JP2017141382A - Radiation-curable inkjet composition and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-curable inkjet composition capable of achieving the low odor property of the composition itself and the low odor property of a cured film formed from the composition.SOLUTION: The radiation-curable inkjet composition according to the present invention comprises: a monomer A having a linear or branched chain structure having one group selected from a (meth)acryloyloxy group or (meth)acryloyl group, and at least two oxygen atoms other than the (meth)acryloyloxy group or the (meth)acryloyl group; and a monomer B having a linear or branched chain structure having one group selected from a (meth)acryloyloxy group or (meth)acryloyl group, with the total number of nitrogen atoms and oxygen atoms other than the (meth)acryloyloxy group or (meth)acryloyl group being two or more, and showing a Tg of the homopolymer thereof of 90°C or higher.SELECTED DRAWING: None

Description

  The present invention relates to a radiation curable ink jet composition and an ink jet recording method using the composition.

  In recent years, in order to form an image having high water resistance, solvent resistance, scratch resistance, and the like on the surface of a recording medium, a radiation curable inkjet composition that is cured when irradiated with radiation in an inkjet recording method has been used. ing. Generally, the radiation curable inkjet composition is composed of a polymerizable compound such as a monofunctional monomer or a polyfunctional monomer, and an organic material such as a photopolymerization initiator. For this reason, in the radiation curable inkjet composition, reducing the odor of the cured and dried printed image is one of the important issues.

  For example, Patent Document 1 discloses that a combination of various photopolymerization initiators having low volatility and low odor of a printed image after curing and drying has excellent curability and adhesion to a recording medium, and the odor of the printed image. UV curable process color jet inks are disclosed in which

  Further, Patent Document 2 contains at least 50% by weight of trimethylolpropane formal acrylate (CTFA), and the high Tg monomer is less than 5% by weight, so that the flexibility of the printing stage and end user can be maintained. Ink jet inks are disclosed that have low odor when used.

JP 2007-321034 A JP2015-14409A

  However, the ultraviolet curable process color jet ink disclosed in Patent Document 1 can reduce the odor of the printed image, but cannot reduce the odor of the ink itself. For this reason, an unpleasant odor is filled during printing, and there is a concern about the health damage of workers and the like. On the other hand, in the inkjet ink disclosed in Patent Document 2, the glass transition temperature (Tg) is not sufficiently high, so that the coating film hardness cannot be secured, and unreacted monomers and initiator decomposition products appear on the coating film surface. As a result, sufficient low odor of the printed image cannot be secured.

  Therefore, some aspects of the present invention can achieve both the low odor of the composition itself and the low odor of the cured film formed from the composition by solving at least a part of the above-described problems. A radiation curable inkjet composition is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the radiation curable inkjet composition according to the present invention is:
Monomer having a linear or branched structure having one (meth) acryloyloxy group or one (meth) acryloyl group and two or more oxygen atoms in addition to the (meth) acryloyloxy group and the (meth) acryloyl group A and
It has one (meth) acryloyloxy group or (meth) acryloyl group, the total number of nitrogen atoms and oxygen atoms other than (meth) acryloyloxy group and (meth) acryloyl group is 2 or more, linear or A monomer B having a branched structure and a homopolymer Tg of 90 ° C. or higher;
It is characterized by containing.

  According to the radiation curable inkjet composition of Application Example 1, the odor of the composition itself can be reduced by increasing the standard boiling point of the composition itself. Further, since the surface hardness is sufficiently secured even after curing, volatilization of the uncured monomer into the atmosphere after the coating film is formed is suppressed, and the odor of the cured film can be reduced.

[Application Example 2]
In the radiation curable inkjet composition of Application Example 1,
The monomer B can be contained in an amount of 15% by mass or more based on the total mass of the ink composition.

  According to the radiation curable inkjet composition of Application Example 2, the surface hardness is easily secured even after curing, and volatilization of the uncured monomer into the atmosphere after the coating film is formed is suppressed. Odor can be effectively reduced.

[Application Example 3]
In the radiation curable inkjet composition of Application Example 1 or Application Example 2,
The mole average Tg of the monomer A and the monomer B combined may be 45 ° C. or higher.

  According to the radiation curable inkjet composition of Application Example 3, the surface hardness is easily secured even after curing, and volatilization of the uncured monomer into the atmosphere after forming the coating film is suppressed. Odor can be effectively reduced.

[Application Example 4]
In the radiation curable inkjet composition according to any one of Application Examples 1 to 3, an acyl phosphine oxide photopolymerization initiator may be further contained as a polymerization initiator.

[Application Example 5]
In the radiation curable inkjet composition of Application Example 4,
Content of the said acylphosphine oxide type photoinitiator can be 1 mass% or more and 20 mass% or less with respect to the total mass of a composition.

  According to the radiation curable ink jet composition of Application Example 4 or Application Example 5, the curability of the composition is excellent, and in particular, the curability of the UV-LED curing process tends to be further excellent.

[Application Example 6]
In the radiation curable inkjet composition according to any one of Application Example 1 to Application Example 5, the content of the monomer A may be 10% by mass or more and 40% by mass or less with respect to the total mass of the composition.

  According to the radiation curable inkjet composition of Application Example 6, since the standard boiling point of the composition itself can be increased, the odor of the composition itself can be effectively reduced.

[Application Example 7]
In the radiation curable inkjet composition according to any one of Application Example 1 to Application Example 6, the content of the monomer B may be 15% by mass or more and 60% by mass or less with respect to the total mass of the composition.

  According to the radiation curable inkjet composition of Application Example 7, it is easy to ensure the low odor of the composition itself and the low odor of the cured film formed by the composition.

[Application Example 8]
In the radiation curable inkjet composition according to any one of Application Example 1 to Application Example 7, the total content of the polymerizable compound may be 40% by mass or more and 95% by mass or less with respect to the total mass of the composition. .

  According to the radiation curable inkjet composition of Application Example 8, the viscosity and odor can be further reduced, and the solubility and reactivity of the photopolymerization initiator can be further improved.

[Application Example 9]
In the radiation curable inkjet composition of any one of Application Examples 1 to 8, the monomer A may contain a compound having a glycol ether chain.

  According to the radiation curable inkjet composition of Application Example 9, the composition has excellent curability and can increase the standard boiling point of the composition itself, so that the composition can be further reduced in odor.

[Application Example 10]
In the radiation curable inkjet composition according to any one of Application Examples 1 to 9, the monomer B may contain acrylamides.

  According to the radiation curable inkjet composition of Application Example 10, since the standard boiling point of the composition itself can be increased, the odor of the composition itself can be further reduced. Further, since the surface hardness is sufficiently secured even after curing, volatilization of the uncured monomer into the atmosphere after the coating film is formed is suppressed, and the odor of the cured film can be further reduced.

[Application Example 11]
The radiation curable inkjet composition of any one of Application Examples 1 to 10 may further contain a compound represented by the following general formula (1).
_{^{CH 2 = CR 1 -COOR 2 -O}} -CH = CH-R 3 ··· (1)
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent organic residue having 2 to 20 carbon atoms, and R ³ is a hydrogen atom or a monovalent organic residue having 1 to 11 carbon atoms. Group.)

[Application Example 12]
In the radiation curable inkjet composition of Application Example 11,
Content of the compound represented by the said General formula (1) can be 1 mass% or more and 30 mass% or less with respect to the total mass of a composition.

  According to the radiation curable inkjet composition of Application Example 11 or Application Example 12, the curability of the composition can be further improved, and an increase in the viscosity of the composition can be suppressed. Moreover, it exists in the tendency for the storage stability of a composition to become favorable.

[Application Example 13]
In the radiation curable inkjet composition according to any one of Application Examples 1 to 12, a color material may be further contained.

  According to the radiation curable inkjet composition of Application Example 13, it can be used as a colored ink composition.

[Application Example 14]
One aspect of the inkjet recording method according to the present invention is:
It includes a step of irradiating the radiation-curable inkjet composition of any one of Application Examples 1 to 13 applied on a recording medium with a UV-LED.

[Application Example 15]
In the inkjet recording method of application example 14,
The irradiation energy of the UV-LED may be 50 to 1000 mJ / cm ² .

[Application Example 16]
In the inkjet recording method of Application Example 14 or Application Example 15,
The irradiation intensity of the UV-LED may be 10 to 1000 mW / cm ² .

[Application Example 17]
In the inkjet recording method of any one of Application Example 14 to Application Example 16,
The temperature of the recording medium during recording may be less than 45 ° C.

  According to the inkjet recording method of any one of Application Examples 14 to 17, an inkjet recording method with reduced odor can be realized.

  Hereinafter, preferred embodiments of the present invention will be described. Embodiment described below demonstrates an example of this invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

  In the present specification, “(meth) acryloyl” means at least one of acryloyl and the corresponding methacryloyl, and “(meth) acrylate” means at least one of the acrylate and the corresponding methacrylate. , “(Meth) acryl” means at least one of acrylic and methacryl corresponding thereto.

1. Radiation curable inkjet composition The radiation curable inkjet composition according to the present embodiment (hereinafter also simply referred to as “inkjet composition” or “composition”) is a composition used by being ejected from an inkjet head by an inkjet method. is there. Hereinafter, a radiation curable inkjet ink composition will be described as one embodiment of the radiation curable inkjet composition, but the composition may be a composition other than the ink composition, for example, a composition used for 3D modeling. . Moreover, although it may describe as "ultraviolet ray curable type" as one embodiment of "radiation curable type", in this embodiment, if the composition is a radiation curable composition used by being cured by irradiation with radiation. Well, an ultraviolet curable composition or an ultraviolet curable composition may be read as a radiation curable composition or a radiation curable composition. Examples of radiation include ultraviolet rays, infrared rays, visible rays, and X-rays. As the radiation, ultraviolet rays are preferable because a radiation source is easily available and widely used, and a material suitable for curing by ultraviolet radiation is easily available and widely used.

  The radiation curable inkjet composition according to this embodiment has one (meth) acryloyloxy group or (meth) acryloyl group, and two oxygen atoms in addition to the (meth) acryloyloxy group and the (meth) acryloyl group. A monomer A having a linear or branched chain structure as described above and one (meth) acryloyloxy group or (meth) acryloyl group, and a nitrogen atom other than (meth) acryloyloxy group and (meth) acryloyl group And a monomer B having a total number of oxygen atoms of 2 or more, a linear or branched structure, and a homopolymer Tg of 90 ° C. or higher.

  Hereinafter, components that can be included in the radiation-curable inkjet composition according to this embodiment will be described.

1.1. Polymerizable compound 1.1.1. Monomer A
Monomer A is a kind of polymerizable compound, has one (meth) acryloyloxy group or (meth) acryloyl group, and has two or more oxygen atoms in addition to (meth) acryloyloxy group and (meth) acryloyl group. It is a monofunctional monomer having a linear or branched structure. Since the composition according to this embodiment contains the monomer A, the standard boiling point of the composition itself can be increased, so that the odor of the composition itself can be reduced. On the other hand, linear or branched having one (meth) acryloyloxy group or one (meth) acryloyl group and having 0 or one oxygen atom in addition to the (meth) acryloyloxy group and the (meth) acryloyl group A monofunctional monomer having a chain structure is unlikely to have the effect of increasing the standard boiling point of the composition itself, and tends to increase the odor of the composition itself.

  The monomer A is preferably a compound having a glycol ether chain. By being such a compound, there exists a tendency which can reduce the odor of composition itself more suitably, and can suppress a viscosity low. The glycol ether chain preferably has an alkylene glycol unit having 2 to 5 carbon atoms, and the number of repeating glycol ether units is preferably 1 to 5.

  Specific examples of the monomer A include methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, and methoxydipropylene glycol (meth) acrylate. , 2- (meth) acryloyloxyethyl succinic acid, and derivatives thereof. Among these, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and ethoxydiethylene glycol (meth) acrylate are preferable from the viewpoint of low viscosity and low odor. Monomer A may be used individually by 1 type, and may be used in combination of 2 or more type.

  The upper limit of the content of monomer A in the composition according to this embodiment is preferably 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, with respect to the total mass of the composition. . Since the standard boiling point of the composition itself can be increased when the upper limit value of the content of the monomer A is within the above range, the effect of reducing the odor of the composition itself is excellent. On the other hand, when the content of the monomer A exceeds the above range, the composition balance with the monomer B may be lost, and the odor strength of the cured film may be poor.

The lower limit of the content of the monomer A in the composition according to this embodiment is preferably 10% by mass or more, more preferably 14% by mass or more, and particularly preferably 20% by mass or more with respect to the total mass of the composition. is there. Since the standard boiling point of the composition itself can be increased when the lower limit of the content of the monomer A is in the above range, the effect of reducing the odor of the composition itself is excellent.

1.1.2. Monomer B
Monomer B is a kind of polymerizable compound, has one (meth) acryloyloxy group or one (meth) acryloyl group, and contains nitrogen atoms and oxygen atoms other than (meth) acryloyloxy group and (meth) acryloyl group. It is a monofunctional monomer having a total number of 2 or more, a linear or branched structure, and a homopolymer Tg of 90 ° C. or higher. Since the composition according to the present embodiment contains the monomer B, the standard boiling point of the composition itself can be increased, so that the odor of the composition itself can be reduced and the surface hardness is sufficiently secured even after curing. Therefore, volatilization of the uncured monomer into the air after forming the coating film is suppressed, and the odor of the cured film can be reduced.

  It has one (meth) acryloyloxy group or (meth) acryloyl group, and the total number of nitrogen atoms and oxygen atoms other than (meth) acryloyloxy group and (meth) acryloyl group is 0 or 1, linear Monofunctional monomers having a chain or branched structure tend to have a strong odor. Therefore, it becomes difficult to achieve both the low odor of the composition itself and the low odor of the cured film formed by the composition.

  Moreover, even if it has said specific structure, the monofunctional monomer whose Tg of homopolymer is less than 90 degreeC tends to become inadequate surface hardness after hardening, and the air | atmosphere after forming a coating film into air | atmosphere Volatilization of the uncured monomer tends to increase the odor of the cured film.

  "The total number of nitrogen atoms and oxygen atoms is 2 or more" means having 2 or more nitrogen atoms, having 2 or more oxygen atoms, and having 2 or more nitrogen atoms and oxygen atoms in total. It includes cases.

  As the monomer B, acrylamides are preferable. By being such a compound, there exists a tendency which can reduce the odor of a cured film more suitably. Specific examples of the monomer B include hydroxyethyl (meth) acrylamide, dimethylaminopropyl acrylamide, and derivatives thereof. Monomer B may be used individually by 1 type, and may be used in combination of 2 or more type.

  The upper limit of the content of monomer B in the composition according to this embodiment is preferably 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, with respect to the total mass of the composition. . When the upper limit value of the content of the monomer B is within the above range, it is easy to ensure the low odor of the composition itself and the low odor of the cured film formed by the composition.

  The lower limit of the content of the monomer B in the composition according to this embodiment is preferably 15% by mass or more, more preferably 18% by mass or more, and particularly preferably 20% by mass or more with respect to the total mass of the composition. is there. When the lower limit value of the content of the monomer B is in the above range, it is easy to ensure the low odor of the composition itself and the low odor of the cured film formed by the composition.

1.1.3. Other Monomers In addition to the monomer A and the monomer B, various monomers and oligomers other than the monomer A and the monomer B such as monofunctional, bifunctional, and trifunctional or more polyfunctional can be used.

  Although it does not specifically limit as a monofunctional monomer, The conventionally well-known monofunctional monomer which has a polymerizable functional group, especially the polymerizable functional group which has the unsaturated double bond between carbon can be used.

  Specific examples of the monofunctional monomer include, for example, unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid; salts of the unsaturated carboxylic acid; esters of the unsaturated carboxylic acid , Urethanes, amides and anhydrides; acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethanes; N-vinylformamide, N-vinylcarbazole, N-vinylacetamide, N-vinyl Examples include N-vinyl compounds such as pyrrolidone and N-vinylcaprolactam. These monofunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these monofunctional monomers, from the viewpoint of improving the curability of the composition, monofunctional (meth) acrylic acid esters, that is, monofunctional (meth) acrylates are preferable.

  Monofunctional (meth) acrylates include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) ) Acrylate, 2-hydroxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, lactone-modified flexible (meth) acrylate , T-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acryloylmorpholine, cyclic trimethylolpropane formal (meth) acrylate, (2- Examples include methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate and 2- (meth) acrylic acid-1,4-dioxaspiro [4,5] dec-2-ylmethyl.

  Among the above monofunctional (meth) acrylates, it is also preferable to contain a monofunctional (meth) acrylate having an aromatic skeleton. It is preferable to contain a monofunctional (meth) acrylate having an aromatic skeleton because the solubility of the photopolymerization initiator described later tends to be good and the curability tends to be improved. In particular, when an acylphosphine oxide photopolymerization initiator or a thioxanthone photopolymerization initiator is used, the solubility tends to be good. Among monofunctional (meth) acrylates having an aromatic skeleton, phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are preferred, but phenoxyethyl (meth) acrylate is more preferred because of its lower odor.

  Among the above monofunctional (meth) acrylates, it has one (meth) acryloyloxy group or (meth) acryloyl group, and in addition to the (meth) acryloyloxy group and the (meth) acryloyl group, a nitrogen atom and an oxygen atom It is also preferable to contain a monomer having a cyclic structure having one or more of each. By containing such a monomer, the standard boiling point of the composition itself can be further increased, and the odor of the composition itself can be more suitably reduced. Moreover, it is excellent in sclerosis | hardenability, volatilization of the monofunctional monomer to air | atmosphere can be reduced, and the odor property of the cured film obtained can also be reduced more suitably.

Such a monomer is preferably a compound having a (meth) acryloyl group, and more preferably a compound in which a (meth) acryloyl group is directly bonded to a nitrogen atom. Moreover, it is preferable to contain at least any one of a nitrogen atom and an oxygen atom as an atom which comprises a ring, and it is more preferable that a cyclic structure has a heterocyclic structure. With such a compound, the odor of the composition itself and the odor of the cured film can be more suitably reduced.

  Specific examples include N-acryloylmorpholine, N-methacryloylmorpholine, 1-acryloylpyrrolidin-2-one, 1-methacryloylpyrrolidin-2-one, 1-acryloylpiperidin-2-one, 1-methacryloylpiperidine-2. -Ones and their derivatives. Among these, N-acryloyl morpholine and N-methacryloyl morpholine are preferable.

  Moreover, what contains a vinyl ether group as monofunctional (meth) acrylate is also mentioned. Such monofunctional (meth) acrylates are not particularly limited, and examples thereof 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-vinyl (meth) acrylate Loxypropyl, 2-vinyloxybutyl (meth) acrylate, 4-vinyloyl (meth) acrylate Cycyclohexyl, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethyl (meth) acrylate Cyclohexylmethyl, (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, ( 2-methacrylic acid (meth) acrylic acid Poxy) propyl, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, (meth ) 2- (vinyloxyethoxyisopropoxy) propyl acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, (meth) Acrylic acid 2- (vinyloxyethoxyethoxy) Ii) Isopropyl, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) (meth) acrylate ) Isopropyl, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) ethyl (meth) acrylate , 2- (Isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (Isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (Isopropenoxyethoxyethoxyethoxyethoxy) acrylate (meth) acrylate ethyl,( Data) Polyethylene glycol monovinyl ether acrylate, and (meth) acrylic acid polypropylene glycol monovinyl ether.

Among the above monofunctional (meth) acrylates containing vinyl ether groups, the composition can be further reduced in viscosity, has a high flash point, and is excellent in curability of the composition, and therefore is represented by the following general formula (1). Vinyl ether group-containing (meth) acrylates are preferred.
_{^{CH 2 = CR 1 -COOR 2 -O}} -CH = CH-R 3 ··· (1)
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent organic residue having 2 to 20 carbon atoms, and R ³ is a hydrogen atom or a monovalent organic residue having 1 to 11 carbon atoms. Group.)

  When the composition according to the present embodiment contains the vinyl ether group-containing (meth) acrylate represented by the general formula (1), the curability of the composition can be made excellent, and the composition The viscosity can also be reduced. Furthermore, it is more preferable to use a compound having both a vinyl ether group and a (meth) acryl group in one molecule than using a compound having a vinyl ether group and a compound having a (meth) acryl group separately. This is preferable for improving the curability of the resin.

In the general formula (1), the divalent organic residue having 2 to 20 carbon atoms represented by R ² may be a linear, branched or cyclic substituted group having 2 to 20 carbon atoms. A good alkylene group, an optionally substituted alkylene group having an oxygen atom by an ether bond and / or an ester bond in the structure, and an optionally substituted divalent fragrance having 6 to 11 carbon atoms Group groups are preferred. Among these, C2-C6 alkylene groups 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 due to an ether bond in the structure is preferably used.

In the general formula (1), the monovalent organic residue having 1 to 11 carbon atoms represented by R ³ may be linear, branched or cyclic substituted having 1 to 10 carbon atoms. A good alkyl group and an optionally substituted aromatic group having 6 to 11 carbon atoms are preferred. Among these, C6-C2 aromatic groups, such as a C1-C2 alkyl group which is a methyl group or an ethyl group, a phenyl group, and a benzyl group, are used suitably.

  When each of the organic residues 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.

  The content of the vinyl ether group-containing monofunctional (meth) acrylate, particularly the vinyl ether group-containing (meth) acrylate represented by the general formula (1) is preferably based on the total mass (100% by mass) of the composition. 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and particularly preferably 5% by mass or more and 22% by mass or less. When the content of the vinyl ether group-containing monofunctional (meth) acrylate is 1% by mass or more, the viscosity of the composition can be reduced and the curability of the composition can be further improved. On the other hand, when the content is 30% by mass or less, the storage stability of the ink can be maintained in an excellent state.

  The content of the monofunctional monomer other than the monomer A and the monomer B is preferably 50% by mass or less with respect to the total mass (100% by mass) of the composition from the viewpoint of improving the curability of the composition. More preferably, it is 1 mass% or more and 45 mass% or less, Most preferably, it is 5 mass% or more and 40 mass% or less.

Examples of the bifunctional (meth) acrylate include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and dipropylene glycol di (meth). ) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, bisphenol A EO (ethylene oxide) adduct di (meth) ) Acrylate, PO-bisphenol A (propylene oxide) adduct di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate.

  Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and caprolactam modification Dipentaerythritol hexa (meth) acrylate is mentioned.

  The content of the bifunctional or higher polyfunctional (meth) acrylate is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass with respect to the total mass (100% by mass) of the composition. It is not more than mass%, particularly preferably not less than 2 mass% and not more than 8 mass%. By setting it as the said preferable range, it exists in the tendency which is excellent with sclerosis | hardenability, storage stability, and discharge stability.

  The composition according to the present embodiment is a non-aqueous composition containing the largest amount of the polymerizable compound among the medium components in which solid components such as a photopolymerization initiator and a coloring material are dissolved or dispersed. It is preferable in terms of curability and storage stability. The medium component having the largest mass ratio among the medium components contained in the composition is a polymerizable compound. The content of the polymerizable compound is preferably 40% by mass to 95% by mass, more preferably 50% by mass or more, still more preferably 60% by mass or more, based on the total mass (100% by mass) of the composition. More preferably, it is less than 80% by weight, and more preferably less than 80% by weight. When the content of the polymerizable compound is within the above range, the viscosity and odor can be further reduced, and the solubility and reactivity of the photopolymerization initiator can be further improved.

1.2. Photopolymerization initiator The composition according to this embodiment preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited. For example, known photopolymerization such as alkylphenone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, titanocene photopolymerization initiator, and thioxanthone photopolymerization initiator. Initiators are mentioned. Of these, acylphosphine oxide photopolymerization initiators are preferred. By containing an acyl phosphine oxide-based polymerization initiator, the curability of the composition is excellent, and in particular, the curability by the curing process by UV-LED tends to be further excellent.

  Examples of the acylphosphine oxide polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis- (2,6-dimethoxy). And benzoyl) -2,4,4-trimethylpentylphosphine oxide.

Examples of commercially available acylphosphine oxide polymerization initiators include IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), IRGACURE 1800 (bis- (2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexyl-phenyl ketone in a mass ratio of 25:75), IRGACURE TPO (2,4,4
6-trimethylbenzoyldiphenylphosphine oxide) (all manufactured by BASF).

  A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the photopolymerization initiator is preferably 1% by mass or more and 20% by mass or less, more preferably 15% by mass or less, in terms of further excellent curability and discharge stability with respect to the total mass (100% by mass) of the composition. Is more preferably 13% by mass or less, and particularly preferably 10% by mass or less. Moreover, 3 mass% or more is further more preferable, and 5 mass% or more is especially preferable.

1.3. Other Additives The composition according to this embodiment may further contain additives such as a coloring material, a dispersant, a polymerization inhibitor, a slip agent, a photosensitizer, and a polymerization inhibitor, as necessary.

<Color material>
The composition according to this embodiment may further include a color material. When the composition according to the present embodiment includes a coloring material, it can be used as a colored ink composition. As the color material, at least one of a pigment and a dye can be used.

(Pigment)
By using a pigment as the color material, the light resistance of the ink composition can be improved. As the pigment, both inorganic pigments and organic pigments can be used.

  As the inorganic pigment, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, iron oxide, and titanium oxide can be used.

  Organic pigments include insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc. Polycyclic pigments, dye chelates (eg basic dye chelates, acid dye chelates, etc.), dye rakes (basic dye rakes, acid dye rakes), nitro pigments, nitroso pigments, aniline black, daylight A fluorescent pigment is mentioned.

More specifically, as a carbon black used for black ink, No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. (Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (above, Columbia Carbon, Carbon 1 Rubbi 400, Carbon Co. Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch
880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (manufactured by Cabot Corporation (CABOT JAPAN K.K.)), Color Black FW1, Color Black FW2, Color Black VLC, Color Black FW2, Color Black FW , Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Speck Black
k 4A, Special Black 4 (manufactured by Degussa).

  Examples of pigments used in white ink include C.I. I. Pigment white 6, 18, and 21.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 155, 167, 172, 180.

  Examples of pigments used in magenta ink include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50.

  Examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4, 60.

  Examples of pigments other than magenta, cyan, and yellow include C.I. I. Pigment green 7, 10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63.

  The said pigment may be used individually by 1 type, and may use 2 or more types together.

  When using said pigment, the average particle diameter has preferable 300 nm or less, and 50-200 nm is more preferable. When the average particle diameter is in the above range, the ink composition is more excellent in reliability such as ejection stability and dispersion stability, and an image with excellent image quality can be formed. Here, the average particle diameter in the present specification is measured by a dynamic light scattering method.

(dye)
A dye can be used as the coloring material. The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. Direct Red 1, 4, 9, 80, 81, 225, 227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive black 3, 4, and 35 are mentioned.

  The said dye may be used individually by 1 type, and may use 2 or more types together.

  The content of the color material is preferably 1% by mass or more and 20% by mass or less with respect to the total mass (100% by mass) of the ink composition. It is good also as a clear composition (clear ink) which does not contain a coloring material or contains a coloring material to such an extent that it does not aim at coloring (for example, 0.1 mass% or less).

<Dispersant>
When the ink composition contains a pigment, it may further contain a dispersant in order to improve pigment dispersibility. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used for preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned. Specific examples include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, sulfur-containing polymers, fluorine-containing polymers, and epoxies. The thing which has 1 or more types of resin as a main component is mentioned. Commercially available polymer dispersants include Ajinomoto Fine-Techno's Adisper Series, Avecia and Noveon Solsperse Series (Solsperse 36000, etc.), BYK Additives & Instruments Dispervic Series , Disparon series manufactured by Enomoto Kasei.

<Polymerization inhibitor>
The composition according to this embodiment may further contain a hindered amine compound or other substances as a polymerization inhibitor. Other polymerization inhibitors include, but are not limited to, for example, p-methoxyphenol, hydroquinone monomethyl ether (MEHQ), hydroquinone, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-butylphenol), and 4,4′-thiobis (3-methyl-6-t) -Butylphenol). A polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the polymerization inhibitor is preferably 0.05% by mass or more and 0.5% by mass, more preferably 0.1% by mass or more and 0.5% by mass with respect to the total mass (100% by mass) of the composition. It is as follows.

<Slip agent>
The composition according to this embodiment may further contain a slip agent. As the slip agent, a silicone-based surfactant is preferable, and polyester-modified silicone or polyether-modified silicone is more preferable. Examples of the polyester-modified silicone include BYK-347, 348, BYK-UV3500, 3510, 3530 (manufactured by BYK Additives & Instruments) and the like, and examples of the polyether-modified silicone include BYK-3570 (manufactured by BYK Additives & Instruments). Can be mentioned. A slip agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the slip agent is preferably 0.01% by mass or more and 2% by mass, more preferably 0.05% by mass or more and 1% by mass or less, with respect to the total mass (100% by mass) of the composition.

<Photosensitizer>
The composition according to this embodiment may further contain a photosensitizer. Photosensitizers include amine compounds (aliphatic amines, amines containing aromatic groups, piperidine, reaction products of epoxy resins and amines, triethanolamine triacrylate, etc.), urea compounds (allylthiourea, o-tolylthiourea). Etc.), sulfur compounds (sodium diethyldithiophosphate, soluble salts of aromatic sulfinic acid, etc.), nitrile compounds (N, N-diethyl-p-aminobenzonitrile, etc.), phosphorus compounds (tri-n-butylphosphine, Sodium diethyldithiophosphide), nitrogen compounds (Michler ketone, N-nitrisohydroxylamine derivatives, oxazolidine compounds, tetrahydro-1,3-oxazine compounds, formaldehyde or a condensate of acetaldehyde and diamine), chlorine compounds (tetrachloride) Arsenide, hexachloroethane, etc.), and the like.

1.4. Physical Properties In the radiation curable inkjet composition according to this embodiment, the mole average Tg of the monomer A and the monomer B combined is 45 ° C. or higher, preferably 46 ° C. or higher, more preferably 48 ° C. or higher, and still more preferably 50 ° C. As described above, particularly preferably, the surface hardness is sufficiently secured even after curing by being 55 ° C. or higher, so that volatilization of uncured monomers into the atmosphere is suppressed, and the odor of the resulting cured film is reduced. Can do.

The “mol average Tg” in the present invention is the value of the glass transition temperature (Tg) when the monomers A and B included in the composition are homopolymers, and the monomer A and the monomer included in the composition. This is a value calculated by the following formula (2) from the ratio (molar fraction) of the amount of each monomer occupying the total amount of B.
mol average Tg = m ₁ × Tg ₁ + m ₂ × Tg ₂ + (2)
_{(Wherein, m} 1, m 2 _... is, .Tg 1 representing the proportion of the amount of material occupied by each monomer to the total amount of substance of monomers A and monofunctional monomer B contained in the composition (mole _fraction), Tg ₂ ... represents the value of the glass transition temperature (Tg) when each monomer is a homopolymer.)

  The viscosity at 20 ° C. of the composition according to this embodiment is preferably 25 mPa · s or less, and more preferably 5 to 20 mPa · s. When the viscosity of the composition at 20 ° C. is in the above range, the composition can be discharged from the nozzle in an appropriate amount, and the flight bending and scattering of the composition can be further reduced. Therefore, the composition can be suitably used for an ink jet recording apparatus. . The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

  The surface tension at 20 ° C. of the composition according to this embodiment is preferably 20 mN / m or more and 30 mN / m or less. When the surface tension of the composition at 20 ° C. is in the above range, the composition is less likely to get wet with the nozzle subjected to the liquid repellent treatment. Accordingly, an appropriate amount of the composition is ejected from the nozzle, and the flight bending and scattering of the composition can be further reduced. Therefore, the composition can be suitably used for an ink jet recording apparatus. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by confirming the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. be able to.

1.5. Method for Producing Composition The composition can be produced (prepared) by mixing the components contained in the composition and stirring the components so that they are sufficiently uniformly mixed. In the present embodiment, the composition is prepared by subjecting a mixture obtained by mixing the photopolymerization initiator and at least a part of the polymerizable compound to at least one of ultrasonic treatment and heating treatment in the course of preparation. It is preferable to have a process. Thereby, the dissolved oxygen amount of the composition after preparation can be reduced, and it can be set as the composition excellent in discharge stability and storage stability. The said mixture should just contain said component at least, and may further contain the other component contained in a composition, and may contain all the components contained in a composition. The polymerizable compound included in the mixture may be at least part of the polymerizable compound included in the composition.

2. Inkjet recording method The inkjet recording method according to the present embodiment includes a step of irradiating the radiation-curable inkjet composition coated on a recording medium with a UV-LED (ultraviolet light emitting diode). In this way, a cured film is formed at the location where the composition is applied on the recording medium.

<Application process>
In the step of applying the composition onto the recording medium, a known ink jet recording apparatus can be used. When discharging the composition, as described above, the viscosity of the composition at 20 ° C. is preferably 25 mPa · s or less, and more preferably 5 to 20 mPa · s. If the viscosity of the composition is within the above range, the composition can be discharged at room temperature or without heating the composition. On the other hand, the viscosity may be preferably discharged by heating the composition to a predetermined temperature. In this way, good discharge stability is realized.

  A radiation curable inkjet composition generally has a higher viscosity than a water-based ink composition used for inkjet applications, and therefore has a large viscosity variation due to temperature variation during ejection. Viscosity fluctuation of such a composition has a great influence on the change of the droplet size and the change of the droplet discharge speed, and can cause image quality deterioration. Therefore, it is preferable to keep the temperature of the composition during ejection as constant as possible.

  The recording medium is not particularly limited, and examples thereof include plastics such as polyvinyl chloride, polyethylene terephthalate, polypropylene, polyethylene, and polycarbonate, those whose surfaces are processed, glass, coated paper, and the like.

<Curing process>
Next, in the curing step, the composition applied on the recording medium is cured by irradiation with UV-LED. In other words, the coating film of the composition formed on the recording medium becomes a cured film by UV-LED irradiation. This is because the photopolymerization initiator that can be contained in the composition is decomposed by irradiation with ultraviolet rays to generate starting species such as radicals, acids, and bases, and the polymerization reaction of the photopolymerizable compound functions as the starting species. It is because it is promoted by. Or it is because the photopolymerization reaction of a polymeric compound starts by irradiation of an ultraviolet-ray. At this time, if a sensitizing dye is present together with the photopolymerization initiator in the composition, the sensitizing dye in the system absorbs actinic radiation to be in an excited state and contacts the photopolymerization initiator to decompose the photopolymerization initiator. And a more sensitive curing reaction can be achieved.

  Further, by using a UV-LED as an ultraviolet ray source, it is possible to reduce the size of the apparatus and reduce the cost. Since the UV-LED as the ultraviolet ray source is small, it can be mounted in the ink jet recording apparatus. For example, it can be attached to a carriage (both ends along the medium width direction and / or the medium conveyance direction side) on which a print head for discharging the composition is mounted. Furthermore, low energy and high speed curing can be realized due to the composition of the composition described above. The irradiation energy is calculated by multiplying the irradiation time by the irradiation intensity. Therefore, the irradiation time can be shortened and the printing speed is increased. On the other hand, the irradiation intensity can also be reduced. Thereby, since the temperature rise of printed matter can be reduced, it leads also to the low odor of a cured film.

The irradiation energy, from the viewpoint of reducing the odor of the cured film is preferably 50~1000mJ / cm ^2, more preferably ^{100~700mJ / cm 2, 200~600mJ / cm} 2 is particularly preferred.

The irradiation intensity, from the viewpoint of reducing the odor of the cured film is preferably 10 to 1,000 / cm ^2, more preferably ^{30~700mW / cm 2, 50~500mW / cm} 2 is particularly preferred.

  Further, the temperature of the recording medium during recording is preferably less than 45 ° C., more preferably 40 ° C. or less, and particularly preferably 35 ° C. or less. By setting the temperature of the recording medium at the time of recording within the above range, the temperature of the recording medium is smaller than the mol average Tg of the monofunctional monomer in the above composition, so that the monomer to the atmosphere after forming the coating film Volatilization is suppressed, and low odor can be achieved.

3. Examples Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.

3.1. Preparation of Composition First, a part of a coloring material, a dispersant, and a polymerizable compound (VEEA, ECA in Examples 10 and 12) are weighed and placed in a pigment dispersion tank, and a ceramic bead mill having a diameter of 1 mm is placed in the tank. By adding and stirring, a pigment dispersion in which the coloring material was dispersed in the polymerizable compound was obtained. Next, the remaining polymerizable compound, photopolymerization initiator, slip agent, and polymerization inhibitor are placed in a mixture tank, which is a stainless steel container, and mixed and stirred so that the composition shown in Table 1 or Table 2 is obtained. After complete dissolution, the pigment dispersion obtained above was added, mixed and stirred at room temperature for 1 hour, and further filtered through a 5 μm membrane filter to obtain each composition.

The components used in the table are as follows.
<Polymerizable compound>
(Monomer A)
ECA (trade name “Biscoat # 190”, manufactured by Osaka Organic Chemical Industry Co., Ltd., ethyl carbitol acrylate)
ME-4S (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., methoxypolyethylene glycol acrylate)
・ MTG (trade name “Biscoat #MTG”, manufactured by Osaka Organic Chemical Industry Co., Ltd., methoxytriethylene glycol acrylate)
(Monomer B)
・ HEAA (trade name, manufactured by KJ Chemicals, hydroxyethylacrylamide)
・ DMAPAA (trade name, manufactured by KJ Chemicals, dimethylaminopropylacrylamide)
(Other monomers)
DMAEA (trade name “DMAEA-BQ”, manufactured by KJ Chemicals Co., Ltd., dimethylaminoethyl acrylate benzyl chloride quaternary salt)
・ DMAA (trade name, manufactured by KJ Chemicals, dimethylacrylamide)
・ 2-MTA (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd., methoxyethyl acrylate)
・ IOAA (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd., isooctyl acrylate)
VEEA (trade name, manufactured by Nippon Shokubai Co., Ltd., 2- (2-vinyloxyethoxy) ethyl acrylate)
・ ACMO (trade name, manufactured by KJ Chemicals, acryloylmorpholine)
-PEA (trade name “Biscoat # 192”, manufactured by Osaka Organic Chemical Industry Co., Ltd., phenoxyethyl acrylate)
(Polyfunctional monomer)
・ DPHA (trade name, manufactured by Daicel Ornex Co., Ltd., dipentaerythritol hexaacrylate)
<Photopolymerization initiator>
IRGACURE 819 (trade name, manufactured by BASF, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide)
・ TPO (trade name “IRGACURE TPO”, manufactured by BASF, 2,4,6-trimethylbenzoyldiphenylphosphine oxide)
<Polymerization inhibitor>
MEHQ (trade name “p-methoxyphenol”, manufactured by Kanto Chemical Co., Inc., hydroquinone monomethyl ether)
<Slip agent>
BYK-UV3500 (trade name, manufactured by BYK Additives & Instruments, polyether-modified polydimethylsiloxane having an acrylic group)
<Color material>
・ Carbon black (trade name “MA-100”, manufactured by Mitsubishi Chemical Corporation)
<Dispersant>
Solsperse 36000 (trade name, manufactured by Lubrizol, polymer dispersant)

3.2. Production of Printed Material Using an inkjet printer PX-G5000 (manufactured by Seiko Epson Corporation), each nozzle row was filled with the composition obtained above. On a PET film (trade name “PET50A PL Thin”, manufactured by Lintec Co., Ltd.) at room temperature and normal pressure, a solid pattern image is formed by applying a composition having a film thickness of 8 μm (film thickness after curing) to a substrate. While printing, ultraviolet rays with an irradiation intensity of 500 mW / cm ² were irradiated from a UV-LED having a peak wavelength at 395 nm in an ultraviolet irradiation device mounted on the side of the carriage. Note that the solid pattern image was completely cured by setting the integrated irradiation energy to be about 1.5 times the amount of energy for tack-free. As described above, a printed matter having a solid pattern image recorded on a PET film was produced.

3.3. Evaluation method (1) mol average Tg of monofunctional monomer
The mol average Tg was calculated from the mol average of the blended monofunctional monomer by the following formula (2).
mol average Tg = m ₁ × Tg ₁ + m ₂ × Tg ₂ + (2)
_{(Wherein, m} 1, m 2 _... is, .Tg 1 representing the proportion of the amount of material occupied by each monomer to the total amount of substance of monomers A and monofunctional monomer B contained in the composition (mole _fraction), Tg ₂ ... represents the value of the glass transition temperature (Tg) when each monomer is a homopolymer.)

(2) Odor evaluation of composition The odor of each composition obtained above was directly sniffed immediately after preparation, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
AAA: Odorless AA: Finally a odor that can be sensed A: A weak odor that understands what odor is B: A smell that can be easily detected C: A strong odor D: A strong odor

(3) Odor evaluation of cured film The smell of the cured film immediately after curing of each printed matter obtained above was sniffed directly and evaluated based on the following evaluation criteria.
(Evaluation criteria)
AA: Odorless A: Smell that can finally be sensed B: Weak smell that understands what odor is C: Smell that can be easily sensed D: Strong smell E: Strong smell

(4) Evaluation of composition dischargeability According to the above-mentioned “3.2. Preparation of printed matter”, ten printed matters were continuously prepared. Whether or not the nozzles of the ink jet printer are clogged during the production of the printed material was evaluated based on the following evaluation criteria.
A: No nozzle clogging occurred.
○: Although clogging occurred in one or two locations of the nozzle, printing could be performed continuously.
Δ: Clogging occurred at three or more locations on the nozzle, but continuous printing was possible.
X: Since clogging of the nozzle occurred, it was impossible to continue printing.

3.4. Evaluation results Tables 1 and 2 below show the compositions of the compositions used in Examples and Comparative Examples, and the evaluation results. In addition, the numerical value of each component shown in each Example and each comparative example in a table | surface represents the mass%.

From Tables 1 and 2, the compositions of Examples 1 to 14 according to the present invention have a low odor as the composition itself, a sufficient surface hardness is ensured even after curing, an uncured monomer and a photopolymerization initiator. Volatilization of the decomposition product was suppressed, and it was confirmed that the cured film had a low odor.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (17)

Monomer having a linear or branched structure having one (meth) acryloyloxy group or one (meth) acryloyl group and two or more oxygen atoms in addition to the (meth) acryloyloxy group and the (meth) acryloyl group A and
It has one (meth) acryloyloxy group or (meth) acryloyl group, the total number of nitrogen atoms and oxygen atoms other than (meth) acryloyloxy group and (meth) acryloyl group is 2 or more, linear or A monomer B having a branched structure and a homopolymer Tg of 90 ° C. or higher;
A radiation curable ink jet composition comprising:   The radiation-curable inkjet composition according to claim 1, wherein the monomer B is contained in an amount of 15% by mass or more based on the total mass of the ink composition.   The radiation curable inkjet composition according to claim 1 or 2, wherein a mol average Tg of the monomer A and the monomer B is 45 ° C or higher.   The radiation curable inkjet composition according to any one of claims 1 to 3, further comprising an acylphosphine oxide photopolymerization initiator as a polymerization initiator.   The radiation curable inkjet composition according to claim 4, wherein the content of the acylphosphine oxide photopolymerization initiator is 1% by mass or more and 20% by mass or less based on the total mass of the composition.   The radiation curable inkjet composition according to any one of claims 1 to 5, wherein the content of the monomer A is 10% by mass or more and 40% by mass or less with respect to the total mass of the composition.   The radiation curable inkjet composition according to any one of claims 1 to 6, wherein a content of the monomer B is 15% by mass or more and 60% by mass or less with respect to a total mass of the composition.   The radiation-curable inkjet composition according to any one of claims 1 to 7, wherein the total content of the polymerizable compound is 40% by mass or more and 95% by mass or less with respect to the total mass of the composition.   The radiation curable inkjet composition according to any one of claims 1 to 8, wherein the monomer A contains a compound having a glycol ether chain.   The radiation curable inkjet composition according to any one of claims 1 to 9, wherein the monomer B contains acrylamides. Furthermore, the radiation curable inkjet composition as described in any one of Claims 1 thru | or 10 containing the compound represented by following General formula (1).
_{^{CH 2 = CR 1 -COOR 2 -O}} -CH = CH-R 3 ··· (1)
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent organic residue having 2 to 20 carbon atoms, and R ³ is a hydrogen atom or a monovalent organic residue having 1 to 11 carbon atoms. Group.)   The radiation curable inkjet composition according to claim 11, wherein the content of the compound represented by the general formula (1) is 1% by mass or more and 30% by mass or less with respect to the total mass of the composition.   The radiation curable inkjet composition according to any one of claims 1 to 12, further comprising a coloring material.   An inkjet recording method comprising a step of irradiating the radiation-curable inkjet composition according to any one of claims 1 to 13 with UV-LED applied on a recording medium. The inkjet recording method according to claim 14, wherein the irradiation energy of the UV-LED is 50 to 1000 mJ / cm ² . Irradiation intensity of the UV-LED is 10 to 1,000 / cm ^2, the ink jet recording method according to claim 14 or claim 15.   The inkjet recording method according to any one of claims 14 to 16, wherein a temperature of the recording medium during recording is less than 45 ° C.