WO2017073926A1

WO2017073926A1 - Diacetylene aqueous ink, hydrochromic polydiacetylene test paper manufactured using same, and use thereof

Info

Publication number: WO2017073926A1
Application number: PCT/KR2016/011398
Authority: WO
Inventors: 김종만; 박동훈
Original assignee: 한양대학교 산학협력단
Priority date: 2015-10-30
Filing date: 2016-10-12
Publication date: 2017-05-04

Abstract

Provided are a diacetylene aqueous ink, a hydrochromic polydiacetylene test paper manufactured using the same, and a use thereof. The aqueous ink contains a diacetylene monomer and a mixed solvent of water and an alcohol. The diacetylene monomer has an ionic functional group represented by R⁺X^- wherein X^- is F^-, Cl^-, Br^-, I^-, PF₆ ^-, BF₄ ^-, bis(trifluoromethane)sulfonimide (Tf₂N^-, TFSI), trifluoromethanesulfonate (TfO^-), SCN^-, or CH₃COO^-; and R⁺ is an N⁺-R₁- heterocyclic quaternary ammonium.

Description

Diacetylene water based ink, hydrochromic polydiacetylene test paper prepared using the same and use thereof

TECHNICAL FIELD The present invention relates to polydiacetylene, and more particularly, to a hydrochromic polydiacetylene moisture test paper.

Polydiacetylene is a polymer of diacetylene monomers. It is a conjugated polymer having characteristics that are produced through photopolymerization such as ultraviolet or gamma irradiation when the diacetylene monomers are arranged through self-assembly. . Such polydiacetylenes have alternating double and triple bonds in the polymer main chain, and generally have a maximum absorption wavelength at about 640 nm, which is blue, and exhibits external conditions (heat, solvent, pH, force, molecular recognition, etc.). As a result, the maximum absorption wavelength shifts to about 540 nm and turns red. Various kinds of sensors have been researched and developed by using the discoloration feature of the polydiacetylene.

The prior art has the disadvantage that the base material used in the production of hydrochromic polydiacetylene thin film is glass, PET film and OHP film, and the film is easily peeled off or peeled off after the production of the thin film. The amount of the die acetylene complex required a large amount and may be generated unevenly, there was a disadvantage that the sensor function may be lost by sensitively reacting to moisture in the atmosphere when the thin film is manufactured and stored.

Accordingly, the problem to be solved by the present invention is to provide a polydiacetylene-containing moisture test paper that provides excellent binding force to the base material and reduced sensitivity to humidity.

Technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention to achieve the above technical problem provides an aqueous ink containing a diacetylene monomer. The aqueous ink contains a diacetylene monomer represented by Formula 1 below, and a mixed solvent of water and alcohol.

[Formula 1]

In Formula 1, a is an integer of 1 to 20, b is an integer of 1 to 20, c is an integer of 0 to 2, d is an integer of 1 to 10, L is

,

,

,

, or

And, wherein E, E _1, and E ₂ is O or S, regardless of each other, X ^- is ^{^{^{F -, Cl -, Br -}}} , I -, PF 6 -, BF 4 -, Tf 2 N - (bis ( and a heterocyclic quaternary ammonium (heterocyclic quarternary ammonium), - trifluoromethane ) sulfonimide (TFSI)), TfO - (trifluoromethanesulfonate), SCN -, or CH ₃ COO ^-, and, R ⁺ is to N ⁺ -R ₁ represented by the formula (2a) R ⁺ is X ^-together with N ⁺ -R ₁ -heterocyclic quaternary ammonium salt, * is a bond,

[Formula 2a]

In Formula 2a, ring B is a 5-membered or 6-membered heterocyclic compound having N of 1 to 3 and O of 0 to 1 as a hetero member, and saturated or unsaturated. Heterocyclic compound, wherein R ₁ is cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms.

N ⁺ -R ₁ of formula 2a - heterocyclic quaternary ammonium is N ⁺ -R ₁ shown in the following formula 2b or 2c to the formula - may be a heterocyclic ring quaternary ammonium.

[Formula 2b]

[Formula 2c]

In Formula 2b, Ring C is a 5-membered or 6-membered unsaturated heterocyclic compound having N of 2 to 3 as a hetero member, and in Formula 2c, Ring D has N of 2 to 3 as heteromember Is a 5-membered or 6-membered unsaturated heterocyclic compound, R ₁ and R ₁ ′ are each independently a cyanoalkyl having 1 to 16 carbon atoms, a haloalkyl having 1 to 16 carbon atoms, or a hydroxyl having 1 to 16 carbon atoms. Alkyl, or aminoalkyl having 1 to 16 carbon atoms.

The N ⁺ -R ₁ -heterocyclic quaternary ammonium is N ⁺ -R ₁ -azolium, N ⁺ -R ₁ -azinium, or N ⁺ -R ₁ R ₂ -piperazini It may be piperazinium.

The N ⁺ -R ₁ - Ah sleepiness is N ⁺ -R ₁ - can be a tri-O sleepiness (triazolium) - imidazolium diamond (diazolium) or N ⁺ -R _1. The N ⁺ -R ₁ - imidazolium diamond is to N ⁺ -R ₁ represented by formula 2-1 may be a pyrazolyl imidazolium-imidazolidin N ⁺ -R ₁ represented by the following Formula 2-2 or sleepiness. The N ⁺ -R ₁ -triazolium may be represented by the following formula 2-3.

In Formulas 2-1 and 2-2, R _a may be an alkylene group having 1 to 16 carbon atoms, and Y _a may be a cyan group, a halogen, a hydroxy group, or an amine group. In Formula 2-3, R _a1 and R _a2 may be an alkylene group having 1 to 16 carbon atoms regardless of each other, and Y _a1 and Y _a2 may be a cyan group, a halogen, a hydroxyl group, or an amine irrespective of each other.

The alcohol may be ethyl alcohol. The water and the alcohol may have a volume ratio of 1: 0.03 to 1: 0.7. The diacetylene monomer may be contained at a concentration of 50 ~ 300 mM.

Another aspect of the present invention to achieve the above technical problem provides a moisture-test paper (moisture-test paper). The moisture test paper is provided with a paper substrate in which cellulose fibers are irregularly entangled. A polydiacetylene region having hydrochromic polydiacetylene represented by the following Chemical Formula 3 is disposed on the paper substrate.

[Formula 3]

In Formula 3, a, b, c, d, L, R +, and X ^- is of the formula 1 a, b, c, d , L, R +, and X ^- and the like, respectively.

The polydiacetylene region may represent blue. The polydiacetylene region may be water discolored at about 20 degrees (° C.) or more. The paper substrate may be an exposed -OH group of the cellulose fiber. The moisture test paper may be a pores mapping paper.

Another aspect of the present invention to achieve the above technical problem provides a method for producing a moisture test paper. First, printing is performed using the aqueous ink containing the diacetylene monomers of the formula (1) on a paper substrate in which cellulose fibers are irregularly entangled. The ink printed on the paper substrate is dried to form a diacetylene region in which the diacetylene monomers are self-assembled and disposed. Ultraviolet or gamma rays are irradiated onto the die acetylene region to photopolymerize the die acetylene monomers to form hydrochromic polydiacetylene.

The paper substrate may be an exposed -OH group of the cellulose fiber. The moisture test paper may be a pores mapping paper.

As described above, according to the present invention, as the diacetylene monomer is provided with a quaternary ammonium cation, it may be dissolved in a mixed solvent of water and ethanol to obtain an aqueous ink. In addition, the quaternary ammonium of the diacetylene monomer interacts with the cellulose fiber of the paper substrate to provide excellent binding to the paper substrate, thereby preventing the diacetylene monomer or polydiacetylene formed by photopolymerization thereof from being detached from the paper substrate. Can be. In addition, polydiacetylene may have a reduced sensitivity to humidity.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a schematic diagram showing the moisture test paper according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing the moisture test paper according to another embodiment of the present invention.

FIG. 3 is a schematic diagram showing water discoloration of the water test paper shown in FIG. 2.

Figure 4 is a schematic diagram showing the results of adding moisture to the test paper and the selected region prepared in accordance with an embodiment of the present invention.

5 is a graph showing a) UV-vis absorption spectrum, b) fluorescence emission spectrum, c, d) Raman spectrum before and after adding water to a water test paper prepared according to the water test paper preparation example.

FIG. 6 is a photograph showing a reaction according to a temperature of a moisture test paper prepared according to a moisture test paper preparation example, and solubility of water in DA-1 according to temperature.

Figure 7 is a photograph showing the degree of water discoloration according to the relative humidity of the moisture test paper prepared according to the moisture test paper production example.

8 is a photograph showing the water discoloration characteristics of the water test paper according to the water test paper production example (b) and the water test paper comparative example (a).

9 is a photograph showing an optical image and a fluorescence image after the thumb contact on the moisture test paper prepared according to the moisture test paper production example.

FIG. 10 shows fluorescence images obtained after contacting the same thumb on four different moisture test papers prepared according to a water test paper preparation example.

FIG. 11 is a photograph comparing latent fingerprints obtained using ninhydrin from a thumb such as a fluorescence image obtained after contacting a thumb on a water test paper prepared according to a water test paper preparation example.

12 is a threshold image (a-2) in which only the pores are exposed using the position tracking method of the pore distribution map (a-1) obtained using the moisture test paper prepared according to the example of the preparation of the moisture test paper; In addition, it is a threshold (b-2) image in which only the pores are exposed by using the pore distribution (b-1) and position tracking of the same finger obtained using ninhydrin.

13 is a result of the pores distribution test of the entire palm using a water test paper.

14 is a result of the pores distribution test of the sole using a moisture test paper.

Fig. 15 shows results of pores distribution test on the back using a moisture test paper.

16 is a photograph showing the thumb pores distribution test results of the A4 paper, kent paper, OHP film, and PET film, the ink is printed according to the ink preparation example.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to describe the present invention in more detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. In the figures, where a layer is said to be "on" another layer or substrate, it may be formed directly on the other layer or substrate, or a third layer may be interposed therebetween. In the present embodiments, "first", "second", or "third" is not intended to impose any limitation on the components, but should be understood as a term for distinguishing the components.

As used herein, unless otherwise defined, "alkyl" refers to an aliphatic hydrocarbon group and may be "saturated alkyl" that does not include a double bond or a triple bond. Saturated alkyl groups can be linear.

As used herein, unless otherwise defined, "alkylene" refers to a divalent group which is a radical of an alkane which is saturated hydrocarbon, and may be linear alkylene.

In the present specification, when " carbon number X to carbon number Y ", the case having the number of carbon atoms corresponding to all integers between carbon number X and carbon number Y should also be interpreted as being described together.

As used herein, "halogen" or "halo" is an element belonging to Group 17, specifically, it may be a fluorine, chlorine, bromine, or iodine group.

In the present specification, when "X to Y" is described, the number corresponding to all integers between X and Y should be interpreted as being described together.

Diacetylene Monomer

One embodiment of the present invention provides a diacetylene monomer as shown in the following formula (1).

[Formula 1]

In Formula 1, a may be an integer of 1 to 20. As an example, a may be an integer of 6 to 18, specifically 10 to 12. b may be an integer from 1 to 20. As an example, b may be an integer of 2 to 12, specifically 2 to 8.

L is

,

,

,

, or

And E, E ₁ , and E ₂ may be O or S irrespective of each other. c may be an integer from 0 to 2. As an example, c may be 1. d may be an integer of 1 to 10, for example 1 to 5, specifically 2 to 4.

In addition, R ⁺ is a quaternary ammonium group, and the quaternary ammonium may be, for example, N ⁺ -R ₁ -heterocyclic quaternary ammonium represented by the following Formula 2a.

[Formula 2a]

In Formula 2a, Ring B may be a 5-membered or 6-membered heterocyclic compound, a saturated or unsaturated heterocyclic compound, at least one N, specifically 1 to N of 3 and 0 of 0 may be provided as a hetero member. In addition, in Formula 2a, R ₁ may be cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms. Specifically, R ₁ may be represented by * -R _a -Y _a , wherein * is a bond, and R _a is an alkylene group having 1 to 16 carbon atoms as an example, 1 to 6 carbon atoms specifically, 1 to 3 carbon atoms May be an alkylene group, and Y _a may be _a cyan group, a halogen, a hydroxy group, or an amine group.

[Formula 2b]

[Formula 2c]

Formula 2b is * -N ⁺ -R ₁ -heterocyclic quaternary ammonium, ring C is a 5-member or 6-membered unsaturated heterocyclic compound, it may be provided with N of 2 to 3 as a hetero member.

In Formula 2c, Ring D is a 5-membered or 6-membered unsaturated heterocyclic compound, and may have N of 2 to 3 as a hetero member. In addition, R ₁ and R ₁ ′ may be cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms, irrespective of each other. And * -R _a -Y _a . R _a and Y _a may be as defined above.

The N ⁺ -R ₁ -heterocyclic quaternary ammonium is, for example, N ⁺ -R ₁ -azolium, N ⁺ -R ₁ -azinium, or N ⁺ -R ₁ R ₂ It may be piperazinium.

The N ⁺ -R ₁ - Ah sleepiness is N ⁺ -R ₁ - can be a tri-O sleepiness (triazolium) - imidazolium diamond (diazolium) or N ⁺ -R _1. N ⁺ -R ₁ - imidazolium diamond is N ⁺ -R ₁ - imidazolium (imidazolium), or N ⁺ -R ₁ - pyrazol may be sleepiness (pyrazolium), the N ⁺ -R ₁ - imidazolium has the formula It may be represented by 2-1, the N ⁺ -R ₁ -pyrazolium may be represented by the formula 2-2. On the other hand, N ⁺ -R ₁ -triazolium can be represented by the following formula 2-3.

The N ⁺ -R ₁ - Ah Genie Titanium is N ⁺ -R ₁ - can be a help pyrazol Genie (pyrazinium) - pyrimidinyl minyum (pyridiminium) or N ⁺ -R _1. N ⁺ -R ₁ -pyrimidinium may be represented by the following Chemical Formula 2-7 or 2-8, and N ⁺ -R ₁ -pyrazinium may be represented by the following Chemical Formula 2-9.

N ⁺ -R ₁ R ₂ -piperazinium may be * -N ⁺ -R ₁ R ₂ -piperazinium, which may be represented by the following formula (2-14).

In Formulas 2-1 to 2-3, 2-7 to 2-9, and 2-14, R _a and Y _a are as described above, and R _a1 and R _a2 have 1 to 16 carbon atoms regardless of each other. Alkylene group as an example may be an alkylene group having 1 to 6 carbon atoms specifically, Y _a1 and Y _a2 may be a cyan group, a halogen, a hydroxyl group, or an amine group irrespective of each other. R _b may be an alkylene group having 1 to 16 carbon atoms, for example, an alkylene group having 1 to 6 carbon atoms, and Y _b may be hydrogen, a cyan group, a halogen, a hydroxyl group, or an amine group. .

The die acetylene monomer may further contain a counter anion (counter anion). The counter anion (X ^-) is ^{^{^{F -, Cl -, Br -}}} , I -, PF 6 -, BF 4 -, Tf 2 N - (bis (trifluoromethane) sulfonimide), TfO - (trifluoromethanesulfonate), SCN -, or CH ₃ COO ^- may be.

As such, the diacetylene monomer may exhibit amphiphilicity by containing a quaternary ammonium group at one end of an aliphatic hydrocarbon chain. The quaternary ammonium group may improve the water solubility of the diacetylene monomer exhibiting the amphiphilic property, thereby facilitating dissolution in water in a polar protic solvent specifically. In other words, the diacetylene monomer may be water soluble as a whole. Furthermore, solubility can be further improved when R ₁ bonded to N ⁺ of the quaternary ammonium device is * -R _a -Y _a , ie cyanoalkyl, haloalkyl, hydroxyalkyl, or aminoalkyl.

Water-based ink for printing paper with a diacetylene monomer

The aqueous ink according to one embodiment of the present invention may contain the above-described diacetylene monomer and a solvent. The solvent may be a polar protic solvent. The polar protic solvent may be water, alcohol or a combination thereof. As one example, the solvent may be a mixture of water and alcohol. The alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. As an example, the alcohol may be methyl alcohol, ethyl alcohol or ethylene glycol.

The water and the alcohol may have a volume ratio of 1: 0.03 to 1: 0.7, for example, a volume ratio of 1: 0.1 to 1: 0.5 and more specifically 1: 0.2 to 1: 0.3. In addition, the diacetylene monomer may be contained at a concentration of 50 ~ 300 mM.

As described above, the diacetylene monomer may be dissolved in the polar protic solvent as it includes a quaternary ammonium cation. Therefore, the ink may be a homogeneous solution in which the diacetylene monomer is dissolved in the solvent, specifically, the die acetylene monomer in the ink may not have a self-assembled form such as micelles. In addition, the ink may exhibit transparent colorlessness.

Specifically, when the diacetylene monomer is mixed with water, gelation may occur. Thus, the alcohol can be added to prevent gelation to obtain the homogeneous solution. In other words, the alcohol may further improve the solubility of the diacetylene monomer to lower the viscosity of the ink. Such a homogeneous solution of ink can greatly reduce the clogging phenomenon of the cartridge when printing after input to the ink cartridge.

In addition, the ink may not contain a surfactant. Furthermore, it may contain only the diacetylene monomer and the solvent.

Test paper with ink containing diacetylene monomer

Referring to FIG. 1, a paper substrate 100 may be provided. The paper substrate 100 is an entangled cellulose fiber, and may be an uncoated paper whose surface is not coated with paint or the like among various kinds of paper substrates. Furthermore, it may be a printing paper that can be used in a printer, specifically, an uncoated printing paper. However, the present invention is not limited thereto, and in particular, any surface can be used as long as the paper substrate 100 has a -OH functional group exposed on the surface thereof.

The DA acetylene region in which the diacetylene monomers are disposed on the paper substrate 100 may be located. The DA region 200 may be a region to which the ink containing the above-described die acetylene monomer is applied, specifically, a region where the solvent is dried after the ink is applied. At this time, the coating may be performed using an inkjet printer after injecting the ink into the cartridge. On the other hand, the shape of the DA area 200 is not limited to what is shown, it is natural that the user can print as desired.

In the DA region 200, the diacetylene monomers may exist in a self-assembled state. Specifically, the quaternary ammonium cation group (R +) may be disposed adjacent to the cellulose fiber exposed to the hydrophilic functional group, specifically the OH group, and the aliphatic hydrocarbon chain including the diacetylene group may be self-assembled on the cellulose fiber while being disposed outward. . However, it is not limited to this theory. However, while partially adsorbed on the cellulose fiber, it may be present in the partial aggregation and self-assembly.

The DA area 200 may be a colorless transparent area. However, the DA area 200 may be converted to blue by ultraviolet irradiation described later. Therefore, the DA layer 200 may be used as a pattern for determining whether the forgery, and the test paper having the DA layer 200 may be used as a test paper with a forgery determination pattern, for example, a bill. have.

Polydiacetylene Moisture-test paper with regions containing

Referring to FIG. 2, a polydiacetylene region, ie, a PDA region 300, on which a polydiacetylene is disposed on a paper substrate 100 may be located.

Specifically, the DA region 200 of the test paper described with reference to FIG. 1 is self-assembled and disposed adjacently by irradiating ultraviolet rays, specifically, 254 nm ultraviolet rays, or gamma rays, for 1 to 300 seconds. Diacetylene monomers may be photopolymerized to form the PDA region 300 containing polydiacetylene.

The polydiacetylene may have a repeating unit represented by the following Formula 3.

[Formula 3]

In Formula 3, a, b, c, d, L, R +, and X ^- is of the formula 1 a, b, c, d , L, R +, and X ^- it may be the same with each.

The PDA region 300 exhibits a maximum absorption wavelength at about 600 nm to 680 nm, specifically about 620 nm to 660 nm, for example about 640 nm, indicating blue, which is a double and This is because it has a highly π-conjugated backbone due to triple bonds.

On the other hand, the hydrophilic functional group of cellulose and the quaternary ammonium cation group (R +) of polydiacetylene in the ink can have a hydrophilic-hydrophilic interaction, so that the PDA region 300 is not easily detached from the paper substrate 100. Stable bond strength.

Referring to FIG. 3, when water comes into contact with the PDA region 300, the polydiacetylene is geometrically deformed, so that the π-conjugated main chain structure is decomposed, and the maximum absorption wavelength of the PDA region 300 is about 490 to 490. Blue shift to about 590 nm, specifically 520 to about 570 nm, as an example 540 nm. As a result, the PDA region 300 in contact with water may exhibit a reddish color. At the same time, the PDA region 300 may generate fluorescence. Accordingly, the polydiacetylene may be referred to as a water color change agent. Specifically, when water is in contact with the PDA region 300, it is presumed that the polyacetylacetylene is geometrically deformed due to the formation of voids while the diacetylene monomer remaining as a monomer without forming a polymer is dissolved in water. However, it is not bound to this theory.

As such, the paper having the PDA area 300 according to an embodiment of the present invention exhibits a color change by contact with moisture (liquid or gas), and thus may serve as a moisture sensor specifically as a moisture test paper. have. In detail, the moisture test paper may be used to sense humidity or moisture in an organic solvent. Furthermore, the moisture test paper or the PDA can be discolored from blue to red even by a very small amount of moisture from the pores, and can be used as a pores mapping paper. Specifically, it is possible to effectively map the pores of the entire body area, such as palms, soles, back, face, as well as fingers, thereby expanding the application field of the existing technology. In this way, it is possible to analyze the biological information such as the distribution of the pores of the body, it can be used in the medical field, beauty field, or criminal investigation field. Specifically, it may be used in the medical field, such as active pores distribution analysis or analysis of age-specific pores activity of hyperhidrosis patients, the cosmetic field for the development of deodorant or sweat inhibitors, and the field of criminal investigation through analysis of the pores map of fingerprints.

On the other hand, when the water test paper or the polydiacetylene is at a specific temperature or more, specifically about 20 degrees (° C.) or more, for example, 25 degrees (° C.) or more, color change may be caused by contact of moisture. Furthermore, when it is 30 degrees C or more, a vivid color change can be exhibited by contact of moisture. This may mean that while the moisture test paper is insensitive to moisture contained in the atmosphere, sensitivity to moisture secreted from the human body may be selectively improved.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

<< 다이아세틸렌Diacetylene 단량체 Monomer 합성예들Synthesis Examples >>

Synthesis Example 1: DA-1 [3- ( Cyanomethyl ) -1- (3- ( pentacosa -10,12- diynamido ) propyl) -1H-imidazol-3-ium bromide]

In 20 mL of methylene chloride, PCDA (10,12-pentacosadiynoic acid, 0.75 g, 2 mmol), N-hydrosuccinimide (NHS, 0.35 g, 3 mmol), EDC (1-ethyl-3- (3-dimethylaminopropyl) ) carbodiimide, 0.77 g, 4 mmol) was dissolved at room temperature overnight. Thereafter, the mixture was concentrated in vacuo, and the residue was dissolved in ethyl acetate again, and the solution was separated with a separatory funnel with water to obtain an organic solution layer. The organic solution was dehydrated and concentrated in vacuo to give white powdery PCDA-NHS (2,5-dioxopyrrolidin-1-yl pentacosa-10,12-diynoate). The PCDA-NHS (0.94 g, 2 mmol) and triethylamine (TEA, 0.51 g, 5 mmol) were dissolved in 10 ml of methylene chloride to obtain a first solution, and in 10 ml of methylene chloride in the first solution. A second solution obtained by dissolving 1- (3-aminopropyl) imidazole (1- (3-aminopropyl) imidazole, 0.38 g, 3.00 mmol) was added thereto, followed by stirring at room temperature overnight. After that, it was concentrated in vacuo to give a residue, which was put into silica gel column chromatography (methylene chloride / methanol, 96/4) to give N- (3- (1H-imidazole) as a white solid. -1-yl) propyl) pentacosa-10,12-diyneamide (N- (3- (1H-imidazol-1-yl) propyl) pentacosa-10,12-diynamide, 0.77 g, 80%) was obtained. .

N- (3- (1H-imidazol-1-yl) propyl) pentacosa-10,12-diyneamide (0.70 g, in 20 ml of acetonitrile containing bromoacetonitrile (0.28 g, 2.32 mmol) 1.45 mmol) was added and refluxed with stirring overnight. After that, it was concentrated in vacuo to give a solid, which was washed three times with hexane to give DA-1 (0.75 g, 86%) as a yellowish powder. mp: 89 ° C., IR (KBr, cm ⁻¹ ): ν max 611, 624, 652, 719, 757, 860, 927, 1022, 1168, 1382, 1423, 1453, 1467, 1538, 1642, 1651, 2267, 2849, 2919, 3070, 3094, 3255, 3358. 1 H NMR (600 MHz, dimethyl sulfoxide- d 6, δ): 9.39 (s, 1H), 7.96 (t, J = 6 Hz, 1H), 7.95 (t , J = 1.8 Hz, 1H), 7.93 (t, J = 1.8 Hz, 1H), 5.63 (s, 2H), 4.22 (t, J = 6.6 Hz, 2H), 3.05 (q, J = 6 Hz, 2H ), 2.26 (t, J = 7.2 Hz, 4H), 2.06 (t, J = 7.8 Hz, 2H), 1.92 (quint, J = 6.6 Hz, 2H), 1.50-.40 (m, 6H), 1.30- .23 (m, 26H), 0.85 (t, J = 7.2 Hz, 3H); 13 C NMR (75 MHz, CDCl 3, δ): 174.82, 137.88, 123.53, 123.22, 114.08, 65.50, 65.44, 48.29, 38.71, 36.70, 35.77, 32.14, 29.88, 29.86, 29.72, 29.58, 29.34, 29.24, 29.11 , 28.60, 26.04, 22.92, 19.44, 14.37.

Synthesis Example 2: DA-2 [3- ( Cyanomethyl ) -1- (3- ( tricosa -10,12- diynamido ) propyl ) -1H-imidazol-3-ium bromide]

Dissolve TCDA-NHS (2,5-dioxopyrrolidin-1-yltricosa-10,12-diynoate, 0.89 g, 2.00 mmol) and TEA (0.41 g, 4 mmol) in 10 mL of methylene chloride to obtain a first solution. A second solution obtained by dissolving 1- (3-aminopropyl) imidazole (1- (3-aminopropyl) imidazole, 0.38 g, 3.00 mmol) in 10 ml of methylene chloride was added thereto, followed by stirring at room temperature overnight. After that, it was concentrated in vacuo to give a residue, which was put into silica gel column chromatography (methylene chloride / methanol, 96/4) to give N- (3- (1H-imidazole) as a white solid. -1-yl) propyl) tricosa-10,12-dyinamide (N- (3- (1H-Imidazol-1-yl) propyl) tricosa-10,12-diynamide, 0.74 g, 82%) was obtained. .

N- (3- (1H-imidazol-1-yl) propyl) tricosa-10,12-diyneamide (0.32 g, in 20 ml of acetonitrile containing bromoacetonitrile (0.13 g, 1.06 mmol) 0.70 mmol) was added and refluxed with stirring overnight. Thereafter, the mixture was concentrated in vacuo to obtain a solid, which was washed three times with hexane to obtain DA-2 (0.33 g, 83%) as a yellowish powder. IR (KBr, cm ^-1 ): ν max 611, 624, 651, 721, 758, 859, 927, 1022, 1168, 1383, 1423, 1454, 1466, 1538, 1642, 1652, 2266, 2850, 2921, 3072 , 3093, 3255, 3350. 1 H NMR (600 MHz, dimethyl sulfoxide- d 6, δ): 9.38 (s, 1H), 7.95 (t, J = 6 Hz, 1H), 7.94 (t, J = 1.8 Hz , 1H), 7.92 (t, J = 1.8 Hz, 1H), 5.62 (s, 2H), 4.22 (t, J = 7.2 Hz, 2H), 3.05 (q, J = 6.6 Hz, 2H), 2.26 (t , J = 7.2 Hz, 4H), 2.06 (t, J = 7.2 Hz, 2H), 1.92 (quint, J = 6.6 Hz, 2H), 1.50-.40 (m, 6H), 1.30-.24 (m, 22H), 0.85 (t, J = 7.2 Hz, 3H); 13 C NMR (75 MHz, dimethyl sulfoxide-d 6, δ): 173.12, 138.19, 123.87, 123.42, 115.42, 66.02, 47.87, 37.63, 36.08, 35.78, 31.99, 30.34, 29.58, 29.36, 29.09, 28.92, 28.87, 28.43, 28.39, 25.90, 22.79, 18.97, 14.65.

Synthesis Example 3: DA-3 [3- ( Cyanomethyl ) -1- (3- ( heptadecaa -4,6- diynamido ) propyl) -1H-imidazol-3-ium bromide]

Dissolve the HDDA-NHS (2,5-dioxopyrrolidin-1-ylheptadeca-4,6-diynoate, 0.72 g, 2.00 mmol) and TEA (0.41 g, 4 mmol) in 10 ml of methylene chloride to obtain a first solution. To 1 solution, a second solution obtained by dissolving 1- (3-aminopropyl) imidazole (0.38 g, 3.00 mmol) in 10 ml of methylene chloride was added, followed by stirring at room temperature overnight. After that, it was concentrated in vacuo to give a residue, which was added to silica gel column chromatography (methylene chloride / methanol, 96/4) to give N- (3- (1H-imidazole-) as a yellow liquid. 1-yl) propyl) heptadeca-4,6-diyneamide (N- (3- (1H-Imidazol-1-yl) propyl) heptadeca-4,6-diynamide, 0.57 g, 77%) was obtained.

N- (3- (1H-imidazol-1-yl) propyl) heptadeca-4,6-diyneamide (0.26 g, in 20 ml of acetonitrile containing bromoacetonitrile (0.13 g, 1.06 mmol) 0.70 mmol) was added and refluxed with stirring overnight. After that, it was concentrated in vacuo to give a solid, which was washed three times with hexane to give DA-3 (0.29 g, 85%) as a yellowish powder. IR (KBr, cm ^-1 ): ν max 610, 623, 720, 758, 859, 927, 1024, 1167, 1380, 1424, 1453, 1466, 1543, 1650, 2267, 2850, 2920, 3066, 3095, 3222 , 3324. 1 H NMR (600 MHz, CDCl 3, δ): 10.09 (s, 1H), 8.04 (s, 1H), 7.78 (s, 1H), 7.76 (t, J = 5.4 Hz, 1H), 6.04 (s, 2H), 4.46 (t, J = 6 Hz, 2H), 3.27 (d, J = 4.2 Hz, 2H), 2.59 (t, J = 7.2 Hz, 2H), 2.50 (t, J = 7.2 Hz , 2H), 2.23-.16 (m, 4H), 1.48 (quint, J = 7.8 Hz, 2H), 1.34-.24 (m, 14H), 0.86 (t, J = 6.6 Hz, 3H); 13 C NMR (75 MHz, CDCl 3, δ): 172.20, 137.83, 123.33, 123.27, 114.09, 66.16, 65.23, 48.17, 38.71, 35.86, 34.77, 32.05, 29.84, 29.75, 29.68, 29.47, 29.28, 29.11, 28.54 , 22.83, 19.38, 15.84, 14.28.

Synthesis Example 4: DA-4 [3- ( Cyanomethyl ) -1- (3- ( pentacosa -10,12- diynamido ) propyl) -1H-imidazol-3-ium chloride]

DA-4 was obtained by the same method as Synthesis Example 1 except that chloroacetonitrile was used instead of bromoacetonitrile. 1 H NMR (600 MHz, CDCl 3, δ): 10.32 (s, 1H), 7.92 (t, J = 3 Hz, 1H), 7.79 (t, J = 6 Hz, 1H), 7.74 (t, J = 1.8 Hz , 1H), 6.01 (s, 2H), 4.40 (t, J = 6.6 Hz, 2H), 3.22 (q, J = 6 Hz, 2H), 2.24-2.20 (m, 6H), 2.12 (t, J = 7.8 Hz, 2H), 1.57-1.46 (m, 6H), 1.34-1.23 (m, 26H), 0.85 (t, J = 7.2 Hz, 3H).

<잉크 Ink 제조예Production Example >>

DA-1 was dissolved in distilled water to obtain an aqueous DA-1 solution (100 × 10 ⁻³ M), and ethanol (20 vol% based on distilled water) was added thereto to dilute the ink to prepare an ink.

<수분 시험지(moisture-test <Moisture-test paperpaper ) ) 제조예Production Example >>

Black ink was removed from the inkjet cartridge (HP 703) and the cartridge was washed with ethanol and water and dried with nitrogen purge. The ink prepared in the ink preparation example was placed in the cartridge, and an arbitrary image was printed on A4 paper using an inkjet printer (HP deskjet Ink Advantage K209g), followed by drying at room temperature for at least 1 minute. The image immediately after printing was not seen, and a blue image appeared by 30 seconds of UV irradiation (254 nm, 1 mWcm ⁻² ). This blue image may mean that polydiacetylene is formed.

<수분 시험지 <Moisture test paper 비교예Comparative example >>

Dissolve 0.750 g of CsOH in Di-water (diionized water), then dissolve 1.87 g of PCDA (10,12-pentacosadiynoic acid) in 9.6 mL of THF (tetrahydrofuran, tetrahydrofuran) and then dissolve the CsOH solution in PCDA Drop by drop and mix. The solution composition obtained by stirring for 1 hour to mix evenly was put in a cartridge, printed on A4 paper using an inkjet printer (HP deskjet Ink Advantage K209g), and dried at room temperature for at least 1 minute. Did not show an image of the print immediately after UV irradiation for 30 seconds ^- by (254 nm, 1 mWcm ²⁾ was a blue image. This blue image may mean that polydiacetylene is formed.

Figure 4 is a schematic diagram showing the results of adding moisture to the moisture test paper and the selected region prepared according to the moisture test paper production example.

Referring to FIG. 4, the ink according to the ink preparation example was printed on an A4 sheet based on an original image, but the printed image (DA-1 printing) was colorless and transparent and was not visually confirmed. . After 30 seconds of UV ^{irradiation-have} appeared blue color image having different gray scale by ^{(254 nm, 1 mWcm 2)} (UV irradiation). Such a blue image may mean that polydiacetylene is formed, and different gray scales of the image may mean that concentrations of polydiacetylene are different in the printed area. Thereafter, water was printed on a region corresponding to the red color of the original image at room temperature. As a result, the corresponding area was changed to red to generate a red-water image (water-jet printing image), and the non-water-printed area retained the previous blue color image. The red image may mean that distortion occurs in the main chain of the polydiacetylene. The gray scale of the red image may also mean that the application amount of water is different.

Referring to FIG. 5A, it can be seen that the maximum absorption wavelength before moisture exposure is shifted to about 540 nm (red) after exposure to moisture at about 640 nm (blue). This may mean that distortion occurs in the main chain of polydiacetylene.

Referring to FIG. 5B, when the test paper was irradiated with 488 nm excitation light, fluorescence was not generated before the water exposure, but after the water exposure, the fluorescence emission band appeared at 550 nm.

Referring to FIG. 5C, after the water exposure, the 2079 and 1452 cm ^-1 bands corresponding to the alkyne-alkene bands are shifted to the 2120 and 1515 cm ^-1 bands, respectively. .

Referring to FIG. 5D, looking at the CC stretching regions associated with the structure of the aliphatic alkyl chains, a strong Raman band at 1081 cm ⁻¹ and two weak bands at 1105 and 1126 cm ⁻¹ appeared before moisture exposure. This corresponds to alkyl chains having all-trans form. However, after moisture exposure, all three bands disappeared and one main band appeared at 1068 cm ⁻¹ . From this, it can be seen that before the moisture exposure, the all-trans CC form is converted into a gauche form.

From the results of FIGS. 5C and 5D, it can be estimated that not only the twisting of the main chain but also the morphological change of the aliphatic alkyl chain occurs after the water exposure. From this it was speculated that the effective pi-orbital superposition was interrupted, resulting in a transition from blue to red.

Referring to FIG. 6A, the color change did not appear when the blue polydiacetylene region was rubbed with ice. However, when the finger of the experimenter was contacted with the ice contacted region, the color change to red was clear.

Referring to FIG. 6B, after drawing a circle with 0 degree cold water on the blue polydiacetylene region, when the temperature was raised, a red circle was observed at about 20 degrees, and the red color became clear at 25 and 30 degrees. .

FIG. 6C shows that when a sample in which DA-1 is put in water is placed in a plastic bag and then placed on a paper printed with A, and the temperature is increased, the lower portion of A begins to be visible from about 20 degrees to 25 degrees and 30 degrees. A became clear.

Referring back to FIG. 6, it can be inferred that unpolymerized diacetylene remaining in the polydiacetylene region is insoluble in water, causing main chain distortion of the polydiacetylene to induce water discoloration from blue to red.

Figure 7 is a photograph showing the degree of water discoloration according to the relative humidity of the moisture test paper prepared according to the moisture test paper production example. Specifically, the degree of water discoloration in a state exposed to a specific relative humidity for 30 minutes is shown.

Referring to FIG. 7, the moisture test paper prepared according to the moisture test paper preparation example did not discolor even when exposed for 30 minutes at a relative humidity of 20 to 95%. However, when exposed to 100% relative humidity, it turned red. From this, it can be seen that the water test strip according to the present embodiment is water discolored only when directly exposed to water without being greatly affected by the humidity of the surrounding environment.

Referring to FIG. 8, the test paper according to the moisture test paper comparative example (a) is not discolored by water, but the test paper according to the moisture test paper manufacturing example (b) is discolored by water. From this, it can be seen that the polyacetylacetylene formed from the diacetylene monomer having a quaternary ammonium ion at the terminal represented by Formula 1 specifically the diacetylene monomers according to the present embodiments is characterized by a characteristic of water discoloration.

<땀구멍 <Pores 매핑(sweat pore mapping)예Example of a pore mapping >>

Fingertips, palms, and / or soles were gently contacted on the water test paper according to the water test paper preparation example.

9 is a photograph showing an optical image and a fluorescence image after the thumb contact on the moisture test paper prepared according to the moisture test paper production example. Fluorescence microdots showing sweat-secreting active pores were analyzed using a fluorescence spectrometer (510-550 nm excitation).

Referring to FIG. 9, it can be seen from the optical image on the left that the red dots corresponding to the pores were generated by the minute amount of sweat discharged from the pores in the blue polydiacetylene paper film. can do.

In the fluorescence image on the right side, it is also possible to analyze the pore distribution by obtaining the red fluorescence image expressed by sweat at each pore position.

Referring to FIG. 10, the results of confirming the reliability of the analysis of the pore distribution using hydrochromic polydiacetylene through the position of the four pore distribution maps superimposed well.

Referring to FIG. 11, when the two images were compared and compared, it was confirmed that the pores observed on the water test paper and the latent fingerprint obtained through ninhydrin were very well matched.

Referring to FIG. 12, it can be seen that the position of the pores is also well matched in the image from a-3 and b-3, which analyzes whether the two pores are identical by using a computer program.

Referring to Figure 13, a is a photograph of a water test paper having a palm-shaped image obtained in the water test paper manufacturing example, b is the distribution of pores (fluorescence) of the entire palm hole obtained after lightly pressing the palm on the produced water test paper. . The red dots of b are all sweat spots in the palms of the palm of the hand, and the color change and fluorescence of hydrochromic polydiacetylene can be used for analyzing the distribution of the pores. b-1 shows an enlarged portion of the palm under the thumb, showing the effective distribution of pores.

Referring to FIG. 14, a is a photograph of the sole, and b is a distribution of pores (optics) of the entire sole of the foot obtained after pressing the water test paper obtained in the moisture test paper manufacturing example with the sole of the foot. It can be seen that there are red dots along the shape of the sole of the film, which are the positions where color changes and fluorescence of the water-discolored polydiacetylene due to sweating out of the pores of the sole of the foot. c is an enlargement of the heel portion of the sole, showing that the distribution of pores can be effectively obtained.

Referring to FIG. 15, the position of the pores in which the color change and fluorescence of the hydrochromic polydiacetylene may be confirmed.

Referring back to Figures 13, 14, and 15, although there may be differences depending on the amount of sweat coming out of the pores from which sweat occurs regardless of the body part using a hydrochromic polydiacetylene paper film, that is, a moisture test paper. All can analyze the pore distribution.

FIG. 16 is a thumb pores distribution test after a water test film was made of A4 paper, kent paper, OHP film, and PET film printed with ink according to an ink preparation example by UV irradiation (254 nm, 1 mWcm ^- ² ) for 30 seconds. Photo shows the result. Specifically, the image is observed through a fluorescence microscope after contacting the bottom of the thumb for about 1 second on each substrate.

Referring to FIG. 16, it can be seen that the ink according to the ink preparation example can produce a water test film exhibiting water discoloration characteristics by a small amount of water discharged through the pores on all substrates.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. This is possible.

Claims

A diacetylene monomer represented by Formula 1 below; And

Water-based inks containing a mixed solvent of water and alcohol:

[Formula 1]

In Chemical Formula 1,

a is an integer from 1 to 20, b is an integer from 1 to 20, c is an integer from 0 to 2, d is an integer from 1 to 10,

L is
,
,
,
,
,
,
,
, or
E, E 1 , and E 2 are O or S irrespective of each other,

X - is F -, Cl -, Br - , I -, PF 6 -, BF 4 -, Tf 2 N - (bis (trifluoromethane) sulfonimide), TfO - (trifluoromethanesulfonate), SCN -, or CH 3 COO - and ,

R + is N + -R 1 -heterocyclic quaternary ammonium represented by the following Chemical Formula 2a, * is a bond,

[Formula 2a]

In Formula 2a, Ring B is a 5-membered or 6-membered heterocyclic compound having N of 1 to 3 and O of 0 to 1 as a hetero member,

R 1 is cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms.
The method of claim 1,

Of formula 2a N + -R 1 - heterocyclic quaternary ammonium to N + -R 1 shown in formula 2b or 2c to the formula - the water-based ink heterocyclic quaternary ammonium:

[Formula 2b]

[Formula 2c]

In Formula 2b, Ring C is a 5-membered or 6-membered unsaturated heterocyclic compound having N of 2 to 3 as a hetero member,

In Formula 2c, Ring D is a 5-membered or 6-membered unsaturated heterocyclic compound having N of 2 to 3 as a hetero member,

R 1 and R 1 ′ are each independently cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms.
The method of claim 1,

The N + -R 1 -heterocyclic quaternary ammonium is N + -R 1 -azolium, N + -R 1 -azinium, or N + -R 1 R 2 -piperazini Aqueous ink that is piperazinium.
The method of claim 3,

The N + -R 1 - Ah sleepiness is N + -R 1 - in the aqueous ink-trimethyl imidazolium O (triazolium) - imidazolium diamond (diazolium) or N + -R 1.
The method of claim 4, wherein

The N + -R 1 - imidazolium diamond is to N + -R 1 represented by Formula 2-1-imidazolidin N + -R 1 represented by the following Formula 2-2 or imidazolium-aqueous ink-pyrazol sleepiness:

In Formulas 2-1 and 2-2, R a is an alkylene group having 1 to 16 carbon atoms,

Y a is a cyan group, a halogen, a hydroxy group, or an amine group.
The method of claim 4, wherein

The N + -R 1 -triazolium is an aqueous ink represented by the following formula 2-3:

In Formula 2-3, R a1 and R a2 are each independently an alkylene group having 1 to 16 carbon atoms,

Y a1 and Y a2 are a cyan group, a halogen, a hydroxy group, or an amine irrespective of each other.
The method of claim 1,

Wherein the water and the alcohol have a volume ratio of 1: 0.03 to 1: 0.7.
The method of claim 1,

The die acetylene monomer is an aqueous ink contained at a concentration of 50 ~ 300 mM.
Paper substrates in which cellulose fibers are irregularly entangled;

And a polydiacetylene region in which hydrochromic polydiacetylene represented by Formula 3 is disposed on the paper substrate.

[Formula 3]

In Chemical Formula 3,

a is an integer from 1 to 20, b is an integer from 1 to 20, c is an integer from 0 to 2, d is an integer from 1 to 10,

L is
,
,
,
,
,
,
,
, or
E, E 1 , and E 2 are O or S irrespective of each other,

X - is F -, Cl -, Br - , I -, PF 6 -, BF 4 -, Tf 2 N - (bis (trifluoromethane) sulfonimide), TfO - (trifluoromethanesulfonate), SCN -, or CH 3 COO - and ,

R + is N + -R 1 -heterocyclic quaternary ammonium represented by the following Chemical Formula 2a, * is a bond,

[Formula 2a]

In Formula 2a, Ring B is a 5-membered or 6-membered heterocyclic compound having N of 1 to 3 and O of 0 to 1 as a hetero member,

R 1 is cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms.
The method of claim 9,

And the polydiacetylene region is blue.
The method of claim 9,

The polydiacetylene region is a water test paper that is discolored at 20 degrees (° C.) or more.
The method of claim 9,

The paper substrate is a moisture test paper that the -OH group of the cellulose fiber is exposed.
The method of claim 9,

The moisture test paper is a moisture test paper is a pores mapping paper.
Printing using an aqueous ink containing the diacetylene monomers of claim 1 on a paper substrate in which cellulose fibers are irregularly entangled;

Drying the ink printed on the paper substrate to form a diacetylene region in which the diacetylene monomers are self-assembled and disposed; And

Irradiating ultraviolet rays or gamma rays on the die acetylene region to photopolymerize the die acetylene monomers to form a hydrochromic polydiacetylene.
The method of claim 14,

The paper base material is a test paper manufacturing method of the -OH group of the cellulose fiber exposed.
The method of claim 14,

The moisture test paper is a moisture test paper manufacturing method of the pores mapping paper.