JPS59104995A - Diazo base heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To provide the titled recording material free from transferring of a developed color image onto the surface of a ticket holder, wherein a high polymeric substance having an SP value (solubility parameter) of not lower than a specified value is supported on a base as a binder together with a diazo compound and a coupler. CONSTITUTION:In a diazo base heat-sensitive recording material comprising a diazo compound (e.g., a compound of the formula) and a coupler (e.g., naphthol AS) supported on a base together with a binder, a high polymeric substance having an SP value (solubility parameter) of not lower than 9.5 (e.g., a vinyl chloride-vinyl acetate resin, an epoxy resin, an acrylic resin) is used as the binder.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a heat-sensitive recording material, particularly a heat-sensitive recording material that can be photofixed. In other words, the present invention is a diazo-based material that develops color when recorded with a thermal spatula at a certain temperature, loses its ability to develop color in non-printed areas when irradiated with light, and does not recolor when heated again. This invention relates to heat-sensitive recording materials.

[Prior art]

In addition to being used as copy paper for books and documents, thermosensitive recording materials are also used as output recording paper for computers, facsimile machines, medical measuring machines, etc., as well as thermal recording magnetic ticket paper and thermal recording label paper. be done. In addition, heat-sensitive recording materials are also being considered for use as paper for creating securities, gift certificates, admission tickets, certificates, slips, etc. by taking advantage of their ease of automatic recording. In order to obtain high recording reliability, the heat-sensitive recording material must be able to be fixed.

As such fixable heat-sensitive recording materials, various diazo-based heat-sensitive recording materials have been proposed that utilize a color-forming reaction between a diazo compound and a cassiller.

By the way, when such a diazo thermosensitive recording material is used as a commuter pass, etc., it is usually stored in a nomis case made of soft polyvinyl chloride. There is a problem in that the colored image area is transferred to the pass case. for that,
If the flea case is dirty and difficult to use, or
Inconveniences such as the commuter pass being tampered with using the colored image transferred to the ξ scale surface are also likely to occur.

〔the purpose〕

The present invention was completed as a result of various studies aimed at solving the problem of the transferability of colored images to the surface of the ξ scale, which is observed in conventional diazo thermosensitive recording materials.

〔composition〕

That is, according to the present invention, in a product in which a diazo compound and a coupler are supported together with a binder on a support, a polymeric substance having an SP value (solubility/♀ ram) of 9.5 or more is used as the binder. Provided is a diazo-based heat-sensitive recording material characterized by using the following.

The binder used in the present invention has an SP value of 95 or more, preferably 10 or more, and the SP value in this case indicates the solubility parameter of the polymer and is expressed by the following formula.

5P=(E/V)' E... Cohesive energy density of polymer (cat/m
ot)■・・・・・・Molar volume of polymer (crl/m
o A) The details are described in, for example, the Chemical Handbook, Applied Edition (Nippon Kagaku Kinwa). According to the research of the present invention, it has been confirmed that when such a polymeric binder having an SP value of 95 or more is used, transfer of a colored image to the surface of the Tux case is effectively prevented. S
If a polymer with a P value of less than 95 is used, it becomes difficult to effectively prevent the transfer of a colored image.

Examples of polymers having an sp value of 95 or more used in the present invention include polyvinyl chloride, polymethyl chloroacrylate, ethyl cellulose, nitrocellulose, polyacrylonitrile, polyethylene terephthalate, cellulose diacetate, epoxy resin, polyvinyl chloride, Examples include 7.6.6-nylon, nylon 8, polyacrylonitrile, polyvinyl alcohol, and the like.

This binder is added to 00% of solid content in the coating layer.
It is used in a proportion of 5 to 1 part by weight, preferably 8 to 0.5 part by weight.

The diazo compound and coupler used in the present invention are those commonly used in diazo photosensitive paper, and include, for example, those shown below.

Diazo Compound: As the diazo compound used in the present invention, a commonly used diazo compound, for example, one represented by the following general formula is used.

R3R3 9 However, in the general formula CD, (II:] and I]ll, R1+ R6rR8 is hydrogen, halogen, C1-C
The alkyl group in 5 is also R9 hydrogen, halogen, alkyl/14 of self to C5 or alkoxyl group, R4! R5 is the same or different C1 to C5 alkyl group, hydroquine alkyl group or alkoxyl group, or halogen), R7 is hydrogen, halogen, trifluoromethyl group, C
1-C5 alkyl group or alkoxyl group, Ml
, M2 and M3 are acid residues or acid residues forming a double salt with a metal salt. In this case, the acid residue is preferably a halogen ion or a fluorine-containing inorganic acid ion such as BF4' or PFg, while the metal salt that forms a double salt with the acid residue is, for example, ZnCt2. , Cd
Ct2, 5nCj! 2 etc.

Specific examples of those corresponding to general formula [I] include the following.

1 CH3 Specific examples of those corresponding to the general formula [■] include the following.

Specific examples of those corresponding to general formula (4) include the following.

CH3 In the present invention, in order to obtain a product with further improved long-term shelf life, HBF4 and HPF4 are used as the diazo compound.
Advantageously, it is used in the form of a water-insoluble salt such as a fluorine-containing salt such as 6.

Katsupura m: Cassilla used in the present invention includes phenol, resorcin, methylresorcin, 4,4-bisresorcin,
Phloroglucin, resorcinic acid, phloroglucinic acid, 2
-Methyl-5-methoxy-1,3-dihydroxybenzene, 5-methoxy-1,3-dihydroxybenzene, 4
-N,N-dimethylphenol, 2,6-dimethyl-1
,3゜5-)! J hydroxybenzene, 2y6'
) Hydroxybenzoic acid, 2,6-hydroxyhydroxy-3,5
- Phenol derivatives such as cyfurome-4-methoxybenzoic acid, α-naphthol, β-naphthol, 4-methoxy-1-naphthol, 2,3-dihydroxynaphthalene,
Sodium 2,3-dihydroxynaphthalene-6-sulfonate, 2-hydroxy-3-propylmorpholinonaphthoic acid, 2-hydroxy-3-naphtho-0-)luidide, 2
-Hydroxy-3-naphthoic acid morpholinopropylamide, naphthol derivatives such as naphthol derivatives, acetanilide, 4-benzoylamino-2,5-jethoxyacetanilide, N-acetoacer octadecylamine,
Examples include active methylene compounds such as N,N'-bis(acetoaceto)decane-1,10-diamine, 294#6F lipromoacetoacetaniliP, but are not limited to these, of course. However, any compound that can act as a coupler for the diazo compound can be applied.

In the present invention, thermofusible substances are preferably used in order to enhance rapid color development. Specific examples of such things include, for example, the following:

Alcohol derivatives such as 2-tribromoethanol, 2,2-dimethyltrimethylene glycol, l,2-cyclohexanediol, acid derivatives such as malonic acid, curtaric acid, maleic acid, methylmaleic acid, and animals such as beeswax and shellac wax. Fuchs, vegetable waxes such as carnauba wax, mineral waxes such as montan wax,
Petroleum waxes such as paraffin wax and microcrystalline wax, and other synthetic waxes such as polyhydric flucol esters of higher fatty acids, higher amines, higher amides, condensates of fatty acids and amines, condensates of aromatic acids and amines, and synthetic waxes. (
Roughin, chlorinated paraffin, metal salts of higher fatty acids, higher linear glycols, 3,4-epoxyhexahide, dialkyl phthalate, 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.

If the melting point or softening point is less than 50°C, the shelf life of the product tends to deteriorate, and if it 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 should be used in an amount of 2 to 30 parts by weight, preferably 5 to 1 part by weight, per 1 part by weight of the diazo compound.
0i is used as a division of parts. If this amount is less than the above range, the color development will be insufficient, and the resulting product will be
This makes it 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 addition, in the present invention, the heat-sensitive coloring layer consisting of one or more coating layers containing a diazo compound and a coupler may further contain acidic substances, basic substances, fillers and other substances as auxiliary components, if necessary. It can be included.

Acidic substance: An acidic substance is added as necessary to prevent a coupling reaction and for storage stability, and examples thereof include the following.

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

Filler: A filler is added to improve the matching property with a thermal head when heating is performed by a thermal head, etc., 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.

As other auxiliary ingredients, zinc chloride, zinc sulfate, sodium citrate, guanidine/sulfate, calcium gluconate, sorbitol, saccharose, etc. are used to suppress or assist color development.

Supports used in the present invention include paper, synthetic paper, plastic films, and bases prepared by precoating paper with synthetic resins, fillers, and the like.

〔effect〕

Since the diazo-based heat-sensitive recording material of the present invention contains the specific binder in the heat-sensitive layer, the problem of transfer of colored images to other solid surfaces, which was seen in conventional materials, is avoided. do not have.

〔Example〕

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

Reference example C2H5 Methyl cell solve 67 〃B liquid: Phthol AS 3 parts by weight Sodium benzoate 15//Silica 2 〃10φ polyvinyl alcohol aqueous solution g (sp value 23) 20 n water
58 〃C
Solution: Epoxy resin (sp value 9
．． 8) is used.

Solution D: Acrylic resin (S
p value 15.0) was used.

In addition, the said A liquid and C liquid were stirred and dissolved for 1 hour, and were prepared. Further, the B liquid and the D liquid were dispersed in a ball mill for 24 hours to prepare respective dispersion liquids B and D.

Example 1 h'fi- (plastic sea) (2oofF/m'')
After coating and drying, the amount of adhesion is 2F! −/m” 1st
A layer is provided, and liquid B is applied on top of this to give a coating weight of 5'f after drying.
/ m'' second layer was formed to obtain a heat-sensitive recording sheet.

Examples 2 to 4 A first layer and a second layer were formed in the same manner as in Example 1 with the contents shown in Table 1 below to obtain a thermosensitive recording sheet.

Comparative Examples 1 to 3 Solution B: Polystyrene resin (S
p value 8.6) was used.

B liquid: Use polyethylene resin (sp value 7.9) instead of polyvinyl alcohol in B liquid.

The first test was carried out in the same manner as in Example 1 with the contents shown in Table 1 below.
A thermosensitive recording sheet was obtained by forming a layer and a second layer.

Table 1 Each of the diazo thermosensitive recording sheets obtained as described above was printed using Rifax 3o3 (manufactured by Rico Co., Ltd.) with GllMo1 mode, and then printed with Ricopi 4 Hyster) 205 (■
After fully exposing and fixing the images using a RICOH product, and storing them in a soft polyvinyl chloride pass case for 3 months, we observed the transfer of the image area and found that the adhesive of the present invention was used in each layer. It was confirmed that the obtained product had no transfer transfer and was of high quality compared to the comparative example.

Patent applicant Ricoh Co., Ltd. Agent Patent Attorney Toshiaki Ikeura

Claims (1)

[Claims] (1) A diazo thermosensitive material in which a diazo compound and a coupler are supported together with a binder on a support, characterized in that the binder is a polymeric substance with an SP value (solubility parameter) of 95 or more. Recording materials.