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Description  |
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BACKGROUND OF THE INVENTION
a. Field of the Invention
The present invention relates to a heat sensitive recording material, and
more particularly, to a heat sensitive recording material having excellent
transparency and anti-scratch property.
b. Description of the Prior Art
A heat-sensitive recording method has many advantages in that no particular
developing step is required, (2) if paper is used as a support, the
recording material can have a quality akin to that of plain paper, (3)
handling of the recording material used is easy, (4) the images recorded
have high color density, (5) this method can be effected using a simple
and cheap apparatus and (6) no noise is caused during recording.
Therefore, heat-sensitive recording materials have recently enjoyed a
markedly increasing demand, particularly for use with a facsimile or
printer, and have come to be used for many purposes.
From this situation, it has been desired to devise transparent
heat-sensitive recording materials which enable direct recording with a
thermal head in order to adapt them for multicolor development, or to make
them usable for an overhead projector (hereafter abbreviated as OHP).
To satisfy the above desire, recently, a heat sensitive recording material
having an excellent transparency was proposed which comprises a support
having thereon a heat sensitive layer said heat sensitive layer being
formed by coating a solution including an emulsified dispersion obtained
by dispersing microcapsules containing colorless or light colored electron
donating dye precursor and color developer dissolved in an organic solvent
slightly soluble or insoluble in water then drying it.
On the otherhand, generally, bad chance such as being scratched is
increased when a heat sensitive recording material is used for OHP or
multi color recording, then a protective layer should be provided on the
heat sensitive layer in practice.
However, the tranceparency of before mentioned heat sensitive layer is
reduced when a protective layer is provided on the heat sensitive layer.
Therefore, more improvement on the transparency has been requested to the
protective layer in order to make the heat sensitive recording material
usable for OHP or to reproduce a faithful color in multi coloring.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a heat
sensitive recording material having higher transparency than that of the
conventional one.
The above-described object is attained with an improved heat sensitive
recording material which comprises a support having thereon a heat
sensitive layer and a protective layer successively, in which said heat
sensitive layer is prepared by coating a composition containing an
emulsified dispersion prepared by dispersing a color developer dissolved
into an organic solvent slightly soluble or insoluble in water and
microcapsules containing a colorless or light colored electron donating
dye precursor and then drying the coat, and said protective layer is
comprised of at least a modified polyvinylalcohol with silicon and a
colloidal silica.
A heat sensitive recording material of the present invention has heat
sensitivity high enough to enable the image formation using a thermal head
of facsimile or the like, not reducing a transparency of its heat
sensitive layer as well as a transparency of a protective layer.
Accordingly, when a transparent film is used as the support of the present
material, the resulting material can have such a usage that the material
receives image information by means of facsimile, and is submitted
immediately to projection with an overhead projector. Moreover, when the
present material is so designed as to function as multicolor recording
material, color images developed are excellent in sharpness and color
reproduction and scratches are hardly seen on a surface.
DETAILED DESCRIPTION OF THE INVENTION
The modified polyvinylalcohol with silicon, which is used in the present
invention is not restricted particularly if it has a silicon atom in its
molecular structure, however, it is preferable in usual to use those
having a substituted active group such as an alkoxyl group, an acyloxyl
group, a hydroxyl group obtained by hydrolysis and so on or an alkali
metal salt thereof at the silicon atom contained in the molecule.
Details of a production process of such a polyvinylalcohol having a silicon
atom in its molecular structure is described in Japanese Patent
Application (OPI) No. 193189/83. The polyvinylalcohol containing silicon
atom in its molecule, which is used in the present invention, can also
prepared by these known method.
Preferred particle size of the colloidal silica is from 10 m .mu. to 100 m
.mu. and preferred specific gravity of it is from 1.1 to 1.3. In this case
preferred PH value of the colloidal solution is from about 4 to about 10.
When a protective layer comprising at least above mentioned modified
polyvinylalcohol with silicon and colloidal silica is prepared on a
surface of a heat sensitive material, to a great surprise, a transparency
of the protective layer is quite excellent, therefore a transparency of
the heat sensitive material can be remarkably improved.
A proper mixing ratio of the modified polyvinylalcohol with silicon to the
colloidal silica, in the present invention, is 0.5-3 parts by weight
preferably 1-2 parts by weight of colloidal silica per one part by weight
of modified polyvinylalcohol with silicon. If the amount of the colloidal
silica is less than 0.5 part by weight, it can not bring sufficient effect
for improvement on a transparency, and if it is used in an amount more
than 3 parts by weight a crack occurs in the protective layer which
reduces the transparency.
In the protective layer, more than one other polymers can be used together
with above polymer. Some of these polymers are a methylcellulose, a
carboxymethylcellulose, a hydroxymethylcellulose, a starchs, a gelatin, a
gum arabic, a casein, a hydrolyzed product of styrene-maleic anhydride
copolymer, a hydrolyzed half-ester product of styrene-maleic anhydride
copolymer, a polyvinylalcohol, a modified polyvinylalcohol with carboxyl
group, a polyacrylamide derivatives, a polyvinyl pyrrolidone, a
polystyrene sodium sulfate, a water soluble polymer such as sodium
alginate, styrene-butadiene rubber latex, acrylnitrile-butadiene rubber
latex, methylacrylatebutadiene rubber latex, a water insoluble polymer
such as polyvinylacetate emulsion. A preferred amount to be used together
is from 0.01 to 0.5 part by weight per 1 part by weight of modified
polyvinylalcohol with silicon.
In the protective layer, a pigment, metal soap, wax or cross-linking agent
etc. can be added in order to improve matching of the heat sensitive
material with thermal head when thermal recording is performed or to
improve water resisting property of the protective layer.
Some of the pigments are a zinc oxide, a calcium carbonate, a barium
sulfate, a titanium oxide, a lithopone, a talc, an agalmatolite, a kaolin,
an aluminum hydroxide, an amorphous silica etc., an amount to be added is
0.05-2 times of an amount of total weight of polymer, especially 0.1-0.5
times are preferable. An amount less than 0.05 times can not improve the
matching of the heat sensitive recording material with thermal head, on
the other hand an amount more than 2 times reduces both transparency and
sensitivity of heat sensitive recording material remarkably, which causes
damage on commercial value.
Some of the metal soaps are an emulsion of metal salt of higher fatty acid
(e.g., a zinc stearate, a calcium stearate, an aluminum stearate) etc.,
and its amount to be added is 0.5-20 weight %, preferably 1-10 weight %
against total weight of the protective layer. Some of the waxes are a
paraffin wax, a microcrystalline wax, a carnauba wax, a methylol
stearoamide, a polyethylene wax, an emulsion of silicone etc., and an
amount thereof to be added is 0.5-40 weight %, preferable 1-20 weight %
against total weight of the protective layer.
In a coating solution for the protective layer a surface active agent is
added in order to prepare the protective layer uniforming on the heat
sensitive layer. Some of the active agents are an alkali metal salt of
sulfosuccinic acid system and an active surface agent containing fluorine
atoms etc., concretely they are a sodium salt or an ammonium salt etc., of
a di-(2-ethylhexyl) sulfosuccinic acid or di-(n-hexyl) sulfosuccinic acid
etc.
Other surface active agents or polymer electrolytes can also be added in
the protective layer as an antistatic agent.
A preferable amount of the protective layer to be coated is usually 0.2-5
g/m.sup.2, particularly 1 g-3 g/m.sup.2 at the solids coverage.
Precursors of basic dyes to be employed in the present invention are
selected properly from known colorless or light colored compounds of the
kind which can develop their colors by donating an electron or accepting a
proton of an acid or the like. These compounds have such a skeleton as
that of lactone, lactam, sultone, spiropyran, ester, amide, etc., as a
part of their structures, and these skeletons undergo ring-opening or bond
cleavage upon contact with a color developer. Preferred examples of such
compounds include triarylmethane compounds, diphenylmethane compounds,
xanthene compounds, thiazine compounds, spiropyran compounds and so on.
Particularly preferred compounds are those represented by the following
general formula:
##STR1##
In the foregoing formula, R.sub.1 represents an alkyl group containing 1 to
8 carbon atoms; R.sub.2 represents an alkyl or alkoxyalkyl group
containing 4 to 18 carbon atoms, or a tetrahydrofuryl group; R.sub.3
represents a hydrogen atom, an alkyl group containing 1 to 15 carbon
atoms, or a halogen atom; and R.sub.4 represents a substituted or
unsubstituted aryl group containing 6 to 20 carbon atoms. As substituent
group for R.sub.4, alkyl, alkoxy and halogenated alkyl groups containing 1
to 5 carbon atoms, and halogen atoms are preferred.
Microencapsulation of the above-described color former in the present
invention can prevent generation of fog during production of a heat
sensitive material and, at the same time, can improve a freshness keeping
quality of a heat sensitive material and a keeping quality of the record
formed. Therein, the image density at the time of recording can be
heightened by properly selecting a material and a method for forming a
microcapsule wall. A preferred amount of the color former used is 0.05 to
5.0 g per square meter.
Suitable examples of wall materials for microcapsules include polyurethane,
polyurea, polyester, polycarbonate, urea/formaldehyde resin, melamine
resin, polystyrene, styrene/methacrylate copolymer, styrene/acrylate
copolymer, gelatin, polyvinyl pyrrolidone, polyvinyl alcohol, and so on.
These macromolecular substances can be used in combination of two or more
thereof in the present invention.
Of the above-cited macromolecular substances, polyurethane, polyurea,
polyamide, polyester, and polycarbonate are preferred in the present
invention. In particular, polyurethane and polyurea can bring about good
results.
Microcapsules to be employed in the present invention are preferably
prepared by emulsifying a core material containing a reactive substance
like a color former, and then forming a wall of a macromolecular substance
around the droplets of the core material to microencapsulate the core
material. Therein, reactants to produce a macromolecular substance are
added to the inside and/or the outside of the oily droplets. For details
of microcapsules which can be preferably employed in the present
invention, e.g., for production methods of microcapsules which can be
preferably used, descriptions in Japanese Patent Application (OPI) No.
222716/84 (the term "OPI" as used herein means an "unexamined published
application" ), and so on can be referred to.
An organic solvent to constitute the above-described oily droplets can be
properly selected from those used generally as pressure sensitive oil. In
particular, the use of such an organic solvent as to be well suited for
dissolution of color developers described hereinafter is desirable,
because solubilities of leuco dyes therein are high, a color density of
the developed image and a color development speed upon thermal printing
can be increased thereby, and fog density upon thermal printing can be
reduced thereby.
A preferred size of microcapsules to be employed in the present invention
is 2 microns or less, particularly 1 micron or less, on a volume average
basis according to the evaluation method described, e.g., in Japanese
Patent Application (OPI) No. 214990/85.
Desirable microcapsules which are produced in the above-described manner
are not those of the kind which are disrupted by heat or pressure, but
those of the kind which have a microcapsule wall through which reactive
substances present inside and outside the individual microcapsules
respectively can be passed under a thermally fused condition to react with
each other.
Multicolored neutral tints can be effected by preparing some kinds of
microcapsules having walls differing in glass transition point through
proper selection of wall materials, and optional addition of glass
transition point controlling agents (e.g., plasticizers described in
Japanese Patent Application No. 119862/85) to the wall materials,
respectively, and further by combining selectively colorless electron
donating dye precursors differing in hue with their respective color
developers. Therefore, the present invention is not limited to a
monochromatic heat sensitive paper, but can be applied to a two-color or
multicolor heat sensitive paper and a heat sensitive paper suitable for
recording of graded image.
In addition, a photodiscoloration inhibitor as described, e.g., in Japanese
Patent Application Nos. 125470/85, 125471/85 and 125472/85 can be added,
if desired.
Color developers to be employed in the present invention, which undergo the
color development reaction with basic colorless dyes in a thermally fused
condition, can be those selected properly from known color developers. For
instance, suitable examples of color developers to be combined with leuco
dyes include phenol compounds, triphenylmethane compounds,
sulfur-contained phenolic compounds, carboxylic acid compounds, sulfon
compounds, urea or thiourea compounds, and so on. Details of the color
developers are described, e.g., in "Kami Pulp Gijutsu Times, pp. 49-54,
and pp. 65-70 (1985)". Of such color developers, those having melting
points of 50.degree. to 250.degree. C., particularly phenols and organic
acids which have melting points of 60.degree. to 200.degree. C. and are
hardly soluble in water, are preferred over others. Combined use of two or
more of color developers is desirable because of increase in solubility.
Color developers preferred particularly in the present invention are
represented by the following general formulae (I) to (IV):
##STR2##
R.sub.1 is an alkyl group, an aryl group, or an aralkyl group. In
particular, methy group, ethyl group and butyl groups are preferred as
R.sub.1.
##STR3##
R.sub.2 is an alkyl group. In particular, butyl group, pentyl group, heptyl
group, and octyl group are preferred as R.sub.2.
##STR4##
R.sub.3 is an alkyl group, or an aralkyl group.
In the present invention, such a color developer is used in a form of
emulsified dispersion. The dispersion can be prepared by dissolving color
developers in an organic solvent slightly soluble or insoluble in water,
and mixing the resulting solution with an aqueous phase which contains a
surface active agent, and a water-soluble high polymer as a protective
colloid to emulsify and to disperse the solution in the aqueous phase.
An organic solvent to be used for dissolving the color developers can be
properly selected from known oils. Especially, esters and oils having more
than 2 benzene rings and containing less than a certain numbers of hetero
atoms are preferred. Examples of the latter oils include compounds
represented by the following general formula (V) to (VII), triarylmethanes
(such as tritoluylmethane, toluyldiphenylmethane), terphenyl compounds
(such as terphenyl), alkylated diphenyl ethers (such as propyldiphenyl
ether), hydrogenated terphenyl compounds (such as hexahydroterphenyl),
diphenyl ethers, and so on.
Of these oils, esters are particularly preferred in the present invention
from standpoints of stabilization of emulsified dispersion of the color
developers and dissolving ability for the color developers.
Specific examples of esters include phosphates (e.g.,triphenyl phosphate,
tricresyl phosphate, butyl phosphate, octyl phosphate, cresyl-bi-phenyl
phosphate), phthalates (e.g., dibutyl phthalate, 2-ethylhexyl phthalate,
ethyl phthalate, octyl phthalate, butylbenzyl phthalate, tetrahydro
dioctyl phthalate, benzoates (e.g., ethyl benzoate, propyl benzoate, butyl
benzoate, isopentyl benzoate, benzyl benzoate), abietates (e.g., ethyl
abietate, benzyl abietate ), dioctyl adipate, isodecyl succinate, dioctyl
azelate, oxalates (e.g., dibutyl oxalate, dipentyl oxalate), diethyl
malonate, maleates (e.g., dimethyl maleate, diethyl maleate, dibutyl
maleate), tributyl citrate, sorbic esters (methyl sorbate, ethyl sorbate,
butyl sorbate), sebacic esters (dibutyl sebacate, dioctyl sebacate),
ethyleneglycol esters (e.g., formic acid monoesters and diesters, butyric
acid monoesters and diesters, lauric acid monoesters and diesters,
palmitic acid monoesters and diesters, stearic acid monoesters and
diesters, oleic acid monoesters and diesters), triacetin,
diethylcarbonate, diphenylcarbonate, ethylenecarbonate,
propylenecarbonate, boric acid esters (e.g., tributyl borate, tripentyl
borate ). Of these esters, it is particularly preferred to use tricresyl
phosphate from the standpoint of stabilization of emulsified dispersion of
the color developers.
##STR5##
In the above formula, R.sup.1 represents a hydrogen atom or an alkyl group
containing 1 to 18 carbon atoms; R.sup.2 represents an alkyl group
containing 1 to 18 carbon atoms; and p.sup.1 and q.sup.1 each represents
an integer of 1 to 4, provided that the total number of alkyl groups
therein is 4 or less. Preferred alkyl groups represented by R.sup.1 and
R.sup.2 are those containing 1 to 8 carbon atoms.
##STR6##
In the above formula, R.sup.3 represents a hydrogen atom, or an alkyl group
containing 1 to 12 carbon atoms; R.sup.4 represents an alkyl group
containing 1 to 12 carbon atoms; and n is 1 or 2. p.sup.2 and q.sup.2 each
represents an integer of 1 to 4. The total number of alkyl groups is 4 or
less in case of n=1, while it is 6 or less in case of n=2.
##STR7##
In the above formula, R.sup.5 and R.sup.6, which may be the same or
different, each represents a hydrogen atom, or an alkyl group containing 1
to 18 carbon atoms. m represents an integer of 1 to 13. p.sup.3 and
q.sup.3 each represents an integer of 1 to 3, provided that the total
number of alkyl groups is 3 or less.
Of alkyl groups represented by R.sup.5 and, R.sup.6, those containing 2 to
4 carbon atoms are particularly preferred.
Specific examples of the compounds represented by the formula (V) include
dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, and the
like.
Specific examples of the compounds represented by the formula (VI) include
dimethylbiphenyl, diethylbiphenyl, diisopropylbiphenyl,
diisobutylbiphenyl, and the like.
Specific examples of the compounds represented by the formula (VII)include
1-methyl-1-dimethylphenyl-1-phenylmethane,
1-ethyl-1-dimethylphenyl-1-phenylmethane,
1-propyl-1-dimethylphenyl-1-phenylmethane, and the like.
The above-cited oils can be used as a mixture of two or more thereof, or in
combination with other oils.
Further, auxiliary solvents, which have low boiling points and act as
dissolution aid, can be added to the foregoing organic solvents in the
present invention. As examples of particularly preferred auxiliary
solvents, mention may be made of ethyl acetate, isopropyl acetate, butyl
acetate, methylene chloride, and the like.
Water soluble high polymers to be contained as a protective colloid in an
aqueous phase, which is to be mixed with an oily phase wherein color
developers are dissolved, can be selected properly from known anionic,
nonionic or amphoteric high polymers. Of these high polymers,
polyvinylalcohol, gelatin, cellulose derivatives and the like are
preferred.
Surface active agents to be contained additionally in the aqueous phase can
be selected properly from anionic or nonionic surface active agents of the
kind which do not cause any precipitation or condensation by interaction
with the above-described protective colloids. As examples of surface
active agents which can be preferably used, mention may be made of sodium
alkylbenzenesulfonates (such as sodium laurylbenzenesulfonate), sodium
dioctylsulfosuccinates, polyalkylene glycols (such as polyoxyethylene
nonylphenyl, ether) and so on.
An emulsified dispersion of color developers to be used in the present
invention can be prepared with ease by mixing an oily phase containing the
color developers and an aqueous phase containing a protective colloid and
a surface active agent with a general means for preparing a fine grain
emulsion, such as a high-speed stirrer, an ultrasonic disperser or so on,
to disperse the former phase into the latter phase.
To the emulsified dispersion thus obtained, melting point depressants for
the color developers can be added, if desired. Some of these melting point
depressants have such a function as to control glass transition points of
the capsule walls described hereinbefore, too. Specific examples of such
melting point depressants include hydroxy compounds, carbamate compounds,
sulfonamide compounds, aromatic methoxy compounds and so on. Details of
these compounds are described in Japanese Patent Application No.
244190/84.
These melting point depressants can be used in an amount of 0.1 to 2 parts
by weight, preferably 0.5 to 1 part by weight, per 1 part by weight of
color developer whose melting point is to be depressed. It is to be
desired that the melting point depressant and the color developer, whose
melting point can be depressed thereby, should be used in the same place.
When they are added to separate places, a preferred addition amount of the
melting point depressant is 1 to 3 times of that of the above-described
one.
For the purpose of prevention of sticking to a thermal head, and
improvement on writing quality, pigments such as silica, barium sulfate,
titanium oxide, aluminium hydroxide, zinc oxide, calcium carbonate, etc.,
styrene beads, or fine particles of urea/melamine resin and so on can be
added to the heat sensitive recording material of the present invention.
In order to keep the transparency of the heat sensitive layer, it is to be
desired that the above-described pigments and so on should be added to a
protective layer which is provided on the heat sensitive layer in a
conventional manner for the purpose of acquisition of keeping quality and
stability. Details of the protective layer are described in "Kami Pulp
Gijitsu Times", pp. 2 to 4 (Sept. 1985).
Also, metal soap can be added for the purpose of prevention of the sticking
phenomenon. They are used at a coverage of 0.2 to 7 g/m.sup.2.
The heat sensitive recording material of the present invention can be
formed using a coating technique with the aid of an appropriate binder.
As for the binder, various kinds of emulsions, such as a polyvinyl alcohol
emulsion, a methyl cellulose emulsion, a carboxymethyl cellulose emulsion,
a hydroxypropyl cellulose emulsion, a gum arabic emulsion, a gelatin
emulsion a polyvinyl pyrrolidone emulsion, a casein emulsion, a
styrene-butadiene latex, an acrylonitrile-butadiene latex, a polyvinyl
acetate emulsion, a polyacrylate emulsion, an ethylene-vinyl acetate
copolymer emulsion, and so on, can be employed. An amount of the binder
used is 0.2 to 5 g per square meter on a solids basis.
The heat sensitive recording material of the present invention is produced
by providing a heat sensitive layer on a support, such as paper, a
synthetic resin film, etc., coating and drying a coating composition, in
which microcapsules enclosing a color former therein and a dispersion
containing at least a color developer in an emulsified condition are
contained as main components, and further a binder and other additives are
incorporated, according to a conventional coating method, such as a bar
coating method, a blade coating method, an air knife coating method, a
gravure coating method, a roll coating method, a spray coating method, a
dip coating method, or so on. A coverage of the heat sensitive layer is
controlled to 2.5 to 25 g/m.sup.2 on a solids basis. It is a surprise to
find that thus prepared heat sensitive layer has very excellent
transparency, though the reason for its transparency is not elucidated
yet.
As for the paper to be used as a support, neutralized paper which is sized
with a neutral sizing agent like an alkylketene dimer and shows pH 6-9
upon hot extraction (Japanese Patent Application (OPI) No. 14281/'80) is
employed to advantage in the respect of long-range preservation.
In order to prevent the penetration of a coating composition into paper,
and in order to effect a close contact between a heat recording head and a
heat sensitive recording layer, paper described in Japanese Patent
Application (OPI) No. 116687/82, which is characterized by
Stokigt sizing degree/(meter basis weight).sup.2 .gtoreq.3.times.10.sup.-3
and Bekk smoothness of 90 seconds or more, is used to advantage.
In addition, paper having optical surface roughness of 8 microns or less
and a thickness of 40 to 75 microns, as described in Japanese Patent
Application (OPI) No. 136492/83; paper having a density of 0.9 g/cm.sup.3
or less and optical contact rate of 15% or more, as described in Japanese
Patent Application (OPI) No. 69097/83; paper which is prepared from pulp
having received a beating treatment till its freeness has come to 400 cc
or more on a basis of Canadian Standard Freeness (JIS P8121) to prevent
permeation of a coating composition thereinto, as described in Japanese
Patent Application (OPI) No. 69097/83; raw paper made with a Yankee paper
machine, which is to be coated with a coating composition on the glossy
side and thereby, improvements on developed color density and resolution
are intended, as described in Japanese Patent Application (OPI) No.
65695/83; raw paper which has received a corona discharge processing and
thereby, its coating aptitude has been enchanced, as described in Japanese
Patent Application (OPI) No. 35985/84; and so on can be employed in the
present invention, and can bring about good results. In addition to the
above-described papers, all supports which have so far been used for
general heat sensitive recording papers can be employed as the support of
the present invention.
In the present invention, back layer may be employed behind the support in
order to improve properties such as curling, antistatic and smoothness. As
for components of the back layer it is desired to use similar one utilized
in the protective layer.
EXAMPLES
The present invention is illustrated in greater detail by reference to the
following examples. However, the invention should not be construed as
being limited to these examples.
(Preparation of Capsule Solution)
14 g of Crystal Violet lactone (leuco dye), 60 g of Takenate D 110N (Trade
name of capsule wall material, produced by Takeda Yakuhin K.K. ) and 2 g
of Sumisoap 200 (Trade name of ultraviolet absorbent, produced by Sumitomo
Kagaku K.K.) were added to a mixed solvent consisting of 55 g of
1-phenyl-1-xylylethane and 55 g of methylene chloride, and dissolved
therein. The solution of the above-described leuco dye was mixed with an
aqueous solution constitued with 100 g of a 8% water solution of polyvinyl
alcohol, 40 g of water and 1.4 g of a 2% water solution of sodium
dioctylsulfosuccinate (dispersant), and emulsified with stirring at 10,000
r.p.m. for 5 minutes using Ace Homogenizer made by Nippon Seiki K.K..
Then, the resulting emulsion was diluted with 150 g of water, and allowed
to stand at 40.degree. C. for 3 hours to conduct the microencapsulation
reaction therein. Thus, a solution containing microcapsules having a size
of 0.7 micron was obtained.
(Preparation of Color Developer-emulsified Dispersion)
The color developers (a), (b) and (c) represented by the structural
formulae illustrated below were added in amounts of 8 g, 4 g and 30 g,
respectively, to a solvent mixture of 8.0 g 1-phenyl-1-xylylethane and 30
g of ethyl acetate, and dissolved thereinto. The thus obtained solution of
the color developers was mixed with 100 g of a 8% water solution of
polyvinyl alcohol, 150 g of water and 0.5 g of sodium
dodecylbenzensulfonate, and emulsified with stirring at 10,000 r.p.m. for
5 minute at ordinary temperature using Ace Homogenizer made by Nippon
Seiki k.k. to prepare an emulsified dispersion having a grain size of 0.5
micron.
##STR8##
Production of Heat Sensitive Material No. 1
A 5.0 g portion of the foregoing capsule solution, a 10.0 g portion of the
foregoing color developer-emulsified dispersion and 5.0 g of water were
mixed with stirring, coated on a 70.mu.-thick transparent polyethylene
terephthalate (PET) film support at a coverage of 15 g/m.sup.2 on a solids
basis, and dried. Thereon, a 2.mu.-thick protective layer having the
following composition was further provided to produce a transparent heat
sensitive film.
______________________________________
(Composition of Protective Layer)
______________________________________
Modified Polyvinylalcohol with silicon
1 weight part
(PVA R2105: manufactured by Kurare K.K.)
(solid basis)
Colloidal silica 1.5 weight part
(Snowtex 30: manufactured by Nissan
(solid basis)
Kagaku K.K.)
Zinc stearate 0.02 weight part
(Hidolin Z-7: manufactured by Chukyo
(solid basis)
Yushi K.K.)
Paraffin Wax 0.02 weight part
(Hidolin P-7: manufactured by Chukyo
(solid basis)
Yushi K.K.)
______________________________________
Production of heat sensitive material No. 2
A sample No. 2 was obtained in the same manner as in sample No. 1 except
that the components of the protective layer were changed as follows.
______________________________________
Modified Polyvinylalcohol with silicon
1 weight part
(PVA R2105: manufactured by Kurare K.K.)
(solid basis)
Colloidal silica 1.8 weight part
(Snowtex 30: manufactured by Nissan
(solid basis)
Kagaku K.K.)
Amorphous silicon 0.1 weight part
(P-832: manufactured by Mizusawa
(solid basis)
Kagaku K.K.)
Zinc stearate 0.02 weight part
(Hidolin Z-7: manufactured by Chukyo
(solid basis)
Yushi K.K.)
______________________________________
Production of heat sensitive material (Comparison-1)
A sample (Comparison-1) was prepared in the same manner as in sample No. 1
except using a polyvinyl alcohol (PVA 217: manufactured by Kurare K.K.)
instead of the modified polyvinylalcohol with silicon which was employed
as one of components of the protective layer of sample No. 1.
Production of heat sensitive material (Comparison-2)
A sample (Comparison-2) was prepared in the same manner as in sample No. 1
except that the colloidal silica employed as one of components of the
protective layer of sample No. 1 was not used.
Production of heat sensitive material (Comparison-3)
A sample (Comparison-3) was prepared in the same manner as in sample No. 1
except that the colloidal silica and the modified polyvinylalcohol with
silicon which were employed as the components of the protective layer of
sample No. 1 were not used and an oxidized starch (MS 3800: manufactured
by Nishoku K.K.) was used instead of the latter.
Production of heat sensitive material (Comparison-4)
A sample (Comparison-4) was prepared in the same manner as in sample No. 2
except that the colloidal silica employed as one of components of the
protective layer of sample No. 2 was not used.
Production of heat sensitive material (Comparison-5)
A sample (Comparision-5) was prepared in the same manner as in sample No. 2
except that a half ester salt of styrene-maleic acid copolymer (Polymaron
385: manufactured by Arakawa Kagaku K.K.) was used instead of the modified
polyvinylalcohol by silicon which was used as one of the components of the
protective layer of sample No. 2.
Production of heat sensitive material (Comparison-6)
A sample (Comparision-6 ) was prepared in the same manner as in sample No.
2 except that the colloidal silica and the modified polyvinylalcohol with
silicon which were employed as the components of the protective layer of
sample No. 2 were not used and a polyvinyl alcohol (PVA 217: manufactured
by Kurare K.K.) was used instead of the latter.
The result of measurements of Haze (%) on above prepared samples using HTR
meter (integrating-sphare photometer) manufactured by Nippon Seimitsu
Kogyo K.K. were shown in the following table.
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Sample Haze (%)
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No. 1 16
No. 2 17
Comparison-1 40
Comparison-2 42
Comparison-3 47
Comparison-4 39
Comparison-5 38
Comparison-6 40
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From the above results, it was proved that the heat sensitive recording
material of the present invention realized an excellent transparency.
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