JP2017186418A - (meth)acrylate resin and printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a (meth)acrylate resin showing an excellent balance in fluidity and misting resistance and having high curability when used for a printing ink, a curable composition and a printing ink comprising the resin, and a printed matter printed with the printing ink.SOLUTION: The (meth)acrylate resin is prepared from, as essential reaction raw materials, a monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, an aliphatic monohydroxy (meth)acrylate compound (B), and a polyisocyanate compound (C).SELECTED DRAWING: None

Description

  The present invention relates to a (meth) acrylate resin that can be suitably used for printing ink applications, a curable composition and printing ink containing the resin, and a printed material obtained by printing the printing ink.

  Conventionally, diallyl phthalate resins have been widely used as binder resins for UV curable printing inks, but in recent years, the toxicity of diallyl phthalate, which is the raw material of the diallyl phthalate resin, has been pointed out, and there is no toxic concern instead. Development is required.

  As a binder resin for ultraviolet curable printing inks other than diallyl phthalate resin, for example, a polyfunctional isocyanate compound and 2-hydroxyethyl acrylate are reacted in an excess ratio of isocyanate groups, and then the reaction product obtained A urethane acrylate resin obtained by reacting an acid diol and a polyol with a residual isocyanate group is known (see Patent Document 1). Such a urethane acrylate resin does not leave 2-hydroxyethyl acrylate with high skin irritation in the resin and is excellent in safety and hygiene in handling printing ink, but it has curability and fluidity, Various performances such as misting resistance were not sufficient.

JP 2001-151848 A

  Accordingly, the problem to be solved by the present invention is that a (meth) acrylate resin having an excellent balance between fluidity and misting resistance when used in printing ink and having high curability, and a curable composition containing the same And a printing ink and a printed matter obtained by printing the printing ink.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have obtained monohydroxy compounds having aliphatic saturated hydrocarbon groups having 4 to 50 carbon atoms, aliphatic monohydroxy (meth) acrylate compounds, and polyisocyanate compounds. The (meth) acrylate resin having an essential reaction raw material has high curability and has been found to have a good balance between fluidity and misting resistance when used in printing ink, and has completed the present invention.

  That is, in the present invention, a monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, an aliphatic monohydroxy (meth) acrylate compound (B), and a polyisocyanate compound (C) are essential. It is related with the (meth) acrylate resin characterized by making it a reaction raw material.

  The present invention further relates to a curable composition containing the (meth) acrylate resin.

  The present invention further relates to a printing ink using the curable composition.

  The present invention further relates to a printed matter obtained by printing the printing ink.

  According to the present invention, a (meth) acrylate resin having excellent balance between fluidity and misting resistance when used in printing ink and having high curability, a curable composition and printing ink containing the same, and the printing A printed matter obtained by printing ink can be provided.

  The (meth) acrylate resin of the present invention comprises a monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, an aliphatic monohydroxy (meth) acrylate compound (B), and a polyisocyanate compound ( C) is an essential reaction raw material.

  The monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms may be any other compound as long as it has an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms in the molecular structure. The specific structure is not limited, and various compounds can be used. Specific examples of the monohydroxy compound (A) include, for example, the following structural formulas (1) to (3):

［式（１）中のＲ^１は炭素原子数３〜４９の直鎖型又は分岐型の脂肪族飽和炭化水素基である。式（２）中のＲ^２はそれぞれ独立に炭素原子数１〜４８の直鎖型又は分岐型の脂肪族飽和炭化水素基であり、二つのＲ^２の炭素原子数の合計は３〜４９である。式（３）中のＲ^３はそれぞれ独立に炭素原子数１〜４７の直鎖型又は分岐型の脂肪族飽和炭化水素基であり、三つのＲ^３の炭素原子数の合計は４〜４９である。］
の何れかで表される分子構造を有するモノヒドロキシ化合物（Ａ１）や、これらモノヒドロキシ化合物（Ａ１）とモノヒドロキシカルボン酸化合物とのエステル化物であるモノヒドロキシ化合物（Ａ２）、下記構造式（４）〜（６）

[R ¹ in Formula (1) is a linear or branched aliphatic saturated hydrocarbon group having 3 to 49 carbon atoms. R ² in formula (2) is each independently a linear or branched aliphatic saturated hydrocarbon group having 1 to 48 carbon atoms, and the total number of carbon atoms of the two R ² is 3 to 49. is there. R ³ in Formula (3) is each independently a linear or branched aliphatic saturated hydrocarbon group having 1 to 47 carbon atoms, and the total number of three R ³ carbon atoms is 4 to 49. is there. ]
A monohydroxy compound (A1) having a molecular structure represented by any of the following, a monohydroxy compound (A2) which is an esterified product of these monohydroxy compound (A1) and a monohydroxycarboxylic acid compound, the following structural formula (4) )-(6)

［式（４）中のＲ^４は炭素原子数３〜４９の直鎖型又は分岐型の脂肪族飽和炭化水素基である。式（５）中のＲ^５はそれぞれ独立に炭素原子数１〜４８の直鎖型又は分岐型の脂肪族飽和炭化水素基であり、二つのＲ^５の炭素原子数の合計は３〜４９である。式（６）中のＲ^６はそれぞれ独立に炭素原子数１〜４７の直鎖型又は分岐型の脂肪族飽和炭化水素基であり、三つのＲ^６の炭素原子数の合計は４〜４９である。］
の何れかで表されるカルボキシ化合物と、ポリオール化合物とのエステル化物であるモノヒドロキシ化合物（Ａ３）等が挙げられる。

[R ⁴ in Formula (4) is a linear or branched aliphatic saturated hydrocarbon group having 3 to 49 carbon atoms. R ⁵ in Formula (5) is each independently a linear or branched aliphatic saturated hydrocarbon group having 1 to 48 carbon atoms, and the total number of carbon atoms of the two R ⁵ is 3 to 49. is there. R ⁶ in formula (6) is each independently a linear or branched aliphatic saturated hydrocarbon group having 1 to 47 carbon atoms, and the total number of carbon atoms of three R ⁶ is 4 to 49. is there. ]
Or a monohydroxy compound (A3) which is an esterified product of a carboxy compound represented by any of the above and a polyol compound.

Among the compounds represented by the structural formula (1), the monohydroxy compound (A1) is a (meth) acrylate resin having an excellent balance between fluidity and misting resistance. The number of carbon atoms of R ¹ is more preferably in the range of 8-30, and particularly preferably in the range of 10-26. Specific examples of the compound represented by the structural formula (1) include, for example, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 2-methyl-1-decanol, 1-dodecanol (lauryl alcohol). 2-butyl-1-octanol, 1-tridecanol, 2-propyldecan-1-ol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol (palmityl alcohol), 1-heptadecanol 1-octadecanol (stearyl alcohol), isooctadecanol (isostearyl alcohol), 1-nonadecanol, 1-icosanol, 2-octyl-1-dodecanol, 1-henicosanol, 1-docosanol, 1-tricosanol, 1 -Tetracosanol, 2-decyl-1-tetradecano Etc. The.

Among the compounds represented by the structural formula (2), since it becomes a (meth) acrylate resin having an excellent balance between fluidity and misting resistance, at least one of the two R ^{2 in} the structural formula (2). Is more preferably an aliphatic saturated hydrocarbon group having 8 to 30 carbon atoms, particularly preferably a compound in which at least one of R ² is an aliphatic saturated hydrocarbon group having 10 to 26 carbon atoms. Specific examples of the compound represented by the structural formula (2) include 2-decanol, 2-undecanol, 3-undecanol, 2-dodecanol, 3-dodecanol, 2-tridecanol, 3-tridecanol, 3 -Ethylundecan-3-ol, 2-tetradecanol, 3-tetradecanol, 2-pentadecanol, 3-pentadecanol, 2-hexadecanol, 3-hexadecanol, 4-hexadecanol, Examples include 2-heptadecanol, 3-heptadecanol, 2-octadecanol, 3-octadecanol, 2-nonadecanol, 2-icosanol, 3-icosanol, 2-henicosanol, and 11-henicosanol.

Among the compounds represented by the structural formula (3), since it becomes a (meth) acrylate resin having an excellent balance between fluidity and misting resistance, at least one of the three R ^{3 in} the structural formula (3). Is more preferably a compound having a saturated aliphatic hydrocarbon group having 8 to 30 carbon atoms, and particularly preferably a compound in which at least one of R ³ is a saturated aliphatic hydrocarbon group having 10 to 26 carbon atoms. Specific examples of the compound represented by the structural formula (3) include 2-methyldecan-2-ol, 2-methyl-2-undecanol, 2-methyl-2-dodecanol, 2-methyl-2-tridecanol, 3 -Methyl-3-tridecanol, 2-methyl-2-tetradecanol, 3-ethyltridecan-3-ol, 3-methyl-3-pentadecanol, 1,1-dimethyl-1-pentadecanol, 2 -Methylheptadecan-2-ol, 7-methylnonadecan-7-ol, 11-pentylhexadecan-11-ol, 9-octylheptadecan-9-ol and the like.

  The monohydroxy compound (A2) is an esterified product of the monohydroxy compound (A1) represented by any one of the structural formulas (1) to (3) and a monohydroxycarboxylic acid compound. Examples of the monohydroxycarboxylic acid compound used as a raw material for the monohydroxy compound (A2) include malic acid, itamaric acid, 3-methyl-3-hydroxyglutaric acid, 4-hydroxypimelic acid, and 2,4-dimethyl-3. -Hydroxyglutaric acid etc. are mentioned. These may be used alone or in combination of two or more.

  When the monohydroxycarboxylic acid compound is a bifunctional or higher functional carboxylic acid compound, the monohydroxy compound (A1) to be reacted with the monohydroxycarboxylic acid compound is a compound represented by any one of the structural formulas (1) to (3). One type may be used alone, or two or more types may be used in combination. Especially, since it becomes (meth) acrylate resin excellent in the balance of fluidity | liquidity and misting resistance, what is obtained using the compound represented by the said Structural formula (1) is preferable.

The monohydroxy compound (A3) is an esterified product of a carboxy compound represented by any one of the structural formulas (4) to (6) and a polyol compound. R ⁴ , R ⁵ and R ⁶ in the structural formulas (4) to (6) are (meth) acrylate resins having an excellent balance between fluidity and misting resistance, and therefore exist in the monohydroxy compound (A2). Preferably, at least one of R ⁴ , R ⁵ and R ⁶ is a saturated aliphatic hydrocarbon group having 8 to 30 carbon atoms, and at least one is a saturated aliphatic hydrocarbon group having 10 to 26 carbon atoms. It is particularly preferred. R ⁴ , R ⁵ and R ⁶ are more preferably straight chain aliphatic saturated hydrocarbon groups.

  Examples of the polyol compound used as a raw material for the monohydroxy compound (A3) include ethylene glycol, propanediol, 2-methylpropanediol, butanediol, neopentylglycol, 3-methylpentanediol, hexanediol, glycerin, and trimethylolethane. And aliphatic polyol compounds such as trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol. These may be used alone or in combination of two or more.

  When the polyol compound is a tri- or higher functional polyol compound, the carboxy compound to be reacted with the polyol compound is one of the carboxy compounds represented by any one of the structural formulas (4) to (6). Alternatively, two or more types may be used in combination. Especially, since it becomes (meth) acrylate resin excellent in the balance of fluidity | liquidity and misting resistance, what is obtained using the compound represented by the said Structural formula (4) is preferable.

  Among these monohydroxy compounds (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, a (meth) acrylate resin having an excellent balance between fluidity and misting resistance and excellent curability is obtained. Therefore, a compound having a secondary or primary hydroxyl group is preferred.

  The aliphatic monohydroxy (meth) acrylate compound (B) is a compound having an aliphatic hydrocarbon group as a main skeleton and one hydroxyl group and one or more (meth) acryloyl groups in the molecular structure. For example, aliphatic monohydroxy mono (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl acrylate; glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, penta Examples thereof include aliphatic monohydroxy poly (meth) acrylate compounds such as erythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. These may be used alone or in combination of two or more. Among these, the aliphatic monohydroxy mono (meth) acrylate compound is preferable because it becomes a (meth) acrylate resin having excellent curability.

  In the present invention, the aliphatic monohydroxy (meth) acrylate compound (B) and other monohydroxy (meth) acrylate compound (B ′) may be used in combination as desired. In this case, the aliphatic monohydroxy (meth) acrylate compound (B) and other monohydroxys are obtained because the (meth) acrylate resin has an excellent balance between fluidity and misting resistance and also has excellent curability. It is preferable that the said aliphatic monohydroxy (meth) acrylate compound (B) is 50 mass% or more with respect to the total mass with a (meth) acrylate compound (B '), and it is more preferable that it is 80 mass% or more. .

  Examples of the other monohydroxy (meth) acrylate compound (B ′) include 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, Aromatic monohydroxy mono (meth) acrylate compounds such as 3-hydroxy-4-acetylphenyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate, the aliphatic monohydroxy (meth) acrylate compound (B) or the fragrance Group monohydroxy mono (meth) acrylate compounds, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, Polyoxyalkylene-modified monohydroxy (meth) acrylate compound obtained by ring-opening polymerization with various cyclic ether compounds such as luglycidyl ether; polycondensation of the monohydroxy (meth) acrylate compound with a lactone compound such as ε-caprolactone Lactone-modified monohydroxy (meth) acrylate compound obtained by the above. These may be used alone or in combination of two or more.

  Examples of the polyisocyanate compound (C) include aliphatic diisocyanate compounds such as hexamethylene diisocyanate; alicyclic diisocyanate compounds such as isophorone diisocyanate; tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 1, Aromatic diisocyanate compounds such as 5-naphthalene diisocyanate; the following structural formula (4)

［式中、Ｒ^４はそれぞれ独立に水素原子、炭素原子数１〜６の炭化水素基の何れかである。Ｒ^５はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、又は構造式（４）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｍは１〜３の整数であり、ｎは１以上の整数である。］
で表される繰り返し構造を有するポリメチレンポリフェニルポリイソシアネート；これらのイソシアヌレート変性体、アダクト変性体、ビウレット変性体、アロファネート変性体等が挙げられる。これらはそれぞれ単独で使用しても良いし、２種類以上を併用しても良い。

[Wherein, R ⁴ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁵ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a bonding point that connects to a structural moiety represented by the structural formula (4) via a methylene group marked with *. It is. m is an integer of 1 to 3, and n is an integer of 1 or more. ]
Polymethylene polyphenyl polyisocyanate having a repeating structure represented by: These isocyanurate-modified products, adduct-modified products, biuret-modified products, allophanate-modified products, and the like. These may be used alone or in combination of two or more.

  Among them, since it becomes a (meth) acrylate resin having an excellent balance between fluidity and misting resistance, a polyisocyanate compound having a ring structure in the molecular structure, that is, a polyisocyanate compound having an isocyanurate ring structure, the alicyclic type The diisocyanate compound, the aromatic diisocyanate compound, and polymethylene polyphenyl polyisocyanate having a molecular structure represented by the structural formula (4) are preferable. Furthermore, a polyisocyanate compound having an aromatic ring in the molecular structure, that is, the aromatic diisocyanate compound, a polymethylene polyphenyl polyisocyanate having a molecular structure represented by the structural formula (4), and their nurate-modified products, Adduct modified products, biuret modified products, and allophanate modified products are particularly preferable.

  The polymethylene polyphenyl polyisocyanate having a molecular structure represented by the structural formula (4) preferably contains 30% by mass or more of a component in which n in the structural formula (4) is 2 or more. Moreover, the thing whose viscosity measured with an E-type viscosity meter (25 degreeC) is the range of 100-700 mPa * s is preferable.

  The (meth) acrylate resin of the present invention comprises a monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, an aliphatic monohydroxy (meth) acrylate compound (B), and a polyisocyanate compound. In addition to (C), other reaction raw materials may be used in combination. Examples of other reaction raw materials include a polyol compound (D).

  The polyol compound (D) may be a compound having a plurality of hydroxyl groups in the molecular structure, such as ethylene glycol, propanediol, 2-methylpropanediol, butanediol, neopentylglycol, 3-methylpentanediol, Aliphatic polyol compounds such as hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol; the above aliphatic polyol compounds and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl Obtained by ring-opening polymerization with various cyclic ether compounds such as ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. A polyoxyalkylene-modified polyol compound; a lactone-modified polyol compound obtained by polycondensation of the aliphatic polyol compound and a lactone compound such as ε-caprolactone; the aliphatic polyol compound; and succinic acid, adipic acid, sebacic acid, (Anhydrous) Polyester polyols obtained by cocondensation with dicarboxylic acids such as phthalic acid, maleic acid, fumaric acid and 1,4-cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.

  Among them, the aliphatic polyol compound is preferable because it is a (meth) acrylate resin having excellent balance between fluidity and misting resistance when used in printing ink, and having high curability, glycerin, trimethylolethane, A trifunctional aliphatic polyol compound such as trimethylolpropane is more preferable. Moreover, it is preferable that 50 mass% or more of a polyol compound (D) is the said aliphatic polyol compound, and it is more preferable that 80 mass% or more is the said aliphatic polyol compound.

  In the (meth) acrylate resin of the present invention, the proportion of each component in the reaction raw material is appropriately adjusted according to desired resin properties such as molecular weight and (meth) acryloyl group equivalent, and is particularly limited. is not. For example, when the (meth) acrylate resin of the present invention uses the components (A), (B), (C) and components (B ′), (D) used as necessary as reaction raw materials, It is preferable to react with 1 mol of the isocyanate group in the reaction raw material at a ratio such that the hydroxyl group in the reaction raw material is in the range of 0.95 to 1.05 mol.

  As a more preferable resin design of the (meth) acrylate resin, since it becomes a (meth) acrylate resin excellent in balance between fluidity and misting resistance, 0.1 to 30 parts by mass in a total of 100 parts by mass of reaction raw materials Is preferably a monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, and 0.3 to 15 parts by mass of the aliphatic saturated hydrocarbon having 4 to 50 carbon atoms. A monohydroxy compound (A) having a group is particularly preferred.

When the (meth) acrylate resin uses the polyol compound (D) as a reaction raw material, the (meth) acrylate resin having an excellent balance between fluidity and misting resistance when used in printing ink and having high curability Therefore, the hydroxyl group of the monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, the hydroxyl group of the aliphatic monohydroxy (meth) acrylate compound (B), and as necessary The ratio of the total number of moles of hydroxyl groups possessed by the other monohydroxy (meth) acrylate compound (B ′) used in accordance with the number of moles of hydroxyl groups possessed by the polyol compound (D) [(A _OH + B _OH + B ′ _OH ) / (D _OH )] is preferably in the range of 8/2 to 5/5.

  The method for producing the (meth) acrylate resin of the present invention is not particularly limited, and for example, it can be produced by a general method for producing a urethane acrylate resin. As an example of the production method, for example, the monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, the aliphatic monohydroxy (meth) acrylate compound (B), used as necessary. After reacting the other monohydroxy (meth) acrylate compound (B ′) and the polyisocyanate compound (C) to obtain an isocyanate group-containing intermediate, the intermediate and the polyol compound (if necessary) ( And D).

Specifically, first, the polyisocyanate compound (C) is charged into a reaction vessel and heated to 20 to 120 ° C., and the monohydroxy compound (A) having the aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms. , The aliphatic monohydroxy (meth) acrylate compound (B), and the other monohydroxy (meth) acrylate compound (B ′) used as necessary are continuously or intermittently added to the reaction system to react them. . In the reaction, a known and usual urethanization catalyst such as zinc octylate, various antioxidants, polymerization inhibitors and the like may be used as desired. Next, the polyol compound (D) used as necessary is added to the reaction system, and further reacted in a temperature range of 20 to 120 ° C., and the end point of the reaction is determined in an infrared absorption spectrum of 2250 cm ⁻¹ indicating an isocyanate group. Confirm and obtain the desired (meth) acrylate resin.

  Since the weight average molecular weight (Mw) of the (meth) acrylate resin of the present invention is excellent in fluidity and misting resistance when used for printing ink, it may be in the range of 1,000 to 30,000. Preferably, it is in the range of 3,000 to 20,000.

  In the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

  In addition, the (meth) acryloyl group content of the (meth) acrylate resin of the present invention has high curability and is excellent in gloss on the printed surface when used in printing ink applications, so that it is 1.5 to 4.0 mmol / It is preferably in the range of g, more preferably in the range of 2.0 to 3.5 mmol / g, and particularly preferably in the range of 2.5 to 3.5 mmol / g. In the present invention, the (meth) acryloyl group content of the (meth) acrylate resin is a theoretical value calculated from the reaction raw material used.

  The curable composition of the present invention contains, in addition to the (meth) acrylate resin, other (meth) acrylate compounds (X), a polymerization initiator (Y), various additives, and the like as desired. .

  The other (meth) acrylate compound (X) includes, for example, various (meth) acrylate monomers (X1), urethane (meth) acrylate (X2) other than the (meth) acrylate resin of the present invention, and epoxy (meta). ) Acrylate (X3) and the like.

  The (meth) acrylate monomer (X1) is, for example, an aliphatic mono (meth) acrylate compound such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate; cyclohexyl (meta ) Cycloaliphatic mono (meth) acrylate compounds such as acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; Aromatic mono (meth) acrylate compounds such as (meth) acrylate and phenoxy (meth) acrylate; hydroxyl-containing mono (medium) such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate ) Acrylate compounds; polyoxyalkylene-modified mono (meth) in which polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polyoxytetramethylene chains, etc. are introduced into the molecular structures of the various mono (meth) acrylate compounds. Acrylate compounds; lactone-modified mono (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of the various mono (meth) acrylate compounds;

  Aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate Alicyclic di (meth) acrylate compounds such as norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate; biphenol Aromatic di (meth) acrylate compounds such as di (meth) acrylate and bisphenol di (meth) acrylate; polyoxyethylene chains, polyoxypropylene in the molecular structures of the various di (meth) acrylate compounds Polyoxyalkylene-modified di (meth) acrylate compounds into which polyoxyalkylene chains such as polyoxytetramethylene chains are introduced; (poly) lactone structures are introduced into the molecular structures of the various di (meth) acrylate compounds. Lactone-modified di (meth) acrylate compound;

  Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) Hydroxyl-containing tri (meth) acrylate compounds such as acrylates; polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polyoxytetramethylene chains, etc. were introduced into the molecular structures of the various tri (meth) acrylate compounds. A polyoxyalkylene-modified tri (meth) acrylate compound; a lactone-modified tri (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various tri (meth) acrylate compounds;

  Tetra- or higher functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; dipentaerythritol tetra (meth) acrylate, di A tetra- or higher functional hydroxyl group-containing poly (meth) acrylate compound such as pentaerythritol penta (meth) acrylate; a polyoxyethylene chain, a polyoxypropylene chain, a polyoxytetramethylene in the molecular structure of the various poly (meth) acrylate compounds A poly (alkylene) -modified poly (meth) acrylate compound having four or more functional groups introduced with a polyoxyalkylene chain such as a chain; a (poly) lactone structure is introduced into the molecular structure of the various poly (meth) acrylate compounds. The tetrafunctional or more lactone-modified poly (meth) acrylate compounds, and the like.

  Examples of the urethane (meth) acrylate compound (X2) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as necessary. Examples of the polyisocyanate compound include diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and 4,4′-diphenylmethane diisocyanate, or nurate-modified products, adduct-modified products, and biuret-modified products. . Examples of the hydroxyl group-containing (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane diacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and These polyoxyalkylene modified products, polylactone modified products and the like can be mentioned. Examples of the polyol compound include ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

  Examples of the epoxy (meth) acrylate compound (X3) include bisphenol type epoxy resins and (meth) acrylic acid esters of epoxy group-containing compounds such as trimethylolpropane triglycidyl ether.

  These other (meth) acrylate compounds (X) may be used alone or in combination of two or more. Among them, the (meth) acrylate monomer (X1) is preferable and a tri- or higher functional (meth) acrylate compound is more preferable because of its high curability and excellent gloss on the printed surface when used for printing ink. Furthermore, aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; polyoxyethylene chain and polyoxypropylene in the molecular structure of the aliphatic tri (meth) acrylate compound Polyoxyalkylene-modified tri (meth) acrylate compounds into which polyoxyalkylene chains such as polyoxytetramethylene chains are introduced; pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) ) A tetrafunctional or higher aliphatic poly (meth) acrylate compound such as an acrylate; In the molecular structure of the tetrafunctional or higher aliphatic poly (meth) acrylate compound, a polyoxyethylene chain, a polyoxypropylene chain, a poly Alkoxy polyoxyalkylene chain introduced tetrafunctional or more polyoxyalkylene-modified poly (meth) acrylate compounds such as tetramethylene chain are particularly preferred.

  When these other (meth) acrylate compounds (X) are used, the curability is high, and the gloss of the printed surface when used for printing ink is excellent. Therefore, the (meth) acrylate resin of the present invention is used. It is preferable to use other (meth) acrylate compound (X) in the range of 5-300 mass parts with respect to 100 mass parts, and it is more preferable to use in the range of 50-200 mass parts.

  Examples of the polymerization initiator (Y) include an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator, and any of them may be used. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-1- {4- [4 -(2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2- Acetophenone compounds such as diethoxy-1,2-diphenylethane-1-one; 1- [4- (phenylthio)-, 2- ( -Benzoyloxime)], 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like, 3,6- Carbazole compounds such as bis (2-methyl-2-morpholinopropanyl) -9-butylcarbazole, benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether;

  2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane Aminoalkylphenones such as -1-one, 2-methyl-2-morpholino ((4-methylthio) phenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone Compounds: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Acylphosphine oxide compounds such as pentylphosphine oxide; benzyl, methylphenyl Li oxy esters.

  Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, and acrylic. Benzophenone compounds such as benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4-dimethyl Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; aminobenzophenes such as 4,4′-bisdimethylaminobenzophenone and 4,4′-bisdiethylaminobenzophenone Emissions-based compound; Other 10-butyl-2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  These polymerization initiators (Y) may be used alone or in combination of two or more. Among these, aminoalkylphenone compounds are preferable from the viewpoint of excellent curability, and particularly when a UV-LED light source that generates ultraviolet rays having an emission peak wavelength in the range of 350 to 420 nm is used as an active energy ray source. Is preferably used in combination with an aminoalkylphenone compound, an acylphosphine oxide compound, and an aminobenzophenone compound from the viewpoint of excellent curability.

  The addition amount of the polymerization initiator (Y) is preferably in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the curable composition.

  The curable composition of the present invention may contain a photosensitizer in combination with the polymerization initiator (Y). Examples of the photosensitizer include amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate, s-benzylisothuronium-p-toluenesulfonate, and the like. . It is preferable that the addition amount of these photosensitizers is the range used as 0.1-10 mass parts with respect to a total of 100 mass parts of a curable composition.

  The curable composition of the present invention further includes a pigment, a dye, an extender pigment, an organic or inorganic filler, an organic solvent, an antistatic agent, an antifoaming agent, a viscosity modifier, a polymerization inhibitor, a light resistance stabilizer, a weather resistance stabilizer, You may contain additives, such as a heat stabilizer, a ultraviolet absorber, antioxidant, a leveling agent, a pigment dispersant, and a wax.

  Examples of the pigment include publicly known organic pigments for coloring, such as organic pigments for printing inks published in “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)”. Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinones A pigment, a quinophthalone pigment, a metal complex pigment, a diketopyrrolopyrrole pigment, a carbon black pigment, and other polycyclic pigments can be used. Although the optimum amount of these pigments varies depending on the type of pigment and the like, it is preferably in the range of 5 to 30 parts by mass with respect to 100 parts by mass in total of the curable composition.

  Examples of the extender pigment include titanium oxide, kraftite, zinc, lime carbonate powder, precipitated calcium carbonate, gypsum, clay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, Barite powder, glass beads, etc. are raised. The optimum amount of these extender pigments varies depending on the type of pigment and the like, but is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the curable composition.

  The composition of the printing ink of the present invention is not particularly limited as long as the (meth) acrylate resin of the present invention is used, and the composition and blending ratio are adjusted appropriately according to the intended printing application and performance. can do. Examples of the production method include a method in which a mixture of each component is stirred and mixed with a mixer or the like, and then kneaded using a dispersing machine such as a three-roll mill or a bead mill.

  The printing ink of the present invention can be cured by irradiation with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of light sources include germicidal lamps, fluorescent lamps for ultraviolet rays, UV-LEDs, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, and natural light sources. And an electron beam by a scanning type or curtain type electron beam accelerator.

  The printing ink of the present invention can be printed on various substrates such as paper and various plastic films. Specifically, paper substrates used for catalogs, posters, flyers, CD jackets, direct mails, pamphlets, cosmetics and beverages, pharmaceuticals, toys, packaging of equipment, etc .; polypropylene films, polyethylene terephthalate films, foods and beverages, Plastic film base materials for packaging materials such as cosmetics; aluminum foil, synthetic paper, and other various base materials conventionally used as printing base materials can be used as printing objects.

  The printing method of the printing ink of the present invention is not particularly limited, and for example, printing can be performed by planographic offset printing, relief printing, gravure printing, gravure offset printing, flexographic printing, screen printing, and the like. Among these, in particular, it can be suitably used in lithographic offset printing in which water is continuously supplied to the plate surface. Offset printers that continuously supply water are manufactured and sold by a number of printer manufacturers. Examples include Heidelberg, Komori Corporation, Ryobi MHI Graphic Technology, Man Roland, KBA, etc. The present invention can be suitably used in any sheet feeding system, such as a sheet-fed offset printing machine using sheet-type printing paper, an offset rotary printing machine using reel-type printing paper. More specifically, offset printing machines such as Heidelberg's Speedmaster series, Komori Corporation's Lislon series, Ryobi MHI Graphic Technology's diamond series, and the like can be mentioned.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

Measurement conditions of infrared absorption spectrum [Model] FT / IR-4100 manufactured by JASCO Corporation
[Measurement conditions] Completion of the reaction was confirmed by confirming an infrared absorption spectrum of 2250 cm ^-1 indicating an isocyanate group.

Measurement conditions of weight average molecular weight (Mw) The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions.
Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

Example 1 Production of (Meth) acrylate Resin (1) A four-necked flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer has a repeating structure represented by the following structural formula (4-1). Polymethylene polyphenyl polyisocyanate (BASF INOAC Polyurethane Co., Ltd. “Lupranate M20S”: isocyanate group content 31% by mass) 56.6 parts by mass, tertiary butylhydroxytoluene 0.5 parts by mass, methoxyhydroquinone 0.05 parts by mass Then, 0.02 part by mass of zinc octylate was added, and the temperature was raised to 50 ° C. While stirring the reaction system, 34.6 parts by mass of 2-hydroxyethyl acrylate and 6 parts by mass of 1-dodecanol (lauryl alcohol) were added dropwise over 1 hour. After reacting at 90 ° C. for 3 hours, 2.8 parts by mass of glycerin was added. The reaction was continued at 90 ° C., and it was confirmed that the infrared absorption spectrum of 2250 cm ⁻¹ indicating an isocyanate group had disappeared, and (meth) acrylate resin (1) was obtained. The weight average molecular weight (Mw) of the (meth) acrylate resin (1) was 2,644, and the theoretical value of the (meth) acryloyl group content calculated from the reaction raw material was 2.98 mmol / g.

［式中、Ｒ^５はそれぞれ独立に水素原子又は構造式（４−１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｍは１〜３の整数であり、ｎは１以上の整数である。］

[Wherein, R ⁵ is each independently a hydrogen atom or a bonding point linked to a structural moiety represented by the structural formula (4-1) via a methylene group marked with *. m is an integer of 1 to 3, and n is an integer of 1 or more. ]

Examples 2 to 9 Production of (meth) acrylate resins (2) to (9) (Meth) acrylate in the same manner as in Example 1 except that the types and amounts used of the respective raw material components were changed as shown in Table 1 below. Resins (2) to (9) were obtained.

(*) Isocyanurate modified form of hexamethylene diisocyanate: “Sumidule N3300” isocyanate group content 22% by mass, manufactured by Sumika Bayer Urethane Co., Ltd.

Comparative Production Example 1 Production of (Meth) acrylate Resin (1 ′) In a four-necked flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, 16.3 parts by mass of tolylene diisocyanate and tertiary butylhydroxytoluene 0.1 part by mass, 0.02 part by mass of methoxyhydroquinone and 0.02 part by mass of zinc octylate are added, the temperature is raised to 75 ° C., and 3.7 parts by mass of 2-hydroxyethyl acrylate is added dropwise with stirring over 1 hour. did. After dripping, after reacting at 75 ° C. for 3 hours, as a second step, 80.0 parts by mass of polypropylene glycol (“Accor D-3000” number average molecular weight 3000 manufactured by Mitsui Chemicals) is added, and further reacted at 75 ° C. And a reaction was carried out until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappeared to obtain a (meth) acrylate resin (1 ′). The weight average molecular weight (Mw) of the (meth) acrylate resin (1 ′) was 5,680, and the theoretical value of the (meth) acryloyl group content calculated from the reaction raw material was 0.32 mmol / g.

Examples 10 to 18 and Comparative Example 1
Each component was blended in the proportions shown in Tables 2 and 3 below and stirred using a mixer (single-axis dissolver), and then the blend was kneaded using a three-roll mill to prepare a printing ink. Various evaluations were performed on the obtained printing ink under the following conditions. The results are shown in Tables 2 and 3.

Details of each component used for the preparation of the printing ink are as follows. Other (meth) acrylate compound (X-1): ethylene oxide-modified trimethylolpropane triacrylate (“MIRAMER M3130” manufactured by MIWON, Inc.) Viscosity: 50-70 mPa · s (25 ° C.) ethylene oxide average addition number per molecule: 3)
Pigment: “SYMULER FAST YELLOW 4342” manufactured by DIC Corporation
Body Pigment: Hydrous Magnesium Silicate (Matsumura Sangyo Co., Ltd. Body Pigment “High Filler # 5000PJ”)
Wax: Polyolefin wax (Shamrock Wax “S-381-N1”)
Polymerization inhibitor: N-nitrosophenylhydroxylami aluminum salt (“Q-1301” manufactured by Wako Pure Chemical Industries, Ltd.)
Polymerization initiator (Y-1): α-aminoalkylphenone (“Irgacure 907” manufactured by BASF)
Polymerization initiator (Y-2): 4,4′-bisdimethylaminobenzophenone (“EAB-SS” manufactured by Daido Kasei)

Evaluation of fluidity 1 Measurement of diameter value Measurement was carried out by a spread meter method (parallel plate viscometer) according to JIS K5101, 5701. The printing ink sandwiched between two parallel plates placed horizontally was observed to spread over time by the weight of the load plate (115 grams) over time, and the ink spreading diameter after 60 seconds (mm) Was evaluated as a diameter value. The evaluation criteria are as follows.
A: Diameter value is 37 mm or more B: Diameter value is 34 mm or more and less than 37 mm C: Diameter value is less than 34 mm

Evaluation of fluidity 2 Measurement of fluidity of glass plate In a room conditioned at 25 ° C, 1.0 ml of printing ink was placed on the upper end of the glass plate forming an angle of 70 ° with the ground plane, and the distance of fluidization after one day was measured. . It shows that fluidity | liquidity is so favorable that a numerical value is large.

Evaluation of Misting 1.31 ml of printing ink was placed on an incometer type misting tester and rotated at a machine temperature of 32 ° C. and 1200 rpm for 3 minutes. The printing ink spattered with rotation, and the misting superiority and inferiority were compared by the change in mass increase of the papers arranged along the rotating body. When the misting resistance is poor, the amount of printing ink flying increases and the paper mass increases.
(Evaluation criteria)
A: Less than 0.050 g B: 0.050 g or more Less than 0.075 g C: 0.075 g or more

Evaluation of curability Using a simple color developing machine (RI tester, manufactured by Toyoe Seiko Co., Ltd.), using 0.10 ml of the above printing ink, it was uniformly stretched on the rubber roll and metal roll of the RI tester, and transparent PET tack paper (DIC) The color was developed so as to be uniformly applied to the surface area of about 220 cm ^{2 on} the surface of “Dai-Tac UVPET Transparent 25EMH-S” manufactured by the manufacture, and a color-exposed product was produced.
The developed product after the printing ink was applied was irradiated with ultraviolet rays (UV) to cure the printing ink to obtain a printed product. Specifically, a UV-irradiation device (made by Eye Graphics Co., attached with a cold mirror) equipped with a water-cooled metal halide lamp (output: 100 W / cm 1 light) and a belt conveyor is mounted on the conveyor, and the lamp Directly below (irradiation distance 11 cm) was passed under the predetermined conditions described below. The ultraviolet irradiation amount in each condition was measured using an ultraviolet integrated light quantity system (UNIMETER UIT-150-A / light receiving device UVD-C365 manufactured by USHIO INC.).
The curability was confirmed immediately after irradiation by the nail scratch method on the printed surface. The fastest conveyor speed (m / min) is indicated, in which the color-exposed product is irradiated with ultraviolet rays while changing the conveyor speed (m / min) of the UV irradiation apparatus, and is not damaged even when rubbed strongly with a nail after curing. It shows that the sclerosis | hardenability of printing ink is so favorable that the numerical value of a conveyor speed is large.

Gloss evaluation Using a simple color developing machine (RI tester, produced by Toyoe Seiko Co., Ltd.), UV-curable overprint varnish (made by DIC "UV Carton ACT OP Varnish") on the developed color used in the curability evaluation ) Overprinted 0.15 ml. The conveyor speed was set to 30 m / min with a UV irradiation device under the same conditions as in the curability evaluation, and the printing ink and overprint varnish were cured. About the obtained printed matter, the gloss of the printing surface was measured and evaluated. Higher gloss values indicate better ink overprint varnish acceptability.
(Evaluation criteria)
A: Gloss 45 or more B: Gloss less than 45

Claims (10)

A monohydroxy compound (A) having an aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms, an aliphatic monohydroxy (meth) acrylate compound (B), and a polyisocyanate compound (C) are used as essential reaction raw materials. (Meth) acrylate resin characterized by The (meth) acrylate according to claim 1, wherein 0.1 to 30 parts by mass of the reaction raw material is a monohydroxy compound (A) having the aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms. resin. The (meth) acrylate resin according to claim 1, wherein the polyisocyanate compound is a polyisocyanate compound having an aromatic ring in a molecular structure. Furthermore, (meth) acrylate resin of Claim 1 which uses a polyol compound (D) as an essential reaction raw material and 50 mass% or more of a polyol compound (D) is an aliphatic polyol compound. Monohydroxy compound (A), aliphatic monohydroxy (meth) acrylate compound (B), polyisocyanate compound having aliphatic saturated hydrocarbon group having 4 to 50 carbon atoms occupying in 100 parts by mass of reaction raw material The (meth) acrylate resin according to claim 1, wherein the total mass of (C) and the aliphatic polyol compound is 80 parts by mass or more. The (meth) acrylate resin according to claim 1, wherein the weight average molecular weight (Mw) is in the range of 1,000 to 30,000.   The curable composition containing the (meth) acrylate resin as described in any one of Claims 1-6.   The curable composition of Claim 7 containing the said (meth) acrylate resin and other (meth) acrylate compound (X).   Printing ink which uses the curable composition of Claim 7 or 8.   A printed matter obtained by printing the printing ink according to claim 9.