JPS5927957A - Heat-sensitive diazo recording material - Google Patents

Abstract

PURPOSE:To provide the titled recording material which has excellent durability and prevents image after fixation from being altered, by providing a specified adhesive layer between a support and a heat-sensitive color-developing layer. CONSTITUTION:An adhesive layer is formed by using a compsn. consisting of a resin such as polyolefin or phenolic resin and a filler having an oil absorption of 50ml/100g or below, such as silicon oxide having a particle size of 1-5mu or fine styrene resin particle, in a weight ratio of 5/1-1/1. A soln. (dispersion) of the above compsn. is applied to a support and dried to form an adhesive layer of 5-30mu in film thickness. A heat-sensitive layer-coating soln. (a soln. contg. a diazo compd., a coupler, a heat-fusible material, a binder, etc.) is then applied thereto, and dried to form a heat-sensitive color-developing layer, thus obtaining a heat-sensitive diazo recording material.

Description

[Detailed description of the invention] The present invention relates to a diazo thermosensitive recording material.

Diazo thermosensitive recording materials, in which a thermosensitive coloring layer containing a diazo compound, a cup 2-1 thermofusible substance, and a binder are provided on a support such as paper or plastic, are easy to print and manufacture. It is widely used for several reasons. In particular, diazo-based heat-sensitive recording materials have excellent fixing properties, so even if a recording is performed once by heating printing and then another heating printing is performed again, it will not be tampered with. Therefore, it is suitable for fields where reliability is required, such as commuter passes and certificates.

However, although the conventional method can prevent tampering due to heated printing as described above, it has the disadvantage that the image area can be erased and tampered with using a sand eraser or the like. Furthermore, since commuter passes and the like are subject to repeated use and wear and tear, there has been a desire for improved durability.

An object of the present invention is to solve the above-mentioned problems and provide a diazo-based heat-sensitive recording material that prevents tampering of the image area after fixing and has excellent durability.

That is, the present invention provides a diazo compound, a coupler,
It relates to a diazo thermosensitive recording material having a thermosensitive coloring layer containing a thermofusible substance and a binder, and is characterized by the presence of a resin and an oil absorption i 50 m between the support and the thermosensitive coloring layer.
1/1001 or more filler resin/filler = 5/1~1
This is due to the provision of an adhesive layer with a ratio of 1/1 (weight ratio).

As the resin constituting the adhesive layer according to the present invention, both thermoplastic and thermosetting resins can be used.

Examples of thermoplastic resins include polyolefins, -rivinyl compounds, saturated polyester resins, polyurethanes, and polyamides.

Thermosetting resins include phenolic resin, area resin,
Examples include melamine resin, alkyd resin, unsaturated resin, 4-lyester resin, and epoxy resin.

Providing an adhesive layer of the resin between the support and the thermosensitive coloring layer improves durability (prevents layer peeling), but in addition, in order to prevent tampering with the image area, the adhesive layer resin has an oil absorption of 5.
0 tit / 100 or more (JI8 to 15101
Disperse the filler (according to the method).

This prevents the image from soaking into the adhesive layer and being tampered with by sand erasers or the like.

However, if the oil absorption amount of the filler is lower than 50 ml/100 t, a sufficient effect cannot be expected and there is a disadvantage that the amount of the filler must be increased. In addition, the blending ratio of resin and filler is resin/filler = 5/1 to 1/1, preferably 4/1 to V
s (weight ratio). If the amount of filler exceeds 1/1, the binding force between the adhesive layer and the support will decrease, and if it is less than 5/l, the penetration will be insufficient (which is not preferred).

The particle size of the filler is preferably 1 to 5μ, and the material is inorganic such as silicon oxide, alumina, kaolin, talc, titanium, calcium carbonate, magnesium hydroxide, aluminum hydroxide, styrene resin particles, urea-formalin condensate resin particles, etc. , organic entrainment particles can be used.

Next, the basic thermosensitive color forming layer forming material used in the present invention will be explained in detail.

Diazo compound and cup 2- used in the present invention
Those commonly used for diazo photosensitive paper are applicable, and examples thereof include those shown below.

Diazo compound Sea urchin The diazo compound used in the present invention may be a conventional one, for example one represented by the following general formula.

R Seal R.

However, in the general formula [direct], [eyes] and (II), R1
tR6#R, is hydrogen, halogen, c, ~c, alkyl group or alkoxyl group, or -〇: Same as R1),
R7, bird, Ro is hydrogen, hydrogen, C1 to CI alkyl group or alkoxyl group.

R6 to R1 are the same or different C1-C alkyl group, hydroxyalkyl group, alkyl group or alkoxyl group, or halogen), R
1 is hydrogen, halogen, trifluoromethyl group, C3-C
6 alkyl group or alkoxy group), Ml, Ml, N
, is an acid residue or an acid residue forming a double salt with a metal salt. In this case, the acid residues include halogen ions, BP,
It is preferable to use fluorine-containing inorganic acid ions such as ", PF, ', etc. On the other hand, examples of metal salts that form double salts with acid groups include ZnO, CaO, and SnC.

Y represents -CH yo or -CO-, and n is O or 1.

Specific examples of things that fall under the general formula [summer] include the following:

OCH.

Q.C., H.

OCR.

Q.C., H.

QC4H.

Specific examples of those corresponding to general formula (1) include the following.

C! Specific examples of those corresponding to the general formula [11] include, for example, linear ones.

Q.C., H.

Q.C., H.

Cpu Q.C., H.

In the present invention, K for obtaining a product with further improved long-term shelf life is a diazo compound such as -BF or -PF6.
Advantageously, they are used in the form of water-insoluble salts such as fluorine-containing salts.

Coupler: Cup 2- used in the present invention includes phenol, resorcinol, methylresorcinol, 4,4-bisresorcinol,
Phloroglucin, resorcinic acid, fe70 glucicic acid,
2-methyl-5-methoxy-1,3-dihydroxybenzene, 5-methoxy-1,3-dihydroxybenzene,
4-N,N-dimethylphenol, 2,6-dimethy7y
-1, a, 5-to! 7hi)'Roxybenzene, 2.6-
Dihydroxybenzoic acid, 2,6-hydroxy-3,5
- Phenol derivatives such as dibromo-4-methoxybenzoic acid, α-su7thol, β-naphthol, 4-methoxy-1-su7)-/”, 2,3-hydroxynaphthalene,
2゜3-dihydroxynaphthalene-6-sulfonic acid 7-
F, 2-hydroxy-3-propylmorpholinonaphthoic acid, 2-hydroxy-3-naphtho-〇-toluicide, 2
-Hydroxy-3-naphthoic acid morpholinopropylamide and other naphthol derivatives, but of course these are not limited to the above, and any one that can act as a cup 2- to diazo compounds can be applied. be done.

Thermofusible substances: Examples of thermofusible substances include the following.

114 alcohols such as 2-tribromoethanol, 2,2-dimethyltrimethylene glycol, l,2-cyclohexanediol, acid derivatives such as malon [,/lutaric acid, maleic acid, methylmaleic acid, beeswax, shellac wax] Animal waxes such as Carnano Export, vegetable waxes such as Carnano Export, mineral waxes such as Montan wax, petroleum waxes such as rough-in wax and microcrystalline wax, and other synthetic socks, such as those containing higher fatty acids. Alcohol esters, higher amines, higher amides, condensates of fatty acids and amines, condensates of aromatics and amines, synthesis/I! 2fin, 2fin chloride, metal salts of higher fatty acids, higher linear glycols, dialkyl 3,4-epoxyhexahydrontalate, N-alkylcarno9moylbenzene, etc.

The thermofusible substance used in the present invention preferably has a melting point or softening point in the range of 50 to 250°C.

When the melting point or softening point is less than 50°C, the shelf life of the product tends to decrease.

If the temperature exceeds 250°C, the thermal response of the product to the thermal head becomes unsatisfactory. In addition, from the viewpoint of obtaining a product with high-speed coloring property (high-speed recording property), these thermofusible substances used in the present invention are
It is used in an amount of 2 to 30 parts by weight, preferably 5 to 10 parts by weight. If this amount is less than the above range, color development will be insufficient and the resulting product will be unsuitable as a recording material for high-speed recording.

In the case of the present invention, it is particularly preferable to use 5 parts by weight or more for high-speed output recording such as facsimile.

On the other hand, if the amount added is too large, blurring of the image may occur during color development by heating, which is undesirable. Therefore, in the case of the present invention, the amount of the thermofusible substance added is preferably kept within the above range.

In the present invention, a binder is used as necessary in order to firmly support the heat-sensitive coloring layer on the support.
Examples of such devices include those shown below.

Polyvinyl acetate, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyacrylic ester, polystyrene, polybutadiene, polyacrylamide, styrene/butadiene/acrylic copolymer, petroleum resin, polyvinyl alcohol, acrylamide, casein, gelatin ,
Starch and its derivatives, polyvinylpyrrolidone.

Calz? F-dimethylcellulose, methylcellulose,
Ethylcellulose, polyester, styrene, chlorinated rubber, styrene-maleic anhydride copolymer, styrene-
Water-soluble, organic solvent-soluble, or water-dispersed resins such as vinyltoluene copolymers, rosin modified resins, iso(or diiso)butylene-maleic anhydride copolymers, phenolic resins, and melamine resins.

The binder used in the present invention has a melting point or softening point of 50
It is preferable to use one having a temperature of 250° C. to 250° C. from the viewpoint of obtaining a product with rapid color development. Further, the binders described above can be used alone or in the form of a mixture.

Further, in the present invention, the heat-sensitive coloring layer may further contain acidic substances, basic substances, fillers, and other substances as auxiliary components, if necessary.

Acidic substance: Acidic substances are added as necessary to prevent coupling reactions and for storage stability, and include, for example, the following.

Tartaric acid, citric acid, boric acid, lactic acid, gluconic acid, sulfuric acid, etc.

Basic substance: A basic substance is added as necessary to cause a coupling reaction during heating, and examples thereof include the following.

Caustic alkalis and alkali carbonates such as sodium hydroxide, calcium hydroxide, potassium carbonate, etc.

Substances that generate basicity when heated include urea, thiourea and their derivatives, alkali salts of trichloroacetic acid,
Ammonium chloride, Bunmon sulfate, ammonium citrate.

Filler: A filler is added to improve the matching property to a thermal head when heating is performed by a thermal head, and examples of such fillers include the following.

Organic and inorganic solid particles such as styrene resin particles, urea-formalin condensate resin particles, aluminum hydroxide, magnesium hydroxide, calcium carbonate, titanium, talc, kaolin, silica, and alumina.

Other auxiliary ingredients used include zinc chloride, zinc sulfate, sodium citrate, guanidine sulfate, calcium gluconate, sorbitol, and saccharose to suppress or assist color development.

To obtain the heat-sensitive recording material according to the present invention, each layer-forming coating solution is prepared by dissolving or dispersing the layer-forming components described above in an appropriate solvent, and first, the adhesive layer coating solution is coated on a support.
It is coated and dried to a film thickness of 5 to 30μ, preferably 10 to 20μ, and then the heat-sensitive layer coating solution is applied at a rate of 1.08/m.
It is sufficient to apply the coating and dry it so that it becomes "~5.08/m".

The heat-sensitive layer may be a single layer type or a laminated type.

The solvent for dissolving or dispersing the layer-forming components is appropriately selected depending on the properties of the layer to be formed and the purpose of formation. Such solvents include water or an aqueous solvent in which an organic solvent is dissolved in water, benzene, toluene, xylene, n-hexane, n-hebutane, cyclohexane, kerosene, methyl isobutyl ketone, methyl cellosolve, acetone, methyl ethyl ketone, Examples include nonpolar or polar organic solvents such as dimethyl ether and siloxane.

Note that, if necessary, a hydrophobic resin coating may be provided on the heat-sensitive coloring layer formed as described above, and is coated and dried to a thickness of 1 to 10 μm.

Product. Examples of the resin include polystyrene, polyester, vinyl chloride/vinyl acetate, and styrene/vinyltoluene copolymer.

The heat-sensitive recording material of the present invention can be advantageously applied in various fields of heat-sensitive recording, particularly as wrapping paper for commuter passes and train tickets that require high-speed recording.Moreover, in the case of the present invention, the surface of The recorded characters and images can be fixed by forming the image by heating and then decomposing the unreacted diazo compound with light. Further, the heat-sensitive recording material of the present invention can be used to record securities, gift certificates, etc. by utilizing its fixing properties.
Recording of necessary information for admission tickets, certificates, slips, etc.
It can be applied to their creation.

Next, the present invention will be explained in more detail with reference to Examples.

Example 51 Stearic acid amide 15 II n-hexane 73 l The above composition was dispersed for 24 hours using a ball mill to prepare dispersion liquid A.

B liquid: Phloroglucin 5-layer lid part N
- Octaded Crane Lupamoylbenzene 0 I Silica
213# Toluene 80 parts by weight The above composition was dispersed for 24 hours using a mail mill to prepare dispersion B.

Liquid C stearamide 511 cyclohexane 90 l The above composition was dispersed for 24 hours using a mail mill to prepare a dispersion liquid Ct.

Liquid D: Polystyrene resin (s, p, 150'c) 10
11 Cyclohexane 85 # The above composition was dispersed for 24 hours using I-Lumil to prepare a dispersion liquid.

H liquid: j! (tg=!J″'/(50″-yyfyp, <)
8-Water
71 Used in the above composition "4tyR-lumi/L'1,
Dispersion E was prepared by dispersing for 24 hours.

F liquid Niacrylic resin (30% latex) 10 parts by weight water 2' The above composition was dispersed for 24 hours using a mail mill to obtain dispersion liquid F.
-, was made.

Liquid C Toluene 11 parts by weight The above composition was dispersed for 24 hours using a ball mill to form a dispersion liquid G.
'& prepared.

Solution H: 1 Methyl ethyl ketone 41 Above composition Y11? - Lumi #tl' was used and dispersed for 24 hours to prepare a dispersion liquid (■).

A diazo heat-sensitive recording material was prepared by applying the dispersions A-H prepared as above onto a support in the combinations shown in Table 1 and drying them.

In addition, the thickness of the adhesive layer (E-H liquid) is 15 to 20μ, A,
Liquids B and C were 1.0 to 5.0 f 7m" (solid content), and the thickness of the resin coating (liquid D) was 3 to 5 μm. Polyester was used as the support, and the thickness was 188 μm. And so.

Table 1 (In the table, the first layer is from the support side.) Regarding the recording materials obtained as described above, Lifx 3
03 (manufactured by Kikisuko) in G-11 mode, and then completely exposed and fixed with Lifbee High Start Type 4 [manufactured by Kikisuko]. These materials did not develop color even when heated, and the images did not disappear due to organic solvents.

Next, measure the load on the printed area obtained above using a crockmeter with a sand eraser attached to the tip. /an' VCL round trip 50
Table 2 shows the results of checking the degree of erasure of the printed portion by repeating the printing several times.

Furthermore, the sample after fixing was sized 5.5 x 8. It was cut into pieces of 0 cm size and stirred in a NJi L washing machine for 30 minutes to see if the layers were removed. In addition, color density gauge fax 303 (7)
G-1 mode peta printing density using Macbeth Densitometer RD-
Measured at 514.

In order to test the horizontal head matching property, Liftx 30
The occurrence of stitching during solid printing in the G-11 mode of No. 3 was investigated. Furthermore, there is a gate nose test at the automatic ticket gate.
．． I did it 000 times. The results are shown in Table-2.

(Margins below) Table 2 * Sand eraser; ○: Print density remaining ×: Completely erased * Washing test; 02 layer no peeling ×: 1 Yes * Gate removal; ○: No problem X: Problem within 500 times (Occurrence of scratches and stains) From the results shown in Table 2, it is clear that the product of the present invention &i is excellent in preventing tampering of the image area after fixing and in terms of durability by 1°C.

Claims (1)

[Claims] 1. In a diazo heat-sensitive recording material having a heat-sensitive coloring layer containing a diazo compound, a cup 2-1 thermofusible substance, and a binder on a support, a resin is disposed between the support and the heat-sensitive coloring layer. A diazo-based heat-sensitive recording material characterized in that it has an adhesive layer in which a filler having an oil-absorbing capacity of Jtk50/1o01 or more is blended in a resin/filler ratio of 5/1 to 1/1 (by weight).