EP0704317B1 - Heat-sensitive recording material - Google Patents
Heat-sensitive recording material Download PDFInfo
- Publication number
- EP0704317B1 EP0704317B1 EP19940115223 EP94115223A EP0704317B1 EP 0704317 B1 EP0704317 B1 EP 0704317B1 EP 19940115223 EP19940115223 EP 19940115223 EP 94115223 A EP94115223 A EP 94115223A EP 0704317 B1 EP0704317 B1 EP 0704317B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- sensitive recording
- sensitive
- color
- color developing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3331—Macromolecular compounds
Definitions
- the present invention relates to a heat-sensitive recording material.
- the present invention further relates to the use of a dispersing agent having excellent dispersing capability for heat-sensitive dyes and color developing agents which is suited for producing heat-sensitive recording materials.
- the present invention still further relates to a process for producing aqueous dispersions having a dispersoid of a particulate heat-sensitive dye or color developing agent.
- Heat-sensitive recording materials comprise a paper, plastic film or metal-deposited paper and, provided thereon, a heat-sensitive recording layer that will undergo, by heat energy, chemical or physical change to form color and give recorded images.
- the heat-sensitive recording materials have advantages of giving recorded images by simple heating, requiring no complex treatments such as developing and fixing, causing no noise upon recording and providing relatively inexpensive recording system.
- the materials therefore have been widely used as recording materials for electronic calculators, word processors, telex machines, facsimiles and various calculators.
- These heat-sensitive recording materials generally have a heat-sensitive recording layer comprising a colorless or light-color leuco dye and an acid such as an organic acid or a phenol, that reacts upon heating with the leuco dye, thereby causing it to form color.
- a heat-sensitive recording layer comprising a colorless or light-color leuco dye and an acid such as an organic acid or a phenol, that reacts upon heating with the leuco dye, thereby causing it to form color.
- a heat-sensitive recording material having heat-sensitive recording layer in which a heat-sensitive dye and a color developing agent (developer) having a particle diameter of not more than 1 ⁇ m are dispersed uniformly and present in high density and in a thin layer, so that the color or the texture of the substrate used is not observable.
- a heat-sensitive dye and a color developing agent (developer) having a particle diameter of not more than 1 ⁇ m are dispersed uniformly and present in high density and in a thin layer, so that the color or the texture of the substrate used is not observable.
- Known dispersing agents for heat-sensitive dyes and color developing agents include a partially saponified polyvinyl alcohol having a low molecular weight (JP-A-62-105687 (1987)), a sulfonic acid group-modified polyvinyl alcohol having a low molecular weight (JP-B-2-52637 (1990)), and alkali metal salts or ester of an ⁇ -olefin-maleic anhydride copolymer (JP-A-63-214479 (1998)).
- these agents have been incapable of exhibiting sufficient performance.
- the partially saponified polyvinyl alcohol having a low molecular weight has insufficient dispersing capability for heat-sensitive dyes and color developing agents and cannot stably disperse them in a particle size of not more than 1 ⁇ m.
- the sulfonic acid-modified polyvinyl alcohol having a low molecular weight has a dispersing capability of some level but makes considerably visible the texture color of the substrate.
- the maleic anhydride-based copolymer is, when used in a coating liquid, only insufficiently compatible with the binder contained in the liquid, thereby often causing agglomeration of dispersed particles or viscosity increase of the liquid and, further, has the problem of making considerably visible the texture color of the substrate.
- an object of the present invention is to provide a heat-sensitive recording material capable of making invisible the texture color of the substrate and giving clear images even upon high-speed printing.
- Another object of the present invention is to provide the use of a dispersing agent having excellent dispersing capability for particulate heat-sensitive dyes and color developing agents and suited for producing heat-sensitive recording materials.
- Still another object of the present invention is to provide a process for producing aqueous dispersions having a dispersoid of a particulate heat-sensitive dye or color developing agent.
- the modified polyvinyl alcohol (hereinafter the term “polyvinyl alcohol” is sometimes referred to as "PVA”) used in the present invention should contain 2.5 to 8 mole % of units from a carboxyl group-containing monomer and have a degree of saponification of 40 to 65 mole % and a viscosity average degree of polymerization of 50 to 500.
- the content of the carboxyl group-containing monomer units be 2.5 to 8 mole %, preferably 3 to 6 mole %.
- the degree of modification by carboxyl group being less than 2.5 mole %, the printed parts on the heat-sensitive recording material have a low color density and the PVA has low dispersing capability for heat-sensitive dyes and color developing agents so that the dispersoid agglomerates after an aqueous dispersion has been prepared.
- the degree of modification exceeding 8 mole %, the non-printed part on the heat-sensitive recording material has a low whiteness and aqueous dispersions prepared with the PVA also have a very low whiteness.
- carboxyl group-containing monomer unit there is no specific limitation to the type of the carboxyl group-containing monomer unit and its examples include units from fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, trimellitic anhydride and itaconic anhydride.
- monomer units dibasic acids are preferred and itaconic acid is particularly preferred.
- the modified PVA has a degree of saponification of 40 to 65 mole %, preferably 45 to 60 mole % and more preferably 50 to 60 mole %. If the degree of saponification is less than 40 mole %, the dispersing capability for heat-sensitive dyes and color developing agents will decrease and aqueous dispersions prepared with the PVA will, after preparation thereof, cause the dispersoid to agglomerate, so that a usable heat-sensitive recording material cannot be obtained.
- the resulting heat-sensitive recording material will give printed parts having a low color density and, besides, aqueous dispersions prepared with the PVA will have too high a viscosity to be handled with ease so that the concentration of the dispersions cannot be elevated.
- the viscosity average degree of polymerization (hereinafter simply referred to as "degree of polymerization") of the modified PVA should be in a range of 50 to 500 and is preferably in a range of 100 to 300. If the degree of polymerization is less than 50, the PVA will become incapable of dispersing fine particles and, after preparation of an aqueous dispersion, the dispersoid will agglomerate, whereby a usable heat-sensitive recording material cannot be obtained.
- the resulting heat-sensitive recording material will give printed parts having a low color density and, besides, aqueous dispersions prepared with the PVA will have too high a viscosity to be handled with ease so that the concentration of the dispersions cannot be elevated.
- the carboxyl group-modified PVA can be prepared by any process with no specific restrictions.
- one of the above mentioned carboxylic acids is reacted with polyvinyl alcohol by post-reaction, or a copolymer of vinyl acetate and an ethylenically unsaturated carboxylic acid is saponified.
- Concrete examples of such processes are disclosed in Japanese Patent Publication No. 21312/1970 and Japanese Patent Application Laid-open Nos. 91995/1978, 28389/1979 and 28390/1979.
- the carboxyl groups in the PVA of the invention may either be present in the form of an alkali metal salt such as COONa or in the form of COOH. Where the carboxyl group-containing monomer is a dibasic acid, one of the two carboxylic acids present in the monomer may form a lactone ring.
- the carboxyl group-modified polyvinyl alcohol used in the present invention may be copolymerized with other monomers or its ends may be modified by using a chain transfer agent.
- Any ethylenically unsaturated monomer may be copolymerized with a vinyl ester as long as it is copolymerizable therewith.
- Examples of such monomers are ⁇ -olefins, e.g. ethylene, propylene, n-butene, isobutene and 1-hexadecene; carboxylic acid-containing monomers, e.g.
- (meth)acrylic acid fumaric acid, crotonic acid, maleic acid and maleic anhydride, and salts of the foregoing;
- (meth)acrylic acid esters e.g. methyl (meth)acrylate, n-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and stearyl (meth)acrylate; other esters, e.g. dimethyl fumarate, dimethyl itaconate, dimethyl maleate, monomethyl maleate and methyl crotonate; vinyl ethers, e.g.
- sulfonic acid group-containing monomers e.g. vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid, and salts of the foregoing; amido group-containing monomers, e.g.
- (meth) acrylamide N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-t-butoxy(meth)acrylamide, N-t-octyl(meth)acrylamide and N-vinylpyrrolidone; quaternary ammonium salt-containing monomers, e.g. dimethylaminoethyl(meth)acrylamide; silyl group-containing monomers, e.g. vinylhydroxysilane and 3-trimethoxysilylpropyl (meth)acrylate; and acetyl group-containing monomers, e.g. allyl acetate, dimethylallyl acetate and isopropenyl acetate.
- quaternary ammonium salt-containing monomers e.g. dimethylaminoethyl(meth)acrylamide
- silyl group-containing monomers e.g. vinylhydroxysilane and 3-trimethoxysilylpropyl (
- the modified PVA can be contained in a heat-sensitive recording layer of the heat-sensitive recording material in any amount with no particular limitation. However, it is preferred that the modified PVA be contained in an amount of 3 to 30 parts by weight based on 100 parts by weight of the sum of the amounts of a heat-sensitive dye and a color developing agent, more preferably 5 to 20 parts by weight and most preferably 7 to 16 parts by weight on the same basis.
- the dye or agent is dispersed by using a dispersing agent of the above modified PVA.
- the dispersing agent can be used in any amount, but preferably in an amount of 3 to 30 parts by weight based on 100 parts by weight of the heat-sensitive dye or the color developing agent, more preferably 5 to 20 parts by weight and most preferably 7 to 16 parts by weight on the same basis.
- the finished aqueous dispersion preferably has a dispersoid concentration of 20 to 70% by weight, more preferably 40 to 60% by weight.
- Dispersing operation for the heat-sensitive dye or the color developing agent is carried out in a sand mill containing a multiplicity of glass beads having an average particle diameter of 0.2 to 3 mm (preferably 0.3 to 0.8 mm)
- the dispersing operation is completed in 1 hour to 1 week (preferably 3 hours to 4 days, in particular 1 to 4 days where it is desired to obtain fine dispersoid particles having an average particle diameter of not more than 0.45 ⁇ m).
- the use of the dispersing agent of the present invention can give aqueous dispersions having a dispersoid of a heat-sensitive dye or a color developing agent having a particle diameter ranging from 0.1 to 1 ⁇ m (preferably 0.3 to 0.8 ⁇ m, more preferably 0.2 to 0.6 ⁇ m and most preferably 0.2 to 0.45 ⁇ m).
- Any heat-sensitive dye being used for conventional pressure- or heat-sensitive papers can be used in the present invention and its concrete examples include triarylmethane-based compounds, e.g. 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (Crystal Violet Lactone), 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide and 3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthalide; diphenylmethane-based compounds, e.g.
- the color developing agent used in the present invention be selected from phenol derivatives and aromatic carboxylic acid derivatives, in particular from bisphenols.
- phenols e.g. p-octylphenol, p-tert-butylphenol, p-phenylphenol, 1,1-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)pentane, 2,2-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)hexane, 2,2-bis(p-hydroxyphenyl)hexane, 1,1-bis(p-hydroxyphenyl)-2-ethyl-hexane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane and dihydroxydiphenyl ether; and aromatic carboxylic acid derivatives, e.g.
- binders usable for this purpose are cellulose derivatives, e.g. starch, starch derivatives, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose; water-soluble polymers, e.g.
- polyvinyl alcohol poly(sodium acrylate), polyvinylpyrrolidone, acrylamide/acrylic acid ester copolymers, acrylamide/acrylic acid ester/methacrylic acid ternary copolymers, alkali metal salts of styrene/maleic anhydride copolymer, alkali metal salts of isobutylene/maleic anhydride copolymer; polyacrylamide, sodium alginate, gelatin and casein; emulsions of polyvinyl acetate, polyurethanes, polyacrylic acid, polyacrylic acid esters, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, ethylene/vinyl acetate copolymer and the like; and latices of styrene/butadiene copolymer, styrene/butadiene/acrylic acid ester and the like.
- the aqueous binder is added preferably in an amount of 1 to 20 parts by weight based on 100 parts by weight of the sum of the amounts of the dye and the color developing agent.
- the heat-sensitive recording layer may incorporate, besides a heat-sensitive dye and a color developing agent, auxiliary additives used for conventional heat-sensitive recording materials, such as a filler, surfactant, heat-fusible substance (or lubricant) and agent for preventing color development under pressure.
- auxiliary additives used for conventional heat-sensitive recording materials, such as a filler, surfactant, heat-fusible substance (or lubricant) and agent for preventing color development under pressure.
- the heat-sensitive recording layer can be formed by any of known processes, e.g. air-knife coating, plate coating, embossing, roll coating, spraying, dipping, bar coating and extrusion coating.
- any substrate can be used for the heat-sensitive recording material.
- Appropriate selection is made for example from various papers, synthetic papers and synthetic resin films. It is, however, generally desirable to use a paper.
- the heat-sensitive recording materials of the present invention give printed parts having good color development and non-printed part that hardly fogs (coloration of substrate).
- the heat-sensitive recording materials of the present invention having excellent high-speed printability and excellent resolution of images, are suitably usable in the field requiring high-speed printing, such as facsimile.
- the dispersing agent used in the present invention having excellent dispersing capability for heat-sensitive dyes and color developing agents, can give aqueous dispersion having a dispersoid of a particulate heat-sensitive dye or color developing agent in a high concentration and having a low viscosity.
- the aqueous dispersion obtained having excellent applicability to the surface of the base paper upon preparation of heat-sensitive recording papers and containing dispersoids of a heat-sensitive dye and a color developing agent dispersed in fine particles, can produce heat-sensitive recording materials having markedly high resolution.
- Leuco dye S-205, made by Yamada Kagaku K.K. 20% Ten % aqueous solution of a carboxyl group-modified PVA (modified by copolymerization of 4 mole % of itaconic acid; degree of polymerization: 500; degree of saponification: 46 mole %) 20% Water 59.9% Antifoam (SURFYNOL® 440, made by Nisshin Chemical Co., Ltd.) 0.1%
- aqueous mixtures A and B were each transferred into a sand mill (batch type, desk-top sand mill made by Kansai Paint Co.), and 300 cc of glass beads (soda quartz glass having a diameter of 0.5 mm) was added. Dispersion was effected at a high rotation (2,170 rpm) for 6 hours.
- the aqueous mixture C was dispersed in a homogenizer (10,000 rpm) for 2 minutes.
- the aqueous dispersion A of the heat-sensitive dye was evaluated according to the following methods.
- the particle diameter was measured with a laser diffraction particle size analyzer (SALD-1000, made by Shimadzu Corp.).
- the aqueous dispersion was allowed to stand for about 1 hour after completion of 6-hour dispersion and then tested for viscosity at 30°C.
- the aqueous dispersion was allowed to stand for about 1 hour after completion of 6-hour dispersion and then tested for whiteness with a color and color and color difference meter (Z-1001DP, made by Nippon Denshoku Kogyo Co., Ltd.).
- the whiteness value of "0" means completely white, and the degree of discoloration increases with the absolute value of the negative values.
- a coating liquid for heat-sensitive recording layer was prepared by mixing with stirring 1 part of the aqueous dispersion A, 4 parts of the aqueous dispersion B, 2 parts of the aqueous dispersion C and 2 parts of a 10% aqueous solution of polyvinyl alcohol (degree of polymerization: 1,750, degree of saponification: 98.5 mole %).
- the coating liquid was applied with a wire bar coater on a base paper (woodfree paper having a weight of 52 g/m 2 ) in an amount of 6 g/m 2 (solid base), dried at 50° C for 10 minutes and then surface-treated with a super calender (linear pressure: 30 kg/cm; roll diameter: top (metal): 20 cm, bottom (rubber): 30 cm), to obtain a heat-sensitive recording paper.
- a base paper woodfree paper having a weight of 52 g/m 2
- 6 g/m 2 solid base
- the heat-sensitive recording paper thus obtained was evaluated in the following manner.
- Printing was made on the paper with a printer for heat-sensitive facsimile (RIFAX 300, made by Ricoh Co.) and the color density of the printed parts were measured with a Macbeth color density tester (RD-514, made by Macbeth Co.).
- RIFAX 300 made by Ricoh Co.
- RD-514 made by Macbeth Co.
- the non-printed part was measured for color density with the same Macbeth tester as above.
- a Macbeth density of 0 and 1.82 means completely white and completely black, respectively.
- Example 1 was repeated except that itaconic acid-modified polyvinyl alcohols as shown in Table 1 were used, instead of the itaconic acid-modified polyvinyl alcohol used in Example 1, to prepare coating liquids (dispersions of the heat-sensitive dye and the color developing agent). The obtained coating liquids were then used to prepare heat-sensitive recording materials in the same manner. The results are shown in table 1.
- Example 1 was repeated except that various polyvinyl alcohols as shown in Table 1 were used, instead of the itaconic acid-modified polyvinyl alcohol used in Example 1, to prepare coating liquids (dispersions of the heat-sensitive dye and the color developing agent). The obtained coating liquids were then used to prepare heat-sensitive recording materials in the same manner. The results are also shown in table 1.
- Dispersing agent Aqueous dispersion of heat-sensitive dye Properties of heat-sensitive recording paper(color density) Comonomer D.M. (mole %) D.S. (mole %) D.P. Dia. ( ⁇ m) Viscosity (cs) Whiteness Printed part Non-printed part Ex. 1 IA 4.0 46 500 0.44 38.0 -8.0 1.34 0.08 Ex. 2 " 4.0 42 300 0.35 17.1 -7.4 1.36 0.07 Ex. 3 " 4.0 52 200 0.28 15.4 -7.6 1.38 0.07 Ex.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
The present invention relates to a heat-sensitive
recording material.
The present invention further relates to the use of a dispersing
agent having excellent dispersing capability for heat-sensitive
dyes and color developing agents which is suited for
producing heat-sensitive recording materials.
The present invention still further relates to a
process for producing aqueous dispersions having a
dispersoid of a particulate heat-sensitive dye or color
developing agent.
Heat-sensitive recording materials comprise a paper,
plastic film or metal-deposited paper and, provided thereon,
a heat-sensitive recording layer that will undergo, by heat
energy, chemical or physical change to form color and give
recorded images. The heat-sensitive recording materials
have advantages of giving recorded images by simple heating,
requiring no complex treatments such as developing and
fixing, causing no noise upon recording and providing
relatively inexpensive recording system. The materials
therefore have been widely used as recording materials for
electronic calculators, word processors, telex machines,
facsimiles and various calculators.
These heat-sensitive recording materials generally have
a heat-sensitive recording layer comprising a colorless or
light-color leuco dye and an acid such as an organic acid or
a phenol, that reacts upon heating with the leuco dye,
thereby causing it to form color.
In recent years, in particular in the field of
facsimiles and the like, where the printing speed has been
increasing year by year, there has been desired a heat-sensitive
recording material capable of giving clearer
images and conforming to high-speed printing. With respect
to recorded images, there is required a heat-sensitive
recording material capable of giving precise and dirt-free
images not only for characters but also for drawings and
photographs.
As a result, strongly desired is a heat-sensitive
recording material having heat-sensitive recording layer in
which a heat-sensitive dye and a color developing agent
(developer) having a particle diameter of not more than
1 µm are dispersed uniformly and present in high density
and in a thin layer, so that the color or the texture of the
substrate used is not observable.
Known dispersing agents for heat-sensitive dyes and
color developing agents include a partially saponified
polyvinyl alcohol having a low molecular weight
(JP-A-62-105687 (1987)),
a sulfonic
acid group-modified polyvinyl alcohol having a low molecular
weight
(JP-B-2-52637 (1990)),
and alkali metal salts or ester of an α-olefin-maleic
anhydride copolymer
(JP-A-63-214479 (1998)).
However, these agents have been
incapable of exhibiting sufficient performance.
The partially saponified polyvinyl alcohol having a low
molecular weight has insufficient dispersing capability for
heat-sensitive dyes and color developing agents and cannot
stably disperse them in a particle size of not more than 1
µm.
The sulfonic acid-modified polyvinyl alcohol having a
low molecular weight has a dispersing capability of some
level but makes considerably visible the texture color of the
substrate.
The maleic anhydride-based copolymer is, when used in a
coating liquid, only insufficiently compatible with the
binder contained in the liquid, thereby often causing agglomeration
of dispersed particles or viscosity increase of the
liquid and, further, has the problem of making considerably
visible the texture color of the substrate.
Accordingly, an object of the present invention is to
provide a heat-sensitive recording material capable of
making invisible the texture color of the substrate and
giving clear images even upon high-speed printing.
Another object of the present invention is to provide the use of
a dispersing agent having excellent dispersing capability for
particulate heat-sensitive dyes and color developing agents
and suited for producing heat-sensitive recording materials.
Still another object of the present invention is to
provide a process for producing aqueous dispersions having a
dispersoid of a particulate heat-sensitive dye or color
developing agent. These objects are achieved by the invention.
Subject matters of the present invention are:
The modified polyvinyl alcohol (hereinafter the term
"polyvinyl alcohol" is sometimes referred to as "PVA") used
in the present invention should contain 2.5 to 8 mole % of
units from a carboxyl group-containing monomer and have a
degree of saponification of 40 to 65 mole % and a viscosity
average degree of polymerization of 50 to 500.
It is necessary that the content of the carboxyl group-containing
monomer units be 2.5 to 8 mole %, preferably 3 to
6 mole %. With the degree of modification by carboxyl group
being less than 2.5 mole %, the printed parts on the heat-sensitive
recording material have a low color density and
the PVA has low dispersing capability for heat-sensitive
dyes and color developing agents so that the dispersoid
agglomerates after an aqueous dispersion has been prepared.
With the degree of modification exceeding 8 mole %, the non-printed
part on the heat-sensitive recording material has a
low whiteness and aqueous dispersions prepared with the PVA
also have a very low whiteness.
There is no specific limitation to the type of the
carboxyl group-containing monomer unit and its examples
include units from fumaric acid, maleic acid, itaconic acid,
maleic anhydride, phthalic anhydride, trimellitic anhydride
and itaconic anhydride. Among these monomer units, dibasic
acids are preferred and itaconic acid is particularly
preferred.
It is necessary that the modified PVA has a degree of
saponification of 40 to 65 mole %, preferably 45 to 60 mole
% and more preferably 50 to 60 mole %. If the degree of
saponification is less than 40 mole %, the dispersing capability
for heat-sensitive dyes and color developing agents
will decrease and aqueous dispersions prepared with the PVA
will, after preparation thereof, cause the dispersoid to
agglomerate, so that a usable heat-sensitive recording material
cannot be obtained. If the degree of saponification
exceeds 65 mole %, the resulting heat-sensitive recording
material will give printed parts having a low color density
and, besides, aqueous dispersions prepared with the PVA will
have too high a viscosity to be handled with ease so that the
concentration of the dispersions cannot be elevated.
The viscosity average degree of polymerization (hereinafter
simply referred to as "degree of polymerization") of
the modified PVA should be in a range of 50 to 500 and is
preferably in a range of 100 to 300. If the degree of polymerization
is less than 50, the PVA will become incapable of
dispersing fine particles and, after preparation of an
aqueous dispersion, the dispersoid will agglomerate, whereby
a usable heat-sensitive recording material cannot be
obtained. If the degree of polymerization exceeds 500, the
resulting heat-sensitive recording material will give
printed parts having a low color density and, besides,
aqueous dispersions prepared with the PVA will have too high
a viscosity to be handled with ease so that the concentration of
the dispersions cannot be elevated.
The carboxyl group-modified PVA can be prepared by any
process with no specific restrictions. For example, one of
the above mentioned carboxylic acids is reacted with
polyvinyl alcohol by post-reaction, or a copolymer of vinyl
acetate and an ethylenically unsaturated carboxylic acid is
saponified. Concrete examples of such processes are
disclosed in Japanese Patent Publication No. 21312/1970 and
Japanese Patent Application Laid-open Nos. 91995/1978,
28389/1979 and 28390/1979.
The carboxyl groups in the PVA of the invention may either
be present in the form of an alkali metal salt such as
COONa or in the form of COOH. Where the carboxyl group-containing
monomer is a dibasic acid, one of the two carboxylic
acids present in the monomer may form a lactone ring.
The carboxyl group-modified polyvinyl alcohol used in
the present invention may be copolymerized with other monomers
or its ends may be modified by using a chain transfer
agent. Any ethylenically unsaturated monomer may be copolymerized
with a vinyl ester as long as it is copolymerizable
therewith. Examples of such monomers are α-olefins, e.g.
ethylene, propylene, n-butene, isobutene and 1-hexadecene;
carboxylic acid-containing monomers, e.g. (meth)acrylic
acid, fumaric acid, crotonic acid, maleic acid and maleic
anhydride, and salts of the foregoing; (meth)acrylic acid
esters, e.g. methyl (meth)acrylate, n-butyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate
and stearyl (meth)acrylate; other esters, e.g. dimethyl
fumarate, dimethyl itaconate, dimethyl maleate, monomethyl
maleate and methyl crotonate; vinyl ethers, e.g. methyl vinyl
ether, butyl vinyl ether, lauryl vinyl ether and stearyl
vinyl ether; sulfonic acid group-containing monomers, e.g.
vinylsulfonic acid, allylsulfonic acid, methallylsulfonic
acid and 2-acrylamide-2-methylpropanesulfonic acid, and
salts of the foregoing; amido group-containing monomers,
e.g. (meth) acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide,
N-t-butoxy(meth)acrylamide, N-t-octyl(meth)acrylamide
and N-vinylpyrrolidone; quaternary
ammonium salt-containing monomers, e.g. dimethylaminoethyl(meth)acrylamide;
silyl group-containing monomers, e.g.
vinylhydroxysilane and 3-trimethoxysilylpropyl (meth)acrylate;
and acetyl group-containing monomers, e.g. allyl
acetate, dimethylallyl acetate and isopropenyl acetate.
The modified PVA can be contained in a heat-sensitive
recording layer of the heat-sensitive recording material in
any amount with no particular limitation. However, it is
preferred that the modified PVA be contained in an amount of
3 to 30 parts by weight based on 100 parts by weight of the
sum of the amounts of a heat-sensitive dye and a color developing
agent, more preferably 5 to 20 parts by weight and
most preferably 7 to 16 parts by weight on the same basis.
For the preparation of aqueous dispersions of a heat-sensitive
dye or a color developing agent according to the
present invention, the dye or agent is dispersed by using a
dispersing agent of the above modified PVA. The dispersing
agent can be used in any amount, but preferably in an amount
of 3 to 30 parts by weight based on 100 parts by weight of
the heat-sensitive dye or the color developing agent, more
preferably 5 to 20 parts by weight and most preferably 7 to
16 parts by weight on the same basis. In general, it is
desirable to prepare aqueous dispersions of a heat-sensitive
dye and a color developing agent separately and then mix the
two dispersions. The finished aqueous dispersion preferably
has a dispersoid concentration of 20 to 70% by weight, more
preferably 40 to 60% by weight.
Dispersing operation for the heat-sensitive dye or the
color developing agent is carried out in a sand mill
containing a multiplicity of glass beads having an average
particle diameter of 0.2 to 3 mm (preferably 0.3 to 0.8 mm)
The dispersing operation is completed in 1 hour to 1 week
(preferably 3 hours to 4 days, in particular 1 to 4 days
where it is desired to obtain fine dispersoid particles having
an average particle diameter of not more than 0.45 µm).
The use of the dispersing agent of the present
invention can give aqueous dispersions having a dispersoid
of a heat-sensitive dye or a color developing agent having a
particle diameter ranging from 0.1 to 1 µm (preferably 0.3
to 0.8 µm, more preferably 0.2 to 0.6 µm and most preferably
0.2 to 0.45 µm).
Any heat-sensitive dye being used for conventional
pressure- or heat-sensitive papers can be used in the
present invention and its concrete examples include
triarylmethane-based compounds, e.g. 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide
(Crystal Violet
Lactone), 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide,
3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide
and 3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthalide;
diphenylmethane-based compounds, e.g. 4,4'-bisdimethylaminobenzhydrine
benzyl ether and N-halophenylleucoauramine;
xanthene-based compounds, e.g. rhodamine B-anilinolactam,
3-diethylamino-7-benzylamino-fluorane, 3-diethylamino-7-butylaminofluorane,
3-diethylamino-7-(chloroanilino)fluorane,
3-diethylamino-6-methyl-7-anilinofluorane,
3-piperidino-6-methyl-7-anilinofluorane, 3-ethyl-tolylamino-6-methyl-7-anilinofluorane,
3-cyclohexyl-methylamino-6-methyl-7-anilinofluorane,
3-diethylamino-6-chloro-7-(β-ethoxyethyl)aminofluorane,
3-diethylamino-6-chloro-7-(γ-chloropropyl)aminofluorane,
3-(N-ethyl-N-isoamyl)-6-methyl-7-phenylaminofluorane
and 3-dibutylamino-6-methyl-7-anilinofluorane;
thiazine-based compounds, e.g. benzoyl leuco
methylene blue and p-nitrobenzoyl leuco methylene blue; and
spiro compounds, e.g. 3-methyl-spiro-dinaphthopyrane, 3-ethyl-spiro-dinaphthopyrane,
3-benzyl-spiro-dinaphthopyrane,
3-methylnaphto-(3-methoxy-benzo)-spiro-pyrane. These compounds
may be used singly or in combination of two or more.
These heat-sensitive dyes are appropriately selected according
to the use of the intended heat-sensitive recording
material.
It is desirable that the color developing agent used in
the present invention be selected from phenol derivatives
and aromatic carboxylic acid derivatives, in particular from
bisphenols. Their concrete examples are phenols, e.g. p-octylphenol,
p-tert-butylphenol, p-phenylphenol, 1,1-bis(p-hydroxyphenyl)propane,
1,1-bis(p-hydroxyphenyl)pentane, 2,2-bis(p-hydroxyphenyl)propane,
1,1-bis(p-hydroxyphenyl)hexane,
2,2-bis(p-hydroxyphenyl)hexane, 1,1-bis(p-hydroxyphenyl)-2-ethyl-hexane,
2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane
and dihydroxydiphenyl ether; and aromatic carboxylic acid
derivatives, e.g. p-hydroxybenzoic acid, ethyl p-hydroxybenzoate,
butyl p-hydroxybenzoate, 3,5-di-tert-butylsalicylic
acid and 3,5-di-α-methylbenzylsalicylic acid and multivalent
metal salts of the above carboxylic acids.
It is desirable, in the present invention, to use an
aqueous binder in a heat-sensitive recording layer.
Examples of binders usable for this purpose are cellulose
derivatives, e.g. starch, starch derivatives, hydroxymethylcellulose,
hydroxyethylcellulose, carboxymethylcellulose,
methylcellulose and ethylcellulose; water-soluble polymers,
e.g. polyvinyl alcohol, poly(sodium acrylate), polyvinylpyrrolidone,
acrylamide/acrylic acid ester copolymers,
acrylamide/acrylic acid ester/methacrylic acid ternary
copolymers, alkali metal salts of styrene/maleic anhydride
copolymer, alkali metal salts of isobutylene/maleic anhydride
copolymer; polyacrylamide, sodium alginate, gelatin and
casein; emulsions of polyvinyl acetate, polyurethanes, polyacrylic
acid, polyacrylic acid esters, vinyl chloride/vinyl
acetate copolymer, polybutyl methacrylate, ethylene/vinyl
acetate copolymer and the like; and latices of styrene/butadiene
copolymer, styrene/butadiene/acrylic acid ester and
the like.
The aqueous binder is added preferably in an amount of
1 to 20 parts by weight based on 100 parts by weight of the
sum of the amounts of the dye and the color developing
agent.
In the present invention, the heat-sensitive recording
layer may incorporate, besides a heat-sensitive dye and a
color developing agent, auxiliary additives used for
conventional heat-sensitive recording materials, such as a
filler, surfactant, heat-fusible substance (or lubricant)
and agent for preventing color development under pressure.
In the present invention, the heat-sensitive recording
layer can be formed by any of known processes, e.g. air-knife
coating, plate coating, embossing, roll coating,
spraying, dipping, bar coating and extrusion coating.
In the present invention, any substrate can be used for
the heat-sensitive recording material. Appropriate selection
is made for example from various papers, synthetic
papers and synthetic resin films. It is, however, generally
desirable to use a paper.
The heat-sensitive recording materials of the present
invention give printed parts having good color development
and non-printed part that hardly fogs (coloration of
substrate). The heat-sensitive recording materials of the
present invention, having excellent high-speed printability
and excellent resolution of images, are suitably usable in
the field requiring high-speed printing, such as facsimile.
The dispersing agent used in the present invention, having
excellent dispersing capability for heat-sensitive dyes and
color developing agents, can give aqueous dispersion having
a dispersoid of a particulate heat-sensitive dye or color
developing agent in a high concentration and having a low
viscosity. The aqueous dispersion obtained, having excellent
applicability to the surface of the base paper upon
preparation of heat-sensitive recording papers and
containing dispersoids of a heat-sensitive dye and a color
developing agent dispersed in fine particles, can produce
heat-sensitive recording materials having markedly high
resolution.
Other features of the invention will become apparent in
the course of the following descriptions of exemplary embodiments
which are given for illustration of the invention
and are not intended to be limiting thereof. In the
Examples and Comparative Examples that follow, "parts" and
"%" mean "parts by weight" and "% by weight", respectively,
unless otherwise indicated. The viscosity values in the
following description are those measured with a Brookfield
viscometer made by Tokyo Keiki Co., Ltd. at 30°C and a rotor
rotation of 12 rpm.
| Leuco dye (S-205, made by Yamada Kagaku K.K.) | 20% |
| Ten % aqueous solution of a carboxyl group-modified PVA (modified by copolymerization of 4 mole % of itaconic acid; degree of polymerization: 500; degree of saponification: 46 mole %) | 20% |
| Water | 59.9% |
| Antifoam (SURFYNOL® 440, made by Nisshin Chemical Co., Ltd.) | 0.1% |
| Bisphenol A | 20% |
| Ten % aqueous solution of a carboxyl group-modified PVA (same as one used above) | 20% |
| Water | 59.9% |
| Antifoam (SURFYNOL® 440, made by Nisshin Chemical Co., Ltd.) | 0.1% |
| Stearylamide | 10% |
| Calcium carbonate | 20% |
| Five % aqueous solution of a carboxyl group-modified PVA (same as one used above) | 30% |
| Water | 40% |
The above aqueous mixtures A, B and C were separately
prepared and stirred preliminarily for 15 minutes.
The aqueous mixtures A and B were each transferred into
a sand mill (batch type, desk-top sand mill made by Kansai
Paint Co.), and 300 cc of glass beads (soda quartz glass
having a diameter of 0.5 mm) was added. Dispersion was
effected at a high rotation (2,170 rpm) for 6 hours.
The aqueous mixture C was dispersed in a homogenizer
(10,000 rpm) for 2 minutes.
The aqueous dispersion A of the heat-sensitive dye was
evaluated according to the following methods.
Six hours after starting dispersion, the particle
diameter was measured with a laser diffraction particle size
analyzer (SALD-1000, made by Shimadzu Corp.).
The aqueous dispersion was allowed to stand for about 1
hour after completion of 6-hour dispersion and then tested
for viscosity at 30°C.
The aqueous dispersion was allowed to stand for about 1
hour after completion of 6-hour dispersion and then tested
for whiteness with a color and color and color difference
meter (Z-1001DP, made by Nippon Denshoku Kogyo Co., Ltd.).
The whiteness value of "0" means completely white, and the
degree of discoloration increases with the absolute value of
the negative values.
A coating liquid for heat-sensitive recording layer was
prepared by mixing with stirring 1 part of the aqueous
dispersion A, 4 parts of the aqueous dispersion B, 2 parts
of the aqueous dispersion C and 2 parts of a 10% aqueous
solution of polyvinyl alcohol (degree of polymerization:
1,750, degree of saponification: 98.5 mole %). The coating
liquid was applied with a wire bar coater on a base paper
(woodfree paper having a weight of 52 g/m2) in an amount of
6 g/m2 (solid base), dried at 50° C for 10 minutes and then
surface-treated with a super calender (linear pressure: 30
kg/cm; roll diameter: top (metal): 20 cm, bottom (rubber):
30 cm), to obtain a heat-sensitive recording paper.
The heat-sensitive recording paper thus obtained was
evaluated in the following manner.
Printing was made on the paper with a printer for heat-sensitive
facsimile (RIFAX 300, made by Ricoh Co.) and the
color density of the printed parts were measured with a
Macbeth color density tester (RD-514, made by Macbeth Co.).
The non-printed part was measured for color density
with the same Macbeth tester as above.
A Macbeth density of 0 and 1.82 means completely white
and completely black, respectively.
The results of evaluations on the above aqueous
dispersion A of the heat-sensitive dye and the heat-sensitive
recording material are shown in Table 1.
Example 1 was repeated except that itaconic acid-modified
polyvinyl alcohols as shown in Table 1 were used,
instead of the itaconic acid-modified polyvinyl alcohol used
in Example 1, to prepare coating liquids (dispersions of the
heat-sensitive dye and the color developing agent). The
obtained coating liquids were then used to prepare heat-sensitive
recording materials in the same manner. The
results are shown in table 1.
Example 1 was repeated except that various polyvinyl
alcohols as shown in Table 1 were used, instead of the
itaconic acid-modified polyvinyl alcohol used in Example 1,
to prepare coating liquids (dispersions of the heat-sensitive
dye and the color developing agent). The obtained
coating liquids were then used to prepare heat-sensitive
recording materials in the same manner. The results are
also shown in table 1.
Obviously, numerous modifications and variations of the
present invention are possible in light of the above
teachings. It is therefore to be understood that within the
scope of the appended claims, the invention may be practiced
otherwise than as specifically described herein.
| Dispersing agent (PVA) | Aqueous dispersion of heat-sensitive dye | Properties of heat-sensitive recording paper(color density) | |||||||
| Comonomer | D.M. (mole %) | D.S. (mole %) | D.P. | Dia. (µm) | Viscosity (cs) | Whiteness | Printed part | Non-printed part | |
| Ex. 1 | IA | 4.0 | 46 | 500 | 0.44 | 38.0 | -8.0 | 1.34 | 0.08 |
| Ex. 2 | " | 4.0 | 42 | 300 | 0.35 | 17.1 | -7.4 | 1.36 | 0.07 |
| Ex. 3 | " | 4.0 | 52 | 200 | 0.28 | 15.4 | -7.6 | 1.38 | 0.07 |
| Ex. 4 | " | 5.5 | 61 | 100 | 0.35 | 16.0 | -7.8 | 1.36 | 0.07 |
| Ex. 5 | " | 4.0 | 49 | 50 | 0.45 | 30.0 | -7.6 | 1.33 | 0.07 |
| Ex. 6 | " | 8.0 | 56 | 200 | 0.29 | 18.5 | -12.6 | 1.34 | 0.09 |
| Ex. 7 | " | 6.6 | 50 | 200 | 0.30 | 17.1 | -10.1 | 1.34 | 0.08 |
| Ex. 8 | " | 3.0 | 45 | 200 | 0.33 | 17.3 | -7.7 | 1.36 | 0.07 |
| Ex. 9 | " | 2.5 | 55 | 200 | 0.44 | 21.6 | -7.3 | 1.33 | 0.07 |
| Ex. 10 | " | 4.0 | 65 | 200 | 0.40 | 18.8 | -7.5 | 1.34 | 0.07 |
| Ex. 11 | " | 4.0 | 40 | 200 | 0.42 | 20.0 | -7.9 | 1.33 | 0.08 |
| Comp. Ex. 1 | SA | 2.0 | 88 | 240 | 0.63 | 43.6 | -16.0 | 1.20 | 0.13 |
| Comp. Ex. 2 | IA | 4.0 | 59 | 550 | 0.80 | 60.0 | -7.8 | 1.10 | 0.07 |
| Comp. Ex. 3 | " | 4.0 | 49 | 30 | 0.78 | 78.0 | -7.7 | 1.11 | 0.08 |
| Comp. Ex. 4 | " | 9.0 | 54 | 200 | 0.31 | 16.0 | -20.0 | 1.32 | 0.18 |
| Comp. Ex. 5 | " | 2.0 | 63 | 200 | 0.70 | 57.5 | -7.9 | 1.15 | 0.08 |
| Comp. Ex. 6 | " | 4.0 | 70 | 200 | 0.72 | 27.0 | -8.0 | 1.16 | 0.08 |
| Comp. Ex. 7 | " | 4.0 | 35 | 200 | Dispersion gelled. | - | - | ||
| Comp. Ex. 8 | - | 0 | 42 | 200 | Dispersion gelled. | - | - |
Claims (3)
- A heat-sensitive recording material having a heat-sensitive recording layer comprising a modified polyvinyl alcohol, a heat sensitive dye and a color developing agent, said polyvinyl alcohol containing 2.5 to 8 mole % units of a carboxyl group-containing monomer and having a degree of saponification of 40 to 65 mole % and a viscosity average degree of polymerization of 50 to 500.
- Use of the modified polyvinyl alcohol as defined in Claim 1 for dispersing a heat-sensitive dye or a color developing agent that can make the heat-sensitive dye form color upon heating.
- A process for producing aqueous dispersions which comprises dispersing a heat-sensitive dye or a color developing agent that can make the heat-sensitive dye form color upon heating, in an aqueous medium with a dispersing agent of the modified polyvinyl alcohol according to Claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1994609522 DE69409522T2 (en) | 1994-09-27 | 1994-09-27 | Heat sensitive recording material |
| EP19940115223 EP0704317B1 (en) | 1994-09-27 | 1994-09-27 | Heat-sensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP19940115223 EP0704317B1 (en) | 1994-09-27 | 1994-09-27 | Heat-sensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0704317A1 EP0704317A1 (en) | 1996-04-03 |
| EP0704317B1 true EP0704317B1 (en) | 1998-04-08 |
Family
ID=8216331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19940115223 Expired - Lifetime EP0704317B1 (en) | 1994-09-27 | 1994-09-27 | Heat-sensitive recording material |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0704317B1 (en) |
| DE (1) | DE69409522T2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59159394A (en) * | 1983-03-03 | 1984-09-08 | Ricoh Co Ltd | Thermal recording material |
| JPS62105687A (en) * | 1985-11-01 | 1987-05-16 | Fuji Photo Film Co Ltd | Thermosensitive recording material |
| JP2604367B2 (en) * | 1987-01-16 | 1997-04-30 | 株式会社クラレ | Ink jet recording sheet with excellent water resistance |
| JPH01111439A (en) * | 1987-10-26 | 1989-04-28 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of aluminum hydroxide dispersed aqueous suspension |
| JP3194644B2 (en) * | 1993-04-05 | 2001-07-30 | 株式会社クラレ | Thermal recording material |
-
1994
- 1994-09-27 DE DE1994609522 patent/DE69409522T2/en not_active Expired - Lifetime
- 1994-09-27 EP EP19940115223 patent/EP0704317B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69409522T2 (en) | 1998-10-15 |
| DE69409522D1 (en) | 1998-05-14 |
| EP0704317A1 (en) | 1996-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8101546B2 (en) | Thermal recording material | |
| JPH01275183A (en) | Thermal recording material | |
| US4962079A (en) | Overcoated heat-sensitive record materials | |
| JPH0142835B2 (en) | ||
| US4228222A (en) | Heat-sensitive record material | |
| EP0799711B1 (en) | Paper coating agent | |
| JPH0635210B2 (en) | Thermal recording | |
| US5478792A (en) | Heat-sensitive recording material | |
| JPH0848076A (en) | Heat-sensitive recording material | |
| EP0704317B1 (en) | Heat-sensitive recording material | |
| US4826807A (en) | Heat-sensitive recording material | |
| US5091357A (en) | Heat sensitive recording material | |
| KR0143703B1 (en) | Thermosensitive recording material | |
| JP3795939B2 (en) | Thermal recording material | |
| US4833121A (en) | Heat-sensitive recording material | |
| GB2111702A (en) | Heat-sensitive recording materials | |
| EP0272099A2 (en) | Color-forming sheet recording material | |
| US4614955A (en) | Heat sensitive recording paper | |
| JPH0662004B2 (en) | Thermal recording paper | |
| JPH07112580A (en) | Thermal recording material | |
| JP3784814B2 (en) | Thermal recording material | |
| JPH0872409A (en) | Thermal recording material | |
| JPS63312883A (en) | Thermosensitive recording material | |
| JPH0696344B2 (en) | Recording material | |
| JP2516348B2 (en) | Thermal recording material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19950412 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE ES FR GB |
|
| 17Q | First examination report despatched |
Effective date: 19960802 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES FR GB |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19980408 |
|
| REF | Corresponds to: |
Ref document number: 69409522 Country of ref document: DE Date of ref document: 19980514 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20120926 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20120926 Year of fee payment: 19 Ref country code: DE Payment date: 20120919 Year of fee payment: 19 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20130927 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20140530 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69409522 Country of ref document: DE Effective date: 20140401 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130927 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130930 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140401 |