FR3127950A1 - COMPOSITION BASED ON SPECIFIC COLORED INDICATOR(S) USABLE IN A SCREEN PRINTING PROCESS - Google Patents

Abstract

The invention relates to a composition which can be used for a process for printing a support by screen printing comprising: - at least one colored indicator chosen from anthraquinone compounds, azo compounds, triarylmethane compounds, xanthene compounds, indigo compounds , metal complexes, compounds comprising at least one stilbene group, coumarin compounds, compounds comprising at least one cyanine group, compounds comprising at least one phthalocyanine group, compounds comprising at least one porphyrin group, compounds comprising at least a hydrazone group; -at least one polymeric thickening agent; and -at least one organic solvent.

Description

COMPOSITION BASED ON SPECIFIC COLORED INDICATOR(S) USABLE IN A SCREEN PRINTING PROCESS

The present invention relates to new compositions comprising at least one specific indicator which can be used for deposition on a support, for example paper, via a screen printing process.

The present invention can find application, once the compositions have been deposited on a support, in the detection of toxic chemical compounds, such as toxic warfare compounds and, in particular, organophosphorus compounds; toxic industrial chemical compounds (known as TIC); vesicants; pesticides and arsenic compounds.

In general, organophosphorus compounds are in the form of organic compounds with proven toxicity to the human body. Indeed, these compounds may be involved in the mechanism of inhibition of serine proteases and, in particular, of acetylcholinesterase, which intervenes in synaptic junctions and whose dysregulation of activity can prevent muscle relaxation and thus cause death. by asphyxiation.

These compounds can be included in the formulation of insecticides, pesticides or even chemical combatants (such as organophosphorus compounds of the G series, such as sarin or organophosphorus compounds of the V series, such as VX) and due to the high lethality of these compounds, their proliferation, it is important to be able to have detection systems.

Some detection systems used to date are based on technologies involving physical measurement means, such as ion mobility spectroscopy, flame photometry, IR and Raman spectroscopy, with the difficulties that these systems require complex equipment. expensive and not necessarily suitable for all operating environments in terms of mass and size, to which must be added the expertise of the operator to be considered.

The authors of the present invention have placed themselves in the field of detection systems involving chemical means and, in particular, based on the chromatic shift of colored indicator(s) deposited on a support and, of this starting point, have set themselves the objective of developing compositions (or inks) comprising at least one specific colored indicator that can be used for deposition on a support by a screen printing process, with the following advantages in view:

- the possibility of using these compositions with screen printing frames with a relatively fine pitch (for example, less than or equal to 150 μm and opening of holes less than 100 μm;

-an ability to be deposited on a support via a screen printing frame and compatible with the deposition means and without excessive spreading of the printing dots on the chosen support; And

- an ability to preserve the ability to change color(s) of the colored indicator.

Thus, the invention relates to a composition that can be used for a process for printing a support by screen printing comprising (or even consisting exclusively of):

-at least one colored indicator chosen from anthraquinone compounds, azo compounds, triarylmethane compounds, xanthene compounds, indigo compounds, metal complexes, compounds comprising at least one stilbene group, coumarin compounds, compounds comprising at least a cyanine group, compounds comprising at least one phthalocyanine group, compounds comprising at least one porphyrin group, compounds comprising at least one hydrazone group;

at least one polymeric thickening agent; And

-at least one organic solvent.

By colored indicator, it is meant a chemical substance which takes on at least one characteristic color in the presence of a chemical compound, i.e., in other words, a chemical substance which has at least two colored states, a colored state existing when the chemical substance is not in the presence of the chemical compound to be detected and at least one other colored state when the chemical substance is in the presence of the chemical compound to be detected. The detection indicator can consist of one or more compounds allowing detection.

According to the invention, the colored indicator can be chosen from anthraquinone compounds, azo compounds, triarylmethane compounds, xanthene compounds, indigo compounds, metal complexes, compounds comprising at least one stilbene group, coumarin compounds, compounds comprising at least one cyanine group, compounds comprising at least one phthalocyanine group, compounds comprising at least one porphyrin group, compounds comprising at least one hydrazone group.

As examples of anthraquinone compounds, mention may be made of 1,4-dihydroxyanthraquinone, 1-aminoanthraquinone, carminic acid, 1,5-diaminoanthraquinone, 1,2-diaminoanthraquinone, 1,4 -diamino-5-nitroanthraquinone, 1,4,5,8-tetraaminoanthraquinone (Disperse Blue 1), 1-methylamino-4-(2-hydroxyethyl)aminoanthraquinone (Disperse Blue 3), 1-amino-2-methylanthraquinone (Disperse Orange 11), 1,4- bis- (p-tolylamino)anthraquinone (Solvent Green 3).

As examples of xanthene compounds, mention may be made of [9-(2-carboxyphenyl)-6-diethylamino-3-xanthenylidene]-diethylammonium chloride (also called "Rhodamine 610"), rhodamine 6G optionally under perchlorate salt form, rhodamine B, sulforhodamine 101 hydrate, fluoresceinamine (especially Isomer I), rhodamine 110 chloride.

As examples of indigo compounds, mention may be made of indigo.

As examples of metal complexes, mention may be made of trisodium 5-nitroso-6-oxidonaphthalene-2-sulfonate complexed with iron (III) (also called "Naphthol Green B").

As examples of compounds comprising at least one stilbene group, mention may be made of the dye known by the English terminology “Fluorescent Brightener 28”.

As examples of coumarin compounds, mention may be made of 7-amino-4-(trifluoromethyl)coumarin, 7-amino-4-methylcoumarin, 3-(2-N-Methylbenzimidazolyl)-7-N ,N-diethylaminocoumarin (also called “Coumarin 30”), 2,3,6,7-tetrahydro-10-(3-pyridyl)-1H,5H,11H-[1]benzopyrano[6,7,8-ij ]quinolizin-11-one (also known as “Coumarin 510”), 3-(2-Benzothiazolyl)-7-(diethylamino)coumarin (also known as “Coumarin 6”).

As examples of compounds comprising a cyanine group, mention may be made of indocyanine green, 5,5′-dichloro-11-diphenylamino-3,3′-diethyl-10,12-ethylenethiatricarbocyanine perchlorate ( also says IR140).

As examples of compounds comprising a phthalocyanine group, mention may be made of phthalocyanine iron (III) chloride, phthalocyanine-4,4',4'',4'''-tetrasulfonic acid of iron ( III), 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine.

More precisely, the colored indicator can be chosen, advantageously, from azo compounds and triarylmethane compounds.

With regard to azo compounds, mention may be made of 10-(2',4'-dinitrophenylazo)-9-phenanthrol, 6-hydroxy-5-[(2-methoxy-5-methyl-4-sulfophenyl)azo] disodium -2-naphthalenesulfonate (also called Allura AC red), 4-dimethylaminoazobenzene (also called methyl yellow), 4-(2-carboxyphenylazo)-N,N-dipropylaniline (also called “Propyl red” according to the terminology English), 3-(diethylamino)-7-{(E)-[4-(dimethylamino)phenyl]diazenyl}-5-phenylphenazin-5-ium chloride (also known as “Janus Green B”), N, N-dimethyl-4,4'-azodianiline, N-ethyl-1-((4-phenyldiazenyl)phenyl)diazenyl)naphthalen-2-amine (also known as "Sudan Red 7B"), amaranth, dihydrochloride 4-[[3-[(2,4-diaminophenyl)diazenyl]phenyl]diazenyl]benzene-1,3-diamine (also called “Bismarck brown Y”), 4-hydroxy-3-[(4- disodium sulfo-1-naphthalenyl)azo]-1-naphthalenesulfonate (also called "Chromotrope FB"), benzidinediazo-bis-1-naphthylamine-4-sulfonic acid (also called "Congo Red"), 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol (also called "Disperse Black 9" according to English terminology), 2,2'-[[4-[(4-nitrophenyl)azo]phenyl] imino]bisethanol (also known as “Disperse Red 19” according to English terminology), (4Z)-4-[(1-hydroxynaphthalen-2-yl-hydrazinylidene]-7-nitro-3-oxo Y-naphthalene-1- sodium sulfonate (also called "eriochrome black T"), 4'-(4-(diethylamino)phenylazo)acetophenone, 4-[(E)-(4-nitrophenyl)diazenyl]-N-phenylaniline (also called " Disperse Orange 1"), helianthine (also called methyl orange), 4-(4-nitrophenylazo)aniline (also called "Disperse Orange 3"), 4-[4-(phenylazo)-1-naphthylazo] phenol (also known as “Disperse Orange 13”), 3-[N-ethyl-4-(4-nitrophenylazo)phenylamino]propionitrile (also known as “Disperse Orange 25”), 4-amino-5-hydroxy-3- Sodium (4-nitrophenylazo)-6-(phenylazo)naphthalene-2,7-disulphonate (also known as "Black blue naphthol"), (2,2-dimethyl-1,3-dihydroperimidin-6-yl)-( 4-phenylazo-1-naphthyl)diazene (also called "Sudan Black B" according to English terminology), disodium 6-hydroxy-5-[(4-sulfonatophenyl)azo]naphthalene-2-sulfonate (also called "yellow orange S”), brilliant yellow (also called “Brilliant Yellow”) whose precise formula is explained below, tartrazine, Evans blue, 4-[4-(phenylazo)phenylazo]-o-cresol (called also "Disperse Yellow 7" according to the English terminology), 4'-nitro-4-dimethylaminoazobenzene.

More specifically, in the case of azo compounds, they may be azo compounds comprising aromatic groups on either side of the –N=N- function and, in particular diphenyldiazo compounds, colored indicators of this type which are particularly suitable being 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol known under the name “ Disperse Black 9 ” (and also designated by the abbreviation DB9) and corresponding to the formula next :

or brilliant yellow (Brilliant Yellow) corresponding to the following formula:

Regarding triarylmethane compounds, mention may be made of aniline diammonium blue, bromophenol blue, m-cresol violet, cresol red, gentian violet (also called "Crystal Violet" in English terminology), chlorophenol red, sodium salt of (4-(α-(p-(diethylamino)phenyl)-2,4-disulfobenzylidene)-2,5-cyclohexadiene-1-ylidene)diethylammonium hydroxide (also called "Patent blue V sodium salt"), methyl blue, rosolic acid, pyrocatechol violet, brilliant green BS, pararosaniline base, fuchsin, thymol blue, 4-(dimethylamino) -α-[4-(dimethylamino)phenyl]-α-phenyl-benzenemethanol, bromcresol purple as a sodium salt.

More specifically, when it comes to triarylmethane compounds, of which at least one of the aryl groups is a cresol group, particularly suitable color indicators are bromocresol purple in the form of a sodium salt (and also designated by the abbreviation BCP), which corresponds to the following formula:

or bromcresol green corresponding to the following formula:

or thymol blue corresponding to the following formula:

According to the invention, the thickening agent is a polymeric thickening agent and can be, more specifically, a polymeric thickening agent chosen from polycarbonates, copolymers comprising at least one styrene repeating unit and at least one (meth)acrylate repeating unit, very particularly, when the colored indicator is chosen from azo compounds and triarylmethane compounds.

More specifically, when the thickening agent is a polycarbonate, it means a polymer or copolymer comprising, in its main chain, a -CO-O- group, suitable examples of polycarbonates suitable for the implementation of the invention being :

- a polycarbonate resulting from the polycondensation of bisphenol-A and a carbonate and having as a repeating unit the unit of the following formula:

this polycarbonate also being called poly(Bisphenol A carbonate);

- a polycarbonate being a copolymer of carbon dioxide and propylene oxide and having as a repeating unit the unit of the following formula:

this polycarbonate being also called propylene polycarbonate.

More specifically, when the thickening agent is a copolymer comprising at least one repeating styrene unit and at least one (meth)acrylate unit, it may be, in particular, a copolymer resulting from the copolymerization of styrene and methacrylate of methyl, this copolymer also being called poly(styrene-co-methyl methacrylate).

According to the invention, the compositions comprise at least one organic solvent and, more specifically, the organic solvent(s) can be chosen from ketone solvents, alkyl halide solvents, ether solvents and mixtures thereof.

More specificly :

- when it is a ketone solvent, it may be, in particular, a dialkyl ketone solvent and, even more particularly, methyl ethyl ketone (known by the abbreviation MEK);

- when it is an alkyl halide solvent, it may be, in particular, an alkyl chloride solvent, such as dichloromethane;

-when it is an ether solvent, it may be, in particular, a diethylene glycol alkyl ether solvent and even more particularly, diethylene glycol n-butyl ether of formula CH ₃ - (CH ₂ ) ₃ - O-(CH ₂ ) ₃ -O-CH ₂ -CH ₂ -OH.

The thickening agent is present, advantageously, in a content ranging from 10 to 20% by mass relative to the total mass of the thickening agent and the organic solvent(s), while the organic solvent(s) is (are) present ( s) in a content ranging from 80 to 90% by mass relative to the total mass of the thickening agent and of the organic solvent(s).

The colored indicator may be present at a content not exceeding 5% by mass relative to the total mass of the thickening agent and of the organic solvent(s), preferably, ranging from 0.01% to 5% by mass, preferably ; from 0.01% to 1% by mass relative to the total mass of the thickening agent and the organic solvent(s).

In particular, specific compositions of the invention consist exclusively of:

-at least one colored indicator chosen from azo colored indicators, triarylmethane colored indicators;

-at least one polymeric thickening agent chosen from carbonate polymers, the copolymers comprising at least one styrene repeating unit and at least one (meth)acrylate repeating unit; And

-at least one organic solvent chosen from ketone solvents, alkyl halide solvents, ether solvents and mixtures thereof.

Specific compositions in accordance with the invention and which are particularly advantageous are the following compositions:

-a composition comprising (or even consisting of), as a colored indicator, Disperse Black 9 (or 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol) or bromcresol purple in the form of a sodium salt , as thickening agent, poly(styrene-co-methyl methacrylate) and as organic solvent, methyl ethyl ketone, the thickening agent and the organic solvent possibly being present at the rate of respective contents of 10% by mass and 90% by mass relative to the total mass of the thickening agent and of the organic solvent and, where appropriate, bromocresol purple in the form of a sodium salt which can be dissolved beforehand in diethylene glycol n-butyl ether;

-a composition comprising (or even consisting of), as a colored indicator, Disperse Black 9 (or 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol) or bromcresol purple in the form of a sodium salt , as thickening agent, poly(Bisphenol A carbonate) and as organic solvent, dichloromethane, the thickening agent and the organic solvent possibly being present at the rate of respective contents of 10% by mass and 90% by mass with respect to the mass of the thickening agent and the organic solvent and, if necessary, Disperse Black 9 which can be dissolved beforehand in methyl ethyl ketone and bromocresol purple in the form of a sodium salt which can be dissolved beforehand in diethylene glycol n- butyl ether;

-a composition comprising (or even consisting of), as a colored indicator, Disperse Black 9 (or 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol) or bromcresol purple in the form of a sodium salt , as thickening agent, propylene polycarbonate and as organic solvent, methyl ethyl ketone, the thickening agent and the organic solvent possibly being present at the rate of respective contents of 10% by mass and 90% by mass relative to the total mass of the thickening agent and organic solvent and, if necessary, Disperse Black 9 which can be dissolved beforehand in methyl ethyl ketone and bromocresol purple in the form of a sodium salt which can be dissolved beforehand in diethylene glycol n-butyl ether.

Furthermore, the invention also relates to:

- the use of a composition as defined above to print a support by screen printing;

-a process for printing a support by screen printing comprising at least one step of depositing a composition as defined above on the support via a screen printing mask, such as a polymeric mask (for example, a mask polyester) or a metal mask;

-a system for the colorimetric detection of at least one chemical compound comprising a support covered, in whole or in part, by printing dots resulting from a composition as defined above.

The constituent support is advantageously a porous support. It can be a non-woven or woven support. In particular, it may comprise natural fibers (such as cellulose fibers, lignite fibers), synthetic polymeric fibers (such as polyamide fibers, polyester fibers or polyolefin fibers), glass fibers and mixtures thereof. More specifically, the constituent support may comprise glass fibers optionally mixed with polymer fibers or may include polyolefin fibers, polyamide fibers, polyester fibers optionally mixed with cellulose fibers. Even more specifically, the constituent support may be a non-woven support comprising a mixture of cellulose and polyester fibers, a support comprising a mixture of glass fibers and polymer fibers, a cellulosic support, for example a filter paper support, chromatography paper or ordinary paper, a support comprising entangled polyolefin fibers or a woven support comprising polymer fibers, such as polyamide fibers, polyester fibers. It is understood that this support must be able to be impregnated by the points of detection indicators.

It is understood that the printing dots comprising at least one colored indicator and at least one polymeric thickening agent as defined above, the organic solvent(s) being able to be evaporated in whole or in part.

Other characteristics and advantages of the invention will appear better on reading the additional description which follows, which relates to examples of compositions in accordance with the invention and comparative compositions.

Of course, the following example is only given by way of illustration of the object of the invention and in no way constitutes a limitation of this object.

DETAILED DISCUSSION OF PARTICULAR EMBODIMENTS

EXAMPLE

This example illustrates compositions based on a colored indicator and their behavior during deposition on chromatography paper or aluminum film via a metal mask or a polyester mask.

The table below lists the various compositions tested and the results obtained.

Mask used Composition/Ink Composition number Result metallic mask PVP360 1% /
Ethylene glycol 1 On chromato graphy paper: Random penetration without the pattern being respected

On aluminum film: no pattern deposit metallic mask D139 (hydrophobic fluorinated ink 2 On chromatography paper: pattern visible only for the largest perforations. Otherwise: continuous film of ink, too much ink passing through the mask. metallic mask BCP /
Diethylene glycol dimethyl ether 3 On chromatography paper: Passes too easily through the mask. metallic mask BCP /
Diethylene glycol dimethyl ether with 50% EG, then 75% EG, then 90% EG 4 On chromatography paper: Less ink on the paper, but still passes too much on the paper. No pattern visible. metallic mask BCP /
Cyclopentanone 5 On chromatography paper: Passes too easily through the mask Polyester mask BCP /
Diethylene glycol dimethyl ether 6 On chromatography paper: Passes too easily through the mask metallic mask DB9 /
PS 3000 0.5%
Diethylene glycol butyl ether 99.5% 7 On chromatography paper: Passes too easily through the mask, No pattern, a large stain.

On aluminum film: ^1st squeegee: no deposit of the pattern, 2 ^nd squeegee: passage of the ink. Polyester mask DB9 /
PS 3000 0.5%
Diethylene glycol butyl ether 99.5% 7 On chromatography paper: Good passage of the ink through the frame. The ink void areas remain empty when the frame is removed, but the ink continues to spread less colored than the drop areas.

On aluminum film: Passage of the ink but dewetting Polyester mask DB9 /
Diethylene glycol butyl ether 100% 8 On chromatography paper: Good passage of the ink through the frame. But spreading of the ink, instant loss of the pattern. Polyester mask DB9 /
PS 100000 0.5%
Diethylene glycol butyl ether 99.5% 9 Ditto DB9 / PS 3000 0.5% ink; Diethylene glycol butyl ether 95%
Disappearance of the screen-printed pattern faster than with PS 3000. Polyester mask DB9 /
PS 35000 2%
Diethylene glycol butyl ether 50%
MEK 50% 10 On chromatography paper: Good passage of the ink through the frame. But spreading of the ink, instant loss of the pattern Polyester mask DB9 /
PS 35000 2%
Diethylene glycol butyl ether 25%
MEK 75% 11 On chromatography paper: Ditto: Good passage of the ink through the frame. But spreading of the ink, instant loss of the pattern. Faster drying. Polyester mask DB9 /
PS 3000 0.5%
Diethylene glycol butyl ether 50%
MeOH 50% 12 On chromatography paper: Good passage of the ink through the frame. Borrow that fades: no pattern defined, ink already in the white areas. Polyester mask DB9 /
PS 3000 0.5%
Diethylene glycol butyl ether 50%
MEK 50% 13 On chromatography paper: Good passage of the ink through the frame. But spreading of the ink, instant loss of the pattern. Polyester mask DB9 /
PS 3000 0.5%
2-butoxyethanol 100% 14 On chromatography paper: Good passage of the ink through the frame. But spreading of the ink, rapid loss of the pattern. Polyester mask DB9 /
PS 3000 0.5%
2-Butoxyethanol 50%
MEK 50% 15 On chromatography paper: Good passage of the ink through the frame. But spreading of the ink, instant loss of the pattern. Polyester mask DB9 /
PS 3000 0.5%
2-Butoxyethanol 50%
EtOH 50% 16 On chromatography paper: Good passage of the ink through the frame. But spreading of the ink, instant loss of the pattern. Polyester mask DB9 /
HP 3000 2%
Diethylene glycol butyl ether 100% 17 On chromatography paper: Reproduction with more polymer, better resolved and pattern loss slower than with 0.5% PS 3000. Polyester mask DB9 /
1,2-Dimethoxyethane 100% 18 On chromatography paper: Evaporation of the solvent too quickly on the frame when scraping, the squeegee catches.
Polyester mask DB9 /
γ-Butyrolactone 100% 19 On chromatography paper: Good passage of the ink through the frame, Appearance of patterns at the end of scraping (when there is less ink). Good definition of the patterns, but the ink continues to spread less colored than the drop zones. Polyester mask DB9 /
Diethylene glycol butyl ether 25%
1,2-Dimethoxyethane 75% 20 On chromatography paper: Evaporation of the solvent too quickly on the frame when scraping, the squeegee catches.
Good passage of ink through the frame. But no reason. Polyester mask DB9 /
Diethylene glycol butyl ether 75%
1,2-Dimethoxyethane 25% 21 On chromatography paper: Easy scraping.
Good passage of ink through the frame. Borrowing, but no pattern. Polyester mask DB9 /
Tego Disperse 710 0.6%
Diethylene glycol butyl ether 100% 22 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line -> Impression only), but the ink continues to spread more slowly thanks to the thickener. Little effect of this thickener. Polyester mask DB9 /
Tego Disperse 710 5%
Diethylene glycol butyl ether 95% 23 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line -> Impression only), but the ink continues to spread more slowly thanks to the thickener. Little effect of this thickener Polyester mask DB9 /
Tego Disperse 710 10%
Diethylene glycol butyl ether 90% 24 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line -> Impression only), but the ink continues to spread more slowly thanks to the thickener. Little effect of this thickener Polyester mask DB9 /
Tego Disperse 655 5%
Diethylene glycol butyl ether 95% 25 DB9 turns green in the presence of the thickener.
On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line), but the ink continues to spread more slowly thanks to the thickener Polyester mask DB9 /
Tego Disperse 670 5% Diethylene glycol butyl ether 95%
26 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line), but the ink continues to spread more slowly thanks to the thickener. Disappearance of patterns. Polyester mask DB9 /
Tego Disperse 655 10%
Diethylene glycol butyl ether 45%
MEK 45% 27 DB9 turned green in the presence of thickener and MEK.
On chromatography paper: Good passage of the ink through the frame. Difficult to scrape off. Good definition of the patterns (large square and small line), Fixed pattern. Too much thickener to add given the effect obtained Polyester mask DB9 /
Tego Disperse 710 15%
Diethylene glycol butyl ether 42.5%
MEK 42.5% 28 On chromatography paper: Good passage of the ink through the frame. Difficult to scrape off. Good definition of the patterns (large square and small line). Too much thickener to add given the effect obtained Polyester mask DB9 /
Tego Disperse 670 5%
Diethylene glycol butyl ether 66%
MEK 33% 29 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line), but the ink continues to spread despite the thickener. Disappearance of patterns. The ink seems thin
Polyester mask DB9 /
Byk D410 2%
Diethylene glycol butyl ether 98% 30 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line), but the ink continues to spread despite the thickener. Disappearance of patterns.
Polyester mask DB9 /
Byk E410 30%
Diethylene glycol butyl ether 35%
MEK 35% 31 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line). Frame difficult to clean. DB9 toning overnight drying.
Polyester mask DB9 /
12-Hydroxydecanoic acid 5%
Diethylene glycol butyl ether 50%
MEK 50% 32 On chromatography paper: Good passage of the ink through the frame. No pattern after drying
Polyester mask DB9 /
PVC 5%
MEK 95% 35 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line).
Persistence of the pattern after drying. DB9 turns pink while drying.
Polyester mask DB9 /
PVDF (TRFE CFE 63009) 5%
MEK 95% 36 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line).
Persistence of the pattern after drying. DB9 turns pink while drying. Polyester mask DB9 /
XM220 (OP) 5%
MEK 95% 37 No dispersion of polymer beads. Polyester mask DB9 /
XM220 (OP) 5%
Diethylene glycol butyl ether 95% 38 On chromatography paper: Good passage of the ink through the frame. But spreading of the ink, instant loss of the pattern. Polyester mask DB9 /
Starch 5%
Diethylene glycol butyl ether 95% 39 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line), but the ink continues to spread despite the thickener. Disappearance of patterns.
Polyester mask DB9 /
Starch 5%
MEK 95% 40 DB9 turns green.
Polyester mask DB9 /
Triethanolamine 5% Diethylene glycol butyl ether 95%
41 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line), but the ink continues to spread despite the triethanolamine. Disappearance of patterns. Triethanolamine does not dry (Ɵeb 335.4°C).
Polyester mask DB9 /
Poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) 4%
MEK 96% 43 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line).
Persistence of the pattern after drying. DB9 turns pink while drying Polyester mask DB9 /
Poly(styrene-co-methyl methacrylate) 5%
MEK 95% 44 On chromatography paper: Good passage of the ink through the frame Polyester mask DB9 /
Poly(styrene-co-methyl methacrylate) 10%
MEK 90% 45 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line).
Persistence of the pattern after drying. No toning of DB9 or BCP during drying. (DB9 and BCP presolubilized in diethylene glycol butyl ether) Polyester mask DB9 /
Poly(styrene-co-methyl methacrylate) 20%
MEK 80% 46 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns (large square and small line).
Persistence of the pattern after drying. No toning of DB9 or BCP during drying.
Polyester mask DB9 /
PMMA 10%
MEK 90% 47 On chromatography paper: Good passage of the ink through the frame. Reasons poorly resolved.
Polyester mask DB9 /
PMMA 10%
Dichloromethane 90% 48 Gel ink Polyester mask DB9 /
PMMA 0.05%
Dichloromethane 100% 49 On chromatography paper: Good passage of the ink through the frame. Good pattern definition.
Persistence of the pattern after drying. Color change after 24 hours. Polyester mask DB9 /
Triethanolamine 29%
MEK 71% 50 On chromatography paper: Good passage of the ink through the frame. Good definition of the patterns but the ink continues to spread despite the triethanolamine. Disappearance of patterns. Triethanolamine does not dry (Ɵeb 335.4°C).
Polyester mask DB9 ε MEK /
PolyBisphenol A carbonate 10%
Dichloromethane 90% 51 On chromatography paper: Good passage of the ink through the frame. Good pattern definition.
Persistence of the pattern after drying. No toning of DB9 or BCP during drying. (and BCP ε Diethylene glycol butyl ether) Polyester mask DB9 /
Triethanolamine 5%
MEK 95% 54 On chromatography paper: Good passage of the ink through the frame. Good pattern definition.
But the patterns slowly fade away Polyester mask DB9 ε MEK/
Propylene polycarbonate 10%
MEK 90% 55 On chromatography paper: Good passage of the ink through the frame. Good pattern definition.
Persistence of the pattern after drying. No toning of DB9 or BCP during drying. (and BCP ε Diethylene glycol butyl ether)

The following abbreviations used in this table correspond to the following products:

-PVP: polyvinylpyrrolidone;

-PVC: polyvinyl chloride;

-PVDF: polyvinylidene fluoride;

-PMMA: polymethyl methacrylate;

-XM220 (OP): Fine polyethylene powder (UHMWPE), Average particle size: 30 µm (Mitsui Chemicals MIPELON XM-220).

It emerges from this table that the compositions in accordance with the invention (Compositions Nos. 44, 45, 46, 51 and 55) make it possible to obtain the best results.

Other tests were carried out with other colored indicators: bromocresol purple in the form of sodium salt, brilliant yellow (Yellow Brilliant), bromocresol green and thymol blue in two types of compositions:

-a first type of composition comprising, in addition to the colored indicator, poly(styrene-co-methyl methacrylate) and methyl ethyl ketone (with a first composition comprising respectively 0.1% by mass of colored indicator, 10% by mass of poly(styrene-co-methyl methacrylate) and 90% by mass of methyl ethyl ketone and a second composition comprising respectively 1% by mass of colored indicator, 10% by mass of poly(styrene-co-methyl methacrylate) and 89% by mass of methyl ethyl ketone);

-a second type of composition comprising, in addition to the colored indicator, propylene polycarbonate and methyl ethyl ketone (with a first composition comprising respectively 0.1% by mass of colored indicator, 10% by mass of propylene polycarbonate and 90% by mass methyl ethyl ketone and a second composition comprising respectively 1% by mass of colored indicator, 10% by mass of propylene polycarbonate and 89% by mass of methyl ethyl ketone.

These different compositions were deposited by manual screen printing via a polyester mask with convincing results.

Claims (18)

Composition which can be used for a process for printing a support by screen printing, comprising:
-at least one colored indicator chosen from anthraquinone compounds, azo compounds, triarylmethane compounds, xanthene compounds, indigo compounds, metal complexes, compounds comprising at least one stilbene group, coumarin compounds, compounds comprising at least a cyanine group, compounds comprising at least one phthalocyanine group, compounds comprising at least one porphyrin group, compounds comprising at least one hydrazone group;
at least one polymeric thickening agent; And
-at least one organic solvent. Composition according to Claim 1, in which the colored indicator is chosen from azo compounds and triarymethane compounds. A composition according to claim 1 or 2, wherein the color indicator is an azo compound. A composition according to any preceding claim, wherein when the color indicator is an azo compound, it is a diphenyldiazo compound. Composition according to any one of the preceding claims, in which, when the colored indicator is an azo compound, it is 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol corresponding to the following formula:

or the brilliant yellow corresponding to the following formula:
Composition according to claim 1 or 2, in which the color indicator is a triarylmethane compound. A composition according to claim 1 or 2, wherein when the color indicator is a triarylmethane compound, it is bromocresol purple as a sodium salt, bromocresol green or thymol blue. Composition according to any one of the preceding claims, in which the polymeric thickening agent is a polymeric thickening agent chosen from polycarbonates, copolymers comprising at least one styrene repeating unit and at least one (meth)acrylate repeating unit. Composition according to Claim 8, in which, when the thickening agent is a polycarbonate, it is chosen from:
- a polycarbonate resulting from the polycondensation of bisphenol-A and a carbonate and having as a repeating unit the unit of the following formula:

this polycarbonate also being called poly(Bisphenol A carbonate); Or
-a polycarbonate being a copolymer of carbon dioxide and propylene oxide and having as a repeating unit the unit of the following formula:

this polycarbonate being also called propylene polycarbonate. Composition according to Claim 8, in which, when the thickening agent is a copolymer comprising at least one styrene repeating unit and at least one (meth)acrylate unit, it is a copolymer resulting from the copolymerization of styrene and methyl methacrylate. Composition according to any one of the preceding claims, in which the organic solvent is chosen from ketone solvents, alkyl halide solvents, ether solvents and mixtures thereof. Composition according to Claim 11, in which:
- when the organic solvent is a ketone solvent, it is a dialkyl ketone solvent;
- when the organic solvent is an alkyl halide solvent, it is an alkyl chloride solvent;
-when the organic solvent is an ether solvent, it is a diethylene glycol alkyl ether solvent. Composition according to any one of the preceding claims, in which the thickening agent is present in a content ranging from 10 to 20% by mass relative to the total mass of the thickening agent and of the organic solvent(s), while the the organic solvents is (are) present in a content ranging from 80 to 90% by mass relative to the total mass of the thickening agent and of the organic solvent(s). Composition according to Claim 1, which consists exclusively of:
-at least one colored indicator chosen from azo colored indicators, triarylmethane colored indicators;
at least one polymeric thickening agent chosen from carbonate polymers, the copolymers comprising at least one styrene repeating unit and at least one (meth)acrylate repeating unit; And
-at least one organic solvent chosen from ketone solvents, alkyl halide solvents, ether solvents and mixtures thereof. Composition according to Claim 1, which is a composition chosen from the following compositions:
-a composition comprising, as color indicator, 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol or bromocresol purple in the form of a sodium salt, as thickening agent, poly(styrene-co -methyl methacrylate) and as organic solvent, methyl ethyl ketone, the thickening agent and the organic solvent being present at the rate of respective contents of 10% by mass and 90% by mass relative to the total mass of the thickening agent and organic solvent and, where appropriate, bromcresol purple in the form of a sodium salt which can be dissolved beforehand in diethylene glycol n-butyl ether;
-a composition comprising, as color indicator, 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol or bromocresol purple in the form of a sodium salt, as thickening agent, poly(Bisphenol A carbonate ) and as organic solvent, dichloromethane, the thickening agent and the organic solvent being present at the rate of respective contents of 10% by mass and 90% by mass relative to the total mass of the thickening agent and the organic solvent and, where appropriate, 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol which can be dissolved beforehand in methyl ethyl ketone and bromocresol purple in the form of a sodium salt which can be dissolved beforehand in diethylene glycol n- butyl ether;
-a composition comprising, as color indicator, 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol or bromcresol purple in the form of a sodium salt, as thickening agent, propylene polycarbonate and as organic solvent, methyl ethyl ketone, the thickening agent and the organic solvent being present at the rate of respective contents of 10% by mass and 90% by mass relative to the total mass of the thickening agent and the organic solvent and, if optionally, 2,2′-[4-(4-Aminophenylazo)phenylimino]diethanol which can be dissolved beforehand in methyl ethyl ketone and bromocresol purple in the form of a sodium salt which can be dissolved beforehand in diethylene glycol n-butyl ether. Use of a composition as defined according to any one of Claims 1 to 15 for printing a support by screen printing. Process for printing a support by screen printing comprising at least one step of depositing a composition as defined according to any one of Claims 1 to 15 on the support via a screen printing mask. System for the colorimetric detection of at least one chemical compound comprising a support covered, in whole or in part, by printing dots resulting from a composition as defined according to any one of Claims 1 to 15.