JP5094507B2 - Tube pump, ink jet recording apparatus, ink jet recording method and printed matter - Google Patents

Description

  The present invention relates to a tube pump, an ink jet recording apparatus including the tube pump, an ink jet recording method using the ink jet recording apparatus, and a printed matter.

  As an image recording method for forming an image on a recording medium such as paper based on an image data signal, there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like. In particular, the ink jet method can be implemented with an inexpensive apparatus, and ink is ejected only to the required image portion to form an image directly on the recording medium, so that the ink can be used efficiently and the running cost is reduced. Is cheap. Furthermore, there is little noise and it is excellent as an image recording method.

The ink jet recording apparatus includes an ink jet recording head that receives ink supplied from an ink cartridge, and a paper feeding unit that moves the recording paper relative to the recording head, and performs recording while moving the recording head according to a print signal. Recording is performed by ejecting ink droplets onto a sheet to form dots.
In an ink jet recording apparatus, a mechanism for sucking and discharging ink is required to fill the recording head with ink and forcibly suck and discharge ink from the recording head for the purpose of preventing clogging of nozzle openings. . In order to suck and / or discharge such ink, a so-called tube pump is used.

Patent Document 1 discloses an ink wetted member used in an ultraviolet curable ink jet recording apparatus, wherein the ink wetted member has a compression set of 15% or less and a tear strength of 10 N after being immersed in 60 ° C. ink for 1 week. An ink wetted member is disclosed which is an elastic body having a tensile strength of 5 MPa or more per mm / mm or more.
Patent Document 2 discloses a tube pump characterized in that a tube made of an addition reaction vulcanized rubber substance having a hardness of 34 to 46 degrees is used as the flexible tube.

JP 2007-38604 A JP 2001-234875 A

  When the tube pumps described in Patent Document 1 and Patent Document 2 are used in an ink composition containing a large amount of monofunctional monomer, ink leakage cannot be completely prevented, and the leaked ink reduces the strength of the pump frame. There was a problem.

  The present invention solves the above problems. That is, an object of the present invention is to provide a tube pump that can prevent a decrease in strength due to an ink composition of a pump frame and can stably feed and / or waste ink. Another object of the present invention is to provide an ink jet recording apparatus having excellent ejection stability, and an ink jet recording method and printed matter using the same.

The above-described problems of the present invention have been solved by means described in <1>, <7>, <9> and <10> below. It describes below with <2>-<6> and <8> which are preferable embodiments.
<1> A flexible tube and a tube support surface that regulates the outer shape of the flexible tube, and at least one selected from the group consisting of polyamide resin, high-density polyolefin resin, polyester resin, and metal A pump frame made of a material; and a roller that pressurizes and deforms the flexible tube, and the flexible tube is pressurized and deformed by the roller to feed and / or waste the ink composition. Tube pump, characterized by
<2> The tube pump according to <1>, wherein the flexible tube is made of silicon rubber and / or fluorine rubber.
<3> The above <1> or <2>, wherein the ink composition contains a polymerizable monomer, and the monofunctional polymerizable monomer is 40% by weight or more and 100% by weight or less based on the total amount of the polymerizable monomer. Tube pump as described in the
<4> The tube pump according to the above <3>, wherein the polymerizable monomer contains a polymerizable monomer containing a nitrogen atom,
<5> The tube pump according to <3> or <4>, wherein the polymerizable monomer contains phenoxyethyl acrylate,
<6> The tube pump according to any one of <1> to <5> above, wherein the ink composition contains a perfluoroalkyl group-containing polymer.
<7> An ink jet recording head that discharges an ink composition onto a recording medium from an ink jet nozzle, a tube pump that feeds the ink composition to the ink jet recording head, and / or the ink composition from an ink jet recording head. An inkjet recording apparatus, wherein the tube pump is the tube pump according to any one of <1> to <6> above,
<8> The ink jet recording apparatus according to the above <7>, further comprising active energy ray irradiating means for irradiating and curing the active energy ray on the ink composition ejected on the recording medium,
<9> An ink jet recording method using the ink jet recording apparatus according to <7> or <8>,
<10> Printed matter obtained by the inkjet recording method according to <9> above.

  According to the present invention, it is possible to provide a tube pump capable of preventing ink strength of the pump frame from being reduced by the ink composition and stably feeding and / or waste ink. Moreover, according to this invention, the inkjet recording device excellent in discharge stability, the inkjet recording method using the same, and printed matter could be provided.

(1) Tube Pump The tube pump of the present invention has a flexible tube (hereinafter also simply referred to as “tube”) and a tube support surface that regulates the outer shape of the flexible tube. A pump frame formed of at least one material selected from the group consisting of a density polyolefin resin, a polyester resin, and a metal; and a roller that pressurizes and deforms the flexible tube. The ink tube (hereinafter simply referred to as “ink”) is fed and / or waste liquid by pressurizing and deforming the property tube.

Hereinafter, description will be made with reference to the drawings as appropriate.
FIG. 1 is a schematic view showing an example of a tube pump that can be suitably used in the present invention.
In FIG. 1, the tube pump 1 includes a tube 10, a pump frame 11, and rollers 12 (12a and 12b). The tube 10 is arranged along the tube support surface formed on the pump frame 11, for example, substantially all around, or As shown in FIG. 1, it is arranged so as to draw an arc shape over almost a half circumference.
The rollers 12 a and 12 b are rotatably attached to the pump wheel 14, and the roller 12 a or 12 b is pressed against the pump frame 11 by rotating the pump wheel 14. The roller 12a or 12b rotates while crushing (pressing and deforming) the tube 10, thereby generating pressure in the tube 10. As a result, the pressure in the tube 10 on the upstream side of the portion accommodated in the pump frame 11 is reduced.

The tube pump of the present invention is used to feed and / or waste ink composition. In FIG. 1, the ink composition is indicated by A.
The tube pump of the present invention can also be used as a liquid feed pump for feeding ink to an ink jet recording head (hereinafter also simply referred to as “recording head” or “head”). It can also be used as a suction pump that forcibly sucks ink from the outlet, and is not particularly limited. Details will be described later.

(Pump frame)
In the present invention, the material for forming the pump frame is selected from the group consisting of polyamide resin, high-density polyolefin resin, polyester resin, and metal.
By forming the pump frame with the above material, even when the ink composition oozes out into the tube pump, it is possible to suppress a decrease in the strength of the pump frame due to the polymerizable compound of the ink composition, The liquid feeding stability is improved.
Conventionally used pump frames are made of acrylic resin, polycarbonate resin or the like. For this reason, when the ink composition oozes out into the pump frame, the pump frame is plasticized, the pump frame is cracked, and the print quality is deteriorated.
When the tube pump is used to send ink from the ink tank to the ink jet recording head, if the pump frame is cracked, the tube is not pressurized enough and cannot be fed normally. As a result, ink cannot be fed to the ink jet recording head, resulting in poor ejection and poor print quality.
According to the present invention, the above problem can be solved, and when an ink composition containing a polymerizable compound having a high plasticizing ability such as a monofunctional polymerizable monomer or a low molecular weight polymerizable monomer is used. Even in this case, high print quality can be maintained.

The pump frame includes at least one material selected from the group consisting of the polyamide resin, the high-density polyolefin resin, the polyester resin, and the metal, and contains a total of 50% by weight or more thereof. The total of the above materials is preferably 60% by weight or more, more preferably 70% by weight or more.
Moreover, what is necessary is just to contain at least 1 material selected from the said group, and multiple types can also be used together. For example, the aspect which covers the tube support surface of the pump frame produced with the metal with a polyamide resin can be illustrated.
In the present invention, other components that the pump frame may contain include fillers, lubricants, heat stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, pigments, modifiers, flame retardants, and antistatic agents. , Reinforcing agents, tackifiers, fillers, fungicides and the like.

As the polyamide resin, it can be used by appropriately selecting from known polyamide resins, but 6-nylon, 6,6-nylon, 8-nylon, 11-nylon, 12-nylon, 6/12 copolymer nylon, Examples thereof include 6/66/12 copolymer nylon, amorphous nylon, transparent nylon, and polyamide elastomer.
Among these, as the polyamide resin, 6-nylon, 6,6-nylon, and 6/12 copolymer nylon are more preferable, and 6-nylon and 6,6-nylon are more preferable.

Examples of the high-density polyolefin resin include an ethylene homopolymer, an α-olefin homopolymer, and an ethylene-α-olefin copolymer. Generally, a Ziegler catalyst, a Philips catalyst, a metallocene catalyst, etc. are used. It is a polyolefin resin that is polymerized by a slurry method, a solution method or a gas phase method. Specific examples of the α-olefin include α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. , 1-tetradecene, 1-octadecene and the like. The density is 0.930 g / cm ³ or more and 0.975 g / cm ³ or less (in the present invention, “0.930 g / cm ³ or more and 0.975 g / cm ³ or less” is replaced with “0.930 g / cm ³ to 0.975 g / cm ³ ”or“ 0.930 to 0.975 g / cm ³ ”. The same applies hereinafter.), More preferably 0.940 to 0.970 g. / Cm ³ , more preferably 0.942 to 0.965 g / cm ³ , which can be appropriately selected from known high-density olefin resins.
Among these, as a high density polyolefin resin, a high density polyethylene resin and a high density polypropylene resin are preferable, and it is preferable to use a high density polyethylene resin.
High-density polyolefin resins are commercially available, and examples thereof include the Hi-Zex series (manufactured by Mitsui Chemicals, Inc., such as Hi-Zex 1300J) and Novatec HD (manufactured by Nippon Polyethylene Co., Ltd.).

  As a polyester resin, it can select from a well-known polyester resin suitably and can be used. It is preferable to use a polyester resin that can be easily molded, and examples thereof include PET (polyethylene terephthalate) and PET copolyester.

As the metal, stainless steel can be preferably used, and the stainless steel can be appropriately selected from known stainless steels.
Specifically, SUS304, SUS309S, SUS310S, SUS316, SUS317, SUS430, SUS403, SUS410, SUS420J2, SUS440C, and SUS630 can be exemplified.

Among these, from the viewpoint of processability and resistance to the ink composition, polyamide resins, high-density polyolefin resins, and metals are preferable, polyamide resins and metals are more preferable, and polyamide resins are more preferable.
In addition, it is preferable to form a tube support surface (contact surface with a tube) with the said raw material especially among pump frames.

The method for producing the pump frame is not particularly limited, and can be appropriately selected from known methods such as injection molding, extrusion molding, and compression molding. Moreover, when using a metal, press molding can be used.
Examples of the injection molding method include a plunger method, a plunger pre-pull method, a screw pre-pull method, and an in-line screw method. Among these, it is particularly preferable that the pump frame of the present invention is manufactured by an in-line screw method because of good molding accuracy.

(tube)
The tube used in the tube pump of the present invention has flexibility. Here, flexibility is a concept that includes the meaning of elasticity.
The material of the tube can be appropriately selected from the restoring force of the tube after being crushed.
In the present invention, the tube pump is preferably formed of silicon rubber or fluorine rubber. By forming the tube from silicon rubber or fluorine rubber, it is possible to obtain high resistance to ink and to obtain a tube pump having excellent temporal stability.
Silicon rubber and fluorine rubber are preferred because they are excellent in heat and cold resistance and weather resistance.

  The material of the tube is preferably 80 or less in hardness (JIS-6301-1962), more preferably 70-50. It is preferable for the hardness to be in the above range since the restoring force of the tube after crushing is excellent and a desired flow rate can be obtained.

As the silicon rubber, an addition reaction vulcanizate of silicon rubber is preferable. More specifically, a product obtained by addition reaction vulcanization of methyl vinyl silicon, methyl phenyl silicon, fluoro silicon or the like is preferable. As a method for forming addition reaction vulcanization, a crosslinkable monomer such as a vinyl compound or a divinyl compound is used, and this is subjected to addition bonding with heat or heat and a catalyst, or by crosslinking with irradiation of light, radiation or the like. The method of forming can be illustrated.
Silicone rubber tubes are commercially available. Specifically, Tygon (trade name) 3355-L high performance platinum vulcanized silicone tube for roller pump (manufactured by Saint-Gobain Co., Ltd.), high strength roller pump silicone tube (( Examples include Hagitech Co., Ltd.), silicone tubes for roller pumps (Hagitec Co., Ltd.), and the like.

Examples of the fluorine rubber include FKM (vinylidene fluoride rubber), FEPM (tetrafluoroethylene-propylene rubber), and FFKM (tetrafluoroethylene-purple olovinyl ether rubber).
Fluoro rubber tubes are commercially available. Specifically, King Perflo tube (manufactured by King Seisakusho Co., Ltd.), Kalrez (trademark) tube (manufactured by DuPont), EXLON-THV soft fluororesin tube (Co., Ltd.) ) Manufactured by Iwase Co., Ltd.) and Furlan F-5500-A (manufactured by Saint-Gobain Co., Ltd.).

In the present invention, the tube is preferably made of silicon rubber and / or fluorine rubber, but 50% by weight or more of all components constituting the tube may be silicon rubber and / or fluorine rubber, All components are not limited to silicon rubber and / or fluorine rubber. The content of silicon rubber and / or fluorine rubber is preferably 60 to 100% by weight, more preferably 70 to 100% by weight, and still more preferably 80 to 100% by weight.
It is preferable that the content of the silicon rubber and / or the fluorine rubber is in the above-mentioned range since it is excellent in resistance to the ink composition and good printing stability can be obtained.
Examples of components contained other than silicon rubber or fluorine rubber include reinforcing fillers, wetting agents, and various additives.

Further, in the present invention, it is preferable that the tube has an ultraviolet light shielding function, and as a method for that purpose, a silicon rubber and / or fluorine rubber is mixed with a light shielding compound such as carbon black, or the light shielding property. The method of coat | covering with other members can be illustrated.
Moreover, it is preferable to have an air blocking function, and it is preferable to cover the tube with a material having low air permeability.

  As a manufacturing method of the said tube, it can select suitably from a conventionally well-known method, For example, extrusion molding and injection molding can be illustrated and it does not specifically limit.

  In FIG. 1, the tube pump is provided with one tube, but it may be provided with two or more tubes. In addition, when a tube pump is provided with two or more tubes, it is preferable that at least one is formed with silicon rubber and / or fluorine rubber.

(roller)
In the present invention, the roller abuts against the tube and moves along the tube. The roller is formed on a pump wheel and is driven by a motor that rotates the pump wheel.
In the present invention, the material of the roller can be selected from known materials and is not particularly limited. Among these, like the pump frame, it is preferable that the ink composition is formed of a material that does not decrease in strength even if the ink composition oozes out from the tube, and this is preferable because it can stably feed and / or waste liquid. .

(Ink composition)
The pump tube of the present invention is used for feeding and / or draining the ink composition. The ink composition that can be particularly suitably used for the pump tube of the present invention will be described in detail below.
In the present invention, the ink composition preferably contains a polymerizable monomer. In the present invention, the ink composition is preferably a radiation curable ink composition. Here, the radiation in the present invention is not particularly limited as long as it is a radiation that can impart energy capable of generating an initiation species (polymerization initiation species) in the ink composition by the irradiation, and broadly α rays, Including gamma rays, X rays, ultraviolet rays (UV), visible rays, electron beams, etc. Among them, ultraviolet rays and electron beams are preferable from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are particularly preferable. Therefore, in the present invention, the ink composition is preferably an ultraviolet curable ink composition that can be cured by irradiating ultraviolet rays as radiation.

  In the present invention, the ink composition preferably contains a perfluoroalkyl group-containing polymer in addition to the polymerizable monomer, and preferably contains a polymerization initiator and a colorant. Further, in addition to the above components, surfactants, sensitizing dyes, co-sensitizers, antioxidants, polymerization inhibitors, ultraviolet absorbers, anti-fading agents and the like may be added. Hereinafter, each component will be described.

<Polymerizable monomer>
In the present invention, as the polymerizable monomer, any of a radical polymerizable monomer and a cationic polymerizable monomer can be used, and it is particularly preferable to use a radical polymerizable monomer. The radical polymerizable monomer is a compound having at least one ethylenically unsaturated bond in the molecule (ethylenically unsaturated compound).

In the present invention, the ink composition preferably contains a polymerizable monomer, and 40 to 100% by weight of the polymerizable monomer is preferably a monofunctional polymerizable monomer. Monofunctional polymerizable monomers include monofunctional acrylates (monofunctional acrylates), monofunctional methacrylates (monofunctional methacrylic esters), monofunctional vinyloxy compounds, monofunctional N-vinyl compounds, monofunctional acrylamides, and monofunctional acrylamides. It is more preferably a monofunctional polymerizable monomer selected from the group consisting of functional methacrylamides (hereinafter also referred to as monofunctional radical polymerizable monomer).
It is preferable that the content of the monofunctional radical polymerizable monomer is 40% by weight or more because the viscosity is good and the ejection property is excellent, the sensitivity is high, and the obtained image is excellent in flexibility.
The content of the monofunctional radically polymerizable monomer is more preferably 50% by weight or more and 99.5% by weight or less, more preferably 60% by weight or more and 99% by weight or less of the entire polymerizable monomer, and 65% by weight. % To 98% by weight is particularly preferable.

In the present invention, the polymerizable monomer preferably has a molecular weight of 1,000 or less, more preferably 50 to 800, and still more preferably 60 to 400.
In particular, in the present invention, the low molecular weight polymerizable monomer having a molecular weight of 100 to 250 is preferably contained in an amount of 40 to 100% by weight, more preferably 50 to 100% by weight, and still more preferably 60% by weight. ~ 100% by weight. By increasing the content of the low molecular weight polymerizable monomer, an ink composition having excellent flexibility after curing can be obtained.

[Monofunctional radical polymerizable monomer]
In the present invention, the ink composition preferably contains a monofunctional polymerizable monomer in an amount of 40% by weight to 100% by weight, and includes monofunctional acrylates (monofunctional acrylates) and monofunctional methacrylates (monofunctional methacrylic acid). Acid esters), monofunctional vinyloxy compounds, monofunctional N-vinyl compounds, monofunctional acrylamides and monofunctional methacrylamides (also referred to as monofunctional radical polymerizable monomers). Is preferably contained in an amount of 40% by weight to 100% by weight of the polymerizable monomer.

Monofunctional acrylates (monofunctional acrylates) have one acryloyloxy group in the molecule and other radical polymerizable functional groups (methacryloyloxy group, acrylamide group, methacrylamide group, vinyloxy group and N -No vinyl group). The same applies to monofunctional methacrylates, monofunctional vinyloxy compounds, monofunctional N-vinyl compounds, monofunctional acrylamide compounds, and monofunctional methacrylamide compounds.
That is, in the present invention, the ink composition contains 1 ethylenically unsaturated double bond group selected from the group consisting of acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, vinyloxy group and N-vinyl group. It is preferable to contain 40 to 100% by weight of the monofunctional radical polymerizable monomer having only one of the polymerizable monomers.
Among these, monofunctional acrylates, monofunctional methacrylates, monofunctional N-vinyl compounds, monofunctional acrylamides and monofunctional methacrylamides are preferable, and monofunctional acrylates, monofunctional methacrylates and monofunctional N are more preferable. -Vinyl compounds. In the present invention, it is preferable to use a monofunctional acrylate and a monofunctional N-vinyl compound or a monofunctional methacrylate and a monofunctional N-vinyl compound in combination as the monofunctional radical polymerizable monomer. It is particularly preferable to use a functional N-vinyl compound in combination.

The monofunctional radical polymerizable monomer has only one ethylenically unsaturated double bond group selected from the group consisting of acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group and N-vinyl group. It is more preferable to use a monomer having a cyclic structure.
Examples of the radically polymerizable monomer that can be suitably used in the present invention include an ethylenically unsaturated compound represented by the following formula (1).

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group.
X ¹ represents a first divalent linking group in which (—C (O) O—) or (—C (O) NH—) is bonded to the ethylenically unsaturated double bond represented by Formula (1). In the first divalent linking group, a single bond, an ether bond (—O—), an ester bond (—C (O) O— or —OC (O) —), an amide bond (—C (O) NH -Or -NHC (O)-), a carbonyl bond (-C (O)-), an optionally substituted alkylene group having 20 or less carbon atoms, or a second divalent combination thereof. A linking group may be bonded, and when it has only the first divalent linking group or the second divalent linking group, those having an ether bond, an ester bond and an alkylene group having 20 or less carbon atoms are preferred.
R ² is a group having at least one cyclic structure, an aromatic group containing a monocyclic aromatic group and a polycyclic aromatic group, and an alicyclic carbonization containing a cycloalkane skeleton, an adamantane skeleton and a norbornane skeleton. Represents a hydrogen group. The cyclic structure of the above aromatic group and alicyclic hydrocarbon group may contain heteroatoms such as O, N, and S.

In the formula (1), the aromatic group represented by R ² is preferably a monocyclic aromatic phenyl group or a polycyclic aromatic group having 2 to 4 rings. Specifically, naphthyl group, anthryl group, 1H-indenyl group, 9H-fluorenyl group, 1H-phenenyl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, naphthacenyl group, tetraphenyl group, biphenylenyl group, as- Preferred examples include an indacenyl group, an s-indacenyl group, an acenaphthylenyl group, a fluoranthenyl group, an acephenanthrenyl group, an aceanthrylenyl group, a chrysenyl group, and a preadenyl group.

  These aromatic groups may be aromatic heterocyclic groups containing heteroatoms such as O, N, and S. Specifically, furyl group, thienyl group, 1H-pyrrolyl group, 2H-pyrrolyl group, 1H-pyrazolyl group, 1H-imidazolyl group, isoxazolyl group, isothiazolyl group, 2H-pyranyl group, 2H-thiopyranyl group, pyridyl group, Examples include a monocyclic aromatic heterocyclic group such as a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a 1,2,3-triazolyl group, and a 1,2,4-triazolyl group.

  Moreover, thiantenyl group, benzofuranyl group, isobenzofuranyl group, chromenyl group, isochromenyl group, 4H-chromenyl group, xanthenyl group, phenoxathiinyl group, indolizinyl group, isoindolyl group, indolyl group, indazolyl group, purinyl group, 4H -Quinolinidyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthate Examples thereof include polycyclic aromatic heterocyclic groups such as a rolinyl group, a phenazinyl group, a phenothiazinyl group, a phenoxazinyl group, and a pyrrolidinyl group.

  The aromatic group may have one or more halogen atoms, hydroxyl groups, amino groups, thiol groups, siloxane groups, and substituents having 30 or less carbon atoms. For example, you may form the cyclic structure containing hetero atoms, such as O, N, and S, by two or more substituents which an aromatic group has like phthalic anhydride and phthalimide anhydride.

R ² in formula (1) may be an alicyclic hydrocarbon group. Moreover, the alicyclic hydrocarbon group containing hetero atoms, such as O, N, and S, may be sufficient.
The alicyclic hydrocarbon group may be a group having a cycloalkane having 3 to 12 carbon atoms.
Specific examples of the alicyclic hydrocarbon group containing a heteroatom such as O, N, and S include a pyrrolidinyl group, a pyrazolidinyl group, an imidazolidinyl group, an isoxazolidinyl group, and an isothiazolidinyl group. And piperidinyl group, piperazinyl group, morpholinyl group, thiomorpholinyl group and the like.
These alicyclic hydrocarbon groups and alicyclic hydrocarbon groups having a heteromonocycle may have one or more substituents, such as a halogen atom, a hydroxyl group, an amino group, Examples thereof include a thiol group, a siloxane group, and a hydrocarbon group having a total carbon number of 30 or less which may have a substituent. Moreover, it may have an oxy group (= O) as a divalent substituent, and is a heterocyclic structure containing two or more substituents of an alicyclic hydrocarbon group and containing a heteroatom such as O, N, or S May be formed.

R ² in the formula (1) may be a group having an adamantane skeleton represented by the following formula (I) or an alicyclic hydrocarbon group having a norbornane skeleton represented by the formula (II).

R ³ and R ⁴ in formula (I) or formula (II) each independently represent a substituent, and can be bonded at any position on each alicyclic hydrocarbon structure. Further, q R ³ and r R ⁴ may be the same or different.
R ³ present in q and R ⁴ present in r may each independently be a monovalent or polyvalent substituent. As the monovalent substituent, a hydroxyl group, a substituted or unsubstituted amino group may be used. Group, thiol group, siloxane group, a hydrocarbon group or a heterocyclic group having a total carbon number of 30 or less which may have a substituent, or an oxy group (= O) as a divalent substituent. preferable.
The substitution number q of R ³ represents an integer of 0 to 5, and the substitution number r of R ⁴ represents an integer of 0 to 5.
Further, one carbon atom in the adamantane skeleton in the formula (I) may be substituted with a carbonyl bond (—C (O) —) and / or an ester bond (—C (O) O—). One carbon atom in the norbornane skeleton may be substituted with an ether bond (—O—) and / or an ester bond (—C (O) O—).

  The norbornane skeleton represented by formula (II) may have a cyclic hydrocarbon structure as represented by formula (III). N in the formula (III) represents a cyclic hydrocarbon structure, and both ends thereof may be substituted at any position of the norbornane skeleton, and may be a monocyclic structure or a polycyclic structure. In addition to the hydrocarbon bond, the cyclic hydrocarbon structure may contain a carbonyl bond (—C (O) —) and / or an ester bond (—C (O) O—).

  The cyclic structure represented by the formula (III) is preferably a structure represented by the formula (IV), the formula (V) or the formula (VI).

In formula (IV), formula (V) and formula (VI), R ⁵ , R ⁶ and R ⁷ each independently represent a substituent, s, t and u each independently represent an integer of 0 to 5; Further, s R ⁵ , t R ⁶ , and u R ⁷ may be the same or different.
X ^{1 in} formula (1) can be bonded at any position on each alicyclic hydrocarbon structure shown below in formula (IV), formula (V) or formula (VI).
R ⁵ , R ⁶ and R ⁷ in formula (IV), formula (V) or formula (VI) each independently represent a substituent, and each of the following fats in formula (IV), formula (V) or formula (VI) The bond can be made at any position on the cyclic hydrocarbon structure. The substituents in R ⁵ , R ⁶ and R ⁷ are synonymous with the substituents in R ³ and R ⁴ in formulas (I) to (III), and the preferred ranges are also the same.

  In the present invention, monofunctional acrylates, monofunctional methacrylates, monofunctional vinyloxy compounds, monofunctional acrylamides and monofunctional methacrylamides include phenyl group, naphthyl group, anthracenyl group, pyridinyl group, tetrahydrofurfuryl group, piperidinyl. A monofunctional radically polymerizable monomer having a group having a cyclic structure such as a group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, an isobornyl group, or a tricyclodecanyl group is preferred.

As the monofunctional radically polymerizable monomer that can be used in the present invention, preferably, norbornyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclo Octyl (meth) acrylate, cyclodecyl (meth) acrylate, dicyclodecyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-benzyl (meth) acrylate, phenoxyethyl (Meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, ethylene Sid (EO) modified cresol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol ( (Meth) acrylate, N-phthalimidoethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, N-cyclohexylacrylamide, N- (1,1-dimethyl-2-phenyl) ethylacrylamide, N-diphenylmethylacrylamide, N-phthalimidomethylacrylamide, N- (1,1′-dimethyl-3- (1,2,4- Riazor-1-yl)) propyl acrylamide, can be exemplified 5- (meth) acryloyloxy-methyl-5-ethyl-1,3-oxa-cyclohexane.
Among these, phenoxyethyl acrylate (the following (M-56)) can be used conveniently.

Furthermore, preferable specific examples of the monofunctional radically polymerizable monomer that can be used in the present invention are shown in the following M-1 to M-56.
In some of the following exemplary compounds, the hydrocarbon chain is described by a simplified structural formula in which symbols of carbon (C) and hydrogen (H) are omitted.

-Cyclic monomer having a N-vinyl group (monofunctional N-vinyl compound)-
In the present invention, it is preferable to use a radical polymerizable monomer having an N-vinyl group and a group having a cyclic structure as the monofunctional radical polymerizable monomer. Of these, N-vinylcarbazole, 1-vinylimidazole, and N-vinyllactams are preferably used, and N-vinyllactams are more preferably used.
Preferable examples of N-vinyl lactams that can be used in the present invention include compounds represented by the following formula (2).

  In formula (2), m represents an integer of 1 to 5, and m is 2 to 4 from the viewpoint of flexibility after the ink composition is cured, adhesion to a recording medium, and availability of raw materials. It is preferable that m is 2 or 4, and m is 4, that is, N-vinylcaprolactam is particularly preferable. N-vinylcaprolactam is preferable because it is excellent in safety, is general-purpose and can be obtained relatively inexpensively, and provides particularly good ink curability and adhesion of a cured film to a recording medium or a support.

  The N-vinyl lactams may have a substituent such as an alkyl group or an aryl group on the lactam ring, and may be linked with a saturated or unsaturated ring structure. The N-vinyl lactams may be included in the ink composition alone or in a plurality of types.

In the present invention, the ink composition preferably contains the monofunctional N-vinyl lactam represented by the formula (2) in an amount of 5 to 40% by weight or more, more preferably 10 to 35% by weight based on the whole ink composition. Preferably, the content is 12 to 30% by weight.
When the use amount of the monofunctional N-vinyl lactam is within the above numerical range, the curability, the cured film flexibility, and the adhesion of the cured film to the support are excellent. N-vinyl lactams are compounds having a relatively high melting point. When the content of N-vinyl lactam is 40% by weight or less, good solubility is exhibited even at a low temperature of 0 ° C. or less, and the temperature range in which the ink composition can be handled is widened.

  In the present invention, the ink composition has only one ethylenically unsaturated double bond group selected from the group consisting of acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, vinyloxy group and N-vinyl group. The monofunctional radically polymerizable monomer having at least one group having a cyclic structure is preferably contained in an amount of 60% by weight or more, more preferably 60 to 90% by weight, based on the total ink composition. More preferably, it is contained in an amount of ˜85% by weight. It is preferable for it to be within the above numerical values since the viscosity of the ink composition is moderate and excellent in curability.

As the monofunctional radical polymerizable monomer, the following acyclic monofunctional monomer can be used in combination. The acyclic monofunctional monomer has a relatively low viscosity, and can be preferably used, for example, for the purpose of reducing the viscosity of the ink composition. However, the ratio of the following acyclic monofunctional monomer to the entire ink composition is 20% by weight or less from the viewpoint of suppressing the stickiness of the cured film and giving a high film strength that does not cause scratches during molding. It is preferable. More preferably, it is 15 weight% or less.
Specifically, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, 2 -Hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, 2-ethylhexyl-diglycol acrylate, polyethylene glycol (meth) acrylate monomethyl ether, polypropylene glycol (meth) acrylate monomethyl ether, polytetraethylene glycol (meth) acrylate monomethyl ether, etc. Is mentioned.
Besides these, (poly) ethylene glycol mono (meth) acrylate, (poly) ethylene glycol (meth) acrylate methyl ester, (poly) ethylene glycol (meth) acrylate ethyl ester, (poly) ethylene glycol (meta) ) Acrylate phenyl ester, (poly) propylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate phenyl ester, (poly) propylene glycol (meth) acrylate methyl ester, (poly) propylene glycol (meth) acrylate Ethyl ester, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, isooctyl acrylate, n-lauryl acrylate N-tridecyl acrylate, n-cetyl acrylate, n-stearyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy Examples include acrylic acid derivatives such as acrylate.
Further, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, isooctyl methacrylate, n-lauryl methacrylate, n-tridecyl methacrylate, n-cetyl methacrylate, Examples thereof include methacrylic acid derivatives such as n-stearyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate and dimethylaminomethyl methacrylate, and derivatives of allyl compounds such as allyl glycidyl ether.
Further, 2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, ethoxy Examples include phenyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, lactone-modified flexible acrylate, butoxyethyl acrylate, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, etc. it can.

[Polyfunctional polymerizable monomer]
2 radicals of ethylenically unsaturated double bonds selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an acrylamide group, a methacrylamide group, a vinyloxy group, and an N-vinyl group as the radical polymerizable monomer. One or more polyfunctional polymerizable monomers can be used together. Other polyfunctional polymerizable monomers can also be used. By containing a polyfunctional polymerizable monomer, an ink composition having high cured film strength can be obtained. However, from the viewpoint of maintaining a cured film stretchability suitable for molding, the ratio of the following polyfunctional polymerizable monomer to the polymerizable monomer is preferably 60% by weight or less.

Examples of the polyfunctional polymerizable monomer having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and salts thereof, ethylene Anhydrides having an unsaturated group, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethane (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, urethanes A compound having two or more ethylenically unsaturated double bond groups, which is a (meth) acrylic acid ester such as a monomer or a prepolymer, is preferably used.
Specific examples include neopentyl glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, bisphenol A propylene oxide (PO) adduct di (meth) acrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, EO adduct di (meth) acrylate of bisphenol A, EO-modified pentaerythritol triacrylate, PO-modified pentaerythritol triacrylate, EO-modified pentaerythritol tetraacrylate, PO-modified pentaerythritol tetraacrylate, EO-modified dipentaerythritol Toraacrylate, PO-modified dipentaerythritol tetraacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, EO-modified tetramethylolmethane tetraacrylate, PO-modified tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, etc. Methacryl derivatives, diallyl phthalate, tri Derivatives of allyl compounds such as ril trimellitate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, hydroxypivalate neopentyl glycol diacrylate, tetramethylol methane Triacrylate, dimethylol tricyclodecane diacrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, tolylene diisocyanate urethane prepolymer, Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, ditrimethylolpropante Tora acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, and more specifically, Junzo Yamashita “Crosslinker Handbook” (1981, Taiseisha); (Raw material edition) ”(1985, Polymer publications); Radtech study edition,“ Application and market of UV / EB curing technology ”, p. 79 (1989, CMC); Eiichiro Takiyama“ Polyester resin handbook ”(1988) , Nikkan Kogyo Shimbun) or the like, or radically polymerizable or crosslinkable monomers, oligomers and polymers known in the industry can be used.

  Other specific examples include bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethyl Roll methane tetraacrylate, tetramethylol methane triacrylate, dimethylol tricyclodecane diacrylate, modified glycerin triacrylate, modified bisphenol A diacrylate, PO adduct diacrylate of bisphenol A, EO adduct diacrylate of bisphenol A, dipenta Examples include erythritol hexaacrylate and caprolactone-modified dipentaerythritol hexaacrylate.

[Vinyl ether compound]
Furthermore, it is also preferable to use a vinyl ether compound as the radical polymerizable compound. Suitable vinyl ether compounds include, for example, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol. Di- or trivinyl ether compounds such as divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octade Vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, n- propyl vinyl ether, isopropyl vinyl ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.
Of these vinyl ether compounds, divinyl ether compounds and trivinyl ether compounds are preferable from the viewpoints of curability, adhesion, and surface hardness, and divinyl ether compounds are particularly preferable. A vinyl ether compound may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.

  In the present invention, the monomers listed as the polymerizable compound described above have high reactivity, low viscosity, and excellent adhesion to a recording medium.

  In the present invention, the total amount of polymerizable monomers in the ink composition is preferably 55 to 95% by weight, more preferably 60 to 90% by weight, based on the total amount of the composition. It is preferable for it to be in the above range since the curability is excellent and the viscosity is moderate.

<Perfluoroalkyl group-containing polymer>
In the present invention, the ink composition preferably contains a perfluoroalkyl group-containing polymer (hereinafter also referred to as a fluoropolymer). In the present invention, when the ink composition contains a perfluoroalkyl group-containing polymer, an ink composition having excellent blocking resistance can be provided.
The content of the perfluoroalkyl group-containing polymer is preferably 0.1% by weight or more and 5% by weight or less of the entire ink composition, more preferably 0.5 to 5% by weight, and still more preferably 1 to 5% by weight. 5% by weight.
When the content of the perfluoroalkyl group-containing polymer is 0.1% by weight or more, good blocking resistance is obtained, which is preferable. Further, if it is 5% by weight or less, an ink composition having a low viscosity and excellent ejection stability can be obtained, which is preferable.

In the present invention, the perfluoroalkyl group-containing polymer preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 10,000 to 30. , 000.
When the molecular weight of the perfluoroalkyl group-containing polymer is 1,000 to 100,000, good blocking resistance is obtained, and an ink composition having low viscosity and excellent ejection stability can be obtained.

  In the present invention, the perfluoroalkyl group-containing polymer is not particularly limited as long as it is a polymer containing a perfluoroalkyl group. For example, fluorochemical surfactants described in JP-T-2004-536925, JP Fluorine polymerized using at least a monomer containing a fluorinated alkyl group and an ethylenic double bond described in 2007-003945 and a monomer containing a silicone chain and an ethylenic double bond Examples of the copolymer include fluorine-based surfactants having a perfluoroalkyl group in the molecule described in JP-A No. 2004-323578.

In the present invention, the perfluoroalkyl group-containing polymer is preferably a polymer obtained by polymerizing a monomer having an addition polymerizable group (preferably an ethylenically unsaturated group), and contains a perfluoroalkyl group (meta ) A polymer obtained by polymerizing acrylate is more preferable.
Moreover, it is preferable that it is a polymer obtained by polymerizing only (meth) acrylate, and it is a copolymer of a perfluoroalkyl group-containing (meth) acrylate monomer and a perfluoroalkyl group-free (meth) acrylate monomer. Is more preferable.
As the perfluoro group in the raw material monomer or perfluoroalkyl group-containing polymer, —CF ₂ CF ₃ (—C ₂ F ₅ ), —CF ₂ CF ₂ CF ₂ CF ₃ (—C ₄ F ₉ ), CF _{2 are used.} CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ (—C ₆ F ₉ ) is preferable, and —C ₄ F ₈ or —C ₆ F ₉ is more preferable.
In the present invention, the perfluoroalkyl group-containing polymer preferably satisfies the requirements described in the following (a) or (b).
(A) A polymer having a group derived from a fluoroaliphatic compound produced by a telomerization method or an oligomerization method (also referred to as a fluoroaliphatic group) in the side chain (b) represented by the following formula (I) Polymer having a structure

（式（Ｉ）中、Ｒ₂及びＲ₃はそれぞれ独立に水素原子又は炭素数１〜４個のアルキル基を表し、Ｙは高分子鎖を表し、Ｘは単結合又は２価の連結基（有機基）を表し、ｍは０以上の整数を表し、ｎは１以上の整数を表す。なお、ｍが２以上の場合、互いに隣接する炭素上の官能基（すなわち、隣り合う炭素にそれぞれ結合しているＲ₂同士やＲ₃同士）は結合して脂肪族環を形成してもよい。）

(In formula (I), R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents a polymer chain, and X represents a single bond or a divalent linking group ( M represents an integer greater than or equal to 0, and n represents an integer greater than or equal to 1. When m is greater than or equal to 2, functional groups on adjacent carbons (that is, bonded to adjacent carbons, respectively) R ₂ or R ₃ ) may be bonded to form an aliphatic ring.)

  The perfluoroalkyl group-containing polymer including a polymer that satisfies the requirements described in the above (a) or (b) may be in the form of any polymer. Specific forms include acrylic resin, methacrylic resin, styryl resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation resin, polyvinylphenol resin, maleic anhydride / α-olefin resin. , Α-hetero-substituted methacrylic resin and the like can be used. Among these, acrylic resins, methacrylic resins, styryl resins, polyester resins, and polyurethane resins are preferable, and acrylic resins, methacrylic resins, and polyurethane resins are particularly preferable.

(A) Polymer having a side chain having a group derived from a fluoroaliphatic compound produced by a telomerization method or an oligomerization method In the present invention, a perfluoroalkyl group-containing polymer (fluorine polymer) is a telomerization A polymer having a side chain derived from a fluoroaliphatic compound produced by a method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) is preferable. Regarding the method for producing the above fluoroaliphatic compound, for example, “Synthesis and Function of Fluorine Compound” (Supervision: Nobuo Ishikawa, Issue: CMC Co., 1987), “Chemistry of Organic Fluorine Compounds II” (Monograph 187, Ed by Milos Hudlicky and Attila E. Pavlath, American Chemical Society 1995), pages 747-752.

  The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen. As a specific example, Synthesis Example 1 below is shown.

  The obtained terminal iodinated telomer is usually subjected to appropriate terminal chemical modification as in, for example, Synthesis Example 2 below, and led to a fluoroaliphatic compound. These compounds are further converted into a desired monomer structure as necessary, and used for the production of a fluoroaliphatic group-containing polymer.

  As the monomer synthesized by the telomer method, a monomer represented by the following formula [TM-1] is preferable.

  In the above formula [TM-1], T represents one group selected from the following (T County), Z represents one group selected from the following (Z County), and n represents an integer of 0 to 20 .

  In addition, in the above formula [TM-1], the compound in which the group represented by Z is one group selected from the following (Z ′ group) has an acryloyl group or a methacryloyl group at the molecular end, A polymer having a group derived from the above-described fluoroaliphatic compound in the side chain can be easily obtained by vinyl polymerization, which is particularly preferable.

  In the present invention, a specific example of a compound produced by the telomer method suitable as a compound led to the side chain of a perfluoroalkyl group-containing polymer (mainly a monomer represented by the above formula [TM-1]) As the compound), for example, fluorine chemical products A-1110, A-1210, A-1310, A-1420, A-1620, A-1820, A-2020 sold by Daikin Chemicals Sales Co., Ltd. , A-1260, A-1460, A-1660, A-1860, A-1435, A-1635, A-1835, A-1473, A-1637, A-1837, A-1514, A-3420, A -3620, A-3820, A-4020, A-3260, A-3460, A-3660, A-3860, A-3737, A-3737, A-5 10, A-5410, A-5610, A-5810, A-7110, A-7210, A-7310, A-9210, C-1100, C-1200, C-1300, C-1400, C-1500, C-1600, C-1700, C-1800, C-1900, C-2000, C-5200, C-5400, C-5600, C-5800, C-5208, C-5408, C-5608, C- 6008, C-8200, C-8300, C-8500, C-9111, C-8208, C-8308, C-8508, C-9216, E-1430, E-1630, E-1830, E-2030, E-3430, E-3630, E-3830, E-4030, E-5244, E-5444, E-5644, E-5844, F-1420, F-1620, -1820, F-2020, I-1200, I-1300, I-1400, I-1600, I-1700, I-1800, I-2000, I-1420, I-1620, I-1820, I-2020 , I-3200, I-3400, I-3600, I-3800, I-4000, I-3620, I-3820, I-4020, I-5200, I-5400, I-5600, I-8208, I -8207, I-8407, I-8607, M-1110, M-1210, M-1420, M-1620, M-1820, M-2020, M-3420, M-3620, M-3820, M-4020 , M-3433, M-3633, M-3833, M-4033, M-5210, M-5410, M-5610, M-5810, M-6010, M-721 0, M-7310, R-1110, R-1210, R-1420, R-1620, R-1820, R-2020, R-1433, R-1633, R-1833, R-3420, R-3620, R-3820, R-4020, R-3433, R-5210, R-5410, R-5610, R-5810, 6010, R-7210, R-7310, U-1310, U-1710 and Nippon Mektron Corporation CHEMINOX FA, FA-M, FAAC, FAAC-M, FAMAC, FAMAC-M, etc. manufactured by a company are listed.

  The compound produced by the telomer method can be easily led to a polymer having a fluoroaliphatic group in the side chain by a method known to those skilled in the art.

  In the present invention, a fluoroaliphatic compound produced by an oligomerization method (oligomer method) is also preferable as the perfluoroalkyl group-containing polymer. The oligomerization method is a method for producing an oligomer by cationic polymerization of tetrafluoroethylene in a polar solvent such as diglyme using potassium fluoride or cesium fluoride as a catalyst. As a specific example, Synthesis Example 3 below is shown. The fluoroaliphatic compound obtained by the oligomer method, like the compound by the telomer method described above, uses a reactive group (unsaturated bond) in the oligomer obtained by polymerization and undergoes appropriate chemical modification, and then the fluoroaliphatic compound. A polymer derived from a compound can be led to a polymer having a side chain (that is, a perfluoroalkyl group-containing polymer).

(B) Polymer having the structure represented by the formula (I) In the present invention, the pearl fluoroalkyl group-containing polymer preferably has the structure of the following formula (I) from the viewpoint of uneven distribution on the ink surface. .

In formula (I), R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents a polymer chain, X represents a single bond or a divalent linking group (organic Group), m represents an integer of 0 or more, and n represents an integer of 1 or more. When m is 2 or more, functional groups on adjacent carbons (that is, R ₂ or R ₃ bonded to adjacent carbons) may be bonded to form an aliphatic ring. .

  Among the perfluoroalkyl group-containing polymers having the structure represented by the above formula (I), n in the formula (I) is preferably 1 to 10, more preferably 1 to 4, 2 or 3 is particularly preferred.

  That is, in the present invention, the perfluoroalkyl group-containing polymer has a structure represented by the following formula (IB) of the side chain moiety bonded to the polymer chain, and in particular, n = 2 or 3 It was found that very good performance was exhibited.

In formula (IB), R ₂ and R ₃ , X, m, and n are all synonymous with R _2, R ₃ , X, m, and n in formula (I).

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₂ and R ₃ in the formulas (I) and (IB) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Tert-butyl group and the like, and R ₂ and R ₃ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the formula (I) and the formula (IB), the single bond represented by X represents a case where it is directly bonded to the polymer main chain. Examples of the divalent linking group (organic group) include —O—, —S—, —N (R ₄ ) —, —CO—, and the like. Among these, -O- is more preferable.

R ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. R ₄ is preferably a hydrogen atom or a methyl group.

  m represents an integer of 0 or more, an integer of 2 to 8 is preferable, and m = 2 is particularly preferable. When m is 2 or more, functional groups on adjacent carbons may be bonded to form an aliphatic ring.

  n represents an integer of 1 or more, and an integer of 1 to 10 is preferable. Here, n is more preferably 1 to 4, and further preferably n is 2 or 3.

In the formula (I), Y represents a polymer chain. Examples of the polymer chain represented by Y include the following examples.
Specific forms include acrylic resin, methacrylic resin, styryl resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation resin, polyvinylphenol resin, maleic anhydride / α-olefin resin, An α-hetero-substituted methacrylic resin or the like can be used. Among these, acrylic resins, methacrylic resins, styryl resins, polyester resins, and polyurethane resins are useful, and acrylic resins and methacrylic resins are particularly useful.

(Method for producing perfluoroalkyl group-containing polymer)
Next, a more specific method for producing a perfluoroalkyl group-containing polymer that is suitably used in the present invention, including a polymer that satisfies the requirements described in the above (a) and (b) will be described. In the present invention, the perfluoroalkyl group-containing polymer can be easily obtained by a method known to those skilled in the art, such as condensation polymerization, addition polymerization, and ring-opening polymerization, using an appropriate polymerizable monomer.
The polymer satisfying the requirement (a) can be produced by appropriately selecting a raw material for the fluorine-containing monomer. The polymer satisfying the requirement (b) can be produced by appropriately selecting raw materials at the time of production and polymerization of the monomer, and further mixing as necessary or mixing the polymer after polymerization.

  The following are examples of acrylic resins and methacrylic resins that are most useful and excellent in polymer production suitability, and in particular have polymers that satisfy the requirements of (b) above (that is, have the structure represented by the formula (I)). The method for producing the polymer) will be described in more detail.

  Among the perfluoroalkyl group-containing polymers, as a preferred embodiment of the polymer corresponding to the acrylic resin, a polymer polymerized using a monomer represented by the following formula (II) can be given. That is, it is a polymer obtained by homopolymerizing the monomer represented by the formula (II) or copolymerizing it with another copolymerizable monomer.

In formula (II), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted methyl group or an optionally substituted ethyl group. R ₂ and R ₃ , X, m and n are all the same as R ₂ and R ₃ in formula (IB), X, m and n.

In the formula (II), examples of the halogen atom represented by R ₁ include a fluorine atom, a chlorine atom, and a bromine atom.

  Next, specific examples of the monomer represented by the formula (II) used in the present invention (including specific examples of the monomer used for producing the polymer having the structure represented by the formula (I)) are shown below.

  As a monomer used for producing a perfluoroalkyl group-containing polymer suitably used in the present invention, among the fluorine-based monomers represented by the above formula (II), n in the formula (II) is 1 to 10. Is more preferable, 1 to 4 is more preferable, and 2 or 3 is particularly preferable.

  In the present invention, the perfluoroalkyl group-containing polymer preferably contains 4 mmol or more of fluorine atoms in 1 g molecule from the viewpoint of surface orientation, and 25 mmol or less in 1 g molecule from the viewpoint of ink solubility. preferable. A more preferable range is 4 mmol to 8 mmol in 1 g molecule.

In the present invention, the perfluoroalkyl group-containing polymer preferably has a monomer having a radical polymerizable group copolymerizable with the monomer represented by the formula (II) as a copolymerization component.
The radical polymerizable group is preferably a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization. The radical polymerizable group (radical polymerization type polymerizable group) will be described in detail below.

-Radically polymerizable group-
Examples of the radical polymerizable group include a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization, and any substituent having at least one ethylenically unsaturated bond capable of radical polymerization in the polymer may be used. It may be a thing. Examples of polymerizable groups having an ethylenically unsaturated bond capable of radical polymerization include acrylic acid ester groups, methacrylic acid ester groups, itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, and maleic acid ester groups. Examples thereof include radically polymerizable groups such as unsaturated carboxylic acid ester groups and styrene groups. Among these, a methacrylic acid ester group and an acrylic acid ester group are preferable.

  In the present invention, a preferred embodiment of the perfluoroalkyl group-containing polymer is a methacrylic resin or an acrylic resin.

  Below, the preferable specific example of a perfluoroalkyl group containing polymer is given. The present invention is not limited to these specific examples. In addition, the following polymers are represented by weight ratio of monomer units.

Among these, preferred examples of the perfluoro group-containing polymer include FRP-3, FRP-5, FRP-8, FRP-9, FRP-10, and FRP-11, and particularly preferably FRP-3 and FRP-. 5, FRP-8 and FRP-9.
The perfluoroalkyl group-containing polymer may have an ethylenically unsaturated bond in the side chain. In the present invention, the molecular weight of the polymerizable monomer is 1,000 or less, and the perfluoropolymer having a molecular weight exceeding 1,000 is used. Even if the alkyl group-containing polymer has an ethylenically unsaturated bond, it does not correspond to a polymerizable monomer.

<Polymerization initiator>
The polymerization initiator that can be used in the present invention is preferably a radical polymerization initiator, and a known radical polymerization initiator can be used. The radical polymerization initiator that can be used in the present invention may be used alone or in combination of two or more. Moreover, you may use together a radical polymerization initiator and a cationic polymerization initiator.
The radical polymerization initiator that can be used in the present invention is a compound that absorbs external energy to generate a polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat and actinic radiation, and a thermal polymerization initiator and a photopolymerization initiator are used, respectively. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.
In the present invention, the ink composition contains at least a radical polymerization initiator as a polymerization initiator, and when a cationic polymerizable compound is used as a polymerizable compound, it is preferable to use a cationic polymerization initiator in combination.

[Radical polymerization initiator]
The radical polymerization initiator that can be used in the present invention includes (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, and (e) thio compounds. (F) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, (l) carbon halogen bond And (m) an alkylamine compound. These radical polymerization initiators may use the above compounds (a) to (m) alone or in combination. The radical polymerization initiator in the present invention is preferably used alone or in combination of two or more.

  Preferable examples of (a) aromatic ketones and (e) thio compounds include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. FOUASSIER J.M. F. RABEK (1993), pp. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77-117. Preferred examples of (a) aromatic ketones, (b) acylphosphine compounds, and (e) thio compounds include α-thiobenzophenone compounds described in JP-B-47-6416, JP-B-47-3981. Benzoin ether compounds described in Japanese Patent Publication No. 47-22326, α-substituted benzoin compounds described in Japanese Patent Publication No. 47-22326, benzoin derivatives described in Japanese Patent Publication No. 47-23664, and aroylphosphonic acid esters described in Japanese Patent Publication No. 57-30704. Dialkoxybenzophenone described in JP-B-60-26483, benzoin ethers described in JP-B-60-26403, JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318 791 and European Patent No. 0284561A1, α-amino Nzophenones, p-di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597 And acylphosphine described in JP-B-2-9596, thioxanthones described in JP-B-63-61950, and coumarins described in JP-B-59-42864.

  Examples of the benzophenone compound include benzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4'-methylphenyl sulfide and the like. Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and the like.

In addition, (a) aromatic ketones are preferably α-hydroxy ketones such as 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- ON, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone and the like.
Among these, as the (a) aromatic ketone, a 1-hydroxycyclohexyl phenyl ketone compound is particularly preferable. In the present invention, the 1-hydroxycyclohexyl phenyl ketone compound means a compound in which 1-hydroxycyclohexyl phenyl ketone and 1-hydroxycyclohexyl phenyl ketone are substituted with an arbitrary substituent. The substituent can be arbitrarily selected as long as it can exhibit the ability as a radical polymerization initiator, and specific examples thereof include alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group). it can.

Moreover, as the (b) acylphosphine compound, an acylphosphine oxide compound is preferable.
Examples of the acylphosphine oxide compound include those having the structural formula of formula (7) or formula (8) in the structure of the compound.

  In particular, as the acylphosphine oxide compound, those having a chemical structure of the formula (9) or the formula (10) are particularly preferable.

（式中、Ｒ₆、Ｒ₇、Ｒ₈はメチル基又はエチル基を置換基として有していてもよい芳香族
炭化水素基を表す。）

(In the formula, R ₆ , R ₇ and R ₈ represent an aromatic hydrocarbon group which may have a methyl group or an ethyl group as a substituent.)

（式中、Ｒ₉、Ｒ₁₀、Ｒ₁₁はメチル基又はエチル基を置換基として有していてもよい芳香
族炭化水素基を表す。）

(In formula, R < ₉ >, R < ₁₀ >, R < ₁₁ > represents the aromatic hydrocarbon group which may have a methyl group or an ethyl group as a substituent.)

  As the acylphosphine oxide compound, a monoacylphosphine oxide compound, a bisacylphosphine oxide compound, or the like can be used. As the monoacylphosphine oxide compound, a known monoacylphosphine oxide compound can be used. Examples thereof include monoacylphosphine oxide compounds described in JP-B-60-8047 and JP-B-63-40799. Specific examples include isobutyrylmethylphosphinic acid methyl ester, isobutyrylphenylphosphinic acid methyl ester, pivaloylphenylphosphinic acid methyl ester, 2-ethylhexanoylphenylphosphinic acid methyl ester, pivaloylphenylphosphinic acid isopropyl Ester, p-toluylphenylphosphinic acid methyl ester, o-toluylphenylphosphinic acid methyl ester, 2,4-dimethylbenzoylphenylphosphinic acid methyl ester, p-tert-butylbenzoylphenylphosphinic acid isopropyl ester, acryloylphenylphosphinic acid methyl ester , Isobutyryl diphenyl phosphine oxide, 2-ethylhexanoyl diphenyl phosphine oxide, o-toluyl diphenyl phosphite Oxide, p-tert-butylbenzoyldiphenylphosphine oxide, 3-pyridylcarbonyldiphenylphosphine oxide, acryloyl-diphenylphosphine oxide, benzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid vinyl ester, adipoylbisdiphenylphosphine oxide, pivaloyl Diphenylphosphine oxide, p-toluyldiphenylphosphine oxide, 4- (tertiarybutyl) benzoyldiphenylphosphine oxide, terephthaloylbisdiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, versatoyldiphenylphosphine oxide, 2-methyl-2 -Ethylhexanoyldiphenylphosphine oxide, 1- Chill - cyclohexanoyl diphenylphosphine oxide, pivaloyl phenyl phosphinic acid methyl ester and pivaloyl phenyl phosphinic acid isopropyl ester.

  A known bisacylphosphine oxide compound can be used as the bisacylphosphine oxide compound. Examples thereof include bisacylphosphine oxide compounds described in JP-A-3-101686, JP-A-5-345790, and JP-A-6-298818. Specific examples include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxy. Phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthyl Phosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) decylphosphite Oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5- Dimethylphenylphosphine oxide, bis (2,6-dichloro3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2- Methyl-1-naphthoyl) -2-naphthy Phosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methoxy-1-naphthoyl) ) -4-engineered phenylphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Etc.

  Among these, in the present invention, as the acylphosphine oxide compound, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819: manufactured by Ciba Specialty Chemicals), bis (2,6-dimethoxybenzoyl) Preferred are -2,4,4-trimethyl-pentylphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Darocur TPO: Ciba Specialty Chemicals, Lucirin TPO: BASF).

(C) As aromatic onium salt compounds, elements of Groups 15, 16 and 17 of the periodic table, specifically N, P, As, Sb, Bi, O, S, Se, Te, or I fragrances Group onium salts are included. For example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-96514, European Patent Nos. 370693, 233567, and 297443 are disclosed. The diazonium salts described in the specifications of U.S. Pat. Nos. 2,974,279, 279210, and 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760013, 4,734,444, and 2,833,827. Benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine, etc.), N-alkoxypyridinium salts, etc. (for example, US Pat. No. 4,743,528, JP-A-63) -138345, JP-A-63 142345, JP-A-63-142346, and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc. Kosho 52-1
No. 47277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

  (D) The organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include 3,3 ′, 4,4′-tetra- ( t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-hexylperoxycarbonyl) ) Benzophenone, 3,3 ′, 4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (cumylperoxycarbonyl) benzophenone, 3,3 ′, Perester ester compounds such as 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di-t-butyldiperoxyisophthalate Thing is preferable.

  (F) Examples of hexaarylbiimidazole compounds include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2 , 2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5 ' Tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 Examples include ', 5,5'-tetraphenylbiimidazole.

  (G) Examples of the ketoxime ester compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane-3. -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminotan-2-one, 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  (H) Examples of the borate compound include compounds described in US Pat. Nos. 3,567,453, 4,343,891, European Patents 109,772, and 109,773. Can be mentioned.

  (I) Examples of azinium compounds include those disclosed in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537, and JP-B-46-42363. The compound group which has NO bond of each gazette description can be mentioned.

  (J) Examples of metallocene compounds include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705. And the iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  (K) Examples of the active ester compound include the specifications of European Patent Nos. 0290750, 046083, 156153, 271851, and 0388343, U.S. Pat. Nos. 3,901,710, and 4,181,531. Nitrobenzol ester compounds described in JP-A-60-198538 and JP-A-53-133022, European Patents 0199672, 84515, 199672, 0441115, and 0101122. No. 4,618,564, U.S. Pat. No. 4,371,605, and U.S. Pat. No. 4,431,774, and JP-A 64-18143, JP-A-2-245756, and JP-A-4-365048. Iminosulfonate compound, Japanese Examined Patent Publication No. 62-6223, Japanese Examined Publication No. 63 No. 14340, and compounds, and the like described in the JP-A No. 59-174831.

  (L) Preferable examples of the compound having a carbon halogen bond include, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, Examples thereof include compounds described in Japanese Utility Model Publication No. 53-133428, compounds described in German Patent No. 3337024, and the like.

Further, compounds described in J. Org. Chem., 29, 1527 (1964) by FC Schaefer et al., Compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and the like can be mentioned. it can. Compounds as described in German Patent No. 2641100, compounds described in German Patent No. 3333450, compounds described in German Patent No. 3021590, or German Patent No. 3021599 And the like, and the like.

In the present invention, the ink composition preferably contains an acyl phosphine oxide compound, more preferably an acyl phosphine compound and a benzophenone compound or a thioxanthone compound are used in combination, or an acyl phosphine compound and an α-aminoketone compound are used in combination. Particularly preferably, an acylphosphine compound and a benzophenone compound are used in combination. By the above combination, an ink composition having excellent curability and blocking resistance can be obtained.

(Cationic polymerization initiator)
In the present invention, when a cationically polymerizable compound is used, it is preferable to use a radical polymerization initiator and a cationic polymerization initiator in combination. As the cationic polymerization initiator (photoacid generator) that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization is used (Organic Electronics Materials Research Group, “For Imaging”). “Organic materials”, Bunshin Publishing (1993), pages 187-192).

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salt of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, phosphonium, etc. be able to. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide can also be used. Fourthly, an iron allene complex can be mentioned.

In the ink composition that can be used in the present invention, the total use amount of the polymerization initiator is preferably 0.01 to 35% by weight, more preferably 0.5 to 20%, based on the total use amount of the polymerizable monomer. % By weight, more preferably in the range of 1.0 to 15% by weight. When the content is 0.01% by weight or more, the composition can be sufficiently cured, and when it is 35% by weight or less, a cured film having a uniform degree of curing can be obtained.
In the present invention, when a sensitizer described later is used in the ink composition, the total amount of the polymerization initiator is preferably a polymerization initiator: sensitizer weight ratio with respect to the sensitizer. Is in the range of 200: 1 to 1: 200, more preferably 50: 1 to 1:50, and even more preferably 20: 1 to 1: 5.

<Colorant>
In the present invention, the ink composition may contain a colorant in order to improve the visibility of the formed image portion.
The colorant that can be used in the present invention is not particularly limited, but pigments and oil-soluble dyes that are excellent in weather resistance and excellent in color reproducibility are preferable, and are arbitrarily selected from known colorants such as soluble dyes. Can be used. As a colorant that can be suitably used in the ink composition, it is preferable to select a compound that does not function as a polymerization inhibitor in a polymerization reaction that is a curing reaction, from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation.

Although it does not necessarily limit as a pigment which can be used for this invention, For example, the organic or inorganic pigment of the following number described in a color index can be used.
Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 42, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36,
Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17-1,22,27,28,29,36,60 as a blue or cyan pigment ,
As a green pigment, Pigment Green 7, 26, 36, 50,
As yellow pigments, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137 , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193,
As the black pigment, Pigment Black 7, 28, 26,
As a white pigment, Pigment White 6, 18, 21
Etc. can be used according to the purpose.

Below, the oil-soluble dye which can be used by this invention is demonstrated.
The oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the weight of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Therefore, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.

  Among the oil-soluble dyes that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Examples include methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dye species such as quinophthalone dyes, nitro / nitroso dyes, acridine And dyes and acridinone dyes.

  Of the oil-soluble dyes usable in the present invention, any magenta dye can be used. For example, aryl or hetaryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Among the oil-soluble dyes applicable to the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components; indigo / thioindigo dyes;

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated. In this case, the counter cation may be an alkali metal or ammonium. Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a partial structure may be used.

Although not limited to the following, preferred specific examples include C.I. I. Solvent Black 3, 7, 27, 29 and 34; C.I. I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; C.I. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; I. Solvent Violet 3; C.I. I. Solvent Blue 2,11,25,35,38,67 and 70; I. Solvent Green 3 and 7; I. Solvent orange 2; and the like.
Among these, particularly preferred are the Black Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue chemistry 2606e Bile 2OSe 2B eO (Manufactured by Co., Ltd.), Aizen Spillon Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, and Neo42 Cy FF4012.
In the present invention, the oil-soluble dye may be used alone or in combination of several kinds.

Moreover, when using an oil-soluble dye as a colorant, other water-soluble dyes, disperse dyes, pigments, and other colorants can be used in combination as long as the effects of the present invention are not impaired.
In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. The disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent. Preferable specific examples of the disperse dye include C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1,177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse Violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 , 257, 266, 267, 287, 354, 358, 365 and 368; I. Disperse Green 6: 1 and 9;

  The colorant that can be used in the present invention is preferably appropriately dispersed in the ink after being added to the ink composition. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.

In preparing the ink composition, the colorant may be added directly with each component, but in order to improve dispersibility, it is added in advance to a dispersion medium such as a solvent or a radical polymerizable compound used in the present invention. It can also be blended after being uniformly dispersed or dissolved.
In the present invention, in order to avoid the problem of deterioration of solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent, the colorant is a radical polymerizable compound. It is preferable to add and mix in advance in such a dispersion medium. In consideration of only dispersibility, it is preferable to select a monomer having the lowest viscosity as the polymerizable compound used for the addition of the colorant.

  These colorants may be used by appropriately selecting one type or two or more types according to the purpose of use of the ink composition.

When using a colorant such as a pigment that remains solid in the ink composition, the average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm, more preferably 0.01 to It is preferable to set the colorant, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so as to be 0.45 μm, more preferably 0.015 to 0.4 μm. This particle size control is preferable because clogging of the head nozzle can be suppressed and ink storage stability, ink transparency, and curing sensitivity can be maintained.
The content of the colorant in the ink composition is appropriately selected depending on the color and purpose of use, but is preferably 0.01 to 30% by weight with respect to the weight of the whole ink composition.

  In the present invention, the weight ratio of the dispersant to the pigment is such that when the weight of the pigment in the ink composition is P and the weight R of the dispersant in the ink composition, the weight ratio (R / P) is 0. 0.05 ≦ R / P ≦ 15 is preferable, 0.1 ≦ R / P ≦ 10 is more preferable, and 0.1 ≦ R / P ≦ 5 is further more preferable. It is preferable that the weight ratio of the dispersant to the pigment is 0.5 or more because an ink composition excellent in storage stability with time can be obtained without causing aggregation and sedimentation of the pigment after storage with time and increase in ink viscosity. In addition, an ink composition having a low ink viscosity and excellent ejection stability can be obtained at a ratio of 15 or less.

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

Dispersor BYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-164D, DisperBYK-164D, , DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA5080, EFKA5504, EFKA5504, EFKA5504, 5, polymer dispersing agents such as EFKA7462, EFKA7500, EFKA7570, EFKA7575, EFKA7580 (manufactured by Fuka Additive), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (Sannopco); Solsperse (Solsperse) 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, etc. (Abyssia); Adeka Pluronic L31 , F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F10 , L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Enomoto Kasei Co., Ltd. “Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ”.
The content of the dispersant in the composition is appropriately selected depending on the purpose of use, but it is preferably 0.05 to 15% by weight with respect to the total weight of the ink composition.

<Other ingredients>
Components other than the above components can be added to the ink composition as necessary.
Examples of other components include sensitizers, co-sensitizers, surfactants, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, solvents, polymer compounds, basic compounds, and the like. .

[Sensitizer]
A sensitizer may be added to the ink composition to absorb specific actinic radiation and promote decomposition of the polymerization initiator, particularly when used for ink jet recording. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the polymerization initiator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
As a sensitizer that can be used in the present invention, a sensitizing dye is preferable.
Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squalium (for example, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

  More preferable examples of the sensitizing dye include compounds represented by the following formulas (IX) to (XIII).

In the formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

In formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in Formula (IX).

In the formula (XI), A ₂ represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with adjacent A ₂ and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (XII), A ³ and A ⁴ each independently represent —S—, —NR ⁶² — or —NR ⁶³ —,
R ⁶² and R ⁶³ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a group together with adjacent A ³ , A ⁴ and adjacent carbon atoms. R ⁶⁰ and R ⁶¹ are each independently a hydrogen atom or a monovalent non-metallic atomic group or bonded to each other to form an aliphatic or aromatic group. Sex rings can be formed.

In the formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or ═NR ⁶⁷ . R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

  Preferable specific examples of the compounds represented by formulas (IX) to (XIII) include (E-1) to (E-20) shown below.

  In the present invention, the content of the sensitizer in the ink composition is appropriately selected depending on the purpose of use, but is generally 0.05 to 4% by weight with respect to the weight of the entire ink composition. preferable.

[Co-sensitizer]
The ink composition preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizer to actinic radiation or suppressing polymerization inhibition of the polymerizable compound by oxygen.
Examples of such co-sensitizers include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethyl phosphite etc.), Si-- described in JP-A-8-54735 H, Ge-H compound, etc. are mentioned.
The content of the co-sensitizer in the ink composition is appropriately selected depending on the purpose of use, but is preferably 0.05 to 4% by weight with respect to the weight of the entire ink composition.

[Surfactant]
A surfactant may be added to the ink composition that can be used in the present invention in order to provide stable ejection for a long time.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts.

[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in US Pat. No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, and so-called fluorescent brighteners.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.5 to 15% by weight in terms of solid content.

〔Antioxidant〕
An antioxidant can be added to improve the stability of the ink composition. Examples of the antioxidant include European Published Patent Nos. 223739, 309401, 309402, 310551, 310552, 457416, and German Patent No. 3435443. JP-A-54-48535, JP-A-62-262047, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, and JP-A-3 No. 112449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

[Anti-fading agent]
In the ink composition, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex-based antifading agent include nickel complexes and zinc complexes. No. 17643, Nos. VII to I, J. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

[Conductive salts]
Conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition for the purpose of controlling ejection properties.

〔solvent〕
It is also effective to add an extremely small amount of an organic solvent to the ink composition in order to improve the adhesion to the recording medium.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether Examples include ether solvents.
In this case, it is effective to add the solvent within the range that does not cause the problem of solvent resistance and VOC. % Range.

[Polymer compound]
Various polymer compounds can be added to the ink composition in order to adjust film properties. High molecular compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, as a copolymer composition of the polymer compound, a copolymer containing “carboxyl group-containing monomer”, “alkyl methacrylate ester” or “alkyl acrylate ester” as a structural unit is also preferably used.

[Basic compounds]
The basic compound is preferably added from the viewpoint of improving the storage stability of the ink composition. As the basic compound that can be used in the present invention, known basic compounds can be used. For example, basic inorganic compounds such as inorganic salts, and basic organic compounds such as amines can be preferably used. .

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, polymerization to inhibit the adhesion to recording media such as polyolefin and PET, and the like, The tackifier which does not do can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifier resin having a polymerizable unsaturated bond.

<Ink physical properties>
The ink composition preferably has a viscosity at 25 ° C. of 40 mPa · s or less in consideration of dischargeability. More preferably, it is 5-40 mPa * s, More preferably, it is 7-30 mPa * s. Moreover, it is preferable that the viscosity in discharge temperature (Preferably 25-80 degreeC, More preferably, 25-50 degreeC) is 3-15 mPa * s, and it is more preferable that it is 3-13 mPa * s. It is preferable that the composition ratio of the ink composition is appropriately adjusted so that the viscosity is in the above range. By setting the viscosity at room temperature high, even when a porous recording medium is used, ink penetration into the recording medium can be avoided and uncured monomer can be reduced, which is preferable. Further, it is preferable because ink bleeding at the time of ink droplet landing can be suppressed, and as a result, the image quality is improved.

  The surface tension of the ink composition at 25 ° C. is preferably 20 to 35 mN / m. More preferably, it is 23-33 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 35 mN / m or less.

(2) Inkjet recording apparatus and inkjet recording method The tube pump of the present invention can be suitably used for an inkjet recording apparatus.
An ink jet recording apparatus includes: an ink jet recording head that ejects an ink composition onto a recording medium from an ink jet nozzle; a tube pump that feeds the ink composition to the ink jet recording head; and / or ink jet recording the ink composition. A tube pump for draining liquid from the head, and the tube pump is the tube pump of the present invention.
The ink jet recording apparatus of the present invention preferably further comprises an active energy ray irradiating means for irradiating the ink composition ejected onto the recording medium with an active energy ray to be cured.
The ink jet recording method of the present invention is characterized by using the ink jet recording apparatus.
This will be described in detail below.

This will be described with reference to FIGS. 2 and 3, the same reference numerals represent the same objects.
FIG. 2 is a schematic diagram showing an example of the main configuration of the inkjet recording apparatus 20 of the present invention. FIG. 3 is a schematic view showing an example of an ink jet recording apparatus in which the tube pump of the present invention is incorporated.
The ink jet recording apparatus 20 includes a transport unit (not shown) that transports the recording medium 21 forward at the time of printing, and each color (in FIG. 2, yellow (Y), magenta (M), cyan (C ), Black (K)), a plurality of recording heads (inkjet recording heads) 22 for discharging ink, and the recording target for curing the ink composition discharged from the recording heads 22 for each of the plurality of colors It has a carriage 24 that houses active energy ray irradiating means 23 for irradiating and curing the active energy ray on the medium. Further, a maintenance unit 30 having a capping unit 32 for suction and a cleaning unit 31 for performing maintenance of the recording head 22, and a carriage 24 is guided along the horizontal direction (arrow A) during printing or maintenance. A guide rail 25, a home position 40 having a moisturizing cap 41 serving as a stand-by for the carriage 24, and a control unit (illustrated) for controlling each of these parts are provided. In the present invention, the moisturizing cap 41 is not an essential requirement, but it is preferable to include a moisturizing cap in order to prevent the nozzle tip from drying.
2 and 3, reference numeral 50 denotes an ink tank for supplying ink, and the ink composition sent from the ink tank 50 is stored in the intermediate tank 51 at one end and then supplied to the ink supply path through the supply valve 52. 60 is sent to the recording head 22 through 60. In addition, as shown in FIG. 3, it can also be set as the structure which has a circulation flow path which sends the ink composition sent to the recording head 22 to the intermediate tank 51. FIG.
The intermediate tank is an ink tank that is usually provided at a position below the recording head in order to adjust the back pressure of the ink in the recording head, but is not limited thereto.
Alternatively, the ink composition can be directly fed from the ink tank 50 to the liquid chamber 80 provided in the recording head 22 without providing the intermediate tank 51.

The image forming process will be described. A conveyance means (attached illustration) conveys the recording medium 21 on the image forming area C in accordance with the operation of the carriage 24 after the ejection of the ink composition and the irradiation of the active energy ray, and generates an image signal. In response to the ejection of the ink from the recording head 22 and the active energy ray irradiation means 23 (for example, ultraviolet ray irradiation) by the active energy ray irradiation means 23 after the ejection, the recording medium 21 is imaged upon completion. It is conveyed from the formation region C downward (arrow B).
Although not shown in FIG. 2, with respect to the recording medium 21 that has been subjected to inkjet ejection and active energy ray irradiation by scanning, the second recording medium is further moved to a downstream position where the recording medium is transported after the printing area. These actinic radiation irradiation means may be attached to irradiate actinic radiation.

Next, the maintenance process will be described. The maintenance unit 30 includes a capping unit 32 that covers the ink nozzles 81 on the discharge surface 82 of the recording head 22 and sucks the ink composition from the discharge port. A cleaning unit 31 including a blade for wiping off the remaining ink and an ink absorber is formed.
In FIG. 2, a plurality of capping units 32 for sucking ink are provided side by side, and a plurality of recording heads 22 can be sucked at a time during maintenance. However, the present invention is not limited to this, and the recording head 22 can be sucked by sequentially moving one capping portion 32.

At the maintenance timing, the carriage 24 is controlled so that the ejection surface 82 of the recording head 22 and the capping unit 32 face each other. Thereafter, the moving unit is controlled to move the maintenance unit 30 upward (arrow D) until the capping unit 32 and the ejection surface 82 of the recording head 22 are sealed.
When the capping unit 32 covers the nozzle 81 of the recording head 22 and seals the ejection surface 82, a control unit (illustrated) controls the suction pump 74 and sucks ink from the nozzle 81 through the cap unit. The sucked ink is discharged into the collection tank 53 through the liquid feeding tube 83.
When the suction is completed, the moving unit moves the maintenance unit 30 downward (in the direction opposite to the arrow D) so that the ejection surface 82 of the recording head 22 is below the tip of the capping unit 32, and capping. The part 32 is separated from the ejection surface 82, the carriage 24 is stopped on the spot, and the maintenance unit 30 is moved.
During this movement, the blade of the cleaning unit 31 passes through the recording head 22 while rubbing the ejection surface 82 and wiping and cleaning the ink. As a result, the ink remaining on the ejection surface 82 is wiped off and adhered to the sliding surface of the blade, and the ink attached to the blade flows down toward the absorber and is absorbed by the absorber. .

The tube pump of the present invention can be used as a pump 71 for feeding the ink composition from the ink tank 50 to the intermediate tank 51. Further, it may be used as a pump 72 for feeding liquid from the intermediate tank 51 to the recording head 22. Further, it can be used as a pump 73 for feeding liquid from the liquid chamber 80 of the recording head 22 to the intermediate tank 51.
Further, in the maintenance process, it can be used as a pump 74 for sucking ink from the ink jet recording head and discharging it.
In FIG. 3, the arrows indicate the direction of ink feeding.

Furthermore, in the present invention, ink can be filled into the ink jet recording head by the pump 74 shown in FIG. In this case, a cock is provided in the liquid feeding pipe between the intermediate tank 51 and the head 22, and the cock is turned off after sucking with the pump 74 from the nozzle 81 side in the closed state to make the head negative pressure. A method of opening and filling ink from the intermediate tank 51 to the inkjet head 22 can be exemplified. At this time, after the cock is opened, liquid feeding using the pump 72 can be used in combination.
Further, in order to remove bubbles entrained at the time of ink filling, the suction / stop by the pump 74 can be repeated and the bubbles can be discharged from the head.
The ink jet recording apparatus of the present invention is not particularly limited as long as the tube pump of the present invention is used for feeding the ink composition and / or waste liquid.
Among these, it is preferable to use for the waste liquid (liquid absorption) from an inkjet recording head.

(3) Printed matter The printed matter of this invention will not be specifically limited if it is a printed matter obtained by the said inkjet recording device and / or the inkjet recording method.
In the present invention, the material used for the recording medium is not particularly limited, and any material may be used. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film on which the above-mentioned metal is laminated or deposited. A preferable support includes a polyester film and an aluminum plate.

  EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In Examples, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

(Preparation of ink composition)
The materials of the ink composition (radical polymerizable composition) used in the present invention are as shown below.
・ IRGALITE BLUE GLVO (Cyan Pigment, Ciba Specialty Chemicals)
・ CINQUASIA MAGENTA RT-335 D (Magenta pigment, manufactured by Ciba Specialty Chemicals)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
SPECIAL BLACK 250 (black pigment, manufactured by Ciba Specialty Chemicals)
・ Taipeku CR60-2 (white pigment, manufactured by Ishihara Sangyo Co., Ltd.)
・ N-Vinylcaprolactam (NVC, manufactured by BASF)
FA-513A (dicyclopentanyl acrylate, manufactured by Hitachi Chemical Co., Ltd.)
SR9003 (propylene glycol modified neopentyl glycol diacrylate, manufactured by Sartomer)
Solsperse 36000 (Noveon dispersant)
DisperBYK-168 (BYK168, BYK Chemie polymer dispersant, solid content 30%)
NK ester AMP-10G (NK AMP-10G, PEA (phenoxyethyl acrylate), manufactured by Shin-Nakamura Chemical Co., Ltd.)
-Rapi-Cure DVE-3 (DVE-3, triethylene glycol divinyl ether, manufactured by ISP Europe)
FIRSTCURE ST-1 (polymerization inhibitor, manufactured by Chem First)
Irgacure 819 (polymerization initiator (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), manufactured by Ciba Specialty Chemicals)
Irgacure 184 (polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone), manufactured by Ciba Specialty Chemicals)
Darocur TPO (polymerization initiator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), manufactured by Ciba Specialty Chemicals)
・ Benzophenone (Photoinitiator, Wako Pure Chemical Industries, Ltd.)

(Preparation of cyan mill base A)
300 parts by weight of IRGALITE BLUE GLVO, 500 parts by weight of NK AMP-10G, and 200 parts by weight of BYK168 were mixed with stirring to obtain cyan mill base A. Cyan mill base A was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of magenta mill base B)
300 parts by weight of CINQUASIA MAGENTA RT-335 D, 400 parts by weight of NK AMP-10G, and 300 parts by weight of BYK168 were mixed with stirring to obtain magenta mill base B. The magenta mill base B was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 8 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of yellow mill base C)
300 parts by weight of NOVOPERM YELLOW H2G, 400 parts by weight of NK AMP-10G, and 300 parts by weight of BYK168 were mixed with stirring to obtain Yellow Mill Base C. The yellow mill base C was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 8 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of black mill base D)
300 parts by weight of SPECIAL BLACK 250, 400 parts by weight of NK AMP-10G, and 300 parts by weight of BYK168 were mixed with stirring to obtain a black mill base D. The black mill base D was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 6 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of white mill base E)
A white mill base E was obtained by stirring and mixing 500 parts by weight of Tyco CR60-2, 450 parts by weight of NK AMP-10G, and 50 parts by weight of Solsperse 36000. The white mill base E was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Ink production)
Each material was mixed with a stirrer to obtain an ink composition. The formulations are shown in Tables 1 to 4 below. In addition, in the table | surface, the addition amount of each raw material is shown by weight%.
Also, the total amount of monofunctional monomers (% by weight) relative to the total amount of the ink composition, the total amount of polycyclic monomers (% by weight) relative to the total amount of the ink composition, and the ratio of the monofunctional monomer to the total amount of polymerizable monomers (weight) %).

(Production of tube pump)
<Tube>
[Fluorine rubber tube]
A Kalrez (trade name) tube (manufactured by DuPont) was used as the fluorine rubber tube.

[Silicon rubber tube]
As the silicon rubber tube, Tygon (trade name) 3355-L high performance platinum vulcanized silicone tube for roller pump (manufactured by Saint-Gobain Co., Ltd.) was used.

[Polyvinyl chloride tube]
An EXLON-soft PVC hose (manufactured by Iwase Co., Ltd.) was used as the polyvinyl chloride tube.

<Pump frame>
[Manufacture of pump frame made of polyamide resin]
The pump frame made of polyamide resin was produced by injection molding using 6-nylon.

[Manufacture of pump frames made of high-density polyolefin resin]
A pump frame made of high-density polyolefin resin was produced by injection molding using high-density polyethylene resin.

[Manufacture of pump frame made of polyester resin]
A pump frame made of a polyester resin was produced by injection molding.

[Manufacture of pump frames made of metal]
The pump frame made of metal was produced by press molding using SUS304.

[Manufacture of pump frame made of polycarbonate resin]
A pump frame made of polycarbonate was produced by an injection molding method.

<Manufacture of tube pump>
The tube and pump frame manufactured as described above were assembled as shown in FIG. 1 to produce a tube pump.

(Image recording and evaluation)
<Image recording>
The prepared ink sets 1 to 3 were subjected to an inkjet printing experimental machine (droplet ejection frequency: 6.2 KHz, nozzle number: 636, nozzle density: 300 npi (nozzle / inch, the same applies hereinafter), drop size: 6 pl to 42 pl in 7 stages. A variable head was mounted, and exposure was performed using a metal halide lamp.
The tube pump was attached to the position of the pump 74 in FIG. The pump 74 was connected with a liquid feeding tube 83 and a rubber capping unit 32. At the time of ink filling, the capping unit 32 was pressed against the nozzle 81 of the recording head 22 to suck the ink with a negative pressure. This filled each recording head with the ink composition.
Next, after the ink composition set is ejected onto the recording medium by the head loaded with the ink set, the metal halide lamp is irradiated with ultraviolet rays (wavelength 365 nm) at a light intensity of 3,000 mW / cm ² to form an image. Immobilized.
In this case, the drawn image is a line drawn at 600 dpi in the main scanning direction and 150 dpi in the sub-scanning direction (use of 1 drop: 6 pL droplet ejection).
The recording medium was conveyed by roll conveyance, and easy-adhesion-treated PET (HK-31WF: manufactured by Higashiyama Film) was used as the recording medium.

(Evaluation of support member)
Using the above printer, images were created at 10 sheets / day, and the cracks of the pump-carrying member after one month of use were observed and evaluated with the naked eye. At the start of image formation on the 1st, 10 ml of the ink composition was sucked from the nozzle side using the tube pump in order to replace the ink remaining in the head with new ink.
Further, using the number of rotations of the roller required for sucking 10 ml of ink at the start of use, the same ink suction operation was performed one month later, and the amount of the ink composition discharged from the pump was measured.
The evaluation criteria are as follows.
3: No change is observed in the supporting member, and the pump discharge amount is 10 ml. 2: The supporting member is partially cracked and the pump discharge amount is 10 ml or less. 1: The supporting member is cracked and the pump is discharged. The volume is 5ml or less

[Flexibility evaluation method: Bending test]
A bending test was performed as a method of evaluating the flexibility of the color image printed matter.
In the bending test, the recording medium on which an image was formed was bent once, five times and ten times at 25 ° C., and evaluated by the presence or absence of cracks in the image portion.
The evaluation criteria are as follows.
3: No cracking occurs in the bent portion of the color image print 10: 2: No crack is generated in the bent portion of the color image print 5; No crack is generated in the bent portion of 1, but no crack is generated in the bent portion 10 Occurrence 1: Cracks are generated in the bent portion of the color image printed matter. The results are shown in the following table.

It is the schematic which shows an example of the tube pump which can be used conveniently in this invention. It is the schematic which shows an example of the main structures of the inkjet recording device of this invention. It is a schematic diagram which shows an example of the inkjet recording device incorporating the tube pump of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Tube pump 10 Tube 11 Pump frame 12a, 12b Roller 14 Pump wheel 20 Inkjet recording device 21 Recording medium 22 Recording head 23 Active energy ray irradiation means 24 Carriage 25 Guide rail 30 Maintenance unit 31 Cleaning part 32 Capping part 40 Home position 41 Moisturizing cap 50 Ink tank 51 Intermediate tank 52 Supply valve 53 Recovery tank 60 Ink supply paths 71, 72, 73, 74 Pump 80 Liquid chamber 81 Nozzle 82 Discharge surface 83 Liquid supply tube

Claims (10)

A flexible tube;
A pump frame having a tube support surface that regulates the outer shape of the flexible tube, and formed of at least one material selected from the group consisting of polyamide resin, high-density polyolefin resin, polyester resin, and metal;
A roller that pressurizes and deforms the flexible tube,
The flexible tube is pressure-deformed by the roller to feed and / or waste the ink composition ;
The tube pump, wherein the ink composition contains a polymerizable monomer, and the monofunctional polymerizable monomer is 40 wt% or more and 100 wt% or less with respect to the total amount of the polymerizable monomer .   The tube pump according to claim 1, wherein the flexible tube is made of silicon rubber and / or fluorine rubber.   The tube pump according to claim 1 or 2, wherein the pump frame is a pump frame formed of a polyamide resin. The tube pump according to any one of claims 1 to 3, wherein the polymerizable monomer contains a polymerizable monomer containing a nitrogen atom. The tube pump according to any one of claims 1 to 4, wherein the polymerizable monomer contains phenoxyethyl acrylate.   The tube pump according to claim 1, wherein the ink composition contains a perfluoroalkyl group-containing polymer. An ink jet recording head for ejecting an ink composition from an ink jet nozzle onto a recording medium;
A tube pump for feeding the ink composition to the ink jet recording head, and / or a tube pump for draining the ink composition from the ink jet recording head,
An ink jet recording apparatus, wherein the tube pump is the tube pump according to any one of claims 1 to 6.   The ink jet recording apparatus according to claim 7, further comprising active energy ray irradiating means for irradiating and curing the ink composition ejected on the recording medium with active energy rays.   An ink jet recording method using the ink jet recording apparatus according to claim 7.   A printed matter obtained by the inkjet recording method according to claim 9.

Images