JP2002356061A - Heat sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a heat sensitive recording material excellent in antistatic properties. SOLUTION: In the heat sensitive recording material, in which a heat sensitive color developing layer mainly including a normally colorless or light-colored color forming compound and a color developing compound, which forms color in the color forming compound under heat, a polyoxypropylene alkylether- phosphate is included under the condition that the support is made of a plastic film or a synthetic paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a heat-sensitive recording material. More specifically, the present invention relates to a heat-sensitive recording material having excellent antistatic properties.

[0002]

2. Description of the Related Art Generally, a thermosensitive recording material is prepared by separately dispersing a developer such as a leuco dye and a phenolic substance into fine particles, and then mixing the two with a binder, a sensitizer, a filler, Additives such as lubricants to make a coating liquid, applied to paper, film, synthetic paper, etc., and record the color by the chemical reaction that occurs when one or both of the leuco dye and the developer are melted and contacted by heating Is what you get. For color development of the heat-sensitive recording sheet, a thermal printer or the like having a built-in thermal head is used. Compared with other recording methods, this thermal recording method is (1) no noise during recording, (2) there is no need for development and fixing, (3) maintenance-free, (4) machine is relatively inexpensive. With features such as
Facsimile field, computer output, printer field such as calculator, medical measurement recorder field,
It is widely used in the field of automatic ticket vending machines, the field of thermal recording labels and the like.

In recent years, with the spread of POS systems in retail stores, supermarkets, convenience stores, and the like, heat-sensitive recording materials have been used extensively for labels and price tags, and the objects of such use have been short-lived items such as fresh foods and daily products. In addition to shelf goods such as supplies and high-end goods, the use of in-process products in FA (factory automation), product management, and price tags is progressing. Environmental conditions in the use of these heat-sensitive recording materials include water, oil, plasticizer, etc., and long-term use, and more recently, in consideration of environmental issues, disposal methods, recovery and recycling, and materials similar to product containers. The use of plastic films and synthetic papers as supports (substrates) has been increasing in order to cope with the development of materials. However, the generation of static electricity, which was not considered a problem when paper was used as a support, has frequently occurred in the production and use of heat-sensitive recording materials in the case of plastic films and synthetic paper. Adverse effects have been found.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a manufacturing method of a thermosensitive recording material which does not cause a danger of a disaster due to the generation of static electricity, and that the product is likely to adhere to dust and dirt which are likely to occur when printing with a thermal printer. There is no thermal recording material.

[0005]

Means for Solving the Problems The present inventors have made various studies to achieve the above object, and as a result, completed the present invention. That is, the present invention

(1) A heat-sensitive recording material comprising, as a main component, a heat-sensitive color-forming layer containing, as a main component, a colorless compound which is usually colorless or light-colored, and a color-forming compound capable of forming a color when heated. The present invention relates to a thermosensitive recording material containing a polyoxypropylene alkyl ether / phosphate ester and wherein the support is a plastic film or synthetic paper.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a colorless or pale-colored color-forming compound and a color-developing compound, polyoxypropylene alkyl, capable of coloring the color-forming compound when heated on a support (plastic film or synthetic paper) are usually used. Uses ethers and phosphates as the main components, respectively, and uses the following binders and other necessary fillers, sensitizers (thermally fusible compounds), and heat-sensitive additives. A coloring layer is prepared.

In forming the thermosensitive coloring layer in the present invention, the color-forming compound is usually 1 to 50% by weight, preferably 5 to 30% by weight, and the color-developing compound is usually 1 to 60% by weight.
Preferably 5 to 30% by weight, polyoxypropylene alkyl ether / phosphate ester is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and the binder is usually 1 to 10% by weight.
90% by weight, a filler and a sensitizer (a heat-fusible compound) are each usually 0 to 80% by weight, and other lubricants, surfactants, defoamers, ultraviolet absorbers and the like are each in an arbitrary ratio. Usually, each is used in an amount of 0 to 30% by weight (weight% is the weight ratio of each component in the thermosensitive coloring layer).

In a more preferred embodiment, of the above composition, the color-developing compound is used in an amount of usually 0.5 to 20 times, preferably 1 to 5 times the color-forming compound 1.

The polyoxypropylene alkyl ether / phosphate ester used in the present invention is, for example, of the following formula (1)

[0011]

Embedded image

(In the formula (1), R represents an alkyl group, and n represents 1
To 10 respectively. )

Is a compound represented by the formula: The alkyl group in the formula (1) preferably has 20 or less carbon atoms, and n is preferably 2 to 5. Specific examples include, for example, polyoxypropylene butyl ether / phosphate (CAS No. 507).
69-39-6), polyoxypropylene octyl ether / phosphate (CAS No. 31800-8)
8-1), polyoxypropylene decyl ether / phosphate (CAS No. 9004-80-2), polyoxypropylene dodecyl ether / phosphate (CAS No. 25852-45-3), polyoxypropylene tridecyl Ether / phosphate ester (CA
S No. 68311-04-6), polyoxypropylene tetradecyl ether / phosphate (CAS)
No. 84687-18-3), polyoxypropylene pentadecyl ether / phosphate ester (CAS N
o. 68797-58-0) and the like.

The polyoxypropylene alkyl ether / phosphate ester can be used for the intermediate layer or the overcoat layer (protective layer) described below. It is most effective to include it.

As the plastic film or synthetic paper used as a support in the present invention, for example, a polymer film such as a polyester film, a polycarbonate film, a polyolefin film, a polystyrene film, a polyamide film or the like and an inorganic pigment-containing film are used. The same film or the same film containing voids (cavities) is used. Its thickness is about 20-500 μm,
These films or synthetic papers have a surface wetting tension of 35 dyn / c due to the need to provide a thermosensitive coloring layer as a support.
m or more, preferably 40 dyn / cm or more, more preferably 50 dyn / cm or more. Therefore, for a film having a low wetting tension, a film having the above wetting tension can be obtained by applying a corona discharge treatment or applying a polymer resin, a surfactant or the like, and the coatability between the film and the thermosensitive coloring layer can be obtained. And the adhesion can be improved.

The color-forming compound used in the present invention is not particularly limited as long as it is generally used for pressure-sensitive recording paper or heat-sensitive recording paper. Examples of color-forming compounds that can be used include, for example, fluoran compounds, triarylmethane compounds, spiro compounds, diphenylmethane compounds, thiazine compounds, lactam compounds,
Fluorene compounds and the like.

Specific examples of fluoran compounds that can be used include, for example, 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-
7-anilinofluoran, 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isopentylamino)-
6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluoran, 3- [N-ethyl-N- (3-ethoxypropyl) Amino] -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-hexylamino) -6
Methyl-7-anilinofluoran, 3-dipentylamino-6-methyl-7-anilinofluoran, 3- (N-
Methyl-N-propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tetrahydrofurylamino) -6-methyl-7-anilinofluoran, 3-diethylamino-6 Methyl-7- (p-chloroanilino) fluoran, 3-diethylamino-6-methyl-7- (p-fluoroanilino) fluoran, 3-
[N-ethyl-N- (p-tolyl) amino] -6-methyl-7-anilinofluoran, 3-diethylamino-6
-Methyl-7- (p-toluidino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino)
Fluorane, 3-diethylamino-7- (o-fluoroanilino) fluoran, 3-dibutylamino-7- (o
-Fluoroanilino) fluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3-
Pyrrolidino-6-methyl-7-anilinofluoran, 3
-Diethylamino-6-chloro-7-ethoxyethylaminofluoran, 3-diethylamino-6-chloro-7
-Anilinofluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7-octylfluoran,
3- [N-ethyl-N- (p-tolyl) amino] -6
Methyl-7-phenethylfluoran and the like.

Specific examples of triarylmethane compounds that can be used include, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone or CVL),
3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,
2-dimethylaminoindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3- (2-phenylindole-
3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrole-2
-Yl) -6-dimethylaminophthalide and the like.

Further, specific examples of spiro compounds that can be used include, for example, 3-methylspirodinaphthopyran,
Ethylspirodinaphthopyran, 3,3′-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-propylspirobenzopyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 1,3,3
-Trimethyl-6-nitro-8'-methoxyspiro (indoline-2,2'-benzopyran) is a specific example of a diphenylmethane-based compound, for example, N-halophenyl-leuco auramine, 4,4-bis-dimethyl Aminophenylbenzhydryl benzyl ether, N-2,
Specific examples of thiazine compounds include 4,5-trichlorophenylleuco auramine and the like, for example, benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue and the like, specific examples of lactam compounds include
For example, rhodamine B anilinolactam, rhodamine B-
Specific examples of fluorene-based compounds such as p-chloroanilinolactam include, for example, 3,6-bis (dimethylamino) fluorenespiro (9,3 ′)-6′-dimethylaminophthalide, 3,6-bis (Dimethylamino) fluorenespiro (9,3 ′)-6′-pyrrolidinophthalide,
3-dimethylamino-6-diethylaminofluorenespiro (9,3 ')-6'-pyrrolidinophthalide and the like. These coloring compounds are used alone or in combination.

As the color-developing compound used in the present invention, any compounds can be used as long as they are generally used for pressure-sensitive recording paper or heat-sensitive recording paper, and are not particularly limited. Specific examples include, for example, α-naphthol, β-naphthol, p-octylphenol, 4-t-octylphenol, pt-butylphenol, p-phenylphenol, 1,1-bis (p-hydroxyphenyl)
Propane, 2,2-bis (p-hydroxyphenyl) propane (alias: bisphenol A or BPA), 2,2
-Bis (p-hydroxyphenyl) butane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 4,
4'-thiobisphenol, 4,4'-cyclo-hexylidenediphenol, 2,2'-bis (2,5-dibromo-4-hydroxyphenyl) propane, 4,4'-isouropyridenebis (2- t-butylphenol),
2,2′-methylenebis (4-chlorophenol),
4,4′-dihydroxydiphenyl sulfone, 2,4 ′
-Dihydroxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-benzyloxydiphenylsulfone, bis (4-hydroxyphenyl) acetic acid Methyl, bis (4-
Phenolic compounds such as hydroxyphenyl) butyl acetate and benzyl bis (4-hydroxyphenyl) acetate;
-Benzyl benzoate, ethyl p-hydroxybenzoate, dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate, ethyl 5-hydroxyisophthalate, 3,5-di-t-butylsalicylic acid, 3,5
Examples thereof include aromatic carboxylic acid derivatives such as -di-α-methylbenzylsalicylic acid, aromatic carboxylic acids and polyvalent metal salts thereof, but are not limited thereto.

Specific examples of sensitizers (thermofusible compounds) that can be used in the present invention include animal and plant waxes,
Waxes such as synthetic waxes, higher fatty acids, higher fatty acid amides, higher fatty acid anilides, naphthalene derivatives, aromatic ethers, aromatic carboxylic acid derivatives, aromatic sulfonic acid ester derivatives, carbonic or oxalic acid diester derivatives, biphenyl derivatives, terphenyl Derivatives, sulfone derivatives, and the like that are solid at room temperature and have a melting point of about 70 ° C. or more can be used.

Specific examples of waxes include, for example, wood wax, carnauba wax, shellac, paraffin, montan wax, paraffin oxide, polyethylene wax, polyethylene oxide, etc., and higher fatty acids such as stearic acid, behenic acid, etc. As higher fatty acid amides, for example, stearic acid amide, oleic acid amide, N-methylstearic acid amide, erucic acid amide, methylolbehenic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide, etc. For example, stearic acid anilide, linoleic acid anilide and the like, as naphthalene derivatives, for example, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester and the like,
Examples of the aromatic ether include 1,2-diphenoxyethane, 1,4-diphenoxybutane, 1,2-bis (3-methylphenoxy) ethane, and 1,2-bis (4-
Methoxyphenoxy) ethane, 1,2-bis (3,4-
Dimethylphenyl) ethane, 1-phenoxy-2- (4
-Chlorophenoxy) ethane, 1-phenoxy-2-
(4-methoxyphenoxy) ethane and the like; and aromatic carboxylic acid derivatives such as p-hydroxybenzoic acid benzyl ester, p-benzyloxybenzoic acid benzyl ester and terephthalic acid dibenzyl ester; and aromatic sulfonic acid ester derivatives Examples thereof include p-toluenesulfonic acid phenyl ester, phenylmesitylenesulfonate, and 4-methylphenylmesitylenesulfonate. Examples of the carbonic acid or oxalic acid diester derivatives include, for example, diphenyl carbonate, dibenzyl oxalate, and dioxalate. 4-chlorobenzyl) ester and oxalic acid di (4-methylbenzyl) ester include biphenyl derivatives such as p-benzylbiphenyl and p-benzylbiphenyl.
Examples of allyloxybuphenyl and the like and terphenyl derivatives include, for example, m-terphenyl, and examples of the sulfone derivative include diphenylsulfone and the like.

Specific examples of the binder that can be used include, for example, methyl cellulose, methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose, polyvinyl alcohol (PVA), carboxyl group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, Polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, starch and derivatives thereof, casein, gelatin, water-soluble isoprene rubber, alkali salt of styrene / maleic anhydride copolymer, iso (or diiso) butylene / maleic anhydride copolymer Water-soluble ones such as alkali salts or polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polystyrene, polyacrylate, polyurethane, styrene / Hydrophobic polymer emulsions such as tadiene (SB) copolymer, carboxylated styrene / butadiene (SB) copolymer, styrene / butadiene / acrylic acid copolymer, and composite particles of colloidal silica and acrylic resin are used. Can be

Specific examples of the filler that can be used include, for example, calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, and polystyrene resin. And urea-formalin resins.

Further, in the present invention, various additives other than those described above can be used. Examples of other additives which can be used include, for example, stearin for the purpose of preventing thermal head abrasion and sticking. Higher fatty acid metal salts such as zinc acid and calcium stearate, phenol derivatives for imparting antioxidant or antiaging effects, ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds, various surfactants, defoamers And the like.

Using the above materials, the heat-sensitive recording material of the present invention is prepared, for example, by the following method. That is, first, a color-forming compound and a color-developing compound are separately pulverized and dispersed in a dispersing machine such as a ball mill, an attritor, or a sand mill together with a binder or other additives as necessary (see, for example). When the pulverization and dispersion are performed by a wet method, water is usually used as a medium). The polyoxypropylene alkyl ether / phosphate ester may be mixed with the color-forming compound or the color-developing compound at the time of pulverization or dispersion, or may be added at the time of preparing the thermosensitive coloring layer coating solution. The heat-sensitive color-forming layer coating solution containing the above-described color-forming compound, color-developing compound and polyoxypropylene alkyl ether / phosphate ester as essential components on a plastic film or synthetic paper so as to have a dry weight of usually 1 to 20 g / m ^2. Is coated with a bar coater or a blade coater and dried to obtain the heat-sensitive recording material of the present invention. If necessary, an intermediate layer may be provided between the thermosensitive coloring layer and the support, or an overcoat layer (protective layer) may be provided on the thermosensitive coloring layer. The intermediate layer and the overcoat layer (protective layer) are pulverized and dispersed in the same manner as in the preparation of the thermosensitive coloring layer coating solution together with, for example, the above-mentioned binder or other additives as necessary, or the intermediate layer coating solution or After forming an overcoat layer (protective layer) coating solution, the solution is applied by drying so as to have a weight of usually about 0.1 to 10 g / m ² and dried. Polyoxypropylene alkyl ether / phosphate ester can be used for the intermediate layer or the overcoat layer (protective layer). However, in order to exhibit the antistatic effect in the range from the production stage of the thermosensitive recording material to the use of the product. It is most effective to include it in the thermosensitive coloring layer.

The heat-sensitive recording material of the present invention, which contains a colorless or light-coloring compound, a color-developing compound, and a polyoxypropylene alkyl ether / phosphate ester on a support (plastic film or synthetic paper), is conventionally known. The present invention provides a production environment and recording characteristics of a heat-sensitive recording material having an antistatic effect as compared with those of Example 1.

[0028]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" indicates parts by weight and "%" indicates% by weight.

Example 1 (Formation of thermosensitive coloring layer) A mixture having the following composition was pulverized and dispersed using a sand grinder so as to have an average particle diameter of 1 μm or less, and the solutions [A], [B], [ C] was prepared. [A] solution: 3-dibutylamino-6-methyl-7-anilinofluoran 25 parts 25% PVA aqueous solution 20 parts water 55 parts [B] solution: bis (3-allyl-4-hydroxyphenyl) sulfone 25 parts 25% PVA aqueous solution 20 parts Water 55 parts

Next, a coating solution for the thermosensitive coloring layer was prepared by mixing at the following ratio, and a transparent polyester film (thickness: 38) was prepared.
μm) was applied and dried under the following conditions so that the dry weight was 7 g / m 2 to obtain a thermosensitive coloring layer. [A] Liquid 12 parts [B] Liquid 24 parts Polyoxypropylene butyl ether / phosphate 1 part 20% aqueous stearamide dispersion 45 parts 50% polystyrene aqueous dispersion 12 parts 50% carboxylated styrene / butadiene copolymer Latex 8 parts

The coating of the heat-sensitive coloring layer was performed at a coating speed of 60 m / min using a coater of a reverse gravure head system, and drying was performed through a chamber having a temperature of 50 ° C. and a length of 25 m. At this time, the amount of static electricity at a distance of 5 cm from the coating film on the exit side of the drying chamber was 0 to-
0.1 kv. The surface resistivity of the obtained thermosensitive coloring layer was 10 ¹⁰ .

(Formation of Protective Layer) Further, a protective layer coating solution having the following ratio was applied onto the above-mentioned thermosensitive coloring layer so that the weight when dried was 3 g / m ^2, and dried to form a protective layer. A heat-sensitive recording material of the present invention was obtained. 40% styrene / acrylate copolymer emulsion 17 parts 5% bentonite aqueous dispersion 30 parts 30% zinc stearate aqueous dispersion 4 parts

Example 2 A heat-sensitive recording material of the present invention having a protective layer was obtained in the same manner as in Example 1, except that a transparent polystyrene film (thickness: 40 μm) was used instead of the transparent polyester film of Example 1.

Example 3 A heat-sensitive recording material of the present invention having a protective layer was obtained in the same manner as in Example 1 except that a white polystyrene film (thickness: 65 μm) was used instead of the transparent polyester film of Example 1.

Example 4 The heat-sensitive recording material of the present invention having a protective layer in the same manner as in Example 1 except that a polyolefin-based void-containing synthetic paper (80 μm thick) was used instead of the transparent polyester film of Example 1. I got

Example 5 The heat-sensitive recording of the present invention having a protective layer in the same manner as in Example 1 except that polyoxypropylene octyl ether / phosphate was used instead of the polyoxypropylene butyl ether / phosphate in Example 1 The material was obtained.

Example 6 In the same manner as in Example 1 except that polyoxypropylene dopentadecyl ether / phosphate was used instead of the polyoxypropylene butyl ether / phosphate of Example 1, the present invention having a protective layer was used. A heat-sensitive recording material was obtained.

Comparative Example 1 A comparative thermosensitive recording material was obtained in the same manner as in Example 1 except that the polyoxypropylene butyl ether / phosphate ester of Example 1 was used.

The following quality performance tests were carried out on the heat-sensitive recording materials of the present invention and comparative heat-sensitive recording materials obtained as described above.

Table 1 Quality performance test Background 1) Color density 2) Static electricity amount 3) Surface resistance value 4) Print quality 5) Example 1 0.07 1.63 0 to -0.1 10 ¹⁰ ○ Example 20 0.07 1.64 0 10 ¹⁰ ○ Example 3 0.03 1.61 0 10 ¹⁰ ○ Example 4 0.04 1.65 0 10 ⁹ ○ Example 5 0.07 1.63 0 -0.1 10 ¹⁰ ○ Example 6 0.07 1.64 0 to -0.1 10 ¹⁰ ○ Comparative Example 1 0.07 1.61 -3 to -4 10 ¹³ △ △

1) Background: The uncolored portion of the sample was measured with a Macbeth reflection densitometer (RD-914, manufactured by Macbeth) (Macbeth reflection density). 2) Color density: Macbeth reflection density value of a color portion printed using a commercially available POS label printer (D-805P, manufactured by Ishida Co., Ltd.). 3) Amount of static electricity: At a distance of 5 cm from the surface of the thermosensitive coloring layer coated film on the outlet side of the drying chamber, a charging checker (KSD-0101, manufactured by Kasuga Electric Co., Ltd.)
The amount of static electricity (kV) measured in the above. 4) Surface resistance: Hiresta resistance meter (MCP-HT2, manufactured by Mitsubishi Chemical Corporation) in a constant temperature and humidity room at 24 ° C. and 65% RH.
Surface resistance value (Ω / □) of the thermosensitive coloring layer-coated film measured by using the above-mentioned method. 5) Print quality: The uniformity of the colored portion printed using the above printer. ○ --- No white spots (pinhole shape). Δ --- There are times when white spots occur. × --- White spots frequently occur.

As is clear from the table, the heat-sensitive recording material of the present invention has no static electricity generated at the time of coating the heat-sensitive coloring layer, has a low surface resistance value, and has white spots which are likely to occur due to dust and dust in actual printing. I can't.

[0043]

As described above, a heat-sensitive recording material having excellent antistatic properties was obtained.

Claims (1)

[Claims] (1) A thermosensitive recording material comprising, as a main component, a heat-sensitive coloring layer containing, as a main component, a colorless compound which is usually colorless or pale, and a color developing compound capable of forming a color when heated. A heat-sensitive recording material containing an oxypropylene alkyl ether / phosphate ester and wherein the support is a plastic film or synthetic paper.