JP5860786B2 - Ink composition, inkjet recording method, printed matter, and bisacylphosphine oxide compound - Google Patents

Description

  The present invention relates to an ink composition, an inkjet recording method, a printed material, and a bisacylphosphine oxide compound.

In recent years, an inkjet recording method has attracted attention as an image recording method for forming an image on a recording medium based on an image data signal. The inkjet recording method has an advantage that a high-definition image can be recorded at a low running cost by ejecting very fine droplets with less noise.
In particular, an ink composition for ink jet recording (a radiation curable ink composition for ink jet recording) that can be cured by irradiation with radiation such as ultraviolet rays is cured by irradiation with radiation such as ultraviolet rays, and most of the components of the ink composition are cured. It is an excellent method in that it can be printed on various recording media because it is excellent in drying properties compared to the solvent-based ink composition and the image is not easily smeared.
Patent document 1 is mentioned as a conventional inkjet ink composition.
Moreover, as a conventional bisacylphosphine oxide compound, the compound described in patent document 2 or 3 is mentioned.

Special table 2011-500932 gazette JP 2007-39453 A US Patent Application Publication No. 2012/0142805

When using inkjet inks for food and toy applications, there should be no or only very low levels of components that volatilize or elute from the ink image. However, the photocurable ink-jet ink has a problem that unreacted initiator and decomposition product of the initiator remain in the film with a low molecular weight and volatilize or elute.
In response to this problem, Patent Document 1 discloses a radical curable liquid containing a polymerizable initiator. Patent Document 1 discloses an acylphosphine oxide compound having a polymerizable functional group. However, when this compound is used, phosphonoyl radicals are taken into the film, but less reactive benzoyl radicals are not taken into the cured film, and as a result, the benzaldehyde compound elutes. There is a problem that the safety does not reach a desired level and the adhesion to the substrate is lowered by the low molecular weight compound remaining in the film.
Patent Document 2 discloses a dental material containing a bisacylphosphine oxide compound having a polymerizable group. However, when the compound shown in this document is used as an ink composition, there is a problem that a polymerization rate is slow and a desired curing sensitivity cannot be obtained.
Patent Document 3 discloses an ink composition containing a bisacylphosphine oxide compound having a polymerizable functional group. However, when this compound is used, there is a problem that the benzaldehyde compound is eluted as in Patent Document 1.

An object of the present invention is an ink composition having excellent adhesion to a recording medium, a small amount of elution (migration) of components in the ink film after curing to the outside, and an odor of a printed matter being suppressed, and the ink composition It is to provide an ink jet recording method using a product and a printed product.
Another object of the present invention is to provide a novel bisacylphosphine oxide compound.

The above-described problems of the present invention have been solved by means described in the following <1> or <12> to <15>. It is described below together with <2> to <11> and <16>, which are preferred embodiments.
<1> An ink composition comprising a bisacylphosphine oxide compound having a polymerizable functional group in an acyl group, and a polymerizable compound;
<2> The ink composition according to <1>, wherein the bisacylphosphine oxide compound is a compound represented by the following formula (1):

（式（１）中、Ｒ¹〜Ｒ⁶はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は重合性官能基を有する基を表し、Ｒ¹〜Ｒ⁶のうち少なくとも１つは重合性官能基を有する基であり、Ｒ⁷はアルキル基又はアリール基を表す。）

(In the formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group having a polymerizable functional group, and at least one of R ^{1 to} R ⁶ is (It is a group having a polymerizable functional group, and R ⁷ represents an alkyl group or an aryl group.)

<3> The ink composition according to <2>, wherein at least one of R ^{1 to} R ⁶ is a group having a polymerizable functional group represented by formula (2).

（式（２）中、Ｒ⁸は水素原子又はメチル基を表し、Ｌ¹は−ＣＯＯ−、−ＣＯＮＨ−又はフェニレン基を表し、Ｘは二価の連結基を表し、Ｌ²は−ＣＯＯ−又は−ＣＯＮＨ−を表し、Ｒ⁹は炭素数１〜４のアルキレン基を表し、ｎは０〜３の整数を表し、−＊はベンゼン環との結合を表す。）

(In formula (2), R ⁸ represents a hydrogen atom or a methyl group, L ¹ represents —COO—, —CONH— or a phenylene group, X represents a divalent linking group, and L ² represents —COO—. or represents -CONH-, R ⁹ represents an alkylene group having 1 to 4 carbon atoms, n represents an integer of 0 to 3, - * represents a bond of benzene ring).

<4> X is a chain or cyclic alkylene group having 1 to 12 carbon atoms, a chain or cyclic alkenylene group having 2 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or one or more cyclic alkylenes The ink composition according to the above <3>, which is a divalent group in which a group, the alkenylene group and / or arylene group and one or more ester bond, ether bond or urethane bond are combined;
<5> The ink composition according to <3> or <4>, wherein R ⁹ is —CH ₂ —.
<6> The ink composition according to <3>, wherein n is 0.
<7> The ink composition according to any one of <2> to <6>, wherein R ⁷ is a phenyl group.
<8> The ink composition according to any one of <3> to <6>, wherein L ¹ is —COO—.
<9> The ink composition according to any one of <3> to <6> and <8>, wherein R ⁸ is a hydrogen atom.
<10> The ink composition according to any one of <1> to <9>, which is an inkjet ink composition,
<11> The ink composition according to any one of <1> to <10>, which is an ink composition for food package printing,
<12> (a ¹ ) A step of discharging the ink composition according to any one of the above <1> to <11> on a recording medium, and (b ¹ ) active on the discharged ink composition Irradiating radiation to cure the ink composition, and an ink jet recording method,
<13> Printed matter produced using the inkjet recording method according to <12> above,
<14> A bisacylphosphine oxide compound, which is a compound represented by the following formula (3):

（式（３）中、Ｒ¹⁰〜Ｒ¹⁵はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は−ＣＨ₂Ｂｒを表し、Ｒ¹⁰〜Ｒ¹⁵のうち少なくとも１つは−ＣＨ₂Ｂｒであり、Ｒ¹⁶は炭素数１〜２０のアルキル基又は炭素数６〜１２のアリール基を表す。）

(In the formula (3), R ¹⁰ ~R ¹⁵ independently represents a hydrogen atom, an alkyl group or a -CH ₂ Br 1 to 4 carbon atoms, at least one of R ¹⁰ to R ¹⁵ is -CH ₂ Br and R ¹⁶ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

  <15> A bisacylphosphine oxide compound, which is a compound represented by the following formula (1 ′):

（式（１’）中、Ｒ¹〜Ｒ⁶はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は式（４）で表される基を表し、Ｒ¹〜Ｒ⁶のうち少なくとも１つは式（４）で表される基であり、Ｒ⁷はアルキル基又はアリール基を表す。）

(In Formula (1 ′), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by Formula (4), and at least of R ^{1 to} R ⁶ . One is a group represented by the formula (4), and R ⁷ represents an alkyl group or an aryl group.)

（式（４）中、Ｒ¹³は水素原子又はメチル基を表し、Ｌ³は−ＣＯＯ−又は−ＣＯＮＨ−を表し、−＊はベンゼン環との結合を表す。）

(In the formula (4), R ¹³ represents a hydrogen atom or a methyl group, L ³ represents a -COO- or -CONH-, - * represents a bond with the benzene ring.)

<16> The bisacylphosphine oxide according to <15>, wherein R ^{1 to} R ⁶ are each independently a methyl group or a group represented by the formula (4), and the R ⁷ is a phenyl group. Compound,
<17> The bisacylphosphine oxide compound according to <15> or <16>, wherein L ³ is —COO—.
<18> The bisacylphosphine oxide compound according to any one of <15> to <17>, wherein R ¹³ is a hydrogen atom.

According to the present invention, an ink composition having excellent adhesion to a recording medium, a small amount of elution (migration) to the outside of the components in the ink film after curing, and the odor of the printed matter is suppressed, and the ink composition Inkjet recording methods using printed materials and printed materials can be provided.
In addition, according to the present invention, a novel bisacylphosphine oxide compound can be provided.

1 is a schematic diagram showing an example of an ink jet recording apparatus suitably used in the present invention.

Hereinafter, the present invention will be described in detail.
In addition, in this specification, description of "xx-yy" represents the numerical range containing xx and yy.
“(Meth) acrylate” and the like are synonymous with “acrylate and / or methacrylate” and the like.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
Hereinafter, the present invention will be described in detail.

(Ink composition)
The ink composition of the present invention includes a bisacylphosphine oxide compound having a polymerizable functional group in an acyl group, and a polymerizable compound.
The ink composition of the present invention is an ink composition curable by actinic radiation. “Actinic radiation” is radiation that can give energy to generate an initial species in the ink composition by irradiation, and includes α rays, γ rays, X rays, ultraviolet rays, visible rays, electron rays, and the like. Of these, ultraviolet rays and electron beams are preferable from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are more preferable.
The ink composition of the present invention is an actinic radiation curable ink composition, and is preferably an oil-based ink composition. The ink composition of the present invention preferably contains as little water and volatile solvent as possible, and even if it contains, it is preferably 5% by mass or less, and preferably 1% by mass with respect to the total mass of the ink composition. More preferably, it is more preferably 0.5% by mass or less.
Further, the ink composition of the present invention can be suitably used as an ink composition for ink jet recording (also referred to as “inkjet ink composition”).
Furthermore, the ink composition of the present invention can be suitably used as an ink composition for package printing, and can be more suitably used as an inkjet ink composition for package printing.

The bisacylphosphine oxide compound is decomposed by light to produce a benzoyl radical and a phosphinoyl radical, but the reactivity of the benzoyl radical is lower. For this reason, a large amount of benzaldehyde compound generated from unreacted benzoyl radicals not involved in curing remains in the cured ink film. Moreover, not all initiators are decomposed and unreacted bisacylphosphine oxide compounds are also present.
As a result of detailed studies by the present inventors, the use of a bisacylphosphine oxide compound having a polymerizable functional group in the acyl group in the ink composition allows the aforementioned two compounds that are likely to remain together with the polymerizable compound to form a film. It was found that it is possible to reduce the amount of low molecular weight compound eluted from the image formed by the ink composition and the odor generated from the image because it is taken in.
For example, the printed matter obtained by conventional actinic radiation curable ink jet printing has a problem that unreacted polymerization initiator, polymerization initiator residue, etc. migrate from the cured film, and is particularly suitable for package printing for food packaging. When used, there is a problem that the amount transferred to the package inclusion, that is, the so-called migration (elution, transfer) amount is large. There is also a problem that the cured film has a strong odor and the odor moves to the inclusions and surrounding foods. Furthermore, the low molecular weight compound remains in the film, which causes a problem that the strength of the film is lowered and the adhesion to the support is lowered.
By using the ink composition of the present invention, it is possible to provide a printed material that not only has excellent adhesion to the recording medium, but also has a small amount of migration of components in the film to the outside and the odor of the printed material is suppressed. Can do.
Hereinafter, the ink composition of the present invention will be described in detail.

<Bisacylphosphine oxide compound having a polymerizable functional group in the acyl group>
The ink composition of the present invention contains a bisacylphosphine oxide compound having a polymerizable functional group in the acyl group (hereinafter, also referred to as “specific polymerization initiator”).
The specific polymerization initiator has a polymerizable functional group in at least one of two acyl groups bonded to a phosphorus atom.
The bonding position of the polymerizable functional group can be bonded to any position of the acyl group.
The acyl group that the specific polymerization initiator has may be an aliphatic acyl group or an aromatic acyl group, but is preferably an aromatic acyl group, and may have a substituent. More preferably, the polymerizable functional group is a benzoyl group bonded directly or via a linking group.
Further, when the acyl group is the benzoyl group, the position at which the polymerizable functional group is bonded directly or via a linking group is the 2-position, 4-position, and 1-position of the carbonyl group on the benzene ring. The 6th position is preferable, and the 4th position is preferable from the viewpoint of production suitability.
In the specific polymerization initiator, each of the two acyl groups bonded to the phosphorus atom may have a polymerizable functional group.

The number of polymerizable functional groups possessed by the specific polymerization initiator is preferably 1 from the viewpoint that the shrinkage of the film that occurs during curing hardly occurs, and from the viewpoint of the curing speed and adhesion, 2, 3 or 4 is preferred.
Moreover, when the said acyl group has a polymerizable functional group, the number of the polymerizable functional groups should just be 1 or more, it is preferable that it is 1-3, and it is more preferable that it is 1 or 2. More preferably.
When the acyl group is the benzoyl group and the number of polymerizable functional groups is 2 to 4, the position at which the polymerizable functional group is bonded directly or via a linking group is on the benzene ring. It is preferable that the bonding position of the carbonyl group is at the 1st position and that it is at least the 2nd and 4th positions.

The acyl group in the specific polymerization initiator can have any substituent other than having a polymerizable functional group bonded directly or via a linking group. As a substituent, an alkyl group and an alkoxy group are mentioned preferably, a C1-C4 alkyl group and a C1-C4 alkoxy group are mentioned more preferably, and a methyl group is especially preferable.
The linking group includes a chain or cyclic alkylene group having 1 to 12 carbon atoms, a chain or cyclic alkenylene group having 2 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or one or more of the alkylene groups A divalent group in which a group, the alkenylene group and / or an arylene group and one or more ester bond, ether bond or urethane bond are combined, a chain or cyclic alkylene group having 1 to 8 carbon atoms, carbon More preferably, it is an arylene group of 6 to 12, or a divalent group in which one or more alkylene groups and / or arylene groups are combined with one or more ester bonds, ether bonds or urethane bonds, 1 to 8 chain alkylene groups or one or more chain alkylene groups having 1 to 8 carbon atoms and one or more ester bonds More preferably combined a divalent group, and particularly preferably a methylene group. Moreover, it is preferable that carbon number of the said coupling group is 1-40, It is more preferable that it is 1-20, It is still more preferable that it is 1-12.

The polymerizable functional group in the present invention includes an anion polymerizable group, a cation polymerizable group, and a radical polymerizable group. When the specific polymerization initiator has two or more polymerizable functional groups, the respective polymerizable functional groups may be the same or different, but are preferably the same from the viewpoint of production suitability.
Anionic polymerizable functional groups include (meth) acryloyl group, (meth) acrylamide group, styryl group, conjugated polyene group, maleate group, fumarate group, maleimide group, itaconic acid residue, vinyl ketone group, vinyl halide group, cyanide Examples thereof include a vinylated group, a cyano (meth) acrylate group, a nitrated vinyl group, and an epoxy group.
Examples of the cationic polymerizable functional group include a styryl group, an epoxy group, a vinyl ether group, and an oxetane group.
Examples of the radical polymerizable functional group include (meth) acryloyl group, (meth) acrylamide group, (meth) allyl group, styryl group, and maleimide group.
Among these, the polymerizable functional group is preferably a group having an ethylenically unsaturated bond, more preferably a radical polymerizable functional group, and a (meth) acryloyl group from the viewpoint of curing speed. preferable.
The specific polymerization initiator is preferably a compound represented by the following formula (1).

（式（１）中、Ｒ¹〜Ｒ⁶はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は重合性官能基を有する基を表し、Ｒ¹〜Ｒ⁶のうち少なくとも１つは重合性官能基を有する基であり、Ｒ⁷はアルキル基又はアリール基を表す。）

(In the formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group having a polymerizable functional group, and at least one of R ^{1 to} R ⁶ is (It is a group having a polymerizable functional group, and R ⁷ represents an alkyl group or an aryl group.)

R ^{1 to} R ⁶ are each independently preferably a hydrogen atom, a methyl group or a group having a polymerizable functional group, more preferably a group having a methyl group or a polymerizable functional group. If it is the said aspect, there will be less migration of the component in a film | membrane and the printed matter by which odor was suppressed more will be obtained.
Furthermore, in the formula (1), the group having a polymerizable functional group may have only one polymerizable functional group or two or more, but in the group having a polymerizable functional group, The number of polymerizable functional groups is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
R ⁷ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. Further, an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group is particularly preferable. The alkyl group and aryl group may be substituted. Examples of the substituent include an alkyl group, an alkoxy group, an aryl group, and a halogen atom.
Moreover, it is preferable that it is group represented by Formula (2) as group which has a polymerizable functional group in R < ¹ > -R < ⁶ >. When a plurality of groups represented by the formula (2) are present in the formula (1), the groups represented by the formula (2) may be the same or different from each other. preferable.

（式（２）中、Ｒ⁸は水素原子又はメチル基を表し、Ｌ¹は−ＣＯＯ−、−ＣＯＮＨ−又はフェニレン基を表し、Ｘは二価の連結基を表し、Ｌ²は−ＣＯＯ−又は−ＣＯＮＨ−を表し、Ｒ⁹は炭素数１〜４のアルキレン基を表し、ｎは０〜３の整数を表し、＊はベンゼン環との結合位置を表す。）

(In formula (2), R ⁸ represents a hydrogen atom or a methyl group, L ¹ represents —COO—, —CONH— or a phenylene group, X represents a divalent linking group, and L ² represents —COO—. Or -CONH-, R ⁹ represents an alkylene group having 1 to 4 carbon atoms, n represents an integer of 0 to 3, and * represents a bonding position with a benzene ring.)

R ⁸ is preferably a hydrogen atom.
L ¹ is preferably —COO— or —CONH—, and more preferably —COO—.
The bonding direction of —COO— and —CONH— in L ¹ and L ² may be any direction, but in L ¹ , the carbonyl group of —COO— or —CONH— is ethylenically unsaturated. It is preferable that it is combined with a bond.
X is not particularly limited as long as it is a divalent linking group, but is a linear or cyclic alkylene group having 1 to 12 carbon atoms, a linear or cyclic alkenylene group having 2 to 12 carbon atoms, or an arylene having 6 to 12 carbon atoms. Or a divalent group in which at least one alkylene group, at least one alkenylene group and / or an arylene group is combined with at least one ester bond, ether bond, or urethane bond. A chain or cyclic alkylene group, an arylene group having 6 to 12 carbon atoms, or a divalent group in which one or more alkylene groups and / or arylene groups are combined with one or more ester bonds, ether bonds, or urethane bonds. More preferably, it is a chain alkylene group having 2 to 8 carbon atoms, or one or more chain alkylene groups having 1 to 8 carbon atoms and 1 or more. It is further preferred combination of ester bonds is a divalent group.
Further, X preferably has a smaller molecular weight from the viewpoint of curability per addition amount (% by mass) to the ink composition. Specifically, the molecular weight of X is preferably 290 or less, preferably 170 or less, and more preferably 80 or less. Moreover, it is preferable that it is 14 or more.
R ⁹ is preferably a methylene group.
n is preferably 0 from the viewpoint of curability per addition amount (% by mass) to the ink composition.

  Specific examples of the bisacylphosphine oxide compound having a polymerizable functional group in the acyl group are shown below, but are not limited thereto.

  Although there is no restriction | limiting in particular about content of the bisacylphosphine oxide compound which has a polymerizable functional group in the acyl group in the ink composition of this invention, 0.1-20 mass% with respect to the whole quantity of an ink composition. It is preferably 1 to 15% by mass.

<Polymerizable compound>
The ink composition of the present invention contains a polymerizable compound (also simply referred to as “monomer” or “polymerizable monomer”).
The polymerizable compound is not particularly limited as long as it is a compound that causes a polymerization reaction by being imparted with some energy and cures, and can be used regardless of the type of monomer, oligomer, or polymer. Various known polymerizable monomers known as radically polymerizable monomers that cause a polymerization reaction with an initiation species generated from the polymerization initiator are preferred.

  The polymerizable compounds can be used alone or in combination as a mixture for the purpose of adjusting the reaction rate, the properties of the cured film, the physical properties of the ink composition, and the like. The polymerizable compound may be a monofunctional compound or a polyfunctional compound. When the proportion of the monofunctional polymerizable compound is large, the cured product tends to be flexible, and when the proportion of the polyfunctional polymerizable compound is large, the curability tends to be excellent. Therefore, the ratio between the monofunctional polymerizable compound and the polyfunctional polymerizable compound is arbitrarily determined according to the application.

As the polymerizable compound, various known radically polymerizable monomers that cause a polymerization reaction by an initiation species generated from a photoradical initiator can also be used.
Examples of the radical polymerizable monomer include (meth) acrylates, (meth) acrylamides, aromatic vinyls and the like. In the present specification, when referring to both or one of “acrylate” and “methacrylate”, when referring to both “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” And may be described respectively.

  Examples of (meth) acrylates used as radical polymerizable monomers include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional (meth) acrylate, and pentafunctional. (Meth) acrylate, hexafunctional (meth) acrylate, and the like.

  Examples of monofunctional (meth) acrylates include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth) acrylate. , Stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2 -Ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoe (Meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) Ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) Ak Rate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate,

4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxy Silylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl Ether (meth) acrylate, polyethylene oxide monoalkyl ether ) Acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxytyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate , Ethylene oxide (EO) modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (meta Acrylate, propylene oxide (PO) modified nonylphenol (meth) acrylate, EO modified-2-ethylhexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) Examples include acrylate, (3-ethyl-3-oxetanylmethyl) (meth) acrylate, and phenoxyethylene glycol (meth) acrylate.

  Examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4-dimethyl. -1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene Glycol di (meth) acrylate, 2-ethyl-2-butylbutanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate Bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol di ( (Meth) acrylate, 1,9-nonane di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, PO-modified neopentyl glycol di (meth) acrylate, and the like.

Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) a Relate, propoxylated trimethylolpropane tri (meth) acrylate, and the like ethoxylated glycerol triacrylate.
Examples of the tetrafunctional (meth) acrylate include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, and ethoxylated penta Examples include erythritol tetra (meth) acrylate.
Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Examples of hexafunctional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and ε-captolactone-modified dipentaerythritol hexa (meth). ) Acrylate and the like.

  Examples of (meth) acrylamides used as the radical polymerizable monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and Nn-. Butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide , N, N-diethyl (meth) acrylamide and (meth) acryloylmorpholine.

  Examples of the aromatic vinyl used as the radical polymerizable monomer include styrene, dimethyl styrene, trimethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, methyl vinyl benzoate. Ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexyl Styrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, oct Nirusuchiren, 4-t-butoxycarbonyl styrene, include 4-t-butoxystyrene.

Furthermore, examples of the radical polymerizable monomer used in the present invention include vinyl esters (such as vinyl acetate, vinyl propionate, vinyl versatate), allyl esters (such as allyl acetate), and halogen-containing monomers (vinylidene chloride). Vinyl chloride), vinyl ether (methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy vinyl ether, 2-ethylhexyl vinyl ether, methoxyethyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether, triethylene glycol divinyl ether, etc.), vinyl cyanide ((meta ) Acrylonitrile), olefins (ethylene, propylene, etc.), N-vinyl lactams (N-vinyl caprolactam, etc.) and the like. Etc.
More specifically, Shinzo Yamashita “Cross-linking agent handbook” (1981, Taiseisha); Kato Kiyosumi “UV / EB curing handbook (raw material)” (1985, Polymer publication society); Ed. “Application and Market of UV / EB Curing Technology” on page 79 (1989, CMC Publishing Co., Ltd.); “Polyester Resin Handbook” by Eiichiro Takiyama (1988, Nikkan Kogyo Shimbun) Radical polymerizable or crosslinkable monomers, oligomers and polymers known in the industry can be used.

The content of the polymerizable compound in the ink composition of the present invention is preferably 50 to 95% by mass and more preferably 55 to 92% by mass with respect to the total mass of the ink composition from the viewpoint of curability.
The ratio of the polyfunctional polymerizable compound in the polymerizable compound in the ink composition of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the polymerizable compound. More preferably, it is 95 mass% or more. It is excellent in sclerosis | hardenability as it is the said aspect, and can suppress the migration and odor of a cured film more.
The polymerizable compound preferably contains at least a bifunctional polymerizable compound and a trifunctional polymerizable compound. It is excellent in sclerosis | hardenability as it is the said aspect, and can suppress the migration and odor of a cured film more.

<Other polymerization initiators>
The ink composition of the present invention can contain a polymerization initiator other than the bisacylphosphine oxide compound having a polymerizable functional group in the acyl group, if necessary.
The other polymerization initiator is preferably a radical polymerization or cationic polymerization initiator, and a radical polymerization initiator is particularly preferable. For example, a polymerization initiator described in JP 2009-138172 A can be used.

-Sensitizer-
The ink composition of the present invention absorbs a specific actinic ray as a polymerization initiator and promotes the decomposition of the polymerization initiator, so that it also functions as a sensitizer (hereinafter also referred to simply as “sensitizer”). ) May be contained.
Examples of the sensitizer include polynuclear aromatics (eg, pyrene, perylene, triphenylene, 2-ethyl-9,10-dimethoxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose Bengal etc.), cyanines (eg thiacarbocyanine, oxacarbocyanine etc.), merocyanines (eg merocyanine, carbomerocyanine etc.), thiazines (eg thionine, methylene blue, toluidine blue etc.), acridines (eg , Acridine orange, chloroflavin, acriflavine, etc.), anthraquinones (eg, anthraquinone, etc.), squaliums (eg, squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin, etc.) and the like.
Moreover, a sensitizer may be used individually by 1 type and may use 2 or more types together.

-Co-sensitizer-
The ink composition of the present invention may contain a co-sensitizer for the purpose of further improving sensitivity or suppressing polymerization inhibition by oxygen.
Examples of the co-sensitizer include amines (for example, M. R. Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51- 82102, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research And compounds described in Disclosure No. 33825). Specific examples of the amines include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.
Examples of the co-sensitizer include thiols and sulfides (for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142277, A disulfide compound disclosed in JP-A-56-75643 is also preferable. Specific examples of the thiols and sulfides include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like.
Examples of the co-sensitizer include amino acid compounds (for example, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (for example, tributyltin acetate), and JP-B-55. No. 34414, a hydrogen donor described in JP-A-6-308727, a sulfur compound described in JP-A-6-308727 (for example, trithiane), a phosphorus compound described in JP-A-6-250387 (diethylphosphite, etc.), Examples thereof include Si—H and Ge—H compounds described in JP-A-8-54735.

  The total content of other polymerization initiators is preferably 1 to 20% by mass of the total ink composition, more preferably 2 to 18% by mass, and further preferably 5 to 15% by mass. 10 to 15% by mass is particularly preferable. It is excellent in curability as it is the said range.

<Colorant>
The ink composition of the present invention can contain a colorant, if necessary.
Although there is no restriction | limiting in particular as a coloring agent, The pigment and oil-soluble dye which were excellent in weather resistance and were rich in color reproducibility are preferable, and it can select and use arbitrarily from well-known coloring agents, such as a soluble dye. As the colorant, it is preferable to select a compound that does not function as a polymerization inhibitor from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation.

The pigment functions as a colorant for the ink composition. However, in the present invention, the fine pigment having a particle size as described later is uniformly and stably dispersed in the ink composition. The ink composition has excellent color developability, and can form a sharp and excellent weather-resistant image.
The pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include known organic pigments and inorganic pigments. Resin particles dyed with dyes, commercially available pigment dispersions, The surface-treated pigment (for example, a pigment dispersed in an insoluble resin or the like using a pigment as a dispersion medium, or a pigment grafted with a resin on the pigment surface) can also be used. Examples of the pigment include, for example, “Dictionary of Pigments” (2000), edited by Seijiro Ito. Herbst, K.M. Examples include those described in Hunger “Industrial Organic Pigments”, Japanese Patent Application Laid-Open No. 2002-12607, Japanese Patent Application Laid-Open No. 2002-188025, Japanese Patent Application Laid-Open No. 2003-26978, and Japanese Patent Application Laid-Open No. 2003-342503.

  Examples of the organic pigment and inorganic pigment include yellow pigment, magenta pigment, blue, cyan pigment, green pigment, orange pigment, brown pigment, violet pigment, black pigment, and white pigment.

  The yellow pigment is a pigment exhibiting a yellow color. I. Pigment Yellow 1 (Fast Yellow G etc.), C.I. I. Monoazo pigments such as CI Pigment Yellow 74; I. Pigment Yellow 12 (disaji yellow, etc.), C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 155, C.I. I. Disazo pigments such as CI Pigment Yellow 219; I. Non-benzidine azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100 (eg Tartrazine Yellow Lake); I. Pigment yellow 95 (condensed azo yellow, etc.), C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. Condensed azo pigments such as C.I. Pigment Yellow 166; I. Pigment Yellow 115 (quinoline yellow lake, etc.), etc., acidic dye lake pigments, C.I. I. Basic dye lake pigments such as C.I. Pigment Yellow 18 (such as thioflavine lake); I. Anthraquinone pigments such as C.I. Pigment Yellow 24 (Flavantron Yellow, etc.); I. Quinophthalone pigments such as C.I. Pigment Yellow 110 (e.g., Quinophthalone Yellow); I. Pigment yellow 139 (isoindoline yellow, etc.) and the like, isoindoline pigments such as C.I. I. Pyrazolone pigments such as C.I. Pigment Yellow 60 (Pyrazolone Yellow, etc.); I. Pigment yellow 120, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 167, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. An acetolone pigment such as C.I. Pigment Yellow 194; I. Pigment complex pigments such as CI Pigment Yellow 150, C.I. I. Nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.), C.I. I. Metal complex azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow, etc.); I. And pigment yellow.

  The magenta pigment is a pigment exhibiting red or magenta color. I. Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Pigment red 1, C.I. I. Pigment red 4, C.I. I. Pigment Red 6 and other B-naphthol pigments, C.I. I. Disazo pigments such as CI Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.) and C.I. I. Pigment Red 57: 1 (Brilliant Carmine 6B etc.), C.I. I. Pigment red 52: 1, C.I. I. Pigment Red 48 (B-oxynaphthoic acid lake, etc.) azo lake pigment, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment red 220, C.I. I. Pigment red 214, C.I. I. Pigment red 221, C.I. I. Condensed azo pigments such as C.I. Pigment Red 242 (condensed azo red and the like), C.I. I. Pigment Red 174 (Phloxine B lake, etc.), C.I. I. Pigment Red 172 (Erythrosin Lake, etc.) and other acidic dye lake pigments, C.I. I. Basic dye lake pigments such as C.I. Pigment Red 81 (Rhodamine 6G 'lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as CI Pigment Red 88 (Thioindigo Bordeaux and the like), C.I. I. Perinone pigments such as CI Pigment Red 194 (perinone red, etc.); I. Pigment red 149, C.I. I. Pigment red 179, C.I. I. Pigment red 178, C.I. I. Pigment red 190, C.I. I. Pigment red 224, C.I. I. Perylene pigments such as CI Pigment Red 123; I. Pigment violet 19 (unsubstituted quinacridone), C.I. I. Pigment red 122, C.I. I. Pigment red 262, C.I. I. Pigment red 207, C.I. I. Quinacridone pigments such as CI Pigment Red 209; I. Pigment Red 180 (Isoindolinone Red 2BLT, etc.), etc., isoindolinone pigments, C.I. I. Alizarin lake pigments such as C.I. Pigment Red 83 (Mada Lake, etc.); I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 185, C.I. I. Naphtholone pigments such as CI Pigment Red 208; I. Naphthol AS-based lake pigments such as CI Pigment Red 247; I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 21, C.I. I. Pigment red 170, C.I. I. Pigment red 187, C.I. I. Pigment red 256, C.I. I. Pigment red 268, C.I. I. Naphthol AS pigments such as C.I. Pigment Red 269; I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. And diketopyrrolopyrrole pigments such as CI Pigment Red 272.

  The cyan pigment is a pigment exhibiting blue or cyan color. I. Disazo pigments such as C.I. Pigment Blue 25 (dianisidine blue, etc.); I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Phthalocyanine pigments such as C.I. Pigment Blue 16 (phthalocyanine blue, etc.); I. Acidic dye lake pigments such as C.I. Pigment Blue 24 (peacock blue lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Blue 1 (such as Biclothia Pure Blue BO Lake); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. And alkaline blue pigments such as CI Pigment Blue 18 (Alkali Blue V-5: 1).

The green pigment is a pigment exhibiting a green color. I. Pigment green 7 (phthalocyanine green), C.I. I. Phthalocyanine pigments such as C.I. Pigment Green 36 (phthalocyanine green); I. Pigment green 8, C.I. I. And azo metal complex pigments such as CI Pigment Green 10.
The orange pigment is a pigment exhibiting an orange color. I. Pigment Orange 66 (Isoindoline Orange) and the like, C.I. I. Anthraquinone pigments such as C.I. Pigment Orange 51 (dichloropyrantron orange); I. Pigment orange 2, C.I. I. Pigment orange 3, C.I. I. Pigment Orange 5 and the like-naphthol pigments such as C.I. I. Pigment orange 4, C.I. I. Pigment orange 22, C.I. I. Pigment orange 24, C.I. I. Pigment orange 38, C.I. I. Naphthol AS pigments such as CI Pigment Orange 74; I. Pigment Orange 61 and other isoindolinone pigments, C.I. I. Perinone pigments such as CI Pigment Orange 43; I. Pigment orange 15, C.I. I. Disazo pigments such as CI Pigment Orange 16; I. Pigment orange 48, C.I. I. Quinacridone pigments such as CI Pigment Orange 49; I. Pigment orange 36, C.I. I. Pigment orange 62, C.I. I. Pigment orange 60, C.I. I. Pigment orange 64, C.I. I. An acetolone pigment such as C.I. Pigment Orange 72; I. Pigment orange 13, C.I. I. And pyrazolone pigments such as CI Pigment Orange 34.
The brown pigment is a pigment exhibiting a brown color. I. Pigment brown 25, C.I. I. And naphthron pigments such as CI Pigment Brown 32.
The violet pigment is a pigment exhibiting a purple color. I. Naphtholone pigments such as CI Pigment Violet 32, C.I. I. Perylene pigments such as CI Pigment Violet 29, C.I. I. Pigment violet 13, C.I. I. Pigment violet 17, C.I. I. Naphthol AS pigments such as CI Pigment Violet 50, C.I. I. Pigment violet 23, C.I. I. And dioxazine pigments such as CI Pigment Violet 37.

The black pigment is a pigment exhibiting black color, such as carbon black, titanium black, C.I. I. Indazine pigments such as CI Pigment Black 1 (aniline black); I. Pigment black 31, C.I. I. And perylene pigments such as CI Pigment Black 32.
Examples of the white pigment include basic lead carbonate (2PbCO ₃ Pb (OH) ₂ , so-called silver white), zinc oxide (ZnO, so-called zinc white), titanium oxide (TiO ₂ , so-called titanium white), And strontium titanate (SrTiO ₃ , so-called titanium strontium white). The inorganic particles used for the white pigment may be a simple substance or, for example, oxides such as silicon, aluminum, zirconium and titanium, organometallic compounds, and composite particles with organic compounds.
Among them, the titanium oxide has a smaller specific gravity than other white pigments, a large refractive index, and is chemically and physically stable, so that it has a high hiding power and coloring power as a pigment, and further, an acid or an alkali. Since it is excellent in durability against other environments, it is preferably used. In addition to the titanium oxide, another white pigment (may be other than the above-described white pigment) may be used in combination.

For the dispersion of the pigment, for example, a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and the like Can be preferably used.
In the present invention, it is particularly preferable to add a dispersant described later when the pigment is dispersed.
In addition, when dispersing the pigment, a synergist according to various pigments may be added as a dispersion aid if necessary. The content of the dispersion aid in the ink composition is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

  The dispersion medium used when the pigment is dispersed in the ink composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polymerizable compound having a low molecular weight may be selected from the dispersion medium. Or a solvent may be used as the dispersion medium. However, the ink composition of the present invention is a radiation curable ink, and is preferably solvent-free without containing the solvent in order to cure the ink after it is applied to the recording medium. This is because if the solvent remains in the cured ink image, the solvent resistance is deteriorated or a VOC (Volatile Organic Compound) problem of the remaining solvent occurs. For this reason, it is preferable to use the polymerizable compound as the dispersion medium, and to select a polymerizable compound having the lowest viscosity among them in terms of dispersion suitability and handling property of the ink composition.

There is no restriction | limiting in particular as an average particle diameter of the said pigment, Although it can select suitably according to the objective, Since it is excellent in color developability so that it is fine, about 0.01-0.4 micrometer is preferable, and 0.02- 0.2 μm is more preferable. The maximum particle size of the pigment is preferably 3 μm, more preferably 1 μm. The particle size of the pigment can be adjusted by selecting the pigment, dispersant, dispersion medium, setting dispersion conditions, filtering conditions, etc., and controlling the particle size of the pigment suppresses clogging of the head nozzle. In addition, ink storage stability, ink transparency and curing sensitivity can be maintained.
The particle diameter of the pigment in the ink composition can be measured by a known measurement method. Specifically, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, a laser diffraction / scattering method, and a dynamic light scattering method.

As content in the ink composition of the said pigment, when the said pigment is an organic pigment, 1-20 mass% is preferable in conversion of solid content, and 2-10 mass% is more preferable. Moreover, when the said pigment is an inorganic pigment, 1-30 mass% is preferable in conversion of solid content, and 2-25 mass% is more preferable.
The content of the colorant in the ink composition is appropriately selected depending on the color and purpose of use, but is preferably 0.01 to 30% by mass with respect to the mass of the entire ink composition.

<Dispersant>
The ink composition of the present invention preferably contains a dispersant. In particular, when a pigment is used, a dispersant is preferably contained in order to stably disperse the pigment in the ink composition. As the dispersant, a polymer dispersant is preferable. The “polymer dispersing agent” in the present invention means a dispersing agent having a weight average molecular weight of 1,000 or more.

Examples of the polymer dispersant include DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-166, and DISPERBYK-166. , DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-182 (manufactured by BYK Chemie); EFKA 7462, EFKA 7500, EFKA 7570, EFKA 7575, EFKA 7580 (manufactured by EFKA Additive); Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000 Various Solsperse dispersants (manufactured by Noveon) such as 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000; Adeka Pluronic L31, F38, L42, L44 , L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, -123 (manufactured by ADEKA Co., Ltd.), Ionette S-20 (manufactured by Sanyo Chemical Industries, Ltd.); Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester type) (manufactured by Enomoto Kasei Co., Ltd.).
The content of the dispersant in the ink composition is appropriately selected depending on the purpose of use, but is preferably 0.05 to 15% by mass with respect to the mass of the entire ink composition.

<Surfactant>
A surfactant may be added to the ink composition of the present invention in order to impart stable ejection properties for a long time.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. Moreover, you may use a fluorine-type surfactant (for example, organic fluoro compound etc.) and silicone type surfactant (for example, polysiloxane compound etc.) as said surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826. The polysiloxane compound is preferably a modified polysiloxane compound in which an organic group is introduced into part of the methyl group of dimethylpolysiloxane. Examples of modification include polyether modification, methylstyrene modification, alcohol modification, alkyl modification, aralkyl modification, fatty acid ester modification, epoxy modification, amine modification, amino modification, mercapto modification, etc. is not. These modification methods may be used in combination. Of these, polyether-modified polysiloxane compounds are preferred from the viewpoint of improving ejection stability in inkjet. Examples of polyether-modified polysiloxane compounds include, for example, SILWET L-7604, SILWET L-7607N, SILWET FZ-2104, SILWET FZ-2161 (manufactured by Nippon Unicar Co., Ltd.), BYK306, BYK307, BYK331, BYK333, BYK347. , BYK348 and the like (manufactured by BYK Chemie), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, Examples thereof include KF-6020, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Of these, silicone surfactants are preferred.
The content of the surfactant in the ink composition of the present invention is appropriately selected depending on the purpose of use, but is preferably 0.0001 to 1% by mass with respect to the mass of the entire ink composition.

<Solvent>
In order to improve the adhesion to the recording medium, it is also effective to add a solvent to the ink composition of the present invention.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether and triprolylene Examples include glycol ether solvents such as glycol monomethyl ether, cyclic ester solvents such as γ-butyrolactone, amide solvents such as 2-methylpyrrolidone and 2-pyrrolidone. It is.
In this case, it is effective to add the solvent within a range that does not cause the problem of solvent resistance and VOC, and the amount of the solvent is preferably 0.1 to 5% by mass with respect to the total mass of the ink composition. The mass% is more preferable.
As a dispersion medium for various components such as pigments in the ink composition, a solvent may be added, or a polymerizable compound may be used as a dispersion medium without a solvent. It is an active energy ray-curable ink composition, and it is preferable that the ink composition be solvent-free in order to be cured after the ink composition is applied onto a recording medium. This is because if the solvent remains in the cured ink image, the solvent resistance is deteriorated or a VOC (Volatile Organic Compound) problem of the remaining solvent occurs. From such a viewpoint, a polymerizable compound is used as the dispersion medium, and among them, it is preferable to select a polymerizable monomer having the lowest viscosity from the viewpoint of improving dispersibility and handling properties of the ink composition.
In the ink composition of the present invention, various additives can be used in combination according to the purpose. For example, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration. In addition, an antioxidant can be added to improve the stability of the ink composition.

Further, the ink composition of the present invention may contain various known additives in addition to the above-described components.
Examples of additives other than those described above include, for example, various organic and metal complex antifading agents, potassium thiocyanate, lithium nitrate, ammonium thiocyanate, dimethylamine hydrochloride for the purpose of controlling ejection properties. Examples thereof include conductive salts such as polymer compounds for the purpose of adjusting film properties.

Various polymer compounds can be added to the ink composition of the present invention for the purpose of adjusting film properties. High molecular compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination.
In addition to this, if necessary, for example, basic compounds, leveling additives, matting agents, waxes for adjusting film properties, adhesion to recording media such as polyolefin and polyethylene terephthalate (PET). In order to improve this, a tackifier (tackifier) that does not inhibit the polymerization can be contained.

The ink composition of the present invention preferably has a viscosity of 0.5 to 30 mPa · s at a temperature at the time of discharge in consideration of dischargeability from an inkjet nozzle, and preferably 0.5 to 20 mPa · s. It is more preferable that it is 1-15 mPa · s. It is preferable that the composition ratio is appropriately adjusted and determined so as to be within this range.
The viscosity of the ink composition at 25 ° C. (room temperature) is preferably 1 mPa · s or more and 200 mPa · s or less, more preferably 2 mPa · s or more and 50 mPa · s or less, and 2.5 mPa · s or less. More preferably, it is 30 mPa · s or less. By setting the viscosity at room temperature high, even when a porous recording medium is used, the ink composition can be prevented from penetrating into the recording medium, the uncured monomer can be reduced, and the odor can be reduced. Dot blurring at the time of droplet landing can be suppressed, and as a result, the image quality is improved. Further, when the viscosity of the ink composition at 25 ° C. is 200 mPa · s or less, delivery of the ink composition to an inkjet head or the like in the apparatus is easy.

  The surface tension of the ink composition of the present invention is preferably 20 to 40 mN / m, and more preferably 23 to 35 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and uncoated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and 35 mN / m or less is preferable from the viewpoint of wettability.

The ink composition of the present invention thus prepared is suitable for recording by printing the ink composition on a recording medium with an ink jet printer, and then curing the printed ink composition by irradiation with active rays. It can be carried out.
Since the printed matter obtained from the ink composition of the present invention is excellent in the strength of the image portion, in addition to the image formation by the ink composition, various other methods such as the formation of an ink receiving layer (image portion) of a lithographic printing plate can be used. Can be used for applications.

(Inkjet recording method, inkjet recording apparatus and printed matter)
In the ink jet recording method of the present invention, the ink composition of the present invention is ejected onto a recording medium (support, recording material, etc.) for ink jet recording, and the ink composition ejected onto the recording medium is irradiated with active energy rays. The inkjet ink composition is cured to form an image.

More specifically, the inkjet recording method of the present invention comprises (a ¹ ) a step of ejecting the ink composition of the present invention onto a recording medium, and (b ¹ ) an active line on the ejected ink composition. It is preferable to include a step of curing the ink composition by irradiation.
By including the steps (a ¹ ) and (b ¹ ), the ink jet recording method of the present invention forms an image with the ink composition cured on the recording medium.
In addition, the inkjet recording method of the present invention is a multi-pass mode in which the above steps (a ¹ ) and (b ¹ ) are performed twice or more on the same part on the recording medium, that is, the same part is printed by overstrike. Preferably it is done. By using the ink composition of the present invention, an image superior in glossiness can be obtained when printing is performed in a multipass mode.
The printed matter of the present invention is a printed matter recorded with the ink composition of the present invention, and is preferably a printed matter recorded by the ink jet recording method of the present invention.

The ink composition of the present invention is suitable for package printing, and particularly suitable for package printing for food packaging. In that case, the inkjet recording method preferably includes the following steps in this order.
(Step a) A step of discharging an inkjet ink composition from an inkjet head and printing on a support for a package having a film thickness of 150 μm or less, and
(Step b) Step of irradiating the ejected inkjet ink composition with active rays

In the step (a ¹ ) and the step (a) in the ink jet recording method of the present invention, an ink jet recording apparatus described in detail below can be used.

<Inkjet recording apparatus>
There is no restriction | limiting in particular as an inkjet recording device which can be used for the inkjet recording method of this invention, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, any known inkjet recording apparatus including a commercially available product can be used to discharge the ink composition onto the recording medium in steps (a ¹ ) and (a) of the inkjet recording method of the present invention. it can.

Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an active energy ray source.
The ink supply system includes, for example, an original tank containing the ink composition of the present invention, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head preferably has a multi-size dot of 1 to 100 pl, more preferably 8 to 30 pl, preferably 320 × 320 to 4,000 × 4,000 dpi, more preferably 400 × 400 to 1,600 ×. It can be driven so that it can discharge at a resolution of 1,600 dpi, more preferably 720 × 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.

As described above, the ink composition of the present invention is preferably provided with a means for stabilizing the temperature of the ink composition in the ink jet recording apparatus because the ink composition to be ejected is preferably kept at a constant temperature. The parts to be kept at a constant temperature are all the piping systems and members from the ink tank (intermediate tank if there is an intermediate tank) to the nozzle ejection surface. That is, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion.
The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors in each piping portion and perform heating control according to the flow rate of the ink composition and the environmental temperature. The temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

  A radiation curable ink composition such as the ink composition of the present invention generally has a higher viscosity than a water-based ink composition usually used in an ink composition for ink jet recording, and therefore has a large viscosity fluctuation due to temperature fluctuations during ejection. Viscosity fluctuation of the ink composition has a great influence on the change of the droplet size and the change of the droplet discharge speed, and thus causes the image quality deterioration. Therefore, it is necessary to keep the temperature of the ink composition during ejection as constant as possible. Therefore, in the present invention, the temperature control range of the ink composition is preferably set to ± 5 ° C. of the set temperature, more preferably ± 2 ° C. of the set temperature, and further preferably set temperature ± 1 ° C. .

Next, the (b ¹ ) step and the (b) step will be described.
The ink composition discharged onto the recording medium is cured by irradiating with active energy rays (active rays). This is because the polymerization initiator contained in the ink composition of the present invention is decomposed by irradiation with active energy rays to generate polymerization initiation species such as radicals, and the polymerization reaction of the polymerizable compound is a function of the initiation species. This is because it is created and promoted. At this time, if the sensitizer is present together with the polymerization initiator in the ink composition, the sensitizer in the system absorbs the active energy ray to be in an excited state, and the polymerization initiator is decomposed by contact with the polymerization initiator. It can be accelerated and a more sensitive curing reaction can be achieved.

  Here, α-rays, γ-rays, electron beams, X-rays, ultraviolet rays, visible light, infrared rays, or the like can be used as active energy rays. Although the peak wavelength of the active energy ray depends on the absorption characteristics of the sensitizer, for example, it is preferably 200 to 600 nm, more preferably 300 to 450 nm, still more preferably 320 to 420 nm, The active energy ray is particularly preferably ultraviolet light having a peak wavelength in the range of 340 to 400 nm.

In addition, the polymerization initiation system of the ink composition of the present invention has sufficient sensitivity even with a low output active energy ray. Therefore, it is appropriate to cure the exposed surface with an illuminance of 10 to 4,000 mW / cm ² , more preferably 20 to 2,500 mW / cm ² .

Mercury lamps, gas / solid lasers, etc. are mainly used as active energy ray sources, and mercury lamps and metal halide lamps are widely used as light sources for curing UV photocurable ink jet recording ink compositions. Are known. However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curable ink jets.
In addition, a light emitting diode (LED) and a laser diode (LD) can be used as an active energy ray source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit active energy rays centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. A particularly preferable active energy ray source in the present invention is a UV-LED, and a UV-LED having a peak wavelength at 340 to 400 nm is particularly preferable.
The maximum illumination intensity on the LED recording medium is preferably 10 to 2,000 mW / cm ^2, more preferably 20 to 1,000 mW / cm ^2, is 50 to 800 mW / cm ² It is particularly preferred.

The ink composition of the present invention is suitably irradiated with such active energy rays for 0.01 to 120 seconds, more preferably for 0.1 to 90 seconds.
The irradiation conditions of active energy rays and the basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink composition discharge device, and the head unit and the light source are scanned by a so-called shuttle method. The irradiation with the active energy ray is performed for a certain period of time after the ink composition has landed (preferably 0.01 to 0.5 seconds, more preferably 0.01 to 0.3 seconds, and still more preferably 0.01 to 0.15). Seconds). As described above, by controlling the time from the landing of the ink composition to the irradiation to an extremely short time, it is possible to prevent the ink composition that has landed on the recording medium from bleeding before being cured. In addition, since the ink composition can be exposed to a porous recording medium before it penetrates to a deep part where the light source does not reach, it is preferable because residual unreacted monomer can be suppressed.
Further, the curing may be completed by another light source that is not driven. International Publication No. 99/54415 pamphlet discloses a method using an optical fiber or a method of irradiating a recording unit with UV light by applying a collimated light source to a mirror surface provided on the side of the head unit as an irradiation method. Such a curing method can also be applied to the ink jet recording method of the present invention.

By adopting the ink jet recording method as described above, the dot diameter of the landed ink composition can be kept constant even on various recording media having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. By superimposing the ink compositions in order of low lightness, it becomes easy for the irradiation rays to reach the lower ink composition, and good curing sensitivity, reduction of residual monomers, and improvement in adhesion can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.
Thus, the ink composition of the present invention can form an image on the surface of a recording medium by being cured with high sensitivity by irradiation with active energy rays.

The ink composition of the present invention is preferably used as an ink set comprising a plurality of ink jet recording inks.
In the inkjet recording method of the present invention, the order of the respective colored ink compositions to be ejected is not particularly limited, but is preferably applied to the recording medium from a colored ink composition having high brightness, and yellow, cyan, magenta When black is used, it is preferably applied on the recording medium in the order of yellow → cyan → magenta → black. In addition, when white is used in addition to this, it is preferable to apply on the recording medium in the order of white → yellow → cyan → magenta → black. Furthermore, the present invention is not limited to this, and the ink set of the present invention including at least seven colors of yellow, light cyan, light magenta, cyan, magenta, black and white ink compositions can be preferably used. In this case, it is preferable to apply on the recording medium in the order of white → light cyan → light magenta → yellow → cyan → magenta → black.

FIG. 1 is a schematic diagram of an ink jet recording apparatus preferably used in the present invention. The support 6 stretched on the support take-up rolls 5 and 5 ', which is a support transport means, is transported in the direction of the arrow, and is provided with an ink jet head provided with a droplet ejection head for discharging the ink composition of each color. In the unit 7, ink compositions (K: black, Y: yellow, M: magenta, C: cyan, W: white) of each color are ejected.
As shown in FIG. 1, the LED light source unit 1 is surrounded by an inert gas blanket 2 and is connected to an inert gas generator 4 via an inert gas pipe 3. An inert gas generator 4 which is a means for making the atmosphere in the inert gas blanket 2 an oxygen-poor atmosphere supplies an inert gas into the inert gas blanket 2 via an inert gas pipe 3. In the initial state, the atmosphere in the inert gas blanket 2 is air, but when the inert gas generator 4 is operated, the air in the inert gas blanket 2 is replaced with the inert gas. As described above, N ₂ or the like can be used as the inert gas.

<Recording medium>
The recording medium to which the ink composition of the present invention can be applied is not particularly limited, and various non-absorbent resin materials used for ordinary non-coated paper, coated paper, and so-called soft packaging, or films thereof. A resin film molded into a shape can be used.
As various plastic films, for example, PET (polyethylene terephthalate) film, OPS (biaxially stretched polystyrene) film, OPP (biaxially stretched polypropylene) film, ONy (biaxially stretched nylon) film, PVC (polyvinyl chloride) film, Examples include PE (polyethylene) film, TAC (cellulose triacetate) film, and the like.
In addition, examples of the plastic that can be used as the recording medium material include polycarbonate, acrylic resin, ABS (acrylonitrile-butadiene-styrene copolymer), polyacetal, PVA (polyvinyl alcohol), and rubbers. Metals and glasses can also be used as a recording medium.

Since the ink composition of the present invention contains a specific polymerization initiator, it can be suitably used as a curable inkjet ink composition that can be cured by irradiation with active energy rays. In addition, the ink composition of the present invention can be suitably used for producing a large-area printed material because a high-quality image can be directly formed on a non-absorbent recording medium based on digital data.
The ink composition of the present invention can be cured even at a low exposure by containing a specific polymerization initiator. For this reason, it seems that it contributes to the improvement of the printing speed by reducing the system and running cost by using an inexpensive light source with low exposure intensity, and shortening the exposure time. Further, since the curing speed after exposure is high, blurring of the image can be suppressed, and a clear image can be formed.

(Bisacylphosphine oxide compound)
The bisacylphosphine oxide compound of the present invention is a compound represented by the following formula (1 ′) or formula (3).

（式（１’）中、Ｒ¹〜Ｒ⁶はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は式（４）で表される基を表し、Ｒ¹〜Ｒ⁶のうち少なくとも１つは式（４）で表される基であり、Ｒ⁷はアルキル基又はアリール基を表す。）

(In Formula (1 ′), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by Formula (4), and at least of R ^{1 to} R ⁶ . One is a group represented by the formula (4), and R ⁷ represents an alkyl group or an aryl group.)

（式（４）中、Ｒ¹³は水素原子又はメチル基を表し、Ｌ³は−ＣＯＯ−又は−ＣＯＮＨ−を表し、−＊はベンゼン環との結合を表す。）

(In the formula (4), R ¹³ represents a hydrogen atom or a methyl group, L ³ represents a -COO- or -CONH-, - * represents a bond with the benzene ring.)

（式（３）中、Ｒ¹⁰〜Ｒ¹⁵はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は−ＣＨ₂Ｂｒを表し、Ｒ¹⁰〜Ｒ¹⁵のうち少なくとも１つは−ＣＨ₂Ｂｒであり、Ｒ¹⁶は炭素数１〜２０のアルキル基又は炭素数６〜１２のアリール基を表す。）

(In the formula (3), R ¹⁰ ~R ¹⁵ independently represents a hydrogen atom, an alkyl group or a -CH ₂ Br 1 to 4 carbon atoms, at least one of R ¹⁰ to R ¹⁵ is -CH ₂ Br and R ¹⁶ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

R ^{1 to} R ⁶ in the compound represented by the formula (1 ′) are each independently preferably a hydrogen atom, a methyl group or a group represented by the formula (4), and may be a methyl group or a heavy formula (4). It is more preferable that it is group represented by these. In the above embodiment, a polymer with less migration in the polymer and a more suppressed odor can be obtained.
Furthermore, the compound represented by the formula (1 ′) may have only one group represented by the formula (4), or may have two or more groups.
R ⁷ in the compound represented by the formula (1 ′) is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and preferably an aryl group having 6 to 12 carbon atoms. More preferred is a phenyl group. The alkyl group and aryl group may be substituted. Examples of the substituent include an alkyl group, an alkoxy group, an aryl group, and a halogen atom.
When a plurality of groups represented by formula (4) are present in formula (1 ′), the groups represented by formula (4) may be the same or different from each other. Preferably there is.
R ¹³ is preferably a hydrogen atom.
L ³ is preferably —COO—.

R ^{10 to} R ¹⁵ in the formula (3) are each independently preferably a hydrogen atom, a methyl group or —CH ₂ Br, more preferably a methyl group or —CH ₂ Br.
In formula (3), it is preferable that at least one of R ^{10 to} R ¹² is —CH ₂ Br and at least one of R ^{13 to} R ¹⁵ is —CH ₂ Br.
R ¹⁶ in Formula (3) is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. Preferably, it is a C6-C12 aryl group, and it is especially preferable that it is a phenyl group. The alkyl group and aryl group may be substituted. Examples of the substituent include an alkyl group, an alkoxy group, and an aryl group.

As a method for producing the compound represented by formula (3) is not particularly limited, the portion becomes a -CH ₂ Br are using a compound which is -CH ₃ in the formula (3), brominated the -CH ₃ Thus, a method of synthesizing can be preferably exemplified. Specifically, for example, in a compound in which the moiety that is —CH ₂ Br in the formula (3) is —CH ₃ , a thermal radical generator such as azoisobutyronitrile and benzoyl peroxide and N-bromosuccinimide A method in which a brominating agent is allowed to act is preferably mentioned.
There is no restriction | limiting in particular as a manufacturing method of the compound represented by Formula (1), or the compound represented by Formula (1 '), What is necessary is just to synthesize | combine by a well-known method. Of these, a method of introducing a polymerizable functional group or a group having a polymerizable functional group by using a compound represented by the formula (3) and substituting the bromine atom of —CH ₂ Br in the formula (3) can be preferably exemplified. .

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis of A-1>
-Synthesis of benzyl bromide intermediate-
To a 2 L three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 12 g (28.7 mmol) of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819, manufactured by Ciba Japan Co., Ltd.) ), 5.11 g (28.7 mmol) of N-bromosuccinimide and 1,500 mL of chlorobenzene were added, and the mixture was heated and stirred at 65 ° C. under a nitrogen stream for 1 hour. After the solid was completely dissolved, 0.2 g of azoisobutyronitrile was added and reacted for another 6 hours. After allowing the solution to cool, the mixture was partitioned twice with ethyl acetate and water, and then the benzyl bromide intermediate of compound A-1 was isolated by column chromatography (hexane: ethyl acetate = 7: 3).
¹ H NMR (400 MHz, CDCl ₃ )
δ = 2.04 (6H, s), 2.11 (6H, s), 2.25 (3H, s) 4.36 (2H, s), 6.78 (2H, s), 7.04 ( 2H, s), 7.41-7.48 (2H, m), 7.55-7.65 (1H,), 7.74-7.80 (2H, m)

-Synthesis of A-1-
12.20 g (37.44 mmol) of cesium carbonate was added to a mixed solution of dimethylformamide (DMF, 40 mL) and pure water (8 mL) and dissolved. Subsequently, the mixture was stirred for 12 hours under reduced pressure and concentrated. 1.35 g (18.72 mmol) of acrylic acid was added, a DMF (30 mL) solution of 9.3 g (18.72 mmol) of benzyl bromide intermediate of A-1 was added, and the mixture was stirred at room temperature (25 ° C.) for 5 hours. After liquid separation twice with ethyl acetate and water, Compound A-1 was isolated by column chromatography (hexane: ethyl acetate = 8: 2).
¹ H NMR (400 MHz, CDCl ₃ )
δ = 2.08 (6H, s), 2.11 (6H, s), 2.25 (3H, s) 5.20 (2H, s), 5.86 (1H, d), 6.20 ( 1H, t), 6.45 (1H, d), 6.78 (2H, s), 7.00 (2H, s), 7.41-7.48 (2H, m), 7.55-7 .65 (1H,), 7.74-7.80 (2H, m)

<Synthesis of A-2, A-3, A-5, A-6, A-13, A-14, A-17, A-18, and A-22>
In the synthesis of A-1, A-2, A-3, A- are the same as the synthesis of A-1, except that each component used and the amount added thereof are changed as shown in Table 1 or Table 2. 5, A-6, A-13, A-14, A-17, A-18 and A-22 were respectively synthesized.

The ¹ H NMR data of benzyl bromide intermediates of A-2 and A-3, benzyl bromide intermediates of A-3 and A-5, and A-5 are shown below.

<A-2>
¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.96 (3H, t), 2.08 (6H, s), 2.11 (6H, s), 2.25 (3H, s) 5.19 (2H, s), 5.57 (1H, d), 6.45 (1H, d), 6.78 (2H, s), 7.00 (2H, s), 7.41-7.48 ( 2H, m), 7.55 to 7.65 (1H,), 7.74 to 7.80 (2H, m)

<Benzyl bromide intermediate of A-3>
¹ H NMR (400 MHz, CDCl ₃ ): δ = 2.04 (12H, s), 4.36 (4H, s), 7.02 (4H, s), 7.41-7.48 (2H, m ), 7.55 to 7.65 (1H,), 7.74 to 7.80 (2H, m)

<A-3>
¹ H NMR (400 MHz, CDCl ₃ ): δ = 2.08 (12H, s), 5.20 (4H, s), 5.86 (2H, d), 6.20 (2H, t), 6. 45 (2H, d), 7.00 (4H, s), 7.41-7.48 (2H, m), 7.55-7.65 (1H,), 7.74-7.80 (2H , M)

<Benzyl bromide intermediate of A-5>
¹ H NMR (400 MHz, CDCl ₃ ): δ = 2.04 (9H, s), 4.36 (6H, s), 7.02 (3H, s), 7.04 (1H, s), 7. 41 to 7.48 (2H, m), 7.55 to 7.65 (1H,), 7.74 to 7.80 (2H, m)

<A-5>
¹ H NMR (400 MHz, CDCl ₃ ): δ = 2.08 (9H, s), 5.20 (6H, s), 5.86 (3H, d), 6.20 (3H, m), 6. 45 (3H, d), 7.00 (3H, s), 7.02 (1H, s), 7.41-7.48 (2H, m), 7.55 to 7.65 (1H,), 7.74-7.80 (2H, m)

<Synthesis of A-20>
To a 200 ml eggplant flask, 1.81 g (78.8 mmol) of metallic sodium and 76.6 g of dehydrated toluene were added and stirred at 98 ° C. 3.53 g (19.7 mmol) of p, p-dichlorophenylphosphine was added dropwise over 1 hour, and the mixture was further stirred for 16 hours. Subsequently, 2.92 g (39.4 mmol) of tert-butanol was added dropwise over 1 hour.
To the obtained reaction solution, 8.87 g (39.6 mmol) of 3-isocyanate-2,4,6-trimethylbenzoyl chloride was added dropwise at 35 ° C., and the mixture was further stirred for 1 hour.
To the obtained reaction solution, 6.70 g (59.1 mmol) of 30% hydrogen peroxide was dropped, and the mixture was further stirred for 1 hour. After treatment with 20 g of 5% aqueous NaHCO ₃ solution, the organic layer was removed. After liquid separation twice with ethyl acetate and water, Compound A-20 was isolated by column chromatography (hexane: ethyl acetate = 8: 2).

<Inkjet recording method>
In the ink jet apparatus shown in FIG. 1, CA3 heads manufactured by TOSHIBA TEC CO., LTD. Are arranged in parallel as four ink jet heads, and the heads are heated to 45 ° C., and can be drawn with a droplet ejection size of 42 pL. So that the frequency was controlled. As a light source, an LED light source unit (LEDZero Solidcure, manufactured by Integration Technology) having a peak wavelength of 385 nm is arranged in an inert gas blanket, and an N ₂ gas generator with compressor, Maxi-Flow30 (manufactured by Inhouse Gas) is used as an inert gas source. ) At a pressure of 0.2 MPa · s, and N ₂ is allowed to flow at a flow rate of ₂ to 10 L / min so that the N ₂ concentration in the blanket (N ₂ partial pressure) is in the range of 90 to 99%. N ₂ concentration was set. As a support, pyrene film-OTP3162 (A4 size, polypropylene sheet, film thickness 40 μm) was operated at a speed of 30 m / min to draw a 100% solid image, and various performance tests shown below were performed.

(Preparation of each mill base)
<Preparation of cyan mill base A>
300 parts by mass of IRGALITE BLUE GLVO (cyan pigment, manufactured by BASF Japan Ltd.), 620 parts by mass of SR9003 (PO-modified neopentyl glycol diacrylate, manufactured by Sartomer), and SOLPERSE 32000 (a dispersant manufactured by Noveon) Cyan mill base A was obtained by mixing with 80 parts by mass. Cyan mill base A was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Examples 1-17 and Comparative Examples 1-5)
<Method for producing ink composition>
Each ink composition was obtained by mixing and stirring by the quantity (mass part) which described the raw material of Tables 3-5. Compounds B-1 and B-2 each have the following structure.

In addition, the symbol of Tables 3-5 other than having mentioned above is as showing below.
<Polymerizable compound (monomer)>
TPGDA :: Tripropylene glycol diacrylate, SR306 manufactured by Sartomer
NPGPODA: PO-modified neopentyl glycol diacrylate, SR9003 manufactured by Sartomer
EOTMPTA: EO-modified trimethylolpropane triacrylate, SR454 manufactured by Sartomer
APG-100: Dipropylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Phenoxyethyl acrylate: SR339 manufactured by Sartomer
DVE-3: bifunctional vinyl ether compound, triethylene glycol divinyl ether, manufactured by ISP Europe Co., Ltd. OXT-221: bifunctional oxetane compound, bis (3-ethyl-3-oxetanylmethyl) ether, manufactured by Toagosei Co., Ltd. Other polymerization initiators>
-ITX: Isopropylthioxanthone, SPEEDCURE ITX, manufactured by LAMBSON-ESACURE KIP150: The following compound, manufactured by Lamberti-IRGACURE 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by BASF-IRGACURE 369: 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, manufactured by BASF Japan, IRGACURE 127: bis (α-hydroxyketone) compound shown below, manufactured by BASF <surfactant >
BYK307: Silicone surfactant, manufactured by BYK Chemie

（式中、ｎは２以上の整数を表し、Ｒは末端基を表す。）

(In the formula, n represents an integer of 2 or more, and R represents a terminal group.)

<Migration evaluation method>
10 mL of a mixture of water: ethanol = 70: 30 is dropped onto the surface of the printed material, and the printed material cut into a size of 10 square decimeters is put in a glass sealed container so that the mixed solvent does not volatilize, and left at 40 ° C. for 10 days. did. Then, the total elution amount (overall migration amount: OML) contained in the water-ethanol mixed solution from the printed matter was calculated, and evaluated in 1 to 5 stages. The total volume was measured by allowing the water-ethanol mixed solution to volatilize after standing for 10 days and measuring the mass of the remaining components.
5: Elution amount is 50 ppb or less 4: Elution amount exceeds 50 ppb, 200 ppb or less 3: Elution amount exceeds 200 ppb, 1,000 ppb or less 2: Elution amount exceeds 1,000 ppb, 2,000 ppb or less 1: Elution amount Exceeds 2,000 ppb

<Odor evaluation method>
The image obtained by the inkjet image recording method was enclosed in a 30 cm × 30 cm zip plastic bag and left for 24 hours.
Thereafter, the zip was released and the odor was evaluated. The evaluation was performed with 10 people, and the evaluation with the largest number of people was adopted. When there are a plurality of evaluations of the largest number of people, the average value of the evaluation values is adopted.
5: Almost odorless 4: Slight odor but little concern 3: Some odor but not uncomfortable level 2: Strong odor 1: Very strong odor

<Base material adhesion>
Using the inkjet recording method, the support was changed to Priplak (film thickness 0.8 mm, polypropylene sheet, manufactured by Robert Horne), and a printed material was created. The adhesiveness between the cured film and the recording medium is evaluated by a cross hatch test (EN ISO 2409), and represented by notations 5B to 1B by the ASTM method. It is evaluated that 5B has the most excellent adhesiveness, and 3B or more is a level having no practical problem.

<Nail scrub resistance evaluation>
The obtained image was rubbed 10 times with a nail, the image surface was observed, and the degree of scratches was evaluated according to the following criteria. In addition, it is a level which is satisfactory practically at 3 or more.
5: Even if the printed material is observed with a magnifying glass, no scratches are seen on the surface. 4: When the printed material is observed with a magnifying glass, a slight scratch is seen, but at a distance of 50 cm, the scratch is not visible. 3: At a distance of 50 cm from the printed material. Slight scratches are visible when observed, but scratches are not visible from a distance of 1 m 2: Slight scratches are visible when observed at a distance of 1 m from the printed material 1: Clearly observed when observed at a distance of 1 m from the printed material I see scratches on the surface

  The evaluation results in Examples 1 to 17 and Comparative Examples 1 to 5 are summarized in Table 6.

  1: LED light source unit, 2: inert gas blanket, 3: inert gas pipe, 4: inert gas generator, 5, 5 ': support winding roll, 6: support, 7: inkjet head unit

Claims (16)

A bisacylphosphine oxide compound having a polymerizable functional group in the acyl group, and
Containing a polymerizable compound,
The ink composition, wherein the bisacylphosphine oxide compound is a compound represented by the following formula (1).

(In the formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group having a polymerizable functional group, and at least one of R ^{1 to} R ⁶ is (It is a group having a polymerizable functional group, and R ⁷ represents an alkyl group or an aryl group.) The ink composition according to claim 1, wherein at least one of R ^{1 to} R ⁶ is a group having a polymerizable functional group represented by formula (2).

(In formula (2), R ⁸ represents a hydrogen atom or a methyl group, L ¹ represents —COO—, —CONH— or a phenylene group, X represents a divalent linking group, and L ² represents —COO—. or represents -CONH-, R ⁹ represents an alkylene group having 1 to 4 carbon atoms, n represents an integer of 0 to 3, - * represents a bond of benzene ring).   X is a linear or cyclic alkylene group having 1 to 12 carbon atoms, a linear or cyclic alkenylene group having 2 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or one or more cyclic alkylene groups, The ink composition according to claim 2, which is a divalent group in which an alkenylene group and / or an arylene group and one or more ester bonds, ether bonds, or urethane bonds are combined. The ink composition according to claim _2, wherein R ⁹ is —CH ₂ —.   The ink composition according to claim 2, wherein n is 0. The ink composition according to claim 1, wherein R ⁷ is a phenyl group. The ink composition according to claim 2, wherein L ¹ is —COO—. The ink composition according to claim 2, wherein R ⁸ is a hydrogen atom.   The ink composition according to any one of claims 1 to 8, which is an inkjet ink composition.   The ink composition according to any one of claims 1 to 9, which is an ink composition for printing food packages. (A ¹⁾ on a recording medium, a step of discharging the ink composition according to any one of claims 1 to 10 and,
(B ¹ ) A step of irradiating the discharged ink composition with actinic radiation to cure the ink composition. A bisacylphosphine oxide compound characterized by being a compound represented by the following formula (3).

(In the formula (3), R ¹⁰ ~R ¹⁵ independently represents a hydrogen atom, an alkyl group or a -CH ₂ Br 1 to 4 carbon atoms, at least one of R ¹⁰ to R ¹⁵ is -CH ₂ Br and R ¹⁶ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.) A bisacylphosphine oxide compound characterized by being a compound represented by the following formula (1 ').

(In Formula (1 ′), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by Formula (4), and at least of R ^{1 to} R ⁶ . One is a group represented by the formula (4), and R ⁷ represents an alkyl group or an aryl group.)

(In the formula (4), R ¹³ represents a hydrogen atom or a methyl group, L ³ represents a -COO- or -CONH-, - * represents a bond with the benzene ring.) The bisacylphosphine oxide compound according to claim 13 , wherein R ^{1 to} R ⁶ are each independently a methyl group or a group represented by the formula (4), and R ⁷ is a phenyl group. The bisacylphosphine oxide compound according to claim 13 or 14 , wherein L ³ is -COO-. The bisacylphosphine oxide compound according to any one of claims 13 to 15 , wherein R ¹³ is a hydrogen atom.

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