JP2009263524A - Resin composition, ink composition, and printed matter printed by using these compositions - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition and an ink composition having fluorescent emission in a predetermined condition, and to provide printed matter printed by using these compositions. <P>SOLUTION: The resin composition comprises a resin comprising a polyfunctional acrylate and a radical photopolymerization initiator. The radical photopolymerization initiator undergoes intramolecular cleavage by light absorption to produce a radical. The resin composition forms an excited-substance by irradiating with a first excitation wavelength band λ1 and emits light by two-photon excitation in which the excited-substance is excited by irradiating with a second excitation wavelength band λ2 after irradiating with the first excitation wavelength band λ1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition, an ink composition, and a printed material thereof that have fluorescence emission under predetermined conditions.

  Anti-counterfeiting technology is applied to valuable goods such as banknotes, passports, securities, stamps, product tags, toll road tickets, and various valuable tickets. Therefore, for such valuables, printed matter is formed using ink containing an inorganic or organic fluorescent material, and it does not normally emit fluorescence under visible light, but emits fluorescence when irradiated with ultraviolet light. False discrimination is performed.

  For example, fluorescent dye A having an absorption peak wavelength for fluorescence emission at 300 to 400 nm and emitting fluorescence in the visible region, and p-quaterphenyl and p-terphenyl emitting fluorescence in the ultraviolet region of 300 to 400 nm , 2,5-diphenyloxazole, 2- (1-naphthyl) -5-phenyloxazole, 2-phenyl-5- (4-biphenyl)-, 1,3,4-oxadiazole A fluorescent ink composition for ink-jet using at least one of these as an essential constituent material is disclosed (for example, see Patent Document 1).

  Further, a fluorescent light-emitting ink containing a phosphor that emits fluorescence when irradiated with ultraviolet light and an ink vehicle, and a printed product of the ink, and having a wavelength in the first visible light region when irradiated with ultraviolet light of the first wavelength. A first phosphor that emits fluorescence and is substantially transparent to visible light, and has a wavelength in a second visible light region different from the wavelength in the first visible light region by irradiation with ultraviolet light of the second wavelength. A fluorescent light-emitting ink and a fluorescent image formed product containing a second fluorescent material that emits fluorescence and is substantially transparent to visible light are disclosed (for example, see Patent Document 2).

Japanese Examined Patent Publication No. 04-062871 (page 1-5) Japanese Patent Laid-Open No. 10-251570 (page 1-11, FIGS. 4, 5)

However, the fluorescent light-emitting inks of Patent Documents 1 and 2 form printed matter using ink containing an inorganic or organic fluorescent material. Inorganic or organic fluorescent materials are generally expensive special fluorescent inks, and as a result, printed matter printed with such inks is also expensive. In recent years, fluorescent light-emitting inks have become easily available, and their effectiveness in fields such as counterfeiting, alteration, and falsification has declined. Furthermore, with the recent popularization and development of printers, counterfeiting by printers tends to increase. there were. In addition, a printed matter using an ink containing an inorganic or organic fluorescent material emits light by an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² used in a general handy type or the like. There is a risk that the area where the fluorescent light-emitting ink is used is easily judged and forged.

The present invention aims to solve such conventional problems, and a resin composition or an ink composition that emits fluorescence under a predetermined condition even when an inorganic or organic fluorescent material is not contained, and the resin The printed matter printed with the composition or the ink composition emits fluorescence even when irradiated with ultraviolet rays by an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² which is used in a general 365 nm handy type or the like. Without irradiating a medium wave ultraviolet ray with a metal halide lamp, a mercury lamp, etc. about 50 mJ / cm ^2, and then irradiating with an ultraviolet ray irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² used in a general handy type etc. In this case, an object of the present invention is to propose a resin composition, an ink composition, and a printed material that can obtain fluorescence.

  The present invention relates to a resin composition comprising a resin comprising a polyfunctional acrylate and a radical photopolymerization initiator, and the radical photopolymerization initiator generates radicals by intramolecular cleavage by light absorption. The resin composition is excited by forming an excitation substance by irradiation of the first excitation wavelength region λ1, and irradiating the second excitation wavelength region λ2 after irradiation of the first excitation wavelength region λ1. It is a resin composition that emits light by two-photon excitation excited by a substance.

  Moreover, the resin comprising the polyfunctional acrylate in the resin composition of the present invention has a functional group density of acryloyl groups of 0.5 mmol / g or more.

  Moreover, the radical photopolymerization initiator in the resin composition of the present invention includes α-hydroxy ketones, a compound represented by the formula (1) and / or α-amino ketones, a compound represented by the formula (2). It consists of

（ただし、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１及びＲ_１２は、それぞれ独立に水素原子及びアルキル基を表す。）

(However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom and an alkyl group. .)

（ただし、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８及びＲ_１９は、それぞれ独立に水素原子及びアルキル基を表す。）

(However, R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represent a hydrogen atom and an alkyl group.)

  Further, the radical photopolymerization initiator of the formula (1) in the present invention is 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl)-represented by the following formula (3). Benzyl] -phenyl} -2-methyl-propan-1-one,

を含んで成る樹脂組成物である。

Is a resin composition comprising

  Further, the radical photopolymerization initiator of the present invention formula (2) is 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one represented by the following formula (4),

を含んで成る樹脂組成物である。

Is a resin composition comprising

  Moreover, the radical photoinitiator in the resin composition of this invention is a resin composition comprised 0.1 to 10weight% with respect to 100 weight% of resin.

  The resin composition of the present invention is a resin composition further comprising a diluent.

  The diluent in the resin composition of the present invention comprises at least one compound selected from the group consisting of a monofunctional acrylate monomer, a polyfunctional acrylate monomer, a monofunctional acrylate oligomer, and a polyfunctional acrylate oligomer.

  In addition, the first excitation wavelength region λ1 and the second excitation wavelength region λ2 in the resin composition of the present invention have a relationship of λ1 <λ2.

  In addition, the first excitation wavelength region λ1 in the resin composition of the present invention is 260 nm or more and less than 330 nm, and the second excitation wavelength region λ2 is 330 nm or more and 410 nm or less.

  In the resin composition of the present invention, the emission peak wavelength of the resin composition that emits light by two-photon excitation is in the range of 580 to 680 nm.

  The present invention is also an ink composition comprising the above-described resin composition.

  The present invention also provides an ink composition comprising the above-described resin composition containing a coloring material.

The present invention also provides an ink composition in which the color material contained in the resin composition contains at least one compound selected from the group consisting of a coloring dye, a coloring pigment, a fluorescent dye, a fluorescent pigment, and a pearl pigment. is there.

  Moreover, this invention is a printed matter formed by printing on a base material with the resin composition or ink composition as described above.

  Since the resin composition and ink composition of the present invention do not contain an expensive inorganic or organic fluorescent material, the resin composition and the ink composition emit fluorescent light under predetermined conditions, so that a printed matter that emits fluorescent light can be produced at low cost. The resin composition of the present invention can be used for paint compositions, coating compositions, ink compositions, and other resin molding compositions, and is particularly effective in fields such as counterfeiting, alteration, and falsification.

The printed matter printed with the resin composition and the ink composition of the present invention is fluorescent even if it is irradiated with ultraviolet rays by an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² that is used in a general handy type or the like. Excitation intermediate (excited state) is formed by irradiating medium-wave ultraviolet light with an ultraviolet irradiation device of about 50 mJ / cm ² with a metal halide lamp, mercury lamp, etc. without emitting light, and a general handy type etc. Fluorescence emission can be obtained when the ultraviolet ray is irradiated with an ultraviolet ray irradiation apparatus having an ultraviolet ray intensity of about 1.5 mW / cm ² . Therefore, since the fluorescent light emission does not occur only by the ultraviolet irradiation having an ultraviolet intensity of about 1.5 mW / cm ² that is used in a general handy type, the resin composition of the present invention is placed in any area of the printed matter. Since it is not easily judged whether it is used, it has an effect of preventing duplication.

In addition, the printed matter printed with the resin composition and the ink composition of the present invention is a general handy type after irradiating a medium wave ultraviolet ray with a metal halide lamp, a mercury lamp or the like with an ultraviolet ray irradiation device of about 50 mJ / cm ^2. Fluorescence is emitted when the ultraviolet ray is irradiated with an ultraviolet ray irradiation apparatus having an ultraviolet ray intensity of about 1.5 mW / cm ² used in the above, so that authenticity can be determined depending on whether or not the fluorescent light is emitted in such a procedure. Therefore, it is excellent in the appraisal element.

Moreover, the printed matter printed with the resin composition and the ink composition of the present invention is obtained by irradiating a medium wave ultraviolet ray with a metal halide lamp, a mercury lamp or the like with an ultraviolet ray irradiating device having a wavelength of about 50 mJ / cm ^2, thereby producing an excitation intermediate ( Excited state) is then formed, and then fluorescence emission can be obtained by irradiating ultraviolet rays with an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² used in a general handy type or the like. Since the excited intermediate (excited state) returns to the ground state by thermal radiation metabolism over time or returns to the ground state by heating (about 85 ° C.), the fluorescence emission intensity is attenuated and finally becomes general. Even if it irradiates with ultraviolet rays with an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² that is used in various handy types, it does not emit fluorescence. In this case, an intermediate (excited state) is formed by irradiating ultraviolet light with a metal halide lamp, a mercury lamp, etc. with an ultraviolet irradiation device of about 50 mJ / cm ² , and a general handy type is again formed. Fluorescence emission can be obtained by irradiating ultraviolet rays with an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² used in the above. Therefore, since a resin composition characterized by these states being reversible can be obtained, it is effective for a certificate using the light emission time.

  The best mode for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the best mode for carrying out the invention described below, and includes various other embodiments within the scope of the technology described in the claims.

(Resin composition)
The present invention is a resin composition comprising a resin comprising a polyfunctional acrylate and a radical photopolymerization initiator. The polyfunctional acrylate is a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer. The radical photopolymerization initiator generates radicals by intramolecular cleavage by light absorption. This resin composition forms an excitation substance by irradiation of the first excitation wavelength band λ1, and the excitation substance is excited by irradiation of the second excitation wavelength band λ2 after irradiation of the first excitation wavelength band λ1. Emits light by two-photon excitation. The relationship between the first excitation wavelength region λ1 and the second excitation wavelength region λ2 is characterized by λ1 <λ2, and the first excitation wavelength region λ1 is 260 nm or more and less than 330 nm, and the second excitation wavelength region The region λ2 is not less than 330 nm and not more than 410 nm, and if it is outside this range, it becomes difficult to emit light.

  The emission peak wavelength of the resin composition that emits light by two-photon excitation is in the range of 580 to 680 nm.

  Moreover, the resin comprising the polyfunctional acrylate monomer and / or the polyfunctional acrylate oligomer needs to have a functional group density of acryloyl group of 0.5 mmol / g or more.

  Resins composed of a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer and having a functional group density of acryloyl group of 0.5 mmol / g or more include, for example, 1,4-butanediol diacrylate, 1,4-butanediol oligo Acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol oligoacrylate, hydroxypivalic acid neopentyl glycol diacrylate, tricyclodecane dimethanol acrylate, trimethylolpropane triacrylate, trimethylolpropane oligoacrylate, pentaerythritol Triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, pentaerythritol oligoacrylate, pentae Sri tall tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, epoxy acrylate, urethane acrylate.

  Furthermore, the functional group density of the acryloyl group of the resin comprising a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer is preferably 3.0 mmol / g or more. In addition, when the functional group density of the functional group density of the acryloyl group is less than 0.5 mmol / g, light emission is difficult.

  The radical photopolymerization initiator is a resin composition comprising α-hydroxy ketones, a compound represented by formula (1) and / or α-amino ketones, a compound represented by formula (2). .

（ただし、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１及びＲ_１２は、それぞれ独立に水素原子又はアルキル基を表す。）

(However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group. .)

（ただし、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８及びＲ_１９は、それぞれ独立に水素原子又はアルキル基を表す。）

(However, R < ₁₃ >, R <_14> , R <_15> , R <_16> , R <_17> , R <_18> and R < ₁₉ > each independently represents a hydrogen atom or an alkyl group.)

In the above formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom. Or it is preferable that it is an alkyl group. Especially, it is more preferable that it is a compound represented by following formula (3). The compound represented by the formula (3) is 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one. As a commercial product, there is Irgacure127 (manufactured by Ciba Specialty Chemicals).

In the above formula (2), it is preferable that R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom or an alkyl group. Especially, it is more preferable that it is a compound represented by following formula (4). The compound represented by the formula (4) is 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one, and Irgacure907 (manufactured by Ciba Specialty Chemicals) is available.

  The radical photopolymerization initiator is preferably a resin composition containing 0.1 to 10% by weight with respect to 100% by weight of the resin containing a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer.

Furthermore, in detail, the resin composition of the present invention is applied on a glass plate, and the ultraviolet intensity used in a general handy type or the like for the resin composition is about 1.5 mW / cm ² . It does not emit fluorescence when irradiated with ultraviolet rays. However, when a medium-wave ultraviolet ray is irradiated with an ultraviolet irradiation device of about 50 mJ / cm ² with a metal halide lamp, a mercury lamp or the like, an excitation intermediate (excitation state) having an excitation peak wavelength of 330 nm to 410 nm is formed. When an ultraviolet ray is irradiated with an ultraviolet ray irradiation device having an ultraviolet ray intensity of about 1.5 mW / cm ² used in a handy type or the like, orange or red fluorescent light having an emission peak wavelength of about 580 to 680 nm is emitted.

As a mechanism, when a UV irradiation device of about 50 mJ / cm ² is irradiated with medium-wave ultraviolet light with a metal halide lamp, mercury lamp, etc. at a position different from the UV absorption band of the initiator, a new UV absorption band is formed. The resin composition is characterized in that it emits fluorescence when irradiated with ultraviolet rays by an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² that is used in a general handy type or the like. ) Is considered to be fluorescence emission.

  FIG. 1 is a schematic diagram of the two-photon excitation fluorescence emission of the present invention. The resin composition of the present invention in the ground state (S0) absorbs light in the first excitation wavelength region λ1, becomes the first excited singlet state (S1), and the first excited triplet state at the intersystem crossing. (T1). Next, the light in the second excitation wavelength band λ2 is absorbed, and the second excitation singlet state (S2) at the upper level is obtained, and the second excitation triplet state (T2) is obtained at the intersystem crossing. The second excited triplet state (T2) emits light and returns to the first excited triplet state (T1). The first excited triplet state (T1) returns to the ground state (S0) due to non-radiative deactivation. The first excited triplet state (T1) is 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1- Norrish type 2 reaction of the hydrogen atom of the methylene group of the bisphenol skeleton and / or the hydrogen atom at the α-position of the alkylthio group of 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one This is considered to be an excited state (intermediate) having a certain lifetime in which abstraction occurs and stabilization is achieved by π electron conjugation with the benzene ring.

  FIG. 2 shows a fluorescence emission spectrum at the excitation light of 370 nm before and after the resin composition of the present invention is applied on a glass plate and the resin composition is irradiated with the first excitation wavelength region λ1, and a fluorescent pigment ( It is the figure which contrasted the fluorescence emission spectrum at the time of excitation light 370nm of the resin composition containing Riedel dehaen Rot CD740). As shown in FIG. 2 (a), the resin composition of the present invention does not detect fluorescence before irradiating the first excitation wavelength region λ1, but after irradiating the first excitation wavelength region λ1, As shown in FIG. 2B, fluorescence was detected at around 580 to 680 nm. Further, it can be seen that the fluorescence emission has emission intensity and / or emission wavelength substantially equal to the fluorescence spectrum of the resin composition containing the fluorescent pigment (Riedel dehaen Rot CD740) as shown in FIG.

  In addition, the resin composition of the present invention can further contain a diluent. This diluent may contain at least one compound selected from the group consisting of monofunctional acrylate monomers, polyfunctional acrylate monomers, monofunctional acrylate oligomers and polyfunctional acrylate oligomers.

(Ink composition)
The resin composition of the present invention is used as an ink composition comprising this resin composition, and specifically can be used as OP varnish, transparent ink, and the like. Furthermore, it can be used as an ink composition comprising a colorant in the resin composition of the present invention. This color material can contain at least one compound selected from the group consisting of colored dyes, colored pigments, fluorescent dyes, fluorescent pigments and pearl pigments.

  A printed matter can be obtained by printing on a substrate using the resin composition of the present invention or the ink composition of the present invention. Moreover, a polymerization accelerator, a polymerization inhibitor, an antifoaming agent, etc. can also be mixed suitably.

(Printed matter A1)
A printed matter A1 printed with the resin composition of the present invention is shown in FIG. As shown to Fig.3 (a), the printed pattern 2 printed with the resin composition is formed in the base material 1. FIG. The resin composition is colorless and transparent under visible light, and the printed pattern 2 printed with the resin composition is in a state that is difficult to confirm with the naked eye under visible light.

An ultraviolet irradiation device 3a having an ultraviolet intensity of about 1.5 mW / cm ² used in a general handy type as shown in FIG. 3B is used for the printed matter A1 shown in FIG. When irradiated with ultraviolet rays, no fluorescence is emitted.

The printed material A1 shown in FIG. 3A is irradiated with ultraviolet rays of about 50 mJ / cm ^{2 by} an ultraviolet irradiation device 3b such as a metal halide lamp or a mercury lamp as shown in FIG. When the ultraviolet ray is irradiated using the ultraviolet ray irradiation device 3a having an ultraviolet ray intensity of about 1.5 mW / cm ² used in the above, the printed pattern 2 fluoresces in orange or red.

(Printed matter A2)
FIG. 4A shows a printed matter A2 printed with an ink composition containing a colored pigment in the resin composition of the present invention. As shown to Fig.4 (a), the printed pattern 2 printed with the ink composition containing the colored pigment in the resin composition is formed in the base material 1. FIG. An ink composition containing a colored pigment in a resin composition is colored under visible light. Therefore, the printed pattern 2 printed with the ink composition containing the colored pigment in the resin composition can be confirmed with the naked eye under visible light.

An ultraviolet irradiation device 3a having an ultraviolet intensity of about 1.5 mW / cm ² used in a general handy type as shown in FIG. 4B is used for the printed matter A2 shown in FIG. When irradiated with ultraviolet rays, no fluorescence is emitted.

The printed matter A2 shown in FIG. 4A is irradiated with ultraviolet rays of about 50 mJ / cm ^{2 by} an ultraviolet irradiation device 3b such as a metal halide lamp or a mercury lamp as shown in FIG. When the ultraviolet ray is irradiated using the ultraviolet ray irradiation device 3a having an ultraviolet ray intensity of about 1.5 mW / cm ² used in the above, the printed pattern 2 fluoresces in red or orange.

  By using the resin composition or ink composition of the present invention, it becomes possible to print on a substrate, and a printed matter having a high anti-counterfeit effect can be obtained. The kind of substrate is not particularly limited, and paper, plastic, cloth or the like can be used.

The printed matter printed on the substrate using the resin composition or ink composition of the present invention preferably has an ink film thickness of about 2 to 150 μm in order to confirm light emission with the naked eye.

  The printing method used in the present invention is not particularly limited, but a method of printing by intaglio printing capable of forming an ink film thickness, gravure printing, flexographic printing, screen printing or the like is preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, the content of this invention is not limited to the range of these Examples.

Example 1
Dipentaerythritol penta (hexa) acrylate (Toa Gosei Aronix M-400) 40 wt%, urethane acrylate (Arakawa Chemical Beamset 505A-6) 60 wt%, photopolymerization initiator 2-hydroxy-1- {4- [4- ( 2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure 127) adjusted to a ratio of 3 wt%, the thickness of the cured film is 100 μm This was applied onto a glass plate and irradiated with ultraviolet rays using a metal halide lamp (500 mW / cm ² ) to obtain a coating composition of the resin composition of Example 1. The functional group density of the resin composition is 4.63 mmol / g. The UV illuminance and light intensity are values measured using a UV integrated illuminometer (UVPF-A1 PD-365 Eye Graphic).

  The functional group density of the acrylate is as shown in FIG. 5, and the functional group density of the resin composition is calculated from the blended ratio. Structural formula of 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl) -phenyl] -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure127) Is shown in FIG. 6 (a), and the UV spectrum is shown in FIG. 6 (c).

  Immediately after the production, when a 365 nm black light was applied to the coated resin composition of Example 1, red fluorescent emission having an emission peak wavelength of 610 nm was confirmed. Further, the fluorescence emission was attenuated with the passage of time, and the fluorescence emission could not be confirmed even when irradiated with 365 nm black light.

That is, FIG. 7 shows the UV spectrum when the resin composition coating of Example 1 was repeatedly irradiated with 200 mj / cm ² ultraviolet rays using a metal halide lamp (500 mW / cm ² ). As shown in FIG. 7, an absorption peak that was not confirmed before ultraviolet irradiation was formed in the vicinity of 380 nm in proportion to the amount of ultraviolet irradiation. The fluorescence emission became stronger in proportion to this absorbance. The irradiation amount of the metal halide is a value measured using an integrating photometer. Furthermore, as shown in FIG. 8, it can be confirmed that the absorption band of the coating composition of the resin composition of Example 1 formed in the vicinity of 380 nm is attenuated with time, and red fluorescence is not emitted with 365 nm black light. It was. Further, the fluorescence emission was attenuated by heating (about 85 ° C.), and no red fluorescence emission could be confirmed even when 365 nm black light was irradiated.

(Example 2)
Ditrimethylolpropane tetraacrylate (Toa Gosei Aronix M-408) 10 wt%, urethane acrylate (Arakawa Chemical Beamset 502H) 90 wt%, photopolymerization initiator 2-hydroxy-1- {4- [4- (2-hydroxy-2) -Methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure 127) adjusted at a rate of 3 wt%, so that the thickness of the cured film becomes 100 μm It was applied on top and irradiated with ultraviolet rays using a metal halide lamp to obtain a coating composition of the resin composition of Example 2. The functional group density of the resin composition is 1.28 mmol / g.

  Immediately after the production, when 365 nm of black light was irradiated to the coating composition of the resin composition of Example 2, red fluorescence emission was slightly visible. Further, the fluorescence emission was attenuated with the passage of time, and no red fluorescence emission could be confirmed even when irradiated with 365 nm black light. After the application of the resin composition of Example 2 was irradiated with ultraviolet rays using a metal halide lamp, red fluorescent emission could be visually recognized under a 365 nm black light.

(Example 3)
Bifunctional urethane acrylate (Arakawa Chemical Beamset 505A-6, functional group density 0.8 mmol / g) 100 wt%, photopolymerization initiator 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) ) -Benzyl] -phenyl} -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure 127), adjusted at a rate of 4 wt%, coated on a glass plate, and irradiated with ultraviolet rays using a metal halide lamp Thus, a coated product of the resin composition of Example 3 was obtained.

  Immediately after the production, when a 365 nm black light was applied to the coated product of the resin composition of Example 3, red fluorescent emission could be visually recognized. Further, the fluorescence emission was attenuated with the passage of time, and no red fluorescence emission could be confirmed even when irradiated with 365 nm black light. After the application of the resin composition of Example 3 was irradiated with ultraviolet rays using a metal halide lamp, red fluorescence emission could be visually recognized under a 365 nm black light.

Example 4
Ditrimethylolpropane tetraacrylate (Toa Gosei Aronix M-408) 40 wt%, urethane acrylate (Arakawa Chemical Beamset 505A-6) 60 wt%, photopolymerization initiator 2-methyl-1 [4-methylthio] phenyl] -2-morpho Linopropan-1-one (Ciba Specialty Chemicals Irgacure907) is adjusted at a rate of 4 wt%, applied onto a glass plate so that the thickness of the cured film is 100 μm, and a metal halide lamp (500 mW / cm ² ) The resin composition of Example 4 was obtained by irradiating with ultraviolet rays. The functional group density of the resin composition is 3.89 mmol / g. The structural formula of 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropane-1-ontiva specialty chemicals (Irgacure907) is shown in FIG. 6 (b), and the UV spectrum is shown in FIG. 6 (c). .

  Immediately after the production, when the 365 nm black light was applied to the coating composition of the resin composition of Example 4, orange fluorescent emission was slightly visible. Further, the fluorescence emission was attenuated with time, and the fluorescence emission could not be confirmed even when irradiated with 365 nm black light. After the application of the resin composition of Example 4 was irradiated with ultraviolet rays using a metal halide lamp, orange fluorescence was visible under a black light of 365 nm.

(Comparative Example 1)
Dipentaerythritol penta (hexa) acrylate (Toa Gosei Aronix M-400) 40 wt%, urethane acrylate (Arakawa Chemical Beamset 505A-6) 60 wt%, photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty)・ Chemicals Irgacure 184) The resin composition of Comparative Example 1 was adjusted at a rate of 3 wt%, applied onto a glass plate so that the thickness of the cured film was 100 μm, and irradiated with ultraviolet rays using a metal halide lamp. A coated product was obtained. The functional group density of the resin composition is 4.63 mmol / g.

  The coated resin composition of Comparative Example 1 could not be confirmed to emit fluorescence under a 365 nm black light immediately after production and even when irradiated with ultraviolet rays using a metal halide lamp.

(Comparative Example 2)
Monofunctional ethoxydiethylene glycol oligoacrylate (Osaka Organic Chemistry Biscoat # 190D Functional group density 3.84 mmol / g) 100 wt%, photopolymerization initiator 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl- Propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure 127) adjusted at a rate of 4 wt%, coated on a glass plate, and irradiated with UV light using a metal halide lamp Irradiated to obtain a coated product of the resin composition of Comparative Example 2.

  The coated resin composition of Comparative Example 2 was not observed to emit fluorescence under a 365 nm black light immediately after fabrication and even when irradiated with ultraviolet rays using a metal halide lamp.

(Comparative Example 3)
Bifunctional urethane acrylate (Arakawa Chemical Beamset 502H Functional group density 0.48 mmol / g) 100 wt%, photopolymerization initiator 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl)- Benzyl) -phenyl) -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure 127) 4) Adjust the ratio, apply it on a glass plate, and irradiate it with ultraviolet rays using a metal halide lamp. A coated product of the resin composition of Comparative Example 3 was obtained.

  The coated resin composition of Comparative Example 3 could not be confirmed to emit fluorescence under a 365 nm black light immediately after fabrication and even when irradiated with ultraviolet rays using a metal halide lamp.

(Comparative Example 4)
Ditrimethylolpropane tetraacrylate (Toa Gosei Aronix M-408) 40wt%, urethane acrylate (Arakawa Chemical Beam Set 505A-6) 60wt%, adjusted on the glass plate so that the thickness of the cured film is 30μm It was applied and irradiated with an electron beam using an electron beam irradiation apparatus (Ushio Electric) to obtain a coated resin composition of Comparative Example 4. The functional group density of the resin composition is 3.89 mmol / g.

  The coated resin composition of Comparative Example 4 could not be confirmed to emit fluorescence under a 365 nm black light immediately after fabrication and even when irradiated with ultraviolet rays using a metal halide lamp.

It is a schematic diagram of the excitation state at the time of irradiating 2nd excitation wavelength range (lambda) 2 after irradiating 1st excitation wavelength range (lambda) 1. The fluorescence spectrum of a fluorescent pigment (Riedel dehaen Rot CD740) when using an excitation wavelength of 370 nm, the fluorescence spectrum before irradiation in the first excitation wavelength region λ1, and the fluorescence spectrum after irradiation in the first excitation wavelength region λ1 were compared. FIG. It is a figure which shows printed matter A1 and its effect | action. It is a figure which shows printed matter A2 and its effect | action. It is a figure which shows the molecular weight of acrylate, the number of functional groups, and a functional group density. It is a figure which shows the structural formula and UV spectrum (0.001 mol / L acetonitrile solution) of a photoinitiator. It is a figure which shows the change of a light quantity when a 200 mj / cm < ² > ultraviolet-ray is irradiated to the coating material of the resin composition of Example 1 using a metal halide lamp (500 mW / cm < ² >). After irradiation with ultraviolet rays of 1800 mJ / cm ² using a metal halide lamp (500mW / cm ²⁾ in the coating of the resin composition of Example 1 is a diagram showing changes with time of the UV spectrum.

Explanation of symbols

A1, A2 Printed matter 1 Base material 2 Print pattern 3a, 3b UV irradiation device

Claims (15)

A resin composition comprising a resin comprising a polyfunctional acrylate and a radical photopolymerization initiator,
The radical photopolymerization initiator generates radicals by intramolecular cleavage by light absorption,
The resin composition forms an excitation substance by irradiation of the first excitation wavelength band λ1, and after irradiation of the first excitation wavelength band λ1, irradiation of the second excitation wavelength band λ2 allows the excitation substance Resin composition which emits light by two-photon excitation excited by. The resin composition according to claim 1, wherein the resin comprising the polyfunctional acrylate has a functional group density of acryloyl groups of 0.5 mmol / g or more. 3. The radical photopolymerization initiator comprises α-hydroxy ketones, a compound represented by the formula (1) and / or α-amino ketones, a compound represented by the formula (2). Resin composition.

(However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group. .)

(However, R < ₁₃ >, R <_14> , R <_15> , R <_16> , R <_17> , R <_18> and R < ₁₉ > each independently represents a hydrogen atom or an alkyl group.) The radical photopolymerization initiator of the formula (1) is 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl represented by the following formula (3). } -2-Methyl-propan-1-one,

The resin composition according to claim 1, 2 or 3. The radical photopolymerization initiator of the formula (2) is 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one represented by the following formula (4):

The resin composition according to claim 1, 2 or 3. The resin composition according to claim 1, 2, 3, 4 or 5, wherein the radical photopolymerization initiator is contained in an amount of 0.1 to 10% by weight with respect to 100% by weight of the resin. The resin composition according to claim 1, 2, 3, 4, 5, or 6, further comprising a diluent. 8. The resin composition according to claim 7, wherein the diluent comprises at least one compound selected from the group consisting of a monofunctional acrylate monomer, a polyfunctional acrylate monomer, a monofunctional acrylate oligomer, and a polyfunctional acrylate oligomer. The resin composition according to claim 1, wherein the first excitation wavelength region λ1 and the second excitation wavelength region λ2 satisfy λ1 <λ2. The resin composition according to claim 9, wherein the first excitation wavelength region λ1 is 260 nm or more and less than 330 nm, and the second excitation wavelength region λ2 is 330 nm or more and 410 nm or less. The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein an emission peak wavelength of the resin composition emitting light by the two-photon excitation is in a range of 580 to 690 nm. . An ink composition comprising the resin composition according to any one of claims 1 to 11. An ink composition comprising a colorant in the resin composition according to any one of claims 1 to 11. The ink composition according to claim 13, wherein the coloring material comprises at least one compound selected from the group consisting of a coloring dye, a coloring pigment, a fluorescent dye, a fluorescent pigment, and a pearl pigment. A printed matter obtained by printing on a substrate with the resin composition according to any one of claims 1 to 11 or the ink composition according to any one of claims 12 to 14.

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