JP5630605B2 - UV curable ink composition for inkjet - Google Patents

Description

  The present invention relates to an ultraviolet curable inkjet ink composition.

  Conventionally, as a method of forming a coating film having a metallic luster on a printed material, gold powder produced from brass, aluminum fine particles, etc., printing ink using silver powder as a pigment, foil press printing using metal foil, metal foil was used. Thermal transfer systems have been used.

  In recent years, there have been many examples of application to ink jet recording methods in printing, and one of them is metallic printing, and development of ink having metallic luster has been promoted. For the ink having metallic luster, a flat pigment (hereinafter also referred to as “flat aluminum pigment”) in which aluminum particles are thinly extended is often used.

  As a method for producing a flat aluminum pigment, for example, (1) a method in which aluminum particles produced by an atomizer method are crushed and extended by a ball mill, and (2) an ultrasonic cleaner in which aluminum deposited on a film is evaporated in a solvent. (For example, refer to Patent Document 1).

  On the other hand, in recent years, development of ultraviolet curable inks that are cured when irradiated with ultraviolet rays has been promoted. According to this ultraviolet curable ink, an image having high water resistance, solvent resistance, scratch resistance and the like can be recorded on the surface of the recording medium in the ink jet recording method.

  Therefore, if the above-described flat aluminum pigment is applied to an ultraviolet curable ink, it is expected that an excellent metallic gloss image can be recorded on the surface of a recording medium by an ink jet recording method.

JP 2008-202076 A

  However, in order to apply the flat aluminum pigment as described above to the ultraviolet ray curable ink of the ink jet recording system, there are the following problems.

  The ultraviolet curable ink composition is cured in a short time when irradiated with ultraviolet rays. Therefore, the ultraviolet curable ink composition may be cured before the flat aluminum pigment is flatly laminated (so-called “leafing”) in the dots of the ultraviolet curable ink ejected on the recording medium. . As a result, the image recorded on the recording medium may not be excellent in metallic gloss.

  One of the objects according to some embodiments of the present invention is to provide an ultraviolet curable ink composition for inkjet that can record an image having good metallic gloss.

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

[Application Example 1]
One aspect of the ultraviolet curable ink composition according to the present invention is:
An aluminum pigment,
Phenoxyethyl (meth) acrylate,
An organic solvent,
Containing
The organic solvent is contained in an amount of 2% by mass to 30% by mass with respect to the total mass of the ink composition.

  According to the ultraviolet curable inkjet ink composition of Application Example 1, it is possible to record an image having good ejection stability and good adhesion and metallic gloss.

[Application Example 2]
In application example 1,
The boiling point of the organic solvent may be 80 ° C. or higher and 190 ° C. or lower.

[Application Example 3]
In application example 1 or application example 2,
The organic solvent may be one or more selected from glycols and acetates.

[Application Example 4]
In application example 3,
The glycols may be at least one of butyl cellosolve and diethylene glycol diethyl ether.

[Application Example 5]
In application example 3,
The acetates may be propylene glycol monomethyl ether acetate.

[Application Example 6]
In any one of Application Examples 1 to 5,
The phenoxyethyl (meth) acrylate may be included in an amount of 5% by mass to 70% by mass with respect to the total mass of the ink composition.

[Application Example 7]
In any one of Application Examples 1 to 6,
Furthermore, the monomer shown by following General formula (1) can be contained.
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CH-R 3 ... (1)
(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or 1 to 11 carbon atoms. Represents a monovalent organic residue.)

[Application Example 8]
In Application Example 7,
The monomer represented by the general formula (1) may be 2- (2-vinyloxyethoxy) ethyl (meth) acrylate.

[Application Example 9]
In any one of Application Examples 1 to 8,
Further, it may contain one selected from dicyclopentenyloxyethyl acrylate, dicyclopentenyl acrylate, N-vinylcaprolactam and benzyl (meth) acrylate.

[Application Example 10]
In any one of Application Examples 1 to 9,
The aluminum pigment may be a tabular grain having an average thickness of 5 nm to 30 nm and a 50% average particle size of 0.5 μm to 3 μm.

[Application Example 11]
In any one of Application Examples 1 to 10,
Furthermore, a photopolymerization initiator can be contained.

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

  In the present specification, “(meth) acrylate” means at least one of acrylate and its corresponding methacrylate, and “(meth) acryl” means at least one of acrylic and its corresponding methacryl. To do.

1. UV curable ink composition for ink jet UV curable ink composition for ink jet according to an embodiment of the present invention (hereinafter also simply referred to as “UV curable ink composition”) includes an aluminum pigment, phenoxyethyl (meth) Contains an acrylate and an organic solvent.

  Hereinafter, the additives (components) contained in or contained in the ultraviolet curable ink composition according to the present embodiment will be described in detail.

1.1. Aluminum Pigment The ultraviolet curable ink according to this embodiment contains an aluminum pigment. The aluminum pigment is preferably tabular grains (hereinafter also referred to as “tabular aluminum grains”) from the viewpoint of improving the metallic gloss of an image recorded on a recording medium. The flat aluminum particles can be produced, for example, by the production method shown below.

  (A) First, a composite pigment base material having a structure in which a peeling resin layer and an aluminum or aluminum alloy layer (hereinafter simply referred to as “aluminum layer”) are sequentially laminated on a sheet-like substrate surface is prepared.

  Although it does not restrict | limit especially as a sheet-like base material, Polytetrafluoroethylene, polyethylene, polypropylene, Polyester films, such as a polyethylene terephthalate, Polyamide films, such as nylon 66 and nylon 6, Polycarbonate films, a triacetate film, a polyimide film, etc. And a non-woven film, a paper made of a material capable of absorbing or holding a liquid, and the like.

  The thickness of the sheet-like substrate is not particularly limited but is preferably 10 to 150 μm. If it is 10 μm or more, there is no problem in handleability in the process or the like, and if it is 150 μm or less, it is rich in flexibility and there is no problem in roll formation, peeling and the like.

  The release resin layer is an undercoat layer of an aluminum layer, and is a peelable layer for improving the peelability from the sheet-like substrate surface. As the resin used for the release resin layer, for example, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, cellulose derivative, acrylic acid polymer, or modified nylon resin is preferable.

  The resin layer for peeling can be formed by applying a solution of one or a mixture of two or more of the exemplified resins to a sheet-like substrate and drying it. After coating, additives such as a viscosity modifier can be added.

  For the application of the release resin layer, commonly used techniques such as gravure coating, roll coating, blade coating, extrusion coating, dip coating, and spin coating can be used. After coating and drying, the surface can be smoothed by calendaring if necessary.

  Although the thickness of the resin layer for peeling is not specifically limited, Preferably it is 0.5-50 micrometers, More preferably, it is 1-10 micrometers. If it is less than 0.5 μm, the amount as a dispersion resin is insufficient, and if it exceeds 50 μm, when it is rolled, it tends to peel off at the interface with the aluminum layer.

  As means for laminating the aluminum layer on the peeling resin layer, it is preferable to apply vacuum deposition, ion plating or sputtering.

  The aluminum layer may be sandwiched between protective layers as exemplified in JP-A-2005-68250. Examples of the protective layer include a silicon oxide layer and a protective resin layer.

  The silicon oxide layer is not particularly limited as long as it contains silicon oxide, but is preferably formed from a silicon alkoxide such as tetraalkoxysilane or a polymer thereof by a sol-gel method. An alcohol solution in which silicon alkoxide or a polymer thereof is dissolved is applied and heated and fired to form a silicon oxide layer coating.

  The protective resin layer is not particularly limited as long as it is a resin that does not dissolve in the dispersion medium, and examples thereof include polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, and cellulose derivatives. Of these, it is preferably formed from polyvinyl alcohol or a cellulose derivative.

  When an aqueous solution of one or more of the exemplified resins is applied and dried, a protective resin layer can be formed. Additives such as viscosity modifiers can be added to the coating solution. The silicon oxide and the resin are applied by the same method as the application of the release resin layer.

  (B) Next, the composite pigment base material is peeled off at the interface between the sheet base material surface of the composite pigment base material and the release resin layer in a dispersion medium in which a monomer and an organic solvent described later are mixed. Is then pulverized or refined to prepare an aluminum pigment dispersion containing coarse particles. Furthermore, the obtained aluminum pigment dispersion is filtered to remove coarse particles, whereby a dispersion containing tabular aluminum particles having a predetermined average particle diameter can be obtained.

  In addition, when an aluminum pigment is added into a dispersion medium composed only of a monomer, the monomer and the aluminum pigment may react to cause the dispersion to gel. Therefore, it is preferable to add an aluminum pigment in the organic solvent and the monomer as described above. If it does in this way, since the surface of an aluminum pigment is protected by the organic solvent, the gelatinization of a dispersion liquid can be reduced.

  In addition, the method of performing the fine processing etc. in the monomer and the organic solvent to be described later in the composite pigment raw material has been shown, but the composite pigment raw material is put into a dispersion medium composed only of the organic solvent to be described later, A dispersion containing tabular aluminum particles can be obtained by carrying out the micronization treatment. If it does in this way, since the surface of an aluminum pigment is protected by the organic solvent, the gelatinization of the ultraviolet curable ink composition at the time of adding the monomer mentioned later can be reduced.

  Moreover, although the case where it peeled with the interface of the sheet base material surface of a composite raw material and the resin layer for peeling as a boundary was shown, it is not limited to this, For example, the interface between the resin layer for peeling and an aluminum layer is used as a boundary Can be peeled off.

  The peeling treatment method from the sheet-like substrate is not particularly limited, but is a method that is performed by immersing the composite pigment raw material in a liquid, or the ultrasonic treatment is performed at the same time as the immersion in the liquid. A method of pulverizing the composite pigment thus obtained is preferred. The plate-like aluminum particles obtained as described above have a release resin layer serving as a protective colloid, and a stable dispersion can be obtained simply by performing a dispersion treatment in a dispersion medium.

  Here, the term “tabular particle” refers to an aluminum particle having a substantially flat surface (XY plane) when the major axis on the plane is X, the minor axis is Y, and the thickness is Z. (Z) refers to particles that are substantially uniform. More specifically, the 50% average particle diameter R50 (hereinafter also simply referred to as “R50”) of the equivalent circle diameter determined from the area of the substantially flat surface (XY plane) of the aluminum particles is 0.5 μm or more and 3 μm or less. And what satisfies the thickness (Z) of 5 nm or more and 30 nm or less.

  The “equivalent circle diameter” is a diameter of a circle when assuming a substantially flat surface (XY plane) of the aluminum particle as a circle having the same projected area as the projected area of the aluminum particle. For example, when the substantially flat surface (XY plane) of an aluminum particle is a polygon, the diameter of the circle obtained by converting the polygonal projection surface into a circle is the equivalent circle diameter of the aluminum particle. That's it.

  R50 is preferably 0.5 μm to 3 μm, and more preferably 0.75 μm to 2 μm, from the viewpoint of ensuring good metallic gloss and ejection stability. When R50 is less than 0.5 μm, the metallic gloss may be insufficient. On the other hand, when R50 exceeds 3 μm, ejection stability may be reduced due to nozzle clogging.

  The maximum particle diameter of the equivalent circle diameter determined from the area of the substantially flat surface (XY plane) of the tabular grains is preferably 10 μm or less. By setting the maximum particle size to 10 μm or less, it is possible to prevent clogging of the tabular particles from a nozzle of an ink jet recording apparatus, a foreign matter removal filter provided in an ink flow path, and the like.

  The major axis X, minor axis Y, and equivalent circle diameter on the plane of the tabular grains can be measured using a particle image analyzer. Examples of the particle image analyzer include a flow-type particle image analyzer “FPIA-2100”, “FPIA-3000”, and “FPIA-3000S” (supplied by Sysmex Corporation).

The particle size distribution (CV value) of the tabular grains can be obtained from the following formula (2).
CV value = standard deviation of particle size distribution / average value of particle diameter × 100 (2)
Here, the CV value obtained is preferably 60 or less, more preferably 50 or less, and particularly preferably 40 or less. By selecting tabular grains having a CV value of 60 or less, an effect of excellent printing stability can be obtained.

  The thickness (Z) is preferably 5 nm or more and 30 nm or less, more preferably 10 nm or more and 25 nm or less, from the viewpoint of securing metallic gloss. When the thickness (Z) is less than 5 nm, the metallic luster tends to decrease when a film is formed on the surface of the aluminum particles. On the other hand, even if the thickness (Z) exceeds 30 nm, the metallic gloss tends to decrease.

  The aluminum pigment is preferably aluminum or an aluminum alloy from the viewpoint of cost and ensuring the metallic luster. In the case of using an aluminum alloy, examples of other metal elements or non-metal elements added in addition to aluminum include silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and copper.

  Here, you may provide the process of wash | cleaning the flat aluminum particle contained in the dispersion liquid containing a flat aluminum particle. For the cleaning of the flat aluminum particles, a monomer described later or an organic solvent described later can be used. The dispersion containing the flat aluminum particles may contain the above-described peeling resin layer, or the flat resin particles may have the peeling resin layer attached thereto. Therefore, by washing the flat aluminum particles, it is possible to remove the components of the peeling resin layer and improve the dispersibility in the dispersion medium.

  Although it does not specifically limit as a washing | cleaning method of a flat aluminum particle, For example, it can carry out as follows. First, at least a part of the dispersion medium is removed from the dispersion containing tabular aluminum particles. The dispersion medium is removed by separating the dispersion medium and the flat aluminum particles by an operation such as filtration, centrifugal sedimentation, or centrifugal separation, and removing the dispersion medium contained in the dispersion. Next, a cleaning dispersion medium (such as a monomer or an organic solvent) is added to the flat aluminum particles to disperse the flat aluminum particles in the dispersion medium, and then the cleaning dispersion medium is removed. The step of dispersing the flat aluminum particles in the cleaning dispersion medium and removing the cleaning dispersion medium may be performed a plurality of times. Thereafter, a monomer or an organic solvent described later is added to the flat aluminum particles to obtain a dispersion containing the washed flat aluminum particles.

  The content of the aluminum pigment is preferably 0.5% by mass or more and 7% by mass or less with respect to the total mass of the ink composition. If the content of the aluminum pigment is less than the above range, the metallic gloss of the recorded image may be insufficient. When the content of the aluminum pigment exceeds the above range, the viscosity of the ultraviolet curable ink composition may increase and precipitation of the aluminum pigment may occur.

1.2. Organic solvent The ultraviolet curable ink composition according to the present embodiment contains an organic solvent. Examples of the function of the organic solvent include improving adhesion between the recording medium and the image and facilitating leafing of the aluminum pigment contained in the ultraviolet curable ink composition.

  Hereinafter, the effect that the organic solvent improves the leafing of the aluminum pigment will be specifically described. When dots composed of droplets of the ultraviolet curable ink composition are formed on the recording medium, the aluminum pigment in the dots exhibits excellent metallic luster by leafing. At this time, since the dots are cured in a short time by irradiation with ultraviolet rays, the aluminum pigment in the dots is fixed in the dots as the dots are cured before being leafed to such an extent that the metallic gloss can be expressed. Therefore, the image recorded on the recording medium may not be excellent in metallic gloss.

  On the other hand, the ultraviolet curable ink composition according to the present embodiment contains an organic solvent. When a dot made of an ultraviolet curable ink composition containing an organic solvent is formed on a recording medium, the organic solvent in the dot volatilizes or swells the recording medium before the dot is cured by ultraviolet irradiation. Or enter the recording medium. As a result, the volume of the dots formed on the recording medium decreases, so that the solid content of the aluminum pigment in the dots increases, so the aluminum pigment becomes easy to leaf. In this way, the ultraviolet curable ink composition containing an aluminum pigment can record an image having excellent metallic gloss by the action of an organic solvent.

  The boiling point of the organic solvent is preferably 80 ° C. or higher and 190 ° C. or lower. When the boiling point of the organic solvent is within the above range, an image having excellent ink ejection stability and excellent metallic gloss can be recorded. On the other hand, when the boiling point of the organic solvent exceeds the above range, the volatility of the organic solvent is lowered, so that it is difficult to reduce the dot volume of the ink and the metallic gloss of the image may be lowered. Also, if the boiling point of the organic solvent is less than the above range, the organic solvent is likely to volatilize in the vicinity of the ejection head of the ink jet recording apparatus, so that the viscosity of the ink rises and ink ejection failure may occur.

  The content of the organic solvent is 2% by mass to 30% by mass, and preferably 5% by mass to 20% by mass with respect to the total mass of the ink composition. When the content of the organic solvent is within the above range, it is possible to record an image having excellent metallic gloss and adhesion to the recording medium. On the other hand, if the content of the organic solvent exceeds the above range, the ink may easily adhere to the vicinity of the ejection head, which may cause nozzle clogging and the like, resulting in ink ejection failure. In addition, when the content of the organic solvent is less than the above range, the adhesion of the image to the recording medium decreases, or the aluminum pigment on the recording medium becomes difficult to leaf and the image metallic gloss decreases. Sometimes.

  Examples of the organic solvent include ketones, glycols, and acetates. These organic solvents may be used alone or in combination of two or more.

  Examples of ketones include diacetone alcohol (boiling point: 168.1 ° C.).

  As glycols, butyl glycolate (boiling point: 186 ° C), butyl cellosolve (boiling point: 171.2 ° C), butoxypropanol (boiling point: 171 ° C), 3-methyl-3-methoxybutanol (boiling point: 174 ° C), diethylene glycol Diethyl ether (boiling point: 189 ° C), dipropylene glycol monomethyl ether (boiling point: 190 ° C), propylene glycol-n-propyl ether (boiling point: 150 ° C), propylene glycol-n-butyl ether (boiling point: 170 ° C), dipropylene Glycol dimethyl ether (boiling point: 175 ° C.), ethylene glycol monoethyl ether (boiling point: 135 ° C.), propylene glycol monomethyl ether (boiling point: 121 ° C.), dipropylene glycol isopropyl methyl ether (boiling point: 179 ), And the like diethylene glycol ethyl methyl ether (boiling point 176 ° C.).

  Examples of acetates include ethylene glycol monoethyl ether acetate (boiling point: 156.3 ° C.), isopropyl acetate (boiling point: 85 ° C.), propylene glycol diacetate (boiling point: 190 ° C.), n-propyl acetate (boiling point: 102 ° C), butyl acetate (boiling point: 126 ° C), cyclohexanol acetate (boiling point: 173 ° C), propylene glycol monomethyl ether acetate (boiling point: 146 ° C), ethylene glycol monobutyl ether acetate (boiling point: 188 ° C), 3-methoxybutyl Examples include acetate (boiling point: 171 ° C.), ethylene glycol monomethyl ether acetate (boiling point: 145 ° C.), and the like.

  Among these, propylene glycol monomethyl ether acetate, butyl cellosolve and diethylene glycol diethyl ether are preferably used because they have a boiling point in the range of 80 ° C. or higher and 190 ° C. or lower and are excellent in compatibility with the monomer described later. it can.

1.3. Phenoxyethyl (meth) acrylate The ultraviolet curable ink composition according to the present embodiment contains phenoxyethyl (meth) acrylate (B). Phenoxyethyl (meth) acrylate is a monomer added for the purpose of recording an image excellent in flexibility and elongation durability on a recording medium.

  Moreover, phenoxyethyl (meth) acrylate is excellent also in the capability to melt | dissolve the photoinitiator mentioned later. Therefore, when the ink composition contains phenoxyethyl (meth) acrylate, more photopolymerization initiator can be dissolved in the ink composition than in the case of containing other monomers. It can be cured with ultraviolet rays. Furthermore, since phenoxyethyl (meth) acrylate has good dilutability with respect to other monomers, it has a feature that it is very easy to use.

  The content of phenoxyethyl (meth) acrylate is preferably 5% by mass or more and 70% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, with respect to the total mass of the ink composition. When the content of phenoxyethyl (meth) acrylate is within the above range, good curability is exhibited and a good image with reduced tackiness can be recorded. On the other hand, if the content of phenoxyethyl (meth) acrylate exceeds the above range, the image adhesion may be lowered. Further, when the content of phenoxyethyl (meth) acrylate is less than the above range, the effect of dissolving the photopolymerization initiator in the ink composition is reduced, and the curability of the image may be lowered. In the present specification, “curability” refers to a property of polymerizing and curing in the presence or absence of a photopolymerization initiator by ultraviolet irradiation.

1.4. Monomer The ultraviolet curable ink composition according to the present embodiment may contain a monomer represented by the following general formula (1).
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CH-R 3 ... (1)
(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or 1 to 11 carbon atoms. Represents a monovalent organic residue.)

  The ultraviolet curable ink composition according to the present embodiment can improve the ink curability by containing the monomer represented by the general formula (1).

In the general formula (1), the divalent organic residue represented by R ² is a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, an ether bond in the structure and / or A C2-C20 alkylene group which has an oxygen atom by an ester bond, and a C6-C11 optionally substituted bivalent aromatic group are suitable. Among these, structures such as alkylene groups having 2 to 6 carbon atoms such as ethylene group, n-propylene group, isopropylene group and butylene group, oxyethylene group, oxy n-propylene group, oxyisopropylene group and oxybutylene group Among them, an alkylene group having 2 to 9 carbon atoms having an oxygen atom by an ether bond is preferably used.

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

  Specific examples of the monomer represented by the general formula (1) include, for example, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and 1-methyl-2- (meth) acrylate. Vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, ( 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyl (meth) acrylate Loxypropyl, 2-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexane (meth) acrylate Sil, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexyl (meth) acrylate Methyl, (meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl, (meth) acrylic acid 2- (2 -Vinyloxyethoxy) ethyl, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, (Meth) acrylic acid 2- (vinyloxyisopropoxy) Propyl, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, (meth ) 2- (vinyloxyisopropoxyethoxy) ethyl acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, (meth) acryl 2- (vinyloxyethoxyisopropoxy) propyl acid, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, (meth) acrylic acid 2- (Vinyloxyethoxyethoxy) iso Propyl, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) ethyl (meth) acrylate, ( 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (Meta) a Polyethylene glycol monovinyl ether acrylic acid, and (meth) acrylic acid polypropylene glycol monovinyl ether.

  Among these, from the viewpoint of obtaining an advantageous effect that curability is better, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl (meth) acrylate 2-vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, (meth) acryl 6-vinyloxyhexyl acid, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, ( 2- (vinyloxyethoxyethoxy) ethyl methacrylate, (meth) acrylic acid Acid 2- (vinyloxy ethoxy ethoxy) ethyl are preferred.

  Among these, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate is more preferable from the viewpoint of obtaining an advantageous effect that the viscosity of the ink can be designed to be low, and 2- (2-vinyloxyacrylate) is more preferable. Roxyethoxy) ethyl is particularly preferred.

  The content of the monomer represented by the general formula (1) is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 50% by mass or less with respect to the total mass of the ink composition. . When the content of the monomer represented by the general formula (1) is within the above range, an advantageous effect of low viscosity and good curability can be obtained.

  The method for producing the monomer represented by the general formula (1) is not limited to the following, but is a method of esterifying (meth) acrylic acid and a hydroxyl group-containing vinyl ether (production method B), (meth) acrylic acid halide. And esterification of hydroxyl group-containing vinyl ethers (production method C), method of esterifying (meth) acrylic anhydride and hydroxyl group-containing vinyl ethers (production method D), (meth) acrylic acid esters and hydroxyl group-containing vinyl ethers Of transesterification with aldehydes (Production E), method of esterifying (meth) acrylic acid and halogen-containing vinyl ethers (Production F), (meth) acrylic acid alkali (earth) metal salts and halogen-containing vinyl ethers (Production method G), hydroxyl group-containing (meth) acrylic acid esters and vinyl carboxylate How to vinyl replace the door (Procedure H), hydroxyl group-containing (meth) How to ether exchange and acrylic acid esters and alkyl vinyl ethers (formula I). Among these, since the desired effect can be further exhibited in this embodiment, the production method E is preferable.

1.5. Other Monomers The ultraviolet curable ink composition according to the present embodiment may contain other monomers other than the phenoxyethyl (meth) acrylate and the monomer represented by the general formula (1). As other monomers, conventionally known monofunctional, bifunctional and trifunctional or higher polyfunctional monomers and oligomers can be used. Examples of the monomer include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, salts or esters thereof, urethane, amide and anhydride thereof, acrylonitrile, styrene, various types Unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Examples of the oligomer include oligomers formed from the above monomers such as linear acrylic oligomers, epoxy (meth) acrylate, oxetane (meth) acrylate, aliphatic urethane (meth) acrylate, and aromatic urethane (meth). Examples include acrylate and polyester (meth) acrylate.

  Moreover, an N-vinyl compound may be included as another monofunctional monomer or polyfunctional monomer. Examples of the N-vinyl compound include N-vinylformamide, N-vinylcarbazole, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, and derivatives thereof. Among these, N-vinylcaprolactam is preferably used because it is excellent in compatibility with phenoxyethyl (meth) acrylate and improves the adhesion to the medium to be discharged.

  Of the other monomers, esters of (meth) acrylic acid, that is, (meth) acrylates are preferred.

  Among the above (meth) acrylates, monofunctional (meth) acrylates include, for example, isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, iso Myristyl (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol ( (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) a Relate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, lactone-modified flexible (meth) acrylate, t -Butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. Among these, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate can be preferably used from the viewpoint that the abrasion resistance of the image can be improved. .

  Among the (meth) acrylates, examples of the bifunctional (meth) acrylate include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and tripropylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, EO (ethylene oxide) adduct of bisphenol A di (meth) acrylate, PO of bisphenol A (propylene oxide) ) Adduct di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate.

  Among the above (meth) acrylates, trifunctional or more polyfunctional (meth) acrylates include, for example, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, cowprolactone modified trimethylolpropane tri (meth) acrylate, pentaerythritol Examples include ethoxytetra (meth) acrylate and caprolactam-modified dipentaerythritol hexa (meth) acrylate.

  Among these, it is preferable that another monomer contains a monofunctional (meth) acrylate. In this case, the ink composition has a low viscosity, is excellent in solubility of the photopolymerization initiator and other additives, and is easy to obtain ejection stability during ink jet recording. Furthermore, since the toughness, heat resistance, and chemical resistance of the coating film are increased, it is more preferable to use a monofunctional (meth) acrylate and a bifunctional (meth) acrylate in combination.

  Furthermore, the monofunctional (meth) acrylate preferably has at least one skeleton selected from the group consisting of an aromatic ring skeleton, a saturated alicyclic skeleton, and an unsaturated alicyclic skeleton. When the other monomer is a monofunctional (meth) acrylate having the skeleton, the viscosity of the ink composition can be reduced.

  Examples of the monofunctional (meth) acrylate having an aromatic ring skeleton include 2-hydroxy-3-phenoxypropyl (meth) acrylate. Examples of the monofunctional (meth) acrylate having a saturated alicyclic skeleton include isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Examples of the monofunctional (meth) acrylate having an unsaturated alicyclic skeleton include dicyclopentenyloxyethyl (meth) acrylate.

  It is also preferable to contain amino (meth) acrylate. When the ink composition contains amino (meth) acrylate, the copolymerization reaction is promoted, and the curability can be further improved.

  Said other monomer may be used individually by 1 type, and may use 2 or more types together.

1.6. Photopolymerization initiator The ultraviolet curable ink composition according to the present embodiment may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it generates active species such as radicals and cations by ultraviolet irradiation and initiates the polymerization reaction of the monomer. As the photopolymerization initiator, a radical photopolymerization initiator or a cationic photopolymerization initiator can be used, but it is preferable to use a radical photopolymerization initiator.

  In addition, it is excellent in safety | security by using an ultraviolet-ray (UV) among radiation, and the cost of a light source lamp can be held down. Therefore, the photopolymerization initiator preferably has an absorption peak in the ultraviolet region.

  Examples of the photo radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and the like. Ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

  Among these, at least one selected from an acylphosphine oxide compound and a thioxanthone compound is preferable from the viewpoint of obtaining an advantageous effect of good solubility in monomers and curability, and the acylphosphine oxide compound and the thioxanthone compound are used in combination. More preferably.

  Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine. , Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl Oxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Can be mentioned.

  Examples of commercially available photo radical polymerization initiators include IRGACURE 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), IRGACURE 184 (1-hydroxy-cyclohexyl-phenyl-ketone), DAROCUR 1173. (2-hydroxy-2-methyl-1-phenyl-propan-1-one), IRGACURE 2959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one), IRGACURE 127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one), IRGACURE 907 (2-Methyl-1- (4-methylthiophenyl) -2-morph Linopropan-1-one), IRGACURE 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1), IRGACURE 379 (2- (dimethylamino) -2-[(4- Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), DAROCUR TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), IRGACURE 819 (bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide), IRGACURE 784 (bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-) Yl) -phenyl) titanium), IRGACURE OXE 0 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), IRGACURE OXE 02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), IRGACURE 754 (oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (Mixture of (2-hydroxyethoxy) ethyl ester), Lucirin TPO, LR8883, LR8970 (above, manufactured by BASF Japan), KAYACURE DETX-S (2,4-diethylthioxanthone) (manufactured by Nippon Kayaku Co., Ltd.), Ubekrill P36 (Manufactured by UCB), Speedcure TPO Nil-2,4,6-trimethylbenzoylphosphine oxide), Speedcure DETX (2,4-diethylthioxanthen-9-one) (manufactured by Lambson).

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

  The content of the photopolymerization initiator is preferably 0.5% by mass or more and 10% by mass or less with respect to the total mass of the ink composition. When the content of the photopolymerization initiator is within the above range, the ultraviolet curing rate is sufficiently high, and the photopolymerization initiator is hardly dissolved and there is almost no color derived from the photopolymerization initiator. As described above, when the photopolymerization initiator contained in the ink composition is an acyl phosphine oxide compound and / or a thioxanthone compound, the content of the acyl phosphine oxide compound is based on the total mass of the ink composition. It is preferable that it is 2 mass% or more. On the other hand, the content of the thioxanthone compound is preferably 1% by mass or more based on the total mass of the ink composition.

  Although the addition of a photopolymerization initiator can be omitted by using a photopolymerizable compound as the above-mentioned monomer, the use of a photopolymerization initiator can easily adjust the start of polymerization. Can be preferred.

1.7. Slip agent (leveling agent)
The ultraviolet curable ink composition according to the present embodiment may further contain a slip agent because an advantageous effect that the surface of the printed material becomes smooth due to the leveling action and the scratching property is improved can be obtained. The slip agent is not particularly limited. For example, as the silicone surfactant, polyester-modified silicone or polyether-modified silicone can be used, and polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane is preferably used. . Specific examples include BYK-347, BYK-348, BYK-UV3500, 3510, 3530, 3570 (manufactured by Big Chemie Japan).

1.8. Dispersant The ultraviolet curable ink composition according to the present embodiment may further contain a dispersant from the viewpoint of improving the dispersibility of the aluminum pigment. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used in preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned. Specific examples thereof include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, sulfur-containing polymers, fluorine-containing polymers, and The thing which has 1 or more types as a main component among epoxy resins is mentioned. Commercially available polymer dispersants include Ajinomoto Fine Techno Co., Ltd., Ajisper series, Solspers series (Solsperse 36000, etc.) available from Avecia, BYK Chemie, Dispersic series, Enomoto Kasei Co., Ltd. Ron series.

1.9. Other Additives The ultraviolet curable ink composition according to the present embodiment may contain additives (components) other than the additives listed above. Such a component is not particularly limited, and examples thereof include conventionally known polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), and other additives. Examples of the other additives include conventionally known fixing agents, antifungal agents, preservatives, antioxidants, chelating agents, and thickeners.

2. 2. Inkjet recording method 2.1. Recording medium The ultraviolet curable ink composition according to the present embodiment is ejected onto a recording medium by an inkjet recording method to be described later to obtain a recorded material on which an image is formed on the recording medium. . Examples of the recording medium include an absorptive or non-absorbable recording medium. The ink jet recording method using the ultraviolet curable ink composition according to the present embodiment ranges from a non-absorbable recording medium in which water-soluble ink is difficult to penetrate to an absorbent recording medium in which water-soluble ink is easily penetrated. It can be widely applied to recording media having various absorption performances.

  The absorbent recording medium is not particularly limited. For example, plain paper such as electrophotographic paper having high water-based ink permeability, inkjet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl alcohol). Art paper and coats used for general offset printing with relatively low permeability of water-based ink from (PVA) and inkjet pyrrole (PVP) and other ink-absorbing layers composed of hydrophilic polymers such as polyvinylpyrrolidone (PVP). Examples thereof include paper and cast paper.

  The non-absorbable recording medium is not particularly limited, and examples thereof include plastic films such as polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and polycarbonate (PC). Examples thereof include a plate, a metal plate such as iron, silver, copper, and aluminum, a metal plate produced by vapor deposition of these various metals, a plastic film, and a plate made of an alloy such as stainless steel or brass.

2.2. Inkjet Recording Method The ultraviolet curable ink composition according to this embodiment can be applied to an inkjet recording method. Such an ink jet recording method includes a discharge step of discharging the ink composition onto a recording medium, a curing step of curing the ink composition by irradiating the ink composition discharged in the discharge step with ultraviolet rays, including. In this way, a coating film (cured film) is formed from the ink composition cured on the recording medium.

2.2.1. Discharging Step In the discharging step, a conventionally known ink jet recording apparatus can be used. When the viscosity of the ink composition is preferably 20 mPa · s or less, more preferably 3 to 15 mPa · s, good ejection stability is realized. An ink composition having a high viscosity exceeding 20 mPa · s at 20 ° C. may be ejected by heating the head and / or the ink composition to lower the apparent viscosity.

  Since the ultraviolet curable ink composition of the present embodiment has a higher viscosity than the water-based ink composition used in ordinary ink jet recording inks, the viscosity fluctuation due to temperature fluctuation during ejection is large. Such ink viscosity fluctuation has a great influence on the change in the droplet size and the change in the droplet discharge speed, and can cause image quality deterioration. Therefore, it is preferable to keep the temperature of the ink during ejection as constant as possible.

2.2.2. Curing Step Next, in the curing step, the ink composition ejected on the recording medium is cured by ultraviolet irradiation. This is because the photopolymerization initiator contained in the ink composition is decomposed by ultraviolet irradiation to generate active species such as radicals and cations, and the monomer polymerization reaction is promoted by the function of the active species. It is. Or it is because the polymerization reaction of a photopolymerizable compound starts by ultraviolet irradiation. At this time, if a sensitizing dye is present together with the photopolymerization initiator in the ink composition, the sensitizing dye in the system absorbs actinic radiation to be in an excited state and comes into contact with the photopolymerization initiator. Degradation can be accelerated and a more sensitive curing reaction can be achieved.

  As the ultraviolet light source, a mercury lamp, a gas / solid laser, or the like is mainly used, and as a light source used for curing the ultraviolet curable ink composition, a mercury lamp or a metal halide lamp is widely known. On the other hand, there is a strong demand for mercury-free from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are small, have a long lifetime, high efficiency, and are low in cost, and are expected as light sources for ultraviolet curable ink jets. Among these, UV-LED is preferable.

  Here, it is preferable to use an ultraviolet curable ink composition that can be cured by irradiation with an irradiation energy with an emission peak wavelength of preferably 350 to 420 nm. In this case, it is preferable to use a UV-LED. Such an ink composition can be obtained by including a photopolymerization initiator that decomposes upon irradiation with ultraviolet rays in the above wavelength range and / or a monomer that initiates polymerization upon irradiation with ultraviolet rays in the above wavelength range.

3. Examples Hereinafter, embodiments of the present invention will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to only these examples.

3.1. Preparation of dispersion containing flat aluminum particles On a PET film having a film thickness of 100 μm, 3.0% by mass of cellulose acetate butyrate (butylation rate: 35 to 39%, manufactured by Kanto Chemical Co., Inc.) and diethylene glycol diethyl ether (Nippon Emulsifier) A resin layer thin film was formed on a PET film by uniformly applying a resin layer coating solution comprising 97% by mass by a bar coating method and drying at 60 ° C. for 10 minutes. Next, an aluminum vapor deposition layer having an average film thickness of 20 nm was formed on the resin layer using a vacuum vapor deposition device (“VE-1010 type vacuum vapor deposition device”, manufactured by Vacuum Device Co., Ltd.). Next, the laminate formed by the above method was put into a dispersion medium composed of phenoxyethyl acrylate and an organic solvent, and then peeled, refined, and refined using a VS-150 ultrasonic disperser (manufactured by ASONE CORPORATION). Dispersion treatment was performed at the same time to prepare an aluminum pigment dispersion having an integrated ultrasonic dispersion treatment time of 12 hours. The obtained aluminum pigment dispersion was filtered with a SUS mesh filter having an opening of 5 μm to remove coarse particles, thereby obtaining a dispersion containing flat aluminum particles. The 50% average particle diameter (R50) of the flat aluminum particles (aluminum pigment) was measured using a flow particle image analyzer (manufactured by Sysmex Corporation, model “FPIA-3000S”) at 1.9 μm. there were. Moreover, when the cross section of the flat aluminum particle (aluminum pigment) was observed with the transmission electron microscope, it was confirmed that the thickness is 20 nm. In addition, the organic solvent used for the peeling / miniaturization / dispersion treatment of the laminate was the same as that added in the preparation of the ultraviolet curable ink composition described later. In addition, in the preparation of the ultraviolet curable ink composition described later, for those to which phenoxyethyl acrylate was not added, peeling, refinement, and dispersion treatment were performed using only an organic solvent. In addition, in the preparation of the ultraviolet curable ink composition described later, for those to which no organic solvent was added, peeling / miniaturization / dispersion treatment was performed using only phenoxyethyl acrylate.

3.2. Preparation of UV curable ink composition Completely mixing organic solvent, monomer, polymerization inhibitor, leveling agent, photopolymerization initiator, and oligomer as necessary, so that the composition (mass%) shown in Table 1 is obtained. After dissolution, a flat aluminum particle dispersion was added dropwise to the mixture with stirring so as to achieve the concentrations shown in Table 1. After completion of the dropwise addition, the mixture was mixed and stirred at room temperature for 1 hour, and further filtered through a 5 μm membrane filter to obtain each ultraviolet curable ink composition.

In addition, the component used in Table 1 is as follows.
(Organic solvent)
・ Diethylene glycol diethyl ether (manufactured by Nippon Emulsifier Co., Ltd., boiling point 189 ° C)
・ Isopropyl acetate (manufactured by Daicel Chemical Industries, Ltd., boiling point 85 ° C.)
Propylene glycol monomethyl ether acetate (Daicel Chemical Industries, boiling point 146 ° C)
・ Diethylene glycol monoethyl ether (Daicel Chemical Industries, boiling point 202 ° C.)
・ Methyl acetate (Daicel Chemical Industries, Boiling point 56 ℃)
・ Butyl cellosolve (manufactured by Sankyo Chemical Co., Ltd., boiling point: 171.2 ° C)
(monomer)
・ Phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “V # 192”)
・ 2- (2-hydroxyethoxy) ethyl acrylate (made by Nippon Shokubai Co., Ltd., trade name “VEEA”)
・ Dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name “FA512AS”)
・ Dicyclopentenyl acrylate (trade name “FA511ASL” manufactured by Hitachi Chemical Co., Ltd.)
・ N-Vinylcaprolactam (trade name “N-Vinylcaprolactam” manufactured by BASF Corporation)
・ Benzyl methacrylate (Kyoeisha Chemical Co., Ltd., trade name “Light Ester BZ”)
(Other monomers and oligomers)
・ Dimethylol tricyclodecane diacrylate (manufactured by Sartomer, trade name “SR833”)
Amino acrylate (Daicel Cytec Co., Ltd., trade name “EBECRYL7100”)
・ Urethane acrylate (Daicel Cytec Co., Ltd., trade name “EBECRYL8402”)
(Photopolymerization initiator)
IRGACURE 819 (manufactured by BASF Japan, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, photopolymerization initiator)
Speedcure TPO (manufactured by Lambson, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, photopolymerization initiator)
Speedcure DETX (manufactured by Lambson, 2,4-diethylthioxanthen-9-one, photopolymerization initiator)
(Leveling agent)
-BYK-UV3500 (by Big Chemie Japan Co., Ltd., polydimethylsiloxane having a polyether-modified acrylic group)
(Polymerization inhibitor)
・ P-Methoxyphenol (Kanto Chemical Co., Ltd., trade name “MEHQ”)

3.3. Evaluation of UV-curable ink composition 3.3.1. Evaluation of Curability (1) Preparation of Evaluation Sample Using an inkjet printer PX-G5000 (manufactured by Seiko Epson Corporation), each of the nozzle arrays was filled with the above ultraviolet curable ink composition. An A4 solid pattern image with an ink dot diameter of medium dots and an ink coating film thickness of 2 μm is recorded on a recording medium at room temperature and normal pressure, and at the same time, inside an ultraviolet irradiation device mounted next to the carriage The UV-LED was irradiated with ultraviolet light having a wavelength of 395 nm to cure the A4 solid pattern image. As described above, an evaluation sample in which an A4 solid pattern image was recorded on a recording medium was produced. The recording medium includes PVC film (Mitsubishi Resin Co., Ltd., trade name “Altron # 280”, thickness 0.5 mm), PET film (Teijin DuPont Films Co., Ltd., trade name “Melinex 542”, thickness 0). 0.5 mm) and a PC film (manufactured by Asahi Glass Co., Ltd., trade name “Lexan film 8010”, thickness 0.5 mm) were used.

(2) Curability Evaluation Test As described above, the curability was evaluated by determining the irradiation energy when tack-free when performing the curing process of the solid pattern image recorded on the recording medium. The irradiation energy [mJ / cm ² ] was determined from the product of the irradiation intensity [mW / cm ² ] on the irradiated surface irradiated from the light source and the irradiation duration [s]. The measurement of the irradiation intensity was performed using an ultraviolet intensity meter “UM-10” and a light receiving unit “UM-400” (both manufactured by Konica Minolta Sensing). Whether or not it can be said to be tack-free was determined under the following conditions. That is, the determination was made based on whether the ink sticks to the cotton swab or whether the cured ink on the recording medium is scratched. The cotton swab used at that time was a Johnson swab manufactured by Johnson & Johnson. The number of rubbing was 10 reciprocations and the rubbing strength was 100 g load. Moreover, the film thickness of the ink coating film (cured film) at the time of sclerosis | hardenability evaluation was 2 micrometers. The evaluation criteria are as follows. Of the evaluation criteria, “A” and “B” are practically acceptable criteria. The evaluation results are also shown in Table 1 below.

"A": tack-free time of less than irradiation energy 1200 mJ / cm ² of the "B": tack-free irradiation energy 1200 mJ / cm ² or more 1600 mJ / cm less than ² "C" at the time: irradiation energy 1600 mJ / cm ² or more tack-free time of

  In addition, this item of evaluating curability with irradiation energy at the time of tack-free is not a test to evaluate whether or not it has been cured, but indicates a measure of good curability (rubbed with a cotton swab to the last) Whether or not it shows a predetermined state at times.) Even if it is not scratched when rubbed, it is not always completely cured, and even if it is scratched, it may be somewhat cured.

3.3.2. Evaluation of Glossiness (1) Production of Evaluation Sample Evaluation of glossiness was performed using the evaluation sample used in “3.3.1. Evaluation of Curability (2) Evaluation Test of Curability”.

(2) Evaluation test of glossiness About the image recorded on the evaluation sample, the glossiness of 60 ° was measured using a gloss meter (model “MULTI Gloss 268” manufactured by Konica Minolta Co., Ltd.). The evaluation criteria for the glossiness of the obtained image are as follows. Among the evaluation criteria, “AA”, “A” and “B” are practically acceptable criteria. The evaluation results are also shown in Table 1 below.

“AA”: Glossiness of 300 or more (clear metallic luster)
“A”: glossiness of 250 or more and less than 300 (matte metallic luster)
“B”: Glossiness of 200 or more and less than 250 (a slight metallic luster is recognized)
“C”: Glossiness less than 200 (no metallic luster)

3.3.3. Evaluation of Adhesion (1) Production of Evaluation Sample Adhesion was evaluated using the evaluation sample used in “3.3.1. Evaluation of Curability (2) Evaluation Test for Curability”.

(2) Evaluation of adhesion Each recording medium according to JIS K5600-5-6 (Coating general test method-Part 5: Mechanical properties of coating film-Section 6: Adhesion (cross-cut method)) The adhesion between the image and the image was evaluated. The classification of evaluation criteria is as follows. Of the evaluation criteria, “A” and “B” are practically acceptable criteria. The evaluation results are also shown in Table 1 below.

“A”: Small peeling of the coating film at the intersection of cuts is observed.
“B”: The coating film is peeled along the edge of the cut and / or at the intersection.
“C”: The coating film is partially or completely peeled along the edge of the cut, and / or various portions of the eyes are partially or completely peeled off.

3.3.4. Evaluation of ejection stability (1) Preparation of evaluation sample One of the nozzle rows (180 nozzles) of the head of an inkjet printer PX-G5000 (manufactured by Seiko Epson Corporation) was filled with the above-described ultraviolet curable ink composition. . Then, a test pattern image was continuously recorded for 30 minutes on a PET film at room temperature and normal pressure. The test pattern image was cured by irradiating UV light having a wavelength of 395 nm from a UV-LED in an ultraviolet irradiation device mounted on the side of the carriage.

(2) Evaluation test of ejection stability The test pattern image recorded in “3.3.4. Evaluation of ejection stability (1) Preparation of evaluation sample” was visually observed for the presence or absence of ejection failure, and the following evaluation was performed. The ejection stability was evaluated according to the standard. The “ejection failure” means that ink that should be ejected from the nozzles is not ejected due to nozzle clogging and affects the printing result. Evaluation criteria for ejection stability are as follows. Among the evaluation criteria, “AA”, “A” and “B” are practically acceptable criteria. The evaluation results are also shown in Table 1 below.

“AA”: No discharge failure nozzle is generated.
“A”: The occurrence of one or more defective nozzles is less than one and less than three.
“B”: The occurrence of ejection failure nozzles is 3 or more and less than 5.
“C”: The number of defective ejection nozzles is 5 or more.

３．４．評価結果
表１に示すように、実施例１〜実施例１１の紫外線硬化型インク組成物によれば、光沢性および密着性に優れた画像を記録することができ、インクジェット方式の記録装置で問題なく吐出することができた。また、有機溶媒によって膨潤しにくいＰＥＴフィルムを用いても、密着性に優れた良好な画像を形成できることが示された。

3.4. Evaluation Results As shown in Table 1, according to the ultraviolet curable ink compositions of Examples 1 to 11, images having excellent glossiness and adhesion can be recorded, which is a problem in an ink jet recording apparatus. It was possible to discharge without. Moreover, it was shown that a good image excellent in adhesion can be formed even when a PET film that does not easily swell with an organic solvent is used.

  On the other hand, according to the ultraviolet curable ink composition of Comparative Example 1, since it does not contain an organic solvent, the aluminum pigment contained in the ink ejected onto the recording medium is less likely to be leafed, and the metallic gloss is high. A good image could not be recorded. Further, the ultraviolet curable ink composition of Comparative Example 1 could not obtain the effect of improving the adhesion with the recording medium by the organic solvent, and recorded an image having no excellent image adhesion.

  According to the ultraviolet curable ink composition of Comparative Example 2, when the content of the organic solvent exceeds 30% by mass with respect to the total mass of the ink composition, the ink adheres to the vicinity of the ejection head and the nozzle Clogging occurred and the discharge stability was not excellent.

  According to the ultraviolet curable ink composition of Comparative Example 3, since it did not contain phenoxyethyl acrylate, an image having no excellent curability was recorded.

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

Claims (10)

An aluminum pigment,
Phenoxyethyl (meth) acrylate,
One or more organic solvents selected from the group consisting of ketones, glycols and acetates ;
Containing
An ultraviolet curable inkjet ink composition, wherein the organic solvent is contained in an amount of 2% by mass to 30% by mass with respect to the total mass of the ink composition. In claim 1,
The organic solvent has a boiling point of 80 ° C. or higher and 190 ° C. or lower, and an ultraviolet curable inkjet ink composition. In claim 1 ,
The glycol is an ultraviolet curable inkjet ink composition, wherein the glycol is at least one of butyl cellosolve and diethylene glycol diethyl ether. In claim 1 ,
The said acetates are propylene glycol monomethyl ether acetate, The ultraviolet curable inkjet ink composition. In any one of Claims 1 thru | or 4 ,
The said phenoxyethyl (meth) acrylate is an ultraviolet curable inkjet ink composition contained 5 mass% or more and 70 mass% or less with respect to the total mass of an ink composition. In any one of Claims 1 thru | or 5 ,
Furthermore, the ultraviolet curable inkjet ink composition containing the monomer shown by following General formula (1).
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CH-R 3 ... (1)
(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or 1 to 11 carbon atoms. Represents a monovalent organic residue.) In claim 6 ,
An ultraviolet curable ink jet ink composition, wherein the monomer represented by the general formula (1) is 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. In any one of Claims 1 thru | or 7 ,
Furthermore, the ultraviolet curable inkjet ink composition containing 1 type selected from dicyclopentenyl oxyethyl acrylate, dicyclopentenyl acrylate, N-vinyl caprolactam, and benzyl (meth) acrylate. In any one of Claims 1 thru | or 8 ,
The aluminum pigment is an ultraviolet curable inkjet ink composition, which is a flat particle having an average thickness of 5 nm to 30 nm and a 50% average particle diameter of 0.5 μm to 3 μm. In any one of Claims 1 thru | or 9 ,
Furthermore, an ultraviolet curable inkjet ink composition containing a photopolymerization initiator.