JP6744360B2 - Active energy ray curable ink and method for producing printed matter - Google Patents

Description

The present invention relates to an active energy ray curable ink that can be used for manufacturing various printed matters.

The active energy ray curable ink is excellent in curability and dryness as compared with other inks, and is therefore used for printing on various recording media such as a plastic film.

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, in recent years, tetrahydrofurfuryl acrylate may contain a small amount of tetrahydrofurfuryl alcohol as an impurity or a decomposed product, which may cause effects on the human body such as irritation to the skin. , Tend to avoid using inks 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.

Therefore, from the industrial world, active energy ray curing that does not contain the above-mentioned tetrahydrofurfuryl (meth)acrylate or tetrahydrofurfuryl alcohol, or the content thereof is reduced, and has excellent adhesion performance to a plastic substrate Although there is a demand for the development of functional inks, the fact is that they have not yet been discovered.

JP, 2012-201815, A

Problems to be solved by the present invention include various base materials including a plastic base material even when the content of tetrahydrofurfuryl (meth)acrylate or tetrahydrofurfuryl alcohol is not contained, or even when the content is small. It is to provide an active energy ray curable ink having excellent adhesion performance to.

The present inventor has solved the above problem by using an active energy ray-curable ink containing a polymerizable compound (A) containing an alkyl 2-allyloxymethylacrylate (a5).

The active energy ray-curable ink of the present invention does not contain tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl alcohol, or the like, or even when the content is small, the adhesion performance to a plastic substrate or the like is improved. Since it is excellent, it can be suitably used, for example, in the production of printed matter using an inkjet recording device or the like.

It is a conceptual diagram which shows the method of evaluating the tackiness of the coating film surface.

The active energy ray-curable ink of the present invention is an active energy ray-curable ink containing a polymerizable compound (A) containing at least one selected from the group consisting of 2-allyloxymethyl alkyl acrylate (a5). It is characterized by that.

The alkyl 2-allyloxymethyl acrylate (a5) used in the polymerizable compound (A) will be described.

As the alkyl 2-allyloxymethyl acrylate (a5), a compound represented by the following general formula (6) is used.

(R ¹ in the general formula (6) represents an alkyl group.)

Examples of the alkyl 2-allyloxymethyl acrylate (a5) include compounds in which R ¹ in the general formula (6) is an alkyl group having 1 to 3 carbon atoms, and R ¹ is a methyl group 2 It is more preferable to use methyl allyloxymethyl acrylate in order to obtain an active energy ray-curable ink having excellent adhesion to various substrates such as plastic substrates.

The active energy ray-curable ink containing the alkyl 2-allyloxymethyl acrylate (a5) forms a heterocyclic structure when adhered to the surface of a base material which is a recording medium and cured. This makes it possible to obtain an active energy ray-curable ink having excellent adhesion to various base materials including plastic base materials.

The alkyl 2-allyloxymethyl acrylate (a5) is preferably contained in the range of 5% by mass to 40% by mass, and 8% by mass to 30% by mass with respect to the entire polymerizable compound (A). It is preferable to be contained within the range in order to obtain an active energy ray-curable ink having excellent adhesion to various base materials including a plastic base material.

As the polymerizable compound (A), by using the one containing the 2-allyloxymethyl alkyl acrylate (a5), the polymerizable compound (A) is represented by the chemical formula (5) described later. Not containing the compound (c) having a structure shown in the above, or the content ratio of the compound (c) to the whole polymerizable compound (A) is preferably 0% by mass to 0.2% by mass, more preferably 0% by mass. To 0.1% by mass, and more preferably 0% to 0.05% by mass, active energy ray curability with excellent adhesion to various base materials including plastic base materials. Ink can be obtained.

As the polymerizable compound (A), in addition to the alkyl 2-allyloxymethyl acrylate (a5), a compound (a1) to (a4) described later may be appropriately selected and contained in combination as necessary. Things can be used.

First, the compound (a1) that can be used as the polymerizable compound (A) will be described.

As the compound (a1), a compound having a structure represented by the following general formula (1) and a polymerizable unsaturated double bond is used.

[In the general formula (1), R ¹ is an alkylene group having 1 or more carbon atoms, R ² is an alkylene group having 1 or more carbon atoms which may be the same as or different from R ¹ , and R ³ is a hydrogen atom. Alternatively, it is an alkyl group, and n is an integer of 0 or more. ]

Examples of R ¹ and R ² constituting the general formula (1) include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group and an isobutylene group. R ¹ and R ² may be the same or different. As the R ¹ and R ^2, Among mentioned above, both R ¹ and R ^2, it is ethylene group, with excellent adhesion to various substrates, including plastic substrates activity It is more preferable for obtaining an energy ray curable ink.

Examples of R ³ constituting the general formula (1) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group and a butyl group. Among them, it is more preferable that R ³ is an ethyl group in order to obtain an active energy ray-curable ink having excellent adhesion to various base materials including a plastic base material.

As n constituting the general formula (1), an integer in the range of 0 to 20 is preferable, a range of 0 to 3 is more preferable, and 1 is 1 including the plastic substrate. It is more preferable for obtaining an active energy ray-curable ink having excellent adhesion to various base materials.

Specific examples of the compound (a1) include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, and methoxytriethylene glycol (meth). Acrylate or the like can be used. Among them, as the compound (a1), the use of ethoxyethoxyethyl (meth)acrylate is a compound (c) having a structure represented by the chemical formula (5) described later in the polymerizable compound (A). Or the content ratio of the compound (c) to the whole polymerizable compound (A) is preferably 0% by mass to 0.2% by mass, more preferably 0% by mass to 0.1% by mass, An active energy ray-curable ink having excellent adhesion to various base materials including a plastic base material, even when the content is preferably 0 mass% to 0.05 mass %, particularly preferably 0 mass %. Is particularly preferred for obtaining

The compound (a1) is preferably contained in the range of 20% by mass to 40% by mass, and is contained in the range of 25% by mass to 35% 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 base materials including a plastic base material.

As the polymerizable compound (A), by using a compound containing the compound (a1) having the structure represented by the general formula (1), a compound having a structure represented by the chemical formula (5) described below is used. The content ratio of (c) is preferably 0% by mass to 0.2% by mass, more preferably 0% by mass to 0.1% by mass, and further preferably 0% by mass to the total amount of the polymerizable compound (A). Even in the case of 0.05% by mass, particularly preferably 0% by mass, it is possible to obtain an active energy ray-curable ink having excellent adhesion to various substrates such as plastic substrates.

Next, the compound (a2) and the compound (a3) usable as the polymerizable compound (A) will be described. As the compound (a2), those having a structure represented by the following general formula (2) can be used, and as the compound (a3), those having a structure represented by the following general formula (3) can be used. use.

(R ¹ and R ² in the general formula (2) each independently represent a hydrogen atom or an alkyl group, R ³ represents a hydrogen atom or an alkyl group. R ³ in the general formula (3) is a hydrogen atom or Represents an alkyl group.)

It is presumed that the compound (a2) and the compound (a3) have a high anchoring effect to the base material which is the recording medium and exhibit an excellent adhesion effect to the base material such as a plastic base material.

As the compound (a2) and the compound (a3), compounds having a structure represented by the general formula (2) or the general formula (3) can be used alone or in combination of two or more kinds.

As the compound (a2), it is preferable to use a compound having a structure represented by the general formula (2) in order to further improve the adhesion of the ink to the substrate, and the general formula (2) It is more preferable to use a compound in which R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom. preferable.

As the compound (a2), R ¹ in the general formula (2) is a methyl group, R ² is an ethyl group, and R ³ is a hydrogen atom (2-methyl-2-ethyl-1,3). -Dioxolan-4-yl)methyl acrylate, a compound in which R ¹ is a methyl group, R ² is an isopropyl group, R ³ is a hydrogen atom or a methyl group, and R ¹ and R ² are methyl groups and R ³ is hydrogen. A compound that is an atom or a methyl group can be used, and among them, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate can be used to improve the adhesion to the substrate. It is particularly preferable for obtaining excellent ink.

The compound (a2) is preferably contained in the range of 5% by mass to 40% by mass, and is contained in the range of 8% by mass to 30% by mass, based on the entire polymerizable compound (A). It is preferable for obtaining an active energy ray-curable ink having excellent adhesion to various base materials including a plastic base material.

Further, as the compound (a3), the compound represented by the general formula (3) can be used.

The compound (a3) is preferably contained in the range of 5% by mass to 40% by mass, and is contained in the range of 8% by mass to 30% by mass, based on the entire polymerizable compound (A). It is preferable for obtaining an active energy ray-curable ink having excellent adhesion to various base materials including a plastic base material.

As the polymerizable compound (A), by using a compound containing one or both of the compound (a2) and the compound (a3), the following chemical formula in the polymerizable compound (A) is used. It does not contain the compound (c) having the structure represented by (5), or the content ratio of the compound (c) to the entire polymerizable compound (A) is preferably 0% by mass to 0.2% by mass, and Even in the case of preferably 0% by mass to 0.1% by mass, and more preferably 0% by mass to 0.05% by mass, excellent adhesion to various base materials including a plastic base material is provided. An active energy ray curable ink can be obtained.

As the polymerizable compound (A), those in which the compound (a2) and the compound (a3) are contained in a total amount of 5% by mass to 40% by mass with respect to the entire polymerizable compound (A). It is preferable to use it in order to obtain an active energy ray-curable ink having excellent adhesion to various base materials including a plastic base material.

Next, the compound (a4) usable as the polymerizable compound (A) will be described.

As the compound (a4), the compound (a4) represented by the following general formula (4) is used.

(R ¹ , R ² and R ^{3 in the} general formula (4) 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 (a4) represented by the general formula (4), it is preferable to use one in which R ¹ , R ² and R ^{3 in the} general formula (4) are hydrogen atoms. It is preferable for achieving the effect.

As the compound (a4) represented by the general formula (4), specifically, cyclic trimethylolpropane formal acrylate is preferably used.

The compound (a4) is preferably contained in the range of 5% by mass to 40% by mass, and is contained in the range of 8% by mass to 30% by mass, based on the entire polymerizable compound (A). It is preferable for obtaining an active energy ray-curable ink having excellent adhesion to various base materials including a plastic base material.

As the polymerizable compound (A), by using a compound containing the compound (a4), the compound (c) having a structure represented by the chemical formula (5) described later in the polymerizable compound (A). ) Is not included, or the content ratio of the compound (c) to the entire polymerizable compound (A) is preferably 0% by mass to 0.2% by mass, more preferably 0% by mass to 0.1% by mass, More preferably, even in the case of 0% by mass to 0.05% by mass, an active energy ray curable ink having excellent adhesion to various base materials including a plastic base material can be obtained.

Here, the compound (c) having the structure represented by the chemical formula (5) will be described.

Examples of the compound (c) having the structure represented by the chemical formula (5) include tetrahydrofurfuryl (meth)acrylate and tetrahydrofurfuryl alcohol.

As the polymerizable compound (A) used in the present invention, a compound containing the compound (c) may be used, but the content of the compound (c) is based on the entire polymerizable compound (A). On the other hand, it is preferably 0% by mass to 0.2% by mass, more preferably 0% by mass to 0.1% by mass, further preferably 0% by mass to 0.05% by mass, and particularly preferably 0% by mass. Is desirable.

As the polymerizable compound (A), an alkyl 2-allyloxymethyl acrylate (a5) is used as an essential component, and further, the compound (a1), the compound (a2), the compound (a3) and the compound (a4). Of these, it is preferable to select one or more of them and use them in combination in order to obtain the effect of adhering to the substrate. In particular, as the polymerizable compound (A), it is preferable to use a combination of the compound (a1), the compound (a2), the compound (a4) and the alkyl 2-allyloxymethylacrylate (a5), The combined use of the compound (a2), the compound (a4) and the alkyl 2-allyloxymethyl acrylate (a5) provides even more excellent adhesion to various base materials including plastic base materials and printing. It is preferable for obtaining an active energy ray-curable ink that achieves both reduction of tackiness on the surface (coating film).

Further, as the polymerizable compound (A), in addition to the compound (a1), the compound (a2), the compound (a3), the compound (a4) and the alkyl 2-allyloxymethylacrylate (a5). Optionally containing a compound (b) other than the compound (a1), the compound (a2), the compound (a3), the compound (a4) and the alkyl 2-allyloxymethylacrylate (a5). Things can be used.

As the compound (b), a compound having a polymerizable unsaturated double bond can be used, and a compound having a polymerizable unsaturated double bond in the range of 1 to 6 is preferably used. It is more preferable to use one having a range of 3 from the standpoint of obtaining an ink that is more excellent in terms of flexibility and adhesion to the plastic substrate and the like.

It is more preferable that the compound (b) is used in the range of 50% by mass to 90% 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 (b-1) having a heterocyclic structure other than the chemical formula (5), a compound (b-2) having an aliphatic cyclic structure, and the like can be used.

As the compound (b-1), for example, caprolactone-modified tetrahydrofurfuryl acrylate, acryloylmorpholine, N-vinyl-2-caprolactam, N-vinylpyrrolidone, N-acryloyloxyethyl hexahydrophthalimide and the like can be used. Among them, as the compound (b-1), it is possible to use N-vinyl-2-caprolactam as a compound (c) having a structure represented by the chemical formula (5) in the polymerizable compound (A). Even if the content of the compound (c) is 0 mass% to 0.2 mass% with respect to the entire polymerizable compound (A), various types including a plastic substrate. It is preferable for obtaining an active energy ray-curable ink having excellent adhesion to a substrate.

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 it, and it is more preferable to use it in the range of 5% by mass to 15% by mass in order to obtain an ink having excellent adhesion to various substrates such as plastic substrates.

Further, the compound (b-2) can be used for producing a printed matter having a chemical resistance of a level that does not cause peeling of a coating film even when contacted with a chemical such as alcohol, and Used in combination with the compound (a5), the compound (b-1), or the like, in order to obtain an active energy ray-curable ink having more excellent adhesion to various substrates including a plastic substrate. It is preferable.

Examples of the compound (b-2) include tricyclodecanedimethanol di(meth)acrylate, adamantyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, trimethylcyclohexyl (meth). ) Acrylate, isobornyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate can be used, among which isobornyl (meth)acrylate ) It is more preferable to use an acrylate in order to obtain an ink that can be used for producing a printed matter having a printed coating film having excellent 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 for obtaining an ink that can be used for producing a printed matter having a printed coating film having more excellent chemical resistance.

Particularly, when the compound (a1) is used as the polymerizable compound (A), the combined use of the compounds (a2, a4, a5) and (b-2) reduces the tackiness of the coating film. Preferably, the structure represented by the general formula (1) of the compound (a1), the compound (a2), the compound (a4), the compound (a5), and the compound (b-2) are included. Ratio with the total of the alicyclic structures [structure represented by the general formula (1)/the compound (a2), the compound (a4), the compound (a5) and the compound (b-2). It is preferable to use in combination within a range of 3 to 50].

The active energy ray-curable ink of the present invention may contain 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, benzyl dimethyl 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-diphenylsulfide and the like can be used. ..

As the photopolymerization initiator, it is preferable to use an acylphosphine oxaside photopolymerization initiator among the above.

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. -(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, and 2-isopropylthioxanthone 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 invention may contain a colorant, if necessary, 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 a phthalocyanine pigment used in cyan ink, a quinacridone pigment used in magenta ink, an azo pigment used in yellow ink, carbon black used in black ink, and a white color usable in white ink. Examples include pigments and the like.

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 for 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. Pigment Yellow 120, 151, 154, 175, 180, 181, 1, 65, 73, 74, 116, 12, 13, 13, 81, 83, 150, 155, 214, 128 and other monoazo and disazo pigments are used. can do.

The carbon black used for the black ink is No. Mitsubishi Chemical Corporation. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 45. 52, MA7, MA8, MA100, No. 52. 2200B and the like are Raven 5750, 5250, 5000, 3500, 1255, 700 and the like manufactured by Colombia, and Regal400R, 330R, 660R, Mogul L, 700, Monarch800 and 880 manufactured by Cabot. 900, 1000, 1100, 1300, 1400, etc. are Color Black FW1, FW2, FW2V, FW2, FW18, FW200, ColorBlack S150, S160, S170, Printex 35, and the same manufactured by Degussa. U, the same V, the same 140U, Special Black 6, the same 5, the same 4A, the same 4 and the like.

The white pigment that can be used in the white ink is not particularly limited, and known inorganic white pigments can be used. Examples of the inorganic white pigment include sulfates or carbonates of alkaline earth metals, silicas such as finely divided silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc. , Clay, etc. As the inorganic white pigment, it is also possible to use those in which the surface of the above-mentioned silica or the like is surface-treated by various surface treatment methods.

The volume 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 sufficient image density and light resistance of a printed image, the pigment is preferably contained in the range of 1 to 20% by mass with respect to the total amount of each ink, and is contained in the range of 1 to 10% by mass. Is more preferable, and the most preferable range is 1 to 5% by mass. The magenta ink preferably has a higher pigment concentration than the other color inks. Specifically, the pigment concentration is preferably 1.2 times or more that of the other color inks, and more preferably 1.2 to 4 times.

The volume average particle diameter 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 a printed image, the average particle diameter is 150 nm to 150 nm. It is more preferable to use one having a volume average particle diameter of 400 nm.

The pigment may be used in combination with a pigment dispersant, a pigment derivative (synergist) or the like for the purpose of enhancing the dispersion stability of the polymerizable compound (A) or the like.

As the pigment dispersant, for example, Ajinomoto Fine Techno Co., Ltd., Addisper PB821, PB822, PB817, Avicia Co., Solspers 24000GR, 32000, 33000, 39000, Kusumoto Kasei Co., Ltd. Disparon DA-703-50, DA-705. , DA-725 and the like 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 one having a range of. Further, as the pigment derivative, for example, a sulfonic acid derivative of a pigment or the like can be used.

As the active energy ray-curable ink of the present invention, in addition to the components described above, a polymerization inhibitor such as hydroquinone, metoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, and nitrosamine salt may be added if necessary. It is possible to use those containing. The polymerization inhibitor may be used in the range of 0.01% by mass to 2% by mass with respect to the total amount of the ink of the present 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 containing a sensitizer such as dimethylbenzylamine and 4,4′-bis(diethylamino)benzophenone can be used.

Examples of the active energy ray-curable ink of the present invention include acrylic resins, epoxy resins, terpene phenol resins, non-reactive resins such as rosin esters, etc. in order to further improve adhesion to substrates such as plastic substrates. What is contained can be used.

As the active energy ray-curable ink of the present invention, it is preferable to use one having a viscosity at 25° C. of 3 mPa·sec to 30 mPa·sec, and preferably 5 mPa·sec to 20 mPa·sec. It is more preferable that the effect of ink jet ejection stability be exhibited.

In the active energy ray-curable ink of the present invention, for example, the polymerizable compound (A), and optionally a pigment, a pigment dispersant, and a resin-added mixture are dispersed in the pigment using an ordinary disperser such as a bead mill. After that, a photopolymerization initiator is added, and if necessary, additives such as a polymerization inhibitor, a sensitizer, and a surface tension adjusting agent are added, and the mixture can be stirred and dissolved for production.

The active energy ray-curable ink is a photopolymerization initiator after a high-concentration pigment dispersion (mill base) containing a pigment, a pigment dispersant, a resin, or the like is previously produced by using an ordinary disperser such as a bead mill. 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 dispermat, an SC mill, a nanomizer, and the like, which are known and commonly used, are used. be able to.

The active energy ray-curable ink of the present invention is cured by irradiation with active energy rays, preferably ultraviolet rays. As a light source of ultraviolet rays or the like, a light source usually used for an active energy ray-curable ink jet recording ink, for example, 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 exclusively for printing by an inkjet recording system using an inkjet recording device.

Any conventionally known method can be used as the ink jet recording method. For example, a method of ejecting a droplet by utilizing vibration of a piezoelectric element (a recording method using an inkjet head that forms an ink droplet by mechanical deformation of an electrostrictive element) and a method of utilizing thermal energy can be mentioned.

A printed matter can be produced by ejecting the active energy ray-curable ink onto a substrate that is a recording medium using an inkjet recording apparatus and curing the ink by irradiating with active energy rays. Examples of the printed matter include an advertisement, a signboard, a guide plate, and a promotional item print.

Since the active energy ray-curable ink of the present invention has excellent adhesion to various base materials which are recording media, it can be easily printed even on the surface of a base material having a curved or uneven irregular shape. You can

As the base material, for example, a plastic base material can be used. Specific examples of the plastic base material include ABS (acrylonitrile butadiene styrene) resin, PVC (polyvinyl chloride)/ABS resin, PA (polyamide)/ABS resin, which are used as general-purpose injection molding plastics. , PC (polycarbonate)/ABS resin, PBT (polybutylene terephthalate)/ABS and other ABS polymer alloys, AAS (acrylonitrile/acrylic rubber/styrene) resin, AS (acrylonitrile/styrene) resin, AES (acrylonitrile/ethylene rubber) -Styrene) resin, MS ((meth)acrylic acid ester/styrene)-based resin, PC (polycarbonate)-based resin, acrylic resin, methacrylic-based resin, PP (polypropylene)-based resin, and the like.

Further, as the plastic base material, for example, a thermoplastic resin film used for a packaging material or the like can be used.

Examples of the thermoplastic resin film include those used as a thermoplastic resin film generally used for food packaging, for example, polyethylene retephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film. (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl film, ethylene-vinyl alcohol copolymer Examples thereof include films. As the thermoplastic resin film, it is possible to use a stretched film such as uniaxially stretched or biaxially stretched, or a film whose surface has been subjected to flame treatment or corona discharge treatment.

Hereinafter, the present invention will be described in more detail with reference to examples.

[Preparation example of pigment dispersion]
Preparation Example of Cyan Pigment Dispersion (1) Fastgen Blue TGR-G (DIC Corporation Phthalocyanine Pigment CI Pigment Blue 15:4) 10 parts by mass, Solspurs 32000 (Lubrizol Pigment Dispersant) 4. 5 parts by mass and 85.5 parts by mass of light acrylate PO-A (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) were mixed and stirred with a stirrer for 1 hour, and then treated with a bead mill for 2 hours to prepare a cyan pigment dispersion ( 1) was obtained.

[Example 1]
According to the blending ratio described in Example 1 of Table 1, MIRAMER M3130 (ethylene oxide (EO) modified trimethylolpropane triacrylate manufactured by MIWON) and MIRAMER M240 (ethylene oxide (EO) modified bisphenol A dimanufactured by MIWON) were placed in a container. Acrylate), FX-AO-MA (manufactured by Nippon Shokubai Co., Ltd., methyl 2-allyloxymethyl acrylate), IBXA (Osaka Organic Chemical Industry Co., Ltd., isobornyl acrylate), V-CAP (ISP, N-vinyl-). 2-caprolactam), light acrylate POA (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) and KF-54 (polysiloxane manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed with stirring, and then Irgacure819 (bis (2,4,4, manufactured by BASF). 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 the mixture was stirred and mixed for 10 minutes to obtain an active energy ray-curable ink (C1) that can also be used in inkjet printing.

[Example 2]
FX-AO-MA (Nippon Shokubai Co., Ltd., 2-allyloxymethyl methyl acrylate usage was changed from 20 parts by mass to 27 parts by mass, and POA (Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate) usage was 16 parts. An active energy ray-curable ink (C2) was obtained in the same manner as in Example 1 except that the content was changed from 0.3 parts by mass to 9.3 parts by mass.

[Example 3]
The amount of FX-AO-MA (manufactured by Nippon Shokubai Co., Ltd., methyl 2-allyloxymethyl acrylate) was changed from 20 parts by mass to 34 parts by mass, and the amount of POA (Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate) used was 16 parts. An active energy ray-curable ink (C3) was obtained in the same manner as in Example 1 except that the content was changed from 0.3 parts by mass to 2.3 parts by mass.

[Example 4]
FX-AO-MA (Nippon Shokubai Co., Ltd., the amount of 2-allyloxymethyl methyl acrylate used was changed from 20 parts by mass to 27 parts by mass, and V-CAP (N-vinyl-2-caprolactam manufactured by ISP) was used. An active energy ray-curable ink (C4) was obtained in the same manner as in Example 1 except that the amount used was changed from 12 parts by mass to 5 parts by mass.

[Example 5]
FX-AO-MA (Nippon Shokubai Co., Ltd., 2-allyloxymethyl methyl acrylate amount was changed from 20 parts by mass to 27 parts by mass, and POA (Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate) amount was changed to 16 parts. Example 1 except that 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. An active energy ray-curable ink (C5) was obtained by the same method.

[Example 6]
FX-AO-MA (Nippon Shokubai Co., Ltd., 2-allyloxymethyl methyl acrylate amount was changed from 20 parts by mass to 27 parts by mass, and POA (Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate) amount was changed to 16 parts. Example 1 except that the amount of IBXA (isoboronyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) was changed from 15 parts by mass to 21 parts by mass. An active energy ray-curable ink (C6) was obtained by the same method.

[Comparative Example 1]
FX-AO-MA (Nippon Shokubai Co., Ltd. make 2-allyloxymethyl methyl acrylate used amount was changed from 20 parts by mass to 0 parts by mass, and the amount of POA (Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate) used was 16 parts. An active energy ray-curable ink was prepared in the same manner as in Example 1 except that the amount of tetrahydrofurfuryl acrylate was changed from 0.3 parts by mass to 9.3 parts by mass and the amount of tetrahydrofurfuryl acrylate used was changed from 0 parts by mass to 27 parts by mass. (C'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 part by mass. Except for the above, an active energy ray-curable 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 to 36.3 parts, and the amount of tetrahydrofurfuryl acrylate used from 27 parts to 0 parts by weight. In the same manner as in Comparative Example 1, an active energy ray-curable ink (C′3) was obtained.
[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, and the amount of tetrahydrofurfuryl acrylate was changed from 27 parts by mass to 0 part by mass, IBXA An active energy ray-curable ink (C'4) was prepared in the same manner as in Comparative Example 1 except that the amount of (Isoboronyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) was changed from 15 parts by mass to 21 parts by mass. Got

The abbreviations shown in Table 1 and Table 2 refer to the following compounds.
M3130: manufactured by MIWON, ethylene oxide (EO)-modified trimethylolpropane triacrylate M240: manufactured by MIWON, ethylene oxide (EO)-modified bisphenol A diacrylate FX-AO-MA: manufactured by Nippon Shokubai Co., Ltd. 2-allyloxymethyl methyl acrylate IBXA : Osaka Organic Chemical Industry Co., Ltd. Isobornyl acrylate V-CAP: ISP N-vinyl-2-caprolactam POA: Kyoeisha Chemical Co., Ltd. phenoxyethyl acrylate THFA: Tetrahydrofurfuryl acrylate KF-54: Shin-Etsu Chemical Co., Ltd. Company polysiloxane Irgacure819: BASF Corporation bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide IrgacureTPO: BASF Company 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide/Kayacure DETX-S: Nippon Kayaku Diethylthioxanthone [Irgacure819/IrgacureTPO]: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide to bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide mass ratio

[Examples 6 to 11]
Active energy ray-curable ink jet recording inks were produced according to the composition ratios shown in Tables 3 and 4. Specifically, MIRAMER M3130 (ethylene oxide (EO) modified trimethylolpropane triacrylate manufactured by MIWON), MIRAMER M240 (ethylene oxide (EO) modified bisphenol A diacrylate manufactured by MIWON), V-190 (Osaka Organic) Chemical Industry Co., Ltd. ethoxyethoxyethyl acrylate), MEDOL-10 (Osaka Organic Chemical Industry Co., Ltd. (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate), V200 (Biscoat # 200, Osaka Organic Chemical Industry Co., Ltd. cyclic trimethylol propane formal acrylate), FX-AO-MA (Nippon Shokubai Co., Ltd. 2-allyloxymethyl methyl acrylate), IBXA (Osaka Organic Chemical Industry Co., Ltd. isobornyl) Acrylate), V-CAP (N-vinyl-2-caprolactam manufactured by ISP), light acrylate POA (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.), tetrahydrofurfuryl acrylate composition containing a trace amount of tetrahydrofurfuryl alcohol, KF. -54 (polysiloxane manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with stirring, and then Irgacure 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide manufactured by BASF), 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 mixed by stirring for 10 minutes to obtain active energy ray-curable inks (C6 to C11).

[Substrate adhesion]
The active energy ray-curable ink was applied to a polycarbonate plate (Asahi Glass Co., Ltd., Lexan, thickness 1 mm, PC) and a vinyl chloride sheet (DIC Co., Ltd. vinyl chloride sheet, PVC) using a spin coater. Of 10 μm, then using an 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 tack on the coating surface disappears (tack free Irradiation).

A 5×5 25-mm incision was made on the obtained cured coating film with a cutter knife, and then cellophane tape manufactured by Nichiban Co., Ltd. was attached 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 masses of the coating film remaining on the surface of the polycarbonate plate or the vinyl chloride sheet was confirmed.

Evaluation Criteria ⊚: The mass number of the coating film remaining on the surface of the polycarbonate plate or the vinyl chloride sheet was 25, and the coating film was not chipped near the notch.

◯: The mass number of the coating film remaining on the surface of the polycarbonate plate or the vinyl chloride sheet was 20 or more.

Δ: The mass number of the coating film remaining on the surface of the polycarbonate plate or the vinyl chloride sheet was 15 or more and less than 20.

X: The mass number of the coating film remaining on the surface of the polycarbonate plate or the vinyl chloride sheet was less than 15.

[Solvent resistance]
The active energy ray-curable ink was applied to a polycarbonate plate (Asahi Glass Co., Ltd., Lexan, thickness 1 mm, PC) with a spin coater to a thickness of 10 μm, and then Hamamatsu Photonics Co., Ltd. equipped with a stage moving device. Irradiation was performed using a company-made LED irradiation device (emission wavelength: 385 nm, peak intensity: 500 mW/cm ² ) until tack on the coating film surface disappeared (until tack free).

A cotton swab soaked with a mixture of ethanol and water (content ratio of ethanol: 70% by mass) was placed on the obtained cured coating film and rubbed left and right 10 times with a width of about 2 cm. When there were no scratches on the surface of the coating film, it was evaluated as "◯", and when scratches were confirmed, it was evaluated as "x".

[Coating surface tackiness]
The active energy ray-curable ink was applied to a polycarbonate plate (Asahi Glass Co., Ltd., Lexan, thickness 1 mm, PC) and a vinyl chloride sheet (DIC Co., Ltd. vinyl chloride sheet, PVC) using a spin coater. Of 10 μm, then using an 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 tack on the coating surface disappears (tack free Irradiation).

Next, a stainless petri dish (Φ75 mm) was prepared, and a 15 g weight was attached to the inner side surface portion.

Next, the stainless petri dish with the weight attached thereto was fixed by hand in a state of standing on the coating film surface such that the positional relationship between the weight and the coating film surface became the positional relationship shown in FIG. ..

Next, the hand was removed from the stainless petri dish, and the stainless petri dish was evaluated on the basis of the number of times that the stainless petri dish was shaken to the left and right on the surface of the film and stopped.
○: 8 times or more ○-△: 6 to 7 times △: 5 to 6 times △-x: 3 to 4 times ×: 0 to 2 times

1 Stainless petri dish 2 Weight 3 Coating surface

Claims (13)

An active energy ray-curable ink for printing on a substrate that is a polycarbonate resin or polyvinyl chloride,
The active energy ray curable ink,
Pigments,
2-allyloxymethyl alkyl acrylate (a5),
One or more selected from the group consisting of ethoxyethoxyethyl (meth)acrylate (a1), a compound (a2) having a structure represented by the following general formula (2), and a compound (a4) represented by the following general formula (4). be those containing a polymerizable compound containing bets (a),
The content ratio of the 2-allyloxymethyl alkyl acrylate (a5) to the total amount of the polymerizable compound (A) is 5% by mass to 30% by mass,
The content of the compound (c) having a structure represented by the following chemical formula (5) with respect to the total amount of the polymerizable compound (A) is 0% by mass to 0.2% by mass. Energy ray curable ink.

(R ¹ and R ² in the general formula (2) each independently represent an alkyl group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom.)

(R ¹ , R ² and R ^{3 in the} general formula (4) each independently represent a hydrogen atom, and X ¹ represents a methylene group or an ethylene group.)

The compound (a2) is (2-methyl-2-ethyl 1,3-dioxolan-4-yl)methyl acrylate, and the compound (a4) is cyclic trimethylolpropane formal acrylate. Active energy ray curable ink. The compound (a2), the active energy ray-curable ink according to claim 1 or 2 containing a combination of a said 2 allyloxymethylacrylate alkyl (a5). The compound (a1), the compound (a2), the active energy ray-curable ink according to claim 1 or 2 containing a combination of a said 2 allyloxymethylacrylate alkyl (a5). The compound (a2), the relative total polymerizable compound (A), the active energy ray-curable ink according to any one of claims 1 to 4 comprises in the range of 8% to 40% by weight .. The compound (a4), the active energy ray-curable ink according to claim 1 or 2 containing a combination of a said 2 allyloxymethylacrylate alkyl (a5). Furthermore, as the compound (b-1) having a heterocyclic structure other than the chemical formula (5), caprolactone-modified tetrahydrofurfuryl acrylate, acryloylmorpholine, N-vinyl-2-caprolactam, N-vinylpyrrolidone or N-acryloyloxyethyl is used. the active energy ray-curable ink according to any one of claims 1 to 6 containing a hexahydrophthalimide. Furthermore, as the compound (b-2) having an aliphatic cyclic structure, tricyclodecane dimethanol di(meth)acrylate, adamantyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, 8. The activity according to claim 7 , containing trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate or dicyclopentenyloxyethyl (meth)acrylate. Energy ray curable ink. 1 mass% to 15 mass% of the compound (b-1) is contained in the whole polymerizable compound (A), and 5 mass% of the compound (b-2) is contained in the whole polymerizable compound (A). % To 24% by mass, the active energy ray-curable ink according to claim 8 . The active energy ray-curable ink according to claim 9 , further containing phenoxyethyl acrylate. The active energy ray-curable ink according to any one of claims 1-10 viscosity 25 ° C. is in the range of 5 to 30 MPa · sec. The active energy ray curable ink according to claim 10 , further comprising an acylphosphine oxide photopolymerization initiator. An active energy ray-curable ink according to any one of claims 1 to 12 is discharged onto a base material which is a polycarbonate resin or polyvinyl chloride using an inkjet recording device, and the active energy ray is irradiated. A method for producing a printed matter, comprising: