JP2019001910A - Actinic-ray-curable ink and production method for printed matter - Google Patents

Abstract

To provide an actinic-ray-curable ink which, even when not or hardly containing tetrahydrofurfuryl (meth)acrylate or the like, has excellent performance of adhesiveness to various substrates including plastic substrates.SOLUTION: The invention relates to an actinic-ray-curable ink characterized by containing a polymerizable compound (A) including a compound (a) represented by general formula (1).SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable ink that can be used in the production of various printed materials.

Active energy ray-curable inks are excellent in curability and drying properties compared to other inks, and are therefore used for printing on various recording media such as plastic films.
As the active energy ray-curable ink, for example, an ink composition containing a colorant, a radical polymerization initiator having a specific structure, and a radical polymerizable compound such as tetrahydrofurfuryl acrylate is known (for example, Patent Document 1). reference.).
However, since tetrahydrofurfuryl acrylate is concerned about effects on the human body such as irritation to the skin, the industry tends to avoid using ink containing tetrahydrofurfuryl acrylate.
On the other hand, an ink that does not contain tetrahydrofurfuryl acrylate may cause a decrease in adhesion performance to a plastic substrate.
For this reason, the industry has developed active energy ray-curable inks that do not contain tetrahydrofurfuryl (meth) acrylate or the like, or whose content is reduced and that have excellent adhesion performance to plastic substrates. Although it is sought after, it has not yet been found.

JP 2012-201815 A

  The problem to be solved by the present invention is that it does not contain tetrahydrofurfuryl (meth) acrylate or the like, or even in the case where its content is low, it is in adhesion performance to various substrates including plastic substrates. It is to provide an excellent active energy ray-curable ink.

（一般式（１）中のＲ^１、Ｒ^２及びＲ^３はそれぞれ独立して水素原子またはアルキル基を表し、Ｘ^１は単結合またはアルキレン基を表す。） The present inventor has solved the above problems with an active energy ray-curable ink containing a polymerizable compound (A) containing a compound (a) represented by the following general formula (1).

(R ¹ , R ² and R ^{3 in the} general formula (1) each independently represent a hydrogen atom or an alkyl group, and X ¹ represents a single bond or an alkylene group.)

  The active energy ray-curable ink of the present invention has excellent adhesion performance to tetrahydrofurfuryl (meth) acrylate, and therefore does not contain, for example, a print product using an ink jet recording apparatus or the like. Even if there is little, it can be used conveniently in scenes, such as a plastic substrate.

  The active energy ray-curable ink of the present invention contains a polymerizable compound (A) containing a compound (a) represented by the following general formula (1).

(R ¹ , R ² and R ^{3 in the} general formula (1) each independently represent a hydrogen atom or an alkyl group, and X ¹ represents a single bond or an alkylene group.)

Examples of the alkyl group include a methyl group and an ethyl group. Specific examples of X ¹ include a methylene group and an ethylene group.
As the compound (a) represented by the general formula (1), it is possible to use a compound in which R ¹ , R ² , and R ^{3 in the} general formula (1) are hydrogen atoms. It is preferable for producing the effect.
Specifically, it is preferable to use cyclic trimethylolpropane formal acrylate as the compound (a) represented by the general formula (1).

  The compound (a) is preferably included in the range of 5% by mass to 40% by mass and more preferably in the range of 8% by mass to 30% by mass with respect to the entire polymerizable compound (A). It is preferable for obtaining an active energy ray-curable ink having excellent adhesion to various substrates including plastic substrates.

  The polymerizable compound (A) includes the compound (c) having a structure represented by the chemical formula (2) in the polymerizable compound (A) by using a compound containing the compound (a). Even if the content ratio of the compound (c) to the polymerizable compound (A) is preferably 0% by mass to 0.2% by mass, various substrates including plastic substrates An active energy ray-curable ink having excellent adhesion to the ink can be obtained.

  Examples of the compound (c) having the structure represented by the chemical formula (2) include tetrahydrofurfuryl (meth) acrylate and tetrahydrofurfuryl alcohol. The content of these compounds is the whole of the polymerizable compound (A). 0% by mass to 0.2% by mass, preferably 0% by mass to 0.1% by mass, more preferably 0% by mass to 0.05% by mass, and particularly preferably 0% by mass. preferable.

As said polymeric compound (A), what contains the compound (b) which has polymerizable unsaturated double bonds other than the said compound (a) other than the said compound (a) as needed is used. It is preferable.
The compound (b) is preferably a compound having a polymerizable unsaturated double bond in the range of 1 to 6, and a compound having a polymerizable unsaturated double bond in the range of 1 to 3 can be used for flexibility and the plastic group. It is more preferable for obtaining an ink that is more excellent in terms of adhesion to a material or the like.
The compound (b) is more preferably used in the range of 80% by mass to 95% by mass with respect to the entire polymerizable compound (A) in terms of flexibility and adhesion to the plastic substrate and the like. It is preferable for obtaining excellent ink.

As the compound (b), for example, a compound having a heterocyclic structure such as tetrahydrofurfuryl (meth) acrylate can be used, but a compound having a heterocyclic structure other than the chemical formula (2) (b- It is preferable to use 1) the compound (b-2) having an aliphatic cyclic structure.
Examples of the compound (b-1) include caprolactone-modified tetrahydrofurfuryl acrylate, acryloylmorpholine, N-vinyl-2-caprolactam, N-vinylpyrrolidone, N-acryloyloxyethylhexahydrophthalimide and the like. Especially, as said compound (b-1), use of N-vinyl-2-caprolactam is active energy ray curability provided with excellent adhesion to various substrates including plastic substrates. It is preferable when obtaining ink.

  In order to further improve the long-term storage stability of the ink of the present invention, the compound (b-1) is in the range of 1% by mass to 15% by mass with respect to the total amount of the polymerizable compound (A). It is preferable to use in the range of 5% by mass to 15% by mass in order to obtain an ink having excellent adhesion to various substrates including plastic substrates.

In addition, the compound (b-2) can be used for the production of a printed material having chemical resistance at a level that does not cause peeling of the coating film even when it is in contact with a chemical such as alcohol. In order to obtain an active energy ray-curable ink having even better adhesion to various substrates including plastic substrates, it is used in combination with the compound (a), the compound (b-1), etc. It is preferable.
Examples of the compound (b-2) include tricyclodecane dimethanol di (meth) acrylate, adamantyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, trimethylcyclohexyl (meta) ) Acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate, among which isobornyl (meth) It is more preferable to use an acrylate in order to obtain an ink that can be used for the production of a printed material having a printed film excellent in chemical resistance.
The compound (b-2) is preferably used in the range of 5% by mass to 24% by mass with respect to the entire polymerizable compound (A), and is preferably used in the range of 5% by mass to 20% by mass. It is more preferable to obtain an ink that can be used for the production of a printed material having a more excellent printed film due to chemical resistance.

The active energy ray-curable ink of the present invention may be one containing a photopolymerization initiator in addition to the polymerizable compound (A).
Examples of the photopolymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 6-trimethylbenzoyldiphenylphosphine oxide, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1-hydroxycyclohexylphenyl Ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one And 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide, etc. Can do.
Among the above photopolymerization initiators, acylphosphine oxaside photopolymerization initiators are preferably used.
Further, as the photopolymerization initiator, when a UV-LED light source is used as a light source of active energy rays, 2-benzyl-2-dimethylamino-1 corresponding to the wavelength of light emitted from the UV-LED light source is used. -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-morpholinophenyl) -butan-1-one) Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc. are preferably used. .

  The photopolymerization initiator is preferably used in combination with a sensitizer. Examples of the sensitizer include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4 An amine having no reactivity with the polymerizable compound (A), such as, 4′-bis (diethylamino) benzophenone, can be used.

The active energy ray-curable ink of the present invention may be one containing a colorant as required in addition to the polymerizable compound (A) and the photopolymerization initiator.
As the colorant, for example, a pigment or a dye can be used. Examples of the pigment include phthalocyanine pigments used for cyan ink, quinacridone pigments used for magenta ink, azo pigments used for yellow ink, carbon black used for black ink, and white usable for white ink. And pigments.

  Examples of the phthalocyanine pigment used in the cyan ink include C.I. I. Pigment blue 1, 2, 3, 15: 3, 15: 4, 16: 6, 16, 17: 1, 75, 79, and the like.

  Examples of quinacridone pigments used in magenta ink include C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment violet 19 and the like.

  Examples of azo pigments used in yellow ink include C.I. I. Monoazo and disazo pigments such as CI Pigment Yellow 120, 151, 154, 175, 180, 181, 1, 65, 73, 74, 116, 12, 13, 17, 81, 83, 150, 155, 214, 128, etc. included.

  As carbon black used for black ink, No. of Mitsubishi Chemical Corporation. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. are Raven 5750, 5250, 5000, 3500, 1255, 700, etc. made by Columbia, and Regal 400R, 330R, 660R, Mogu L, 700, Monarch 800, 880, made by Cabot, 900, 1000, 1100, 1300, 1400, etc. are Degussa Color Black FW1, FW2, FW2V, FW18, FW200, ColorBlack S150, S160, S170, Printex 35, U, the same V, the same 140 U, the Special Black 6, the same 5, the same 4 A, the same 4, and the like.

  The white pigment that can be used in the white ink is not particularly limited, and a known inorganic white pigment can be used. Examples of the inorganic white pigment include sulfates or carbonates of alkaline earth metals, silicas such as fine silicate and synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc. And clay. As said inorganic white pigment, what carried out surface treatment of the surface of the above-mentioned silica etc. by various surface treatment methods can also be used.

The average particle diameter of the pigment is preferably in the range of 10 to 300 nm, more preferably 50 to 200 nm.
In order to obtain a sufficient image density and light resistance of a printed image, the pigment is preferably contained in a range of 1 to 20% by mass with respect to the total amount of each ink, and contained in a range of 1 to 10% by mass. Is still more preferable, and it is most preferable that it is contained in the range of 1 to 5% by mass. The magenta ink preferably has a higher pigment concentration than other color inks. Specifically, the pigment concentration is preferably 1.2 times or more, and more preferably 1.2 to 4 times that of other color inks.

  The average particle size of the titanium oxide is preferably 100 to 500 nm, and in order to obtain an ink having further excellent ejection stability and high color development of printed images, 150 nm to 400 nm. It is more preferable to use one having an average particle size of

The pigment may be used in combination with a pigment dispersant, a pigment derivative (synergist) or the like for the purpose of enhancing dispersion stability with respect to the polymerizable compound (A) or the like.
Examples of the pigment dispersant include Ajimoto PB821, PB822, PB817 manufactured by Ajinomoto Fine-Techno Co., Ltd., Solspers 24000GR, 32000, 33000, 39000 manufactured by Lubrizol, Disparon DA-703-50, DA- manufactured by Enomoto Kasei Co., Ltd. 705, DA-725, etc. can be used.
The amount of the pigment dispersant used is preferably in the range of 10 to 100% by mass with respect to the pigment, and 20 to 60% by mass for obtaining an ink having more excellent ejection stability and pigment dispersibility. It is more preferable to use the one in the range. Examples of the pigment derivative include sulfonic acid derivatives of pigments.

  As the active energy ray-curable ink of the present invention, a polymerization inhibitor such as hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salt, etc., as necessary, in addition to the above-described components Can be used. The said polymerization inhibitor can be used in 0.01 mass%-2 mass% with respect to the whole quantity of the ink of this invention.

  Examples of the active energy ray curable ink of the present invention include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N- Those having a sensitizer such as dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone can be used.

  As the active energy ray-curable ink of the present invention, non-reactive resins such as acrylic resin, epoxy resin, terpene phenol resin, rosin ester, etc. are used to further improve the adhesion to a substrate such as a plastic substrate. What is contained can be used.

  As the active energy ray-curable ink of the present invention, those having a viscosity at 25 ° C. of 3 mPa · sec to 30 mPa · sec are preferably used, and those having a viscosity of 5 mPa · sec to 20 mPa · sec are used. It is more preferable for achieving the effect of ink jet discharge stability.

In the active energy ray-curable ink of the present invention, for example, the polymerizable compound (A) and, if necessary, a mixture in which a pigment, a pigment dispersant, and a resin are added, the pigment is dispersed using an ordinary dispersing machine such as a bead mill. Then, it can manufacture by adding a photoinitiator and also adding additives, such as a polymerization inhibitor, a sensitizer, and a surface tension regulator, if necessary, and stirring and dissolving.
The active energy ray-curable ink is prepared by previously producing a high-concentration pigment dispersion (mill base) containing a pigment, a pigment dispersant, a resin, or the like using a conventional dispersing machine such as a bead mill, and then a photopolymerization initiator. It can also be produced by supplying a polymerizable compound (A), an additive and the like, and stirring and mixing.

  As the disperser, in addition to a bead mill, for example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disper mat, an SC mill, and a nanomizer are used. be able to.

  The active energy ray-curable ink of the present invention is cured by irradiation with active energy rays, preferably light such as ultraviolet rays. As a light source such as ultraviolet ray, a light source usually used for an active energy ray curable ink jet recording ink, such as a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a UV-LED lamp, etc. Can be used.

  The active energy ray-curable ink of the present invention can be suitably used for printing in an ink jet recording method using an ink jet recording apparatus exclusively.

Any conventionally known method can be used as the ink jet recording method. For example, a method of ejecting droplets using vibration of a piezoelectric element (a recording method using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element) or a method of using thermal energy can be given.
A printed matter can be produced by discharging the active energy ray-curable ink onto a base material, which is a recording medium, using an ink jet recording apparatus and curing the active energy ray by irradiation with active energy rays. As said printed matter, an advertisement, a signboard, a guide board, sales promotion product printing etc. are mentioned, for example.

Since the active energy ray-curable ink of the present invention is excellent in adhesion to various substrates as recording media, it can be easily printed on the surface of a substrate having a curved surface or an irregular shape with irregularities. Can do.
As the substrate, for example, a plastic substrate can be used. Specifically, as the plastic substrate, ABS (acrylonitrile butadiene styrene) resin, PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin used as general-purpose injection molding plastics , PC (polycarbonate) / ABS resin, ABS polymer alloys such as PBT (polybutylene terephthalate) / ABS, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber) Examples of the base material include styrene resin, MS ((meth) acrylate ester / styrene) resin, PC (polycarbonate) resin, acrylic resin, methacrylic resin, and PP (polypropylene) resin.

In addition, as the plastic substrate, for example, a thermoplastic resin film used for packaging materials can be used.
Examples of the thermoplastic resin film include those generally used as a thermoplastic resin film used for food packaging. For example, a polyethylene terephthalate (PET) film, a polystyrene film, a polyamide film, a polyacrylonitrile film, a polyethylene film. (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene films (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyolefin films, polyvinyl alcohol films, ethylene-vinyl alcohol copolymers A film etc. are mentioned. As the thermoplastic resin film, one that has been subjected to stretching treatment such as uniaxial stretching or biaxial stretching, or one that has been subjected to flame treatment or corona discharge treatment on the surface can also be used.

  Hereinafter, the present invention will be described in more detail by way of examples.

[Example 1]
[Preparation example of cyan pigment dispersion]
Preparation Example of Cyan Pigment Dispersion (1) Fast Gen Blue TGR-G (Phthalocyanine Pigment CI Pigment Blue 15: 4, manufactured by DIC Corporation) 10 parts by mass, Solspers 32000 (polymer pigment dispersant, manufactured by Lubrizol) 4.5 parts by mass and 85.5 parts by mass of light acrylate POA (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) were mixed and stirred for 1 hour with a stirrer, and then treated with a bead mill for 2 hours to obtain a cyan pigment dispersion ( 1) was obtained.

[Example of ink preparation]
According to the blending ratio shown in Table 1, MIRAMER M3130 (ethylene oxide (EO) modified trimethylolpropane triacrylate manufactured by MIWON), MIRAMER M240 (ethylene oxide (EO) modified bisphenol A diacrylate manufactured by MIWON), biscoat are added to the container. # 200 (cyclic trimethylolpropane formal acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), IBXA (isoboronyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), V-CAP (N-vinyl-2-caprolactam manufactured by ISP), Light acrylate POA (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) and KF-54 (polysiloxane manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with stirring, and then Irgacure 819 (manufactured by BASF Corp.). Scan (2,4,6-trimethylbenzoyl) - phenylphosphine oxide), Irgacure. TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF) and Kayacure DETX-S (diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved by mixing at a temperature of 60 ° C. for 30 minutes.
Next, the cyan pigment dispersion (1) was added and stirred for 10 minutes to obtain cyan ink (C1).

[Example 2]
The usage amount of biscort # 200 (produced by Osaka Organic Chemical Industry Co., Ltd., cyclic trimethylolpropane formal acrylate) was changed from 20 parts by mass to 27 parts by mass, and the usage amount of POA (phenoxyethyl acrylate produced by Kyoeisha Chemical Co., Ltd.) was changed. A cyan ink (C2) was obtained in the same manner as in Example 1 except that the amount was changed from 16.3 parts by mass to 9.3 parts by mass.

[Example 3]
The usage amount of Biscoat # 200 (Osaka Organic Chemical Co., Ltd., cyclic trimethylolpropane formal acrylate) was changed from 20 parts by mass to 34 parts by mass, and the usage amount of POA (Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate) was changed. A cyan ink (C3) was obtained in the same manner as in Example 1 except that the amount was changed from 16.3 parts by mass to 2.3 parts by mass.

[Example 4]
V-CAP (N-vinyl-2-caprolactam manufactured by ISP) was changed from 20 parts by mass to 27 parts by mass of biscort # 200 (produced by Osaka Organic Chemical Co., Ltd., cyclic trimethylolpropane formal acrylate). A cyan ink (C4) was obtained in the same manner as in Example 1 except that the amount of was changed from 12 parts by mass to 5 parts by mass.

[Example 5]
The usage amount of biscort # 200 (produced by Osaka Organic Chemical Industry Co., Ltd., cyclic trimethylolpropane formal acrylate) was changed from 20 parts by mass to 27 parts by mass, and the usage amount of POA (phenoxyethyl acrylate produced by Kyoeisha Chemical Co., Ltd.) was changed. Example 1 except that 16.3 parts by mass was changed to 19.3 parts by mass, and the amount of IBXA (Isoboronyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) was changed from 15 parts by mass to 5 parts by mass. A cyan ink (C5) was obtained in the same manner as above.

[Example 6]
The usage amount of biscort # 200 (produced by Osaka Organic Chemical Industry Co., Ltd., cyclic trimethylolpropane formal acrylate) was changed from 20 parts by mass to 27 parts by mass, and the usage amount of POA (phenoxyethyl acrylate produced by Kyoeisha Chemical Co., Ltd.) was changed. Example 1 except that the amount was changed from 16.3 parts by mass to 3.3 parts by mass, and the amount of IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) was changed from 15 parts by mass to 21 parts by mass. A cyan ink (C6) was obtained in the same manner as above.

[Comparative Example 1]
The usage amount of Biscoat # 200 (produced by Osaka Organic Chemical Industry Co., Ltd., cyclic trimethylolpropane formal acrylate) was changed from 20 parts by mass to 0 parts by mass, and the usage amount of POA (phenoxyethyl acrylate produced by Kyoeisha Chemical Co., Ltd.) was changed. The cyan ink (C ′) was changed in the same manner as in Example 1 except that the amount was changed from 16.3 parts by weight to 9.3 parts by weight and the amount of tetrahydrofurfuryl acrylate was changed from 0 parts by weight to 27 parts by weight. 1) was obtained.

[Comparative Example 2]
The amount of POA (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) was changed from 9.3 parts by mass to 36.1 parts by mass, and the amount of tetrahydrofurfuryl acrylate was changed from 27 parts by mass to 0.2 parts by mass. Except for this, cyan ink (C′2) was obtained in the same manner as in Comparative Example 1.

[Comparative Example 3]
Other than changing the amount of POA (Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate) used from 9.3 parts by mass to 36.3 parts by mass and changing the amount of tetrahydrofurfuryl acrylate from 27 parts by mass to 0 parts by mass Obtained a cyan ink (C′3) in the same manner as in Comparative Example 1.
[Comparative Example 4]
The amount of POA (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) was changed from 9.3 parts by mass to 30.3 parts by mass, the amount of tetrahydrofurfuryl acrylate was changed from 27 parts by mass to 0 parts by mass, and IBXA A cyan ink (C′4) was obtained in the same manner as in Comparative Example 1 except that the amount used (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) was changed from 15 parts by mass to 21 parts by mass.

[Base material adhesion]
Spin coater for the active energy ray curable ink jet recording ink on a polycarbonate plate (Asahi Glass Co., Ltd., Lexan, thickness 1 mm, PC), vinyl chloride sheet (DIC Co., Ltd. vinyl chloride sheet, PVC) Using a LED irradiation device (emission wavelength: 385 nm, peak intensity: 500 mW / cm ² ) manufactured by Hamamatsu Photonics Co., Ltd. equipped with a stage moving device, until coating film surface tack is eliminated Irradiated (until tack-free).
The obtained cured coating film was cut with a cutter knife in a 5 × 5 25 square pattern at intervals of 2 mm, and then a cellophane tape manufactured by Nichiban Co., Ltd. was applied and rubbed with a nail about 10 times. The tape was peeled off vigorously at a peeling speed of about 1 cm / sec, and the number of squares on which the coating film remained was confirmed.

Evaluation criteria ○: The number of masses of the coating film remaining on the surface of the polycarbonate plate or the vinyl chloride sheet is 20 or more Δ: The number of masses of the coating film remaining on the surface of the polycarbonate plate or the vinyl chloride sheet is 15 or more and less than 20 ×: The polycarbonate plate Or the number of coatings remaining on the surface of the vinyl chloride sheet is less than 15

[Solvent resistance]
The active energy ray-curable ink jet recording ink was applied to a polycarbonate plate (manufactured by Asahi Glass Co., Ltd., Lexan, thickness 1 mm, PC) with a thickness of 10 μm using a spin coater, and then equipped with a stage moving device. Using an LED irradiation device (emission wavelength: 385 nm, peak intensity: 500 mW / cm ² ) manufactured by Hamamatsu Photonics Co., Ltd., irradiation was performed until the coating surface was free of tack (until tack-free).
A cotton swab dipped in a mixture of ethanol and water (ethanol content 70 mass%) was placed on the resulting cured coating film, and rubbed 10 times to the left and right with a width of about 2 cm. The case where there was no rubbing trace on the surface of the coating film was evaluated as “◯”, and the case where the rubbing trace was confirmed was evaluated as “×”.

[Skin irritation]
It evaluated according to the influence degree of the skin irritation derived from tetrahydrofurfuryl acrylate. “X” indicates that the skin irritation derived from tetrahydrofurfuryl acrylate is considered to be high, “△” indicates that the skin irritation is considered low, and no skin irritation derived from tetrahydrofurfuryl acrylate. The thing was evaluated as “◯”.

Abbreviations in Table 1 and Table 2 refer to the following compounds.
M3130: Ethylene oxide (EO) modified trimethylolpropane triacrylate manufactured by MIWON M240: Ethylene oxide (EO) modified bisphenol A diacrylate manufactured by MIWON V200: Biscoat # 200, cyclic trimethylolpropane formal manufactured by Osaka Organic Chemical Industries, Ltd. Acrylate)
IBXA: Isoboronyl acrylate V-CAP: N-vinyl-2-caprolactam POA manufactured by ISP Kyoeisha Chemical Co., Ltd. Phenoxyethyl acrylate THFA: Tetrahydrofurfuryl acrylate KF-54: Shin-Etsu Chemical Co., Ltd. Polysiloxane Irgacure 819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Irgacure TPO manufactured by BASF: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF ・ KayacureDETX-S: Diethylthioxanthone [manufactured by Nippon Kayaku Co., Ltd.] Irgacure 819 / Irgacure TPO]: bis (2,4,6-trimethyl to 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide Methylbenzoyl) -phenylphosphine oxide weight ratio

Claims (8)

An active energy ray-curable ink comprising a polymerizable compound (A) containing a compound (a) represented by the following general formula (1).

(R ¹ , R ² and R ^{3 in the} general formula (1) each independently represent a hydrogen atom or an alkyl group, and X ¹ represents a single bond or an alkylene group.) The active energy ray curing according to claim 1, wherein a content ratio of the compound (c) having a structure represented by the following chemical formula (2) with respect to the total amount of the polymerizable compound (A) is 0% by mass to 0.2% by mass. Ink.

The active energy ray-curable ink according to claim 1 or 2, wherein the compound (a) is contained in a range of 5% by mass to 40% by mass with respect to the entire polymerizable compound (A). The polymerizable compound (A) contains the compound (a) and a compound (b) having a polymerizable unsaturated double bond other than the compound (a), wherein the compound (b) Contains the compound (b-1) having a heterocyclic structure other than the chemical formula (2), and the compound (b-1) is 1% by mass to 15% with respect to the entire polymerizable compound (A). The active energy ray-curable ink according to any one of claims 1 to 3, which is contained by mass%. The compound (b) further contains a compound (b-2) having an aliphatic cyclic structure, and the compound (b-2) is 1% by mass to 24% with respect to the entire polymerizable compound (A). The active energy ray-curable ink according to claim 4, which is contained by mass%. The active energy ray-curable ink according to claim 1, wherein the viscosity at 25 ° C. is in the range of 5 to 30 mPa · sec. The active energy ray-curable ink according to any one of claims 1 to 6, further comprising an acylphosphine oxide photopolymerization initiator. The active energy ray-curable ink according to claim 1 is cured by ejecting the active energy ray-curable ink onto a recording medium using an inkjet recording apparatus and irradiating the active energy ray. Manufacturing method of printed matter.