JP2003147037A - Energy ray-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an energy ray-curable resin composition coatable without using any organic solvent affecting human health and the environment, giving cured coating film excellent in stability, curability, near-infrared absorption, fluorescence emission, light resistance, peel resistance and printability with thermal head, thus usable as a near-infrared absorption ink or fluorescence emission ink. SOLUTION: This energy ray-curable resin composition comprises (A) a resin having in the molecule ethylenically unsaturated group, (B) a compound exhibiting absorption in the near infrared region of 650 nm to 1,000 nm, (C) a light resistance improving agent and (D) a reactive silicone.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an energy ray-curable resin composition. More specifically, the present invention relates to an energy ray curable near-infrared absorbing ink and a fluorescent light emitting ink which are excellent in stability, curability and light resistance.

[0002]

2. Description of the Related Art Conventionally, a method of printing with an ink containing a material that absorbs near infrared rays and reading it with an infrared sensor is well known. Further, an ink containing a material that emits fluorescence is printed by an inkjet printer or the like, and printing that emits fluorescence by irradiating excitation energy such as ultraviolet light or infrared light, a method for forming marks such as barcodes, or the like. The fluorescent ink used in such a method is described in, for example, Japanese Patent Publication No. 62-24024 and No. 6-500590, and is known.

[Problems to be Solved by the Invention]

However, conventional near-infrared absorbing inks and fluorescent light-emitting inks usually contain an organic solvent, and in view of recent environmental problems and workability, it has been desired to eliminate the solvent. In addition, when the base material to be printed is a base material such as paper that is easily impregnated with a solvent, the material in the ink may soak into the base material together with the solvent, and the original performance may not be obtained. Was there.

The energy ray curable resin is used in many fields because of its simple equipment for curing, solvent-free, high safety and high productivity, and its cured film also has blocking property, abrasion resistance, Due to its excellent chemical resistance and solvent resistance, the amount used has been rapidly increasing in recent years. Also for printing inks, UV-curable inks have been widely used in a considerable number of fields.

However, the energy ray-curable ink needs to be irradiated with energy rays when the ink is cured, and in the case of a near-infrared absorbing ink or a fluorescent light-emitting ink, a compound that absorbs near-infrared rays by its irradiation energy. However, there was a problem that the original performance could not be maintained. At the same time, when the printed matter is left in the sunlight, the near-infrared absorption and fluorescence emission of the printed matter disappear in a short period of time, resulting in insufficient light resistance.

Further, in the case of near infrared absorbing ink or fluorescent emitting ink, it is not desirable that only the printed portion of the near infrared absorbing ink or fluorescent emitting ink is peeled off with a cellophane tape (R) or the like from the printed matter depending on the intended use. There has been a demand for an ink that does not cause peeling of printed matter. further,
When such near infrared absorbing ink or fluorescent light emitting ink is used for a thermal card, printing is performed with a thermal head. In that case, dust adhered to the thermal head, and a sound at the time of printing (sticking sound) There was a demand for something that would not cause such problems. To solve these problems, a method of adding silicone oil etc. can be considered, but in the case of near infrared absorbing ink or fluorescent light emitting ink, the compound that absorbs near infrared rays and the improvement of light resistance are added by the addition of modified silicone oil. Since the compound used as an agent is affected and there is a problem that the original performance cannot be maintained, it is difficult to achieve both the printing characteristics of the thermal head and the stability of the ink.

In any case, the near-infrared absorbing ink or the fluorescent light emitting ink using the energy ray curable resin has good ink stability, curability, emission intensity and light resistance, and is free from peeling of printed matter. Further, the purpose of obtaining a print head having excellent printing characteristics with a thermal head has not yet been achieved.

[0008]

The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention includes (1) a resin (A) having an ethylenically unsaturated group in the molecule, a compound (B) represented by the general formula (1) that absorbs in the near-infrared region of 650 nm to 1000 nm, a general formula An energy ray curable resin composition comprising a light resistance improver (C) represented by (2) and a reactive silicone (D),

[0009]

[Chemical 3]

(In the formula (1), Z1 and Z2 each independently represent an atomic group necessary for forming a nitrogen-containing heterocycle, and R1 and R2 each independently represent an alkyl group which may have a substituent. In the drawing, L1, L2, L3, L4 and L5 each independently represent a methine group which may be substituted, and a plurality of parts thereof may be used to form a ring which may have a substituent. n1 and n2 each independently represent 0 or 1, m1 and m2 each independently represent 0, 1 or 2,
q represents an integer of 0 or more, and X represents an anion or a cation necessary for neutralizing the charge of the molecule. )

[0011]

[Chemical 4]

(In the formula (2), R3 to R10 are each independently an alkyl group which may have a substituent, and the rings A and B may have 1 to 4 substituents.) 2) The energy ray-curable resin composition according to (1), wherein the reactive silicone (D) is a (meth) acryloyl-modified, carbinol-modified, or mercapto-modified reactive silicone, (3) (1) A near-infrared absorbing ink and a fluorescent emitting ink of the energy ray-curable resin composition according to any one of (2) and (2) are provided.

The present invention is a resin (A) having an ethylenically unsaturated group in the molecule, a compound (B) absorbing a near infrared region of 650 nm to 1000 nm, a light resistance improver (C), a reactive silicone (D). ) Is contained in the energy ray-curable resin composition.

The resin (A) having an ethylenically unsaturated group in the molecule used in the present invention is preferably liquid at room temperature, for example, vinyl monomers such as styrene, vinyl acetate, N-vinylpyrrolidone and ( Although (meth) acrylates are mentioned, (meth) acrylates are more preferable. The amount of the resin (A) having an ethylenically unsaturated group in the molecule is preferably 70 with respect to the total weight of the energy ray-curable resin composition in consideration of film performance such as film formability and coating strength. ~ 97% by weight, more preferably 80
Is in the range of up to 95% by weight.

Acrylates are roughly classified into monofunctional monomers having one (meth) acryloyl group, polyfunctional monomers having two or more (meth) acryloyl groups, and oligomers having (meth) acryloyl groups. Polyfunctional monomers and oligomers are preferable from the viewpoints of film-forming ability, curing speed, and film hardness, and the amount used is usually 50 to 100 in the resin (A) having an ethylenically unsaturated group in the molecule.
The monofunctional monomer is used by weight, and is mainly used for the purpose of adjusting the viscosity of the energy ray-curable resin composition and supplementing the solubility of the compound to be added.

Among polyfunctional monomers, examples of trifunctional or higher functional monomers include, for example, trimethylolpropane tri (meth).
Acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxypolypropoxytri (meth) acrylate, tris [(meth ) Acroyloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol polyethoxytetra (meth) acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra ( (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate ) Acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate, and the like.

Examples of the bifunctional monomer include ethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate and bisphenol A.
Alkylene oxide adduct of di (meth) acrylate, tetraethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,12-dodecanediol di (meth) acrylate,
1,14-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,20-eicosanediol di (meth) acrylate, isopentyldiol di (meth) acrylate, 3-ethyl- 1,8-octanediol di (meta)
Examples include acrylate. Examples of the oligomer include epoxy (meth) acrylate, polyethylene (meth) acrylate, polyether (meth) acrylate, silicon (meth) acrylate, polybutadiene (meth) acrylate, polystyrylethyl (meth) acrylate, and polyamide (meth) acrylate. Can be given.

Examples of monofunctional monomers include N, N-
Dimethylaminomethyl (meth) acrylate, N, N-
Dimethylaminoethyl (meth) acrylate, N, N-
Diethylaminoethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxybutyl (meth) acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl (meth) acrylate, dicyclopentanyloxy. Ethyl (meth) acrylate,
Examples include phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, lauryl (meth) acrylate, phenylglycidyl ether (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and acryloylmorpholine. To be
Of these, (meth) acrylate oligomers having a molecular weight of 1000 or more are preferable in consideration of the penetration into the substrate and the solubility with other components. Above all, epoxy (meth) obtained by reacting epoxy resins with (meth) acrylic acid. A compound obtained by reacting an acrylate oligomer or an epoxy resin with (meth) acrylic acid and further reacting a polybasic acid anhydride is more preferable for the use of the present invention.

The epoxy (meth) acrylate oligomer obtained by reacting (meth) acrylic acid with the epoxy resin used in the present invention is (meth) acrylic acid 0.95 to 0.98 per 1 mol equivalent of the epoxy resin. It is obtained by reacting a molar equivalent in the presence or absence of a solvent, for example, at a temperature of 60 to 100 ° C. The compound obtained by reacting the epoxy resin with (meth) acrylic acid and the polybasic acid anhydride is 0.3 to 1 mol equivalent of the polybasic acid anhydride, preferably 1 mol equivalent of the epoxy (meth) acrylate. Is from 0.5
1 molar equivalent, for example in the presence or absence of a solvent, for example 50
It is obtained by reacting at a temperature of -100 ° C until the acid value reaches a desired acid value of 50 mgKOH / g or more. Examples of the epoxy resin include novolac type epoxy resin, bisphenol A type, bisphenol F type, brominated bisphenol A type, amino group-containing, alicyclic or polybutadiene modified glycidyl ether type epoxy resin, and tris (hydroxyphenyl) methane. Examples include base epoxy resins. Examples of polybasic acid anhydrides include maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahidophthalic anhydride, succinic anhydride, itaconic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Examples thereof include dibasic acid anhydrides such as chlorendic anhydride and aromatic polyvalent carboxylic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride. 650 nm to 1000 used in the present invention
The compound (B) which absorbs the near-infrared region of nm will be described. This compound is represented by the general formula (1).

[0020]

[Chemical 5]

In the formula (1), Z1 and Z2 each independently represent an atomic group necessary for forming a nitrogen-containing heterocycle, and R1 and R2 each independently represent an alkyl group which may have a substituent. , L1, L2, L3, L4 and L5 each independently represent a methine group which may be substituted, and a plurality of parts thereof may be used to form a ring which may have a substituent. n1 and n2 each independently represent 0, 1 or 2, m1 and m2 each independently represent 0 or 1, and q
Represents an integer of 0 or more, and X represents an anion or a cation necessary for neutralizing the charge of the molecule.

In the formula (1), Z1 and Z2 each independently represent an atomic group necessary for forming a nitrogen-containing heterocycle. Specifically, as a heterocycle, a pyridine ring, a quinoline ring,
Examples thereof include a thiazole ring, an oxazine ring, an indole ring, an imidazole ring, an indolenine ring, a benzoindolenine ring, a benzothiazole ring, a benzoxazole ring, and a benzoselenazole ring. R1 and R2 each independently represent an alkyl group which may have a substituent, and is represented by the general formula (2)
It may be the same as that shown in. L1, L2, L3, L4 and L5 each independently represent a methine group which may be substituted,
Further, a plurality of parts thereof may be used to form a ring which may have a substituent. As the substituents shown here, an alkyl group having 1 to 8 carbon atoms, a halogen atom such as fluorine, bromine and iodine, an alkoxyl group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a quinolyl group, a dialkylamino group, diphenyl Examples of the ring that may be formed include an amino group and the like, and examples of the ring that may be formed include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a dimethylcyclohexene ring, a thiazole ring, an imidazole ring, an oxazole ring, a pyran ring, and a benzopyran ring. n1 and n2 are independently 0 or 1
And m1 and m2 each independently represent 0 or 1.
q represents an integer of 0 or more, and X represents an anion or a cation necessary for neutralizing the charge of the molecule. In the general formula (1), when the compound does not have a free hydrophilic substituent in the molecule, q needs one anion. When the compound has one free acidic substituent in the molecule, q may be 0. A cation is necessary when the molecule has two or more free acidic substituents. The cation is not particularly limited, and examples thereof include an alkali metal ion (eg, sodium ion, potassium ion, lithium ion), an inorganic or organic ammonium ion (eg, triethylammonium ion, tetraethylammonium ion), and a pyridinium ion. Particularly preferred are alkali metal ions, inorganic or organic ammonium ions.

When the carboxyl group in the molecule is not released, an anion is necessary. The anion may be monovalent or bivalent. Examples of monovalent anions include organic acid monovalent anions and inorganic monovalent anions. As the organic acid monovalent anion, for example, acetate ion, lactate ion, trifluoroacetate ion, propionate ion,
Benzoate, oxalate, succinate, stearate, and other organic carboxylates, methanesulfonate, toluenesulfonate, naphthalenemonosulfonate, chlorobenzenesulfonate, nitrobenzenesulfonate, dodecylbenzene Sulfonate ions, benzenesulfonate ions, ethanesulfonate ions, organic sulfonate ions such as trifluoromethanesulfonate ion, tetraphenylborate ion, organic borate ions such as butyltriphenylborate ion, and the like, preferably Examples include halogenoalkyl sulfonate ions such as trifluoromethane sulfonate ion and toluene sulfonate ion, and alkylaryl sulfonate ions. Examples of the inorganic monovalent anion include halogen ions such as fluorine ion, chlorine ion, bromine ion, and iodine ion, thiocyanate ion, hexafluoroantimonate ion, periodate ion, nitrate ion, tetrafluoroborate ion,
Hexafluorophosphate ion, molybdate ion, tungstate ion, titanate ion, vanadate ion, phosphate ion, borate ion and the like can be mentioned, with preference given to chlorine ion, bromine ion, iodine ion and tetrafluoroborohydride. Examples thereof include acid ion, hexafluorophosphate ion, hexafluoroantimonate ion and the like.

Examples of the divalent anion include naphthalene-1,5-disulfonic acid, R acid, G acid, H acid, benzoyl H acid, p-chlorobenzoyl H acid, p-toluenesulfonyl H acid and carbonyl J acid. , 4,4′-diaminostilbene-2,2′-disulfonic acid, diJ acid, naphthalic acid, naphthalene-2,3-dicarboxylic acid, diphenic acid,
Stilbene-4,4'-dicarboxylic acid, 6-sulfo-2
-Oxy-3-naphthoic acid, anthraquinone-1,8-
Disulfonic acid, 1,6-diaminoanthraquinone-2,
Divalent organic acid ions such as 7-disulfonic acid may be mentioned.

Of these anions, preferred ones include, for example, chlorine ion, bromine ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion, toluene. Examples thereof include sulfonate ion.

650 nm to 1 used in the present invention will be described below.
Specific examples of the compound (B) that absorbs the near infrared region of 000 nm will be listed.

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

The content of the compound (B) which absorbs the near infrared region from 650 nm to 1000 nm is 0.05 to 5%, more preferably 0.1 to 3% in the energy ray-curable resin composition of the present invention. %. 650nm to 1000
The compound (B) that absorbs the near-infrared region of nm may be one that absorbs near-infrared light and emits fluorescence on the longer wavelength side,
It can also be used as a material for fluorescent ink.
The compound represented by the general formula (1) is described in, for example, JP-A-7-32.
It can be obtained by the method described in Japanese Patent No. 9424.

The light resistance improver (C) used in the present invention will be described. The light resistance improver is represented by the following general formula (2).

[0034]

[Chemical 11]

In the formula (2), R3 to R10 are each independently an alkyl group which may have a substituent, and the rings A and B may have 1 to 4 substituents.

The alkyl groups which may have a substituent in R3 to R10 may be the same or different. The alkyl group has preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 8 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. The alkyl moiety may be linear, branched or cyclic. Further, it may have a substituent. Examples of the substituent that can be bonded include halogen atom (eg, F, Cl, Br), hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, isobutoxy group, etc.), alkoxyalkoxy group (eg, methoxyethoxy group, etc.) ), Aryloxy groups (eg, phenoxy group, etc.), acyloxy groups (eg, acetyloxy group, butyryloxy group, hexylyloxy group, benzoyloxy group, etc.), alkyl-substituted amino groups (eg, methylamino group,
Dimethylamino group), cyano group, nitro group, carboxyl group and sulfo group. The carboxyl group and the sulfo group may form a salt such as a metal salt or a quaternary ammonium salt. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

Particularly preferred substituents for R3 to R10 are an unsubstituted alkyl group, a cyano-substituted alkyl group, an alkoxy-substituted alkyl group, an allyl group or a carboxyl-substituted alkyl group, and a sulfo-substituted alkyl group, which are the same. Can also be different. As the unsubstituted alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a ter-butyl group, a pentyl group, a hexyl group, a heptyl group and the like (C1 To C8) alkyl groups and the like. Examples of the cyano-substituted alkyl group include cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2
-Cyanopropyl group, 4-cyanobutyl group, 3-cyanobutyl group, 2-cyanobutyl group, 5-cyanopentyl group, 4-cyanopentyl group, 3-cyanopentyl group, 2
And cyano-substituted (C1-C6) alkyl groups such as cyanopentyl group. Examples of the alkoxy-substituted alkyl group include a methoxyethyl group, an ethoxyethyl group,
3-methoxypropyl group, 3-ethoxypropyl group, 4
Examples thereof include alkoxy-substituted (C1-C6) alkyl groups such as -methoxybutyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, and 5-methoxypentyl group. Examples of the carboxyl-substituted alkyl group include carboxy-substituted groups such as carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-carboxypropyl group, 4-carboxybutyl group, 5-carboxypentyl group (C1-C6). An alkyl group etc. are mentioned. Substituents for rings A and B in formula (1) are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an alkyl-substituted amino group, an amide group, a sulfone. Examples thereof include an amide group, a cyano group, a nitro group and a carboxyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, and the like, and preferably have 1 to 6 carbon atoms. The aryloxy group may have a substituent. Examples of the substituent include a halogen atom (eg, F, Cl, Br), an alkyl group and the like. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the alkyl-substituted amino group include a methylamino group. Examples of the amide group include an acetamide group. Examples of the sulfonamide group include methanesulfonamide. Preferred are those in which ring A and ring B are unsubstituted or substituted with a halogen, a C1-C5 alkyl group, a C1-C5 alkoxy group or a cyano group. The compound represented by the general formula (2) can be obtained, for example, by the method described in JP-B-43-25225.

The light fastness improver (C) used in the present invention may be used alone, but may be used in combination with other types of light fastness improvers for the purpose of improving the light fastness. Examples of compounds that can be used in combination include an aminium compound such as tetrakis {p-di (n-butyl) aminophenyl} phenyleneaminium perchlorate.
Diimonium compounds such as tetrakis {p-di (n-butyl) aminophenyl} phenylenediimonium perchlorate, nickel complex compounds shown in Japanese Patent Application No. 2001-38124, nitroso compounds shown in Japanese Patent Application No. 2001-44452, etc. Can be mentioned.

Next, specific examples of the general formula (2) of the present invention are shown in Table 1.
Shown in. In the table, when the rings A and B are each unsubstituted, it is represented as "4H", and when two halogen atoms are introduced, it is represented as "2Cl". When all of R3 to R10 are butyl groups, it is represented as "4 (n-Bu, n-Bu)", and when one is a butyl group and the rest are cyanopropyl groups, "3 (n-PrCN, n- PrCN) (n-PrC
N, n-Bu) "and the like.

[0040]

【table 1】

The content of these light resistance improvers (C) is 0.005 to 7 in the energy ray-curable resin composition of the present invention.
%, Preferably 0.05 to 5%. Normally 650n
Considering the addition amount of the compound (B) that absorbs the near infrared region from m to 1000 nm, the ratio of (B) :( C) is preferably in the range of 1: 0.1 to 1: 5.

The energy ray-curable resin composition used in the present invention may or may not be cured with an electron beam, but when it is cured with ultraviolet rays, a photopolymerization initiator and, if necessary, photopolymerization are used. Use accelerators. Examples of the photopolymerization initiator include acetophenone, benzophenone, benzoin ether, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, benzyl methyl ketal, thioxanthone, α-acyl oxime ester, acylphosphine oxide, glyoxy ester, and the like. 3-ketocoumarin, 2
-Ethylanthraquinone, camphorquinone, benzyl and the like. As a photopolymerization accelerator, amine compounds such as N-methyldiethanolamine, triethanolammon, diethanolamine, P-dimethylaminobenzoic acid isoamyl ester, N, N-diethyl-P-aminobenzonitrile, and tri-n-butylphosphine. These phosphorus compounds, chlorine compounds such as hexachloroethane, Michler's ketone and the like can be used alone or in combination of two or more. The mixing ratio of these polymerization initiators and accelerators is preferably 1 to 20%, and more preferably 3 to 12%, based on the total weight of the composition.

Reactive Silicone (D) Used in the Present Invention
Is a modified silicone such as amino-modified, epoxy-modified, carboxy-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, (meth) acryloyl-modified. Modified silicones include non-reactive silicones and reactive silicones, but in the use of the present invention, reactive silicones are used in consideration of the durability of effects such as slipperiness, releasability and printability with a thermal head. In the present invention, (meth) acryloyl-modified, carbinol-modified, and mercapto-modified reactive groups are suitable for the present invention.
Further, those having a reactive group on the side chain or one end of the polysiloxane structure are more preferable. The modified silicone (D) can be used alone or in combination of several kinds. It is also possible to use it together with a non-reactive silicone.

The content of the reactive silicone (D) is usually 0.01 in the energy ray-curable resin composition of the present invention.
It is -10%, preferably 0.05-7%.

Further, the energy ray-curable resin composition of the present invention may contain aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, if necessary.
Inorganic powder such as magnesium oxide, aluminum oxide, silicon dioxide, titanium dioxide, talc, clay, kaolin, colloidal silica, metal powder, etc., and inorganic sake fillers such as surface-treated inorganic powder, styrene microballs, polystyrene resin beads, acrylic Resin beads,
Urethane resin beads, polycarbonate resin beads, benzoguanamine-formalin condensate resin powder, benzoguanamine-melamine-formalin condensate resin powder,
Urea-formalin condensate resin powder, aspartic acid ester derivative, zinc stearate, stearic acid amide, epoxy resin powder, polyethylene powder, tetrabromobisphenol A, decabromodiphenyl oxide, tricresyl phosphate, triethyl phosphate, aromatic polyester Organic fillers such as In addition, polymers, antifoaming agents, light stabilizers such as benzotriazole-based UV absorbers, benzophenone-based UV absorbers and hindered amine light stabilizers, antioxidants, polymerization inhibitors, additives such as antistatic agents, types, The amount used can be appropriately selected and used in combination.

The energy ray-curable resin composition of the present invention can be produced, for example, as follows. That is, a resin (A) having an ethylenically unsaturated group in the molecule,
A compound (B) that absorbs in the near-infrared region of 650 nm to 1000 nm, a light resistance improver (C), a reactive silicone (D) and, if necessary, a photoinitiator, a photopolymerization accelerator, and other additives are added. Mix evenly while warming. When a filler is added to the energy ray-curable resin composition, it is dispersed by a known disperser such as a ball mill, a roll mill, a sand mill and a dissolver. At that time, a polycarboxylic acid-based dispersant, a silane coupling agent, a titanate-based coupling agent, a silicone-based dispersant, an organic copolymer-based dispersant, or the like can be used in combination.

The energy ray-curable resin composition thus obtained has a solid content of usually 100% by weight and contains no volatile matter such as an organic solvent but is stable over time.
If necessary, the solvent can be diluted with a solvent during coating.

As a method for forming a cured film of this energy ray-curable resin composition, a bar coater coating, an air knife coating, a gravure coating, an offset printing, a flexographic printing, a screen printing or the like is a known method per se. To apply. The thickness of the cured film is preferably about 0.2 to 100 μm (0.2 to 100 g / m ^{2 in} terms of weight),
It is more preferably about 5 to 50 μm. The energy ray-curable resin composition of the present invention can be used as a near infrared absorbing ink or a fluorescent light emitting ink. Since this ink generally has absorption in the near-infrared region, it can be used for preventing forgery and copying, and for using secret information as a code.

[0049]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited thereto. still,
In the examples, "parts" means "parts by weight".

[0050] Example 1 Dipentaerythritol hexaacrylate 15 parts Bisphenol A epoxy acrylate (Note 1) 30 parts Phenylglycidyl acrylate 15 parts Photopolymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)                                                                   3 parts Photopolymerization initiator (Lucirin TPO; manufactured by BASF) 3 parts 0.5 part of the compound of formula (14) 1.0 part of the compound of formula (35) Methacryloyl modified silicone (Note 2) 2 parts

The above components were mixed and dissolved while heating to 70 ° C. and then cooled to room temperature to obtain an energy ray-curable resin composition of the present invention. Approximately 2 of this was put on a commercially available thermal recording paper (UPP-110S made by Sony) using an RI tester.
Coating to a film thickness of g / m ² (film thickness of about 2 μm), 8
Ultraviolet irradiation device with high pressure mercury lamp of 0 W / cm (GS
The energy ray-curable resin composition of the present invention was cured by irradiating it once with a conveyor speed of 20 m / min (ASE-20; manufactured by Nippon Battery Co., Ltd.).

Example 2 The energy ray-curable resin composition of the present invention was cured in the same manner as in Example 1 except that acryloyl-modified silicone (Note 3) was used in place of the methacryloyl-modified silicone.

Example 3 The energy ray-curable resin composition of the present invention was cured in the same manner as in Example 1 except that mercapto-modified silicone (Note 4) was used in place of the methacryloyl-modified silicone.

Comparative Example 1 An energy ray curable resin composition for comparison was cured in the same manner as in Example 1 except that the methacryl-modified silicone was not used.

Comparative Example 2 In the same manner as in Example 1 except that tetrakis {p-di (n-butyl) aminophenyl} phenylenediimonium perchlorate was used in place of the compound of the formula (35) in Example 3. An energy ray curable resin composition for comparison was cured.

Note 1: Epicoat R-1004 (made by Yuka Shell Epoxy) and a reaction product of acrylic acid (molecular weight about 150)
0) Note 2: BX16-152 (manufactured by Toray Dow Corning Silicone) Note 3: EB350 (manufactured by Daicel UCB) Note 4: X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd.)

The prints thus obtained were evaluated, and the respective results are shown in Tables 2 and 3. Color is developed by a commercially available video graphic printer (UP-860; SO
(Manufactured by NY Co., Ltd.) and evaluated. The evaluation criteria used are as described below.

[0058]

[Table 2]

[0059]

[Table 3]

(1) Stability of Composition The obtained energy ray-curable resin composition was allowed to stand at room temperature for 3 days, and the state of the composition was visually observed to evaluate the stability. ◯: Stable in a state of uniform dissolution or dispersion. Δ: A precipitate is observed, but the redispersibility is good, and a uniform state is obtained by stirring. X: Separation was observed and redispersibility was poor. Or discolor. (2) Curability After irradiation with ultraviolet rays under the conditions of the example, the cured state was examined by touching the cured film with a finger. ◯: It was completely cured. X: It was uncured. (3) Near infrared absorption The near infrared absorption of the cured film of the obtained energy ray curable resin composition was measured. The measurement was performed with a spectrophotometer V-570 (manufactured by JASCO Corporation) at a wavelength of 400 to 1000 nm. ◯: Sufficient absorption in the near infrared was observed. X: No absorption in the near infrared.

(4) Luminous intensity (immediately after curing) The luminous intensity of the cured film of the obtained energy ray-curable resin composition was measured. Measurement is by spectrofluorimeter FP-6600
(Manufactured by JASCO Corporation). First, the optimum excitation light for each cured film was selected from the wavelengths of 630 to 900 nm, the excitation light having a constant bandwidth around the wavelength was irradiated, and the light emission was detected. ◯: There was sufficient emission intensity and there was no problem in detection. X: The emission intensity was insufficient and detection was difficult. (5) Emission intensity (after light resistance test) The cured film of the obtained energy ray-curable resin composition was EY.
E SUPER UVTESTER SUV-W11
(Iwasaki Electric Co., Ltd.), after performing a light resistance test for 4 hours under the conditions of 60 ° C. and 60% RH, the emission intensity was measured by the same method as (4). ◯: There was sufficient emission intensity and there was no problem in detection. X: The emission intensity decreased to 20% or less of the initial level.

(6) Peelability ◯: When 24 mm of Nichiban tape was attached to a cured film of the energy ray-curable resin composition and peeled off, only the tape peeled off without resistance. Δ: There was a slight resistance, but only the tape peeled off easily. X: The cured film of the energy ray-curable resin composition was in close contact with the tape, and the printed matter was peeled off. (7) Abrasion resistance The abrasion resistance of the cured film of the obtained energy ray-curable resin composition was tested using a Gakushin-type friction tester under a load of 500 g and 2000 times with respect to high-quality paper. ◯: There was almost no wear of the film. X: The film was worn. (8) Head-matching The head-matching was evaluated by evaluating the print sound when printed, scratches on the print surface, and dust deposits on the thermal head. ○: Good △: There are some problems but usable level ×; Problems

As is clear from Tables 2 and 3, the energy ray-curable resin composition used in the present invention has good stability and curability, and the cured film has good near-infrared absorption and fluorescence emission. Moreover, the light resistance was good. Further, the printed matter did not peel off at all, and the printing characteristics with the thermal head were good.

[0064]

The energy ray-curable resin composition of the present invention has good stability and curability, and can maintain sufficient near-infrared absorption and fluorescence even when irradiated with ultraviolet rays for producing a cured film. In addition, it has good light resistance. The peelability of the tape is good, the printed matter does not peel off, and the printing characteristics with the thermal head are also good. The energy ray-curable resin composition of the present invention is particularly useful as an energy ray-curable near-infrared absorbing ink and fluorescent light emitting ink.

Continued front page    F-term (reference) 4J027 AE02 AF05 BA07 BA08 BA09                       BA13 BA19 BA20 BA21 BA23                       BA24 BA25 BA26 BA27 BA28                       CA25 CA31 CC06 CD00                 4J039 AE11 BC03 BC33 BC44 BC47                       BC50 BC51 BC53 BC55 BC59                       BC65 BC68 BC72 BC73 BC75                       BC77 BC79 BE33 EA04 EA28                       EA35 EA44

Claims (3)

[Claims] 1. A resin (A) having an ethylenically unsaturated group in the molecule, 650 nm to 100 represented by the general formula (1).
An energy ray-curable resin containing a compound (B) absorbing a near infrared region of 0 nm, a light resistance improver (C) represented by the general formula (2), and a reactive silicone (D). Composition. [Chemical 1] (In the formula (1), Z1 and Z2 each independently represent an atomic group necessary for forming a nitrogen-containing heterocycle, R1 and R2 each independently represent an alkyl group which may have a substituent, and L1 , L2, L3, L4 and L5 each independently represent a methine group which may be substituted, and a plurality of moieties may be used to form a ring which may have a substituent.
n1 and n2 each independently represent 0 or 1, m1 and m2 each independently represent 0, 1 or 2, q represents an integer of 0 or more, and X is necessary for neutralizing the charge of the molecule. Represents an anion or a cation. ) [Chemical 2] (In formula (2), R3 to R10 are each independently an alkyl group which may have a substituent, and rings A and B may have 1 to 4 substituents.) 2. The energy ray-curable resin composition according to claim 1, wherein the reactive silicone (D) is a (meth) acryloyl-modified, carbinol-modified, or mercapto-modified reactive silicone. 3. A near-infrared absorbing ink and a fluorescent emitting ink of the energy ray-curable resin composition according to any one of claims 1 and 2.