JP2019156893A - Cure-type composition, cure-type inkjet ink, cured product, receiving container, 2-dimension or 3-dimension image forming apparatus, and 2-dimension or 3-dimension image forming method - Google Patents

Abstract

To provide a cure-type composition that has both drawability and anti-blocking property and can suppress density unevenness during drawing.SOLUTION: Provided is a cure-type composition containing: N-vinylcaprolactam; a polymerizable monofunctional monomer other than the N-vinylcaprolactam, for example, phenoxyethyl (meth)acrylate, cyclic TMP formal(meth)acrylate, isobornyl(meth)acrylate and the like; and, as a pigment dispersant, a copolymer having a specific structural unit.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, a curable inkjet ink, a cured product, a container, a two-dimensional or three-dimensional image forming apparatus, and a two-dimensional or three-dimensional image forming method.

  Conventionally, photopolymerizable inkjet inks have been supplied and used for offsets, silk screens, topcoats, etc. In recent years due to benefits such as cost reduction by simplifying the drying process and reduction of solvent volatilization as an environmental response. Usage is increasing.

  A lot of water-based and solvent-based inks are used as ink-jet inks, and the usage is properly used according to the characteristics of each. However, for industrial use, the receiving substrate (member to which the ink is applied) is limited, It is expected to be replaced with a photopolymerizable inkjet ink having relatively low volatility, a problem that ink drying energy is large, and adhesion of ink components to the head due to drying. ing.

Therefore, for example, a polymerizable ink that is excellent in curability and has excellent blocking resistance and extensibility of the obtained image has been proposed for printing that requires processability on the printed matter (for example, Patent Document 1).
Further, N-vinylcaprolactam, monofunctional acrylate having an aromatic ring, monofunctional acrylate having an aliphatic hydrocarbon ring, a polyether-modified silicone compound having a (meth) acrylate group, and a glass transition temperature (Tg) of 20 ° C. to 20 ° C. An ink-jet ink composition containing an acrylic resin at 100 ° C. has been proposed (see, for example, Patent Document 2).

Further, an ink containing a structural unit represented by the following general formula (1) and a copolymer containing a structural unit represented by the following general formula (2) has been proposed (see, for example, Patent Document 3). .
R ¹ represents either a hydrogen atom or a methyl group. L ¹ represents any ^one of —COO—, —OCO—, —CONR ¹¹ —, and an optionally substituted phenylene group, and R ¹¹ represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. Represents either. Z ¹ represents any of a single bond, an alkylene group having 1 to 20 carbon atoms, and an alkenylene group having 2 to 20 carbon atoms. m represents an integer of 3 to 30. A represents an aromatic ring.
R ² represents either a hydrogen atom or a methyl group. L ² represents any one of —COO—, —OCO—, —CONR ¹² —, and an optionally substituted phenylene group, and R ¹² represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. Represents either. Z ² represents any of a single bond, an alkylene group having 1 to 20 carbon atoms, and an alkenylene group having 2 to 20 carbon atoms. n represents an integer of 7 to 90. B represents a hydrogen atom, a methyl group, a formyl group, or an acetyl group.

  An object of the present invention is to provide a curable composition that has both stretchability and blocking resistance and can suppress concentration unevenness during stretching.

  The curable composition of the present invention as a means for solving the above problems includes N-vinylcaprolactam, a polymerizable monofunctional monomer other than the N-vinylcaprolactam, and a structure represented by the following general formula (1) A copolymer having a unit and a structural unit represented by the following general formula (2).

[General formula (1)]
In the general formula (1), R ₃ represents a hydrogen atom or a methyl group. L ₁ represents a divalent linking group having a chain length of 1 to 30 and comprising at least one selected from —NR ₆ —, —CO—, —O—, and an alkylene group having 2 to 18 carbon atoms. . However, R ₆ represents a hydrogen atom or a methyl group.

[General formula (2)]
However, in said general formula (2), R < ₁ > and R < ₂ > represents a hydrogen atom or a methyl group. n represents a number from 1 to 90.

  According to the present invention, it is possible to provide a curable composition that has both stretchability and blocking resistance and can suppress concentration unevenness during stretching.

FIG. 1 is a schematic view showing an example of an image forming apparatus according to the present invention. FIG. 2 is a schematic view showing an example of another image forming apparatus according to the present invention. FIG. 3 is a schematic view showing an example of still another image forming apparatus according to the present invention.

(Curable composition)
The curable composition of the present invention is represented by N-vinylcaprolactam, a polymerizable monofunctional monomer other than the N-vinylcaprolactam, a structural unit represented by the following general formula (1), and the following general formula (2). A copolymer having a structural unit, and, if necessary, other components.

[General formula (1)]
In the general formula (1), R ₃ represents a hydrogen atom or a methyl group. L ₁ represents a divalent linking group having a chain length of 1 to 30 and comprising at least one selected from —NR ₆ —, —CO—, —O—, and an alkylene group having 2 to 18 carbon atoms. . However, R ₆ represents a hydrogen atom or a methyl group.

[General formula (2)]
However, in said general formula (2), R < ₁ > and R < ₂ > represents a hydrogen atom or a methyl group. n represents a number from 1 to 90.

The curable composition of the present invention is based on the knowledge that, in the prior art of Patent Document 1, density unevenness occurs when the produced ink film is stretched.
Further, Patent Document 3 discloses a copolymer containing the structural units represented by General Formula (1) and General Formula (2), and the copolymer of Patent Document 3 is used. There is no description or suggestion of solving the problem of density unevenness due to the uneven distribution of N-vinylcaprolactam described in Patent Document 2.

<N-Vinylcaprolactam>
N-vinylcaprolactam is also called N-vinyl-ε-caprolactam and is a polymerizable monofunctional monomer represented by the following structural formula.

  The content of N-vinylcaprolactam is preferably 20 parts by mass or more and 50 parts by mass or less, and more preferably 28 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monofunctional monomer. When the content of N-vinylcaprolactam is 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monofunctional monomer, blocking resistance is improved.

The polymerizable monofunctional monomer other than N-vinylcaprolactam is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenoxyethyl (meth) acrylate, cyclic TMP formal (meth) acrylate, isobornyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, octa / decyl (meth) acrylate, tridecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) An acrylate etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, phenoxyethyl (meth) acrylate and isobornyl (meth) acrylate are preferable.

  In the present invention, when a polyfunctional polymerizable monomer other than the monofunctional polymerizable monomer is used as the polymerizable monofunctional monomer other than N-vinylcaprolactam, there is a problem that stretchability is lowered.

<Curing means>
Examples of means for curing the curable composition of the present invention include heat curing and curing with active energy rays, and among these, curing with active energy rays is preferable.
The active energy ray used for curing the curable composition of the present invention includes a polymerization reaction of polymerizable components in the composition such as electron beam, α ray, β ray, γ ray, X ray in addition to ultraviolet rays. There is no particular limitation as long as it can provide the energy necessary for proceeding the process. In particular, when a high energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. In the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, an ultraviolet light emitting diode (UV-LED) and an ultraviolet laser diode (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are preferable as an ultraviolet light source.

<Polymerization initiator>
The curable composition of the present invention may contain a polymerization initiator. Any polymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays and initiate polymerization of a polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more, and among them, radical polymerization initiators are used. It is preferable. The polymerization initiator is preferably contained in an amount of 5% by mass to 20% by mass with respect to the total mass (100% by mass) of the composition in order to obtain a sufficient curing rate.
Examples of radical polymerization initiators include aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples thereof include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
In addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. The polymerization accelerator is not particularly limited. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl, N, Amine compounds such as N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

<Color material>
The curable composition of the present invention contains a color material. As the coloring material, various pigments imparting black, white, magenta, cyan, yellow, green, orange, glossy color such as gold or silver, etc. are used according to the purpose and required characteristics of the composition in the present invention. be able to. The content of the color material may be appropriately determined in consideration of a desired color density, dispersibility in the composition, and the like, and is not particularly limited. It is preferable that it is 1 mass%-20 mass%.
As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone, or two or more kinds may be used in combination.
As the inorganic pigment, for example, carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, and titanium oxide can be used.
Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, A daylight fluorescent pigment is mentioned.

The curable composition of the present invention contains a pigment dispersant.
As the pigment dispersant, a copolymer having a structural unit represented by the following general formula (1) and the following general formula (2) is used.

[General formula (1)]
In the general formula (1), R ₃ represents a hydrogen atom or a methyl group. L ₁ represents a divalent linking group having a chain length of 1 to 30 and comprising at least one selected from —NR ₆ —, —CO—, —O—, and an alkylene group having 2 to 18 carbon atoms. . However, R ₆ represents a hydrogen atom or a methyl group.

[General formula (2)]
However, in said general formula (2), R < ₁ > and R < ₂ > represents a hydrogen atom or a methyl group. n represents a number from 1 to 90.

  The structural unit of the general formula (1) contained in the copolymer is preferably a structural unit represented by the following general formula (3) or general formula (4), and is represented by the general formula (3). More preferred is a structural unit.

[General formula (3)]
However, In the general formula (3), R ₄ represents a hydrogen atom or a methyl group. L ₂ represents an alkylene group having 2 to 18 carbon atoms.

[General formula (4)]
However, in said general formula (4), a represents the number of 6-10. b represents a number of 0 or 1;

  The method for producing the copolymer having the structural unit represented by the general formula (1) and the general formula (2) is not particularly limited, and various polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension method, and the like. It can be synthesized by a known polymerization method such as a turbid polymerization method or an emulsion polymerization method. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system. Although not limited to these polymerization methods, radical polymerization using the radical polymerization initiator shown below is preferable because the polymerization operation and the adjustment of molecular weight are easy, and a solution polymerization method in which polymerization is performed in a mixed solvent of an organic solvent and water is used. Further preferred.

  The content of the copolymer as a dispersant in the curable composition of the present invention is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the pigment.

The copolymer can be identified using, for example, a ¹ H-NMR spectrum, an IR spectrum, or the like.
The ¹ H-NMR spectrum can be measured using ¹ H-NMR (300 MHz) (manufactured by JEOL) or the like.
The IR spectrum can be measured using FT-IR Spectrum GX (manufactured by PERKIN ELMER).

<Organic solvent>
The curable composition of the present invention may contain an organic solvent, but it is preferable not to contain it if possible. An organic solvent, particularly a volatile organic solvent-free (VOC (Volatile Organic Compounds) free) composition, can further increase the safety of the place where the composition is handled and can prevent environmental pollution. . The “organic solvent” means a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from a reactive monomer. is there. Further, “not including” an organic solvent means that it does not substantially include, and is preferably less than 0.1% by mass.

<Other ingredients>
The curable composition of the present invention may contain other known components as necessary. Other components are not particularly limited. For example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration enhancers, wetting agents (humectants), Fixing agents, viscosity stabilizers, antifungal agents, antiseptics, antioxidants, ultraviolet absorbers, chelating agents, pH adjusting agents, thickeners and the like can be mentioned.

<Preparation of curable composition>
The curable composition of the present invention can be prepared using the various components described above, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant, and the like can be used as a ball mill, a kitty mill, By putting into a dispersing machine such as a disk mill, pin mill, dyno mill and dispersing to prepare a pigment dispersion, and further mixing a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. into the pigment dispersion. Can be prepared.

<Viscosity>
The viscosity of the curable composition of the present invention may be appropriately adjusted according to the application and application means, and is not particularly limited.For example, when applying a discharge means that discharges the composition from a nozzle, The viscosity in the range of 20 ° C. to 65 ° C., desirably the viscosity at 25 ° C. is preferably 3 to 40 mPa · s, more preferably 5 mPa · s to 15 mPa · s, and particularly preferably 6 mPa · s to 12 mPa · s. Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. In addition, the said viscosity uses a cone rotor (1 degree 34'xR24) by Toki Sangyo Co., Ltd. cone plate type rotational viscometer VISCOMETER TVE-22L, rotation speed is 50 rpm, and the temperature of constant temperature circulating water is 20 degreeC. It can be measured by appropriately setting in the range of ~ 65 ° C. VISCOMATE VM-150III can be used for temperature adjustment of circulating water.

<Application>
The application of the curable composition of the present invention is not particularly limited as long as it is a field where curable materials are generally used, and can be appropriately selected according to the purpose. For example, a molding resin, a paint, an adhesive Insulating materials, release agents, coating materials, sealing materials, various resists, various optical materials, and the like.
Further, the curable composition of the present invention is used as an ink to form not only two-dimensional characters and images, and design coatings on various substrates, but also three-dimensional images (three-dimensional objects). It can also be used as a material for three-dimensional modeling. This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder lamination method in which three-dimensional modeling is performed by repeatedly curing and laminating a powder layer, as shown in FIGS. 2 and 3. You may use as a three-dimensional constituent material (model material) and support member (support material) which are used in such a layered modeling method (optical modeling method). 2 is a method of performing three-dimensional modeling by sequentially laminating the cured composition of the present invention onto a predetermined region and irradiating and curing the active energy ray (details will be described later). Irradiates the storage pool (accommodating part) 1 of the curable composition 5 of the present invention with the active energy ray 4 to form a cured layer 6 having a predetermined shape on the movable stage 3, and sequentially laminates the three-dimensional model. It is a method to do.

As a three-dimensional modeling apparatus for modeling a three-dimensional molded article using the curable composition of the present invention, a known one can be used, and is not particularly limited. And those provided with discharge means, active energy ray irradiation means and the like.
The present invention also includes a molded product obtained by processing a cured product obtained by curing a curable composition and a structure in which the cured product is formed on a substrate. The molded product is obtained by subjecting a cured product or structure formed in a sheet shape or a film shape to a molding process such as heat stretching or punching, for example, an automobile, an OA device, an electric -It is suitably used for applications that require the surface to be molded after decorating, such as meters for electronic devices and cameras, and panels for operation units.
The substrate is not particularly limited and can be appropriately selected depending on the purpose. For example, paper, yarn, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof. From the viewpoint of processability, a plastic substrate is preferable.

<Composition container>
The composition storage container of the present invention means a container in which a curable composition is stored, and is suitable for use in the above applications. For example, when the curable composition of the present invention is used for ink, the container in which the ink is stored can be used as an ink cartridge or an ink bottle, thereby enabling operations such as ink transportation and ink replacement. This eliminates the need for direct contact with the ink and prevents dirt on fingers and clothes. In addition, foreign matters such as dust can be prevented from entering the ink. Further, the shape, size, material, and the like of the container itself may be suitable for use and usage, and are not particularly limited, but the material is a light-shielding material that does not transmit light, or the container is shielded from light. It is desirable to be covered with an adhesive sheet.

  In the image forming method of the present invention, active energy rays may be used, and heating may be mentioned. In order to cure the curable composition of the present invention with active energy rays, it has an irradiation step of irradiating with active energy rays, and the image forming apparatus of the present invention comprises irradiation means for irradiating with active energy rays. A container for accommodating the curable composition of the present invention, and the container may be accommodated in the container. Furthermore, you may have the discharge process and discharge means which discharge a curable composition. A method for discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

FIG. 1 is an example of an image forming apparatus provided with an ink jet ejection unit. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by each color printing unit 23 a, 23 b, 23 c, and 23 d including ink cartridges and discharge heads for each color curable ink of yellow, magenta, cyan, and black. Thereafter, the light is cured by irradiating active energy rays from the light sources 24a, 24b, 24c, and 24d for curing the ink, thereby forming a color image. Thereafter, the recording medium 22 is conveyed to the processing unit 25 and the printed matter winding roll 26. Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied by the ink discharge unit. If necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. In addition, as an ink jet recording system, a serial system in which ink is ejected onto a recording medium by moving the head relative to a recording medium that moves intermittently according to the ejection head width, or the recording medium is moved continuously, Any of the line systems in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, and examples thereof include paper, film, ceramics, glass, metal, a composite material thereof, and the like, and may be a sheet shape. Moreover, even if it is the structure which enables only single-sided printing, the structure which also enables double-sided printing may be sufficient. The material is not limited to those used as general recording media, and corrugated cardboards, building materials such as wallpaper and flooring, concrete, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate.
Further, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and the active energy ray may be irradiated from the light source 24d after printing a plurality of colors. Thereby, energy saving and cost reduction can be achieved.
The recorded matter recorded by the ink of the present invention is not only printed on a smooth surface such as ordinary paper or resin film, but also printed on a surface to be printed having irregularities, such as metal or ceramic. It includes those printed on a printing surface made of various materials. Further, by stacking two-dimensional images, it is possible to form an image having a stereoscopic effect (an image composed of two and three dimensions) or a three-dimensional object.

  FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) according to the present invention. The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to transfer the first curable composition from the molded article ejection head unit 30 to the support ejection head unit 31. 32, a second curable composition having a composition different from that of the first curable composition is ejected, and these compositions are laminated while being cured by the adjacent ultraviolet irradiation means 33 and 34. More specifically, for example, the second curable composition is discharged from the discharge head units 31 and 32 for the support on the model support substrate 37, and solidified by irradiation with active energy rays to form the reservoir. After the first support layer is formed, the first curable composition is discharged from the discharge head unit 30 for a molded article to the reservoir, and is solidified by irradiation with active energy rays. The step of forming a layer is repeated a plurality of times while lowering the stage 38 that is movable in the vertical direction in accordance with the number of times of stacking, thereby stacking the support layer and the modeled object layer to manufacture the three-dimensional modeled object 35. Thereafter, the support laminate 36 is removed as necessary. In FIG. 2, only one shaped article discharge head unit 30 is provided, but two or more shaped article discharge head units 30 may be provided.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
[Synthesis of Monomer M1]
62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added. A solution prepared by dissolving 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then at room temperature for 6 hours. Stir. After the obtained reaction solution was washed with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 98/2) as an eluent to obtain 52.5 g of 2-naphthoic acid-2-hydroxyethyl ester.
Next, 42.1 g (155 mmol) of 2-naphthoic acid-2-hydroxyethyl ester was dissolved in 80 mL of dry methyl ethyl ketone and heated to 60 ° C. To this solution, a solution prepared by dissolving 24.0 g (155 mmol) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz MOI) in 20 mL of dry methyl ethyl ketone was added dropwise over 1 hour with stirring. Stir at 12 ° C. for 12 hours. After cooling to room temperature, the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 99/1) as an eluent, and 57.0 g of a monomer having a structure represented by the following structural formula (1) M-1 was obtained.

[Structural formula (1)]

(Synthesis Example 2)
[Synthesis of Monomer M-2]
In Synthesis Example 1, instead of 1,6-hexanediol, 1,16-hexadecanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and in the same manner as Synthesis Example 1, the following structural formula (2) Monomer M-2 having the structure represented was obtained.

[Structural formula (2)]

(Synthesis Example 3)
[Synthesis of Monomer M-3]
Monomer M having a structure represented by the following structural formula (3) in the same manner as in Synthesis Example 1 except that 2-acryloyloxyethyl isocyanate was used instead of 2-methacryloyloxyethyl isocyanate in Synthesis Example 1. -3 was obtained.

[Structural formula (3)]

(Synthesis Example 4)
[Synthesis of Monomer M-4]
62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added.
A solution prepared by dissolving 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then at room temperature for 6 hours. Stir. After the obtained reaction solution was washed with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 98/2) as an eluent, and 52.5 g of a reaction intermediate represented by the following structural formula (4) was obtained. Obtained.

[Structural formula (4)]

  Next, 41.0 g (151 mmol) of the reaction intermediate of the structural formula (4) was dissolved in 250 mL of methylene chloride, and 20.0 g (198 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The solution was cooled in an ice bath, and 20.0 g (191 mmol) of methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring in an ice bath for 1 hour and at room temperature for 3 hours. Stir. The precipitate was filtered off and the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 6/1) as an eluent to obtain 39.4 g of a structure represented by the following structural formula (5). Monomer M-4 was obtained.

[Structural formula (5)]

(Synthesis Example 5)
[Synthesis of Monomer M-5]
150.0 g (1.26 mol) of 1,6-hexanediol and 50.0 g (0.268 mol) of 1-naphthalene acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a reaction vessel and stirred at 70 ° C. Heat and dissolve. 1.30 g of concentrated sulfuric acid was added and stirred at 70 ° C. for 2 hours. After cooling to room temperature, a solution prepared by dissolving 1.06 g of sodium hydroxide in 600 mL of water was added and washed. Ethyl acetate (500 mL) was added, and the organic phase was extracted and further washed with water. The organic phase was isolated and dried over magnesium sulfate and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 3/2) as an eluent, and 61.5 g of a reaction intermediate represented by the following structural formula (6) Got the body.

[Structural formula (6)]

  Next, 43.0 g (150 mmol) of the reaction intermediate represented by the structural formula (6) was dissolved in 250 mL of methylene chloride, and 20.0 g (198 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. It was. The solution was cooled in an ice bath, and 17.4 g (192 mmol) of acrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring in the ice bath for 1 hour and at room temperature for 3 hours. Stir. The precipitate was filtered off and the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 7/1) as an eluent, and 37.6 g of a structure represented by the following structural formula (7) was obtained. Monomer M-5 was obtained.

[Structural formula (7)]

(Synthesis Example 6)
[Synthesis of Monomer M-6]
64.0 g (367 mmol) of 1,10-decanediol (manufactured by Kanto Chemical Co., Inc.) was dissolved in 900 mL of dry tetrahydrofuran, and 17.4 g (220 mmol) of pyridine was added.
A solution prepared by dissolving 35.0 g (183 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then at room temperature for 12 hours. Stir. After adding 500 mL of ethyl acetate and washing with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 4/1) as an eluent, and 43.1 g of a reaction intermediate represented by the following structural formula (8) Got the body.

[Structural formula (8)]

  Next, 32.8 g (100 mmol) of the reaction intermediate of the structural formula (8) was dissolved in 400 mL of methylene chloride, and 17.2 g (170 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The solution was cooled in an ice bath, and 15.0 g (144 mmol) of methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring in an ice bath for 1 hour and at room temperature for 4 hours. Stir. The solvent was distilled off from the reaction solution, dissolved in 300 mL of ethyl acetate, and washed with water. The organic phase was isolated and dried over magnesium sulfate and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / methylene chloride (volume ratio 3/2) as an eluent, and 32.1 g of the structure represented by the following structural formula (9) was obtained. Monomer M-6 having was obtained.

[Structural formula (9)]

(Synthesis Example 7)
[Synthesis of Monomer M-7]
144 g of 2-naphthol, 250 g of ethylene glycol mono-2-chloroethyl ether and 205 g of potassium carbonate were added to 1,000 mL of N-methylpyrrolidone (NMP) and stirred at room temperature for 1 hour. Furthermore, it stirred at 110 degreeC for 10 hours. After the reaction, the solution was cooled until it returned to room temperature, and 5,000 mL of pure water was added to the resulting solution, followed by stirring at room temperature for 1 hour. The precipitated solid was collected by filtration and dried under reduced pressure conditions. 139 g of the solid obtained in the above reaction and 125 mL of triethylamine were added to 500 mL of tetrahydrofuran (THF), and the mixture was stirred at 0 ° C. for 30 minutes. To this solution, 75 g of methacrylic acid chloride was slowly added dropwise, and stirring was further continued at 0 ° C. for 3 hours. After the reaction, 500 mL of ethyl acetate and 200 mL of pure water were added to the resulting solution and stirred. The ethyl acetate layer was separated using a separatory funnel, washed with a saturated saline solution, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, the solution was concentrated, and purified by silica chromatography to obtain 174 g of M-7 having a structure represented by the following structural formula (10).

[Structural formula (10)]

(Synthesis Example 8)
[Synthesis of Monomer M-8]
130 g of 2-hydroxyethyl methacrylate and 167 mL of triethylamine were added to 1000 mL of ethyl acetate and stirred at 0 ° C. for 30 minutes. To this solution, 120 g of methanesulfonyl chloride was slowly added dropwise, and stirring was further continued at 0 ° C. for 3 hours. After the reaction, 500 mL of pure water was added to the resulting solution and stirred. The ethyl acetate layer was separated using a separatory funnel, washed with a saturated saline solution, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off and the solution was concentrated to obtain 207 g of 2-methanesulfonyloxyethyl methacrylate. 48 g of synthesized 2-methanesulfonyloxyethyl methacrylate, 30 g of 2-naphthol, and 43 g of potassium carbonate were added to 200 mL of N-methylpyrrolidone (NMP) and stirred at room temperature for 1 hour. Furthermore, it stirred at 80 degreeC for 10 hours. After the reaction, the precipitated insoluble matter was removed by filtration, and then 500 mL of ethyl acetate and 200 mL of pure water were added to the resulting solution and stirred. The ethyl acetate layer was separated, washed with a saturated saline solution, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, the solution was concentrated, and purified by silica chromatography to obtain 48 g of a monomer M-8 having a structure represented by the following structural formula (11).

[Structural Formula (11)]

(Preparation Example 1)
[Synthesis of Copolymer CP-1]
Dissolve 5.35 g (18.83 mmol) of polyethylene glycol monomethacrylate (n≈4.5) (manufactured by NOF Corporation) and 2.68 g (6.3 mmol) of monomer M-1 in 40 mL of dry methyl ethyl ketone. A monomer solution was prepared.
After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 0.206 g (1.26 mmol) of 2,2′-azoiso (butyronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the remaining monomer solution. The dissolved solution was added dropwise over 1.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was collected, dissolved in tetrahydrofuran (THF), the solvent was removed using a rotary evaporator, and dried under reduced pressure to obtain 8.00 g of copolymer CP-1.

(Preparation Example 2)
[Synthesis of Copolymer CP-2]
In Preparation Example 1, the same procedure as in Preparation Example 1 except that polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈4.5) and monomer M-2. Thus, a copolymer CP-2 was obtained.

(Preparation Example 3)
[Synthesis of Copolymer CP-3]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to methoxypolyethylene glycol methacrylate (n≈23) and monomer M-3 in the same manner as Preparation Example 1. Copolymer CP-3 was obtained.

(Preparation Example 4)
[Synthesis of Copolymer CP-4]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈2) and monomer M-4 in the same manner as Preparation Example 1. Copolymer CP-4 was obtained.

(Preparation Example 5)
[Synthesis of Copolymer CP-5]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to methoxypolyethylene glycol methacrylate (n≈90) and monomer M-5 in the same manner as in Preparation Example 1. As a result, a copolymer CP-5 was obtained.

(Preparation Example 6)
[Synthesis of Copolymer CP-6]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈8) and monomer M-6 in the same manner as Preparation Example 1. Copolymer CP-6 was obtained.

(Preparation Example 7)
[Synthesis of Copolymer CP-7]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈8) and monomer M-7 in the same manner as Preparation Example 1. Copolymer CP-7 was obtained.

(Preparation Example 8)
[Synthesis of Copolymer CP-8]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈2) and monomer M-8 in the same manner as Preparation Example 1. Copolymer CP-8 was obtained.

(Preparation Example 9)
[Synthesis of Copolymer CP-9]
A copolymer CP-9 was obtained in the same manner as in Preparation Example 1 except that polyethylene glycol monomethacrylate (n≈4.5) and the monomer M-1 were changed to the monomer M-1 in Preparation Example 1. .

(Preparation Example 10)
[Synthesis of Copolymer CP-10]
In Preparation Example 1, polyethylene glycol monomethacrylate (n≈4.5) and monomer M-1 were changed to polyethylene glycol monomethacrylate (n≈4.5). Combined CP-10 was obtained.

(Preparation Example of Pigment Dispersion D-1)
300 parts by mass of SPECIAL BLACK 250 (manufactured by Ciba Specialty Chemicals), 100 parts by mass of copolymer CP-1 and 600 parts by mass of phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred and mixed to obtain a pigment mill base. . The pigment mill base was prepared by “Dyno Mill RL” manufactured by Willy et Bacofen, and charged with a zirconia bead having a diameter of 0.5 mm into a dispersion container so that the bead volume would be 80%, followed by a treatment for 30 minutes. went.
It was confirmed that the cumulative 90% particle size (D90) was less than 300 nm by “nano Partica SZ-100” manufactured by HORIBA, Ltd.

(Preparation examples of pigment dispersions D-2 to D-11)
The pigment dispersion D-1 was prepared in the same manner as in the pigment dispersion D-1, except that the copolymer CP-1 as a dispersant was changed to the dispersant shown in Table 1. Dispersions D-2 to D-11 were prepared.

(Preparation Example of Pigment Dispersion D-12)
A pigment dispersion D-12 was prepared in the same manner as in the preparation of pigment dispersion D-1, except that phenoxyethyl acrylate was changed to isobornyl acrylate in the preparation example of pigment dispersion D-1.

* Dispersant in Table 1: Solspers 32000 is a dispersant manufactured by Nihon Lubrizol Corporation.

(Examples 1-13 and Comparative Examples 1-5)
-Preparation of ink-
Based on the ink formulations shown in Tables 2 to 6, the inks of Examples 1 to 13 and Comparative Examples 1 to 5 were prepared by mixing in a conventional manner.
Next, various characteristics of each ink obtained were evaluated as follows. The results are shown in Tables 2-6.

<Extensible>
Using a discharge tester equipped with a GEN4 head (manufactured by Ricoh Printing Systems), a solid image having an average film thickness of 20 μm was drawn on Fasson PE (film thickness: 100 μm, manufactured by Fasson).
About 180 degreeC elongation at break (tensile test), using a tensile tester (Autograph AGS-5kNX, manufactured by Shimadzu Corporation), pulling speed: 20 mm / min, temperature 180 ° C., sample: JIS K6251 dumbbell shape (No. 6) The ratio (length after the tensile test) / (length before the tensile test) was determined. The larger the ratio (length after the tensile test) / (length before the tensile test), the better the stretchability. The ratio (length after the tensile test) / (length before the tensile test) is 2. It is a practically usable level to be 0.0 or more.

<Blocking resistance>
Using a discharge tester equipped with a GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.), a solid image having an average film thickness of 20 μm was drawn on an ester film E5000 (manufactured by Toyobo Co., Ltd.), and then a cured film of the printed material An unprinted ester film E5000 was overlaid on the cured film so as to be entirely covered. Further, a load of 0.200 g / cm ² was applied from the top, and the mixture was left in an atmosphere at 30 ° C. for 1 day, and blocking resistance was evaluated according to the following criteria.
[Evaluation criteria]
4: Transfer to upper film, no sticking 3: Transfer to upper film is less than 1% of the total film area 2: Transfer to upper film is not less than 1% and less than 5% of the total film area 1: Top Transfer to film is 5% or more of the total film area.

<Concentration unevenness during stretching>
The printed material is stretched under the same conditions as the evaluation of stretchability until (length after tensile test) / (length before tensile test) reaches 2.0, and the density unevenness during stretching is visually checked as follows. A: Density unevenness is not seen B: Density unevenness is slightly seen C: Density unevenness is noticeable

Details of the components in Tables 2 to 6 are as follows.
-Polymerizable monomer-
・ N-Vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Hexanediol methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Isobornyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Polymerization initiator-
・ Irgacure 184 (Ciba Specialty Chemicals)
・ Irgacure 819 (Ciba Specialty Chemicals)
-Other ingredients-
・ Hydroquinone monomethyl ether (Tokyo Chemical Industry Co., Ltd.)
・ Benzophenone (Tokyo Chemical Industry Co., Ltd.)

As an aspect of this invention, it is as follows, for example.
<1> N-vinylcaprolactam, a polymerizable monofunctional monomer other than the N-vinylcaprolactam, a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2) A curable composition comprising a copolymer.
[General formula (1)]
In the general formula (1), R ₃ represents a hydrogen atom or a methyl group. L ₁ represents a divalent linking group having a chain length of 1 to 30 and comprising at least one selected from —NR ₆ —, —CO—, —O—, and an alkylene group having 2 to 18 carbon atoms. . However, R ₆ represents a hydrogen atom or a methyl group.
[General formula (2)]
However, in said general formula (2), R < ₁ > and R < ₂ > represents a hydrogen atom or a methyl group. n represents a number from 1 to 90.
<2> In the above <1>, the structural unit represented by the general formula (1) contained in the copolymer is a structural unit represented by the following general formula (3) or the following general formula (4). It is a curable composition of description.
[General formula (3)]
However, In the general formula (3), R ₄ represents a hydrogen atom or a methyl group. L ₂ represents an alkylene group having 2 to 18 carbon atoms.
[General formula (4)]
However, in said general formula (4), a represents the number of 6-10, b represents the number of 0 or 1.
<3> The curable composition according to <2>, wherein the structural unit represented by the general formula (1) contained in the copolymer is a structural unit represented by the general formula (3). is there.
<4> The content of the N-vinylcaprolactam is 20 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the total amount of the polymerizable monofunctional monomer. It is a curable composition of description.
<5> The curable composition according to any one of <1> to <4>, wherein at least one of the polymerizable monofunctional monomers other than the N-vinylcaprolactam is an acrylate or a methacrylate.
<6> Polymerizable monofunctional monomers other than the N-vinylcaprolactam are phenoxyethyl (meth) acrylate, cyclic TMP formal (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- ( <1>, which is at least one selected from 2-ethoxyethoxy) ethyl (meth) acrylate, octa / decyl (meth) acrylate, tridecyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl (meth) acrylate To <5>.
<7> The curable composition according to any one of <1> to <6>, wherein the polymerizable monofunctional monomer other than the N-vinylcaprolactam is phenoxyethyl (meth) acrylate or isobornyl (meth) acrylate. is there.
<8> A curable inkjet ink comprising the curable composition according to any one of <1> to <7>.
<9> A cured product comprising the curable composition according to any one of <1> to <7>.
<10> A storage container comprising the curable composition according to any one of <1> to <7> in a container.
<11> Two-dimensional or characterized by comprising: a housing part that houses the curable composition according to any one of <1> to <7>, and an irradiation unit for irradiating active energy rays. A three-dimensional image forming apparatus.
<12> A two-dimensional or three-dimensional image, wherein the curable composition according to any one of <1> to <7> is irradiated with active energy rays to form a two-dimensional or three-dimensional image. An image forming method.

  The curable composition according to any one of <1> to <7>, the curable ink jet according to <8>, the cured product according to <9>, the container according to <10>, According to the two-dimensional or three-dimensional image forming apparatus described in <11> and the two-dimensional or three-dimensional image forming method described in <12>, the conventional problems are solved, and the object of the present invention is achieved. Can be achieved.

JP 2010-222385 A JP 2014-172971 A JP 2017-155212 A

Claims (10)

A copolymer having N-vinylcaprolactam, a polymerizable monofunctional monomer other than the N-vinylcaprolactam, a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2) And a curable composition comprising:
[General formula (1)]
In the general formula (1), R ₃ represents a hydrogen atom or a methyl group. L ₁ represents a divalent linking group having a chain length of 1 to 30 and comprising at least one selected from —NR ₆ —, —CO—, —O—, and an alkylene group having 2 to 18 carbon atoms. . However, R ₆ represents a hydrogen atom or a methyl group.
[General formula (2)]
However, in said general formula (2), R < ₁ > and R < ₂ > represents a hydrogen atom or a methyl group. n represents a number from 1 to 90. The curable mold according to claim 1, wherein the structural unit represented by the general formula (1) contained in the copolymer is a structural unit represented by the following general formula (3) or the following general formula (4). Composition.
[General formula (3)]
However, In the general formula (3), R ₄ represents a hydrogen atom or a methyl group. L ₂ represents an alkylene group having 2 to 18 carbon atoms.
[General formula (4)]
However, in said general formula (4), a represents the number of 6-10, b represents the number of 0 or 1.   The curable composition according to claim 2, wherein the structural unit represented by the general formula (1) contained in the copolymer is a structural unit represented by the general formula (3).   The content of the N-vinylcaprolactam is 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of polymerizable monofunctional monomers. .   The curable composition according to any one of claims 1 to 4, wherein at least one of the polymerizable monofunctional monomers other than the N-vinylcaprolactam is an acrylate or a methacrylate.   A curable inkjet ink comprising the curable composition according to claim 1.   A cured product comprising the curable composition according to claim 1.   A storage container comprising the curable composition according to any one of claims 1 to 5 in a container.   A two-dimensional or three-dimensional image forming apparatus comprising: a housing unit that houses the curable composition according to any one of claims 1 to 5; and an irradiation unit that irradiates active energy rays. .   A two-dimensional or three-dimensional image forming method, wherein the curable composition according to claim 1 is irradiated with active energy rays to form a two-dimensional or three-dimensional image.