JPH01126382A - Colored water-base ink composition for printing data to x-ray photograph - Google Patents

Abstract

PURPOSE:To obtain the titled water-base composition having excellent safety, writing property and storability, by dissolving an X-ray shielding agent in a specific aqueous solvent in such a manner as to satisfy a specific condition and compounding a specific colorant to the mixture. CONSTITUTION:The objective composition is produced by dissolving an X-ray shielding agent consisting of a simple substance or compound of an element having an atomic number of >=47 (excluding rare gas elements) in an aqueous solvent composed of water and a 2-6C glycol, 3-9C triol or 3-9C alkylene glycol monoalkyl ether and dissolving a triphenylmethane or xanthene dye having sulfonic acid salt group or carboxylic acid salt group in the molecule. The amount of the X-ray shielding agent is selected to give a mass absorption coefficient of >=0.170cm<2>/g to an X-ray having a wavelength of 0.1Angstrom . The X-ray shielding agent is preferably alkali metal tungstate, etc., and the dye is most preferably Acid Red 51, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a colored aqueous ink composition for imprinting data on X-ray photographs, and more specifically, for imprinting required data on paper, woven fabric, non-woven fabric, etc. The present invention relates to a colored aqueous ink composition which is used to write data on an X-ray photograph and to imprint the data on the X-ray photograph when the X-ray photograph is taken.

When an X-ray photograph of the human body or other body is taken, the date of the photograph, the name, gender, and other necessary data of the subject are usually imprinted onto the film at the same time. For this purpose, a method has conventionally been adopted in which single-character lead characters, which are difficult to transmit through X-rays, are manually arranged and attached to one corner of the film cassette. However, when using this method, the work of arranging single-character type is extremely complicated, and the amount of data for imprinting is naturally limited.

Also known is a data imprinting device in which a lead foil serving as a writing surface is exposed and the lead foil is held between films.

To use this device, writing is done on the lead foil, that is, the lead foil is scraped off, which makes it somewhat easier to write on, but since the area covered with lead foil unnecessarily blocks X-rays, X-ray photography There are many parts of the film that cannot be used.

Therefore, for example, in Japanese Patent Publication No. 62-27704,
A paste-like paint is prepared by mixing fine powder of lead compounds such as lead oxide, white lead, and lead sulfide with a quick-drying binder.
For example, a method has been proposed in which required data is written on each folded piece of paper using the above-mentioned paint so that a double copy is made after imaging, and the data is pasted onto an X-ray photographic film.

However, even when using this method, it is not easy to write the data in such a way that it is exactly duplicated.
Furthermore, since the paint is a paste containing fine powder of a lead compound, the fine powder tends to settle, requiring stirring immediately before use, or requiring a special tool for writing, and furthermore, it has poor writability. Inferior. Furthermore, the paint tends to dry out during storage, has poor storage stability, and is easily flammable, resulting in a lack of safety.

The present invention was made in order to solve the above-mentioned problems in the conventional method of imprinting data on X-ray photographs, and is water-based and highly safe. , and has excellent writability and storage stability, allowing for easy and smooth writing even with a normal marking pen, for example,
An object of the present invention is to provide a colored aqueous ink composition for imprinting data onto colored X-ray photographs.

. The colored aqueous ink composition for imprinting data on an X-ray photograph according to the present invention for the purpose of diagnosing is a water-based ink composition in which an element or a compound of an element having an atomic number of 47 or more (excluding noble gas elements) is added to an aqueous solvent. As a radiation shielding agent, the mass absorption coefficient for X-rays with a wavelength of 0.1 is 0.
．． 170 ci/g or more, and a triphenylmethane or xanthene dye having a sulfonic acid group or a carboxylic acid group in the molecule is dissolved, and the aqueous solvent is water and a carbon number of 2 to 6. glycol, triol having 3 to 9 carbon atoms, or alkylene glycol monoalkyl ether having 3 to 9 carbon atoms.

In general, strength ■. The intensity ■ after an X-ray passes through a material with a thickness d (cm) is the density of the material ρ(g/cIl
), then In (Io / I) = u P d (1
) or r = Io exp(-p p d) (2
) holds true, where ρμ(cm-') is X of the substance
The linear absorption coefficient μ(c11/g) for X-rays is defined as the mass absorption coefficient of the material for X-rays.

This mass absorption coefficient is a unique value that each element constituting a substance has when the wavelength of X-rays is determined, and it is known that compounds and mixtures have additivity. That is, when the mass absorption coefficient of each component element constituting a compound or mixture is μm, the weight ratio is Wi, and the density of the compound or mixture is ρ, the mass absorption coefficient μ of the compound or mixture is μ=Σμ ! W! It can be found at

The ink composition according to the present invention uses an element or a compound of an element having an atomic number of 47 or more (excluding rare gas elements) as an X-ray shielding agent, and has a mass absorption coefficient of 0.1 for X-rays at a wavelength of 0.1. 170co! /g or more in an aqueous solvent.

According to experiments conducted by the present inventors, in taking X-ray photographs,
Lead foil with a thickness of 0.01 m or more is effective for shielding X-rays.

In the ink composition according to the present invention, the wavelength of 0.1
Setting the mass absorption coefficient for X-rays to 0°170c+a/g or more allows the ink composition to have an X-ray shielding effect almost equivalent to that of lead foil with a thickness of 0.01 mm or more, that is, a mass absorption coefficient for X-rays. That's true. However, in the present invention, the mass absorption coefficient of the ink composition ignores the X-ray shielding effect of components other than the X-ray shielding agent.

On the other hand, when the X-ray shielding power is μρd in the above equation (1), the X-ray shielding effect of a lead foil with a thickness d of 0.001 cm is as follows: the mass absorption coefficient μ of lead is 3.41 cJ/g, and the density is ρ
is 11.34g/ad, so μρd is approximately 0.0
It is 39.

Therefore, the density of the ink composition according to the present invention should be at least 1.1 g/ci (actually, in most cases, it is greater).

), when writing with an ink composition on an absorbent writing surface, such as paper, the X-ray shielding power of the handwriting is 0.
．． 039, the thickness t of the handwriting is t = 0.039/ (0,170xl, 1) #2.
1 (m). The mass absorption coefficient of the ink composition is 0
．． The required thickness of handwriting becomes smaller as the value becomes larger than 170 crA/g. For example, when the mass absorption coefficient of the ink composition is 0.5 ci/g, the required thickness of the handwriting is approximately 0.7 ci/g. Such a required thickness of handwriting can be easily obtained by selecting the viscosity and permeability of the ink composition, the permeability of the writing surface, and the like.

The following can be exemplified as elements constituting a simple substance or a compound that can be preferably used in the present invention. However, the value in parentheses indicates the mass absorption coefficient (cd/g) of the element for XvA at a wavelength of 0.1.

Ag (1,05), Cd (1,10), In (1,15
), 5n(1,20), 5b(1,25), Te(1,
30), I(1,36), C5(1,48), Ba(1
, 53), La (1, 60), Ce (1, 66), P
'r(1,72), Nd(1,80), Pm(1,86
), Sm (1,93), Eu (2,02), Gd (2,
09), Tb (2,18), Tm (2,50), Lu
(2,66), Hf(2,75), Ta(2,82)
, W(2,90), Re(2,96), 03(3,03
), Ir(3,10), Pt(3,17), Au(3,
23), Hg(3,30), Tl(3,36), Pb(
3,41), Bi (3,45), PO (3,52),
f! r(2,42), Ra(3,70), Ac(3,
75), Th(3,81), Pa(3,86) and t
l(3,91).

In the present invention, the XvA shielding agent preferably has a solubility in water of about 10% by weight or more. Therefore, examples of the above-mentioned single substances or compounds that can be used as the X-ray shielding agent in the present invention include AgF- AgN(h, C
d1z, Cd(NOx)z・4Hzo, 3CdSOt
・4HzO.

5nC1z, NHISnBr44HzO1NEIa, 5
nC1s, SbF 3.5bC1z, KsSbSe・5
HzO5 (NH4) 5stlsa, Li5bS4・1
0t(zO1TeBr4, H2Te04・2H1O1K
tTeOn, IzSII, LiI・3HzO1ZnI
z, Calt, NH4I5Nal, KI, Li(I
O+), Mg1z・8HzO1ICNSCs, GO,,
C! d, C3CI% Cs0HSCsNx, Cs, S
O,, CszMoO,, C5zSe04. BaBrz
, Ba (CN) z, Ba (C10s) z・HzOl
BaIz・2HzO1BaC1,, Ba(C1ot)z
, Laz(Se04)+, La(No:+)+・6Hz
O1La (BrO+)*, MgzLaz (NOs)
1z, (NH4)zLa(NOsun3, CeC1,
, Cez (SO4)s42Hzo, MgCez (NO
3) r t, Mg5Prz(NO*)+z, Mn3P
rz (NO:l) + t, PrC1+・7ngO5
Pr(NOih, Pr(Br(h):+, MgJdz(
NOz) It, MnJdz (NOz)+z, Ndz
(Ser+)! , KNd(Se04)z・4H20,
SmC1+, Sm(Br(h)a, Tb(BrO3)
z, (NH4) zHfFi, TaF5, NazWO,
, KzWOi, C521'104, (NH4)JOa,
C5t (Hot), NHaRt303S sMgP t
(CN) 4, PtC1n・51(zOlKzPt(
CN) a, AuC1z, NaAuC1n・2HzO1K
AuC1a, LiAuC14, Hg (CN) z, H
gz(C1ot)z, HgN0 :l・FIzO, Tl
Cl3・4HzO1TIHzPOi, TlN0+, Tl
OH,PbC1,Pb(CIOz)z・H,01Pb(
NOx)z, Pb(C104)2・31(!0, Pb5
iF,, InBr: r5H2O, InI+, InC11
4HzO1RaBrz, RaC1z, VOzClg・3
)1zO1V(h(N(h)z, 6ngo, Erg(
SOa)s・88zoS Gd(BrOko)+・9H2
0, NH4, Re03S, etc.

As mentioned above, in the ink composition of the present invention, the above-mentioned single substance or compound has a mass absorption coefficient of 0.170c for X-rays having a wavelength of 0.1.
It is dissolved in an aqueous solvent so that the amount is J/g or more, but it is usually contained in an ink composition in an amount of 10% by weight or more. Preferably, the X-ray shielding agent in the ink composition has an X-ray absorption coefficient of 0 for XvA of 0.1 people.
．． It is dissolved to a concentration of 5 Cnl/g or more. Therefore,
The upper limit of the amount of the X-ray shielding agent to be blended is not particularly limited up to its saturated dissolved amount, but is usually 60 weight or less. The above-mentioned single substances or compounds may be blended into the ink composition alone or as a mixture of two or more.

In the present invention, among the above-mentioned X-ray shielding agents, an alkali metal tungstate or ammonium tungstate represented by the formula % (wherein M represents an alkali metal or ammonium) is particularly preferred. used. Preferred specific examples of such tungstates include, for example, Na
Mention may be made of JO4, K2WOn and C5JO4. These may be used alone or as a mixture, and may also be used as a mixture with other single substances or compounds as described above.

In particular, the above-mentioned alkali metal tungstates and ammonium tungstates have significantly lower toxicity than other heavy metal salts, and have a large mass absorption coefficient relative to 0.1 human Xg.For example, Bat, 2B,
O has a mass absorption coefficient of 1.1 for X-rays.
31ad/g, but that of NagWO, -2H20 is 1.68 ctA/g SK! WOa's is 1.
72 ctA/g, that of C5JO<1.8
It is 2 cd/g.

In such an ink composition, the alkali metal tungstate is preferably dissolved in an amount of 15% by weight to less than the saturated amount, particularly preferably 20 to 60% by weight.

Furthermore, preferred ink compositions according to the invention contain an alkali metal base and/or an alkali metal iodide together with the alkali metal tungstate. Ammonia can also be used instead of the alkali metal base.

These alkali metal bases, ammonia, or alkali metal iodides enhance the solubility of tungstate salts in aqueous solvents or enhance the dissolution stability, and are therefore used as dissolution aids for X-ray shielding agents.

The alkali metal base is preferably a strongly alkaline substance, and hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, and lithium hydroxide are particularly preferably used. However, carbonates and hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and cesium carbonate may also be used. The amount of these alkali metal bases or ammonia blended in the ink composition may be any amount sufficient to make the ink composition alkaline. Therefore, although it depends on the alkali used, the amount of the alkali metal base or ammonia in the ink composition is usually 0.01 to 2.0% by weight, preferably in the range of 0.05-0.5% by weight. however,
When cesium carbonate is used, since cesium carbonate itself functions as an X-ray shielding agent, it is used in the ink composition in an amount of 40% by weight or less, preferably 30% by weight or less.

As the alkali metal iodide, for example, sodium iodide, potassium iodide, cesium iodide, etc. are preferably used. The amount of these alkali metal iodides in the ink composition may be equal to or less than the saturated dissolved amount.
The amount is usually 40% by weight or less, preferably 30% by weight or less.

Moreover, in the present invention, in addition to the above-mentioned tungstate, in particular, ^gNo, Zn1. , BaIz・2H1O
1SbC13, HgN0+4zO2PbC1, Kl, N
aI, CsI, CsCO3, CsOH, etc. are preferably used.

When containing barium iodide or zinc iodide as an X-ray shielding agent, hydrochloric acid is added to the ink composition in an amount of about 0.01% by weight or less to stabilize the solubility of these in water. It is preferable to coexist with an inorganic acid such as or an organic acid such as acetic acid.

In the ink composition according to the present invention, when barium iodide, zinc iodide, or the like is used as an X-ray shielding agent, a portion of iodine is liberated and the ink composition is colored. The ink composition can also be colored by adding iodine to an iodine salt such as potassium iodide or sodium iodide. Furthermore, as an xwA shielding agent,
When iodine or an iodine compound is used, starch can also be incorporated as a coloring agent.

However, the coloring of ink compositions by iodine itself tends to fade or become colorless over time.
It is not necessarily preferable as a coloring agent. On the other hand, when the aforementioned tungstate is used as an X-ray shielding agent, iodine does not dissolve in a concentrated aqueous solution of tungstate. Furthermore, even if an iodine salt such as sodium iodide and iodine are added to a concentrated aqueous solution of tungstate, it will eventually become colored, but over time, the coloring caused by iodine will disappear and eventually It becomes completely colorless.

Therefore, according to the present invention, a triphenylmethane dye or a xanthene dye having a sulfonic acid group or a carboxylic acid group in the molecule is blended into the ink composition together with a predetermined organic solvent as a coloring agent. Such dyes alone hardly dissolve in an aqueous solution containing a high concentration of an X-ray shielding agent, but according to the present invention, a glycol having 2 to 6 carbon atoms, a triol having 3 to 9 carbon atoms, or a triol having 3 to 9 carbon atoms When incorporated into an ink composition with the alkylene glycol monoalkyl ether of No. 9, it unexpectedly dissolves relatively well to provide a uniformly colored ink composition. That is, by adding such a dye together with a predetermined organic solvent to an aqueous solution containing a high concentration of an X-ray shielding agent, it is possible to uniformly color an ink composition with a dissolved amount that does not cause salting out. can.

In the present invention, the dye having a sulfonic acid group or a carboxylic acid group may include, for example, lithium in the molecule,
Those having alkali metal salts such as sodium and potassium salts, amine salts such as triethanolamine salts, and ammonium salts containing sulfonic acid groups or carboxylic acid groups are preferably used.

Such dyes include, for example, acid red 50, acid red 51, acid red 52, acid red 87, acid red 92, acid red 94, acid violet 17, acid violet 49, acid blue, Acid Blue 9, Acid Blue 15, Acid Blue 59, Acid Blue 83, Acid Blue 90, Acid Blue 92, Acid Blue 93, Acid Blue 104, Acid Green 9, Acid Yellow 73, etc. can be mentioned.

Among the above, in particular, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red
Blue 9, Acid Blue 90, Acid Yellow 73, etc. are preferably used.

Such dyes are usually used in ink compositions in amounts of 0,00
It is dissolved in a range of 1 to 2.0% by weight, preferably 0.005 to 1.0% by weight. If it is too small, it will not be enough to color the ink composition, and on the other hand, if it is too large, it will be salted out and the X-ray shielding agent will be taken in during the salting out. This is not preferable because it may precipitate or form a salt with the active ingredient of the X-ray shielding agent.

Such dyes, according to the invention, can be dyes containing water and glycols having 2 to 6 carbon atoms, triols having 3 to 9 carbon atoms or 3 to 6 carbon atoms.
It is dissolved in a mixed aqueous solvent consisting of at least one organic solvent selected from No. 9 alkylene glycol monoalkyl ethers.

Examples of the glycol having 2 to 6 carbon atoms include ethylene glycol, propylene glycol, butanediol, hexylene glycol, etc.; examples of the triol having 3 to 9 carbon atoms include glycerin, 3-methylpentane-1,4,5-
triol, trimethylolpropane, etc., and alkylene glycol monoalkyl ethers having 3 to 9 carbon atoms, such as ethylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, diethylene glycol 7-methyl ether, diethylene glycol monoethyl ether, Diethylene glycol motuptyl ether, methyl calpitol, ethyl calpitol, butyl calpitol, etc. are used.

In the ink composition of the present invention, these organic solvents are
It is usually used with 0.1 to 20% by weight, preferably 0.5 to 10% by weight. Water as the main solvent is used
Although it depends on the radiation shielding agent, it is usually used in a range of 10 to 80% by weight.

Furthermore, in the ink composition according to the present invention, in addition to the above-mentioned organic solvents, the aqueous solvent may be used to adjust the permeability of the ink composition to the absorbent writing surface to which it is applied, or to adjust the water-based solvent as necessary. Lower aliphatic alcohols such as methanol, ethanol, isopropanol, funnel oil, etc. may be contained as a co-solvent and/or humectant to suppress the evaporation rate.

These organic solvents are usually contained in a range of 1 to 50% by weight.

The ink composition according to the present invention may further contain additives such as a surfactant, a mackerel inhibitor, and a preservative in addition to the above-mentioned components. Examples of the surfactant include anionic surfactants such as sodium dialkyl sulfosuccinate, sodium alkylbenzenesulfonate, and lead naphthenate, or nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene alkyl ester. Surfactants are preferably used. Also preferably used are acetylene glycols such as 2.4.7.9-tetramethyl-5-decyne-4,7-diol and ethylene oxide adducts thereof.

Moreover, as a rust preventive agent, for example, 1,3.5-benzotriazole can be used, and as a preservative, for example, tetrabutyltin, sodium benzoate, etc. can be used.

The ink composition according to the present invention can be easily manufactured by dissolving each of the above-mentioned components in water. However, the required components may also be formed in the solvent by chemical reactions in an aqueous solvent. For example, barium iodide is produced by reacting barium hydroxide with hydrogen iodide in an aqueous solvent, and an ink composition using this as the xl screening agent can be obtained.

In addition, the alkyl metal tungstate itself may be dissolved in water, but for example, by dissolving sodium carbonate or potassium carbonate and cesium tungstate in water, tungstate can be dissolved on the spot. Sodium or potassium tungstate may also be produced.

When the ink composition according to the invention contains a solubilizing agent for an X-ray shielding agent as described above, such an ink composition is preferably prepared by first dissolving the solubilizing agent in water and then dissolving the solubilizing agent in water. It is manufactured by dissolving the dye and other additives after dissolving the screening agent.

In addition, the ink composition according to the present invention, especially when it contains iodide such as barium iodide, zinc iodide, calcium colat, etc. as an X-ray shielding agent, after its preparation, the ink composition is exposed to air. It absorbs carbon dioxide gas and reacts with iodine compounds to liberate hydrogen iodide and may produce water-insoluble carbonates. However, such an ink composition can also be used if there is no particular problem in writing. Of course, the ink composition may be prepared by filtering off the insoluble carbonate.

As described above, the ink composition according to the present invention may contain by-product water-insoluble compounds or substances in some cases, but in most cases it is a colored aqueous solution with a wavelength of 0.
Its mass absorption coefficient for one person Xi is 0.17 M/g
As described above, by writing the required data on a liquid-absorbing sheet and pasting it on a dry plate containing an X-ray photographic film, this data can be transferred onto the film at the same time as the X-ray photograph is taken. It can be imprinted.

Moreover, since the ink composition according to the present invention is colored, when necessary data is written on a liquid-absorbing sheet, by making the density of the handwriting more than a predetermined level, it is possible to imprint it onto the film. The concentration can be reliably increased.

Furthermore, since the ink composition according to the present invention is substantially an aqueous solution, it can be used for writing using conventional and ordinary writing instruments. Examples of such writing instruments include marking pens, felt-tip pens, water-based ballpoint pens, brush pens, and fountain pens.

Examples of the liquid absorbent sheet include paper, woven fabric, nonwoven fabric, foam, and the like. In this way, by using a liquid-absorbing sheet as a writing surface, the ink dries easily, and an ink layer is formed over the thickness of the sheet to ensure that written data is imprinted. Can be done.

However, it is not preferable to use a sheet made of non-liquid-absorbing glass, resin, metal, or the like as a writing surface, since data imprinting becomes uncertain.

As described above, the ink composition for imprinting data on X-ray photographs according to the present invention can be easily and smoothly written on, for example, with a normal marking pen, and furthermore, it can be written on easily and smoothly using a water-based It is colored, highly safe, and has excellent preservability.For example, the required data is written on paper, woven fabric, non-woven fabric, etc., and this is pasted on X-ray photographic film. Once the X-ray image is attached, the data can be reliably imprinted on the X-ray image at the same time.

Disaster A water-based ink composition having the composition shown below was prepared.

The blending amount is expressed in parts by weight.

Work Z Soil ■Clothing Belly Top Nal 55 parts Water 43
1 part ethylene glycol 1 part Acid Yellow 73 1 part Absorption coefficient 0.643c+J/g Soil Sodium NaJO4,2Hz0 25 parts 1 25 parts Water 40
Part hexylene glycol 9.95 Part Acid Blue 9 0.05 Part type absorption coefficient Q, 730cj/gKtHO
<24 parts NaI 20 parts water 51
Part Glycerin 4.98 parts Acid Red 51 0.02 Part type absorption coefficient 0.646ci/gE Earthen plate Tatsuo Alternative C3zWOa 65 parts NaOHO, 1 part Water 30
Part 3-Methylpentane-1,3,5-triol 4.88 parts Acid Red 87 0.01 Partial type absorption coefficient 1.183 cJ/gヱEarthen dish bottom ■Work Zn12 70 parts Water 25
Part 3-Methyl-3-methoxy- Butanol 4.9 Part Acid Blue 90 0.1 Partial absorption coefficient 0.805c++f/g! ””
Cut 1 Nal 55 parts Water 40
Part ethylene glycol 4.95 Part Acid Red 92 0.05 Part type absorption coefficient 0.643ci/g Non/Tosen Soko Koko KZWo, 1 in 25 parts Water 45
Part Hexylene Glycol 9.95 Parts Acid Blue 9 0.05 Part Type Absorption Coefficient 0.678c11/gKzuoa 26 Parts Nal 19 Parts Water 50
part Glycerin 4.98 parts Acid Red 50 0.02 part type absorption coefficient 0.669 cnl/g mv11 CsJ (L 67 parts Na1l O, 1 part water 28
Part 3-Methoxy-3-Butanol 4.88 Part Acid Red 94 0.02 Partial type absorption coefficient 1.219cj/g Patent applicant Sakura Crevasse Co., Ltd. Agent Patent attorney Itsu Makino Department

Claims (1)

[Claims] (1) The mass absorption coefficient for X-rays with a wavelength of 0.1 Å is 0.170 when an element or compound with an atomic number of 47 or higher (excluding rare gas elements) is used as an X-ray shielding agent in an aqueous solvent.
cm^2/g or more, and a triphenylmethane or xanthene dye having a sulfonic acid group or a carboxylic acid group in the molecule is dissolved, and the aqueous solvent contains water and a carbon number of 2. 1. A colored aqueous ink composition for imprinting data on an X-ray photograph, comprising a glycol having 1 to 6 carbon atoms, a triol having 3 to 9 carbon atoms, or an alkylene glycol monoalkyl ether having 3 to 9 carbon atoms.