JPH03134072A - Ultraviolet-discolorable ink - Google Patents

Abstract

PURPOSE:To improve the stability of ultraviolet discolorability by constituting the title ink of a 1st ink compsn. prepd. by compounding a printing ink vehicle with a photoactivating agent and a 2nd ink compsn. prepd. by compounding a printing ink vehicle with a discolorating agent. CONSTITUTION:A 1st ink compsn. (A) with a viscosity of 100-10,000 cps is obtd. by compounding a printing ink vehicle (a) with a photoactivating agent (b) (e.g. trichloromethyl phenyl sulfone) and, if necessary, an anti-oxidant, a hiding agent, a thickening agent, a color tone modifier, an ultraviolet absorber, etc., (c) and dissolving or dispersing them. Separately, the ingredient (a) is compounded with a discolorating agent (d) (e.g. 3-cyclohexyl-6-chlorofluoran) and the ingredient (c) and they are dissolved or dispersed to obtain a 2nd ink compsn. (B) with a viscosity of 100-10,000 cps. The ingredients A and B are mixed just before use.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention can be applied to a part of an ultraviolet irradiation device to measure its lifespan, to manage secret documents, to record materials, to ink for screen printing, etc. The present invention relates to a two-component separation type ultraviolet color-changing ink that can be used in various fields as various printing inks.

[Prior art and problems to be solved by the invention] Hitherto, there have been almost no ultraviolet measuring means in practical use that can estimate the capacity and lifespan of lighting equipment such as ultraviolet lamps that emit light including ultraviolet rays. Not much is known about the storage management of confidential documents, recording materials, and various printing inks that are colored using ultraviolet light, and only a few hidden inks that use fluorescent coloring are known. It was also not widely used.

The present inventor has previously proposed an ultraviolet color-changing ink containing a photoactivator and a color-changing agent, but it has been found that when the ink is in liquid form, there is still a problem in that the color development stability is not sufficient.

The present invention has been made in view of the above-mentioned circumstances.

Therefore, the purpose of the present invention is to apply ultraviolet rays to a part of the irradiation equipment to measure the lifespan, manage secret documents,
The object of the present invention is to provide an ultraviolet color-changing ink that can be used in various fields as a recording material or various printing inks such as screen printing ink, and has stable ultraviolet color-changing properties.

[Means for Solving the Problems] As a result of study, the present inventor separated the photoactivator and the color-changing agent to create a two-component separation-type ultraviolet color-changing ink that is solid at room temperature or has a specific viscosity. The inventors have discovered that the above object can be achieved by doing so, and have completed the present invention.

That is, the present invention relates to a two-component UV color-changing ink, the first two-component UV color-changing ink having a viscosity of 100% containing a photoactive agent dissolved or dispersed in a printing ink vehicle. A first ink composition of ~10,000 centipoise and a viscosity of 1oo to i containing a color change agent dissolved or dispersed in the printing ink vehicle.
The second ink composition is characterized by having a centipoise of o, ooo centipoise.

A second two-component UV color changing ink comprises a first ink composition containing a photoactive agent dissolved or dispersed in a printing ink solvent, and a viscosity color changing agent containing a color changing agent dissolved or dispersed in a printing ink vehicle. It is characterized by comprising a second ink composition of 100 to 10,000 centipoise.

A third two-component separable UV color-changing ink comprises a first ink composition having a viscosity of 100 to 00 centipoise containing a photoactive agent dissolved or dispersed in a printing ink vehicle, and a first ink composition dissolved or dispersed in a printing ink solvent. The second ink composition contains a color changing agent.

A fourth two-component separable ultraviolet color-changing ink includes a first ink composition containing a photoactive agent dissolved or dispersed in a printing ink vehicle that is solid at room temperature; It is characterized by comprising a second ink composition containing a solid solution or dispersed color change agent.

In addition, in the present invention, "discoloration" means discoloration, that is,
In addition to the case where one color changes to another color, it also includes cases where it means color development or fading.

In the case where the two-component separable ultraviolet color-changing ink of the present invention is liquid at room temperature, when a printing ink vehicle is used in the first ink composition and the second ink composition, the ink compositions have a It is necessary to have a viscosity in the range of 10,000 centipoise, and the preferred viscosity range is 2.000 to 5.000 centipoise. In the present invention, viscosity means a value measured at 25°C using a Brookfield viscometer. When the viscosity of the first ink composition and the second ink composition containing the printing ink vehicle is higher than to, ooo centipoise, the mixing of both ink compositions cannot be carried out well, and printing The ink will not transfer well from the original plate to the printing material. On the other hand, the viscosity is i, oo
If it is lower than o centipoise, the ink will not adhere well to the original printing plate.

Each component used in the present invention will be explained below.

Examples of the photoactive agent used in the first ink composition in the present invention include the following.

Trihalogenomethyl group-containing compounds: for example, tetrabromomethane, p-nitrobenzyl tribromide, bromotrichloromethane, tetrachlorotetrahydronaphthalene, i,i,i-tribromo-2-methyl-2-propatol, trichloroacetamide, etc.

Compound represented by general formula (1): (wherein, R1 represents a substituent, specifically, for example,
Nitro group, halogen atom, alkyl group, haloalkyl group, acetyl group, haloacetyl group, alkylaryl group,
It represents an alkoxy group, etc., and X means 1 to these.

However, when X is 2 or more, both R and R do not need to mean the same substituent. ) For example, 0-nitro-α, α, α-tribromoacetophenone, l-nitro-α, al α-tribromoacetophenone, p-nitro-α, α, α-tribromoacetophenone, α, α, α- Tribromoacetophenone, alpha
, α, α, m-tetrabromoacetophenone, α, α,
α, α′, α′ α′ hexabromo-p-diacetylbenzene, etc.

Compound represented by the general formula (■); R2-5-X (■) (in the formula, R2
represents an alkyl group, an aryl group, or an aryl group having a substituent, and X represents a halogen atom. ) For example, 2,4-dinitrobenzenesulfenyl chloride, 0-nitrobenzenesulfenyl chloride, etc.

Compound represented by general formula (III): /R3 A-C-R4(III) \R5 (wherein A is an optionally substituted heterocyclic compound residue, R3, R4 and R1 are each a hydrogen atom , chlorine atom, bromine atom, but not all of them are hydrogen atoms at the same time.) For example, ω, ω, ω-tribromoquinaldine, 2-ω,
ω, ω-Tribummethyl-4-methylquinoline, ω-promlepidine, 4-phenyl-6-ω, ω, ω-tribromomethylpyrimidine, 2,5-di-tribromomethyl-3,4-dibromothiophene, and the like.

Compounds represented by general formulas (IV) and (V): (IV)
(V) (In the formula, Xl, X2 and X3 are each one selected from a hydrogen atom, a chlorine atom and a bromine atom, but they are not all hydrogen atoms at the same time, and R6 is a substituted or unsubstituted aryl group or heterocyclic residue, or group, X.

Represents C-X2\X3. ) For example, hexabromodimethyl sulfoxide, hexabromodimethyl sulfone, trichloromethyl phenyl sulfone, tribromomethyl phenyl sulfone, 4.6-
dimethylpiILdine-2-tribromomethylsulfone,
Tetrabromodimethylsulfone etc.

The color changing agent used in the second ink composition in the present invention is a compound that changes color due to the action of the free radicals when the above-mentioned photoactive agent generates free radicals under the action of ultraviolet rays. Different color changing agents include those that are originally colorless substances but change to colored due to the action of free radicals, and those that originally have a unique color but change to a different color due to the action of free radicals. Some are bleached.

To give a typical example of the former,
Diphenylamine, dibenzylamine, triphenylamine, N-hydroxyethyl-N-ditylaniline, p
, P'-methylenebis(N,N-diethylaniline)
amine compounds such as leuco crystal violet, leucomalachite green, leuco base of pigments such as leucomethylene blue, 3-diethylamino-7-chlorofluoran, 3-methylamino-6-chlorofluoran,
3-dimethylamino-6-medoxyfluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylaminobenzo(a)-fluorane, 3-diethylamino-6-aminofluorane, 3,6-simethoxy Fluoran compounds such as fluoran, 3-diethylamino-7-sibenzylaminofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, bis(4-diethylamino-2-methylphenyl)phenylmethane, tris(4 -diethylamino-2-methylphenyl)methane, bis(4-dimethylamino-2-methoxyphenyl)
Phenylmethane, bis(4-diethylamino-2-methylphenyl)-(4-diethylaminophenyl)methane, bis(4-diethylamino-2-methylphenyl)
-(3,4-methoxyphenyl)methane, bis(4-dibenzylamino-2-methylphenyl)phenylmethane and other polyarylalkane compounds, ■-phenyl-3-
Examples include compounds such as (p-diethylamino)styryl-5-(p-diethylamino)phenyl-2-pyrazoline.

On the other hand, examples of the latter include various dyes such as diphenylmethane, triphenylmethane, thiazine, oxazine, xanthine, anthraquinone, iminonaphthoquinone, and azomethine. , auramine, Victoria blue, benzoin methylene blue, rhodamine, 4-p-diethylaminophenylimino naphthoquinone, p-methoxybenzoyl-p-
Diethylamino-0-methylphenyliminoacetanilide, l-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and the like can be effectively used.

The printing ink solvent and printing ink vehicle for dissolving, dispersing or solid dissolving the photoactivator and color change agent are as follows:
Conventionally known printing ink solvents and various types of printing ink vehicles can be used, such as evaporative drying type, oxidative polymerization type, thermosetting type, room temperature solid type, etc. Examples of the components that can be used include the following natural resins, naturally processed resins, synthetic resins, waxes, and solvents, which are appropriately selected and used depending on the type of photoactivator and color change agent.

In that case, the first ink composition and the second ink composition are
When they are liquid at room temperature and contain film-forming components, it is necessary to select each component so that the viscosity is within the range of 100 to io, ooo centipoise.

Waxes: carnauba wax, paraffin wax, microcrystalline wax, etc.

Natural resins, naturally processed resins: rosin, maleic acid-modified rosin and other rosin derivatives,
Oil-modified alkyd resins such as shellac, casein, alkyd resins, soybean oil-modified alkyd resins and coconut oil-modified alkyd resins, cellulose derivatives, petroleum resins.

Synthetic resins: Synthetic resin latex such as low molecular weight polyethylene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, vinyl copolymer latex and synthetic rubber latex, amino resin, heat-reactive unsaturated hydrocarbon resin, etc.

Solvents: Machine oil, spindle oil, kerosene and other petroleum solvents, aromatic solvents, alcohols, ketones, esters, water,
Polymerized linseed oil, tung oil, dehydrated castor oil, oitesca oil, etc.

The first and second ink compositions of the present invention may optionally contain antioxidants, hiding agents such as titanium white, zinc oxide, alumina, and aluminum oxide, and thickeners such as silica powder.
Pigments such as carbon black, talc, kaolin, iron oxide, phthalocyanine, and quinacridone, and color tone modifiers such as dyes can also be added.

Furthermore, an ultraviolet absorber can be added to adjust the sensitivity of color change. Examples of the ultraviolet absorber used in the present invention include ultraviolet absorbers that have been commonly used in the past, and specifically, for example, p-aminobenzoic acid derivatives (PABA derivatives), cinnamic acid derivatives, and salicylic acid. Examples include derivatives, camphor derivatives, benzophenone derivatives, urocanic acid derivatives, nitrogen-containing heterocyclic derivatives, and the like.

In the present invention, the blending ratio of the photoactivator, the color change agent, and the ultraviolet absorber added as desired in the ink can be appropriately set depending on the density and color development sensitivity of the printed matter after color development by ultraviolet irradiation. Any prescription can be used.

The two-component separation type ultraviolet color-changing ink of the present invention is used by mixing the first ink composition and the second ink composition immediately before printing. The ultraviolet color-changing ink obtained by mixing can be used in a desired printing method such as intaglio, letterpress, lithographic, stencil, screen, etc.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

Note that all parts in the examples represent parts by weight.

Example 1 Two types of ink compositions having the following compositions were prepared.

First ink composition (photoactivator ink) Trichloromethyl phenyl sulfone 10 parts Ethyl cellulose IO part n-butyl acetate
20 parts xylene
20 parts Viscosity: 2.000 centipoise Second ink composition (color change agent ink) 3-cyclohexyl-6-chlorofluorane 6 parts 2-(2'-
Hydroxy-5'-methylphenyl)benzotriazole 1 part Ethylcellulose
10 parts n-butyl acetate
20 parts xylene 20 parts Viscosity: 2.000 centipoise The above two ink compositions were added immediately before use at a ratio of 1 = 2.
A uniform ultraviolet coloring ink was obtained.

This ultraviolet color-forming ink had suitability as an oil-based screen ink. When screen printing was performed using this ultraviolet color-forming ink, the printed area was initially colorless, but turned orange after being exposed to sunlight for 2 minutes.

Example 2 Two types of ink compositions having the following compositions were prepared.

First ink composition (photoactivator ink) Tribromomethylphenyl sulfone 3 parts Terpene resin 10 parts Toluene
15 parts 4-Methyl-2-pentanone 5 parts Activity: 200 centipoise Second ink composition (color change agent ink) Bis(4-dibenzylamino-2-methylphenyl)phenylmethane 5 parts Terpene resin
10 parts toluene
15 parts 4-methyl-2-pentanone
5 part activity: 200 centipoise The above two types of ink compositions were mixed at a ratio of 1:1 immediately before use to obtain a uniform ultraviolet color-forming ink. This ultraviolet color-forming ink had suitability as an ink for screen printing. When screen printing was performed using this ultraviolet color-forming ink, the printed area was initially colorless, but turned green after being exposed to sunlight for 1 minute.

Example 3 Two types of ink compositions having the following compositions were prepared.

First ink composition (photoactivator ink) Tribromomethylphenylsulfone 5 parts Linseed oil modified alkyd 15 parts Cobalt naphthenate 0.1 part Petroleum-based ink oil (Ink 15 parts Saiil No. 5, manufactured by Nippon Oil Co., Ltd.) Viscosity : 50.000 centipoise Second ink composition (color change agent ink) 3-N-ethyl-N-isopentylamino-6-methyl-7-anilinorfluorane 10 parts Linseed oil modified alkyd 155 parts Petroleum-based ink Oil ink Viscosity: 50,000 centipoise The above two types of ink compositions were mixed in a 1:0 ratio immediately before use.
They were mixed at a ratio of 75:5 to obtain a uniform ultraviolet color-forming ink. This ultraviolet color-forming ink had suitability as an offset ink. When offset printing was performed using this ultraviolet color-forming ink, the printed area was initially colorless, but when irradiated for 10 seconds using four high-pressure mercury lamps with an output of 11.2 and ν, it developed a black color.

Example 4 Two types of ink compositions having the following compositions were prepared.

First ink composition (photoactivator ink) Trichloromethylfuninylsulfone 20 parts acetic acid n-
Butyl 40 parts xylene
40 parts Second ink composition (color change agent ink) 3-cyclohexyl-6-chlorofluorane 6 parts 2-(2'-
Hydroxy-5'-methylphenyl)benzotriazole 1 part Ethylcellulose
50 parts n-butyl acetate
70 parts xylene 70 parts Viscosity: 3.000 centipoise The above two ink compositions were mixed at a ratio of 1:9 immediately before use to obtain a uniform ultraviolet color-forming ink. This ultraviolet color-forming ink had suitability as an oil-based screen ink. When screen printing was performed using this ultraviolet color-forming ink, the printed area was initially colorless, but turned orange after being exposed to sunlight for 2 minutes.

Example 5 Two types of ink compositions having the following compositions were prepared.

First ink composition (photoactivator ink) Trichloromethyl phenyl sulfone 10 parts Ethyl cellulose 10 parts n-butyl acetate
20 parts xylene
20 parts Viscosity: 2.000 centipoise Second ink composition (color change agent ink) 3-cyclohexyl-6-chlorofluorane 6 parts 2-(2'
-Hydroxy-5'-methylphenyl)benzotriazole 1 part Lobutyl acetate
20 parts xylene
20 parts The above two types of ink compositions were mixed at a ratio of 1:2 immediately before use to obtain a uniform ultraviolet color-forming ink. This ultraviolet color-forming ink had suitability as an oil-based screen ink. When screen printing was performed using this ultraviolet color-forming ink, the printed area was initially colorless, but turned orange after being exposed to sunlight for 2 minutes.

Example 6 Two types of ink compositions having the following compositions were prepared.

First ink composition (photoactivator ink) Tribromomethyl phenyl sulfone 3 parts Carnauba wax 10 parts Low molecular weight polyethylene 8 parts Oleic acid
5 part activity: 200 centipoise (however,
ioo℃) Second ink composition (color change agent ink) Tris(4-diethylamino-2-methylphenyl)methane 10 parts carnauba wax 10 parts paper molecular weight polyethylene 8 parts oleic acid
5 part activity: 200 centipoise (however, 1
00°C) The above two types of ink compositions were mixed at 1°C immediately before use.
After heating to 00°C, the mixture was mixed at a ratio of t:O, 5, and the resulting melt was applied onto a 6 m thick polyethylene terephthalate film (trade name: Lumirror, manufactured by Toshi ■) using a hot melt coating method. , a heat-sensitive melt transfer type ink sheet was produced. This ink sheet was cut into a predetermined size, loaded into a cassette case, and printed on high-quality paper using a thermal printer (PC-PR201Tll, manufactured by NEC ■).

The printed area was initially colorless, but when it was irradiated with a xenon flash lamp (input 10fflj/cj), it developed a blue color.

〔Effect of the invention〕

In the two-component separation type ultraviolet color-changing ink of the present invention, the photoactive agent and the color-changing agent are dissolved, dispersed, or solid-dissolved in separate printing ink vehicles, so that the photoactive agent and the color-changing agent have no influence on each other. Therefore, the discoloration of the ink can be maintained stably for a long period of time.

When used, the first ink composition and the second ink composition are mixed and printed on the target object, and when irradiated with ultraviolet rays, the color changes depending on the amount of ultraviolet rays. , develops or fades, e.g. light purple-dark purple, light blue-
Depending on the type of color change agent, various colors such as deep blue, plain thread, fruit and vegetable, and red can be obtained.

Therefore, the two-component separation type ultraviolet color-changing ink of the present invention can be used for measuring the dose of ultraviolet rays, as well as for storage management of secret documents, recording materials, and various printing inks such as screen printing ink. , can be used effectively.

Furthermore, when applying an ultraviolet curable composition and curing it by irradiating it with ultraviolet rays, the two-component ultraviolet color-changing ink of the present invention can be used to coat the edges of one object or the object. By writing lines, drawings, etc. on the parallel objects, the degree of curing of the ultraviolet curable composition can be recognized by the change in color according to the amount of ultraviolet irradiation, which can also be used to control the curing of the composition. It is possible.

Claims (4)

[Claims] (1) a first ink composition having a viscosity of 100 to 10,000 centipoise containing a photoactive agent dissolved or dispersed in a printing ink vehicle; and a viscosity of 100 to 10,000 centipoise containing a color change agent dissolved or dispersed in a printing ink vehicle; 10,0
1. A two-component separation type ultraviolet color-changing ink comprising a second ink composition of 0.00 centipoise. (2) a first ink composition containing a photoactive agent dissolved or dispersed in a printing ink solvent and a color change agent dissolved or dispersed in a printing ink vehicle;
A two-component separation type ultraviolet color-changing ink comprising a second ink composition of 0,000 centipoise. (3) a first ink composition having a viscosity of 100 to 10,000 centipoise containing a photoactive agent dissolved or dispersed in a printing ink vehicle; and a second ink composition containing a color change agent dissolved or dispersed in a printing ink solvent. A two-component separation type ultraviolet color-changing ink characterized by comprising a composition. (4) A first ink composition containing a photoactive agent dissolved or dispersed in a printing ink vehicle that is solid at room temperature, and a color change agent that is dissolved or dispersed in a printing ink vehicle that is solid at room temperature. A two-component separation type ultraviolet color-changing ink comprising a second ink composition.