JP6369584B2 - Inkjet recording method - Google Patents

Description

The present invention relates to an inkjet ink composition, an ink container, and an inkjet recording method.

Conventionally, various methods have been used as a recording method for forming an image on a recording medium such as paper based on an image data signal. Among these, the ink jet system is an inexpensive apparatus, and ink is ejected only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently, and the running cost is low. Furthermore, the inkjet method is excellent as a recording method because of its low noise.

In recent years, an ultraviolet curable ink composition for ink jet recording that cures when irradiated with ultraviolet rays in an ink jet recording method in order to form an image having high water resistance, solvent resistance, scratch resistance, etc. on the surface of a recording medium. Things are being used.
In addition, among the ink compositions for ultraviolet curable ink jet recording, the ink composition containing inorganic metal-based fine particles can provide a good shielding property of the recorded matter recorded using the ink, while the inorganic composition is stored during the storage of the ink. There was a problem that the metal-based fine particles easily settled.

For example, Patent Document 1 discloses a white ink composition containing a hyperbranched polymer.
Patent Document 2 discloses cyan ink and magenta ink containing caprolactone-modified dipentaerythritol hexaacrylate.

JP 2012-17466 A JP 2009-83133 A

However, both of the inks disclosed in Patent Documents 1 and 2 are not yet sufficient in at least one of storage stability, curability, shielding properties, and sedimentation. Also, discharge stability,
There was no ink container excellent in recoverability and durability while having sufficient head durability.

Accordingly, an object of the present invention is to provide an ink composition having excellent storage stability, curability, shielding properties, and sedimentation resistance.
Another object of the present invention is to provide an ink container excellent in recoverability and durability while ensuring sufficient ejection stability and head durability.

As a result of intensive studies to solve the above problems, the inventors of the present invention can improve sedimentation resistance by setting the viscosity to a predetermined range or more in an ink (ink composition) that includes inorganic metal-based fine particles and has excellent shielding properties. Thus, when an ink was prepared using a high-viscosity polymerizable compound capable of adjusting the viscosity to obtain such a viscosity, a trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton was stable in storage. And found to be excellent in curability. Furthermore, the viscosity of the ink composition at 20 ° C. is 8 to 22 mPa · s, including the above-described polymerizable compound.
It was found that the ultraviolet curable inkjet ink composition as s can be useful as an inkjet ink composition, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton;
An ultraviolet curable inkjet ink composition comprising inorganic metal-based fine particles as a coloring material and having a viscosity at 20 ° C. of 8 to 22 mPa · s.
[2]
2. The ultraviolet curable inkjet ink composition according to claim 1, wherein the content of the trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton is 5 to 15 mass% with respect to the ink composition.
[3]
The ultraviolet curable inkjet ink composition according to the above [1] or [2], wherein the content of the inorganic metal-based fine particles is 10 to 25% by mass with respect to the ink composition.
[4]
Furthermore, said [1]-[containing the vinyl ether group containing (meth) acrylic acid ester [
[3] The ultraviolet curable inkjet ink composition according to any one of [3].
[5]
Any of [1] to [4] above, wherein the trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton includes at least one of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. An ultraviolet curable inkjet ink composition according to claim 1.
[6]
A container filled with an ultraviolet curable ink-jet ink composition is provided, and the container is made of a plastic film having an oxygen permeability of 5.0 cc · 20 μm / (m ² · day · atm) or less, and is filled in the container. An ink container, wherein the ink is the ultraviolet curable inkjet ink composition according to any one of [1] to [5].
[7]
A container filled with an ultraviolet curable inkjet ink composition is provided, the container is made of an ethylene vinyl alcohol copolymer, and the ink filled in the container is the above [1] to [
5] is an ultraviolet curable inkjet ink composition according to any one of
Ink container.
[8]
The ink container according to [6] or [7] above, wherein the amount of dissolved oxygen in the filled ultraviolet curable inkjet ink composition is 20 ppm or less.
[9]
An ink jet recording method in which the ultraviolet curable ink composition for ink jet recording according to any one of [1] to [5] is ejected from a head at 20 to 40 ° C. to perform recording on a recording medium.
[10]
When the viscosity of the ink at 20 ° C. of the ultraviolet curable inkjet recording ink composition according to any one of [1] to [5] above is 8 mPa · s or more and less than 15 mPa · s, 20 to An ink jet recording method in which recording is performed on a recording medium by discharging from a head at 30 ° C., or in the case of 15 mPa · s or more and 22 mPa · s or less at 30 to 40 ° C.
[11]
The inkjet recording method according to the above [9] or [10], wherein the ultraviolet curable inkjet recording ink composition discharged from the head has an amount of dissolved oxygen of 20 ppm or less.
[12]
A container filled with the ink composition, the container having an oxygen permeability of 5.0 cc · 20 μm /
(M ² · day · atm) The ink filled with the following plastic film and filled in the container contains inorganic metal fine particles as a coloring material, and the viscosity at 20 ° C. is 8 to 22 m.
It is an ultraviolet curable inkjet ink composition that is Pa · s.
Ink container.
[13]
A container filled with the ink composition, the container is made of an ethylene vinyl alcohol copolymer, and the ink filled in the container includes inorganic metal-based fine particles as a coloring material;
An ultraviolet curable inkjet ink composition having a viscosity at 8 ° C. of 8 to 22 mPa · s,
Ink container.

It is a disassembled perspective view which shows an example of the ink container of this invention. It is a conceptual diagram which shows an example around the head of the inkjet recording device of this invention.

Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

In this specification, “curability” refers to a property of curing in response to light. “Storage stability” refers to the property that the viscosity of an ink composition is difficult to change before and after storage. “Ejection stability” refers to the property of ejecting droplets of a stable ink composition from a nozzle without clogging the nozzle. “Shielding” refers to the difficulty of transmitting light of a recorded matter recorded using ink. “Settling resistance” refers to the difficulty of sedimentation of components in an ink composition during storage of the ink composition. In the present specification, “(meth) acrylate” means at least one of acrylate and its corresponding methacrylate, “(meth) acryl” means at least one of acrylic and its corresponding methacryl, “(Meth) acryloyl” means at least one of acrylic and methacryl corresponding thereto.

[Ultraviolet curable inkjet ink composition]
The ink composition (ink) of this embodiment is an ultraviolet curable ink composition that is cured by irradiation with ultraviolet rays. Moreover, it is an inkjet ink composition used with an inkjet recording device. Inkjet ink composition refers to ink sold for inkjet printers.

[Viscosity of ink composition at 20 ° C.]
The ink composition of the present embodiment has a viscosity at 20 ° C. of 8 to 22 mPa · s. 20 ° C
By setting the viscosity at 8 mPa · s or more, the sedimentation of inorganic metal-based fine particle components that have a relatively high specific gravity and tend to settle during the long-term storage of the ink can be prevented, and the sedimentation resistance can be improved. it can. Further, in order to increase the viscosity of the ink, the viscosity at 20 ° C. is set to 22
By setting the mPa · s or less, the storage stability of the ink can be improved by limiting the content of the high viscosity component such as a polyfunctional monomer or a polymer polymerizable compound contained in the ink. This is because these components tend to be inferior in storage stability as compared with a polymerizable monomer having a small number of functional groups (bifunctional or less). The viscosity at 20 ° C. of the ink is preferably 15 to 22 mPa · s from the viewpoint that the sedimentation resistance can be further improved. On the other hand, 8 to 15 mPa · s is preferable in that the storage stability can be further improved.

In addition, there are the following advantages in setting the viscosity of the ink to the above-mentioned range. First, when the viscosity of the ink is equal to or lower than the above range, the ink viscosity is set to the head during a discharge process described later in which the ink is discharged from the head at a discharge temperature that is a predetermined temperature range (20 to 40 ° C.) described later. It is easy to make it a viscosity that can be stably discharged. Ink having a low viscosity tends to cause deterioration of the head member and inferior durability of the head as compared with ink having a high viscosity. This is because an ink with a low viscosity will contain more of a relatively low viscosity polymerizable compound such as a monofunctional monomer, and an ink with a higher content of a relatively low viscosity polymerizable compound will have a greater
This is considered to be related to the tendency that the durability of the head deteriorates. On the other hand, the durability of the head tended to deteriorate as the ink discharge temperature increased. This is presumably because the higher the temperature, the stronger the effect of deteriorating the ink head member. By making the viscosity of the ink within the above-mentioned range, it is possible to eliminate the deterioration of the head durability caused by the ink, and in order to make the viscosity of the ink suitable for ejection from the head, the ejection temperature is set to over 40 ° C. It is not necessary to lower the viscosity, and the deterioration of the head durability due to the discharge temperature can be eliminated.

In addition, the ink having a low viscosity tended to generate more wrinkles on the cured product after the ink was cured than the ink having a high viscosity. This is because a low viscosity ink will contain more of a relatively low viscosity polymerizable compound such as a monofunctional monomer, and an ink rich in a relatively low viscosity polymerizable compound will cure wrinkles more than an ink that does not. This is thought to be related to the fact that the occurrence of Although the principle of the generation of the following hardening wrinkles is estimated as follows, the scope of the present invention is not limited by the following estimation. Curing wrinkle is the ink film, after the surface of the coating has hardened first, when the inside of the coating is cured later than the surface of the coating, It is presumed that the ink is generated due to irregular flow of the ink inside the coating film until it is cured. In addition, the ultraviolet curable ink having a low viscosity has a polymerization shrinkage rate due to curing (the difference between the volume of the ink and the volume of the ink (cured product) after curing with respect to the volume of the ink before curing having a predetermined mass). Therefore, it is estimated that the occurrence of hardening wrinkles is remarkable. Therefore, by setting the viscosity of the ink to be in the above range or more, it is possible to obtain an ink that is excellent in suppressing curing wrinkles. Furthermore, the ultraviolet curable ink containing a monofunctional (meth) acrylate, which will be described later, and in particular the vinyl ether group-containing (meth) acrylate represented by the general formula (I), has excellent curability,
There was a tendency for hard wrinkles to occur. Even in the case where the ink of this embodiment contains these components, generation of cured wrinkles can be effectively prevented by setting the viscosity within the above-described range.
The viscosity in the present specification adopts the value measured by the method performed in the examples described later. However, this does not mean that the viscosity measuring method is limited, and a conventionally known measuring method can be used. .
Among them, in the present embodiment, the viscosity of the ink can be measured using an E-type viscometer. When using an E-type viscometer, it is within the common sense that it is measured in accordance with the instruction manual of the viscometer. Therefore, the type and rotation speed of the rotor are determined according to the instruction manual. It is needless to say that the viscosity of the ink is set so that it can be measured normally. In this embodiment, the viscosity of the ink is measured according to the instruction manual. It is self-evident to set it to something that can be measured normally.

[Viscosity design method]
When the ink contains various components, the ink composition of the present embodiment only needs to satisfy the above-described viscosity as a whole of the ink composition that is a mixture of the components. Here, an example of an ink design method for setting the viscosity of the ink in a desired range so that the ink composition has such a viscosity will be described.

The mixed viscosity of the entire polymerizable compound contained in the ink is the viscosity of each polymerizable compound used,
It can be estimated from the mass ratio of each polymerizable compound to the ink composition.

It is assumed that the ink contains N kinds of polymerizable compounds A, B,. The viscosity of the polymerizable compound A is VA, and the mass ratio of the polymerizable compound A to the total amount of the polymerizable compound in the ink is MA. The viscosity of the polymerizable compound B is VB, and the mass ratio of the polymerizable compound B to the total amount of the polymerizable compound in the ink is MB. Similarly, the viscosity of the Nth polymerizable compound N is VN, and the mass ratio of the polymerizable compound N to the total amount of the polymerizable compound in the ink is MN. If it shows in confirmation, numerical formula "MA + MB + ... (middle omission) ... + MN = 1" is formed. Further, the mixed viscosity of the entire polymerizable compound contained in the ink is defined as VX. Then, it is assumed that the following formula (1) is satisfied.

MA × LogVA + MB × LogVB + (omitted on the way)… + MN × LogVN = Lo
gVX (1)

For example, when two kinds of polymerizable compounds are contained in the ink, the mass ratio of the polymerizable compounds after MB is set to zero. The number of types of polymerizable compounds can be any number of one or more.

Next, an example of a procedure (steps 1 to 7) for setting the ink viscosity to a desired range will be described.

First, information on the viscosity at a predetermined temperature of each polymerizable compound to be used is obtained (Step 1).
). Examples of the obtaining method include obtaining from a manufacturer catalog or measuring the viscosity of each polymerizable compound at a predetermined temperature. Since the viscosity of a single polymerizable compound may vary depending on the manufacturer even if it is the same polymerizable compound, it is preferable to employ viscosity information from the manufacturer of the polymerizable compound to be used.
Subsequently, the target viscosity is set in VX, and the composition ratio (mass ratio) of each polymerizable compound is determined based on the above formula (1) so that VX becomes the target viscosity (step 2). The target viscosity is the viscosity of the ink composition to be finally obtained, and is set to a certain viscosity within the range of 8 to 22 mPa · s. The predetermined temperature is 20 ° C.

Subsequently, the polymerizable compound is actually mixed to prepare a composition of the polymerizable compound (hereinafter referred to as “polymerizable composition”), and the viscosity at a predetermined temperature is measured (step 3).
Subsequently, when the viscosity of the polymerizable composition is approximately close to the above target viscosity (in Step 4, “
It is sufficient that the target viscosity is ± 5 mPa · s. ), The polymerizable composition, and a component other than the polymerizable compound such as a photopolymerization initiator and a pigment (hereinafter referred to as “component other than the polymerizable compound”);
Is prepared, and the viscosity of the ink composition is measured (step 4). In Step 4, when there is a component other than the polymerizable compound that is mixed with the ink composition in the form of a pigment dispersion such as a pigment, for example, the polymerizable compound previously contained in the pigment dispersion is also used. Since the ink composition is brought into the ink composition, the ink composition has a mass ratio obtained by subtracting the mass ratio of the polymerizable compound carried into the ink composition as a pigment dispersion from the composition ratio of each polymerizable compound determined in Step 2. It is necessary to adjust the composition.

Subsequently, the difference between the measured viscosity of the ink composition and the measured viscosity of the polymerizable composition is calculated,
This is set as VY (step 5). Here, normally, “VY> 0”. VY depends on the content conditions such as the type and content of components other than the polymerizable compound, but in the examples described later, VY
= 3 to 5 mPa · s.

Subsequently, “target viscosity of step 2−VY” is defined for VX, and VX
The composition ratio of each polymerizable compound is determined again so that becomes the “target viscosity of step 2—VY” defined above (step 6).

Subsequently, each polymerizable compound having a composition ratio determined in Step 6 and components other than the polymerizable compound are mixed to prepare an ink composition, and the viscosity at a predetermined temperature is measured (Step 7). If the measured viscosity is the target viscosity, the ink composition adjusted in Step 7 is obtained as an ink composition having the target viscosity.

On the other hand, in step 3, the measured viscosity of the prepared polymerizable compound composition is “target viscosity ±
If it is not within the range of “5 mPa · s”, the following fine adjustment is performed, and the process is repeated from step 3. First, when the measured viscosity is too high, the content of the polymerizable compound having a viscosity as a simple substance higher than the target viscosity is reduced, and the content of the polymerizable compound having a viscosity as a simple substance lower than the target viscosity is increased. Make fine adjustments. On the other hand, when the measured viscosity is too low, the content of the polymerizable compound whose viscosity as a simple substance is lower than the target viscosity is reduced, and the content of the polymerizable compound whose viscosity as a simple substance is higher than the target viscosity is increased. Make fine adjustments. Also,
If the measured viscosity of the prepared ink composition does not reach the target viscosity in step 7, the same adjustment as the above fine adjustment is performed, and the process is repeated from step 7.

[Ink container]
Another embodiment of the present invention relates to an ink container that contains a predetermined ultraviolet curable ink composition for inkjet recording. The ink container is used for storage and transportation of the ink composition before the ink composition is used in the ink jet recording apparatus. To supply. Details of the ink container will be described later.

Hereinafter, additives (components) that are or may be included in the ink composition of the present embodiment.
Will be explained.

(Polymerizable compound)
The polymerizable compound contained in the ink composition can be polymerized at the time of light irradiation alone or by the action of a photopolymerization initiator described later to cure the printed ink.

(Trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton)
The ink composition contains a trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton as the polymerizable compound. The (meth) acrylate has one or more pentaerythritol skeletons (skeleton part of pentaerythritol: C (CH ₂ —O—) ₄ residue) in the molecule, and (meth) as a polymerizable functional group It is a compound having 3 or 4 acrylate groups in the molecule. The compound is advantageous in that it has a high viscosity and makes the ink in a predetermined range, and is excellent in ink curability and storage stability. The (meth) acrylate is not limited to the following, but pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra ( Examples thereof include (meth) acrylate, propylene oxide-modified pentaerythritol tri (meth) acrylate, propylene oxide-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, and caprolactone-modified pentaerythritol tetra (meth) acrylate. Further, it may be a compound having a pentaerythritol skeleton composed of a plurality of pentaerythritol residues.
Dipentaerythritol and tripentaerythritol tri (meth) acrylate, tetra (meth) acrylate, ethylene oxide modified tri (meth) acrylate, ethylene oxide modified tetra (meth) acrylate, propylene oxide modified tri (meth) acrylate, propylene oxide Examples thereof include modified tetra (meth) acrylate, caprolactone-modified tri (meth) acrylate, and caprolactone-modified tetra (meth) acrylate.
Since the (meth) acrylate has a high viscosity, it can impart sedimentation to the ink. Pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate are preferred, and pentaerythritol tri (meth) acrylate is more preferred from the viewpoint of curability, storage stability, and ease of adjusting the viscosity of the ink composition. The (meth) acrylate may be used alone or in combination of two or more. The content of the (meth) acrylate is preferably 3 to 18% by mass with respect to the total mass of the ink composition (100% by mass to 5 to 15%).
The mass% is more preferable. Within the above range, it is possible to further improve the viscosity adjustment, storage stability and curability.

(Other polymerizable compounds)
The ink composition of this embodiment may contain other polymerizable compounds other than trifunctional or tetrafunctional (meth) acrylates having a pentaerythritol skeleton. Among other polymerizable compounds, polymerizable compounds other than the following vinyl ether group-containing (meth) acrylic acid esters will be described later.
(Vinyl ether group-containing (meth) acrylic acid esters)
The ink composition may contain vinyl ether group-containing (meth) acrylic acid esters represented by the following general formula (I) as other polymerizable compounds.
_{^{CH 2 = CR 1 -COOR 2 -O}} -CH = CH-R 3 ··· (I)
Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a divalent organic residue having 2 to 20 carbon atoms, and R ³ is a hydrogen atom or a monovalent organic residue having 1 to 11 carbon atoms. Group.)

When the ink composition contains the vinyl ether group-containing (meth) acrylic acid esters, the ink curability can be improved, and the viscosity of the ink can be lowered. In addition, it is better to use a compound having both a vinyl ether group and a (meth) acryl group in one molecule than to use a compound having a vinyl ether group and a compound having a (meth) acryl group separately. It is preferable for improving curability.

In the above general formula (I), the divalent organic residue having 2 to 20 carbon atoms represented by R ² is a linear, branched or cyclic substituted having 2 to 20 carbon atoms. May be an alkylene group, an optionally substituted alkylene group having an oxygen atom by an ether bond and / or an ester bond in the structure, and an optionally substituted divalent alkylene group having 6 to 11 carbon atoms. Aromatic groups are preferred. Among these, ethylene group, n-propylene group, isopropylene group,
And an alkylene group having 2 to 6 carbon atoms such as a butylene group, an oxyethylene group, an oxy n-propylene group, an oxyisopropylene group, and an oxybutylene group having an oxygen atom due to an ether bond in the structure of 2 to 9 carbon atoms Are preferably used.

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

When each of the above organic residues is an optionally substituted group, the substituent is divided into a group containing a carbon atom and a group not containing a carbon atom. First, when the substituent is a group containing a carbon atom, the carbon atom is counted in the carbon number of the organic residue. As a group containing a carbon atom,
Although not limited to the following, for example, a carboxyl group and an alkoxy group can be mentioned. Next, examples of the group not containing a carbon atom include, but are not limited to, a hydroxyl group and a halo group.

Examples of the vinyl ether group-containing (meth) acrylic acid esters include, but are not limited to, for example, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and 1-methyl (meth) acrylate. 2-vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethyl (meth) acrylate Propyl, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl- (meth) acrylate 2-vinyloxypropyl, (meth) acrylic acid 2-
Vinyloxybutyl, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, (Meth) acrylic acid 2-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenyl Methyl, (meth) acrylic acid 2- (vinyloxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) ethyl,
(Meth) acrylic acid 2- (vinyloxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) propyl, (meth) acrylic acid 2- (Vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (
Vinyloxyethoxyisopropoxy) ethyl, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyl) (meth) acrylate Roxyethoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) propyl, (meth) acrylic acid 2-
(Vinyloxyisopropoxyisopropoxy) propyl, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyl) (meth) acrylate Loxyisopropoxyethoxy) isopropyl, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) (meth) acrylate
Ethyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, (Meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid polyethylene glycol monovinyl ether, and (meth) acrylic Examples include acid polypropylene glycol monovinyl ether.

Among these, since the viscosity of the ink can be further lowered, the flash point is high, and the curability of the ink is excellent, 2- (vinyloxyethoxy) ethyl (meth) acrylate, that is, 2- (vinyloxy) acrylate At least one of ethoxy) ethyl and 2- (vinyloxyethoxy) ethyl methacrylate is preferable, and 2- (vinyloxyethoxy) ethyl acrylate is more preferable. Especially 2- (vinyloxyethoxy) ethyl acrylate and 2-methacrylic acid 2-
Since (vinyloxyethoxy) ethyl has a simple structure and a low molecular weight, the viscosity of the ink can be significantly reduced. (Meth) acrylic acid 2- (vinyloxyethoxy)
Examples of ethyl include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate and 2- (1-vinyloxyethoxy) ethyl (meth) acrylate, and 2- (vinyloxyethoxy) ethyl acrylate Include 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (1-vinyloxyethoxy) ethyl acrylate. Acrylic acid 2
-(Vinyloxyethoxy) ethyl is superior in terms of curability compared to 2- (vinyloxyethoxy) ethyl methacrylate.

The vinyl ether group-containing (meth) acrylic acid esters may be used alone or in combination.
You may use combining more than a seed.

The above-mentioned vinyl ether group-containing (meth) acrylic acid esters, particularly (meth) acrylic acid 2
The content of-(vinyloxyethoxy) ethyl is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and 30 to 50% by mass with respect to the total mass (100% by mass) of the ink composition. Further preferred. When the content is within the above range, the ink curability and storage stability can be further improved.

The method for producing the vinyl ether group-containing (meth) acrylic acid esters 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 (meth) acrylic anhydride and hydroxyl group-containing vinyl ether (production method D), esterification of (meth) acrylic acid ester and hydroxyl group-containing vinyl ether Method of exchange (Production method E), Method of esterifying (meth) acrylic acid and halogen-containing vinyl ether (Method of production F), Method of esterifying alkali (earth) metal salt of (meth) acrylic acid and halogen-containing vinyl ether (Production G), hydroxyl group-containing (meth) acrylic acid ester and carboxylic acid vinyl ester How to vinyl exchange and Le (Procedure H), hydroxyl group-containing (meth) How to ether exchange and acrylic acid ester and an alkyl vinyl ether (Process I)
Is mentioned.

Among these, since the desired effect can be further exhibited in this embodiment, the production method E is preferable.

(Polymerizable compounds other than the above)
Among the other polymerizable compounds, the other polymerizable compounds include conventionally known monofunctional,
Various monomers and oligomers such as bifunctional and trifunctional or more polyfunctional 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). Acrylate and polyester (meth) acrylate are mentioned.

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 other polymerizable compounds, an ester of (meth) acrylic acid, that is, (meth) acrylate is preferable.

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, phenoxyethyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, lactone-modifiable Examples include flexible (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. Among these, phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are preferable.

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 dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane Diol 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)
Examples include adduct di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. Among these, dipropylene glycol di (meth) acrylate is preferable.

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

Among these, other polymerizable compounds preferably include monofunctional (meth) acrylates. In this case, the solubility of the photopolymerization initiator and other additives is excellent, and the ejection stability during ink jet recording is easily obtained. 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, and among them, phenoxyethyl (meth) acrylate and dipropylene glycol. It is more preferable to use di (meth) acrylate in combination.

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

The content of the other polymerizable compound is preferably 5 to 85% by mass and more preferably 15 to 80% by mass with respect to the total mass (100% by mass) of the ink composition. When the content is within the above range, the viscosity and odor can be reduced, and the solubility and reactivity of the photopolymerization initiator can be improved.
Among the above other polymerizable compounds, the content of monofunctional (meth) acrylate (including the above-mentioned vinyl ether group-containing (meth) acrylate and monofunctional (meth) acrylate including ink) is also included. , 40 to 8 with respect to the total mass (100% by mass) of the ink composition
0 mass% is preferable and 50-70 mass% is more preferable.
Further, the content of the monofunctional (meth) acrylate other than the above-mentioned vinyl ether group-containing (meth) acrylate is preferably 10 to 50% by mass, and preferably 20 to 40% by mass with respect to the total mass (100% by mass) of the ink composition. % Is more preferable. By containing these inks having a relatively low viscosity, the viscosity of the ink when used in combination with a tri- or tetrafunctional (meth) acrylate having a relatively high viscosity pentaerythritol skeleton is easily obtained, and the ink is cured. Properties, solubility of components such as a photopolymerization initiator, storage stability and the like can be further improved.
When the ink contains a bifunctional or higher functional (meth) acrylate other than a tri- or tetrafunctional (meth) acrylate having a pentaerythritol skeleton, the content thereof is 2 with respect to the total mass (100% by mass) of the ink composition. -20 mass% is preferable and 5-15 mass% is more preferable.

(Polymerization inhibitor)
The ink composition includes a hindered amine compound as a polymerization inhibitor, p-methoxyphenol, hydroquinone monomethyl ether (MEHQ), hydroquinone, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-butylphenol), and 4,4′-thiobis (3-methyl-6-tert-butylphenol) ) May be included.

A polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the other polymerization inhibitor is not particularly limited, but for example 0.01 to 0 in the ink composition.
. What is necessary is just 5 mass%.

(Photopolymerization initiator)
The ink composition may further contain a photopolymerization initiator. The photopolymerization initiator is used to form a print by curing the ink present on the surface of the recording medium by photopolymerization by ultraviolet irradiation. By using ultraviolet rays (UV) among the radiation, the safety is excellent and the cost of the light source lamp can be suppressed. By the energy of light (ultraviolet rays),
There is no limitation as long as it generates active species such as radicals and cations and initiates the polymerization of the polymerizable compound, but a photoradical polymerization initiator or a photocationic polymerization initiator can be used. It is preferable to use a polymerization initiator.

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.), α-aminoalkyls, and the like. Examples include phenone compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

Among these, since the ink curability can be further improved, a thioxanthone compound is preferable, and a combination of an acylphosphine oxide compound and a thioxanthone compound is more preferable.

Specific examples of photo radical polymerization initiators 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, diethylthio Xanthone, 2-isopropylthioxanthone, 2-
Chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6 -Trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

Among these, diethylthioxanthone is preferable because ultraviolet light (UV light) in a wide range can be efficiently converted into active species.

Examples of commercially available radical photopolymerization 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 2
959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-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-morpholinopropan-1-one), IRGACURE 3
69 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1), IRGACURE 379 (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), DA
ROCUR 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 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), I
RGAURE OXE 02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), IRG
ACURE 754 (mixture of oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester) (above, manufactured by BASF), Speedcure TPO , Speed
dcure DETX (2,4-diethylthioxanthone), Speedcure IT
X (2-isopropylthioxanthone) (above, manufactured by Lambson), KAYACUR
E DETX-S (2,4-diethylthioxanthone) (Nippon Kayaku Co
, Ltd.), Lucirin TPO, LR8883, LR8970 (above, BAS
F) and Ubekrill P36 (UCB).

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

5-20 mass% is preferable with respect to the total mass (100 mass%) of an ink composition, and, as for content of a photoinitiator, 8-15 mass% is more preferable. When the content is within this range, the ultraviolet curing rate can be sufficiently exerted, and the undissolved portion of the photopolymerization initiator and coloring derived from the photopolymerization initiator can be avoided.

In particular, when the photopolymerization initiator contained in the ink composition is an acyl phosphine oxide compound, it is preferable because the ink curability can be further improved. When the acylphosphine oxide compound is included, the content thereof is preferably 7 to 15% by mass and more preferably 8 to 12% by mass with respect to the total mass (100% by mass) of the ink composition.

In addition, it is possible to omit the addition of a photopolymerization initiator by using a photopolymerizable compound as the polymerizable compound described above, but it is easier to start polymerization by using a photopolymerization initiator. It can be adjusted and is preferred.

[Color material]
The ink composition contains inorganic metal-based fine particles as a color material. As inorganic metal-based fine particles,
Examples thereof include metal compound fine particles such as metal oxides, metal carbonates and metal sulfates, and metal fine particles such as metals and alloys. Since the ink contains inorganic metal fine particles, it is possible to increase the shielding property of the recorded matter recorded on the recording medium. For example, a pattern is formed on the transparent recording medium using the ink composition of the present embodiment. Even in this case, it is possible to increase the shielding property of the recorded matter by forming a pattern having excellent shielding property. When the ink contains metal compound fine particles as inorganic metal fine particles, the ink can be a white ink, and when the ink contains metal fine particles as inorganic metal fine particles, the ink can be a metallic ink, and the recording medium These color patterns can be formed. In particular, when the ink is a white ink containing metal compound fine particles as inorganic metal-based fine particles, a white pattern is formed on the recording medium, and a color pattern with color ink is formed on the pattern, thereby providing a highly saturated color image. It can be recorded.
Examples of the metal compound fine particles include metal oxides such as titanium oxide, silicon oxide, aluminum oxide, magnesium oxide, and zinc oxide, and fine particles such as calcium carbonate and barium sulfate. Examples of the metal fine particles include fine particles such as aluminum, silver, gold, titanium, and alloys thereof. When metal fine particles are used, metal fine particles obtained by surface-treating the surfaces of fine particles having the following predetermined average particle diameter obtained by pulverization or the like with a silicon compound or the like are preferable.
The average particle size of the inorganic metal-based fine particles is preferably 150 to 350 nm, more preferably 180 to 280 nm, and even more preferably 200 to 250 in terms of shielding properties and sedimentation resistance. Here, the average particle diameter in the present specification is measured by a dynamic light scattering method and is a volume average particle diameter.
The content of the inorganic metal-based fine particles is preferably 2 to 25% by mass, more preferably 5 to 23% by mass, and still more preferably 8 to 20% by mass in the ink composition in terms of shielding properties and sedimentation resistance. When the ink contains inorganic metal-based fine particles, the shielding property of the recorded matter can be improved, but the density of the inorganic metal-based fine particles tends to be high, so that the ink has a tendency to deteriorate the sedimentation resistance. Is particularly useful.
The ink composition of the present embodiment may further contain other coloring materials such as pigments and dyes in addition to the inorganic metal fine particles.

[Dispersant]
In order to improve the dispersibility of the inorganic metal fine particles in the ink composition, a dispersant may be further included. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used for preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned. Specific examples include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, sulfur-containing polymers, fluorine-containing polymers, and epoxies. The thing which has 1 or more types of resin as a main component is mentioned. Commercially available polymer dispersants include Ajinomoto Fine Techno Co., Ajisper series, Avecia and Noveon (No.
Solspers series (Solsperse 36000, etc.) available from Veon), Disperbic series manufactured by BYKChemie, and Disparon series manufactured by Enomoto Kasei.

[Other additives]
The ink composition may contain additives (components) other than the additives listed above. Such a component is not particularly limited. For example, a conventionally known slip agent (surfactant),
There may be polymerization accelerators, penetration enhancers, and wetting agents (humectants), as well as other additives. Examples of the other additives include conventionally known fixing agents, antifungal agents, preservatives, antioxidants,
An ultraviolet absorber, a chelating agent, a pH adjuster, and a thickener are mentioned.

[Dissolved oxygen content of the UV curable inkjet ink composition]
The ink composition accommodated in the ink container that is one embodiment of the present embodiment preferably has a dissolved oxygen content of 20 ppm or less. By performing treatment such as deaeration so that the amount of dissolved oxygen is 20 ppm or less, an ink composition having excellent ejection stability and curability can be obtained. Thereby, the ink composition can be suitably used for an ink jet recording apparatus.
In addition, when used in an ink jet recording apparatus, the amount of dissolved oxygen may increase because air dissolves in the ink as it passes through the ink flow path. However, if the dissolved oxygen content of the ink composition in the ink container is 20 ppm or less, when the ink is filled from the ink container into the ink jet recording apparatus and recording is performed, the ejection stability and curability are excellent. It is easy to make an ink composition.

Moreover, since the dissolved oxygen amount can further improve curability and storage stability, 1 to 20 p.
pm is more preferable, 3 to 20 ppm is more preferable, and 5 to 15 ppm is particularly preferable.

Here, the “dissolved oxygen amount” in the present specification may be at least within the above predetermined range when the ink composition is filled in the ink jet recording apparatus. More specifically, during a period in which the amount of dissolved oxygen needs to be within the predetermined range, after the ink container is shipped, the ink container or the ink composition in the container is attached to the recording apparatus, filled, or Until just before being used. Further, in the case of a recording apparatus provided with a deaeration mechanism, the amount of dissolved oxygen can be reduced in the recording apparatus. However, even in this case, there is a limit to the deaeration capability, so the amount of dissolved oxygen in the ink container is preferably within the above range. On the other hand, in the case of a recording device in which there is no (almost) change in the amount of dissolved oxygen in the recording device, even if the recording device is not equipped with a deaeration mechanism,
At least the dissolved oxygen amount of the ink in the ink container may be within the above range.
In addition, although the dissolved oxygen amount in this specification can be measured by a conventionally well-known method, the value obtained by the measuring method implemented in the below-mentioned Example shall be employ | adopted for convenience.

Here, when treatment such as deaeration is not performed for the purpose of reducing the amount of dissolved oxygen, the amount of dissolved oxygen in the ink composition is usually about 50 to 60 ppm. Therefore, a treatment such as deaeration is required to make the dissolved oxygen amount 20 ppm or less. Examples of the treatment include, but are not limited to, a degassing mechanism and inert gas bubbling.

[Configuration of ink container]
The shape of the ink container that is one embodiment of the present embodiment is not limited to the following,
For example, a pack, a bottle, a tank, a bottle, and a can are mentioned. Among these, a container (pack) using a flexible film is used as a container filled with ink of the ink container (a member that is filled with ink and substantially holds ink in the ink container). The ink container has a light weight, the container is easy to put in a box-shaped ink container, the volume of the container easily changes following the remaining amount of ink, and the film is heat-sealed (heat sealed) to form a bag It is preferable in that it can be processed into a shape and used.

In addition, as a usage mode of the ink container of the present embodiment, (A) separate from the recording apparatus,
A form of an ink cartridge or the like that is attached to the recording apparatus and sequentially supplies ink to the recording apparatus; and (B) a form that is separate from the recording apparatus and that transfers only ink from the ink container to the recording apparatus when ink is used. (C) at least a form of a tank or the like that is provided in the recording apparatus in advance and contains ink.

The above (A) and (B) can be said to be ink containers from when the ink containers are shipped to just before the ink is supplied (transferred) to the recording apparatus. The above (C) can be said to be an ink container from when the recording apparatus is shipped to before the first use of ink in the recording apparatus is started.
Note that the above (A) and (C) can be referred to as an ink container that performs printing on the recording apparatus in a state where ink is supplied from the ink container to the recording apparatus via a connecting portion such as an ink tube. it can. The above (B) can be said to be an ink container that performs printing with the recording apparatus after ink is transferred from the ink container to the recording apparatus. In addition, as the target to which the ink is transferred in (B), a tank or the like provided in the recording apparatus can be cited.

The constituent material of the container filled with the ink is not limited to the following, but examples thereof include polyethylene terephthalate (PET), polypropylene, polyethylene, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer (EVOH), polystyrene, and the like. These films may be used. The above may be blended at an appropriate ratio, or a plurality of the above may be stacked. In the case of a film, it may be obtained by laminating.

The ink container may be stirred during storage and transportation in order to recover sedimentation of the ink composition to be stored. This is because, when the ink component has settled for a long time, the precipitate may become a cake and recovery may be difficult. Further, when ink is supplied from the ink container to the recording apparatus, it is preferable that the ink container is stirred to recover sedimentation.

When a container (pack) using a flexible film is used, durability that does not cause cracking or tearing is particularly required with the stirring operation. Preferred examples of such a durable film material include plastic films such as polyethylene terephthalate (PET), polypropylene, polyethylene, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, polystyrene, and ethylene vinyl acetate copolymer. A polymer is more preferred.
Preferred examples of the film include stretched plastic films such as high density, low density, or linear low density polyethylene, polypropylene, ethylene-vinyl alcohol copolymer, and polystyrene. It is good also as a laminated | multilayer film which bonded together the film of multiple layers.

Further, among the constituent materials of the container, the oxygen permeability (hereinafter simply referred to as “oxygen permeability”) of the member including the ink is preferably 5.0 cc · 20 μm / (m ² · day · atm) or less. 2.0 cc · 20 μm / (m ² · day · atm) or less. When the oxygen permeability is within the above range, the dissolved oxygen amount of the ink composition being stored is hardly changed. When the member is a film and the oxygen permeability of the plastic film (the plastic film itself) is in the above range, the film can be composed of only the plastic film, or a film in which a gas barrier layer is laminated on the plastic film. By so doing, oxygen permeability may be ensured.
As the gas barrier layer, a metal layer such as an aluminum layer, an inorganic gas barrier layer such as an inorganic oxide layer such as a silicon oxide layer or an aluminum oxide layer may be used, and ethylene vinyl alcohol having a low oxygen permeability in a plastic film may be used. A polymer, polyvinyl alcohol, or the like may be laminated on another plastic film as a gas barrier layer to form a film. The total film thickness is preferably 50 μm or more, preferably 70 μm or more, and 70 to
200 μm is more preferable. When the film thickness is above, the dissolved oxygen content of the ink composition being stored is unlikely to change, and the strength and flexibility of the pack can be obtained. Among these, oxygen permeability is low and strength (
A film made of an ethylene vinyl alcohol copolymer is preferred from the viewpoint of excellent durability.

As described above, when the oxygen permeability of the plastic film (plastic film itself) is within the above-described oxygen permeability range, it is preferable that the dissolved oxygen amount of the ink during storage hardly changes depending on the film constituted by the plastic film. Moreover, it is preferable at the point which the durability of an ink pack is excellent compared with the film which provided the inorganic gas barrier layer. In addition, it is good also as a film which further provided the inorganic gas barrier layer for the purpose of improving the light-shielding property of an ink pack. Such a plastic film is not particularly limited as long as it satisfies the above oxygen permeability, but among them, a film made of an ethylene vinyl alcohol copolymer is more excellent in oxygen permeability and durability and depends on the ink components. This is preferable in that it is less susceptible to erosion.

The oxygen permeability in this specification is expressed in units of cc · 20 μm / (m ² · day · at.
m), and the “atm” is a pressure (atm) under the conditions of 23 ° C. and a humidity of 65%.
In addition, the oxygen permeability was determined by the method defined in ISO 14663-2: 1999 (Annex C), that is, the oxygen permeation rate permeating the film using a coulometric sensor (relative humidity reached an equilibrium state). Sometimes it can be calculated by measuring.

The capacity of the ink composition that can be accommodated in the ink container is not limited to the following, but is 100-2.
, 1,000 mL is preferable, 100-1,000 mL is more preferable, 200-800 mL
Is more preferable. When the capacity is within the above range, all of the curability, storage stability, and ejection stability can be further improved.
When the capacity is within the above range, the ink composition can be used up or stored while the amount of dissolved oxygen in the ink container hardly changes after the start of use of the ink container. There are advantageous effects such as the amount of dissolved oxygen of the ink composition hardly changing. Further, it is particularly preferable that the ink container has the oxygen permeability of the member of the ink container and the capacity of the ink composition that can be stored is in the above range. In addition, “capacity” in this specification
Means volume.

Here, an ink cartridge which is an example of the ink container of the present embodiment will be described. FIG. 1 is an exploded perspective view showing the ink cartridge 40.
The ink cartridge 40 includes an ink pack 70 that is filled with ink, a main body case 76 that houses and protects the ink pack, and a cartridge case 72 that includes a lid portion 78. The ink pack includes an ink supply port 74. The case has a flange 84, a notch 80,
A holding part 82 is provided. The material of the ink pack can be the above.

As described above, according to this embodiment, the ultraviolet curable inkjet ink is excellent in durability and sedimentation resistance, and further excellent in storage stability, curability, and ejection stability of the ink composition to be contained. An ink container containing the composition can be provided.

[Inkjet recording method]
One embodiment of the present invention relates to an ink jet recording method using the ultraviolet curable ink jet ink composition of the above embodiment.

The inkjet recording method includes a discharge step of discharging the ink composition onto a recording medium, and 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 by the ink composition cured on the recording medium.

[Inkjet recording apparatus]
One embodiment of the present invention relates to an inkjet recording apparatus, that is, an inkjet printer. The recording apparatus can use the inkjet recording method of the above embodiment.
A recording apparatus (printer) for carrying out the recording method will be described in detail.

The printer according to the present embodiment can record various colors of ink on a recording medium (form an image). For example, the printer uses four color inks of CMYK (cyan, magenta, yellow, and black). Or forming a background image that imparts excellent concealability to the recording medium using white ink.

Line printers and serial printers can be cited as the types of printers in this embodiment, and any of them can be used. These are different printer systems. A line printer, which is a line-type inkjet recording apparatus, has a head having a nozzle row having a length corresponding to (approximately) the width of a recording medium and the recording medium relative to the scanning direction intersecting the width direction. Ink is ejected onto the recording medium while moving the position, and the head is fixed without moving (substantially) and recording is performed in one pass (single pass).
On the other hand, a serial printer, which is a serial inkjet recording apparatus, normally performs recording in two or more passes (multi-pass) while the head reciprocates (shuttle moves) in a direction perpendicular to the recording medium conveyance direction. It is. In addition, the above-mentioned pass is “main scanning” described later.
In other words.

Hereinafter, the printer of this embodiment will be described in more detail with reference to FIG. The scope of the present invention is not limited to the following drawings. Moreover, in each drawing used for the following description, the scale of each member is appropriately changed in order to make each member a recognizable size. FIG. 2 is a schematic view around the head of a serial printer as an example of the recording apparatus of the present embodiment.

In the carriage unit 100, the head 85 is ejected onto the recording medium stationary in the recording area while ejecting ink while intersecting the transport direction (sub-scanning direction) (hereinafter referred to as "moving direction" or "main scanning"). It is a moving mechanism that moves, ie, scans in a direction. The carriage unit 100 includes a carriage 81 and a carriage motor (not shown). Also,
The carriage 81 detachably holds an ink cartridge (not shown) that stores ultraviolet curable ink. The carriage 81 is reciprocated along the guide shaft 83 by a carriage motor while being supported by a guide shaft 83 that intersects with a conveyance direction to be described later.

The head 85 is for discharging ultraviolet curable ink to a recording medium,
It has a plurality of nozzles. Since the head 85 is provided on the carriage 81, when the carriage 81 moves in the movement direction, the head 85 also moves in the movement direction. Then, by intermittently ejecting the ultraviolet curable ink while the head 85 is moving in the moving direction, a dot row along the moving direction is formed on the recording medium.
In the movement of the head 85, the ultraviolet curable ink is discharged while moving from one end side to the other end side in FIG. 2, but during the movement from the other end side to the one end side, the ultraviolet curable type ink is discharged. Ink is not ejected.

The irradiation unit 90 cures the ultraviolet curable ink by irradiating the ultraviolet curable ink attached (landed) on the recording medium with ultraviolet rays. The dots formed on the recording medium are cured by being irradiated with ultraviolet rays from the irradiation unit 90 to form a cured product. The irradiation unit 90 includes first irradiation units 92 a and 92 b and a second irradiation unit 93 on the downstream side in the transport direction of the head 85.

The first irradiation units 92a and 92b irradiate ultraviolet rays for curing the dots formed on the recording medium. The first irradiation units 92a and 92b are disposed in front of the second irradiation unit 93 where the curing is performed, that is, upstream in the transport direction. To position.

More specifically, the first irradiating units 92a and 92b irradiate ultraviolet rays for temporarily curing the dots formed on the recording medium, whereas the second irradiating unit 93 is temporarily cured. Irradiation with ultraviolet rays for main curing of the dots is performed.

In this specification, “temporary curing” means temporary pinning of ink, and more specifically, curing before the main curing in order to prevent bleeding between dots and control the dot diameter. means. Generally, the polymerization degree of the polymerizable compound in the temporary curing is lower than the polymerization degree of the polymerizable compound by the main curing performed after the temporary curing. Further, “main curing” refers to curing the dots formed on the recording medium to a curing state necessary for using the recorded material.

The second irradiating unit 93 irradiates the ultraviolet rays for completely (ie, substantially) curing the dots formed on the recording medium. The second irradiation unit 93 is provided downstream of the head 85 in the transport direction, and irradiates the dots formed by the head 85 with ultraviolet rays.

It should be noted that ultraviolet light is irradiated from at least one of the first irradiation units 92a and 92b and the second irradiation unit 93 so that the ink is fully cured. Therefore, the first irradiation parts 92a and 92
The curing process may be terminated by irradiating ultraviolet rays from the second irradiating unit 93 without irradiating ultraviolet rays from b. Further, the main curing may be performed by irradiating ultraviolet rays from at least one of the first irradiating portions 92a and 92b regardless of whether the second irradiating portion 93 irradiates the ultraviolet rays. When the main curing is performed in at least one of the first irradiation units 92a and 92b, the second irradiation unit 93 is used.
Is not necessary. As described above, the curing step may perform only the main curing without performing the temporary curing.

As described above, in the present embodiment, while moving the head 85 in the movement direction (main scanning direction), ink is ejected from the head 85 and cured to form at least a part of the image, and the head 85. Sub-scanning in which the relative position of the recording medium and the recording medium is changed in the transport direction (sub-scanning direction) intersecting the main scanning direction is alternately repeated to perform recording. That is, the main scanning performs the above-described ejection process and the curing process, and the sub-scan transports the recording medium in the transport direction. Then, an image can be completed on the recording medium by repeating these main scanning and sub-scanning.

Further, instead of the above-described sub-scanning, the recording medium may not be transported and the carriage unit 100 may be moved in the sub-scanning direction to perform the sub-scanning.

The recording method of the present embodiment is preferably performed by so-called overlap printing. Here, overlap printing in the present embodiment will be described.

The overlap printing in the present embodiment includes the following first aspect or second aspect. Here, “raster line” means a row (dot row) in which pixels are arranged in one row in the main scanning direction.

In the first aspect, in one main scan, there are pixels that form dots and pixels that do not form dots for one raster line, and one raster line is formed by performing multiple main scans. A raster line exists. According to the first aspect, the one raster line can be formed through a plurality of main scans. This aspect can be referred to as an “overlapping raster line”. That is, in the overlap raster line, there are pixels in which dots are formed by one main scan and pixels in which dots are not formed by one main scan but dots are formed by another main scan. To do.

In the second mode, in addition to the first mode, a raster line in which dots are formed in another main scan during the sub-scan direction of the raster lines in which dots are formed in one main scan. Exists. That is, there is a raster line in which dots are not formed in one main scan but dots are formed in another main scan between raster lines in which dots are formed in one main scan.

In the above overlap raster line, the number of passes for forming dots is at least 2.
It may be 3 or more. In addition, out of the total number of pixels in one raster line, it is preferable that 50% or more of the pixels in which dots formed in one pass are not adjacent to each other exist, more preferably 70% or more. preferable. Further, it is preferable that 50% or more of overlap raster lines exist among all the raster lines on which dots are formed.
% Or more is more preferable.
Among the above, when overlapping printing including the second mode is performed, dots formed by one main scanning can be dispersed in the main scanning direction and the sub-scanning direction.

Thus, according to the present embodiment, an ink jet recording apparatus is provided that is excellent in both curability, suppression of curing wrinkles, and solid pattern image and line width (sub-scanning direction and main scanning direction) fillability. can do.

〔head〕
As an ink-jet head provided in the ink-jet recording apparatus, a head using an epoxy adhesive in at least a part of a portion in contact with the ink composition such as the inside or the surface of the head can be used. By using a head using an epoxy adhesive, it is possible to maintain a strong adhesive force between the components of the head even when the temperature of the head changes. Here, “contact with the ink composition” includes direct contact with the ink composition or indirect contact due to penetration of components of the ink composition.
At this time, since the ink composition of the above embodiment can prevent the epoxy adhesive from swelling, it has excellent material resistance. Thus, the photocurable ink composition of the embodiment can be suitably discharged from the head using an epoxy adhesive.

Although not limited to the following as an epoxy-type adhesive agent, For example, the conventionally well-known adhesive agent which hardens the main ingredient containing the compound which has an epoxy group with a hardening | curing agent is mentioned. The compound having an epoxy group contained in the main agent is not limited to the following, for example, bisphenol type epoxy such as bisphenol A type and bisphenol F type, novolak type epoxy such as phenol novolak type and cresol novolak type, epoxy polyol Type epoxy, urethane-modified epoxy, chelate-modified epoxy, and rubber-modified epoxy. Examples of the curing agent include, but are not limited to, amines such as amines and polyamines, amides such as acid anhydrides, amides and polyamides, imidazoles, and polymercaptan. Among these, a combination of bisphenol type epoxy as the main agent and amines as the curing agent is preferable because of excellent adhesive strength. Since the mixing ratio of the main agent and the curing agent (main agent: curing agent) is excellent in the curability of the adhesive, it is 10: 1 to 1 in terms of mass.
: 10 is preferable.

[Recording medium]
A recorded matter is obtained by ejecting the ink composition onto a recording medium using the inkjet recording method of the present embodiment. Examples of the recording medium include an absorptive or non-absorbable recording medium. The ink jet recording method of the present embodiment can be applied to a recording medium having various absorption performances from a non-absorbing recording medium in which the ink composition is difficult to penetrate to an absorbent recording medium in which the ink composition is easily penetrated. Widely applicable. However, when the ink composition is applied to a non-absorbable recording medium, it may be necessary to provide a drying step after being cured by irradiation with ultraviolet rays.

The absorbent recording medium is not particularly limited. For example, plain paper such as electrophotographic paper having high ink permeability, ink jet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl alcohol ( PVA) and polyvinylpyrrolidone (P
VP) and other ink-jet paper with an ink absorbing layer composed of a hydrophilic polymer)
Thus, art paper, coated paper, cast paper and the like used for general offset printing with relatively low ink permeability can be used.

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

[Discharge process]
The ejection process in the present embodiment ejects ultraviolet curable ink from the head toward the recording medium. The temperature of the discharged ultraviolet curable ink is 20 to 40 ° C.

The temperature of 20 to 40 ° C. does not increase the temperature of the ink from room temperature by heating, or is relatively low even when the temperature is increased by heating. Thus, if the temperature of the ejected ink (hereinafter also referred to as “ejection temperature”) is in the above range, an ink heating mechanism for heating the ink is not required or an ink heating mechanism is provided. However, it is easy to stabilize the temperature of the ink because relatively low temperature heating is required, so the heating mechanism can be simplified, and the cost of using the inkjet recording apparatus can be reduced, and the use of the recording apparatus can be reduced. This is advantageous in terms of power saving.
Furthermore, it is preferable that the temperature is in the above range in that the ink having the above-described viscosity is stably ejected from the head. Further, since the deterioration of the head member can be prevented, the durability of the head is excellent. The temperature of the ejected ink is 8 mP at 20 ° C.
20 to 30 ° C. is preferable when the viscosity is a · s or more and less than 15 mPa · s, and 30 to 40 when the ink is 15 mPa · s or more and 22 mPa · s or less at 20 ° C.
° C. is preferable because the head durability and ejection stability can be further improved.

Here, the “temperature of the UV curable ink to be ejected” is the temperature of the member (nozzle plate) on which the nozzles of the head are formed. Further, printing is performed by continuously ejecting ink from the head for a predetermined time (for example, 60 minutes), and during that time, the nozzle temperature is measured at predetermined time intervals (for example, every 5 minutes), and the average value of the measured temperatures is used. It shall represent.

The discharge temperature is 20 to 20 in that the ink heating mechanism is unnecessary and the recording apparatus is further simplified.
30 ° C. is preferred. On the other hand, the discharge temperature is preferably 30 to 40 ° C. in that the ink viscosity at the discharge temperature is made as low as possible to further improve the discharge stability. The viscosity of the ink at the discharge temperature is preferably 22 mPa · s or less, in order to improve the discharge stability, and is preferably 15 mPa · s.
s or less is more preferable, and 13 mPa · s or less is more preferable. The lower limit of the ink viscosity at the time of ejection is not limited, but it is preferably 3 mPa · s or more.

[Curing process]
Next, in the curing step, the ink composition discharged onto the recording medium is subjected to ultraviolet rays (
It is cured by irradiation with light. In other words, the ink coating film formed on the recording medium becomes a cured film when irradiated with ultraviolet rays. This is because the photopolymerization initiator that can be contained in the ink composition is decomposed by irradiation with ultraviolet rays to generate radicals, acids, bases, and other starting species, and the polymerization reaction of the photopolymerizable compound is the starting species. This is because it is promoted by function. Or it is because the photopolymerization reaction of a polymeric compound starts by irradiation of an ultraviolet-ray. At this time, if a sensitizing dye is present together with the photopolymerization initiator in the 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.

Mercury lamps and gas / solid lasers are mainly used as ultraviolet sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV curable ink jet recording ink compositions. Yes. On the other hand, there is a strong demand for mercury-free technology from the viewpoint of environmental protection.
It is very useful environmentally. Furthermore, an ultraviolet light emitting diode (UV-LED) and an ultraviolet laser diode (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for ultraviolet curable ink jets. Among these, UV-LED is preferable.

Here, the emission peak wavelength is preferably in the range of 365 to 405 nm, more preferably 3
It is preferable to use an ink composition that can be cured by irradiating ultraviolet rays having a single wavelength in the range of 80 to 400 nm. The emission peak wavelength is 800 mW / c
m ² or more is preferable, 1,000 mW / cm ² or more is more preferable, and the upper limit is not limited, but it is preferably 3,000 mW / cm ² or less. The irradiation energy is 300m
J / cm ² or less is preferable, and 100 to 250 mJ / cm ² is more preferable.

In the above case, curing at low energy and high speed is possible due to the composition of the ink composition. The irradiation energy is calculated by multiplying the irradiation time by the irradiation intensity. The irradiation time can be shortened by the composition of the ink composition, and in this case, the printing speed is increased. On the other hand
The irradiation intensity can also be reduced by the composition of the ink composition in the present embodiment, and in that case, downsizing and cost reduction of the apparatus are realized. In this case, UV-LED
Is preferably used. Such an ink composition can be obtained by including a photopolymerization initiator that is decomposed by irradiation with ultraviolet rays in the above wavelength range and a polymerizable compound that initiates polymerization by irradiation with ultraviolet rays in the above wavelength range. The emission peak wavelength may be one or plural within the above wavelength range. Even in the case where there are a plurality, the total irradiation energy of the ultraviolet rays having the emission peak wavelength is set as the irradiation energy.

Hereinafter, the embodiments of the present invention will be described more specifically by way of examples. However, the embodiments are not limited to these examples.

1. Ink composition example [used raw material]
The raw materials used in the following examples and comparative examples are as follows.
[Inorganic metal-based fine particles]
・ Titanium dioxide (average particle size 200 nm, manufactured by Ishihara Sangyo Co., Ltd.)
・ Titanium dioxide (average particle size 300nm, manufactured by Ishihara Sangyo Co., Ltd.)
[Trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton]
Pentaerythritol triacrylate (SR444 manufactured by Sartomer, SR in the table)
Abbreviated as 444. )
Pentaerythritol tetraacrylate (NK ester A-TMMT, Shin-Nakamura Chemical Co., Ltd., abbreviated as A-TMMT in the table)

[Other polymerizable compounds]
・ 2- (2-vinyloxyethoxy) ethyl acrylate (manufactured by Nippon Shokubai Co., Ltd., VEEA in the table)
Was abbreviated. )
・ Phenoxyethyl acrylate (V # 192, manufactured by Osaka Organic Chemical Industry Co., Ltd., PEA in the table)
Was abbreviated. )
・ Dipropylene glycol diacrylate (SR508, manufactured by Sartomer, DP in the table)
Abbreviated as GDA. )
Dipentaerythritol hexaacrylate (SR399, manufactured by Sartomer, abbreviated as SR399 in the table)
Tetrahydrofurfuryl acrylate (V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd., abbreviated as THFA in the table)
Benzyl acrylate (V # 160, manufactured by Osaka Organic Chemical Industry Co., Ltd., abbreviated as BZA in the table)
Urethane oligomer (CN3550, manufactured by Sartomer, abbreviated as CN3550 in the table)
Hyperbranched polymer (V # 1000, manufactured by Osaka Organic Chemical Industry Co., Ltd., V # 10 in the table)
(Abbreviated 00)
(Photopolymerization initiator)
IRGACURE 819 (trade name, manufactured by BASF, solid content: 100%, “81” in the table below)
9 ”. )
DAROCURE TPO (BASF brand name, 100% solids, “TP” in the table below)
O ". )

[Other ingredients]
・ C. I. Pigment Blue 15: 3 (Cyanine Blue KRO manufactured by Sanyo Dye Co., Ltd.) In the following table, “Cyan” was abbreviated. )
・ Solsperse 36000 (Noveon brand name, “Sol36” in the table below)
000 ". )
・ Polymerization inhibitor (p-methoxyphenol, manufactured by Kanto Chemical Co., Inc.)
・ Slip agent (BYK-UV3500, trade name of BYK Japan)

[Ink composition]
(Preparation of pigment dispersion)
Prior to preparation of the ink composition, a pigment dispersion was prepared. For each ink composition in the table below, titanium dioxide or C.I. I. Pigment Blue 15: 3, a dispersant, and phenoxyethyl acrylate or benzyl acrylate among the polymerizable compounds as a dispersion medium were mixed and stirred with a stirrer for 1 hour. The mixed liquid after stirring was dispersed with a bead mill to obtain a pigment dispersion. The dispersion conditions were such that zirconia beads having a diameter of 0.65 mm were filled at a filling rate of 70%, the peripheral speed was 9 m / s, and the dispersion time was 2 to 4 hours.

[Preparation of ink composition]
The above-mentioned pigment dispersion and the remaining components in the following table were added so as to have the composition (unit:% by mass) described in the following table, and this was stirred with a high-speed water-cooled stirrer, whereby an ultraviolet curable inkjet. An ink composition was prepared, and after the preparation, the ink was deaerated by a vacuum pump, and the dissolved oxygen amount of each ink was set to 1 ppm to prepare an ink composition. The measurement of the dissolved oxygen amount was performed using the apparatus used for the measurement of the dissolved oxygen amount in the in-pack examples described later.
Using the DVM-E type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.)
The viscosity at 20 ° C. was measured.
As the rotor, a DVM-E type cone having a cone angle of 1 ° 34 ′ and a cone radius of 2.4 cm was used. The rotation speed was 10 rpm.
The evaluation criteria (viscosity rank) of the viscosity were as follows. The composition and viscosity evaluation results are shown in Table 1 below.
A: Less than 8 mPa · s.
B: 8 mPa · s or more and less than 15 mPa · s.
C: 15 mPa · s or more and 20 mPa · s or less.
D: More than 20 mPa · s.

The ultraviolet curable inkjet ink composition prepared in each composition example was evaluated by the method of the following evaluation items.

[1. Storage stability)
100 g of the ink composition was placed in a glass container, and the container was sealed. The container was stored in an oven at 60 ° C. for 20 days. And the viscosity increase rate of the viscosity before and behind storage was calculated | required. The viscosity was measured at 20 ° C. using the same method as the above viscosity measurement.
The evaluation criteria are as follows. The evaluation results are shown in Table 2.
A: 3% or less.
B: More than 3%.

[2. Curability)
Using a bar coater, each ink composition was transferred to a PET film (PET50A PL thin [
Product name], manufactured by Lintec), and an ink coating film having a thickness of 10 μm was prepared. after that,
The coating film was cured by irradiation with ultraviolet rays having an irradiation intensity of 1,100 mW / cm ² and a wavelength of 395 nm. The cured coating film (cured film) was rubbed 10 times with a cotton swab at a load of 100 g, and the cured energy was applied at the time when the scratch was not applied.
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 irradiation intensity was measured using an ultraviolet intensity meter UM-10 and a light receiving unit UM-400 (both manufactured by KONICA MINOLTA SENSING, INC.).
The evaluation criteria are as follows. The evaluation results are shown in Table 2.
A: 200 mJ / cm ² or less.
B: More than 200 mJ / cm ² and 300 mJ / cm ² or less.
C: More than 300 mJ / cm ² .

[3. (Settling resistance)
Each ink composition was put in a 50 mL sample bottle, sealed, and stored in a stationary state. Before storage and after storage for 24 hours, 1 mL ink was collected from the top of the ink composition in the bottle. The collection after storage is the collection of the ink supernatant. The collected ink was diluted 5000 times with ethyl diglycol acetate. The spectrophotometer (product name “Sp”
Electrophotometer U-3300 "(manufactured by Hitachi, Ltd.)
Absorbance (abs value) of the diluted ink at a wavelength of 500 nm was measured. The ratio (%) of the absorbance of the ink after storage to the absorbance of the initial ink was calculated.
A: 98% or more.
B: 95% or more.
C: 93% or more.
D: 90% or more.

[4. (Shielding)
The film provided with the ink coating film obtained by the curability evaluation is set in a declination colorimeter (manufactured by JASCO Corporation, model “ARM-500V”), and visible light region (380 nm to 700 nm)
The transmittance Tn (%) of each wavelength at 1 nm was measured. From the measurement results, the shielding property was evaluated by calculating the average value of the transmittance Tn for each wavelength in the visible light region (380 nm to 700 nm).
A: The average value of the transmittance Tn is 5% or less.
B: The integrated value of the transmittance Tn is more than 5%.

From the above results, trifunctional or tetrafunctional (meth) having a pentaerythritol skeleton.
Contains acrylate and inorganic metal fine particles as a colorant, and has a viscosity at 20 ° C. of 8 to 22.
UV curable inkjet ink composition having mPa · s (Ink composition (1) in the table)
It was found that the composition was superior in all of the curability, storage stability, anti-sedimentation property and shielding property as compared with the other ink composition (described as the ink composition (2) in the table).

Considering details, the ink compositions 10 to 14 which did not contain a tri- or tetrafunctional (meth) acrylate having a pentaerythritol skeleton but had an ink viscosity rank of C were inferior in storage stability or curability. The ink composition 15 containing a tri- or tetrafunctional (meth) acrylate having a pentaerythritol skeleton but having an ink viscosity rank D was inferior in storage stability.
Further, the ink compositions 16 and 17 in which the viscosity rank of the ink was A although containing or not containing a tri- or tetrafunctional (meth) acrylate having a pentaerythritol skeleton were poor in sedimentation resistance. Further, the ink composition 18 containing no inorganic metal-based fine particles was not inferior in settling resistance, although the viscosity rank was A, but inferior in shielding properties.

2. Example of inkjet recording method The serial printer shown in FIG. 2 was used. Specifically, inkjet printer PX
Using -G5000 (manufactured by Seiko Epson Corporation), a light source (UV-LED) described later was attached downstream of the carriage and platen in the sub-scanning direction. In addition, a heater capable of heating the ink is attached to the head so that the ink temperature during ejection can be adjusted. The head was filled with any of the ink compositions prepared in the ink composition examples described above. A white PET film (Lumirror 125E20 manufactured by TORAY Co., Ltd.), which is a recording medium, was printed by performing main scanning while discharging ink from the head. The nozzle row used for printing has a nozzle density of 360 dpi in the sub-scanning direction.

At the time of the main scanning, an LED having a peak wavelength of 395 nm mounted on the side of the carriage is used for each pass (one main scanning), and UV curable ink that has landed and adhered to the recording medium by the main scanning is used. Temporarily cured (the dots were irradiated). At this time, Firefly (irradiation peak intensity 1,000 mW / cm ² ) was used as the LED mounted on the side of the carriage. Further, the irradiation energy in one-pass irradiation was 50 mJ / cm ² .

Next, after performing a sub-scan for transporting the recording medium in the sub-scan direction intersecting the main scan direction, the next main scan was performed, and the main scan and the sub-scan were alternately repeated.

After printing (after the last main scan), a light source equivalent to the width of the recording medium provided separately from the carriage is the same as the light source mounted on the carriage. The UV curable ink was further irradiated with the kind of product) to completely cure the uncured ink. The irradiation energy for the curing was 400 mJ / cm ² .

To supplement the recording conditions (printing conditions), the number of passes (number of main scans) is “2 passes (main scan direction) × 2 passes (sub scan direction) = 4 passes”. Specifically, overlap printing is performed in which dots are formed every other pixel of one raster line in one pass, and another main scan is performed between two raster lines in which dots are formed in one main scan. There is one raster line in which dots are formed. The interval between the nozzle surface and the recording surface of the recording medium was 1 mm.
The recording resolution (sub scanning direction × main scanning direction) was 720 dpi × 720 dpi.

The ink temperature during ejection is as shown in Table 3 below. The said temperature is a value obtained by providing a thermocouple in the nozzle plate and measuring the temperature of the nozzle plate. That is, the temperature of the ink ejected from the nozzles of the head corresponds to the temperature of the nozzle plate. Further, in the examples where the ink temperature at the time of ejection is 30 ° C. or higher among the temperatures shown in the following table, the ink at the time of ejection was heated to the temperature using a temperature control mechanism (heater) mounted on the head. Further, in the case where the ink temperature at the time of ejection was less than 30 ° C., printing was performed at room temperature such that the temperature was kept at room temperature without using the temperature control mechanism. In each example, the voltage of the head drive waveform was adjusted so that the ejection amount was the same between each example and each comparative example.

The above recording method was performed using the ink compositions prepared in the above ink composition examples, and the following evaluation items were evaluated.

[1. (Discharge stability)
Continuous discharge was performed for 5 minutes using ink from 360 nozzles.
The evaluation criteria are as follows. The evaluation results are shown in Table 3 below.
○: During continuous discharge, there were less than 10 non-discharge nozzles.
X: There were 10 or more non-ejection nozzles during printing ejection.

[2. Head durability)
The head durability was evaluated by measuring and calculating the swelling rate of the same adhesive as that used for the head. Epoxy adhesive (EPIK, an epoxy resin manufactured by Shell)
About 0.2 g of OTE 828 and VERSAMID 125, which is a curing agent manufactured by COGNIS, were mixed to obtain an adhesive piece, and the weight was measured. Thereafter, the adhesive pieces were immersed in the ink compositions of Examples and Comparative Examples put in screw tubes, capped, and left in a 60 ° C. environment for 7 days. After leaving, the adhesive piece was taken out and the ink composition was thoroughly washed out, and then the weight was measured. And the swelling rate was computed from the following formula | equation.
Weight change rate (%) = {(weight after charging−weight before charging) / weight before charging} × 100
The evaluation criteria are as follows. The evaluation results are shown in Table 3.
A: 40% or less.
B: More than 40% and 60% or less.
C: Over 60%.

[3. Cured wrinkles)
Under the conditions of each recording method example shown in Table 3, the recorded matter recorded by the above-described recording method was in a state of being cured by the curable evaluation of the ink composition examples described above. The recorded portion of the recorded material was evaluated. Evaluation was performed visually. The evaluation criteria are as follows. The evaluation results are shown in Table 3 below.
A: Wrinkles were not generated at all.
B: It was observed that wrinkles were generated in a part of the cured film (cured coating film).
C: It was observed that wrinkles were generated throughout the cured film.

From the results of Table 3, ink compositions 2 and 3 in which the viscosity rank of the used ink composition is B
The ink compositions 1 and 4 in which the ejection stability and the head durability were excellent at ink temperatures of 20 ° C. and 30 ° C. and the viscosity rank of the used ink composition was C were used. In the example, the ejection stability and the head durability were excellent at ink temperatures of 30 ° C. and 40 ° C. On the other hand, the ink composition 1 in which the viscosity rank of the used ink composition is A
In the examples using 6 and 17, the head durability was inferior at any ink temperature. In addition, the example using the ink composition 15 in which the viscosity rank of the used ink composition is D could not be excellent in both ejection stability and head durability at any ink temperature. . From this, when the viscosity rank of the used ink composition is B or C, it is possible to perform recording with excellent ejection stability and head durability. In addition, the example using the ink compositions 16 and 17 in which the viscosity rank of the used ink composition is A tended to be inferior in curing wrinkles.

3. Ink Container Example Various films were prepared, and the films were stacked and heat-pressed around to create an ink pack as shown in FIG. The ink composition prepared in the ink composition example was added to the ink pack.
The ink supply port was sealed in a state in which 00 mL was filled and the pack was compressed so that air did not enter the ink pack and the pack volume was reduced as much as possible. When the maximum amount of ink that can be stored in the pack was stored, the ink storage rate relative to the maximum ink storage capacity was 90%. The ink pack was housed in the main body case to obtain an ink cartridge as shown in FIG. The main body case was 30 cm long × 10 cm high × 4 cm deep. The pack types in Table 4 are the types of films prepared, and the following films were used.
EVOH pack: ethylene vinyl alcohol copolymer (EVAL, manufactured by Kuraray Co., Ltd., described as EVOH in the table). Thickness 110 μm. Oxygen permeability 2.0cc · 20μm / (m ² · da
y · atm).
PET pack: polyethylene terephthalate (Teijin Tetron Film, manufactured by Teijin DuPont Films, Ltd., described as PET in the table). Thickness 95 μm. Oxygen permeability 10.0cc ・ 2
It was 0 μm / (m ² · day · atm).
-AL pack: Aluminum-deposited PET (shown as AL in the table). An aluminum vapor deposition film of 30 μm was provided on a 35 μm thick polyethylene terephthalate (Teijin Tetron Film, Teijin DuPont Films). The same polyethylene terephthalate film was bonded to the aluminum vapor deposition surface of this film with an adhesive to obtain a laminated film. Oxygen permeability 2.0
cc · 20 μm / (m ² · day · atm).

The following evaluation items were tested using the prepared ink cartridge.
[1. (Recoverability)
1 mL of ink, which was the one before storing the ink cartridge, was collected, and the ink was diluted 5000 times by adding ethyl diglycol acetate. The spectrophotometer (product name “S
The absorbance (abs value) of the diluted ink at a wavelength of 500 nm was measured and used as an initial value using a photophotometer U-3300 (manufactured by Hitachi, Ltd.).
The ink was filled in the ink pack, the ink supply port was sealed, and the ink cartridge was statically placed in such a direction that the 30 cm × 4 cm side surface of the main body case became the bottom surface and stored at room temperature for 180 days. The following durability evaluation was performed after storage. 1 mL of ink in the ink cartridge after settling recovery operation
The sample was collected, diluted as in the initial stage, and the absorbance was measured. Evaluation was performed according to the following evaluation criteria.
○: The ratio (%) of absorbance after storage to the initial value of absorbance is 99% or more.
X: The ratio (%) of absorbance after storage to the initial value of absorbance is less than 99%.

[2. durability〕
The ink cartridge after storage was fixed to the base so that the side of the main body case with the side of 30 cm × 10 cm was the bottom surface, and the base was reciprocated by a distance of 20 cm in the direction of the side of the main body case to perform sedimentation recovery operation. . The moving speed was set to 15 cm / s, and the number of reciprocations was set to the number of times described in the number of stirrings in Table 4. The ink pack of the ink cartridge after the operation was taken out, and the appearance of the ink pack was visually observed. The evaluation criteria were as follows.
○: No change on the surface of the ink pack.
X: A fine crack is visible on the surface of the ink pack.

[3. (Discharge stability)
Except as described below, the ejection stability evaluation was performed in the same manner as the ejection stability evaluation in the above-described recording method examples. As the ink, the ink in the ink cartridge after storing the ink cartridge of the above-described recoverability evaluation and performing the sedimentation recovery operation after the storage was used. The ink temperature is determined based on the viscosity rank A or B according to the viscosity evaluation of the ink composition examples described above.
30 ° C., a viscosity rank C of 40 ° C., and a viscosity rank D of 45 ° C. The evaluation criteria were as follows.
A: The number of non-ejection nozzles was 2 or less during continuous ejection.
B: There were 3 or more and less than 10 non-ejection nozzles during printing ejection.

[4. Measurement of dissolved oxygen amount)
The ink prepared in the above ink composition example (dissolved oxygen amount at the time of creation of 1 ppm) is stored in the ink cartridge according to the above-mentioned recovery evaluation conditions, and the dissolved oxygen amount of the ink in the ink cartridge after storage is measured. , Gas Chromatography Agilent 6890 (
(Manufactured by Agilent Technologies). The carrier gas is helium (He
) Gas was used. The evaluation criteria were as follows.
A: The amount of dissolved oxygen is 20 ppm or less.
B: The amount of dissolved oxygen exceeds 20 ppm.

From the results of Table 4, recovery was obtained in the case of using an ink composition 2, 3, 1, 4 whose viscosity rank was B or C and using an EVOH pack as the ink pack type. Even when the mixture was stirred at such a number of times as to improve the durability, the durability of the pack was excellent, and the discharge stability was also excellent. On the other hand, in the example using the AL pack as the pack type while using the same ink, the durability of the pack cannot be improved even when the number of stirrings is such that the recoverability is good. It was. It was found that the pack provided with the vapor deposition film is inferior in durability. The cracks that occurred in the AL pack
It was a crack in the deposited film of aluminum.

Moreover, in the example using PET as the pack type while using the above ink, the ejection stability was inferior. At that time, the amount of dissolved oxygen is also high, and it is assumed that the generation of bubbles in the head has increased due to the use of ink with a high amount of dissolved oxygen. In addition, since the PET pack has a larger oxygen permeability than the EVOH pack, it is assumed that the dissolved oxygen concentration is likely to increase due to storage.
In the case of the case where the durability is inferior when the AL pack is used, the aluminum vapor deposition film has cracked, resulting in an oxygen permeability equivalent to that of the PET pack as the base material. If the operation is continued, there is a possibility that the dissolved oxygen amount increases and the discharge stability deteriorates. In addition, the durability of the pack is required because stirring for recovery of sedimentation may be performed during storage of the cartridge or the cartridge may be shaken during transportation.

Next, in the case of using the ink compositions 16 and 17 in which the viscosity rank of the used ink composition is A, stirring is performed so that the recoverability is good in any case of the ink pack type. It was not possible to improve the durability of the pack when it was stirred for a number of times. When an ink having inferior sedimentation resistance is used, it is difficult to achieve both recoverability and durability. In the case of using the ink composition 15 having a viscosity rank D of the ink composition used, and using EVOH or AL as the pack type of the ink pack, even when the ink composition is stirred at such a number of times that the recoverability is good Although the durability of the pack could be made excellent, it was difficult to achieve both ejection stability and head durability when using ink with an ink viscosity rank D from the results of the recording method examples described above. is there.

From the above, when the ink composition used is an ink composition whose viscosity rank is B or C, and when EVOH is used as the pack type of the ink pack, the stirring is performed with the number of stirrings so that the recoverability is good. However, it is possible to obtain an ink container that has excellent pack durability, discharge stability, and head durability. In addition, if the ink contains a trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton, the ink can be excellent in terms of storage stability and curability, but an ink that is not so is used. In this case, the curability and storage stability are expected to be inferior, but the irradiation energy for recording is increased, the storage temperature for storing ink is lowered, or the storage period is shortened. As a result, it is possible to obtain an ink container excellent in at least recoverability, durability, ejection stability, and head durability.

40: Ink cartridge, 70: Ink pack 70, 72 ... Cartridge case, 7
DESCRIPTION OF SYMBOLS 4 ... Ink supply port, 76 ... Main body case, 78 ... Cover part, 80 ... Notch part, 81 ... Carriage 81, 82 ... Holding part, 83 ... Guide shaft, 84 ... Gutter part, 85 ... Head 85, 90 ... Irradiation Units 92a ... 92b ... first irradiation unit 93 ... second irradiation unit 100 ... carriage unit.

Claims (16)

The ink composition for ultraviolet curable ink jet recording is heated, and includes a discharge step of discharging from a head to a recording medium at 30 to 40 ° C.,
The ultraviolet ray curable ink composition for ink jet recording includes a trifunctional or tetrafunctional (meth) acrylate having a pentaerythritol skeleton, a metal oxide fine particle as a white coloring material, and a monofunctional (meth) acrylate. a viscosity at 20 ° C. is Ri 8~22mPa · s der, wherein a 8-25 mass% relative to the ink composition content of the fine particles of metal oxide, the content of the monofunctional (meth) acrylate ink The inkjet recording method which is 40-80 mass% with respect to the total mass of a composition .   2. The ink jet recording method according to claim 1, wherein a content of the trifunctional or tetrafunctional (meth) acrylate having the pentaerythritol skeleton is 5 to 15% by mass with respect to the ink composition.   The inkjet recording method according to claim 1 or 2, wherein the content of the metal oxide fine particles is 10 to 25% by mass with respect to the ink composition.   The inkjet recording method according to any one of claims 1 to 3, wherein the ultraviolet curable ink composition for inkjet recording further contains a vinyl ether group-containing (meth) acrylic acid ester.   The trifunctional or tetrafunctional (meth) acrylate having the pentaerythritol skeleton includes at least one of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. The ink jet recording method described in 1. Filling the head with the ultraviolet curable ink jet recording ink composition ink from an ink container comprising a container filled with the ultraviolet curable ink jet recording ink composition;
The ink jet recording method according to claim 1, wherein the container is made of a plastic film having an oxygen permeability of 5.0 cc · 20 μm / (m ² · day · atm) or less.   The inkjet recording method according to claim 6, wherein the container is composed of an ethylene vinyl alcohol copolymer.   The inkjet recording method according to claim 6 or 7, wherein the ultraviolet curable inkjet ink composition filled in the container has an amount of dissolved oxygen of 20 ppm or less. The ink jet recording according to any one of claims 1 to 8, wherein the ultraviolet curable ink composition for ink jet recording has a content of fine particles of the metal oxide of 18 to 25% by mass with respect to the ink composition. Method.   The ink jet recording method according to claim 1, wherein the ultraviolet curable ink composition for ink jet recording has an ink viscosity at 20 ° C. of 15 mPa · s or more and 22 mPa · s or less.   The inkjet recording method according to any one of claims 1 to 10, wherein a dissolved oxygen amount of the ultraviolet ray curable ink composition for inkjet recording discharged from the head is 20 ppm or less.   The inkjet recording according to any one of claims 1 to 11, wherein the ultraviolet curable ink composition for inkjet recording contains 2 to 20% by mass of a bifunctional (meth) acrylate based on the total mass of the ink composition. Method.   The inkjet recording method according to any one of claims 1 to 12, wherein the ultraviolet curable ink composition for inkjet recording contains acylphosphine oxide as a photopolymerization initiator. The inkjet recording method according to claim 1, wherein the metal oxide fine particles have an average particle size of 150 to 350 nm. The inkjet recording method according to any one of claims 1 to 14, wherein the ultraviolet curable ink composition for inkjet recording is non-aqueous or non-solvent. The inkjet recording method according to claim 1, wherein the ultraviolet curable ink composition for inkjet recording contains a photopolymerization initiator in an amount of 5% by mass or more based on the total mass of the ink composition.

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