B) having a structure derived from alkanediol.

In Tables 1 to 3, urethane (meth) acrylate B is a urethane acrylate oligomer (mass average molecular weight: two components of 1,800 and 5300), and as a component, both components are isophorone diisocyanate (IPDI) / butanediol / hydroxyl. It is a urethane (meth) acrylate having ethyl acrylate. That is, it is a urethane (meth) acrylate component (corresponding to component B) having a structure derived from alkanediol.

In Tables 1 to 3, urethane (meth) acrylate C is a urethane acrylate oligomer (mass average molecular weight: 2000), and as a component, isophorone diisocyanate (IPDI) / dipentaerythritol hexaacrylate (DPHA) polyfunctional acrylate ( The number of functional groups is 10). That is, it is a urethane (meth) acrylate component which does not have a structure derived from an alkanediol which does not correspond to the component B).

In Tables 1 to 3, the urethane (meth) acrylate D is a urethane acrylate oligomer (mass average molecular weight: 3000), and is a hydrogenated MDI / hydroxyethyl acrylate (having 2 functional groups) as a component. That is, it is a urethane (meth) acrylate component which does not have a structure derived from an alkanediol which does not correspond to the component B).

In Tables 1 to 3, urethane (meth) acrylate E is a urethane acrylate oligomer (mass average molecular weight: 3500), and as a component, hexamethylene diisocyanate (HDI) / caprolactone / hydroxyethyl acrylate (number of functional groups is 2) It is. That is, it is a urethane (meth) acrylate component which does not have a structure derived from an alkanediol which does not correspond to the component B).

In Tables 1 to 3, the urethane (meth) acrylate F is a urethane acrylate oligomer (mass average molecular weight: 1100), and is an IPDI / PETA-based urethane acrylate (having 6 functional groups) as a component. That is, it is a urethane (meth) acrylate component which does not have a structure derived from an alkanediol which does not correspond to the component B).

In Tables 1 to 3, urethane (meth) acrylate G is a urethane acrylate oligomer (mass average molecular weight: 5300), and hexamethylene diisocyanate (HDI) / caprolactone / hydroxyethyl acrylate (having 3 functional groups) as a component. It is. That is, it is a urethane (meth) acrylate component which does not have a structure derived from an alkanediol which does not correspond to the component B).

In Tables 1 to 3, urethane (meth) acrylate H is a urethane acrylate oligomer (mass average molecular weight: 1000), and is bisphenol A epoxy acrylate (having 2 functional groups) as a component. That is, it is a urethane (meth) acrylate component which does not have a structure derived from an alkanediol which does not correspond to the component B).

In Tables 1 to 3, APO is DAIDO UV-CURE APO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by Daido Kasei Kogyo Co., Ltd. and is a polymerization initiator.

In Tables 1 to 3, BYKUV 3570 is BYKUV 3570 (polyester modified polydimethylsiloxane solution (70% active ingredient)) manufactured by Big Chemie Japan Ltd. and is a surfactant.

In Tables 1 to 3, MEHQ is hydroquinone monomethyl ether, which is a polymerization inhibitor.

In Tables 1 to 3, TDP is antage TDP (phenothiazine) manufactured by Kawaguchi Chemical Industry Co., Ltd. and is a polymerization inhibitor.

In Tables 1 to 3, JR 407 is titanium oxide, which is TITANIX JR 407 manufactured by Tayca Corporation.

In Tables 1 to 3, TEGO 685 is a dispersant and is TEGO Dispers 685 manufactured by Evonik Togsa Japan.

[Production of laminate]

A laminate was manufactured using a film substrate (FNS gloss 50 PAT1 10 μm manufactured by LINTEC Corporation) as a substrate. The active energy ray-curable ink compositions of Examples and Comparative Examples shown in Tables 1 to 3 were produced on the surface of the substrate by an inkjet method. Then, using a metal halide lamp, the ink composition was cured under the conditions of an integrated light amount of 420 mJ / cm ² and a peak illuminance of 3300 mW / cm ² (both measured values in the UV-A wavelength range (320 to 390 nm)). The measurement of the integrated light quantity and the peak illuminance was performed using an ultraviolet light meter UV Power Puck 2 (manufactured by EIT). Thus, a laminate having an ink cured film layer (film thickness: about 10 μm) was formed. In addition, the wet tension measured by the test method based on JISK6768: 1999 of the surface of a film base material was 35 mN / m. Moreover, when elemental analysis was performed on the surface of the film substrate by fluorescent X-ray (XRF), an elemental fluorine (0.4 atomic mass%) was detected.
<Adhesiveness confirmation test>
The adhesion of the cured laminate was confirmed. Specifically, a cellophane adhesive tape is attached to the cured ink film layer in the laminate, and after the ink cured film layer and the cellophane adhesive tape are sufficiently adhered, the cured ink film layer when the cellophane adhesive tape is peeled at 90 degrees The adhesion of the above to the base material was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 4 and 5.
[Evaluation criteria]
◎: Peeling of the ink cured film layer was not observed.
:: A part of the ink cured film layer was peeled off, but at a level causing no problem in practical use.
X: A part of the ink cured film layer was peeled off, which was a level causing a problem in practical use.

<Curable test>
About the layered product after the above-mentioned hardening, curability was checked. Specifically, the cured ink film layer in the laminate was touched with a finger to confirm the curing speed and the adhesion of the ink. And the curability was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 4 and 5.
[Evaluation criteria]
◎: The ink did not adhere to the finger at all and did not feel sticky.
○: The ink did not adhere to the finger, but felt slightly sticky.
X: Ink adhered to the finger.

<Odor confirmation test>
The odor of the cured laminate was confirmed. Specifically, it smelled a smell from a distance of 1.0 cm from the laminate. And the curability was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 4 and 5.
[Evaluation criteria]
◎: There was no unpleasant smell.
○: There was almost no unpleasant odor, and it had a low odor.
X: There was an unpleasant odor (specific odor, irritating odor).

<Viscosity confirmation test>
The viscosities of the active energy ray-curable ink compositions of Examples and Comparative Examples were measured. Specifically, the viscosities of the active energy ray-curable ink compositions of Examples and Comparative Examples were measured at 40 ° C. using a falling ball viscometer based on DIN EN ISO 12058-1. And the curability was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 4 and 5.
[Evaluation criteria]
◎: The viscosity was 7 mPa · s or less.
○: The viscosity was more than 7 mPa · s and not more than 20 mPa · s.
X: The viscosity was over 20 mPa · s.

According to Tables 4 and 5, the active energy ray-curable ink composition of the example in which the content of the predetermined active energy ray polymerizable component is optimized is “adhesion”, “curable”, “odor”, and It has become a good evaluation result in "viscosity".

On the other hand, in the total amount of the active energy ray polymerizable component, the content of the component D) (monofunctional component not containing the component B) exceeds 8.2% by mass, and A in the total amount of the active energy ray polymerizable component Active energy ray-curable ink compositions of Comparative Examples 1 and 2 in which the total content of the component (C) and the component C) is less than 88.0% by mass are carried out in "adhesiveness", "curable" and "odor". The evaluation results are worse than those of the active energy ray curable ink composition of the example.

The active energy ray-curable ink compositions of Comparative Examples 3 and 5 in which the total content of the component A) and the component C) in the total amount of the active energy ray polymerizable component is less than 90.0 mass are: In the "adhesion", the evaluation results are worse than those of the active energy ray-curable ink composition of the example.

Furthermore, the active energy ray-curable type of Comparative Examples 6 to 12 containing a urethane (meth) acrylate component having no structure of each origin instead of Comparative Example 4 not containing B component) and B component) The ink composition has an evaluation result in which the "adhesiveness" is deteriorated as compared with the active energy ray-curable ink composition of the example.

From the above, the active energy ray-curable ink composition of the present invention in which the content of the predetermined active energy ray polymerizable component is optimized is the active energy ray-curable ink on the surface of the substrate having a wetting tension of a predetermined value or less. Even when the composition is applied, it is an active energy ray-curable ink composition excellent in adhesion to a substrate, and good also in "curability", "odor", and "viscosity". It was confirmed that the ink composition was an active energy ray curable ink composition.

Claims

As an active energy ray polymerizable component,
Component A): a bifunctional component represented by the following general formula (1):
Component B): a urethane (meth) acrylate component having a structure derived from an alkanediol,
Component C): a bifunctional component which does not contain the component A) and the component B).
Component D): a monofunctional component which does not contain the component B)
And at least component A) and component B)
In the total amount of the active energy ray polymerizable component,
The total content of the component A) and the component C) is 88.0% by mass or more.
Content of said B component is 1.0 mass% or more and 9.0 mass% or less,
An active energy ray curable ink composition, wherein the content of the component D) is not more than 9.0% by mass.
R 4 -CH = CR 1 -COOR 2 -O-CH = CH-R 3 (1)
(Wherein, 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 1 to 11 carbon atoms. R 4 represents a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
The active energy ray-curable ink composition according to claim 1, which is used on a substrate surface having a wetting tension of 45.0 mN / m or less measured by a test method according to JIS K 6768: 1999.
The active energy ray-curable ink composition according to claim 1 or 2, wherein a content of the component A) in a total amount of the component A) and the component C) is 70.0% by mass or more.
The active energy ray curable ink composition according to any one of claims 1 to 3, which is used as an inkjet ink.
The active energy ray-curable ink composition according to any one of claims 1 to 4, wherein the carbon number of the alkanediol of the component B) is 1 or more and 6 or less.
The active energy ray-curable ink composition according to any one of claims 1 to 5, having a viscosity of 7 mPa · s or less measured at 40 ° C according to DIN EN ISO 12058-1.
The laminated body in which the ink cured film layer which is a cured film of the active energy ray curable ink composition in any one of Claim 1 to 6 was formed in the base-material surface.
The laminate according to claim 7, wherein the wet tension of the surface of the substrate measured by the test method in accordance with JIS K 6768: 1999 is 45.0 mN / m or less.
The image formation method which forms an image and / or an uneven | corrugated image in the base-material surface using the active energy ray-curable ink composition in any one of Claims 1-6.
The image forming method according to claim 9, wherein the wetting tension of the surface of the substrate measured by the test method according to JIS K 6768: 1999 is 45.0 mN / m or less.
The manufacturing method of the printed matter which forms an image and / or an uneven | corrugated image in the base-material surface using the active energy ray-curable ink composition in any one of Claims 1-6.
The method for producing a printed matter according to claim 11, wherein the wet tension of the surface of the substrate measured by the test method in accordance with JIS K 6768: 1999 is 45.0 mN / m or less.