JP6563693B2 - Near-infrared absorption pattern printing sheet and ink composition used therefor - Google Patents

Description

  The present invention relates to a near-infrared absorption pattern printing sheet capable of providing position information by using an infrared camera or the like and an ink composition used therefor.

  In recent years, there has been an increasing need to convert handwritten characters, pictures, symbols, and the like into electronic data that can be handled by an information processing apparatus. In particular, there is an increasing demand for a method for inputting handwritten information to a computer or the like in real time.

  Patent Document 1 discloses an optical film that can be read by an optical pen having an infrared camera, and an optical film obtained by pattern-printing a layer that absorbs near infrared rays or ultraviolet rays on a substrate that diffuses near infrared rays or ultraviolet rays. Is described. The ink used for pattern printing of the near-infrared or ultraviolet absorbing layer described in Patent Document 1 has a disadvantage that the viscosity is low and the contact angle of the dots is small, so that the contrast ratio when viewed with an infrared camera is small. . Moreover, since the near-infrared or ultraviolet absorption layer described in Patent Document 1 is poor in solvent resistance, there is a problem that it is difficult to provide a layer such as an acrylic resin for protection on the absorption layer.

JP 2008-209598 A

  Accordingly, it is an object of the present invention to provide a technique relating to near-infrared absorption pattern printing that has a high contrast ratio when viewed with an infrared camera and is excellent in solvent resistance of dots.

  As a result of intensive studies to solve the above problems, the present inventors have found that a near-infrared absorbing pattern printing sheet on which a layer that absorbs near-infrared rays is pattern-printed, a near-infrared absorbing agent and a specific type of urethane acrylate By pattern printing a layer that absorbs near infrared rays using an ink composition combined at a specific mass ratio, it has a high contrast ratio when viewed with an infrared camera, and is also excellent in solvent resistance of dots. In addition, the present inventors have found that a near-infrared absorption pattern printing sheet can be obtained and completed the present invention.

That is, the present invention is a near-infrared absorption pattern printing sheet in which a layer that absorbs near-infrared rays is pattern-printed on a substrate,
The following components (a) to (c)
(A) Near-infrared absorber (b) A urethane acrylate having a molecular weight of 1000 to 3000, 9 or 10 acryloyl groups, and (c) a urethane acrylate having a molecular weight of 30000 to 70000 and 2 or 3 acryloyl groups. A near-infrared absorption pattern comprising a layer that absorbs near-infrared rays using an ink composition containing and having a mass ratio of component (b) to component (c) of 50 to 90:10 to 50 It is a printed sheet.

The present invention also includes the following components (a) to (c):
(A) Near-infrared absorber (b) A urethane acrylate having a molecular weight of 1000 to 3000, 9 or 10 acryloyl groups, and (c) a urethane acrylate having a molecular weight of 30000 to 70000 and 2 or 3 acryloyl groups. An ink composition comprising: a mass ratio of component (b) to component (c) of 50 to 90:10 to 50.

  Since the near-infrared absorption pattern printing sheet of the present invention can increase the height of the near-infrared absorption pattern (dots) pattern-printed on the substrate, the contrast ratio when viewed with an infrared camera is higher than before. It will be a thing.

  Moreover, since this near-infrared absorption pattern is excellent in solvent resistance, a layer such as an acrylic resin for protection can be easily provided on the near-infrared absorption pattern. Further, it is not necessary to provide a near-infrared reflective layer, which has been conventionally required, on the near-infrared absorption pattern printing sheet.

  Therefore, the near-infrared absorption pattern printing sheet of this invention can be utilized suitably for the various input devices using an infrared camera.

FIG. 1 is a cross-sectional view of one embodiment of the near-infrared absorption pattern printing sheet of the present invention.

  In this specification, near-infrared light refers to light having a wavelength in the range of 750 to 2000 nm. Moreover, molecular weight says what is measured by gel permeation chromatography. Furthermore, the viscosity refers to that measured by an E-type viscometer at 25 ° C. Furthermore, a contact angle means the contact angle 10 seconds after dripping measured with a contact angle meter. Furthermore, the contrast ratio refers to the difference in luminance between the pattern printing part (black) and the non-printing part (white) when confirmed with an infrared camera.

The near-infrared absorption pattern printing sheet of the present invention (hereinafter referred to as “the present invention sheet”) is a substrate on which a layer that absorbs near-infrared radiation is pattern-printed,
The following components (a) to (c)
(A) Near-infrared absorber (b) A urethane acrylate having a molecular weight of 1000 to 3000, 9 or 10 acryloyl groups, and (c) a urethane acrylate having a molecular weight of 30000 to 70000 and 2 or 3 acryloyl groups. The layer which absorbs near infrared rays using the ink composition which is contained and the mass ratio of a component (b) and a component (c) is 50-90: 10-50 is pattern-printed.

  Although the base material which comprises this invention sheet | seat is not specifically limited, For example, what was formed with what is called a transparent material which permeate | transmits visible light is preferable. Examples of such materials include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); triacetyl cellulose (TAC); acrylic resins such as methyl methacrylate copolymers; styrene resins; polysulfone resins; Examples thereof include polyethersulfone resins; polycarbonate resins; vinyl chloride resins; and polymethacrylimide resins. These resins may be colored or colorless. Also, the shape of these resins is not particularly limited, but a sheet is preferable.

  If the near-infrared absorber of the component (a) of the ink composition (hereinafter referred to as “the present invention composition”) that forms the near-infrared absorbing layer constituting the sheet of the present invention is one that absorbs near-infrared radiation. It does not specifically limit, For example, a diimonium salt compound, a phthalocyanine compound, a cyanine compound, an anthraquinone compound, a dithiol compound etc. are mentioned. Among these near-infrared absorbers, diimonium salt compounds are preferable, and in particular, a diimonium salt compound represented by the following general formula (1) is preferable because it is excellent in UV curing resistance and ability to absorb near-infrared rays.

In the general formula (1), the organic groups represented by R _{1 to} R ₈ may be the same or different, and preferred organic groups include, for example, a straight chain optionally substituted with a halogen atom. Or a branched _C1-10 alkyl group, a cyclohexyl alkyl group, a phenylalkyl group etc. are mentioned.

Among the organic groups, examples of the C _1-10 alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert group. -Butyl group, n-amyl group, iso-amyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-dimethylpropyl group, 1,1-dimethylpropyl group, n- A pentyl group, a neopentyl group, an n-hexyl group and the like can be mentioned.

Among the above organic groups, examples of the C _1-10 alkyl group substituted with a halogen atom include a 2-halogenoethyl group, a 2,2-dihalogenoethyl group, and a 2,2,2-trihalogenoethyl group. 3-halogenopropyl group, 3,3-dihalogenopropyl group, 3,3,3-trihalogenopropyl group, 4-halogenobutyl group, 4,4-dihalogenobutyl group, 4,4,4-trihalogeno Examples thereof include halogenated alkyl groups such as butyl group, 5-halogenopentyl group, 5,5-dihalogenopentyl group, and 5,5,5-trifluoropentyl group. More specifically, monofluoroalkyl groups such as 2-fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group, 5-fluoropentyl group and the like can be mentioned.

  Furthermore, among the organic groups, a cyclohexylalkyl group can be represented by the following general formula (2).

In the general formula (2), A represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.

  Specific examples of the cyclohexylalkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a cyclohexylbutyl group, a methyl 2-ethylcyclohexylmethyl group, a 3-methylcyclohexylmethyl group, a 4-methylcyclohexylmethyl group, a 4-methylcyclohexylmethyl group, A methylcyclohexylethyl group, a 4-methylcyclohexylpropyl group, a 4-methylcyclohexylbutyl group, a 4-fluorocyclohexylmethyl group, and the like can be given. Among these, a cyclohexylmethyl group is preferable.

  Furthermore, among the organic groups, a phenylalkyl group can be represented by the following general formula (3).

In the general formula (3), B represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and R ₁₀ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.

  Specific examples of the phenylalkyl group include methylbenzyl group, ethylbenzyl group, propylbenzyl group, butylbenzyl group and the like.

  Among these organic groups, a cyclohexylalkyl group represented by the general formula (2) is particularly preferable, and a cyclohexylmethyl group is particularly preferable. By using these organic groups, the hydrophobicity increases, so that the durability becomes excellent.

Moreover, X < ^- > in the diimonium salt compound represented by General formula (1) is an anion required in order to neutralize the electric charge of a diimonium compound cation, For example, an inorganic anion, an organic acid anion, etc. can be used. Specific examples of anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, perchlorate ion, periodate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion bis. (Trifluoromethanesulfonyl) imidate ion, bis (fluorosulfonyl) imidate ion, etc. are mentioned.

  Among these anions, hexafluorophosphate ion, hexafluoroantimonate ion, bis (trifluoromethanesulfonyl) imidate ion, and bis (fluorosulfonyl) imidate ion are more preferred, and hexafluorophosphate ion or bis (trifluoro) Lomethanesulfonyl) imido ion is preferred.

  As these diimonium salt compounds, for example, those synthesized based on the description in JP 2010-249964 A, commercially available ones, and the like can be used. Examples of commercially available products include CIR-FS163M (manufactured by Nippon Carlit Co., Ltd., terminal: cyclohexylmethyl group), CIR-265 (manufactured by Nippon Carlit Co., Ltd., terminal: ethylbenzyl group) and the like.

  The urethane acrylate having a molecular weight of component (b) of the present invention composition of 1000 to 3000 and having 9 or 10 acryloyl groups is not particularly limited, and examples thereof include alcohols, polyols, and / or hydroxyl group-containing acrylates. A compound obtained by reacting a hydroxyl group-containing compound with an isocyanate or, if necessary, esterifying a polyurethane compound obtained by these reactions with (meth) acrylic acid, or a commercially available product can be used. . Examples of commercially available products include Art Resin H-135 (manufactured by Negami Kogyo Co., Ltd., having a molecular weight of about 1500 urethane acrylate and 10 acryloyl groups), Art Resin UN-901T (manufactured by Negami Kogyo Co., Ltd., molecular weight 4000 urethane acrylate). , Having 10 acryloyl groups), purple light UV-1700B (manufactured by Nippon Synthetic Chemical Co., Ltd., molecular weight of about 2000, having 9 acryloyl groups), purple light UV-7620EA (manufactured by Nippon Synthetic Chemical Co., Ltd., molecular weight of about 4100, having acryloyl group) 9).

  The urethane acrylate having a molecular weight of component (c) of the present invention composition of 30000 to 70000 and having 2 or 3 acryloyl groups is not particularly limited, and examples thereof include alcohols, polyols, and / or hydroxyl group-containing acrylates. A compound obtained by reacting a hydroxyl group-containing compound with an isocyanate or, if necessary, esterifying a polyurethane compound obtained by these reactions with (meth) acrylic acid, or a commercially available product can be used. . Examples of commercially available products include Art Resin UN-5500MI (manufactured by Negami Kogyo Co., Ltd., urethane acrylate having a molecular weight of about 50000, having two acryloyl groups), and purple light UV-3700B (manufactured by Nippon Synthetic Chemical Co., Ltd., molecular weight of about 38000, acryloyl). Having two groups).

  In the composition of the present invention, as in components (b) and (c), the viscosity of the composition (solid content concentration of 30% by mass) will be described later by using a urethane acrylate having a specific molecular weight. Thus, it is possible to obtain a viscosity suitable for pattern printing, and it is possible to make the pattern-printed infrared absorbing layer excellent in solvent resistance. Further, by changing the number of acryloyl groups, the viscosity of the composition does not change, but the solvent resistance of the infrared ray absorbing layer printed by pattern printing can be further improved.

  Moreover, in this invention composition, mass ratio of a component (b) and a component (c) is 50-90: 10-50, Preferably it is 60-70: 40-30, More preferably, it is 60:40 or 70: 30. By doing so, it becomes a pattern printed matter with good solvent resistance without impairing curability.

  Furthermore, an additive such as a solvent, a photopolymerization initiator, an ultraviolet absorber, and a rheology control agent may be added to the composition of the present invention as long as the effects of the present invention are not impaired.

  Examples of the solvent include general solvents such as cyclohexanone, cyclopentanone, toluene, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, methyl acetate, ethyl acetate, butyl acetate, and the like. A mixture etc. are mentioned.

  Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, benzophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-Dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphos Fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, etc. Is mentioned.

  Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl). Phenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine Hydroxyphenyl triazines such as 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) Benzotriazoles such as phenol and 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, benzophenones such as 2,2 ′, 4,4′-tetrahydroxybenzophenone, phenyl salicylate, p-tert-butylphenyl salicylate, etc. These may be used alone or in combination of two or more.

  Examples of the rheology control agent include modified urea, urea-modified polyamide, fatty acid amide, polyurethane, polymer urea derivative, silica, calcium carbonate, smectite and the like.

As a preferable aspect of this invention composition, the following are mentioned, for example.
Near-infrared absorber 5-8 mass%
10 to 15% by mass of urethane acrylate having a molecular weight of 1000 to 3000 and having 9 or 10 acryloyl groups
5-10% by mass of urethane acrylate having a molecular weight of 30000-70000 and having 2 or 3 acryloyl groups
Solvent 60-70 mass%
Photopolymerization initiator 1-3% by mass
UV absorber 1-3% by mass
Rheology control agent 0.1-1% by mass
Mass ratio of component (b) to component (c) 60-70: 40-30

  The composition of the present invention described above can be prepared basically by mixing each component, and specifically, it can be prepared as follows. First, 5 to 8 parts by weight of the component (a) is added to 60 to 70 parts by weight of the solvent and mixed with stirring. Next, 10 to 15 parts by weight of the component (b), 5 to 10 parts by weight of the component (c), 1 to 3 parts by weight of the photopolymerization initiator, and 1 to 3 parts by weight of the ultraviolet absorber as necessary. The rheology control agent can be prepared by adding 0.1 to 1 part by weight and dissolving.

  Further, the solid content concentration of the composition of the present invention is not particularly limited as long as it is a concentration suitable for pattern printing, and the viscosity thereof is not particularly limited, but is, for example, 100 to 300 mPa · s, preferably 200 to 300 mPa · s. s.

  Furthermore, the contact angle of the composition of the present invention is not particularly limited, but is, for example, 30 to 45 °, preferably 40 to 45 ° after 10 seconds of dropping on a flat substrate.

  A method for pattern printing a layer that absorbs near infrared rays using the composition of the present invention thus prepared is not particularly limited. For example, printing methods such as flexographic printing, gravure printing, stencil printing, and ink jet printing may be used. Can be mentioned. Among these printing methods, high-speed printing is possible, suitable for mass production, and gravure printing with high accuracy is preferable. Since the viscosity of the ink composition of the present invention is optimal for gravure printing, it can be printed at high speed and with high accuracy.

  The pattern to be printed is not particularly limited, but is an irregularly arranged dot pattern.

  After the pattern printing, the sheet of the present invention is obtained by passing the solvent through a drying oven for several minutes to volatilize the solvent and then curing it with ultraviolet rays.

  In addition, you may provide an ultraviolet absorption layer further in the back surface of the layer (pattern) which absorbs the near infrared rays of this invention sheet. Thereby, it can prevent that a near-infrared absorption layer deteriorates with an ultraviolet-ray. The ultraviolet absorbing layer can be formed of a (meth) acrylate monomer and / or oligomer resin containing an ultraviolet absorber. The ultraviolet absorber is a dye that absorbs a wavelength of 250 to 400 nm, and specifically includes a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a hydroxyphenyltriazine ultraviolet absorber, and a cyano. An acrylate type ultraviolet absorber, a nickel complex salt type ultraviolet absorber, etc. are mentioned. By providing this ultraviolet absorbing layer, deterioration of the near infrared absorbing layer and internal components due to ultraviolet rays can be prevented, and durability can be improved.

  Moreover, you may provide a protective layer further on the surface of the layer (pattern) which absorbs the near infrared rays of this invention sheet | seat. The layer that absorbs near-infrared rays hardly dissolves in solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene, isopropanol, etc., so that the solvent resistance is high, but by providing this protective layer, the solvent resistance is improved. Further improvement. The protective layer can be formed of a (meth) acrylate monomer and / or an oligomer resin.

  Furthermore, you may provide a hard-coat layer further under the base material of this invention sheet | seat. This prevents damage. The hard coat layer can be formed of a (meth) acrylate monomer and / or an oligomer resin.

  Furthermore, a reflective layer that reflects near infrared rays may be provided on the surface of the layer (pattern) that absorbs near infrared rays of the sheet of the present invention, but in the sheet of the present invention, the thickness of the layer that absorbs near infrared rays is set. The reflection layer is not essential because it is sufficient.

  The ultraviolet absorbing layer, protective layer, hard coat layer, reflective layer and the like described above can be formed by appropriately performing printing, baking, curing and the like according to a known method.

  As a preferable aspect of this invention sheet, it is the structure of a hard-coat layer, a base material, the layer which absorbs a near infrared ray, and a protective layer in order from the bottom, for example.

  In the sheet of the present invention obtained as described above, the pattern-printed near-infrared absorbing layer can be made thicker than the conventional one. For example, the diameter is 130 to 160 μm and the height is 1.0 to 1. .3 μm.

  Therefore, this invention sheet can provide the positional information in the said sheet | seat by recognizing the pattern on a near-infrared absorption pattern printing sheet with the terminal which can be irradiated and detected near-infrared rays, such as an infrared camera. In particular, since the sheet of the present invention has a high contrast ratio, it can be easily recognized by an infrared camera.

  The present invention sheet described above can be provided on the surface of a tablet module, for example. Thereby, position information can be confirmed with an infrared camera from the top of the tablet screen.

  EXAMPLES Hereinafter, although an Example of this invention is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.

Example 1
Ink composition:
20 parts by mass of diimonium dye having a UV curing resistance (manufactured by Nippon Carlit Co., Ltd., CIR-FS163M: terminal cyclohexylmethyl group) was added to methyl isobutyl ketone and mixed with stirring. In this solution, 40 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups), urethane acrylate having a molecular weight of about 50,000 (manufactured by Negami Kogyo Co., Ltd., Art Resin UN-5500MI, solid content 50) %, Solvent: methyl isobutyl ketone, 2 acryloyl groups) 60 parts by mass, photopolymerization initiator (BSF Japan, Irgacure 127) 3 parts, rheology control agent (BIC Chemie, BYK-405) A near-infrared absorbing ink composition having a solid content concentration of 30% was obtained by dissolution (solid content ratio 57:43).

  It was 230 mPa * s as a result of measuring the viscosity in 25 degreeC of the ink composition obtained above using the E-type viscosity meter (made by Tokyo Keiki Co., Ltd.). In addition, the ink composition obtained above was dropped onto a transparent PET (polyethylene terephthalate) substrate, and the contact angle was measured using a contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.). Had a high contact angle.

Example 2
Near-infrared absorption pattern printing sheet:
On the transparent substrate made of a transparent PET substrate having a thickness of 100 μm, the ink composition obtained in Example 1 was printed by gravure printing to form a circular irregular dot-like pattern having a diameter of 130 μm in plan view. Thereafter, the substrate was passed through a drying oven at 100 ° C. for 1 to 2 minutes to volatilize the solvent, and then UV cured at 240 W / cm and an output of 100% to obtain a near infrared absorption pattern printing sheet (dot diameter 130 μm). . A schematic diagram of this near-infrared absorption pattern printing sheet is shown in FIG.

Test example 1
Evaluation of physical properties of near-infrared absorption pattern printing sheet:
(1) Solvent resistance The pattern printed surface portion was wiped 10 times with an industrial wiper impregnated with methyl ethyl ketone (Nippon Paper Crecia Co., Ltd., Kimwipe), and the solvent resistance was evaluated according to the following evaluation criteria.

<Evaluation criteria>
(Evaluation) (Content)
○: Appearance change and no adhesion to wiper △: Appearance change is not seen, but a little adhesion to wiper is observed ×: Appearance change is seen and adhesion to wiper is also observed a lot

  As a result of the above evaluation, there was no change in appearance and no adhesion to the wiper, and it had high solvent resistance (determination ○).

(2) Dot Height When the height of the dot of the near infrared absorption pattern was measured with a stylus type surface shape measuring device, it was found to be 1.1 μm.

(3) Contrast ratio 100 parts by weight of an acrylate oligomer (manufactured by Negami Kogyo, Art Resin UN-901T) and 3 parts by weight of a photopolymerization initiator (manufactured by BASF Japan, Irgacure 127) are mixed in a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone. Thus, a UV curable ink having a solid content concentration of 40% was obtained.

  After the gravure printing of the UV curable ink obtained above on the surface pattern-printed in the same manner as in Example 2, after passing through a drying oven at 100 ° C. for 1 to 2 minutes, the solvent was volatilized, UV curing was performed at 240 W / cm at an output of 100% to obtain an optical film having a near infrared absorption pattern covered with a protective layer.

  This optical film was irradiated with near infrared rays from an infrared camera, the presence or absence of the reflected light was detected, and the contrast ratio of the observed image was visually evaluated according to the following evaluation criteria.

<Evaluation criteria>
(Evaluation) (Content)
○: The pattern printing part (black) is darker and clearer than the non-printing part (white). △: The pattern printing part (black) is slightly thinner than the non-printing part (white). ×: The pattern printing part (black) is thinner than the non-printing part (white) and is not clearly recognized

  As a result of the evaluation, this optical film had a high contrast ratio (determination ○).

Example 3
Ink composition:
In Example 1, 40 to 55 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups) and having a molecular weight of about 50000 (manufactured by Negami Kogyo, art resin) An ink composition was obtained in the same manner as Example 1 except that UN-5500MI, solid content 50%, solvent: methyl isobutyl ketone, 2 acryloyl groups 2) was changed from 60 parts by mass to 30 parts by mass. 79:21). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 160 mPa · s, and the contact angle was 34 °.

Example 4
Near-infrared absorption pattern printing sheet:
In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained in Example 3 was used (dot diameter 150 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was ◯, the dot height was 1.1 μm, and the contrast ratio was ◯.

Example 5
Ink composition:
In Example 1, urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups) is used in an amount of 40 to 62 parts by mass and urethane acrylate having a molecular weight of about 50,000 (manufactured by Negami Kogyo Co., Ltd., Art Resin). An ink composition was obtained in the same manner as in Example 1 except that UN-5500MI, solid content 50%, solvent: methyl isobutyl ketone, 2 acryloyl groups) was changed from 60 parts by mass to 16 parts by mass (solid content ratio). 89:11). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 130 mPa · s, and the contact angle was 32 °.

Example 6
Near-infrared absorption pattern printing sheet:
In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained in Example 5 was used (dot diameter: 160 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was ◯, the dot height was 1.0 μm, and the contrast ratio was ◯.

Example 7
Ink composition:
In Example 1, 40 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups) and urethane acrylate having a molecular weight of 4000 (Art Resin UN-901T, manufactured by Negami Kogyo Co., Ltd., acryloyl) An ink composition was obtained in the same manner as in Example 1 except that the amount was changed to 50 parts by mass (9 bases, solid content 80%) (solid content ratio 57:43). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 240 mPa · s, and the contact angle was 42 °.

Example 8
Near-infrared absorption pattern printing sheet:
In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained in Example 7 was used (dot diameter: 130 μm). Further, when the solvent resistance, the dot height and the contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was ◯, the dot height was 1.2 μm, and the contrast ratio was ◯.

Example 9
Ink composition:
In Example 1, except that the diimonium dye (Nippon Carlit Co., Ltd., CIR-FS163M, terminal: cyclohexylmethyl group) is replaced with a diimonium dye (Nippon Carlit Co., Ltd., CIR-265, terminal: ethylbenzyl group). In the same manner as above, an ink composition was obtained (solid content ratio 57:43). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 230 mPa · s, and the contact angle was 40 °.

Example 10
Near-infrared absorption pattern printing sheet:
In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained in Example 9 was used (dot diameter 130 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was ◯, the dot height was 1.1 μm, and the contrast ratio was ◯.

Comparative Example 1
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, 40 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups) is replaced by 70 parts by mass, and urethane acrylate having a molecular weight of about 50000 (manufactured by Negami Kogyo, Art Resin UN-5500MI, solid content 50%, solvent: methyl isobutyl ketone, 2 acryloyl groups) An ink composition was obtained in the same manner as in Example 1 except that 60 parts by mass was not used (solid content ratio was 100: 0). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 40 mPa · s, and the contact angle was 16 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained above was used (dot diameter 220 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was ◯, the dot height was 0.3 μm, and the contrast ratio was x.

Comparative Example 2
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, 60 parts by mass of urethane acrylate having a molecular weight of about 50000 (manufactured by Negami Kogyo Co., Ltd., Art Resin UN-5500MI, solid content 50%, solvent: methyl isobutyl ketone, 2 acryloyl groups) was replaced by 140 parts by mass, An ink composition was obtained in the same manner as in Example 1 except that 40 parts by mass of 1500 urethane acrylate (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups) was used (solid content ratio was 0: 100). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 400 mPa · s, and the contact angle was 50 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained above was used (dot diameter: 100 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was x, the dot height was 3.0 μm, and the contrast ratio was not measurable. . This result is because the dots are dissolved.

Comparative Example 3
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, except that the urethane acrylate having a molecular weight of about 50,000 (manufactured by Negami Kogyo, Art Resin UN-5500MI, solid content 50%, solvent: methyl isobutyl ketone, two acryloyl groups) is changed from 60 parts by mass to 120 parts by mass. An ink composition was obtained in the same manner as in Example 1 (solid content ratio 40:60). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 310 mPa · s, and the contact angle was 48 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as Example 2 except that the ink composition obtained above was used (dot diameter 110 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was Δ, the dot height was 2.0 μm, and the contrast ratio was Δ. . The contrast ratio was lowered because the dots were slightly dissolved.

Comparative Example 4
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, 40 to 65 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups) and having a molecular weight of about 50000 (made by Negami Kogyo, Art Resin) An ink composition was obtained in the same manner as Example 1 except that UN-5500MI, solid content 50%, solvent: methyl isobutyl ketone, 2 acryloyl groups 2) was changed from 60 parts by mass to 10 parts by mass (solid content ratio). 93: 7). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 80 mPa · s, and the contact angle was 25 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained above was used (dot diameter 210 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was ○, the dot height was 0.5 μm, and the contrast ratio was x. .

Comparative Example 5
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, 60 parts by mass of urethane acrylate having a molecular weight of about 50,000 (manufactured by Negami Kogyo Co., Ltd., Art Resin UN-5500MI, solid content: 50%, solvent: methyl isobutyl ketone, two acryloyl groups) are mixed with urethane acrylate having a molecular weight of 15000 (Art Resin). UN-9200, manufactured by Negami Kogyo Co., Ltd., 2 acryloyl groups) An ink composition was obtained in the same manner as in Example 1 except that the amount was changed to 30 parts by mass (solid content ratio was 57:43). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 70 mPa · s, and the contact angle was 24 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained above was used (dot diameter 210 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was ○, the dot height was 0.4 μm, and the contrast ratio was x. .

Comparative Example 6
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, 40 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Kogyo Co., Ltd., Art Resin H-135, 10 acryloyl groups) and urethane acrylate having a molecular weight of 4900 (Art Resin UN-904, manufactured by Negami Kogyo Co., Ltd., acryloyl) An ink composition was obtained in the same manner as in Example 1 except that the amount was changed to 40 parts) (solid content ratio 57:43). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 250 mPa · s, and the contact angle was 44 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained above was used (dot diameter 120 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was Δ, the dot height was 1.3 μm, and the contrast ratio was Δ. .

Comparative Example 7
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, 40 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Industrial Co., Ltd., Art Resin H-135, 10 acryloyl groups) and urethane acrylate having a molecular weight of 1500 (Art Resin UN-906S, manufactured by Negami Kogyo Co., Ltd., acryloyl) 6 groups) An ink composition was obtained in the same manner as in Example 1 except that the amount was changed to 70 parts (solid content ratio 57:43). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 55 mPa · s, and the contact angle was 40 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as in Example 2 except that the ink composition obtained above was used (dot diameter: 250 μm). Further, when solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was x, the dot height was 0.2 μm, and the contrast ratio was Δ. .

Comparative Example 8
Ink composition and near-infrared absorption pattern printing sheet:
In Example 1, 40 parts by mass of urethane acrylate having a molecular weight of about 1500 (manufactured by Negami Industrial Co., Ltd., Art Resin H-135, 10 acryloyl groups) and urethane acrylate having a molecular weight of 1500 (Art Resin UN-906S, manufactured by Negami Kogyo Co., Ltd., acryloyl) Except for replacing 40 parts with 40 groups, an ink composition was obtained in the same manner as in Example 1 (solid content ratio 57:43). When the viscosity and contact angle of this ink composition were measured in the same manner as in Example 1, the viscosity at 25 ° C. was 230 mPa · s, and the contact angle was 40 °.

  In Example 2, a near-infrared absorption pattern printing sheet was obtained in the same manner as Example 2 except that the ink composition obtained above was used (dot diameter 130 μm). Further, when the solvent resistance, dot height and contrast ratio were examined in the same manner as in Test Example 1, the solvent resistance was Δ, the dot height was 1.0 μm, and the contrast ratio was Δ. .

  Tables 1 and 2 summarize the evaluation results of the ink compositions and near-infrared absorption pattern printing sheets obtained in the above Examples and Comparative Examples.

  An ink composition containing components (a) to (c) and having a mass ratio of component (b) to component (c) of 50 to 90:10 to 50 as in the present invention has a suitable viscosity and contact angle. Thus, it was found that a near-infrared absorption pattern printing sheet excellent in solvent resistance, dot diameter reproducibility, dot height, and contrast ratio can be obtained by pattern printing a layer that absorbs near-infrared rays using this.

  The near-infrared absorption pattern printing sheet of this invention can be utilized suitably for the various devices using an infrared camera etc.

1 Near-infrared absorption pattern printing sheet 2 Layer that absorbs near-infrared rays (dots)
3 Base material

Claims (11)

A near-infrared absorbing pattern printing sheet on which a layer that absorbs near-infrared radiation is printed on a substrate,
The following components (a) to (c)
(A) Near-infrared absorber (b) Urethane acrylate having a molecular weight of 1500 to 4000 , 9 or 10 acryloyl groups (c) A molecular weight of 50000 , containing urethane acrylate having 2 or 3 acryloyl groups , component (b) and the mass ratio of component (c) 57 ~ 89: 43 ~ NIR absorbing pattern printing sheet, characterized in that the pattern printed layer that absorbs near infrared rays by using the ink composition is 11 . Component (a) near infrared absorber is represented by the following general formula (1)

(In formula (1), R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.)
The near-infrared absorption pattern printing sheet of Claim 1 which is a diimonium salt compound represented by these. R _{1 to} R ₈ in the diimonium salt compound represented by the general formula (1) are represented by the following general formula (2)

(In formula (2), A represents an alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)
The near-infrared absorption pattern printing sheet of Claim 2 which is a cyclohexyl alkyl group represented by these.   The near-infrared absorption pattern printing sheet according to claim 1, wherein the ink composition has a viscosity of 100 to 300 mPa · s.   The near-infrared absorption pattern printing sheet according to claim 1, wherein pattern printing is performed by gravure printing.   The near-infrared absorption pattern printing sheet according to any one of claims 1 to 5, wherein an ultraviolet absorption layer is further provided on the back surface of the layer that absorbs near-infrared rays.   The near-infrared absorption pattern printing sheet according to any one of claims 1 to 6, wherein the base material transmits visible light. The following components (a) to (c)
(A) Near-infrared absorber (b) Urethane acrylate having a molecular weight of 1500 to 4000 , 9 or 10 acryloyl groups (c) A molecular weight of 50000 , containing urethane acrylate having 2 or 3 acryloyl groups , component (b) to component mass ratio of (c) 57 ~ 89: 43 ~ ink composition, which is a 11. Component (a) near infrared absorber is represented by the following general formula (1)

(In formula (1), R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.)
The ink composition according to claim 8, which is a diimonium salt compound represented by the formula: R _{1 to} R ₈ in the diimonium salt compound represented by the general formula (1) are represented by the following general formula (2)

(In formula (2), A represents an alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)
The ink composition according to claim 9, which is a cyclohexylalkyl group represented by the formula:   The ink composition according to any one of claims 8 to 10, wherein the viscosity of the ink composition is 100 to 300 mPa · s.

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