JP6477746B2 - Inkjet recording method, ultraviolet curable ink, inkjet recording apparatus - Google Patents

Description

The present invention relates to an ink jet recording method, an ultraviolet curable ink, and an ink jet recording apparatus.

Conventionally, various methods are 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 inkjet recording method using an ultraviolet curable ink in which a monomer is photopolymerized (cured) by irradiating ultraviolet rays forms an image having excellent water resistance and abrasion resistance on a recording surface of a recording medium. Therefore, it is used for manufacturing color filters, printing on printed boards, plastic cards, vinyl sheets, large signs, and plastic parts, and printing barcodes and dates.

Examples of the ink used for inkjet recording include a solvent-based aqueous ink and a solvent-free ultraviolet curable ink (UV ink). Among these, solvent-free UV curable ink has a significantly higher viscosity than solvent-based water-based inks, so viscosity fluctuations due to temperature fluctuations during ejection are large, and this viscosity fluctuation causes changes in droplet size and droplet ejection. It has a great influence on the change in speed, which in turn causes image quality degradation. Therefore, a technique is disclosed in which when ultraviolet curable ink is ejected, the ink is heated to lower the viscosity and then ejected.

For example, in Patent Document 1, since UV ink has a higher viscosity than ordinary ink at normal temperature, it is heated in the recording head and set to a target set temperature (set temperature necessary for the ink to be ejected viscosity). The ink viscosity is 7000 to 500 mPa · s at 5 ° C. and the ink viscosity is 2 at 80 ° C.
There is disclosed a UV ink characterized by changing by heating temperature control so that it becomes 0 to 3 mPa · s (paragraphs 0034, 0041, and 0042 of Patent Document 1).

JP 2003-200559 A

However, the UV ink disclosed in Patent Document 1 has a problem that the head member is deteriorated by heating. Further, since the UV ink has a very high viscosity, there is a problem that when it is attempted to discharge without heating, the discharge stability and the discharge amount stability are poor.

Accordingly, an object of the present invention is to provide an ink jet recording method that is excellent in the durability of the head and the discharge stability and discharge amount stability of the ultraviolet curable ink.

In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies and obtained the following knowledge. First, an ultraviolet curable ink having a very low viscosity (hereinafter, ultraviolet curable ink is also simply referred to as “ink”) was prepared, and a method for discharging the ink without heating was examined. However, according to the method, it has been found that the temperature of the ink is likely to fluctuate due to a change in the environmental temperature, and the ejection stability and ejection amount stability of the ink cannot be improved. Furthermore, it has been found that due to the composition of the ultraviolet curable ink having a very low viscosity, the head member deteriorates, the durability of the head deteriorates, and curing wrinkles easily occur. Therefore, the inventors of the present application tried to heat an ultraviolet curable ink having a relatively low viscosity and a predetermined range of viscosity at a predetermined range of temperatures at a relatively low temperature. As a result, it has been found that deterioration of the head member can be prevented. In addition to this, it was found that the temperature fluctuation at the time of ejection can be reduced, the viscosity fluctuation can be suppressed, and the ejection stability and ejection amount stability of the ultraviolet curable ink are also improved.

Based on the above findings, the inventors of the present invention conducted further studies, and as a result, heated UV curable ink having a viscosity at 28 ° C. of 8 mPa · s or higher, and the temperature of the discharged UV curable ink was adjusted. It has been found that the above problems can be solved by an inkjet recording method in which an ultraviolet curable ink having a viscosity of 28 to 40 ° C. and a viscosity at the temperature of 15 mPa · s or less is cured, and the present invention has been completed.

That is, the present invention is as follows.
[1]
An ejection step of ejecting an ultraviolet curable ink having a viscosity at 28 ° C. of 8 mPa · s or more from a head toward a recording medium;
Curing the ultraviolet curable ink attached to the recording medium, and
The temperature of the ultraviolet curable ink to be discharged is set to 28 to 4 by heating the ultraviolet curable ink.
An ink jet recording method wherein the viscosity of the ultraviolet curable ink at 0 ° C. is 15 mPa · s or less.
[2]
The ink jet recording method according to [1], wherein recording is performed using a line type ink jet recording apparatus including a line head having a length equal to or longer than a width of the recording medium as the head.
[3]
Recording is performed using an ink jet recording apparatus, wherein at least a part of an ink path for supplying the ultraviolet curable ink from an ink container to the head is an ink circulation path for circulating the ultraviolet curable ink [1] or The inkjet recording method according to [2].
[4]
An ink inflow amount of the ultraviolet curable ink supplied to the head from the ink circulation path is
It is at least twice the maximum ink discharge amount for discharging the ultraviolet curable ink from the head.
The ink jet recording method according to [3].
[5]
The ink jet recording method according to [3] or [4], further comprising a heating mechanism that heats the ultraviolet curable ink at a position other than a position connected to the head in the ink circulation path.
[6]
The inkjet recording according to any one of [3] to [5], wherein there are a plurality of heads to which the ultraviolet curable ink is supplied from the ink circulation path, and the ultraviolet curable ink is ejected from the plurality of heads. Method.
[7]
The said ultraviolet curable ink is an inkjet recording method in any one of [1]-[6] containing the vinyl ether group containing (meth) acrylic acid ester represented by the following general formula (I).
_{^{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.)
[8]
[7] The ultraviolet curable ink further contains a monofunctional (meth) acrylate (excluding the vinyl ether group-containing (meth) acrylic acid ester represented by the general formula (I)). Inkjet recording method.
[9]
The ink jet recording method according to any one of [1] to [8], wherein a light source used in the curing step is a light emitting diode.
[10]
The ink-jet recording method according to [9], wherein the light-emitting diode irradiates ultraviolet rays having a peak intensity of 800 mW / cm ² or more.
[11]
The inkjet recording method according to any one of [1] to [10], wherein an epoxy resin is used in the head.
[12]
An inkjet recording apparatus using the inkjet recording method according to any one of [1] to [11].
[13]
An ultraviolet curable ink used in the ink jet recording method according to any one of [1] to [11] or the ink jet recording apparatus according to [12].

It is a block diagram which shows an example of a structure of the inkjet recording device of this invention. FIG. 2 is a schematic cross-sectional view illustrating an example of the periphery of a head unit, a transport unit, and an irradiation unit in a line printer that is an example of the inkjet recording apparatus of the present invention. It is a schematic front view which shows an example of the ink supply apparatus with which the inkjet recording device of this invention is provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
In this specification, “recorded material” refers to a material in which ink is recorded on a recording medium to form a cured product. In addition, the hardened | cured material in this specification means the hardened | cured substance containing a cured film and a coating film.

In this specification, “curing” means that when an ink containing a polymerizable compound is irradiated with light, the polymerizable compound is polymerized and the ink is solidified. “Curable” refers to the property of curing in response to light and is also referred to as photopolymerization. “Curing wrinkles” is a result of an increase in the polymerization volume shrinkage rate caused by the uncured ink existing inside the coating film to be cured flowing irregularly before curing. It means wrinkles generated on the film surface.

Further, in this specification, “ejection stability” refers to the property of ejecting a stable ink droplet from the nozzle without clogging of the nozzle. “Discharge amount stability” refers to the property that, when ink is ejected from a nozzle for a predetermined time, there is little variation in the amount of ink ejected over that time. More specifically, it can be seen that the discharge volume stability can be mainly affected by fluctuations in the heating temperature in the short term, while it can be mainly affected by fluctuations in the environmental temperature in the long term. The present inventors have found out. Therefore, in the present specification, the former discharge amount stability is “short-term discharge amount stability” or “discharge amount stability (short term)”, and the latter discharge amount stability is “long-term discharge amount stability”. Or they may be referred to as “ejection amount stability (long term)”, respectively.

Further, in this specification, “head durability” includes alteration such as swelling when a member of a head (specifically, an adhesive among the head members) constituting the recording apparatus comes into contact with ink. A property that does not easily cause deterioration.

In the present specification, “storage stability” refers to the property that the viscosity before and after storage is difficult to change when the ink is stored. “Abrasion resistance” refers to the property that when the cured product is rubbed, the cured product is difficult to peel off and scratch.

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

[Inkjet recording method]
One embodiment of the present invention relates to an inkjet recording method. The inkjet recording method includes an ejection step of heating an ultraviolet curable ink having a predetermined range of viscosity at 28 ° C. to a predetermined range of viscosity from the head toward the recording medium, and adhering to the recording medium And a curing step of curing the ultraviolet curable ink. In this way
A cured product of the ink is formed by the ink cured on the recording medium.

[Viscosity of UV curable ink at 28 ° C]
The ultraviolet curable ink used in the recording method has a viscosity of 8 mPa · s or more at 28 ° C. By using the ultraviolet curable ink having such a viscosity, generation of cured wrinkles in the obtained cured product can be effectively prevented. The principle of occurrence of hardening wrinkles is estimated as follows, but 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. Also,
The ultraviolet curable ink containing a monofunctional (meth) acrylate described later, in particular, a vinyl ether group-containing (meth) acrylate represented by the general formula (I), tends to cause curing wrinkles. The low-viscosity ultraviolet curable ink containing the vinyl ether group-containing (meth) acrylate represented by (I) is presumed to have significant generation of cured wrinkles.
Even when the ultraviolet curable ink used in the ink jet recording method of the present embodiment contains these components, the occurrence of curing wrinkles can be effectively prevented by setting the viscosity within the above 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.

[Recording medium]
Examples of the recording medium include a non-ink-absorbing or low-absorbing recording medium. Among the recording media, the non-ink-absorbing recording media include, for example, on a substrate such as a plastic film or paper that is not surface-treated for inkjet recording (that is, has no ink absorbing layer formed). And those coated with plastic and those having a plastic film adhered thereto. The plastic here is not limited to the following, for example, polyvinyl chloride (vinyl chloride), polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), polyurethane (P
U), polyethylene (PE), and polypropylene (PP). Examples of the recording medium with low ink absorption include, but are not limited to, printing paper such as art paper, coated paper, and matte paper.

[Discharge process]
The ejection process in the present embodiment ejects ultraviolet curable ink from the head toward the recording medium. And the temperature of the ultraviolet curable ink discharged is 28-40 degreeC, and the viscosity of the ultraviolet curable ink in the said temperature is 15 mPa * s or less.

The temperature of 28 to 40 ° C. is relatively low as the temperature raised by heating. As described above, when the temperature of the ejected ink (hereinafter, also referred to as “ejection temperature”) is relatively low, deterioration of the head member can be prevented, so that the durability of the head is excellent, and Since there is almost no variation in temperature, there is an advantageous effect that ink ejection stability and ejection amount stability are good.

Here, the “temperature of the ultraviolet curable ink to be ejected” in this specification is 6
Ink is continuously discharged for 0 minute, and the temperature of the nozzle is measured every 5 minutes during that time, and is expressed by the average value of the measured temperatures.

Hereinafter, the discharge temperature will be described more specifically. When the temperature is 28 ° C. or higher, it is possible to reduce fluctuations in the discharge amount when viewed over a long period of time. In other words, long-term discharge amount stability is excellent due to suppression of fluctuations in environmental temperature (in the ink path described later). In addition, UV curable inks that can be ejected at temperatures below 28 ° C. have a very low viscosity,
There arises a problem due to this low viscosity, that is, a problem that the head member deteriorates, the durability of the head deteriorates, and hardening wrinkles easily occur. On the other hand, the ink according to the present embodiment can solve the problem.

On the other hand, when the temperature is 40 ° C. or less, it is possible to reduce fluctuations in the discharge amount when viewed in a short time. In other words, short-term discharge amount stability is excellent due to suppression of fluctuations in the heating temperature. In addition, the ink viscosity when the heating temperature exceeds 40 ° C. is 15 mPa ·
UV curable inks of s or less can prevent the occurrence of curing wrinkles, but have a problem that the durability of the head is deteriorated and the discharge amount stability is also deteriorated due to the heating temperature being too high. Arise. On the other hand, the ink according to the present embodiment can solve the problem.

Further, when the viscosity of the ink at the above discharge temperature is 15 mPa · s or less, an advantageous effect that the ink discharge stability and the discharge amount stability are excellent can be obtained. The ejection stability may be deteriorated when the viscosity of the ink is high. However, when the viscosity is 15 mPa · s or less, such a problem does not occur and the ejection stability is excellent. On the other hand, with regard to the discharge amount stability, the lower the viscosity, the smaller the fluctuation range of the discharge amount. If the viscosity is 15 mPa · s or less, the fluctuation range of the discharge amount is sufficiently small, and the discharge amount stability is excellent.

Moreover, in order to make said effect still larger and to solve said problem more reliably, said discharge temperature is preferably 34 to 40 ° C. The upper limit of the viscosity of the ink at a predetermined discharge temperature is preferably 12 mPa · s or less. The lower limit of the viscosity is preferably 5 mPa · s or more, and 7
mPa · s or more is more preferable, and 8 mPa · s or more is more preferable. When the lower limit of the viscosity of the ink at a predetermined discharge temperature is the above value, the durability of the head due to the ink composition becomes better, and the occurrence of curing wrinkles due to the ink composition is effectively prevented. Can
And the instability of discharge resulting from low viscosity can be prevented. The fact that discharge instability due to low viscosity can be prevented means that the discharge stability and discharge amount stability are further improved.

Further, as described above, since the ultraviolet curable ink has a higher viscosity than the water-based ink used in a normal inkjet ink, the viscosity fluctuation due to the temperature fluctuation during ejection is large. Such a variation in the viscosity of the ink has a great influence on the change in the droplet size and the change in the droplet ejection speed, and can cause image quality degradation. Therefore, the temperature of the ejected ink (
The discharge temperature is preferably kept as constant as possible. The ink in the present embodiment has a relatively low discharge temperature, and the discharge temperature can be kept substantially constant by adjusting the temperature by heating. Therefore, the ink in the present embodiment is excellent in image quality.

Here, an example of an ink design method for setting the viscosity of the ink within a desired range 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 in the range of 8 to 15 mPa · s. The predetermined temperature is a certain temperature in the range of 28 to 40 ° 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 supply process]
The recording method of the present embodiment may perform recording using an ink jet recording apparatus in which at least part of an ink path for supplying ink from an ink container to a head is an ink circulation path for circulating ink. . In other words, the recording method includes an ink supply step that includes an ink circulation path that circulates ink in at least a part of an ink path that supplies ink to the head of the inkjet recording apparatus, and circulates ink in the ink circulation path. Further, it may be included. When the ink flowing out from the head circulates in at least a part of the ink path, the temperature of the ink in the ink circulation path is easily stabilized, and the ejection amount stability is further improved.

In the ink supply step, the inflow amount (ink inflow amount) of the ultraviolet curable ink supplied from the ink circulation path to the head may be adjusted, and the ink having the ink inflow amount may be supplied to the head. The ink supply process may be performed during the above-described ejection process. In the ink supply step, it is preferable that the ink inflow amount is larger than the ejection amount for ejecting ink from the head during recording (during printing) because the ink flows out and the ink circulates. Further, the ink inflow amount is more preferably larger than the maximum value of the amount of ink discharged from the head (maximum ink discharge amount described later), and more preferably twice or more the maximum ink discharge amount. It is even more preferable that the maximum ink discharge amount is 2.5 times or more.
When the ink inflow amount is within the above range, the ejection amount stability is further improved. on the other hand,
The upper limit of the ink inflow amount is not particularly limited, but may be four times or less the maximum ink discharge amount. The amount of ink ejected from the head, that is, the ink inflow amount and the maximum ink ejection amount are both volume-based amounts.

The ink supply process can be performed, for example, by providing a device for adjusting an ink supply amount (hereinafter also simply referred to as “ink supply device”) in an ink jet recording apparatus described later. The ink supply device will be described later.

[Curing process]
The curing step included in the recording method of the present embodiment cures the ultraviolet curable ink adhering to the recording medium when irradiated with ultraviolet rays (light) from a light source. In this step, the photopolymerization initiator contained in the ink is decomposed by irradiation with ultraviolet rays, and radicals, acids,
And an initiation species such as a base, and the polymerization reaction of the photopolymerizable compound is promoted by the function of the initiation species. Alternatively, in this step, the polymerization reaction of the photopolymerizable compound is initiated by irradiation with ultraviolet rays. At this time, if the sensitizing dye is present together with the photopolymerization initiator in the ink, the sensitizing dye in the system absorbs ultraviolet rays to be in an excited state, and promotes decomposition of the photopolymerization initiator by contacting with the photopolymerization initiator. And a more sensitive curing reaction can be achieved.

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

As described above, the ultraviolet curable ink in the present embodiment can be suitably used regardless of whether the light source is an LED or a metal halide lamp, but an LED is particularly preferable.

The emission peak wavelength of the light source (ultraviolet source) is preferably in the range of 360 to 420 nm,
A range of 380 to 410 nm is more preferable. When the emission peak wavelength is within the above range, UV
-It is suitable because it is easy to obtain LEDs and is inexpensive.

The light source having an emission peak wavelength in the range (preferably LED) peak intensity (illumination peak intensity) of ultraviolet light emitted from, preferably 800 mW / cm ² or more, more preferably 1,000 mW / cm ² That's it. The upper limit of the irradiation peak intensity is not particularly limited, but is preferably 3,000 mW / cm ² or less. When the irradiation peak intensity is within the above range, the curability is further improved and the generation of curing wrinkles can be more effectively suppressed. The principle of occurrence of curing wrinkles is presumed as described above. However, if the irradiation peak intensity is within the above range, the coating surface can be cured at the same time as the coating surface, and ultraviolet rays are effective in generating curing wrinkles. It is estimated that it can be suppressed. When the viscosity at 28 ° C. of the ultraviolet curable ink in the present embodiment is 8 mPa · s or more, generation of curing wrinkles can be more effectively prevented. In particular, when the ultraviolet curable ink contains a vinyl ether group-containing (meth) acrylic acid ester represented by the general formula (1) described later, and the irradiation peak intensity is within the above range, the curability is further improved, and The generation of cured wrinkles can be more effectively suppressed.

In addition, the irradiation peak intensity | strength in this specification is UV intensity meter UM-10, light-receiving part UM-4.
The value measured using 00 (both manufactured by KONICA MINOLTA SENSING, INC.) Is adopted. However, this does not mean that the measurement method of the irradiation peak intensity is limited, and a conventionally known measurement method can be used.

Further, the light source having an emission peak wavelength in the above range, preferably 600 mJ / cm ² or less, more preferably a curable UV-curable ink irradiation energy of 200~500mJ / cm ^2, the recording method of the present embodiment Use it. In this case, it is easy to increase the output of the LED, and low-cost printing and a high printing speed can be realized. Here, said irradiation energy is total irradiation energy which totaled each irradiation energy, when irradiation is performed in multiple times.

The irradiation energy in this specification is calculated by multiplying the time from the start of irradiation to the end of irradiation by the irradiation peak intensity. Moreover, when irradiation is performed over multiple times, said irradiation energy is represented by the irradiation energy amount which totaled multiple times of irradiation. The emission peak wavelength is
There may be one or more than one in the above preferred wavelength range. Even in the case where there are a plurality, the total irradiation energy amount of the ultraviolet light having the emission peak wavelength in the above range is set as the irradiation energy.

Such an ink can be obtained by containing at least one of a photopolymerization initiator that decomposes when irradiated with ultraviolet rays in the wavelength range and a polymerizable compound that starts polymerization when irradiated with ultraviolet rays in the wavelength range.

Further, the discharge amount (attachment amount and driving amount) per unit area at the time of discharge onto the recording medium is preferably 5 to 16 mg / inch ^{2 in} order to prevent wasteful use of the ink.

Further, the ink discharge amount per unit area varies depending on the recording resolution and the amount of ink applied per recording unit area (pixel) defined by the recording resolution, but the recording resolution (printing resolution) is set to “sub-scanning direction”. Resolution × resolution in the direction crossing the sub-scanning direction (main scanning direction) ”
In this case, 300 dpi × 300 dpi to 1500 dpi × 1500 dpi is preferable.
Then, it is preferable to adjust the nozzle density and the discharge amount of the head according to the recording resolution.
The discharge amount of ink per pixel is preferably 2 to 200 ng / pixel, and 3 to 160.
ng / pixel is more preferred. The nozzle density (distance between nozzles in the nozzle row) is 1
80 to 720 dpi is preferable, and 300 to 720 dpi is more preferable.

As described above, according to the present embodiment, the durability of the head, the discharge stability and the discharge amount stability (short term and long term) of the ultraviolet curable ink, and the photopolymerization initiator contained in the ultraviolet curable ink are further improved. The ink jet recording method can be provided which is excellent in the solubility of UV light, the curability of the ultraviolet curable ink, and the suppression of curing wrinkles.

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

FIG. 1 is a block diagram showing an example of the configuration of the ink jet recording apparatus of the present embodiment.
A printer driver is installed in the computer 130, and print data corresponding to the image is output to the printer 1 in order to cause the printer 1 to record an image. The printer 1 includes a transport unit 20, a head unit 30, an irradiation unit 40, an ink supply unit (not shown), a detector group 110, a memory 123, and an interface (I / F) 1.
21 and a controller 120. The printer 1 that has received the print data from the computer 130, which is an external device, controls each unit by the controller 120, and records an image on a recording medium according to the print data. The situation in the printer 1 is monitored by the detector group 110, and the detector group 110 sends the detection result to the controller 120.
Output to. The controller 120 controls each unit based on the detection result output from the detector group 110. The controller 120 stores print data input via the interface 121 in the memory 123, and the CPU 122 and the unit control circuit 124.
And have. The memory 123 also stores control information for controlling each unit.

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 ink jet recording apparatus, includes a line head having a length equal to or greater than the length corresponding to the width of a recording medium as a head. The line head and the recording medium move from the line head to the recording medium while moving relative to each other in the scanning direction intersecting the width direction, that is, to the recording medium scanned relative to the line head. Is discharged. In the line printer, the head is fixed without moving (almost) and recording is performed in one pass (single pass). Line printers are more advantageous than serial printers because of their high recording speed.

Here, the above-mentioned “line head having a length corresponding to the width of the recording medium” is not limited to the case where the width of the recording medium and the length (width) of the line head completely match each other. May be different. For example, the length (width) of the line head may be different from each other.
Is a length corresponding to the width (recorded width) of the recording medium on which ink should be ejected (image should be recorded).

On the other hand, a serial printer, which is a serial inkjet recording apparatus, performs main scanning (pass) in which ink is ejected while the head moves in the main scanning direction intersecting the sub-scanning direction of the recording medium, and usually two or more passes. (Multi-pass) is used for recording.

[Inkjet head]
The head unit 30 included in the inkjet recording apparatus (printer 1) includes a head (inkjet head) that performs recording by discharging ultraviolet curable ink toward a recording medium. The head includes a cavity for ejecting the stored ink from the nozzle, an ejection driving unit provided for each of the cavities for applying ejection driving force to the ink, and a head of the head provided for each of the cavities. And at least a nozzle for ejecting ink to the outside. A plurality of cavities, and ejection drive units and nozzles provided for each cavity may be provided in one head independently of each other. The ejection drive unit is formed using an electromechanical conversion element such as a piezoelectric element that changes the volume of the cavity by mechanical deformation, or an electrothermal conversion element that generates and discharges bubbles in ink by generating heat. be able to. The ink jet recording apparatus may have one head or a plurality of heads for each color ink. In particular, in the case where a plurality of heads are provided, the line head may be configured by arranging a plurality of heads in the width direction of the recording medium, whereby the above-described recording width can be further increased. In the case where recording is performed using a plurality of colors of ink, the ink jet recording apparatus includes a head for each ink. Here, the head included in the serial printer or the line printer that is the printer of the present embodiment is preferably a head that uses an epoxy resin in at least a part of the inside or the surface of the head that comes into contact with the ink. The epoxy resin can be used, for example, as an adhesive that bonds the members of the head when the head is manufactured. By setting the head using such an epoxy resin adhesive, it is possible to maintain a strong adhesive force between the head members even when the temperature of the head is changed. The above-mentioned “in contact with ink” includes direct contact with ink or indirect contact by permeation of ink components. At this time, the ultraviolet curable ink in this embodiment can prevent the epoxy resin adhesive from swelling, so that deterioration including alteration is less likely to occur, so that the durability of the head is excellent. In this way, the ultraviolet curable ink can be suitably discharged from the head using an epoxy resin adhesive.

Examples of the epoxy resin adhesive include, but are not limited to, a conventionally known adhesive in which a main agent including a compound having an epoxy group is cured by a curing agent. 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, for example, amines such as amines and polyamines, acid anhydrides, amides such as 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 in terms of mass.
˜1: 10 is preferred. The head can be configured, for example, as shown in FIG. 3 of JP-A-2009-279830.

Hereinafter, the printer of this embodiment will be described in more detail with reference to the drawings. 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.

[Line printer]
FIG. 2 is a schematic cross-sectional view illustrating an example of the periphery of the head unit, the transport unit, and the irradiation unit in the above-described line printer that is an example of the printer of the present embodiment.

A transport motor (not shown) rotates a transport roller including the upstream roller 25A and the downstream roller 25B, and the transport drum 26 is driven. The recording medium S is conveyed along the rotation of the conveyance roller along the circumferential surface of the conveyance roller and the conveyance drum 26. Transport drum 2
6, heads including a head K, a head C, a head M, and a head Y are arranged to face the transport drum 26, and ink is ejected and adhered to the recording medium S facing the heads. Recording is performed by a discharge process. On the downstream side in the transport direction of each head, a temporary curing irradiation unit 42 is provided.
a, 42b, 42c, and 42d are arranged, and the recording medium S is irradiated with ultraviolet rays.
A main curing irradiation unit 44 is disposed further downstream in the transport direction. Such a recording apparatus can be configured as shown in FIG. 11 of Japanese Patent Application Laid-Open No. 2010-269471, for example.

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. Here, when simply referred to as “curing” in the present specification, this curing is meant unless otherwise specified.

In addition, since it is only necessary that the main curing irradiation unit 44 is irradiated with ultraviolet rays and the ink is finally cured, the preliminary curing irradiation units 42a, 42b, 42c, and 42d are not irradiated with ultraviolet rays from some or all of them. The curing process may be terminated by irradiating with ultraviolet rays from the main curing irradiation unit 44. As described above, the curing step may perform only the main curing without performing the temporary curing.

[Ink supply device]
As described above, the ink supply unit of the ink jet recording apparatus according to the present embodiment may include a device (ink supply device) that adjusts the ink supply amount. The ink supply amount adjustment step described above can be performed, for example, by providing an ink supply device in an ink jet recording apparatus described later. The ink supply device is provided, for example, between an ink container such as an ink tank or an ink cartridge and a head. The ink supply device has an ink circulation path in at least a part of the ink path for supplying ink from the ink container to the head, thereby adjusting the amount of ink flowing into the head. More specifically,
The ink supply device first adjusts the inflow amount of ink supplied from the ink circulation path to the head. Secondly, the ink supply device causes at least a part of the flow rate to eject ink from the head (
This discharged amount is the discharge amount), and the remainder of the flow rate (ink outflow amount) can be returned from the head to the ink circulation path. Therefore, for example, if the inflow amount of ink supplied to the head is greater than or equal to the amount of ink ejected from the head (ink ejection amount), the ink flows out of the head and returns to the ink circulation path, and the ink circulates. If the ink inflow amount is twice or more the ink discharge amount, the ink outflow amount is one or more times the ink discharge amount.

Hereinafter, the ink supply device will be described with reference to the drawings. FIG. 3 is a schematic front view showing an example of the ink supply device 10 provided in the ink jet recording apparatus of the present embodiment.

(1. Device configuration)
The ink supply device 10 is located between the ink cartridge 50 and the head 60 in the ink jet recording apparatus. The ink supply device 10 includes an ink cartridge 50
An ink path 51 including an ink circulation path 80, a sub tank 70, a heating mechanism 90, a deaeration mechanism 100, and a head 60. The head 60 also belongs to the head unit 30 described above.

The ink cartridge 50 is for containing ultraviolet curable ink. The holder 52 is for mounting the ink cartridge 50. The ink path 51 is a flow path including the ink circulation path 80 through which ink passes from the ink cartridge 50 to the head 60. In other words, at least a part of the ink path 51 that supplies ink from the ink cartridge 50 that is an ink container to the head 60 is the ink circulation path 80 that circulates the ink. In the ink path 51, the pipe between the ink cartridge 50 and the sub tank 70 is
A holder 52, a valve 53, a supply pump 54, and a filter 55 are provided.
The valve 53 is configured to open when the ink cartridge 50 containing ink is attached to the holder 52. The supply pump 54 pushes ink from the ink cartridge 50 to the ink path 51 when the valve 53 is opened. The ink path 51 supplies the ink pushed out from the ink cartridge 50 by the supply pump 54 to the sub tank 70 through the filter 55 that filters foreign matter in the ink. The pressurizing pump 56 pressurizes the sub tank 70 and supplies ink from the sub tank 70 to the ink circulation path 80.

In the sub tank 70, the liquid amount sensor 71 detects the ink amount in the sub tank 70, and
The ink is supplied to the ink circulation path 80 when the liquid amount is equal to or higher than the predetermined first liquid amount, and the ink is received from the ink cartridge 50 when the liquid amount is equal to or lower than the predetermined second liquid amount.

The ink circulation path 80 communicates with the sub tank 70 and the head 60, and ink is supplied from the sub tank 70 to supply the ink to the head 60. Ink circulation path 8
Reference numeral 0 is a pipe having a filter 81, a circulation pump 82, and a head filter 83. The ink supplied from the sub tank 70 is supplied to the ink circulation path 80 by the circulation pump 82.
Circulate. The filter 81 is provided downstream of the circulation pump 82 in the ink circulation path 80, and filters foreign matter in the ink. A part of the ink circulation path 80 is provided in the head 60, and at least a part of the circulated ink is ejected from the head 60 through a head filter 83 that filters foreign matter in the ink.

The heating mechanism 90 and the deaeration mechanism 100 are located in the middle of the ink circulation path 80, that is, between the sub tank 70 and the head 60, respectively.

The heating mechanism 90 is provided at a position other than at least the position connected to the head 60 in the ink circulation path 80. Here, the “position where the ink circulation path 80 is connected to the head 60” corresponds to a coupling portion of the ink circulation path 80 outside the head 60 in FIG. The heating mechanism 90 converts the hot water in the hot water tank 91 by the hot water circulation pump 92 to the temperature control module 9.
4 and the hot water tank 91, while the temperature control module 94 circulates the ink circulation path 80.
The ink is heated. The heater 93 of the hot water tank 91 adjusts the temperature of the circulating ink to a target temperature.

The deaeration mechanism 100 is provided downstream of the temperature control module 94 in the ink circulation path 80 and upstream of the head 60. The deaeration module 102 includes a deaeration chamber (in which ink flows)
(Not shown) and a decompression chamber (in contact with the deaeration chamber through a separation membrane that does not allow liquid such as ink to pass through)
(Not shown). The negative pressure pump 101 depressurizes the decompression chamber. When the decompression chamber is depressurized, the amount of dissolved air in the ink circulation path 80 is reduced and bubbles are removed. In this way, the degassing mechanism 100 degass the ink in the ink circulation path 80.

The head 60 is for ejecting ink toward the recording medium. The head 60 includes a nozzle (not shown) for discharging ink, a nozzle plate having a nozzle surface on which the nozzle is formed, a cavity (not shown) communicating with the nozzle and containing ink, and a reverse flow of ink. A reservoir (not shown) to be prevented, and a discharge drive unit (see FIG. 5) for forming a droplet of ink suitable for discharge by applying a discharge driving force to the ink contained in the cavity and discharging the droplet from the nozzle Not shown). In FIG. 3, for example, the cavity is a pressure generating chamber, and the ejection driving unit is a piezoelectric element. The cap 61 protects the nozzles of the head 60 in order to prevent the ink adhering to the vicinity of the nozzles from drying when the recording apparatus is not used.

In FIG. 3, four heads 60 are provided in parallel in the ink circulation path 80. Thus, it is preferable that there are a plurality of heads 60 to which ink is supplied from the ink circulation path 80, and ink is ejected from the plurality of heads 60. In this case, as will be described later, since there is one ink circulation path 80 for the plurality of heads 60, the ink circulation path 80 and the temperature control module 94 are made common to supply ink to the four heads 60. Can be made uniform, and the cost of the recording apparatus can be reduced.
As demonstrated in the examples described later, according to the recording apparatus of this embodiment, the ink inflow amount is set to a predetermined value even when a plurality of heads are provided and the recordable width is increased. Therefore, the discharge amount stability is excellent.

(2. Operation of the device)
First, ink is initially filled. When the ink cartridge 50 containing the ink is mounted in the holder 52, the valve 53 is opened, and the ink is supplied by the supply pump 54.
The ink is supplied to the sub tank 70 through a filter 55 that filters out foreign matters of ink. When the liquid level sensor 71 detects that the ink level in the sub tank 70 has become equal to or higher than the predetermined first level, the supply pump 54 is stopped and the valve 53 is closed. The sub tank 70 is pressurized by the pressurizing pump 56, and ink is supplied from the sub tank 70 to the ink circulation path 80. Here, before the ink circulation path 80 is completely filled with ink, if the liquid amount in the sub tank 70 falls below a predetermined second liquid amount (that is, an amount smaller than the predetermined first liquid amount), The pressurizing pump 56 is stopped and the sub tank 70 is returned to normal pressure. Then, in the same manner as described above, ink is supplied again from the ink cartridge 50 to the sub tank 70, and ink is supplied again from the sub tank 70 to the ink circulation path 80. By repeating such an operation, the ink circulation path 8
When the ink is completely filled to 0, the pressurizing pump 56 is stopped, the sub tank 70 is returned to the atmospheric pressure, and the liquid amount in the sub tank 70 is set again from the ink cartridge 50 so that the liquid amount becomes equal to or higher than the predetermined first liquid amount. Ink is supplied to the sub tank 70. In this way, the initial ink filling is completed.

When the initial ink filling is completed, the ink is circulated through the ink circulation path 80 by the circulation pump 82. The warming mechanism 90 in which the heater 93 is turned on in advance circulates the warm water in the warm water tank 91 between the temperature control module 94 and the warm water tank 91 by the warm water circulation pump 92. Then, the temperature control module 94 heats the ink circulating in the ink circulation path 80. A filter 81 provided downstream of the circulation pump 82 in the ink circulation path 80 filters ink foreign matter. The deaeration module 102 in the deaeration mechanism 100 includes a deaeration chamber (not shown) through which ink flows, and a decompression chamber in contact with the deaeration chamber through a separation membrane that does not pass a liquid such as ink through a gas such as air. (Not shown). When the decompression chamber is decompressed by the negative pressure pump 101, bubbles and dissolved air contained in the ink in the deaeration chamber escape to the decompression chamber through the separation membrane, so that the amount of dissolved air in the ink in the ink circulation path 80 decreases. Bubbles are removed. Since four deaeration modules 102 are provided in parallel, the deaeration efficiency is increased, and the ink can be deaerated while performing ink circulation. By providing the deaeration mechanism 100 on the downstream side of the temperature control module 94, it is possible to perform deaeration at a position where the ink temperature is highest in the ink circulation path 80. Therefore, the deaeration efficiency of the ink is very high, and the deaeration module 102 is located downstream of the circulation pump 82, so that the ink can be deaerated at a position where the pressure of the ink is high, and the deaeration efficiency is remarkably increased. can do.

In the ink circulation path 80, four heads 60 are provided in parallel. Head 6
In the ink circulation path 80 in 0, a reservoir (not shown) is provided on the downstream side of the head filter 83 that filters foreign matters of ink. The ink that has flowed into the head and passed through the reservoir flows out of the head 60 again, and the ink that has flowed out of each head 60 joins at the coupling portion of the ink circulation path 80 and returns to the sub tank 70. Reservoir is 600 per head
Each pressure generating chamber is connected to a pressure generating chamber (not shown) provided individually, and a piezoelectric element (not shown) provided for each chamber is individually driven to The volume can be changed. Further, a nozzle (not shown) is provided for each pressure generating chamber, and ink can be ejected from the nozzle to the outside. Since the ink supply device is common to the four heads, the four heads 6 can be obtained by making the ink circulation path 80 and the temperature control module 94 common.
The temperature of the ink supplied to 0 can be made uniform, and the cost of the recording apparatus can be reduced. The ink returned to the sub tank 70 is circulated again to the ink circulation path 80. When assembling the head 60 by bonding the members constituting the reservoir, the above-described epoxy resin adhesive is used. In FIG. 3, the ink circulation path 80 passes through the head 60, but the ink circulation path passes outside the head without passing through the head and passes outside the head. Ink may be supplied to a reservoir in the head. In this case, the ink circulates up to the ink circulation path that passes outside the head. However, also in this case, ink flowing into the ink circulation path is ink flowing into the head, and ink flowing out from the ink circulation path is ink flowing out from the head.

Subsequently, preparations are made before starting printing. The ink is circulated for 15 minutes, and the ink circulation path 8
Stabilize the ink temperature within zero. The ink temperature is detected as a nozzle temperature by a temperature sensor (not shown) provided in the vicinity of the nozzle, and is adjusted to the target temperature before and during printing by controlling the heater 93 of the hot water tank 91. ing. When the printing preparation is completed, the piezoelectric elements are individually driven to discharge ink from the nozzles and printing is started.

As described above, the amount of ink flowing into the ink circulation path 80 is preferably larger than the amount of ink discharged from the head during printing. In order to achieve such a relationship between the ink inflow amount and the discharge amount, it is preferable that the ink inflow amount be larger than the above-described maximum ink discharge amount. Further, as described above, the ink inflow amount is more preferably larger than the maximum ink discharge amount,
More preferably, it is twice or more the maximum ink discharge amount. The amount of ink flowing into the head 60 from the ink circulation path 80 is A (mL / min), and all the nozzles of all the heads 60 are driven at the maximum driving frequency during printing, and can be discharged during printing. The maximum ink discharge amount B (mL / min), which is the discharge amount when ink is discharged with the maximum amount of ink, the head 6
Let C (mL / min) be the ink outflow amount flowing out from the head 60 to the ink circulation path 80 when 0 is ejecting at the maximum ink ejection amount. At this time, it is set to satisfy the following mathematical formula (A).

    A ≧ 2B = 2 (AC) (A)

The ink temperature and the deaeration degree can be further stabilized by setting the ink inflow amount to satisfy the above formula (A) and circulating the ink. In addition, by performing such printing preparation, it is possible to stabilize the ink temperature and the degree of deaeration already before the start of printing. The maximum discharge amount of the head can be the above-described maximum ink discharge amount. However, the actual discharge amount during printing can change depending on the discharge state, such as whether or not each nozzle is driven according to the image to be recorded, and the actual ink outflow amount can also change according to this change. . The setting information regarding the ink inflow amount is determined in advance based on the maximum ink discharge amount of the ink jet recording apparatus and stored in the memory 123 and the like. The controller 120 controls the ink inflow amount based on the information. Is called. The maximum ink discharge amount may be grasped by performing discharge under the above-described conditions. When the maximum ink discharge amount per head 60 is D (mL / min), “B = 4D”. During printing, the amount of liquid in the sub tank 70 is gradually consumed as ink is ejected. Therefore, the ink is always supplied to the sub tank 70 by the supply pump 54 during printing so that the liquid amount in the sub tank 70 is always equal to or larger than the predetermined first liquid amount. Although not provided with the ink supply device 10 shown in FIG. 3, in order to stabilize the ink temperature during printing, the temperature adjustment module is provided at an arbitrary position in the ink path 51 between the supply pump 54 and the sub tank 70. May be further provided.

Thus, according to the present embodiment, the photopolymerization initiator included in the ultraviolet curable ink is excellent in the durability of the head, the discharge stability and the discharge amount stability (short term and long term) of the ultraviolet curable ink. It is possible to provide an ink jet recording apparatus that uses an ink jet recording method that is excellent in the solubility of UV light, the curability of ultraviolet curable ink, and the suppression of curing wrinkles.

[UV curable ink]
In addition, an embodiment of the present invention relates to an ultraviolet curable ink that can be used in the ink jet recording method and the ink jet recording apparatus of the above embodiment. As described above, the ultraviolet curable ink is characterized in that the viscosity at 28 ° C., the discharge temperature, and the viscosity at the temperature are in a predetermined range. The ink for setting the viscosity in a predetermined range can be designed by the ink design method as described above.

Hereinafter, additives (components) included in the ultraviolet curable ink of the present embodiment (hereinafter also simply referred to as “ink”) or which may be included as desired will be described.

(Polymerizable compound)
The polymerizable compound contained in the ink of the present embodiment 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. As other polymerizable compounds, conventionally known various monomers and oligomers such as monofunctional, bifunctional, and trifunctional or more polyfunctional can be used. As the monomer, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, their salts or esters, urethanes, amides and anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated Examples include 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.

Among these, an ester of (meth) acrylic acid, that is, (meth) acrylate is preferable. Among the (meth) acrylates, containing a vinyl ether group represented by the general formula (I) (
At least one of (meth) acrylic acid esters and other monofunctional (meth) acrylates is preferable, the vinyl ether group-containing (meth) acrylic acid esters are more preferable, the vinyl ether group-containing (meth) acrylic acid esters and Other monofunctional (
More preferred is (meth) acrylate.
Hereinafter, the polymerizable compound will be described in detail with a focus on these (meth) acrylates.

(1. Vinyl ether group-containing (meth) acrylic acid esters)
The ink of the present embodiment preferably contains a vinyl ether group-containing (meth) acrylic acid ester represented by the following general formula (I).
_{^{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 contains the vinyl ether group-containing (meth) acrylic acid esters, the ink can be reduced in viscosity, and the ink curability can be excellent.
And generation | occurrence | production of hardening wrinkles can be prevented effectively. 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 10 to 60% by mass, and still more preferably 20 to 50% by mass with respect to the total mass (100% by mass) of the ink. . When the content is not less than the above lower limit, the viscosity of the ink can be lowered and the curability of the ink can be further improved. On the other hand, when the content is not more than the above upper limit value, the storage stability of the ink can be maintained in a good state, and the generation of curing wrinkles can be more effectively prevented.

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.

(2. Monofunctional (meth) acrylate)
The ink of this embodiment preferably contains a monofunctional (meth) acrylate. here,
When the ink of this embodiment contains the above-mentioned vinyl ether group-containing (meth) acrylic acid esters (however, only those that are monofunctional (meth) acrylates), the vinyl ether group-containing (meth) acrylic acid esters are also included. Although it shall be contained in the said monofunctional (meth) acrylate, description about the said vinyl ether group containing (meth) acrylic acid ester is abbreviate | omitted. Below, monofunctional (meth) acrylates other than the above-mentioned vinyl ether group containing (meth) acrylic acid esters are demonstrated. When the ink contains the monofunctional (meth) acrylate, the viscosity of the ink can be reduced, and the solubility of the photopolymerization initiator and other additives and the curability of the ink are both excellent. . Furthermore, due to the excellent solubility of the photopolymerization initiator and other additives, the ink ejection stability is excellent, and the toughness, heat resistance, and chemical resistance of the coating film are also improved. Increases nature.

Examples of the monofunctional (meth) acrylate include phenoxyethyl (meth) acrylate, isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate,
Isomyristyl (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) Acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, lactone-modified flexible (meth) acrylate, t- butyl cyclohexyl (meth) acrylate,
Dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated nonylphenyl (meth) acrylate, alkoxylated nonylphenyl (meth) acrylate, p-cumylphenol EO
Modified (meth) acrylate.

Among these, monofunctional (meth) acrylates having an aromatic ring skeleton in the molecule are preferable because they are more excellent in curability, storage stability, and solubility of the photopolymerization initiator. Examples of monofunctional (meth) acrylates having an aromatic ring skeleton include, but are not limited to, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyphenoxypropyl (meth) acrylate, and phenoxydiethylene glycol (meth) ) Acrylate is preferred. Among these, since the viscosity of the ink can be reduced and the curability, abrasion resistance, adhesion, and solubility of the photopolymerization initiator can be excellent, phenoxyethyl ( At least one of meth) acrylate and benzyl (meth) acrylate is preferable, and phenoxyethyl (meth) acrylate is more preferable.

Monofunctional (meth) acrylates other than the vinyl ether group-containing (meth) acrylic acid esters may be used alone or in combination of two or more.

The content of the monofunctional (meth) acrylate other than the vinyl ether group-containing (meth) acrylic acid esters is preferably 10 to 75% by mass, and 10 to 55% by mass with respect to the total mass (100% by mass) of the ink. More preferably, 10-40 mass% is further more preferable. When the content is not less than the above lower limit value, the solubility of the photopolymerization initiator is further improved in addition to the curability. On the other hand, when the content is not more than the above upper limit value, in addition to curability, adhesion is further improved.

In addition, the ink is a vinyl ether group-containing (meth) acrylic acid ester (however,
Limited to monofunctional (meth) acrylates. ), The total content of the monofunctional (meth) acrylates containing this is 35 to 90 with respect to the total mass (100% by mass) of the ink.
% By mass is preferable, and 40 to 70% by mass is more preferable. When the content is within the above range, the ink viscosity, specifically, the ink viscosity at 28 ° C. and the ink viscosity at the discharge temperature can be easily set in the desired range described above.

(3. Polymeric compounds other than the above)
The ink of the present embodiment may further contain a polymerizable compound other than the above (hereinafter referred to as “other polymerizable compound”). Examples of other polymerizable compounds include the monomers and oligomers described above, and among these, (meth) acrylates having 2 or more functional groups are preferable.

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

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

  Other polymerizable compounds may be used alone or in combination of two or more.

When other polymerizable compounds are contained in the ink, the content thereof is the total mass of the ink (10
0 to 50% by mass is preferable with respect to 0% by mass). In particular, when the ink contains a bifunctional (meth) acrylate, the content of the bifunctional (meth) acrylate is equal to the total mass of the ink (100
To 50% by mass, and more preferably 10 to 45% by mass. When the content is within the above range, the ink curability and the rub resistance of the cured product are excellent, and the ink viscosity can be easily designed to a desired viscosity. In addition, a monofunctional (meth) acrylate having a relatively low viscosity of the polymerizable compound, particularly the above-mentioned vinyl ether group-containing (meth) acrylic acid ester having a low viscosity, and other polymerizable compounds having a relatively high viscosity, Are preferably combined. This makes it easy to design the ink viscosity to a desired viscosity.

Although it is possible to omit the addition of a photopolymerization initiator by using a photopolymerizable compound as the polymerizable compound, the use of a photopolymerization initiator can easily adjust the start of polymerization. Can be preferred.

(Photopolymerization initiator)
The ink of this embodiment may 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) in the light, excellent safety,
In addition, the cost of the light source lamp can be reduced. As long as it generates active species such as radicals and cations by the energy of ultraviolet rays and initiates polymerization of the polymerizable compound,
Although there is no restriction | limiting, A photoradical polymerization initiator and a photocationic polymerization initiator can be used, It is preferable to use a photoradical polymerization initiator especially.

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

Among these, an acylphosphine oxide compound is preferable because the curability of the ink can be further improved.

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.

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, trade name manufactured by BASF), KAYACURE DETX-S (2
, 4-Diethylthioxanthone) (trade name, manufactured by Nippon Kayaku Co., Ltd.)
, Speedcure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Speedcure DETX (2,4-diethylthioxanthen-9-one) (above, Lambson product name), Lucirin TPO, LR8883
, LR8970 (trade name, manufactured by BASF) and Ubekrill P36 (trade name, manufactured by UCB).

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

The content of the photopolymerization initiator can improve the ultraviolet curing rate and have excellent curability, and in order to avoid undissolved photopolymerization initiator and coloring derived from the photopolymerization initiator, It is preferably 20% by mass or less with respect to the total mass (100% by mass) of the ink.

In particular, when the photopolymerization initiator includes an acyl phosphine oxide compound, the content thereof is more preferably 5 to 15% by mass, and 7 to 13% by mass with respect to the total mass (100% by mass) of the ink. % Is more preferable. When the content is not less than the above lower limit, the curability is further improved. More specifically, in particular, LEDs (preferred emission peak wavelength: 360
Since a sufficient curing rate can be obtained upon curing by nm to 420 nm), the curability is further improved. On the other hand, when the content is not more than the above upper limit value, the solubility of the photopolymerization initiator is further improved.

[Fluorescent brightener]
The ink of this embodiment may contain a fluorescent brightener (sensitizer). Optical brighteners are UV
It can absorb light having a wavelength in the vicinity of 300 to 450 nm that is visible in the shortwave, and 400
It is a colorless or weakly colored compound capable of emitting fluorescence having a wavelength of about 500 nm. The fluorescent whitening agent is a fluorescent whitening agent (Fluorescent Whiting Agent).
Also known as t). A description of the physical principles and chemistry of optical brighteners can be found in Ullman
n's Encyclopedia of Industrial Chemistry, S
ixth Edition, Electronic Release, Wiley-VCH
1998.

When the ink of this embodiment contains a fluorescent brightening agent, the curability can be further improved.

Examples of fluorescent brighteners include, but are not limited to, naphthalene benzoxazoyl derivatives such as 1,4-bis- (2-benzoxazoyl) naphthalene, 2,5-thiophenediylbis (5-tert-butyl- Thiophenebenzoxazoyl derivatives such as 1,3-benzoxazole), stilbene benzoxazoyl derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives, stilbene derivatives, styryl derivatives of benzene and biphenyl, bis (benzazol-2-yl) derivatives , Carbostyril, naphthalimide, derivatives of dibenzothiophene-5,5′-dioxide, pyrene derivatives, and pyridotriazole.

Commercially available products of optical brighteners include, for example, Hostalux KCB (Clariat (Claria
nt) product name, 1,4-bis- (2-benzoxazoyl) naphthalene), TINOP
ALOB (BASF brand name, 2,5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole)) and the like can be mentioned.

A fluorescent brightener may be used alone or in combination of two or more. The fluorescent brightening agent is preferably 0.1 to 0.5% by mass with respect to the total mass (100% by mass) of the ink. When the content is within the above range, the influence on the hue of the cured film, which can be exerted by the fluorescent whitening agent itself, can be reduced.

[Color material]
The ink of this embodiment may include a color material. As the color material, at least one of a pigment and a dye can be used.

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

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

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

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

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

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

Examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, 2, 3, 1
5, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25,
60, 65, 66, C.I. I. Bat Blue 4, 60.

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

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

When the above pigment is used, the average particle size is preferably 300 nm or less, and 50 to 20
0 nm is more preferable. When the average particle diameter is in the above range, the ink can be more excellent in reliability such as ejection stability and dispersion stability, and an image with excellent image quality can be formed. Here, the average particle diameter in the present specification is measured by a dynamic light scattering method.

(2. Dye)
A dye can be used as the coloring material. The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9
45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct yellow 1,12,24,33,50,55,58
86, 132, 142, 144, 173, C.I. I. Direct red 1, 4, 9, 8
0, 81, 225, 227, C.I. I. Direct blue 1, 2, 15, 71, 86, 8
7, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51,
71,154,168,171,195, C.I. I. Reactive Red 14, 32, 5
5, 79, 249, C.I. I. Reactive black 3, 4, and 35 are mentioned.

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

The content of the color material is excellent in concealment and color reproducibility, so that the total mass of ink (100
1-20 mass% is preferable with respect to the mass%).

[Dispersant]
When the ink of this embodiment includes a pigment, a dispersant may be included in order to improve pigment dispersibility. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used for preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned. Specific examples include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, sulfur-containing polymers, fluorine-containing polymers, and epoxies. The thing which has 1 or more types of resin as a main component is mentioned. Commercially available polymer dispersants include Ajinomoto Fine Techno Co., Ltd. Ajisper series (trade name), Solsperse series (Solsperse 32000, 36000 available from Avecia Co.), etc.
As mentioned above, the Dispersic series (trade name) manufactured by BYK Chemie, and the Disparon series (trade name) manufactured by Enomoto Kasei Co., Ltd. can be mentioned.

A dispersing agent may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the dispersant is not particularly limited, and a preferable amount may be added as appropriate.

(Polymerization inhibitor)
The ink of this embodiment may contain a polymerization inhibitor. When the ink contains a polymerization inhibitor, the polymerization reaction of the polymerizable compound before curing can be prevented.

Although it does not restrict | limit especially as a polymerization inhibitor, For example, a phenol type polymerization inhibitor is mentioned. Examples of the phenol-based polymerization inhibitor include, but are not limited to, for example, p-methoxyphenol, cresol, t-butylcatechol, di-t-butylparacresol, hydroquinone monomethyl ether, α-naphthol, 3,5-di- t-butyl-4-hydroxytoluene, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene -Bis (4-ethyl-6-butylphenol) and 4,4'-thio-bis (3-methyl-6-tert-butylphenol).

Examples of commercially available phenol-based polymerization inhibitors include p-methoxyphenol (trade name, p-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.).
Non-flex MBP (Seiko Chemical Co., Ltd. trade name, 2, 2 '
-Methylene-bis (4-methyl-6-tert-butylphenol)), BHT Swanox (
Seiko Chemical Co., Ltd. trade name, 2,6-di-t-butyl-4-methylphenol).

A polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the polymerization inhibitor is not particularly limited, and a preferable amount may be added as appropriate.

[Surfactant]
The ink of this embodiment may contain a surfactant. Although it does not specifically limit as surfactant, For example, a silicone type surfactant is mentioned. Preferred examples of the silicone surfactant include polyester-modified silicone and polyether-modified silicone, and among these, at least one of polyether-modified polydimethylsiloxane and polyester-modified polydimethylsiloxane is more preferable. Examples of commercially available slip agents include BYK-347, BYK-348, BYK-UV3500, 3510, 3530,
3570 (manufactured by BYK).

Surfactant may be used individually by 1 type and may be used in combination of 2 or more type. The content of the surfactant is not particularly limited, and a preferable amount may be added as appropriate.

[Other additives]
The ink of this embodiment may contain additives (components) other than the additives listed above. Such components are not particularly limited, and may include, for example, conventionally known polymerization accelerators, penetration enhancers, wetting agents (humectants), and other additives. Examples of the other additives include conventionally known fixing agents, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusting agents, and thickeners.

As described above, according to the present embodiment, the inkjet recording method is excellent in the durability of the head, the discharge stability and the discharge amount stability (short term and long term) of the ultraviolet curable ink, and also excellent in suppressing the wrinkle. It is possible to provide an ultraviolet curable ink having excellent curability and solubility of a photopolymerization initiator used in the above.

Hereinafter, the present embodiment will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Materials used]
The materials used in the examples and comparative examples are as shown below.
(Polymerizable compound)
・ 2-MTA (2-methoxyethyl acrylate, OSAKA ORGANIC
CHEMICAL INDUSTRY LTD.) Trade name, monofunctional (meth) acrylate)
・ 4-HBA (4-hydroxybutyl acrylate, trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd., monofunctional (meth) acrylate)
・ VEEA (2- (2-vinyloxyethoxy) ethyl acrylate, Nippon Sangyo (Nippon S
hokubai Co., Ltd.), trade name, monofunctional (meth) acrylate, hereinafter referred to as “VEEA”. )
・ New Frontier PHE (Phenoxyethyl Acrylate, Dai-ichi Kogyo Seiyaku Co., Ltd. (Dai-ic
hi Kogyo Seiyaku Co., Ltd., trade name, monofunctional (meth) acrylate, "PEA"
It was described. )
V # 160 (benzyl acrylate, trade name of Osaka Organic Chemical Industry, monofunctional (meth) acrylate, hereinafter referred to as “BZA”)
・ A-DPH (Tripropylene glycol diacrylate, bifunctional (meth) acrylate, trade name of SHIN-NAKAMURA CHEMICAL CO., LTD., Hereinafter "TPGDA"
It was described. )
SR295 (pentaerythritol tetraacrylate, tetrafunctional (meth) acrylate, trade name of Sartomer Company Inc.)
(Photopolymerization initiator)
・ Lucirin TPO (trade name, manufactured by BASF, hereinafter referred to as “TPO”)
[Fluorescent brightener]
・ Hostalx KCB (1,4-bis- (2-benzoxazoyl) naphthalene, Clariant brand name)
(Polymerization inhibitor)
P-methoxyphenol (trade name, p-methoxyphenol manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as “MEHQ”)
[Surfactant]
BYK-UV3500 (polyether-modified polydimethylsiloxane, manufactured by BYK, hereinafter referred to as “BYK3500”)
[Color material]
Cyanine Blue KRO (CI Pigment Blue 15: 3 (phthalocyanine pigment), SANYO COLOR WORKS, Ltd. trade name, pigment particle size of 80 nm, hereinafter referred to as “Blue 15: 3”. )
[Dispersant]
・ Solsperse 32000 (trade name, manufactured by Avecia, hereinafter “SOL32”)
000 ". )

[Preparation of UV curable inks A to L]
Each material described in Table 1 below was added so that the content (unit: mass%) described in Table 1 was obtained, and this was stirred with a high-speed water-cooled stirrer, whereby ultraviolet curable inks A to L were obtained. Got.

[Measurement / Evaluation Items]
[Ink viscosity rank at 1.28 ° C.]
28 of each ink prepared above using a DVM-E type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.)
The viscosity at 0 ° 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 are as follows. The evaluation results are shown in Table 1 below.
A: It was less than 8 mPa · s.
B: 8 mPa · s or more and 10 mPa · s or less.
C: It was 12 mPa * s or less exceeding 10 mPa * s.
D: It was 15 mPa * s or less exceeding 12 mPa * s.
E: It exceeded 15 mPa * s.

[2. Evaluation of solubility of photopolymerization initiator)
Each ink prepared above was stirred at room temperature for 30 minutes. After stirring, the presence or absence of undissolved photopolymerization initiator was visually observed.
The evaluation criteria are as follows. The evaluation results are shown in Table 1 below. In Table 1, this evaluation column is abbreviated as “initiator solubility”.
A: The undissolved residue of the photoinitiator was not seen.
B: The undissolved residue of the photoinitiator was seen.

[3. (Evaluation of ink curability)
To Lumirror # 125-E20 (trade name, PET film manufactured by Toray Industries, Inc.)
The above inks were applied with a bar coater manufactured by TESTER SANGYO CO., LTD. The applied film thickness was 10 μm after curing. Next, an LED having a peak at a wavelength of 395 nm (Fi
refly [trade name] manufactured by Phoseon Co., Ltd.), irradiation peak intensity 1,000 mW / c
The cured ink film was obtained by irradiating the applied ink with m ² ultraviolet rays for a predetermined time. After irradiation, the surface of the ink coating film was rubbed 20 times with a cotton swab made by Johnson & Johnson under a load of 100 g, and the irradiation energy required until no scratch marks were observed was measured by changing the predetermined time. .
The evaluation criteria are as follows. The evaluation results are shown in Table 1 below.
A: 300 mJ / cm ² or less.
B: It was 400 mJ / cm ² or less exceeding 300 mJ / cm ² .
C: It exceeded 400 mJ / cm < ² >.

The ultraviolet curable inks A, B, C, D, E, F, G, K, and L correspond to inks that can be used as examples, and the ultraviolet curable inks H, I, and J are used as comparative examples. Corresponds to the ink to be produced.
Hereinafter, a recording method in each example and each comparative example will be described.

[Examples 1 to 13, Comparative Examples 2, 4, 5, and 9]
The ink supply device shown in FIG. 3 is provided, and four heads 60 having a length substantially corresponding to the width (recording width) on which an image of a recording medium is to be recorded shown in FIG. 2 are arranged in the width direction. A line printer equipped with a line head was used. The nozzle density of the head was 600 dpi.

The heater provided in the ink circulation device measures the temperature of the nozzle plate with a thermocouple provided on the nozzle plate of the head, and the temperature (discharge temperature) of the ejected ink is shown in Tables 2 to 4 below.
The heating temperature of the heater is adjusted for each of the examples and the comparative examples so that the temperature is described in the above, and the temperature is measured every 5 minutes during 60 minutes of continuous discharge from the head, and the average temperature is measured for each of the examples and comparative examples After confirming that the temperature was reached, the average temperature was used as the ink discharge temperature.

The ink supply device has a diameter of an ink supply pipe for supplying ink to a sub tank and a diameter of an ink pipe of an ink circulation path connecting the sub tank and the head, both 6 mm, the total length of the ink circulation path is 1 m, and the capacity of the sub tank is 100 mL. It was. The maximum ink discharge amount D per head was 10 mL / min, and since four heads were provided, the maximum ink discharge amount B of the ink supply device was 40 mL / min. The ink inflow amount A was set to 80 mL / min, and the ink was circulated with the ink inflow amount. When the ink supply device ejects ink at the maximum ink ejection amount, the ink outflow amount C is 40 mL / min.

Each ink was filled in the head Y of the recording apparatus shown in FIG. The other heads shown in FIG. 2 were not used.

[Comparative Examples 1, 3, 6-8]
Recording was performed in the same manner as in Example 1 except that the heater was turned off and the temperature was not adjusted. At this time, the nozzle temperature was 25 ° C. (ink temperature 25 ° C.).

[Examples 14 to 16, Comparative Example 11]
Recording was performed in the same manner as in Example 1 except that the ink inflow amount A was changed and “ink inflow amount A / maximum ink discharge amount B” was changed to the values described in Tables 3 and 4 below. .

[Comparative Example 10]
Except for the point that the temperature is not adjusted by turning off the heater, the ink inflow amount A is changed, and “ink inflow amount A / maximum ink discharge amount B” is set to the values described in Table 4 below. Recording was performed in the same manner as for 1st grade. At this time, the nozzle temperature was 25 ° C. (ink temperature 25 ° C.
).

[Example 17]
Instead of turning off the heating device in the circulation path, instead of mounting a heater on the head and heating the head, the ink temperature was changed to 33 ° C., the same as in Example 1 above. And recorded.

Note that the heater of the head is one in which a heater is attached to the head as shown in FIG. 2 of Japanese Patent Application Laid-Open No. 2003-200559, and the head including the reservoir is heated.

[Example 18]
Recording was performed in the same manner as in Example 1 except that the number of heads was changed from four to one. Specifically, only one head was ejected, three heads were not ejected, and the inflow of ink was blocked. The ink inflow amount A was twice the discharge amount of one head (10 mL / min). Therefore,
The ink inflow amount A in Example 18 was 20 mL / min.

[Examples 19 to 21]
The irradiation peak intensity in the evaluation of curing wrinkles is 1,000 mW / cm ² to 500 mW / cm ^2.
Recording was performed in the same manner as in Example 1 except that the points were changed.

[Measurement / Evaluation Items]
[1. (Ink viscosity rank during ejection)
Except that the measurement temperature was set to the ejection temperature shown in Tables 2 to 4, the viscosity at the time of ejection of each ink was measured in the same manner as the above-described ink viscosity rank at 28 ° C.
The evaluation criteria are the same as the ink viscosity rank at 28 ° C. described above. The evaluation results are shown in Table 2 below.
To Table 4.

[2. (Discharge stability evaluation)
Evaluation was performed based on the number of non-ejection nozzles when all nozzles of one head were ejected for 5 minutes.
The evaluation criteria are as follows. The evaluation results are shown in Tables 2 to 4 below.
A: The number of non-ejection nozzles was 2 or less.
B: There were 3 to 5 non-ejection nozzles.
X: There were 6 or more non-ejection nozzles.

[3. (Evaluation of short-term discharge volume stability)
Using all the nozzles, the maximum ink discharge amount was discharged for 60 minutes. Install an ink receiver at the bottom of the head and measure the mass of ink ejected from the mass of the ink receiver every 5 minutes during ejection.
The ejection mass per ink droplet was determined from the number of ink droplets ejected to the ink receiver, and the difference between the minimum and maximum ejection mass for 60 minutes was calculated as mass% with respect to the average ejection mass for 60 minutes.
Four heads were provided, and each of the four heads was provided with 600 nozzles, and ejection was performed using all nozzles of all heads. However, in Example 18, one head was evaluated. In addition, non-ejection nozzles due to ejection failure were not treated as ejection nozzles, and the ejected nozzles were measured for ejection mass. The evaluation criteria are as follows. The evaluation results are shown in Table 2 below.
To Table 4.
A: It was 3 mass% or less.
B: It was 5 mass% or less exceeding 3 mass%.
C: It exceeded 5 mass%.

[4. (Evaluation of long-term discharge volume stability)
The short-term evaluation was performed once a day for 10 days, that is, 10 times. And the minimum and the maximum difference of the discharge mass in the said 10 times evaluation (test) with respect to the average of the said 10 times discharge mass were computed by the mass%.
The evaluation criteria are as follows. The evaluation results are shown in Tables 2 to 4 below.
A: It was 3 mass% or less.
B: It was 5 mass% or less exceeding 3 mass%.
C: It exceeded 5 mass%.

[5. Head durability evaluation)
The durability of the head was evaluated by measuring and calculating the swelling rate of the adhesive.
Epoxy resin adhesive (EPIKOTE, an epoxy resin manufactured by Shell)
828 and VERSAMID 125, which is a curing agent manufactured by COGNIS, mixed in an equal amount) were cured to make an adhesive piece, and the weight was measured. Thereafter, the adhesive piece was dipped in each ink placed in a screw tube, capped, and left for 6 months. The temperature during standing was the discharge temperature of each ink described in Tables 2 to 4 below. After leaving, the adhesive piece was taken out and the ink was washed thoroughly, and the weight was measured. And the swelling rate was computed from the following numerical formula.
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 Tables 2 to 4 below.
A: It was less than 50%.
B: It was 50% or more.

[6. (Hardening wrinkle evaluation)
The head and the temporary curing light sources 42a to 42d in FIG. 2 are not used, and 395n is used as the main curing light source.
Place an LED with an irradiation peak intensity of 1000 mW / cm ² having a peak wavelength at m, apply the ink to the film with a bar coater in the same manner as the above-described ink curability evaluation, and transport the film to the main curing light source. Irradiation was performed toward the ink. The irradiation time was adjusted so that the irradiation energy was irradiated until it was cured by the same test method as in the curability test. However, the film thickness after ink curing was 12 μm.
And the surface of the cured film was observed visually. The evaluation criteria are as follows. The evaluation results are shown in Tables 2 to 4 below.
A: Wrinkles were not generated at all.
B: Wrinkles were generated in some areas of the cured film.
C: Wrinkles were generated on the entire surface of the cured film.

Based on the above results, the discharge process includes an ejection process for ejecting an ultraviolet curable ink having a viscosity at 28 ° C. of 8 mPa · s or more, and a curing process for curing the ink. An ink jet recording method (each example) in which the temperature of the ink is 28 to 40 ° C. and the viscosity of the ultraviolet curable ink at the temperature is 15 mPa · s or less,
Compared to other recording methods (comparative examples), the ejection stability, ejection amount stability, and durability of the head are excellent, the solubility of the photopolymerization initiator contained in the ink, the curability of the ink, and It was found that it was excellent in curling wrinkle suppression. Here, there was no difference in curability and curing wrinkles due to the heating temperature. In addition, the larger the value of “ink flow rate / maximum ink discharge amount” in the ink supply device, the better the discharge amount stability. In particular, by making this value more than twice, fluctuations in the discharge amount can be effectively suppressed. I found out that Hereinafter, although considered based on said result, the said consideration does not limit the scope of the present invention at all.

First, when the viscosity of the ink at the time of ejection is 8 to 12 mPa · s, that is, when the evaluation result of the viscosity is “B” or “C”, the recording method using the ink has more ejection stability. Presumed to be excellent. However, the ultraviolet curable ink K is as shown in Table 1 above.
It took a long time to dissolve the photopolymerization initiator, and the solubility of the photopolymerization initiator was slightly inferior. For this reason, it is estimated that the recording method using the ultraviolet curable ink K resulted in a slightly inferior ejection stability due to the precipitation of the photopolymerization initiator.

Further, from the comparison between Example 9 and Comparative Example 9, it is estimated that when the viscosity is 8 mPa · s or more at 28 ° C., the durability of the head is excellent. Further, from the comparison of Example 2 and Example 14, the comparison of Example 8 and Example 15, and the comparison of Example 11 and Example 16, the ink used and the discharge temperature were the same, but “ink inflow / It is estimated that the example in which the value of “maximum ink discharge amount” is larger is superior in discharge amount stability. On the other hand, Comparative Example 3 and Comparative Example 10 use the same ink and discharge temperature, but differ in “ink inflow amount / maximum ink discharge amount”.
The evaluation results were the same. From this, it is presumed that when the ink is not heated, the evaluation result is not affected even if the “ink inflow amount / maximum ink discharge amount” is different.

In Comparative Example 5 and Comparative Example 11, the ink used and the discharge temperature were the same, but the values of “ink inflow amount / maximum ink discharge amount” were different, and the evaluation results were the same. This is because when the discharge temperature is higher than 40 ° C., the ink temperature fluctuation in the circulation path is large, and the evaluation result is better even when “ink inflow amount / maximum ink discharge amount” is 2.5 times. It is presumed that it is insufficient for this. Therefore, when the discharge temperature is 40 ° C. or less, it is estimated that the greater the “ink inflow amount / maximum ink discharge amount”, the better the discharge amount stability (short term, long term).

In the second embodiment and the seventeenth embodiment, the heater is mounted on the circulation path and the head, respectively, at the ink heating position. It was found that the discharge amount fluctuation was better when the ink heating position was the circulation path.

In the first embodiment and the eighteenth embodiment, the number of heads is four and one, respectively. It was found that one head was more excellent in discharge rate stability (short term, long term), but the recordable width became narrower. That is, it was found that the recording method of the present invention is excellent in ejection amount stability by setting the ink inflow amount to a predetermined value even when a plurality of heads are provided and the printable width is increased.

Further, Example 2 and Example 19 are different from each other in that the irradiation peak intensity is different, but it is added that the larger the irradiation peak intensity, the more effectively the generation of curing wrinkles can be prevented. Furthermore, Example 11 and Example 20 are also different from each other in that the irradiation peak intensity is different. However, unlike the case of Example 2 and Example 19 above, since high-viscosity ink is used, irradiation is performed. It is presumed that the occurrence of hardening wrinkles can be prevented regardless of the magnitude of the peak intensity. Furthermore, Example 7 and Example 21 are also different from each other in that the irradiation peak intensity is different, but the ink containing the vinyl ether group-containing (meth) acrylic acid ester represented by the general formula (I) has an irradiation peak. When the strength is large, it is presumed that generation of hardening wrinkles can be prevented.

Further, Comparative Examples 6 to 9 using any one of the inks H, I, and J having an ink viscosity rank of A at 28 ° C. were inferior in curing wrinkle evaluation.
Further, from Examples 19 to 21, considering from the viewpoint of the light source, the irradiation peak intensity is set to 1,000.
When an LED changed from 0 mW / cm ² to 500 mW / cm ² was used, there was an inferior cured wrinkle evaluation.
In addition, although not shown as an Example, it replaces with LED as a light source, and irradiation peak intensity | strength 1, 0
Curing was performed using a 00 mW / cm ² metal halide lamp. As a result, among the examples and comparative examples, in the case where the evaluation result of cured wrinkles was B or C, the cured wrinkle evaluation was improved to one rank superior, and the curability result was further improved. I understood. However, the film was deformed by the heat generated by the metal halide lamp, and the installation space was required because it was a larger light source than the LED. In other words, it has been found that using an LED is preferable in terms of a low heat generation and space-saving recording apparatus, and increasing the irradiation peak intensity of the LED is more preferable in terms of curing wrinkles.

Further, although not shown as an example, recording was performed in the same manner as in Example 1 except that instead of a line printer, a serial printer having an LED with a peak intensity of 500 mW / cm ² mounted on the side of the carriage was used as a light source. Went. The serial printer used is disclosed in JP-A-2
This is an ink jet printer described in FIG. 2 of 010-167777. The nozzle density of the head is 300 dpi, the recording resolution is 600 dpi × 600 dpi, but the recording resolution per pass is 300 dpi × 300 dpi, and dots are formed in the same recording area of the recording medium in four passes (main scanning direction 2 Pass × sub-scanning direction 2 pass). As a result, the cured wrinkle evaluation result was A, but since it was a serial printer, it was found that the recording speed was low. That is, according to the recording method of the present invention, even when high-speed printing is performed by a line printer, it is possible to effectively prevent the occurrence of curing wrinkles by using LEDs and increasing the irradiation peak intensity. It was found that it was possible to make a good record.

DESCRIPTION OF SYMBOLS 1 ... Printer, 10 ... Ink supply apparatus, 20 ... Conveyance unit, 25A ... Upstream roller, 25B ... Downstream roller, 26 ... Conveyance drum, 30 ... Head unit, 40 ... Irradiation unit, 42a, 42b, 42c, 42d ... Irradiation part for temporary curing, 44 ... Irradiation part for main curing, 5
DESCRIPTION OF SYMBOLS 0 ... Ink cartridge, 51 ... Ink path, 52 ... Holder, 53 ... Valve, 54 ... Supply pump, 55 ... Filter, 56 ... Pressure pump, 60 ... Head, 61 ... Cap, 70
DESCRIPTION OF SYMBOLS ... Sub tank, 71 ... Liquid quantity sensor, 80 ... Ink circulation path, 81 ... Filter, 82 ... Circulation pump, 83 ... Head filter, 90 ... Heating mechanism, 91 ... Warm water tank, 92 ... Warm water circulation pump, 93 ... Heater, 94 ... Temperature control module, 100 ... Deaeration mechanism, 101 ... Negative pressure pump, 102 ... Deaeration module, 110 ... Detector group, 120 ... Controller, 121 ...
Interface 122 ... CPU 123 ... Memory 124 ... Unit control circuit 1
30: Computer, K, C, M, Y: Head, S: Recording medium.

Claims (21)

An ejection step of ejecting an ultraviolet curable ink having a viscosity at 28 ° C. of 8 mPa · s or more from a head toward a recording medium;
Curing the ultraviolet curable ink attached to the recording medium, and
The ultraviolet curable ink is heated, the temperature of the discharged ultraviolet curable ink is set to 28 to 40 ° C., and the viscosity of the ultraviolet curable ink at the temperature is 15 mPa · s or less,
In the ultraviolet curable ink, the monofunctional (meth) acrylate having an aromatic ring skeleton is 10% by mass to 75% by mass with respect to the total mass of the ink, and the bifunctional to hexafunctional (meth) acrylate is added to the total of the ink 5 mass% or more and 50 mass% or less with respect to mass, an acyl phosphine oxide compound as a photoinitiator, and the vinyl ether group containing (meth) acrylic acid ester represented by the following general formula (I). ,
An ink jet recording method, wherein the curing step is performed by a light emitting diode using a light source.
_{^{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.)   The inkjet recording method according to claim 1, wherein recording is performed using a line-type inkjet recording apparatus including a line head having a length equal to or longer than a length of a recording medium as the head.   The recording is performed using an ink jet recording apparatus, wherein at least a part of an ink path for supplying the ultraviolet curable ink from an ink container to the head is an ink circulation path for circulating the ultraviolet curable ink. 2. The inkjet recording method according to 2.   4. The inkjet according to claim 3, wherein an ink inflow amount of the ultraviolet curable ink supplied from the ink circulation path to the head is at least twice a maximum ink discharge amount for discharging the ultraviolet curable ink from the head. Recording method.   5. The inkjet recording method according to claim 3, further comprising a heating mechanism that heats the ultraviolet curable ink at a position other than a position connected to the head in the ink circulation path.   The inkjet recording according to claim 3, wherein there are a plurality of heads to which the ultraviolet curable ink is supplied from the ink circulation path, and the ultraviolet curable ink is ejected from the plurality of heads. Method. The ultraviolet curable ink, the general formula vinyl ether group-containing represented by (I) (meth) acrylic acid esters, based on the total weight of the ink, including 10 to 70 wt%, more of claims 1 to 6 The ink jet recording method according to claim 1. The ultraviolet curable ink contains a bifunctional or higher and tetrafunctional (meth) acrylate.
The ink jet recording method according to claim 1.   The inkjet recording method according to claim 1, wherein the light emitting diode has an emission peak wavelength of 360 to 420 nm. The inkjet recording method according to any one of claims 1 to 9, wherein the light emitting diode irradiates ultraviolet rays having a peak intensity of 800 mW / cm ² or more.   The inkjet recording method according to claim 1, wherein an epoxy resin is used in the head.   The inkjet recording method according to claim 1, wherein the ultraviolet curable ink contains 5% by mass or more and 50% by mass or less of bifunctional (meth) acrylate with respect to the total mass of the ink.   The inkjet according to any one of claims 1 to 12, wherein the ultraviolet curable ink contains a monofunctional (meth) acrylate having an aromatic ring skeleton in an amount of 10% by mass to 40% by mass with respect to the total mass of the ink. Recording method.   The inkjet recording method according to claim 1, wherein the ultraviolet curable ink contains an acyl phosphine oxide compound as a photopolymerization initiator in an amount of 5% by mass or more based on the total mass of the ink.   12. The ultraviolet curable ink according to claim 1, comprising a bifunctional to hexafunctional (meth) acrylate in an amount of 5% by mass to 30.3% by mass with respect to the total mass of the ink. Inkjet recording method.   The ultraviolet curable ink includes, as the acylphosphine oxide compound, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis- ( The inkjet recording method according to any one of claims 1 to 15, comprising any of (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.   The inkjet recording method according to claim 1, wherein the viscosity of the ultraviolet curable ink at a temperature of the discharged ultraviolet curable ink is more than 10 mPa · s and not more than 15 mPa · s.   The inkjet recording method according to claim 1, wherein the ultraviolet curable ink has a viscosity at 28 ° C. of 8 mPa · s or more and 15 mPa · s or less.   The inkjet recording according to any one of claims 1 to 18, wherein the temperature of the discharged ultraviolet curable ink is 33 to 40 ° C, and the viscosity of the ultraviolet curable ink at the temperature is 15 mPa · s or less. Method.   An ink jet recording apparatus for performing recording by the ink jet recording method according to claim 1.   The ultraviolet curable ink used for the inkjet recording method of any one of Claims 1-19.

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