ES2205689T3 - THERMOSENSIBLE REGISTRATION MATERIAL. - Google Patents

Abstract

A roll-shaped thermosensitive recording material having a thermosensitive recording layer, which includes as main components an electron donating coloring agent, an electron accepting color developer and a binder resin and which is formed overlying a substrate, wherein the roll-shaped thermosensitive recording material has a variation (R) of thickness of in the lateral direction of not greater than 3 mu m. Preferably the roll-shaped thermosensitive recording material has a difference in thickness between the left side and the right side in the lateral direction of not greater than 0.7 mu m.

Description

Heat sensitive recording material.

Origin of the invention Field of the invention

The present invention relates to a material of thermosensitive register for the use of plate formers which is useful as a block copy to get a plaque for flexography, gravure printing, offset printing and printing of stencil In addition, the present invention relates to a heat sensitive recording material useful as a recording material for CAD.

Origin Discussion

The heat sensitive recording materials are widely known that use a coloring reaction between an electron donor coloring compound (hereinafter referred to as referred to as a coloring agent) and an acceptor compound of electrons (hereinafter referred to as a value developer).

In recent years, employment is on the rise of heat sensitive recording materials, and there is a need for heat sensitive recording materials such as second sheets or original plans for diazo copying. In addition there is a need for this as a block copy movie to get a Useful plate for flexography, gravure printing, printing offset and stencil printing.

In general the characteristics required for These movies are as follows:

one)

 the images Registered formed have high contrast between the areas of image and background areas (good recognition of the image);

two)

the movies of registration have good light protection properties in the Registered image areas and good transmission properties of light and background areas facing a wavelength region ultraviolet (360 nm - 420 nm) so that it is used as the block copy film for employment obtaining plates;

3)

 the movies of heat sensitive record and the images formed have good preservation stability even when preserved under conditions  various environmental conditions such as high temperatures and high humidity, and good lightfastness;

4)

 the images Registered can be easily verified to determine if there is deviation and errors in the images when several films of block copy for use in plate formation overlap each other (good ability to stretched-check);

5)

the images Registered have good dimensional accuracy;

6)

the images Registered have good resolution; and

7)

the movies of thermosensitive register have good matching properties superior when registering images with a head thermal

A thermosensitive record material that has These required properties are proposed in the publication of Japanese patent Laid-Open nº 8-118811. However, when preparing a block copy film for plate-making jobs, there is a case where high levels of precision are required between plates between block copy film (this accuracy is sometimes referred to as inter-plate error) and obliquity. Consequently, problems related to inter-plate accuracy and obliqueness when uses the heat sensitive recording material proposed above as The block copy. As shown in the figure the term "inter-plate accuracy" is defined as the difference in length (La - Lc) and (Lb -Ld), and the term "obliqueness" is defined as the difference in length (The - Lb) and (Lc-Ld).

With respect to the aforementioned problems motivated by precision between plates and obliqueness, precision Dimensional recorded images formed in a film of block copy depends on the conditions under which it is prepared block copy film and printing conditions under which is used the block copy film formed to Print. When preparing a block copy movie using a block copy forming apparatus, the apparatus block copy trainer also has influence on the dimensional accuracy of the block copy film, which is so results provider or more results provider that the influence that the film has on precision dimensional. For example, the precision of film feed and the dimensional accuracy of the heat source such as heads thermal influence on the dimensional accuracy of the resulting images.

Film feeding accuracy is influenced by:

(1)

unequal feed that is caused by friction between the surface of the film and a thermal head that serves as a source of heat, fusion adhesion of the film to the thermal head (a phenomenon called adhesion, that is, a phenomenon in which the surface of a record material is softened or melted by the heat of a thermal head and sticks to the thermal head), and a head powder adhered to the thermal head due to fusion adhesion (called head powder adhesive), and

(two)

simple precision of feeding the film fed by a forming apparatus of image.

The phenomenon of adhesion and dust adhesion in the head caused by fusion adhesion depends largely on the protective layer (or the covering layer) and the registration layer. Even if only the lubricating property of the layer is improved protective and hardens the protective layer film, if the record layer is a layer that softens and crushes after the application of heat, the record layer becomes the cause of phenomenon of adhesion and adhesion of head dust caused by fusion adhesion.

In addition they are a factor of the accuracy of feed changes in the amount of feed due to changes in environmental conditions and temperature inside the apparatus, and expansion and contraction of the film due to the change Of temperature. In addition, changes in voltage when feeding a roll-shaped film, which is produced by loading the film in roll and roll diameter changes are a factor of the feeding accuracy

There is a technique, which is described in the Laid-Open Japanese patent publication 10-166737, to improve problems before indicated. However, even when using this technique it produces a problem in dimensional accuracy, which occurs for reasons other than those indicated above.

Due to these reasons there is a need for have a thermosensitive record material that uses a color reaction between a donor dye compound of electrons and an electron acceptor compound and that can solve  the problems that have been experienced in the past.

Summary of the invention

Thus, an object of the present invention is provide a heat sensitive recording material that uses a color reaction between a donor dye compound of electrons and an electron acceptor compound and where they can obtain high levels of precision between plates between films of block copy for use in obtaining plates and obliquity.

In summary, this object and other objects of the present invention, as will be more readily apparent to They can then be obtained with a record material thermosensitive roll-shaped which is characterized because in a thermosensitive record material where a record layer thermosensitive, which includes as main components a compound electron donor dye, an electron acceptor compound and a binding resin, is formed by superimposing a substrate, not being the variation (R) of the thickness of the heat-sensitive recording material in the form of a roll in the lateral direction greater than 3 µm.

In another aspect of the present invention, provides a heat sensitive recording material that is characterized because in a thermosensitive recording material in roll form where a heat sensitive recording layer that includes as main components a donor coloring compound of electrons, an electron acceptor compound and a resin binder, is formed by superimposing a substrate, a difference (inclination) in the thickness between the right side and the side left of the roll-shaped heat sensitive recording material in the lateral direction it is not more than 0.7 µm.

The thermosensitive record material of the The present invention may have a top layer, which is formed superimposing the heat sensitive recording layer and that includes as main component a resin that has almost the same index refractive than that of the binder resin in the recording layer heat sensitive

The variation (R) of the substrate thickness in roll form in the lateral direction is preferably not greater than 4 µm, and the difference (inclination) in thickness between the right side and the left side of the substrate in roll form in the lateral direction is preferably not greater than 0.6 µm.

The thermosensitive record material of the present invention, in which images are recorded after heat application or the like, is preferably used as a block copy to obtain a plate for flexography, photogravure, offset printing and stencil printing.

These and other objects, features and advantages of the present invention will become apparent after application of the following description of the preferred embodiments of the present invention taken in connection with the accompanying drawings.

Brief description of the drawing

Various other objects, features and advantages derived from the present invention will be more appreciated fully from the detailed description in connection with the accompanying drawing where characters of similar references designate corresponding similar parties through the description and where:

Figure 1 is a schematic view of movies block copy used to define accuracy inter-plates and obliqueness;

Figure 2 is a schematic view illustrating as the obliquity of a block copy film is measured in the present invention;

Figure 3 is a schematic view of a cross section of a heat sensitive recording material or a transparent substrate used to determine the variation (R) of thickness in its lateral direction; and

Figure 4 is a schematic view of a cross section of a heat sensitive recording material or a transparent substrate used to determine the difference of thickness between the left side and its right side in the lateral direction

Detailed Description of the Invention

The precision between plates required for block copy films to use in obtaining plates is not greater, preferably ± 0.1 mm / A0 in size. As described below the accuracy between plates is determined comparing a block copy movie that has a relationship of 70% impression with a block copy film that has a 30% printing ratio. The obliqueness is not superior, of Preference, at 6 0.2 mm / A0 in size. As described to then the obliqueness is defined as a deference between the left side and right side of a copy film of block When the heat source for image registration is a thermal head, the factors on the side of a material of Thermosensitive record to be used are as follows:

(1)

 the variation (R) of the thickness of the heat-sensitive recording material in the direction side;

(two)

The difference of thickness between the left side and the right side of the thermally sensitive registration material in the lateral direction (inclination); and

(3)

expansion and contraction of the recording material, loading of the material registration, which is produced by friction and fusion adhesion between the film surface and thermal head, and changes of environmental conditions and the temperature inside the apparatus.

In particular, in order to obtain a material of thermosensitive register that has high levels of accuracy between plates and obliqueness, the most important factors are the variation (R) of the thickness of the registration material in the direction lateral and the difference (inclination) in thickness between the lateral left and right side of the record material in the lateral direction of the present invention.

In the present invention the precision between plates It is determined as follows:

(1)

one is registered image on a thermo-sensitive recording material using a large plotter used exclusively as a tracing station, TP-6910 (manufactured by Ricoh Co., Ltd.), so that three sheets of A0 size are formed have a printing ratio of 30% and three sheets of size A0 have a print ratio of 70%;

(two)

then one of the films that have a print ratio of 30% (one sheet A of figure 1) and one of the films that have a relation of 70% impression (a sheet B in figure 1) overlaps so that a line (a) of the sheet A overlaps a line (b) of the sheet B, to be determined using an extension glass with a scale manufactured by PEAK CO., Ltd. as a line (a ') and a line (b ') in Figure 1 deviate from each other; and

(3)

 this measurement is carried out with respect to three pairs of movies that have a print ratio of 30% and a print ratio of 70% to obtain an average precision value between plates.

In addition, obliqueness is determined as follow:

(1)

 one is registered image on a thermo-sensitive recording material using a TP-6910 oversized plotter so that a sheet of size A0 is formed with a ratio of 30% print and A0 size sheet with a ratio of 70% impression;

(two)

 a movie that it has a printing ratio of 30% (sheet A in figure 1) it is folded in two so that each point a1 overlaps with a point a2,  as shown in figure 2;

(3)

 the deviation of a point a3 from a point a4 is measured with a extension glass that has a scale manufactured by PEAK Co., Ltd to determine the obliqueness of the sheet having a 30% printing ratio; and

(4)

 this measurement is also carried out with respect to the movie that has a 70% printing ratio to get an average value of the obliquity of the film.

In the present invention the variation (R) of thickness of a roll-shaped recording material (or a roll-shaped substrate) in the lateral direction and the difference thick between the left side and its right side in the Lateral direction is defined as follows:

1) Variation (R) of thickness in the lateral direction

The thickness of a recording material heat-sensitive roll-shaped (or a substrate) in the direction side is measured with a thickness gauge of contact type, Electronic Micrometer K351C manufactured by Anritsu Corp (range of measurement of 0.1 µm), as shown in Figure 3. The thickness is measured with respect to the measurement points as determined by equation 1. Thus, the variation (R) of its thickness is obtained in accordance with equation 2.

\ cdot \ cdot \ cdot Equation 1 \ cdot The number of measuring points = W mm / 10 mm

where W represents the width of the material of record (or the substrate) to be measured in the lateral direction.  The measurement conditions are 20 ± 10 ° C at the temperature and 50 ± 20% RH in moisture relative.

With respect to the measuring points the Measurements are carried out at equal intervals.

\ cdot \ cdot \ cdot Equation 2 \ cdot Variation (R) of thickness = Maximum thickness (Tmax) - Minimum thickness   (Tmin)

2) Difference in thickness between the left side and the right lateral in the lateral direction

As shown in Figure 4, the thickness of a left side part and a right side part of a material of heat-sensitive roll-shaped record (or a substrate) in the lateral direction, each of whose lengths from the edge left and the right edge is 30% of the width, respectively, It is measured with a contact type thickness gauge, Electronic Micrometer K351C (0.1 µm measuring range) manufactured by Anritsu Corp. The thickness is measured with respect to measurement points as determined by equation 3 below, and the difference in thickness between the left side and the side right is obtained by equation 4.

\ cdot \ cdot \ cdot Equation 3 \ cdot The number of measurement points in the part left side and side   right = 0.3 W mm / 10 mm

where W represents the width of the material of record (or substrate) to be measured in the address side.

With respect to the measuring points the Measurements are carried out at equal intervals.

\ cdot \ cdot \ cdot Equation 4. \ cdot Difference in thickness between the side left and right side =  / (Average thickness of the left side part) - (Average thickness of the  part side right)/

In the present invention it is discovered that the accuracy between plates and obliqueness can be dramatically improved imparting the variation (R) of the thickness in the lateral direction not greater than 3 µm for the heat sensitive recording material in roll form or imparting the difference in thickness between the left lateral and right lateral in the lateral direction no greater than 3 µm for heat sensitive recording material in roll form, and thus the requirements of high level of precision between plates and obliqueness.

In addition it has been discovered that a material of heat-sensitive roll-shaped register mentioned above may easily manufactured by imparting the variation (R) of thickness in the lateral direction not exceeding 4 µm to the transparent substrate in roll form, or imparting the difference in thickness between the left lateral and right lateral in the lateral direction no greater than 0.62m to the transparent roll-shaped substrate.

The electron donor coloring compounds suitable for use in the present invention include precursors dyes, which are colorless or pale in themselves, but not They are specifically limited. For example they can be used Fluoran compounds known as the coloring compounds. Specific examples of the fluoran compounds include:

3-diethylamino-7-anilinofluoran,

3-di-n-butylamino-7-anilinofluoran,

3- (N-n-hexyl-ethylamino) -7-anilinofluoran,

3-diethylamino-7-dibenzylaminofluorane,

3-diethylamino-5-methyl-7-dibenzylaminofluorane,

3-diethylamino-7-piperidinofluorane,

3-diethylamino-7- (o-chloroanilino) fluoran,

3-di-n-butylamino-7- (o-chloroanilino) fluoran,

3-dimethylamino-6-methyl-7-anilinofluoran,

3-diethylamino-6-methyl-7-anilinofluoran,

3-di-n-butylamino-6-methyl-7-anilinofluoran,

3-di-n-butylamino-6-methyl-7-anilinofluoran,

3- (N-n-propyl-N-methylamino) -6-methyl-7-anilinofluoran,

3- (N-n-Isopropyl-N-methylamino) -6-methyl-7-anilinofluoran,

3- (N-n-butyl-N-ethylamino) -6-methyl-7-anilinofluoran,

3- (N-isobutyl-N-methylamino) -6-methyl-7-anilinofluoran,

3- (N-n-amyl-N-methylamino) -6-methyl-7-anilinofluoran,

3- (N-isoamil-N-methylamino) -6-methyl-7-anilinofluoran,

3- (N-cyclohexyl-N-methyl) -6-methyl-7-anilinofluoran,

3- (N-n-amyl-N-ethylamino) -6-methyl-7-anilinofluoran,

3- (N-p-tolyl-N-ethylamino) -6-methyl-7-anilinofluoran,

3- (N-2-ethoxypropyl-N-ethylamino) -6-methyl-7-anilinofluoran,

3-pyrrolidino-6-methyl-7-anilinofluoran,

3- (N-tetrahydrofurfuryl-N-ethylamino) -6-methyl-7-anilinofluoran,

3-diethylamino-7- (m-trifluoromethylanilino) fluoran,

3-diethylamino-6-methyl-7- (2 ', 4'-dimethylamino) fluoran,

3-diethylamino-6-chloro-7-anilinofluoran,

3-diethylamino-5-methyl-7- (alpha-phenylethylamino) fluoran,

3- (n-p-tolyl-N-ethylamino) -7- (alpha-phenylethylamino) fluoran

and the like In addition the compounds of Fluoran that have the following formulas (III) - (VIII) are more preferably used as the coloring agents in the present invention

1

wherein R1 represents an alkyl group that has no more than 8 carbon atoms; R2 represents a hydrogen atom or an alkyl group that has no more than 4 carbon atoms; and X represents a halogen atom such as fluoro, chloro, bromo or Similar

two

wherein R3 represents an alkyl group that has no more than 8 carbon atoms; and R4 represents an alkyl group with no more than 8 atoms of carbon.

3

where R5 and R6 independently represent an alkyl group with no more than 8 carbon atoms; and R7 represents a hydrogen atom, a lower alkyl group or a group of alkoxy lower.

4

wherein R8 represents a hydrogen atom; R9 represents an alkyl group that has no more than 8 atoms of carbon; R10 represents a hydrogen atom, an alkyl group lower or a lower alkoxy group, R 11 represents an atom of hydrogen or an alkyl group that has no more than 8 atoms of carbon; and R12 represents an alkyl group that has no more than 8 carbon atoms, a phenyl group or a phenyl group replaced.

5

wherein R13 represents an alkyl group that does not it has more than 8 carbon atoms; R14 represents a methyl group or an ethyl group, R15 represents a hydrogen atom or a group alkyl with no more than 4 carbon atoms; and Y and Z represent, independently, a hydrogen atom, or a halogen atom such as fluorine, chlorine, bromine or Similar.

6

wherein R16 represents an alkyl group with no more than 8 carbon atoms; R17 represents a methyl group or a ethyl group, R18 represents a hydrogen atom or a group alkyl with no more than 4 carbon atoms; Y and Z represent, independently, a hydrogen atom, or a halogen atom such as fluorine, chlorine, bromine or the like; and Ar represents a group phenyl or a group benzyl

Specific examples of the compounds of Fluoran that have the formula (III) include:

2- (o-chlorophenylamino) -6-ethylamino-7-methylfluorane,

2- (o-chlorophenylamino) -6-n-butylamino-7-methylfluoran,

2- (o-fluorophenylamino) -6-ethylamino-7-methylfluorane,

2- (o-chlorophenylamino) -6-n-butylaminofluorane,

2- (o-chlorophenylamino) -6-n-hexylaminofluorane,

2- (o-chlorophenylamino) -6-n-octylaminofluorane,

2- (o-fluorophenylamino) -6-isoamylaminofluorane and

2- (o-fluorophenylamino) -6-n-octylaminofluorane.

Specific examples of the compounds that have Formula (IV) includes:

2- (o-nitrophenylamino) -6-diethylaminofluorane,

2- (o-nitrophenylamino) -6-di-n-butylaminofluorane,

2- (o-nitrophenylamino) -6- (N-ethyl-N-n-butylamino) fluoran, and

2- (o-nitrophenylamino) -6- (N-ethyl-N-isoamylamino) fluoran.

Specific examples of the compounds that have Formula (V) include:

2-amino-6-diethylaminofluorane,

2-amino-6-di-n-butylaminofluorane,

2-amino-3-methyl-6-diethylaminofluorane,

2-amino-3-methyl-6-di-n-butylaminofluorane,

2-amino-3-methyl-6- (N-ethyl-N-isoamylamino) fluoran,

2-amino-3-methoxy-6-diethylaminofljorano, and

2-amino-3-methoxy-6-di-n-butylaminofluorane.

Specific examples of the compounds that have Formula (VI) includes:

2-methylamino-6-n-butylaminofluorane,

2-n-butylamino-6-n-butylaminofluorane,

2-n-octylamino-6-ethylaminofluorane,

2-n-octylamino-3-methyl-6-n-butylaminofluorane,

2-phenylamino-6-ethylaminofluorane,

2-phenylamino-6-n-butylaminofluorane,

2-phenylamino-6-n-octylaminofluorane,

2-phenylamino-3-methyl-6-n-butylaminofluorane,

2-phenylamino-3-methyl-6-ethylaminofluorane,

2-phenylamino-3-methyl-6-n-hexylaminofluorane,

2-phenylamino-3-methyl-6-n-amylaminofluorane,

2-phenylamino-3-methyl-6-isoamylaminofluorane,

3-phenylamino-3-methyl-6-n-butylaminofluorane, and

2-phenylamino-3-methoxy-6-n-hexylaminofluorane.

Specific examples of the compounds that have Formula (VII) includes:

2- (3 ', 4'-dichlorophenylamino) -6-ethylamino-7-methylfluorane,

2- (3 ', 4'-dichlorophenylamino) -6-n-butylamino-7-methylfluorane,

2- (3'-Chloro-4'-fluorophenylamino) -6-ethylamino-7-methylfluorane,

2- (N'-methyl-N-3'-chlorophenylamino) -6-ethylamino-7-methylfluoran,

2- (N-ethyl-N-3'-chlorophenylamino) -6-ethylamino-7-methylfluoran, and

2- (N-methyl-N-4'-chlorophenylamino) -6-ethylamino-7-methylfluorane.

Specific examples of the compounds that have Formula (VIII) includes:

2-phenylamino-3-methyl-6-ethylamino-7-methylfluoran,

2-phenylamino-3-methyl-6-n-butylamino-7-methylfluoran,

2-phenylamino-3-ethyl-6-ethylamino-7-methylfluoran,

2-benzylamino-3-methyl-6-ethylamino-7-methylfluoran,

2-phenylamino-3-chloro-6-ethylamino-7-methylfluorane,

2-phenylamino-3-chloro-6-n-butylamino-7-methylfluorane, and

2-benzylamino-3-chloro-6-ethylamino-7-methylfluoran.

These coloring agents are used alone or in combination.

In the present invention the color developers, which give the color to the coloring agents mentioned above, are of preference phenolic compounds and phosphoric acid compounds organic, which are preferably insoluble or hardly soluble in popular solvents. Specific examples of Phenolic compounds include gallic acid compounds, compounds of protocatechic acid, acid bis (hydroxyphenyl) acetic and the like. Examples Specific organic phosphoric acid compounds include alkylphosphonic acid compounds, acid alpha-hydroxyalkyl phosphonic and the like. Between these compounds organic phosphoric compounds are superior in terms of thermosensitivity of the registration material resulting and dirtied from the background of the registered images resulting.

Among the organic phosphoric acid compounds phosphonic acid compounds are even more preferable than they have the following formula (I) or (II):

\uelm{P}{\uelm{\dpara}{O}}

(OH)_{2}(GO --

 \ uelm {P} {\ uelm {\ dpara} {O}} 

(OH) 2

where R represents a linear alkyl group with 16 to 24 atoms of carbon.

\delm{C}{\delm{\para}{OH}}

H --

\uelm{P}{\uelm{\dpara}{O}}

(OH)_{2}(II) R '-

 \ delm {C} {\ delm {\ para} {OH}} 

H -

 \ uelm {P} {\ uelm {\ dpara} {O}} 

(OH) 2

where R 'represents a linear alkyl group with 13 to 23 atoms of carbon.

Specific examples of acid compounds phosphonic represented by the formula (I) cited above include hexadecyl phosphonic acid, octadecyl phosphonic acid, eicosyl acid phosphonic, docosyl phosphonic acid, tetracosyl phosphonic acid and Similar.

Specific examples of phosphonic acids represented by the aforementioned formula (II) include acid alpha-hydroxytetradecyl phosphonic acid alpha-hydroxyexadecyl phosphonic acid alpha-hydroxyoctadecyl phosphonic acid alpha-hydroxyeicosyl phosphonic acid alpha-hydroxytetracosyl phosphonic and the like.

In the present invention the developers are colored They are used alone or in combination.

In the present invention the color developer for used in the present invention preferably has a diameter of average particle not exceeding 10 µm, and more preferably has an average particle diameter not exceeding 1 µm and not includes particles with a diameter greater than 1 µm, to improve the thermosensitivity of the thermosensitive recording material resulting and resolution of the registered images resulting.

Binding resins for use in the layer thermosensitive materials are preferably that can keep Stably form a colored pigment material, which is produced by an open ring reaction caused by the proton attack of the color developer on the coloring agent mentioned above after application of heat energy and the like while allows the coloring material to be in a rich condition with protons In addition materials that additionally allow the colored material is in a condition where the material Hardly colored discolors are preferably used as the binding resin. For example, compounds that include a group hydroxy or a group of carboxylic acid and they have an index refractive from 1.45 to 1.60 at room temperature are preferable as the binding resin.

Specific examples of a binder resin of these types include polyvinyl butyral (1.48-1.49), polyvinyl acetal (1.50), epoxy resins (1.55-1.61), ethyl cellulose (1.46-1.49), cellulose acetate (1.46-1.50), cellulose acetate butyrate (1.46-1.49), cellulose acetate propionate (1.46-1.49), nitro cellulose (1.49-1.51), styrene-maleic acid copolymers (1.50-1.60) and the like. The values between parentheses mean its refractive index. In addition, when include acidic materials in binder resins such as impurities, or UV absorbers, antioxidants, agents are included anti-aging and the like in the layer of registration can also be observed a condition similar to the condition obtained with the aforementioned binding resins.

In addition, the light resistance of the material of thermosensitive recording in the present invention can be improved including a photo-stabilizer in the layer of heat-sensitive record or a protective layer (or a layer of covering) that is formed on the record layer. As photo-stabilizer can be used absorbents ultraviolet, antioxidants, agents anti-aging, oxygen absorbers in a simple state, and shock absorbers for superoxide anions.

Specific examples of ultraviolet absorbers include benzophenone type ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzo-phenyl, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzogfenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-oxybenzyl benzophenone, 2-hydroxy-4-chlorobenzophenone, 2-hydroxy-5-chlorobenzogenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-n-heptoxybenzophenone, 2-hydroxy-3,6-dichloro-4-methoxy-benzophenone, 2-hydroxy-4-n-heptoxybenzophenone, 2-hydroxy-3,6-dichloro-4-ethoxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl-acryloxy) propoxybenzophenone and the like; benzotriazole type ultraviolet absorbers such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-4 ', 5'-di-t-butylfe-nyl) benzotriazole, 2- (2'-hydroxy-4'-t-butyl-5'-methylphenyl) benzo-triazole, 2- (2'-hydroxy-4'-octoxy) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) 5-chlorobenzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-methylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-5-ethoxyphenyl) benzotriazole and the like; ultraviolet absorbers of phenyl ester type of Salicyclic acid such as phenyl salicylate, p-octylphenyl salicylate, p-t-butylphenyl salicylate, carboxyphenyl salicylate, methylphenyl salicylate, dodecylphenyl salicylate and the like; dimethyl acid ester p-methoxybenzylidenemalonic acid, 2-ethylhexyl-2-cyano-3,3'-diphenyl-acrylate, ethyl-2-cyano-3,3'-diphenylacrylate, 3,5-di-t-butyl-p-hydroxybenzoate,  resorcinolmonobenzoate that is rearranged to benzophenone by rays ultraviolet, 2,4-di-t-butyl phenylbenzoate, 3,5-di-t-butyl-4-hydroxyphenylbenzoate, 3,5-di-t-butyl-4-hydroxybenzoate and the like

Specific examples of antioxidants and anti-aging agents include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butyl-4-phenol, styrene phenol, 2,2'-methylenebis (4 -methyl-6-t-butylphenol), 4,4'-isopropylidenebisphenol, 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methylphenol, 4,4'- thiobis- (3-methyl-6-t-butylphenol), tetrakis- (methylene (3,5-di-t-butyl-4-hydroxyhi-drocinamate) methane, p-hydroxyphenyl-3-naphthylamine, 2,2,4 -trimethyl-1,2-dihydroquinoline, thiobis (beta-naphthol),
mercapto-benzothiazole, mercaptobenzimidazole, aldol-2-naphthylamine, bis (2,2,6,6-tetramethyl-4-pyridyl) sebacate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, dilauryl-3,3 ' thiodipropionate, distearyl-3,3'-thiodipropionate, tris (4-nonylphenol) phosphite and the like.

Suitable buffers for oxygen in a Singlet state include carotenes, dyes, amines, phenols, nickel complexes, sulfides and the like. Specific examples of oxygen absorbers in a singlet state include 1,4-diazabicyclo (2,2,2) octane, beta-carotene,  1,3-cyclohexadiene, 2-diethylamionomethylfuran, 2-phenylaminome-tilfuran, 9-diethylaminomethylantracene, 5-diethylaminomethyl-6-phenyl-3,4-dihydroxypyran, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel3,5-di-t-butyl-4-hydroxybenzyl-o-ethylphosphonate, nickel-3,5-di-butyl-4-hydroxybenzyl-o-butyl phosphonate, nickel {2,2'-thiobis (4-t-octylphenolate)} (n-butylamine, nickel {2,2'-thiobis (4-t-octylphenolate)} (2-n-butylamine, nickel- {2,2'-thiobis (4-t-octylphenolate)} (2-ethylhexylamine, niquelbis- {2,2'-sulfonbis (4-octylphenolate)}, nickel {2-hydroxy-5-methoxy-phenyl-N-n-butylaldoimine), niquelbis (dithiobenzyl), niquelbis- (dithiobiacetyl) and Similar.

Specific examples of shock absorbers for superoxide anions are superoxide dismutase complexes with cobalt (III) or nickel (II) and the like, but not limited to these in The present invention.

These photo stabilizers are Use alone or in combination.

The appropriate substrates for use in the thermosensitive recording material of the present invention include paper or plastic film. The substrate is preferably transparent, and preferably has a refractive index of 1.45 to 1.60 at room temperature.

Specific examples of the substrate include polyester films such as polyethylene terephthalate, polybutyleneterephthalate and the like; derivative films of cellulose such as triacetyl cellulose and the like; films polyolefins such as polypropylene, polyethylene and the like; polystyrene films; and transparent substrates where They laminate two or more of these films.

In the present invention it is preferable to form a adhesive layer between the heat sensitive layer and the substrate. Materials suitable for use in the adhesive layer include Acrylic resins, saturated polyester resins and the like. In addition can also be used for the adhesive layer resins in where these resins crosslink.

In order to obtain a registration material with the high precision mentioned above can improve the properties of head coincidence of the record material to form the layer covering that follows the record layer.

(1)

A organic particulate filler lubricant (a resin of particulate silicone) in a covering layer to impart the coefficient of friction not exceeding 0.1 to the surface of the covering layer; and

(two)

You get the roughness of the surface of the covering layer so that it get a default roughness (1-4 \ mum).

The friction between the surface of the film and a thermal head, fusion adhesion (adhesion phenomenon), head powder adhesion caused by fusion adhesion and similar can be dramatically improved with methods (1) and (2), resulting in the smallest matching properties of head.

The covering layer of the record material of the The present invention is effective for the improvement of resistance to Chemicals, water resistance, abrasion resistance and light resistance, as well as for the improvement of the properties head coincidence (that is, for accuracy improvement dimensional). Therefore it is preferable to form the layer of cover on top of the record material thermosensitive of the present invention.

The layer will be explained in detail below of coverage of the present invention.

Organic fillers for use in the material of thermosensitive recording of the present invention have, of preference, a spherical shape and an average particle diameter of 50% volume (D 50), which is obtained through a distribution of accumulated volume of particles from 1 to 5 µm. In addition, the organic fillers preferably have an oil absorption of flaxseed not less than 50 ml / 100 g. In addition, they are more preferable organic fillers that have lubricating properties such as silicone resins In order to improve the properties of head covering of the covering layer is preferable use a combination of an inorganic filler with a diameter average particle volume of 50% (D 50) not exceeding 0.7 um with an organic filler having a particle diameter 50% average volume (D 50) from 1 to 5. Total content of the inorganic filler and the organic filler in the layer of coverage is preferably less than 50% in a weight ratio solid when cost is considered, properties of head coincidence and other properties.

Specific examples will be presented below. of organic fillers and inorganic fillers for be used in the covering layer.

Organic fillings

Specific examples of organic fillers Include the following.

(1) PMMA type fine particles

Fillers type MP and MX, manufactured by Sohken Chemical Co., Ltd., and Technopolymer MB series

(2) Fine resin type particles of silicone.

Torefill series manufactured by Dow Corning Toray Silicone Co., Ltd., and Tospearl series manufactured by Toshiba Silicone Co., Ltd.

Inorganic filler

Specific examples of inorganic fillers include kaolin, calcined kaolin, calcined clay, talc, calcium carbonate, titanium oxide, zinc oxide, silica, silica colloidal, magnesium carbonate, magnesium oxide, hydroxide aluminum and zinc hydroxide.

Resins that have the same index of refraction as the binder resin that constitutes the recording layer thermosensitive, they are preferably used as a resin that It constitutes the covering layer.

At this point the term of the same index refractive means that the refractive index of the resin that constitutes the covering layer is substantially the same as the of the resin that constitutes the registration layer. When the index refractive of a resin in the covering layer is within the range of about ± 5% compared to that of the resin in the layer For registration, resin refractive indices are considered same in the present invention. The refractive index of the resin in the covering layer it is preferably from 1.45 to 1.60 a room temperature.

Resins appropriate for use in the layer of Coating include water-soluble resin, aqueous emulsions, resins hydrophobic, ultraviolet crosslinking resins, electron beam crosslinking to which segment of silicone as a block or graft. Specific examples of water-soluble resins include polyvinyl alcohols, alcohols modified polyvinyl, cellulose derivatives (methyl cellulose, methoxy cellulose, hydroxyethyl cellulose and the like), casein, gelatin, polyvinyl pyrrolidone, copolymers of styrene-maleic anhydride, copolymers of diisobutylene-maleic anhydride, polyacrylamide, modified polyacrylamide, methyl vinyl copolymers maleic ether-anhydride, polyethylene carboxy-modified block copolymers polyvinyl alcohol / acrylamide resins melamine-formaldehyde, resins urea-formaldehyde and the like. Specific examples of aqueous emulsions and hydrophobic resins include polyvinyl acetate, polyurethanes, copolymers of styrene / butadiene, styrene / butadiene / acryl copolymers, polyacrylic acid, polyacrylic acid esters, copolymers of vinyl chloride / vinyl acetatro, polybutyl methacrylate, ethylene / vinyl acetate copolymers, and the like. These will Use alone or in combination. If desired, a hardener to crosslink the resins.

Then, resins of ultraviolet crosslinking, beam crosslinking resins electrons, and resins to which a silicone segment is connected as a block or graft, which are preferable as the layer of coverage of the present invention.

Appropriate ultraviolet crosslinking resins for use in the covering layer include monomers, oligomers or known prepolymers, which can induce reaction of polymerization after application of ultraviolet rays. Specific examples of these monomers, oligomers or prepolymers include (poly) acrylate ester, (poly) urethane acrylate, epoxy acrylate, polybutadiene acrylate, silicone acrylate, melamine Acrylate and the like. (Poly) acrylate ester includes a product of reaction where a polyhydric alcohol such as 1,6-hexan diol, propylene glycol (used as propylene oxide, diethylene glycol and the like with polybasic acid such as adipic acid, phthalic anhydride, trimellitic acid and similar, and then reacted with acrylic acid. Examples Specific monomers, oligomers and prepolymers are shown in (a) - (c).

(a) Acid Compounds adipic / 1,6-hexanediol / acrylic acid

CH_2 = CH-COO- (CH2) 6 \ abbreg O-CO- (CH 2) 4 COO (CH 2) 6 \ lock OCOCH = CH_ {2}

where n is an integer from 1 to 10.

(b) Phthalic anhydride / oxide compounds propylene / acrylic acid

7

where k is an integer from 1 to 10, m is a integer from 1 to 10 and n is an integer from 1 to 10.

(c) Trimellitic acid / diethylene glycol / acid compounds acrylic

8

(Poly) uretan acrylate is a product of reaction of a compound having an isocyanate group such as tolylene diisocyanate (TDI) with an acrylate having a group hydroxy An example of the structure is shown in (d). In this point, HEA represents 2-hydroxyethyl acrylate, HDO represents 1,6-hexanediol, and ADA represents acid adipic

(d) HEA / TDI / HDO / ADA / HDO / TDI / HEA

9

where n is an integer from 1 to 10.

Epoxy acrylate is broadly classified as bisphenol type A, novolac type and alicyclic type when classified Because of its structure. The epoxy group of these epoxy resins is esterify with acrylic acid in order to change the group functional to an acryloyl group. Specific examples of the structure are shown in (e) - (g).

(e) Bisphenol type compounds A-epichlorohydrin / acrylic acid

10

where n is an integer from 1 to fifteen.

(f) Phenol type compounds novolaca-epichlorohydrin / acrylic acid

eleven

where n is 0 or an integer from 1 to 5.

(g) Alicyclic / acrylic acid type compounds

12

where R represents - (CH 2) n, and n is an integer from 1 to 10.

Polibutadien acrylate is a reaction product in which 1,2-polybutadiene that has a group hydroxy in its extreme positions is reacted with a isocyanate, 1,2-mercaptoethanol or the like, and then It reacts further with acrylic acid and the like. A Example of the structure is shown in (h).

(h) Polybutadiene / TDI / acrylic acid compounds

13

Silicone acrylate is obtained, for example, modifying with methacrylic acid a product that is obtained by condensation reaction (demetanolization reaction) of a organic functional trimethoxy silane with polysiloxane having a silanol group. An example of the structure is shown in (i).

(i) Trimethoxy silane / polysiloxane / acid compounds metacrilic

twenty

where n is an integer from 10 to 14.

When crosslinking resins are used Ultraviolet is optionally used a solvent. Examples Specific of such a solvent include tetrahydrofuran, methyl ethyl ketone, methyl isophenyl isocyanate and Similar. In addition compounds that have a double bond of acrylic type, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and Similar can be used as a solvent. As polyester diols that can be obtained in the market, constitutes An example Adeka New Ace Y4-30 (manufactured by Asahi Denka Kogyo). As polyester triols that can be obtained Sannics TP-400 is an example in the market and Sannics GP-3000 (manufactured by Sanyo Chemical Industries Ltd.).

The molecular weight of the polyester part in the Modified Acrylic Polyurethane Resins by Beam Crosslinking electrons is preferably from 2000 to 4000 in order to obtain flexibility and tenacity, which are requirements for the layer of heat resistant covering. The total molecular weight of the polyurethane resins modified by acryl and crosslinking by electron beam is preferably 20,000 to 50,000 for the same reason above. In resins using resins of acrylic-modified polyurethane that has no more than 5 functional groups, and preferably 7 to 13 functional groups, crosslinking can be accelerated and hardening of The resulting layer.

Electron beam crosslinking resins silicone modified are resin that have the formula next:

14

where R represents - (CH 2) n -, where n is 0 or an integer from 1 to 3; TDI represents 2,4-tolylenediisocyanate; HEM represents 2-hydroxyethyl acrylate; x is an integer of 50 to 100; e y is an integer from 3 to 6.).

These silicone modified resins that crosslinked with electron beam have good properties of film formation and therefore can form a layer thin uniform. In addition, because the resins have a silicone functional group the resulting layer has good sliding properties.

When a resin of Acrylic modified polyurethane and crosslinking by beam of electrons and a silicon-modified resin of electron beam crosslinking the resin silicon-modified beam crosslinking electrons are used in an amount not exceeding 30 parts in weight, and preferably 5 to 20 parts by weight, per 100 parts in Acrylic-modified polyurethane resin weight of electron beam crosslinking.

In the present invention a monomer of electron beam crosslinking that has functional groups plurals are preferably combined in the covering layer to promote crosslinking during layer formation and to improve the heat resistance properties of the layer. Due to which this monomer serves as a crosslinking promoter can an advantage is obtained such that a crosslinked structure is formed complex and high density.

Specific examples of a monomer of this nature includes trimethylolpropane triacrylate, tetraacrylate tetramethylolmethane, pentaerythritol triacrylate, triacrylate dipentaerythritol and the like.

The monomer is added in an amount not greater than 50 parts by weight, and preferably 20 to 50 parts in weight, per 100 parts by weight of the polyurethane queen Acryl-modified crosslinking by beam of electrons When the amount of addition is greater than 50 parts in weight the lubricating effects are weakened, resulting in the deterioration of sliding properties.

Another modality of the covering layer of The present invention is a layer obtained by a resin of the type of phosphazene having a phosphazene skeleton represented by the following formula as repetitive unit.

 - (P = N) -

The covering layer that includes a resin of Phosphazene of this nature has excellent heat resistance.

Specific examples of such a resin includes resins that have the following formula, but without limitation.

  - [NP (A) a (B) b] n -

where a and b are an integer that satisfies The equations following:

 a> 0, b \ geq0 and a + b = two;

A represents a crosslinkable group of polymerization such as the methacryloxyethyl group and the like; and B represents a group that has the following formula:

fifteen

where R1-R5 independently they represent a hydrogen atom, a chlorine atom, an atom of bromine, or a halogenated alkyl group having 1 to 4 atoms carbon; and M represents an oxygen atom, a sulfur atom or a group imino.

When, for example, A is a group of methacryloxyethyl and b is 0 in the resins of phosphazene having the formula indicated above, the resin of Phosphazene can be prepared by opening polymerization of ring of a compound having the following formula:

16

When the resin included in the covering layer it has a crosslinkable polymerization group so that the phosphazene type resins represented by the formula before indicated, the mechanical strength, hardness and heat resistance of the covering layer can be further improved by crosslinking of the resin with ultraviolet rays application, electron beams, heat and Similar.

In addition, in order to impart properties of lubrication to the coating layer, resins are used to A silicone segment is connected as a block or graft.  Because a silicone segment is connected as a block or a graft the resulting covering layer has properties of lubrication against thermal heads. In addition, due to that a silicone is copolymerized with the resin the powder tends not to adhere to the thermal heads.

Specific examples of silicone segments copolymerized with the resin include organopolysiloxanes that they have a siloxane bond and an alkyl group such as a group of methyl connected to a silicone atom that includes a group reactive functional, such as a hydroxy group, a carboxyl group, an epoxy group, an amino group, a mercapto group and the like, in the extreme position of the molecule or in the molecule of organopolysiloxanes.

Specific examples of the resins to which connect these silicone segments as a block or graft, include thermoplastic resins such as acid ester resins poly (meth) acrylic, polyvinyl butyral resins, polyvinyl acetoacetal, ethyl cellulose, methyl cellulose resins, acetyl cellulose, hydroxyethyl cellulose, acetate propionate cellulose, polyurethane resins, polyester resins, resins polyvinyl acetate, styrene-acrylate resins, polyolefin resins, polystyrene resins, type resins polyvinyl chloride, polyether resins, polyamide resins, polycarbonate resins, polyethylene resins, resins polypropylene, polyacrylamide resins and the like. Between these resins are preferred acid ester resins poly (meth) acrylic, polyvinyl butyral resins, polyvinyl acetoacetal resins, cellulose acetate propionate, ethyl cellulose and polyurethane resins because they have good heat resistance and are soluble in solvents.

The content of the silicone segment in the Silicone-modified resins are, preferably 1 to 30% by weight to maintain good lubrication properties, which results in the prevention of a problem of adhesion, and good bonding properties and adhesion properties, resulting in the dust adhesion prevention on thermal heads. In addition, because these resins request-modified in case they have good bonding capacity, the resins can be used alone or as a main component in the covering layer.

Photostabilizers can also be included in the coating layer of the present invention in a manner similar to the thermosensitive recording layer to improve resistance to light covering layer. Photostabilizers for use in The present invention includes ultraviolet absorbers, anti-oxidants, anti-aging agents, oxygen absorbers in a singlet state, and shock absorbers for superoxide anions. The same materials as those for use in the aforementioned heat-sensitive recording layer can be used in the coating layer.

The thermosensitive record material of the The present invention can be manufactured by coating a liquid of heat-sensitive recording layer coating on one side or both sides of a transparent substrate and drying the liquid to form a heat sensitive recording layer, and then forming over this a covering layer that includes a component of resin to form a coating layer. The liquid of heat sensitive recording layer coating can be prepared with  any of the following methods:

(1)

 it disperses evenly a first and only color developer in a organic solvent, and then mixed evenly, one by one, a coloring agent and a binding resin;

(two)

 it disperses from evenly a color developer in a resin solution Binder by dissolving the binder resin in an organic solvent and then a coloring agent and the like mixed with this so uniform; and

(3)

it disperses from uniformly a coloring agent and a color developer in a organic solvent together with a binder resin.

Specific examples of the organic solvent useful for dissolving binding resins include esters such as dibutyl ether, isopropyl ether, dioxane, tetrahydrofuran and Similar; ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone and the like; esters such as ethyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate and Similar; and aromatic hydrocarbons such as benzene, toluene, Xylene and the like. These solvents are used alone or in combination.

The method for coating the layer of covering and the respective coating weight are not particularly limited. However, when the provision of resulting covering layer and the economy is taken into consideration, The coating weight is preferably 1 to 20 µm in coating thickness and more preferably 1 to 10 µm, to maintain good performance of the covering layer as a layer protective, and good provision of registration material resulting.

In the present invention the covering layer is preferably, on the record material so that the resulting record material have good dimensional accuracy improving the head matching properties of the material of record when using the thermal head as the source of hot.

In addition, it is preferably formed on a back side of the recording material an antistatic layer for improve the antistatic properties of the record material.

The antistatic layer is required to have a antistatic capacity such that its surface resistivity is not greater than 10 8 \ Omega \ oblong. Therefore the materials used for the layer are limited and it is general add an electroconductive metal oxide. Agents Antistatics that use an electro-conductive metal oxide are generally expensive. However, metal oxides electroconductors have good antistatic capability even when the weight of the coating is relatively low because the Metal oxide itself has an electroconductive property. In addition, because the coating weight is relatively low, electroconductive metal oxides hardly impair the transparency of the registration material. Examples Specific electroconductive metal oxides include SnO 2, In 2 O 3, ZnO, TiO 2, MgO, Al 2 O 3, BaO, MoO_3 and the like, which are used alone and oxides complexes where these metal oxides are mixed with P, Sb, Sn, Zn and the like, but without limitation. It is preferable that these particulate metal oxides are as fine as possible, since that against finer are the metal oxides the better is the Transparency of the resulting layer. In the present invention you can obtain good transparency by imparting the particle diameter medium not exceeding 0.2 µm to the antistatic agent (oxide metal).

Specific examples of binding resins for Use in combination with these antistatic agents include, by example, aqueous resins, aqueous emulsions, resins hydrophobic, cross-linking resins with ultraviolet light and electron beam crosslinking resins. Specific examples of the water-soluble resins include, for example, alcohols polyvinyl, cellulose derivatives, casein, gelatin, styrene-maleic anhydride, resins of modified carboxy polyethylene and the like. Specific examples of the aqueous emulsions and hydrophobic resins include, by example, polyvinyl acetate, polyurethane, chloride copolymer vinyl / vinyl acetate, polyesters, polybutyl acrylate, polyvinyl butyral, polyvinyl acetal, ethylene / vinyl acetate copolymers and Similar. These are used alone or in combination and, if if necessary, a hardener can be added to crosslink the resins

Ultralight light crosslinking resins suitable for use in the antistatic layer include any known monomer, oligomers or prepolymers, which crosslink while a polymerization reaction is induced with the application of lightning ultraviolet. Electron beam crosslinking resins for employment in the antistatic layer are also not particularly limited to specific resins, but resins that include as main component a crosslinking resin by beam of electrons with a branched molecular structure that has 5 or more functional groups and a polyester skeleton are especially preferable as the electron beam crosslinking resin in The present invention.

With respect to the ratio of the metal oxide vs. the binder resin, the amount of oxide addition metallic is 0.05 to 1 part by weight, and preferably 0.1 to 0.8 parts by weight, per 1 part by weight of the binder resin.

Images are recorded in the registration material transparent thermosensitive of the present invention using a pencil thermal, a thermal head, laser heating, engraving thermal using light, and similar, which depends on the use of images. However, in practice, it is preferable to form images using a thermal head.

Having described this invention in general additional understanding can be obtained with reference to certain specific examples provided here for purposes only Illustrative and not limiting. In the descriptions of the examples which follow the numbers represent weight relations in parts, unless otherwise indicated.

Examples Example 1

The following components were dispersed in a pearl mill so that the average particle diameter of the octadecyl phosphonic acid was 0.3 µm, to prepare a liquid of coating of registration layer.

Liquid coating coating layer

- 2- (2'-Chloroanilino) -6-ethylamino-7-methylfluorane 10 - Octadecyl phosphonic acid 30 - Polyvinyl butyral (Denka Butyral # 3000-2 manufactured by   \ Denki Kagaku Kogyo K.K., refractive index of 1.49) fifteen - Toluene / methyl mixture ethyl ketone (1/1) 285

The following components were dispersed so uniform so that the average particle diameter of the solid components was about 0.4 µm, to prepare liquids A and B.

Coating layer coating liquid

Liquid TO

- Kaolin (UW-90 manufactured by Engelhard Corp.) 10 - Polyvinyl resin butiral modified by silicone   \ (SP-712 manufactured by Dainichiseika Color  \ textamp Chemical   \ Mfg. Co., Ltd., solids content of 12.5%) 8 - Ethyl methyl ketone 12.5

Liquid B

- Stearate zinc 3.3 - Polyvinyl resin butiral modified by silicone   \ SP-712 manufactured by Dainichiseika Color  \ textamp Chemical   \ Mfg. Co., Ltd., solids content of 12.5%) 2.6 - Ethyl methyl ketone 4.1

Liquid C

- Polyvinyl resin butiral modified by silicone   \ (SP-712 manufactured by Dainichiseika Color  \ textamp Chemical   \ Mfg. Co., Ltd., solids content of 12.5%) 80 - Resin solution light crosslinking ultraviolet   \ of the urethane acrylate type (refractive index from   \ 1.56, Unidic V9057 manufactured by Dainippon Ink and   \ Chemicals Inc., solids content of 75%) twenty - Silicone resin in particles (Tospearl 130 manufactured   \ by Toshiba Silicone Co., Ltd, diameter from   \ average particle 3 \ mum) - Silicone oil (X22-161AS manufactured by Sin-etsu   \   Chemical Co., Ltd.) 1.5 - Polyisocyanate compound (Coronate HL manufactured by   \ Nippon Polyuretane INdustry Co., Ltd.) 11.5 - Mix of toluene / methyl ethyl ketone (1/1) 200

The following components are mixed for preparation of a coating liquid antistatic

Antistatic coating coating liquid

- Emulsion dispersion from SnO2 -Sb / polyester   \ (Colcoat SP-2002 manufactured by Colcoat Co., Ltd.) 10 - Methanol / water mixture (1/2) 90

Preparation of heat sensitive recording material

The antistatic coating coating liquid it was coated with a filament bar on the side of a roll-shaped polyester film that has a thickness of 75 um, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a variation (R) of thickness in the lateral direction of 2.0 µm and a difference in thickness between the left side and the right side in the lateral direction of 0.1 µm, and dried to form an antistatic layer with a thickness of 0.3 µm.

On the other side of the polyester film of the coating layer coating liquid was coated with a filament bar, and dried to form a record layer thermosensitive having a thickness of about 13.5 µm. In In addition, a coating coating liquid was coated covering with a filament bar over the record layer and it dried, and an ultraviolet lamp irradiated the coating layer coated with 80W / cm ultraviolet light to form a layer of crosslinked coating having a thickness of about 3.0 \ mum.

Thus, a registration material was prepared thermosensitive of example 1. The variation (R) of the thickness of the thermosensitive recording material in the lateral direction was of 2.3 µm and the difference in thickness between the left side and the right side in the lateral direction was 0.3 µm.

Example 2

The procedure set forth in the Example 1 except that a polyester film was used, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 µm and which had a variation (R) of thickness of the lateral direction of 3.2 µm and a difference in thickness of the left lateral and right lateral in the lateral direction of 0.9 µm.

The variation (R) of the material thickness of resulting thermosensitive record in the lateral direction was 2.9 um and the difference in thickness between the left side and the right lateral in the lateral direction was 0.1 µm.

Example 3

The procedure carried out in the Example 1 except that a polyester film was used, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 µm and which had a variation (R) of thickness of the lateral direction of 4.2 µm and a difference in thickness of the left lateral and right lateral in the lateral direction of 0.5 µm.

The variation (R) of the material thickness of resulting thermosensitive record in the lateral direction was 4.4 um and the difference in thickness between the left side and the right lateral in the lateral direction was 0.4 µm.

Example 4

The procedure carried out in the Example 1 except that a polyester film was used, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 µm and which had a variation (R) of thickness of the lateral direction of 4.2 µm and a difference in thickness of the left lateral and right lateral in the lateral direction of 1.1 µm.

The variation (R) of the material thickness of resulting thermosensitive record in the lateral direction was 4.4 um and the difference in thickness between the left side and the right lateral in the lateral direction was 1.3 µm.

Example 5

The procedure carried out in the Example 1 except that a polyester film was used, Merinex 705 manufactured by E.I. Du Pont de Nemours and Co., which had a thickness of 75 µm and which had a variation (R) of thickness of the lateral direction of 3.4 µm and a difference in thickness of the left lateral and right lateral in the lateral direction of 0.8 µm.

The variation (R) of the material thickness of resulting thermosensitive record in the lateral direction was 4.4 um and the difference in thickness between the left side and the right lateral in the lateral direction was 0.9 µm.

The heat sensitive recording material prepared in examples 1 to 5 and its transparent substrate were evaluated as follow:

(1) Variation (R) of thickness in the direction lateral and difference in thickness between the left lateral and the Right side.

The variation (R) of thickness and difference in thickness of each record material and its transparent substrate is measured with the above method using a thickness gauge contact type, Electron Micrometer K351C manufactured by Anritsu Corp.

(2) Dimensional accuracy and obliqueness between plates.

Images were taken on the materials 1 to 5 thermosensitive recording devices prepared in the examples following using a large plotter for exclusive use As a plotting station, TP6910 manufactured by Ricoh Co., Ltd. The method for measuring dimensional feed accuracy and Obliqueness has been cited before.

The results are shown in Table 1.

(Table goes to page next)

       \ newpage
    

TABLE 1

17

How can they be understood from the description detailed and concrete cited above can obtain the material of thermosensitive record of the present invention for block copy that It has high levels of precision and obliqueness inter-plates, which are required for film block copy to obtain plates for flexography, photogravure, offset printing and stencil printing. Therefore the thermosensitive recording material of the present invention is useful as block copies.

This document claims priority and contains Subject matter related to Japanese Patent No. 10-361063, deposited in December l988.

Claims (14)

1. A heat sensitive recording material in roll shape that has a heat sensitive recording layer that comprises an electron donor coloring compound, a compound electron acceptor and a binder resin and that is formed superimposing a roll-shaped substrate, where the material of thermosensitive register has a variation (R) of thickness in the lateral direction not exceeding 3 µm. 2. A temrosensitive record material in roll shape that has a heat sensitive recording layer, which comprises an electron donor coloring compound, a compound electron acceptor and a binder resin and that is formed superimposing a roll-shaped substrate, where the material of thermosensitive record has a difference in thickness between a left lateral and a right lateral in the lateral direction no greater than 0.7 µm. 3. The heat sensitive recording material in roll form according to claim 1 or claim 2, wherein the roll-shaped substrate is transparent. 4. The heat sensitive recording material in roll form, in accordance with any of the claims 1 to 3, wherein the registration material thermosensitive also has a covering layer comprising a resin that has substantially the same refractive index as the binder resin of the thermosensitive and forming registration layer superimposing the heat sensitive recording layer. 5. The heat sensitive recording material in roll form according to claim 4, wherein the refractive indexes of the resin in the covering layer and the resin binder in the heat sensitive recording layer are comprised between 1.45 and 1.60. 6. The heat sensitive recording material in roll form, in accordance with any of the claims 1 to 5, wherein the roll-shaped substrate has a variation (R) of thickness in the lateral direction not exceeding 4 \ mum. 7. The heat sensitive recording material in roll form, in accordance with any of the claims 1 to 5, wherein the roll-shaped substrate has a difference in thickness between a left side and a side right in the lateral direction not exceeding 0.6 µm. 8. A block copy sheet to get a plate for flexography, photogravure, offset printing, e stencil printing, comprising a recording material heat-sensitive and an image formed in the recording material Heat sensitive after application of heat to the recording material heat-sensitive, wherein said heat-sensitive recording material is a heat sensitive recording material in accordance with any of claims 1 to 7. 9. A method for preparing a sheet block copy to get a plate for flexography photogravure, offset printing and stencil printing comprising heat with image a heat-sensitive recording layer to form an image, wherein said heat sensitive recording material is a heat sensitive recording material in accordance with any of claims 1 to 7. 10. The method, in accordance with the claim 9, wherein the image heating is brought to out using a thermal head. 11. A printing plate for flexography that it is prepared using the block copy sheet of the claim 8. 12. A plate for photogravure that is prepared using the block copy sheet of claim 8. 13. A printing plate for offset printing which is prepared using the block copy sheet of the claim 8. 14. A printing plate for printing stencil that is prepared using the block copy sheet of claim 8.