KR100963962B1 - Poly cross linked naphthalocyanine compounds and ink compositions and pigment comprising said compounds - Google Patents

Abstract

The present invention is a novel compound, such as the following formula 2 cross-linked Naphthalocyanine (Naphthalocyanine) can be usefully used for preventing forgery due to the rapid response to gamma rays, has a high absorption ability in the wavelength range of the near infrared region is useful as a near infrared absorber It relates to a poly-crosslinked naphthalocyanine compound which can be used easily, and a near-infrared absorbing plastic color pigment and ink composition in which the poly-crosslinked naphthalocyanine compound is contained as a near infrared absorber.

<Formula 2>

Naphthalocyanine, gamma ray, near infrared ray, ink, coloring pigment

Description

Poly cross linked naphthalocyanine compounds and ink compositions and pigments containing said compounds which respond to gamma rays, and a near-infrared absorption plastic coloring pigment and ink composition containing the same

The present invention relates to a poly-crosslinked naphthalocyanine compound sensitive to gamma rays, and to a near-infrared absorbing plastic colored pigment and ink composition containing the same, and more particularly, to a gamma ray as a novel compound crosslinked with naphthalocyanine. It has a high speed and can be usefully used for preventing forgery, and has a high absorption ability in the wavelength range of the near infrared region, which can be usefully used as a near infrared absorber, and the polycrosslinked naphthalocyanine compound is contained as a near infrared absorber. A near infrared absorption plastic colored pigment and ink composition.

Various products such as cash cards and credit cards, various certificates such as passports and insurance certificates, vehicle driver's licenses, industrial product materials, production sites, and productions that are given information such as checks, securities, banknotes, brand products, and manufacturing history. Food labels and the like, to which information such as timing is given, are attached with means for discriminating them in order to prevent forgery and tampering of the goods.

As a means for discriminating such forgery and modulation, a magnetic label, a label that absorbs and reflects electromagnetic waves, or a label that fluoresces by visible light is added, and a counterfeit product not attached to the label or a counterfeit product having another label is attached. It is done to select genuine products. For example, electromagnetic waves in a predetermined wavelength range are irradiated, and fluorescence emitted from the information presentation material is detected in accordance with the irradiation of the electromagnetic waves, and forgery or modulation of the article is determined according to the detection result of the fluorescence.

Recently, as a light source for recognizing and detecting an image, a semiconductor laser having a wavelength (700 to 1600 nm) in the infrared region, which cannot be recognized by human eyes, has been developed to mechanically measure absorption and reflection of infrared rays in the wavelength range. It can be used as an automated classification or identification element.

In order to speed up the modulation, it is necessary to use a material that can be sensed in real time by using a high energy sensitive material. However, since the compound used for the anti-counterfeiting label known to date is not known a material that is sensitive to high energy, various kinds of radioactive elements or compounds that absorb and react to low energy are used.

To this end, the present inventor in the Republic of Korea Patent Registration No. 0773089 registered and registered in the "poly-crosslinking phthalocyanine compound and ink composition comprising the same in response to gamma rays" in the reaction rate for gamma rays as shown in the following formula 1 to prevent forgery modulation Poly crosslinked phthalocyanine compounds that can be usefully used have been introduced.

In Formula 1, M ₁ and M ₂ are each a metal selected from samarium, europium, rubidium, cesium, gadolinium, dysprosium, or an oxide thereof, and R is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, or an amino group. It is a sulfonyl group, an alkyl group, and the alkyl group which has a C1-C20 substituent, n is an integer of 0-3.

On the other hand, naphthalocyanine compounds, like phthalocyanine compounds, have high transmittance to visible light, high efficiency of blocking near-infrared light, and excellent ability to selectively absorb in the near-infrared light region. It is widely used in various fields including the field.

Accordingly, the naphthalocyanine compound was intended to be used as an anti-falsification ink composition. However, the naphthalocyanine compound introduced previously has a low absorption capacity in the near-infrared and gamma-ray regions. There was a problem that it is difficult to quickly identify forgery and alteration.

Therefore, the present invention is to solve the above problems, the high energy of the neutron, that is, the response speed to the gamma ray can be quickly detected, the forgery of the article can be quickly determined, has a high absorption capacity in the near-infrared region as a near infrared absorber It is an object to provide a novel cross-linked naphthalocyanine compound that can be usefully used.

In addition, the present invention has another object to provide an ink composition comprising a poly-crosslinked naphthalocyanine compound sensitive to the gamma ray.

Another object of the present invention is to provide a colored pigment comprising a polycrosslinked naphthalocyanine compound that is sensitive to the gamma ray.

According to an aspect of the present invention,

It provides a poly-cross-linked naphthalocyanine compound having a structure of the formula (2).

In Formula 2, M ₁ and M ₂ may be the same or different from each other as selected from metal, metal, metal oxide or metal halide, and R ¹ to R ²⁴ may each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, and a hydroxide. Roxysulfonyl group, aminosulfonyl group, alkyl group, alkyl group having 1 to 20 carbon atoms, selected from SR ²⁵ , SR ²⁶ , OR ²⁷ , NHR ²⁸ or NHR ²⁹ may each be the same or different, wherein R ²⁵ Is a phenyl group having an substituent, an alkyl group or an alkyl group having 1 to 20 carbon atoms, R ²⁶ is a phenyl group having an alkoxy group having 1 to 20 carbon atoms, and R ²⁷ and R ²⁸ are each a phenyl group having one substituent, an arylalkyl group or having 1 to 20 carbon atoms It is an alkyl group, R <^29> is a C1-C20 alkyl group which has a substituent, n is an integer of 1-20.

In addition, the present invention is another object to provide a pigment dispersion ink containing a compound of the formula (2) is sensitive to gamma rays or included as a near-infrared absorber insoluble in plastic color pigments and water-based.

As described above, the poly-crosslinked naphthalocyanine compound and the near-infrared absorbing plastic pigment and ink composition containing the same according to the gamma ray of the present invention can quickly discriminate the forgery of the article due to the fast response to the high energy of neutron, ie gamma ray. It is possible to provide a poly-crosslinked naphthalocyanine compound which can be usefully used for preventing forgery and the forgery preventing ink composition comprising the same.

In addition, when the poly-crosslinked naphthalocyanine compound is added as a near-infrared absorber in the manufacture of plastic injection moldings and inks, it exhibits high absorption ability and gamma-ray response in the near-infrared wavelength band, and thus excellent effect can be obtained even in a small amount. It is also useful.

Hereinafter, the present invention will be described in more detail.

The poly-crosslinked naphthalocyanine compound according to the present invention is a novel compound having a structure represented by the following formula (2), and the compound having such a structure not only has a high absorption capacity in the wavelength range of the near infrared region as compared to the conventionally introduced naphthalocyanine compound. It is excellent in performance of water resistance, light resistance, heat resistance, weather resistance, chemical resistance, etc., and thus can be usefully used as a near infrared absorbent. In particular, the poly-crosslinked naphthalocyanine compound having such a crosslinked structure has a property of absorbing the wavelength of the near infrared region by changing the wavelength band of the conventional monomolecular naphthalocyanine compound.

<Formula 2>

In Formula 2, M ₁ and M ₂ may be the same or different from each other as selected from metal, metal, metal oxide or metal halide, and R ¹ to R ²⁴ may each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, and a hydroxide. Roxysulfonyl group, aminosulfonyl group, alkyl group, alkyl group having 1 to 20 carbon atoms, selected from SR ²⁵ , SR ²⁶ , OR ²⁷ , NHR ²⁸ or NHR ²⁹ may each be the same or different, wherein R ²⁵ Is a phenyl group having an substituent, an alkyl group or an alkyl group having 1 to 20 carbon atoms, R ²⁶ is a phenyl group having an alkoxy group having 1 to 20 carbon atoms, and R ²⁷ and R ²⁸ are each a phenyl group having one substituent, an arylalkyl group or having 1 to 20 carbon atoms It is an alkyl group, R <^29> is a C1-C20 alkyl group which has a substituent, n is an integer of 1-20.

This change can be easily seen from the spectrophotometer analysis results. In general, commercially available naphthalocyanine shows absorbance in the visible region around 600 nm to 800 nm, but the poly-crosslinked naphthalocyanine compound according to the present invention is 750. Absorbance is shown at a wavelength of near infrared rays of ˜1100 nm.

In addition, in the case of conventionally commercialized naphthalocyanine compounds in some cases it was confirmed that the absorbance near the near infrared, but in this case the absorption capacity is very small, the poly-crosslinked naphthalocyanine compound according to the present invention is the maximum at 750 ~ 1100nm According to the present invention, the poly-crosslinked naphthalocyanine compound having the above-described structure exhibits excellent properties as an anti-counterfeiting material in response to gamma rays for a short time according to M1 and M2 metals.

Among the poly-crosslinked naphthalocyanine compounds having the structure of Chemical Formula 2, preferably, R ¹ to R ⁶ , R ² to R ⁵ , R ⁷ to R ¹² , R ⁸ to R ¹¹ , R ¹³ to R ¹⁸ , In R ¹⁴ to R ¹⁷ , R ¹⁹ to R ²⁴ , R ²⁰ to R ²³ , each one is R, and the poly-crosslinked naphthalocyanine compound represented by the following Chemical Formula 3 is preferably hydrogen.

In Formula 3, M ₁ and M ₂ may be the same or different as each other selected from a metal free, metal, metal oxide, or metal halide, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4 .

Here, the metals applicable to M ₁ and M ₂ are lithium, beryllium, boron, sodium, magnesium, aluminum, silicon, phosphorus, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, Copper, Zinc, Gallium, Germanium, Arsenic, Yttrium, Zirconium, Niobium, Molybdenum, Technedium, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Indium, Tin, Antimony, Barium, Lanthanum, Cerium, Preseodymium, Samarium, Europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, actinium, thorium, protactinium, Any one selected from uranium, neptunium and americium can be used. In addition, metal oxides that may be applied to M ₁ and M ₂ include tinanile, vanadil, and molybdenum oxide. In addition, metal halides applicable to M ₁ and M ₂ include magnesium chloride, aluminum chloride, gallium chloride, indium chloride, neodymium chloride, ruthenium chloride, germanium chloride, arsenic chloride, rhodium (III) chloride, hafnium chloride, and manganese chloride. (III), zinc chloride, tin chloride (II), tin chloride (IV) and silicon chloride, zinc iodide may be used.

In the compound of Formula 3, M ₁ and M ₂ are each a poly-crosslinked naphthalocyanine compound represented by the following formula (4), or M ₁ and M ₂ are each a potassium cross-linked naphthalocyanine represented by the following formula (5): The compound is good.

  In Formula 4, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4.

In Formula 5, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4.

More preferably, the poly-crosslinked naphthalocyanine compound represented by the following Chemical Formula 6, in which M ₁ and M ₂ are dysprosium in the compound of Chemical Formula 3, is preferable.

In Formula 6, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4.

More preferably, the poly-crosslinked naphthalocyanine compound represented by the following Chemical Formula 7 in which M ₁ and M ₂ are each gadolinium in the compound of Chemical Formula 3 is preferable.

In formula (7), R is an alkyl group having 4 to 8 carbon atoms, n is an integer of 2 to 4.

More preferably, the poly-crosslinked heterometal naphthalocyanine compound represented by the following Chemical Formula 8 in which M ₁ is potassium and M ₂ is a flow path product in the compound of Chemical Formula 3 is preferable.

In Formula 8, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4.

In addition, a polycrosslinked naphthalocyanine compound represented by the following Chemical Formula 9 wherein R is hydrogen in the compound of Chemical Formula 3 is preferable.

In Formula 9, M ₁ and M ₂ may be the same or different as each other selected from a metal free metal, a metal oxide, or a metal halide, and n is an integer of 2 to 4.

More preferably, in the compound of Formula 9, M ₁ and M ₂ are each a poly-crosslinked naphthalocyanine compound represented by Formula 10 below, or M ₁ and M ₂ are each represented by Formula 11 below: Poly crosslinked naphthalocyanine compounds are preferred.

In Formula 10, n is an integer of 2 to 4.

In Formula 11, n is an integer of 2 to 4.

More preferably, the poly-crosslinked naphthalocyanine compound represented by the following Chemical Formula 12 in which M ₁ and M ₂ are sodium in the poly-crosslinked naphthalocyanine compound of Chemical Formula 9 is preferable.

In Formula 12, n is an integer of 2 to 4.

More preferably, in the poly-crosslinked naphthalocyanine compound of Chemical Formula 9, M ₁ and M ₂ are europium, respectively.

In Formula 13, n is an integer of 2 to 4.

In addition, in the poly-crosslinked naphthalocyanine compound of Chemical Formula 9, a polycrosslinked dissimilar metal naphthalocyanine compound having different M ₁ and M ₂ is preferable, in particular, M ₁ is potassium, and M ₂ is europium. Preferred are crosslinked dissimilar metal naphthalocyanine compounds.

In Formula 14, n is an integer of 2 to 4.

The poly-crosslinked naphthalocyanine compound of the formula (3) according to the present invention described above is composed of dicyanonaphthalene or naphthalphthalic anhydride having a structure of the following formula (15), urea, metal salts or metal chlorides corresponding to M ₁ and M ₂ , and high boiling points. After the solvent and the reaction initiator were mixed at room temperature and reacted for 6 to 8 hours while heating to reflux at 230 to 250 ° C., the mixture was filtered while maintaining the temperature at 70 to 100 ° C., and the diluted acid solution and alkali at 65 to 70 ° C. Each solution was washed with water to obtain a cake from which unreacted substances were removed. The cake thus obtained was dispersed in 5 wt% aqueous solution of ethylene glycol to 5-10 w / w%, then heat-treated and filtered for 2 hours while maintaining 80-120 ° C., and then redispersed in acetone and toluene, respectively, at 80-100 ° C. Purification using the Soxhlet apparatus at and then drying can be easily obtained.

In Formula 15, A ¹ to A ⁶ are each a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, an alkyl group, an alkyl group having 1 to 20 carbon atoms, and SR ²⁵ , SR ²⁶ , OR ²⁷ , NHR ²⁸ or NHR ²⁹ , which may be the same or different from each other, wherein R25 is a phenyl group, an alkyl group having a substituent or an alkyl group having 1 to 20 carbon atoms, and R ²⁶ is a phenyl group having an alkoxy group having 1 to 20 carbon atoms R ²⁷ and R ²⁸ each represent a phenyl group having an substituent, an arylalkyl group or an alkyl group having 1 to 20 carbon atoms, and R ²⁹ is an alkyl group having 1 to 20 carbon atoms having a substituent.

At this time, dicyanonaphthalene or naphthalic anhydride represented by the formula (15) is a reaction force is reduced when the water is mixed, so care should be taken to prevent drying and inflow of water during use, urea can be used as a general product, reaction As a zero-polarity and high boiling point solvent, what was chosen from (alpha)-methyl naphthalene, (alpha)-chloro naphthalene, dichlorobenzene, DM, n-alkylbenzene, or ethylene glycol can be used.

The poly-crosslinked naphthalocyanine compound thus prepared has a cross-linked structure different from the known NaPhthalocyanine compound, and thus the cross-linked poly-crosslinked naphthalocyanine compound has a high absorption capacity in the near infrared region of 750-1100 nm. Because it has the property of absorbing, it can be usefully used as a near-infrared absorbent.

Therefore, this invention provides the plastic coloring pigment ink which contains the polycrosslinked naphthalocyanine compound which has the above-mentioned structure as a near-infrared absorber. In particular, the poly-crosslinked naphthalocyanine has excellent performance in water resistance, light resistance, heat resistance, weather resistance, chemical resistance, and the like, and is well mixed with the components of the plastic resin and other inks, and has low friction and abrasion, so that the NIR absorbers in plastic resins and inks If included as it can exhibit excellent properties, it can exhibit a sufficient effect in a smaller amount than the conventional inorganic infrared absorber.

Poly-crosslinked naphthalocyanine compound according to the present invention can exhibit a sufficient effect when it contains 0.005 to 5 parts by weight based on 100 parts by weight of the total ink composition, and 0.001 to 3 parts by weight based on 100 parts by weight of the plastic resin is sufficient effect. Can be exercised. In this case, the ink composition may be for a conventional pigment dispersion inkjet ink or for a conventional screen printing ink, and may be applied to various inks such as flat printing ink and gravure printing ink. When it is used as a pigment for plastic injection, it can be used as a pigment for injection and extrusion. It can be applied to various purposes if it can produce a great effect in a small amount.

In addition, the poly-crosslinked naphthalocyanine compound having the above-described structure responds to gamma rays in a short time depending on M1 and M2 metals, and various cards such as various cash cards and credit cards, passports, insurance certificates, and vehicle driver's licenses. It is also excellent as a material for preventing counterfeit and tampering of materials, such as certificates, checks, securities, banknotes, branded products, and industrial product materials to which information such as manufacturing history is given. Characteristics.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are presented to aid the understanding of the present invention, but the present invention is not limited thereto.

&Lt; Example 1 >

62 parts by weight of 1,8-naphthalic anhydride 105.11 parts by weight of urea, 101 parts by weight of aluminum salt hexahydrate, 400 parts by weight of alkylbenzene (LAB: dihydrate) and 0.5 parts by weight of molybdenum ammonium salt were mixed and sufficiently stirred, followed by 235 ° C. The temperature was raised to 250 ° C. over 2 hours and then reacted for 3 hours. Nitrogen gas is flowed at a rate of 350 ml / min during the reaction. After distillation under reduced pressure, the solvent was distilled off, and then filtered through 100% by weight of 10% hydrochloric acid solution and 10% sodium hydroxide alkaline solution, and then dried until completely weighed in an 80 ° C. dryer. After dispersing in w%, treated at 80 ° C. for 1 hour, filtered, washed three times with 500 ml of 100 ° C. water, dried at 80 ° C. for 24 hours, and put it in 250 parts by weight of acetone. After purification, and dried and put again in 250 parts by weight of MIBK and purified using a 120 ℃ Soxhlet apparatus and dried.

As a result of measuring the infrared absorption spectrum and ¹³ NMR and UV data of the compound obtained by drying, it was confirmed that the polycrosslinked naphthalocyanine compound having the structure of Chemical Formula 10 was shown. The measured UV data is shown in Table 1 below.

<Formula 10>

<Example 2>

62 parts by weight of 2,3-dicyanonaphthalene having an infrared absorption spectrum as shown in FIG. 1, 210 parts by weight of urea, 30 parts by weight of sodium chloride, and 1 part by weight of molybdenum ammonium salt were sufficiently mixed, followed by temperature over 220 to 230 ° C. over 3 hours. After raising the reaction for 6 hours. Nitrogen gas is flowed at a rate of 300 ml / min during the reaction. After distillation under reduced pressure, the solvent was distilled off and then filtered with 100 parts by weight of 10% hydrochloric acid solution and 10% sodium hydroxide solution. It was dried until it was completely weighed in an 80 ° C. dryer, and then the dried material was dispersed at 10 w / w% in a 5 wt% aqueous solution of ethylene glycol, treated at 80 ° C. for 1 hour, and filtered, and then filtered three times with 500 ml of 100 ° C. water. Washed with water and dried at 80 ° C. for 24 hours, put it in 250 parts by weight of acetone, and refined using 70 ° C. Soxhlet apparatus, followed by drying. Then, put it again in 250 parts by weight of MIBK and purified using 120 ° C. Soxhlet apparatus, then dried. do.

As a result of measuring the infrared absorption spectrum and ¹³ NMR and UV data of the compound obtained by drying, it was confirmed that the compound was a polycrosslinked naphthalocyanine compound having the structure of Formula 12, and the measured UV data is shown in Table 1.

<Formula 12>

<Example 3>

62 parts by weight of 2,3-dicyanonaphthalene having an infrared absorption spectrum as shown in FIG. 1, 105 parts by weight of urea, 184 parts by weight of gadolidium hydrochloride, 1 part by weight of molybdenum ammonium salt, 500 parts by weight of alkylbenzene (LAB: Isu Chemical) After sufficiently mixing the temperature was raised over 2 hours from 220 ℃ to 230 ℃ and reacted for 3 hours. Nitrogen gas is flowed at a rate of 300 ml / min during the reaction. After distillation under reduced pressure, the solvent was distilled off and then filtered with 100% by weight of 10% hydrochloric acid solution and 10% sodium hydroxide solution. It was dried until it was completely weighed in an 80 ° C. dryer, and then the dried material was dispersed at 10 w / w% in a 5 wt% aqueous solution of ethylene glycol, treated at 80 ° C. for 1 hour, and filtered, and then filtered three times with 500 ml of 100 ° C. water. Washed with water and dried at 80 ° C. for 24 hours, put it in 250 parts by weight of acetone, and refined using 70 ° C. Soxhlet apparatus, followed by drying. do.

As a result of measuring the infrared absorption spectrum and ¹³ NMR and UV data of the compound obtained by drying, it was confirmed that the polycrosslinked naphthalocyanine compound having the structure of Chemical Formula 16 was shown. The infrared absorption spectrum measured was shown in FIG. Solid- ¹³ NMR is shown in Figure 3, the transmission spectrum (transmittance spectrum) is shown in Figure 4, UV data is shown in Table 1.

<Example 4>

2,3-dicyanonaphthalene having an infrared absorption spectrum as shown in FIG. 1, 210 parts by weight of urea, 180 parts by weight of europium chloride, and 1 part by weight of molybdenum ammonium salt were sufficiently mixed, and the temperature was raised from 220 ° C. to 230 ° C. over 3 hours. After reacting for 6 hours. Nitrogen gas is flowed at a rate of 300 ml / min during the reaction. After distillation under reduced pressure, the solvent was distilled off and then filtered with 100% by weight of 10% hydrochloric acid solution and 10% sodium hydroxide solution. It was dried until it was completely weighed in an 80 ° C. dryer, and then the dried material was dispersed at 10 w / w% in a 5 wt% aqueous solution of ethylene glycol, treated at 80 ° C. for 1 hour, and filtered, and then filtered three times with 500 ml of 100 ° C. water. Washed with water and dried at 80 ° C. for 24 hours, put it in 250 parts by weight of acetone, and refined using 70 ° C. Soxhlet apparatus, followed by drying and putting it in 250 parts by weight of 2,3-dicyanonaphthalene again. Purify using and dry.

As a result of measuring the infrared absorption spectrum and ¹³ NMR and UV data of the compound obtained by drying, it was confirmed that the polycrosslinked naphthalocyanine compound having the structure of Chemical Formula 13 was obtained. The measured UV data is shown in Table 1 below.

<Formula 13>

Example 5

62 parts by weight of 2,3-dicyanonaphthalene having an infrared absorption spectrum as shown in FIG. 1, 101 parts by weight of urea, 19 parts by weight of potassium chloride, 91 parts by weight of europium chloride, 1 part by weight of molybdenum ammonium salt, and 500 parts by weight of alkylbenzene (LAB : Isuchem) is sufficiently mixed and raised for 3 hours from 220 ° C to 230 ° C and then reacted for 6 hours. Nitrogen gas is flowed at a rate of 300 ml / min during the reaction. After distillation under reduced pressure, the solvent was distilled off and then filtered with 100% by weight of 10% hydrochloric acid solution and 10% sodium hydroxide solution. It was dried until it was completely weighed in an 80 ° C. dryer, and then the dried material was dispersed at 10 w / w% in a 5 wt% aqueous solution of ethylene glycol, treated at 80 ° C. for 1 hour, and filtered, and then filtered three times with 500 ml of 100 ° C. water. Washed with water and dried at 80 ° C. for 24 hours, put it in 250 parts by weight of acetone, and refined using 70 ° C. Soxhlet apparatus, followed by drying. Then, put it again in 250 parts by weight of MIBK and purified using 120 ° C. Soxhlet apparatus, then dried. do.

As a result of measuring infrared absorption spectrum and ¹³ NMR and UV data of the compound obtained by drying, it was confirmed that the polycrosslinked naphthalocyanine compound having the structure of Chemical Formula 14 was obtained. The measured UV data is shown in Table 1 below.

<Formula 14>

<Example 6>

62 parts by weight of 2,3-dicyanonaphthalene having an infrared absorption spectrum as shown in FIG. 1, 202 parts by weight of urea, 38 parts by weight of potassium chloride, 1 part by weight of molybdenum ammonium salt, and 500 parts by weight of alkylbenzene (LAB: dihydrate) After raising the temperature from 220 ° C to 230 ° C over 3 hours, and reacted for 6 hours. Nitrogen gas is flowed at a rate of 300 ml / min during the reaction. After distillation under reduced pressure, the solvent was distilled off and then filtered with 100% by weight of 10% hydrochloric acid solution and 10% sodium hydroxide solution. It was dried until it was completely weighed in an 80 ° C. dryer, and then the dried material was dispersed at 10 w / w% in a 5 wt% aqueous solution of ethylene glycol, heat treated at 80 ° C. for 1 hour, and filtered, and then filtered with 500 ml of water at 90 to 100 ° C. 3 washes with water and dried for 24 hours at 80 ℃, dried again in 250 parts by weight of acetone and purified using a 70 ℃ Soxhlet apparatus, and then dried and put again in 250 parts by weight of MIBK using 120 ℃ Soxhlet apparatus Purify and dry.

As a result of measuring the infrared absorption spectrum and ¹³ NMR and UV data of the compound obtained by drying as described above, it was confirmed that the polycrosslinked naphthalocyanine compound having the structure of Formula 11 was obtained. The measured UV data is shown in Table 1 below.

<Formula 11>

<Example 7>

After the mixing of 62 parts by weight of 2,3-dicyanonaphthalene having an infrared absorption spectrum as shown in FIG. 1, 202 parts by weight of urea, 180 parts by weight of dysprosium chloride, 500 parts by weight of alkylbenzene (LAB: dihydrate) and 220 ° C The temperature was raised to 230 ° C. over 3 hours and then reacted for 6 hours. Nitrogen gas is flowed at a rate of 300 ml / min during the reaction. After distillation under reduced pressure, the solvent was distilled off and then filtered with 100% by weight of 10% hydrochloric acid solution and 10% sodium hydroxide solution. It was dried until it was completely weighed in an 80 ° C. dryer, and then the dried material was dispersed at 10 w / w% in a 5 wt% aqueous solution of ethylene glycol, heat treated at 80 ° C. for 1 hour, and filtered, and then filtered with 500 ml of water at 90 to 100 ° C. 3 washes with water and dried for 24 hours at 80 ℃, dried again in 250 parts by weight of acetone and purified using a 70 ℃ Soxhlet apparatus, and then dried and put again in 250 parts by weight of MIBK using 120 ℃ Soxhlet apparatus Purify and dry.

As a result of measuring infrared absorption spectrum and ¹³ NMR and UV data of the compound obtained by drying, it was confirmed that the polycrosslinked naphthalocyanine compound having the structure of Chemical Formula 17 was obtained. The measured UV data is shown in Table 1 below.

Comparative Example 1

The infrared absorption spectrum and ¹³ NMR and UV data of the magnesium naphthalocyanine compound having the structure of Formula 18 were measured, and the measured infrared absorption spectrum was shown in FIG. 5, and the Solid- ¹³ NMR was shown in FIG. 6. The data is shown in Table 1.

division Core metal (M ₁ , M ₂ ) Absorbance Remarks Example 1 Al, Al 880 Example 2 Na, Na 840 Example 3 Gd, Gd 890 Example 4 Eu, Eu 920 Example 5 K, Eu 950 Example 6 K.K 980 Example 7 Dy, Dy 1050 Comparative Example 1 Al, Nc 650 Merchandise (Ardrich)

As shown in Table 1, the poly-crosslinked narocyanine compounds of Examples 1 to 7 prepared according to the present invention have a maximum absorbance of 840 nm or 1050 nm, which is very high compared to the naphthalocyanine compound of Comparative Example 1, which is a conventional monomolecular form. It can be seen that it absorbs near infrared wavelengths with high absorption capacity. Here, the aluminum naphthalocyanine compound of Comparative Example 1 has an absorption ability in the near infrared region, but its absorption ability is weak, and the wavelength showing the maximum absorbance is 650 nm, rather it is closer to the visible light region.

In addition, when compared to Figures 1 and 2 showing the poly-cross-linked naphthalocyanine compound prepared in Example 1 of the present invention compared to Figures 5 and 6 showing the conventional naphthalocyanine compound of Comparative Example 1 the structural change is clearly You can check it. In addition, looking at the results of the transmission spectrum (transmittance spectrum) of the poly-cross-linked naphthalocyanine compound prepared in Example 1 as shown in Figure 3, it can be seen that there is almost no transmittance to 860nm.

<Examples 8 to 13>

To prepare a dye-type ink composition applied to the inkjet ink as shown in Table 2. The dye-type ink composition is first mixed with a small amount of the surfactant in a suitable amount of distilled water, and then dispersed in a three-mill wheat and then mixed with the remaining amount of distilled water, dye, solvent, antimicrobial agent, viscosity modifier, surfactant residual amount Ink was prepared by filtration with 0.45 micron filter paper. At this time, a black dye Direct Black (CI.No 19) was used as an inkjet dye, N-methhyl pyrrolidone was used as a solvent, Tween 80 (Uniqema, USA) was used as a surfactant, and an antimicrobial agent was used. Bactocide 4000 was used, Ethylene Glycol was used as a viscosity modifier, and the one obtained in Example 3 was used as a near infrared absorber.

The ink thus prepared was printed by an inkjet print, and then tested for near-infrared absorption at 890 nm using a near infrared absorption spectrum (Shimadzu / UV3101 PC). The transmittance is shown in Table 2 below.

division Dye (g) Solvent (g) Surfactant (g) Antibacterial agents
(g) Viscosity modifier (g) Near infrared ray
Absorbent (g) Distilled water
(g) Transmittance
(%) Example 8 6 10 3 One One 0.005 78.995 15 Example 9 6 10 3 One One 0.01 78.99 8 Example 10 6 10 3 One One 0.1 78.9 6 Example 11 6 10 3 One One 0.5 78.5 4 Example 12 6 10 3 One One 2 77 2 Example 13 6 10 3 One One 5 74 One

As shown in Table 2, it can be seen that in Examples 9 to 13 in which the dye-type inkjet ink was prepared by adding the near-infrared absorbent within the preferred range of the present invention, good near-infrared absorptivity of 10% or less was shown.

<Examples 14 to 19>

To prepare a pigment dispersion ink composition applied to the inkjet ink as shown in Table 3. The pigment-type ink composition is first mixed with a small amount of the surfactant in a suitable amount of distilled water and then dispersed in a three-mill wheat and then mixed with the remaining amount of distilled water, and the pigment, solvent, antimicrobial agent, viscosity modifier, surfactant residual amount Ink was prepared by filtration with 0.45 micron filter paper. At this time, Red (CI.No 219) was used as a pigment, methyl ethyl ketone was used as a solvent, as a surfactant (Johnson polymer: John Krill 678), Bactocide 4000 (Asung Fine Chemical) as an antimicrobial agent, Ethylene Glycol was used as a viscosity modifier and the one obtained in Example 3 was used as a near infrared absorber.

The ink thus prepared was printed using an inkjet print, and then tested for near infrared absorption at 890 nm using a near infrared absorption spectrum (Shimadzu / UV3101 PC). The transmittance is shown in Table 3 below.

division Pigment (g) Solvent (g) Surfactant (g) Antibacterial agents
(g) Viscosity modifier (g) Near infrared ray
Absorbent (g) Distilled water (g) Transmittance
(%) Example 14 6 10 3 One One 0.005 78.995 20 Example 15 6 10 3 One One 0.01 78.99 8 Example 16 6 10 3 One One 0.1 78.9 5 Example 17 6 10 3 One One 0.5 78.5 3 Example 18 6 10 3 One One 2 77 2 Example 19 6 10 3 One One 5 74 One

As shown in Table 3, it can be seen that in Examples 15 to 19, in which the pigment-type inkjet ink was prepared by adding a near infrared absorbent within a preferred range of the present invention, a good near infrared absorbance of 10% or less was shown.

<Examples 20 to 25>

To prepare an ink composition applied to the ink for screen printing as shown in Table 4. The ink composition was prepared by mixing distilled water with a pigment, a resin, a penetrant, a stabilizer, an additive, a surfactant, an antimicrobial agent, a near-infrared absorber, and a solvent, followed by dispersing with a sambon mill.

In this case, black (CI.No 51) was used as a pigment, and an alkyd varnish resin was used as a resin, a wax as a penetrant, a wax as a stabilizer, a talc as an additive, and a surfactant (BYK Chemie: BYK 410). ), Bactocide 4000 (Ash Fine Chemical) as an antibacterial agent, a compound obtained in Example 3 as a near infrared absorber, and cyclohexane were used as a solvent.

Screen printing using the ink thus prepared, and then printing, and then tested the near infrared absorption capacity at 890nm with a near infrared absorption spectrum (Shimadzu / UV3101 PC), the transmittance is shown in Table 4 below.

division Pigment
(g) Suzy
(g) Penetrant
(g) stabilizator
(g) additive
(g) Surfactant (g) Antibacterial agents
(g) Near infrared ray
Absorbent (g) solvent
(g) Transmittance
(%) Example 20 5 35 5 9 25 3 One 0.005 16.995 25 Example 21 5 35 5 9 25 3 One 0.01 16.99 10 Example 22 5 35 5 9 25 3 One 0.1 16.9 5 Example 23 5 35 5 9 25 3 One 0.5 16.5 4 Example 24 5 35 5 9 25 3 One 2 15 3 Example 25 5 35 5 9 25 3 One 5 12 2

As shown in Table 4, in Examples 21 to 25, wherein the near-infrared absorber was added within the preferred range of the present invention to prepare a screen printing ink and a gravure ink, a good near-infrared absorptivity of 10% or less was shown. .

<Examples 26 to 31>

In the same manner as in Examples 20 to 25 to prepare an ink composition applied to the ink for screen printing, using a high-energy generator and a detector to irradiate gamma rays to the sample which is the screen-printed printed matter to test the response by gamma rays The experiments were subjected to the gamma rays are shown in Table 5 below.

division Pigment
(g) Suzy
(g) Penetrant
(g) stabilizator
(g) additive
(g) Surfactant (g) Antibacterial agents
(g) Near infrared ray
Absorbent (g) solvent
(g) Induction
Sensitivity Example 26 5 35 5 9 25 3 One 0.005 16.995 - Example 27 5 35 5 9 25 3 One 0.01 16.99 + Example 28 5 35 5 9 25 3 One 0.1 16.9 + Example 29 5 35 5 9 25 3 One 0.5 16.5 ++ Example 30 5 35 5 9 25 3 One 2 15 ++ Example 31 5 35 5 9 25 3 One 5 12 +++

As shown in Table 5 above, the screen printing ink and the gravure ink were prepared by adding the near-infrared absorbent within the preferred range of the present invention, and in Examples 27 to 31, it showed that excellent sensitivity to gamma rays was observed. have.

<Examples 32 to 37>

To the injection molding a composition as shown in Table 6 to prepare a plastic injection. As the plastic injection resin, polycarbonate (LG chemistry) was used, and a near-infrared absorbing pigment was prepared using a compound obtained in Example 3 to prepare a rectangular injection molding of 6.3 × 7.3 × 0.3 cm, and then the near-infrared absorption spectrum of the injection molding ( Shimadzu / UV3101 PC) was tested for near-infrared absorption at 890 nm, and its transmittance is shown in Table 6 below.

division Polycarbonate (g) Near infrared ray absorbent (g) Permeability (%) Example 32 100 0.001 15 Example 33 100 0.01 5 Example 34 100 0.1 3 Example 35 100 0.5 One Example 36 100 One 0.4 Example 37 100 3 0.1

     As shown in Table 6 above, as a result of preparing a plastic injection molded product by adding a near infrared absorbent within the preferred range of the present invention, Examples 33 to 37 showed a near infrared absorptivity of 5% or less, and a less amount of near infrared rays than the ink composition. It can be seen that the absorbent is higher than the ink composition using the absorbent.

1 is a diagram showing an infrared absorption spectrum of 2,3 dicyanonaphthalene used as a raw material of the present invention.

2 is a diagram showing an infrared absorption spectrum of the compound prepared in Example 3 of the present invention.

Figure 3 shows a Solid- ¹³ NMR of the compound prepared in Example 3 of the present invention.

4 is a view showing a transmittance spectrum of the compound prepared in Example 3 of the present invention.

5 is a diagram showing an infrared absorption spectrum of the magnesium naphthalocyanine compound of Comparative Example 1 of the present invention.

6 is a view showing a Solid- ¹³ NMR of the magnesium naphthalocyanine compound of Comparative Example 1 of the present invention.

Claims (23)

Poly-crosslinked naphthalocyanine compound sensitive to gamma rays, characterized by having the structure of the following formula (2). <Formula 2>

In Formula 2, M ₁ and M ₂ are each free of metal or lithium, beryllium, boron, sodium, magnesium, aluminum, silicon, phosphorus, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, Copper, Zinc, Gallium, Germanium, Arsenic, Yttrium, Zirconium, Niobium, Molybdenum, Technedium, Ruthenium, Rhodium, Palladium, Silver, Indium, Tin, Antimony, Barium, Lanthanum, Cerium, Preseodymium, Samarium, Europium, Metals selected from gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, bismuth, actium, thorium, neptunium, americium, The metal oxide, selected from the metal halide, may be the same or different from each other, and R ¹ to R ²⁴ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, or an alkyl group. Group, an alkyl group having 1 to 20 carbon atoms, selected from SR ²⁵ , SR ²⁶ , OR ²⁷ , NHR ^28, or NHR ²⁹ , each of which may be the same or different, wherein R ²⁵ is a phenyl group, alkyl group or carbon number having a substituent An alkyl group having 1 to 20 carbon atoms, R ²⁶ is a phenyl group having an alkoxy group having 1 to 20 carbon atoms, R ²⁷ and R ²⁸ are each a phenyl group having an substituent, an arylalkyl group or an alkyl group having 1 to 20 carbon atoms, and R ²⁹ has a substituent It is a C1-C20 alkyl group and n is an integer of 1-20. The method according to claim 1, M ₁ and M ₂ in the compound of Formula 2 are more preferably beryllium, boron, sodium, aluminum, cobalt, cesium, gold, silver, ruthenium, indium, xenon, calcium, lanthanum, ytterbium, erbium, dysprosium, gadolinium A poly-crosslinked naphthalocyanine compound that is sensitive to gamma rays, which is a metal selected from europium, samarium, ruthetium, tungsten, iridium, platinum, lanthanum and americium, or a metal oxide thereof or a metal halide. The method according to claim 1 or 2, In the compound of Formula 2, each of R ¹ to R ⁴ , R ⁵ to R ⁸ , R ⁹ to R ¹² , and R ¹³ to R ¹⁶ , each of which is R and the remainder of hydrogen, is represented by the following Chemical Formula 3 Poly-crosslinked naphthalocyanine compound in response to. <Formula 3>

In Formula 3, M ₁ and M ₂ may be the same or different as each other selected from a metal free, metal, metal oxide, or metal halide, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4 . The method according to claim 3, Poly-crosslinked naphthalocyanine compound sensitive to gamma rays, characterized in that in the compound of Formula 3 M ₁ and M ₂ are each represented by the following formula (4), which is aluminum. <Formula 4>

In Formula 4, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4. The method according to claim 3, Poly-crosslinked naphthalocyanine compound sensitive to gamma rays, characterized in that in the compound of Formula 3 M ₁ and M ₂ are each represented by the formula (5) is potassium. <Formula 5>

In Formula 5, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4. The method according to claim 3, Poly cross-linked naphthalocyanine compound which is sensitive to gamma rays, characterized in that M ₁ and M ₂ in the compound of Formula 3 are different dissimilar metals. The method according to claim 6, A poly-crosslinked naphthalocyanine compound sensitive to gamma rays, wherein M ₁ is potassium and M ₂ is europium. <Formula 8>

In Formula 8, R is an alkyl group having 4 to 8 carbon atoms, and n is an integer of 2 to 4. The method according to claim 3, Poly-crosslinked naphthalocyanine compound sensitive to gamma rays, characterized in that in the compound of Formula 3 R is hydrogen represented by the following formula (9). <Formula 9>

In Formula 9, M ₁ and M ₂ may be the same or different as each other selected from a metal free metal, a metal oxide, or a metal halide, and n is an integer of 2 to 4. The method according to claim 8, Poly-crosslinked naphthalocyanine compound sensitive to gamma rays, characterized in that in the compound of Formula 9 M ₁ and M ₂ are each represented by the following formula (10) that is aluminum. <Formula 10>

In Formula 10, n is an integer of 2 to 4. The method according to claim 8, In the compound of Formula 9, M ₁ and M ₂ are each represented by the following formula (11) wherein potassium is a poly-crosslinked naphthalocyanine compound sensitive to gamma rays. <Formula 11>

In Formula 11, n is an integer of 2 to 4. The method according to claim 8, Poly-crosslinked naphthalocyanine compound, characterized in that M ₁ and M ₂ in the compound of Formula 9 are different dissimilar metals. The method of claim 11, A poly-crosslinked naphthalocyanine compound sensitive to gamma rays, wherein M ₁ is potassium and M ₂ is europium. <Formula 14>

In Formula 14, n is an integer of 2 to 4. In an ink composition comprising a near infrared absorber, A near-infrared absorbing ink composition, wherein the near-infrared absorber is a poly-crosslinked naphthalocyanine compound having a structure of formula (2). <Formula 2>

In Formula 2, M ₁ and M ₂ are Metal free or lithium, beryllium, boron, sodium, magnesium, aluminum, silicon, phosphorus, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, Yttrium, Zirconium, Niobium, Molybdenum, Technedium, Ruthenium, Rhodium, Palladium, Silver, Indium, Tin, Antimony, Barium, Lanthanum, Cerium, Priseodymium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Metal selected from thulium, ytterbium, ruthenium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, bismuth, actium, thorium, neptunium, americium, the metal oxide thereof, and the metal halide It may be the same or different from each other, R ¹ to R ²⁴ each have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, an alkyl group, a substituent having 1 to 20 carbon atoms Is an alkyl group, SR ²⁵ , SR ²⁶ , OR ²⁷ , NHR ²⁸ or NHR ²⁹ may be the same or different, respectively, wherein R ²⁵ is a phenyl group, alkyl group or alkyl group having 1 to 20 carbon atoms, R ²⁶ Is a phenyl group having an alkoxy group having 1 to 20 carbon atoms, R ²⁷ and R ²⁸ are each a phenyl group having an substituent, an arylalkyl group or an alkyl group having 1 to 20 carbon atoms, R ²⁹ is an alkyl group having 1 to 20 carbon atoms having a substituent, n Is an integer of 1-20. 14. The method of claim 13, The poly-crosslinked naphthalocyanine compound is a near-infrared absorbing ink composition, characterized in that it contains 0.01 to 5 parts by weight based on 100 parts by weight of the total ink composition. The method according to claim 13 or 14, The ink composition is a near-infrared absorbing ink composition, characterized in that for dye-type inkjet ink. The method according to claim 13 or 14, The ink composition is a near-infrared absorbing ink composition, characterized in that for pigmented inkjet ink. The method according to claim 13 or 14, The ink composition is a near-infrared absorbing ink composition, characterized in that for screen printing ink. The method according to claim 13 or 14, The ink composition is a near-infrared absorbing ink composition, characterized in that for printing a flat plate. The method according to claim 13 or 14, The ink composition is a near-infrared absorbing ink composition, characterized in that for gravure printing ink. In the plastic resin composition containing a near infrared absorber, A near-infrared absorbing plastic colored pigment, wherein the near-infrared absorber is a poly-crosslinked naphthalocyanine compound having a structure of formula (2). <Formula 2>

In Formula 2, M ₁ and M ₂ are each free of metal or lithium, beryllium, boron, sodium, magnesium, aluminum, silicon, phosphorus, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, Copper, Zinc, Gallium, Germanium, Arsenic, Yttrium, Zirconium, Niobium, Molybdenum, Technedium, Ruthenium, Rhodium, Palladium, Silver, Indium, Tin, Antimony, Barium, Lanthanum, Cerium, Preseodymium, Samarium, Europium, Metals selected from gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, bismuth, actium, thorium, neptunium, americium, The metal oxide, selected from the metal halide, may be the same or different from each other, and R ¹ to R ²⁴ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, or an alkyl group. Group, an alkyl group having 1 to 20 carbon atoms, selected from SR ²⁵ , SR ²⁶ , OR ²⁷ , NHR ^28, or NHR ²⁹ , each of which may be the same or different, wherein R ²⁵ is a phenyl group, alkyl group or carbon number having a substituent An alkyl group having 1 to 20 carbon atoms, R ²⁶ is a phenyl group having an alkoxy group having 1 to 20 carbon atoms, R ²⁷ and R ²⁸ are each a phenyl group having an substituent, an arylalkyl group or an alkyl group having 1 to 20 carbon atoms, and R ²⁹ has a substituent It is a C1-C20 alkyl group and n is an integer of 1-20. The method of claim 20, The poly-crosslinked naphthalocyanine compound is a near-infrared absorbing plastic colored pigment composition, characterized in that 0.001 to 3 parts by weight based on 100 parts by weight of the total plastic resin composition. The method according to claim 20 or 21, The near-infrared absorbing plastic colored pigment composition, wherein the plastic resin composition is a plastic injection colored pigment. The method according to claim 20 or 21, The near-infrared absorbing plastic colored pigment composition, wherein the plastic resin composition is a plastic extrusion colored pigment.

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