WO1986001158A1

WO1986001158A1 - Acid-base type recording material

Info

Publication number: WO1986001158A1
Application number: PCT/JP1985/000437
Authority: WO
Inventors: Akira Kawai
Original assignee: Mitsubishi Paper Mills, Ltd.
Priority date: 1984-08-17
Filing date: 1985-08-02
Publication date: 1986-02-27
Also published as: AU4637385A; JPS6149886A

Abstract

An acid-base type recording material which forms an image by utilizing a color-forming phenomenon caused by the interaction between a basic leuco dye and an acidic color developer, wherein the acidic color developer is composed of a major component (1) comprising a solid acid which is derived from a clay mineral having a laminar structure comprising tetrahedral silica, which shows an electron beam diffraction pattern based on the laminar structure comprising the tetrahedral silica but does not substantially show the above described laminar structure in an X-ray diffraction pattern, and which contains at least silicon and magnesium and/or aluminum as elements other than oxygen and a subsidiary component (2) comprising a polyvalent metal salt of a salicylic acid derivative and, if desired, a metal compound. This material forms color images with a remarkably improved fastness.

Description

Acid-base recording materials

The present invention relates to an acid-base type recording material that utilizes a color development phenomenon caused by an interaction between a basic silicone dye and an acidic developer for image formation.

As a recording material in this category is exemplified by node on mosquitoes over Bonn pressure sensitive recording materials, heat-sensitive recording materials, sublimation _Π I co dyes, Netsuten 'shoot recording material, and the like with specific examples Can be

Among them, the non-carbon pressure-sensitive recording material was the first recording material that succeeded by using the above-described chromogenic embedding, while the other recording materials were not transformed. Therefore, in this specification, the details will be centered on the pressure-sensitive recording material, but the technical problems and technical solutions will be universal for all acid-base type recording materials. It is something. Background technology

In an acid-base recording material, a basic π-ico dye and an acid developer (hereinafter simply referred to simply as a developer) are in principle two essential components. _{C The} conventional basic rho dyes, which are equally important, include 3,3-bis (P-dimethylaminophenol) -ό-dimethylamino. In non-phthalide (so-called crystal bioreactor) Typical triphenyls, such as methane lactone dyes, 3-methylethylamino-ό-methyl-7-ayurinofluorane Fluorinated dyes, other acylated loycotin dyes, acylilo herocoxazine dyes or JP-A-53-552. Locotriphenyl methane-type dyes, and lactams and shii as described in the specification of No. 3. Mouth pyran is known.

On the other hand, as a color developer, a natural or natural product such as clay, acid clay, activated clay, etc., such as monmoli or nitrate, or apatagulite, is used. The treated clay-based inorganic solid acid was used first. For example, Japanese activated clay silton (trade name) is famous. After that, a mixture of phenol f conjugate, pis phenol conjugate, nopol phenol-aldehyde polycondensation resin, and salicylic acid derivative Organic acids having a phenolic hydroxyl group, such as a valent metal salt, have been proposed as a color developer, and a color image having a higher concentration than that of a conventional clay-based inorganic solid acid can be obtained. In some cases, the use of organic acid developers has been replaced by the fact that the image has better stability against moisture and light, and other reasons. However, organic acid developers also have disadvantages.]) For example, the image coloring speed is slow, and the color image is poor. Contact with everyday chemicals such as plasticizers for plastics and cosmetics may cause fading, and secondary color-forming roico dyes (eg, pen-yllo-iko) The use of image hardening techniques cannot be applied. Which had problems.

Furthermore, recently, as proposed in Japanese Patent Application Laid-Open No. 57-15596, a clay mineral having a layer structure composed of silica regular ffl isomers was dried on a dry basis (105 ° C). 3 hours drying) at Si0 ₂ containing J t is 8 2 to 9 0.5 weight with C

%, And the resulting clay mineral is contacted with an at least partially soluble magnesium and / or aluminum or aluminum compound in an aqueous medium in an aqueous medium. When this soluble compound is other than hydroxide, magnesium and magnesium are neutralized in the acid-treated clay mineral by neutralizing with alkali or acid so that hydroxide is formed. Or, a solid acid produced by introducing a luminous component and drying as desired with J9, or as described in the specification of JP-A-58-217379. As can be seen from the drawing, it is derived from a clay mineral having a layer structure composed of the tetrahedral force of silica, and according to electron diffraction, a layer composed of the tetrahedron of the silica force. A diffraction pattern based on a crystal having a layer structure is shown. According to an _x- ray diffraction, a diffraction pattern based on a crystal having the above layer structure is shown. A solid acid containing at least silicon and magnesium and / or aluminum as elements other than oxygen, or At least one metal compound selected from the group consisting of oxides and hydroxides of calcium, magnesium, magnesium and zinc]), based on the total weight. A solid acid composition ③ containing the metal compound in a ratio of 0.2 to 2 millimoles, or The above-mentioned solid acid and acid-treated octahedral monmite mouth-nitite group clay mineral or natural and octa-octal hydral monmole mouth night A solid acid consisting of a mixture with a group C clay mineral, or at least one selected from the group consisting of oxides and hydroxides of calcium, magnesium and zinc. ), A solid acid composition containing 0.2 to 2 millimoles of the metal compound based on the total weight. (Here, all the solid acids represented by ① to ⑤) are essentially composed of the solid acid defined in ②. Therefore, in this specification, these solid acids newly announced Acid is represented by .②) o.

The suitability of this new solid acid as a color developer in acid-base type recording materials, especially in non-carbon pressure-sensitive recording materials, has been evaluated by various tests. As compared with clay-based inorganic solid acids, remarkable improvements such as remarkable improvement in color developing ability and sustained coloring effect under high humidity were recognized. However, on the other hand, it has been found that the color images have insufficient robustness, for example, light fastness.

Therefore, the applicant of the present application has conducted a study to enhance the light fastness of a color image, and has already filed Japanese Patent Application No.

As proposed in 57-44 19, 57-44 19, 57-44199, etc., a phenolic compound with a specific chemical structure is applied to this new solid acid. It has been found that when added, the light fastness of a color image is significantly increased. The present inventor has continued to study the image solidification of acid-base type recording materials using a new solid acid, and the method of adding a phenolic compound with a specific chemical structure previously proposed] 3 was even better. We found a method and arrived at the present invention. Disclosure of the invention

An object of the present invention is to provide a method for further improving the color image fastness of the acid-base recording material using a new solid acid.

According to the present invention, a developer for an acid-base type recording material comprising a basic silicone dye and an acidic developer has been disclosed in (1) Japanese Patent Application Laid-Open No. 58-21718 / 89. After removing acid-soluble components from a clay mineral having a layer structure composed of silica tetrahedrons to such an extent that they do not show an electron diffraction pattern, they are used as elements. It is mainly composed of a semi-synthetic solid acid, which is obtained by artificially introducing gnesium and Z or aluminum and reconstructing the crystal so as to show an electron diffraction pattern again. (2) salicylic acid derivative polyvalent metal salt as a secondary component for the purpose of enhancing the robustness of the color image .

In particular, in the present invention, a salicylic acid derivative polyvalent metal salt which is more effective than the above-mentioned prior application of the present applicant is used as an auxiliary component. Polyvalent metal salts of tillic acid or its derivatives can be used as acid-base type recording materials such as color formers (developers) for sensitive E copy paper. ό

The announcement of 'get' can be found in, for example, Japanese Patent Publication No. 49-1985- ゃ No. 52-1527, but when the inventor tested it, for example, The color image of the basic pigment dye crystal violet lactone is not fast enough, is very low in everyday life, and is polychlorinated, including plasticizers. It turned out that there was a serious drawback in that the colored image disappeared if it was pinched between the pinion films.

In addition, a phenolic compound having a specific chemical structure disclosed in the prior application of the present applicant, for example, 4-hydroxybenzoic acid benzoyl ester, is disclosed. The added "semi-synthetic solid acid," also shows that the developed layer and the crystallographic image of crystalline biolactolactone, in particular, have insufficient colorfastness against the plasticizer and are discolored. I got it.

Therefore, the present inventor conducted many tests in search of a color developer having high color image fastness. As a result, the new solid acid “semi-synthetic solid acid” as described above was used as a main component. It was found that the combination developer using a carboxylic acid derivative as an auxiliary component was the most successful. BEST MODE FOR CARRYING OUT THE INVENTION

To use the color developer of the present invention as a color developer of an acid-base type recording material, for example, a pressure-sensitive recording medium, it is necessary to use an adhesive on a flat support such as paper. ] 9 Bound for use. At this time, add other additives and auxiliary materials as necessary. Even good Iga, Oh Ku or even the developer of the principal new solid acid "semi-synthetic solid acid" a is whether we color developer constituent of 5 0 weight Nono ⁰ - accounted for an amount greater than the back door down There must be. The balance ie 50 weight c. A salicylic acid derivative metal salt or a salicylic acid derivative metal salt in an amount of less than one cent. Las candy, Magnesium, Cadmium, Aluminum, I &, Titanium, Power / Pepper / Pepper / Pepper It is at least one kind of metal compound such as oxide, hydroxide or carbonate of a polyvalent metal such as gun.

As salicylic acid derivative metal salts, salicylic acid or the benzene nucleus of salicylic acid is an alkyl or cycloalkyl phenol. The above-mentioned salts of polyvalent metals of salicylic acid derivatives having 1 to 4 substituents, such as aryl, aryl, halo, or phenyl, are preferred. .

An example of a new solid acid, "semi-synthetic solid acid" is ^M Silton ss-, manufactured by Mizusawa Chemical Industry Co., Ltd.

In the present invention, it has also been found that a color image having further improved fastness can be obtained by appropriately selecting a basic silicone dye. For example, the use of a lycotriphenyl methane-type basic dye described in Japanese Patent Application Laid-Open No. 555-2522, which is known as "carpaso") This compound has a very slow color development speed on the colorant sheet of the present invention, so that it is a basic dye having a fast color development speed, for example, a crystal pigment. Oretsu It is practical to use it in combination with tractone.

The acid-base type recording material comprising the basic π-ico dye having the above-mentioned structure and the head coloring agent according to the present invention is a chemical agent even if its color image is exposed to light. As it is surprisingly robust against exposure to plasticizers for plastics, it is mentioned as a preferred embodiment in the present invention.

The present invention will be described in more detail by way of examples. In the examples, "parts" means "parts by weight".

Example 1

3,5-Zeta Sharif Zinc zinc salicylate 100 parts Polystyrene sodium sulfonate 5 parts Water 144 parts 5 Total 250 parts And ground for 2 days.

"Semi-synthetic solid acid" manufactured by Mizujun Chemical Industry Co., Ltd. Trade name: Silton ss-180 parts, calcium carbonate 20 parts, and the above-mentioned wet-milled salicylic acid derivative 50 parts of the valent metal salt dispersion were dispersed in 200 parts of water containing 1 part of sodium pyrophosphate, and 50 parts of a 10% aqueous oxidized starch solution and 48 parts of a 48% SBR latex were added. Then, 50 parts of the solution was added to obtain a coating liquid. This coating solution was applied to a base paper of 40 melon ^{2 so} as to have a dry application amount of 59 ^ ^2, and then dried to obtain a developer sheet (sample D).

Similarly, when the above salicylic acid derivative polyvalent metal salt is not added (Sample A), the salicylic acid derivative polyvalent metal salt is not added. The same amount of 4-hydroxybenzoic acid benzoyl ester was added (sample B) and the same amount of zinc oxide was added (sample c). Addition of 15 parts of the solid content of the polyvalent metal salt of the carboxylic acid derivative and 5 parts of zinc oxide (Sample E), 12 parts of the solid content of the polyvalent metal salt of the salicylic acid derivative and 8 parts of zinc oxide With the addition (Sample F), 40 parts of salicylic acid derivative polyvalent metal salt solids (sample ^ &), with salicylic acid derivative polyvalent metal salts solids of 30 parts (Sample H), to which 24 parts of salicylic acid derivative polyvalent metal salt solids and 1 part of oxidized candy (Sample I) were added. In addition, the same mixture (calcium carbonate 100 and salicylic acid derivative polyvalent metal salt solids 40 parts) without adding the “semi-synthetic solid acid” (Sample J) was used. 100 parts of calcium carbonate Li Chi le acid derivatives polyvalent metal salt solids 3 0 parts of oxide Aame 1 0 parts also (Sample kappa) _N same rather percarbonate Le shea © beam 1 0 0 parts of Sa Li Chi le acid was added Each sample (sample L) was prepared by adding 24 parts of the derivative polyvalent metal salt solids and 1 part of zinc oxide.

Basic loco dye sheets include:

Clear standard / ortholectrical tractor 2.5 parts Penso "* il tr dimethylene part 1 part 5-gechilamino--- Methyl

7-anilino full ore 0.5 part diisolohi. A high boiling solvent solution of a basic rho dye, consisting of 9 parts of Micro-mouth cuff based on US Pat. No. 4,25,5,178. Ra Mi emission resin Makuma Lee click b force the cell Le of cell Le 1 0 0 parts wheat starch 2 5 parts (solids), oxidized starch 1 0% aqueous solution of 1 5 0 parts added of 4 0 Zm ² The basic silicone dye sheet (I) applied and dried on the base paper so as to have a dry coating amount of 5 ^ / m ² was used.

A basic silicone dye sheet (I) is placed on the developer sheet (12 types) obtained in this way so that the coated surfaces face each other, and the calender is pressed. After that, the entire surface of the developer sheet coated was colored.

Table 1 shows the software. Pressure 3 0 0 kg / color density of mosquito les emissions Dark-b Lumpur pass after 1 minute and 2 4 hours after _m ² and its these ratios ^ indicates the o

Table 1 Results of color development test Sample ① Concentration after 1 minute ② Concentration after 24 hours ① Ζ② 100 ()

(A) 0.5 2 0.4 0.4 4 7 3

(B) 0.5 ό 0.4 6 6 7 8

(C) 0.5 2 0.4 6 7 0

D 0. 3 4 0. 4 5 7 ό

E 0.34 0.4 5 7 ό

P 0 .5 2 0.4 2 7 ό α 0.5 4 0 .4 5 7 9

Η 0.5 6 0 0.4 7 7 7

I 0.56 0.4 6 7 8

(J) 0.1 1 0.1 0.2 8 3 9

() 0.15 0.4 7 2 8

CL) 0.19 0.9 0.4 1 4 ό

Note: (i) Samples with '() in the sample symbol are comparative examples outside the present invention.

(Ii) mosquitoes Les Nda Russia Lumpur two Tsu pressure _{^{3 0 0 k ^ cm. Z}} o

(iii) In Table 1, densities I and ② are net color densities (reflection densities) obtained by subtracting the base densities.

(iv) (^ D X 100 (%) represents the coloring speed. Table 1 shows that the examples (D, E, F, G, H,

In the case of (I), the color development speed is slightly better than that in the case where the developer is “semi-synthetic solid acid” alone (A, c), and especially in the case of the salicylic acid derivative polyvalent metal salt alone (J, B:, L) yo] ?? shows that the color development speed is large.

Table 2 shows the results of the colorant image fastness test against the plasticizer.

Table 2 Results of plasticizer fastness test

Sample ① Concentration before test ② Concentration after test ② Z① X 100 (%)

(A) 0.6 3 0. 4 2 6 7

(B) 0.6 8 0. 4 0 5 9

(C) 0.6 8 0 0.4 7 ό 9

D 0.6 0.6 0.5 0.5 8 5

E 0.6 7 0 0.5 2 7 8

P 0 .6 2 0.4 6 7 4 α 0.5 .8 0 .4 8 8 5

Η 0.6 0.6 0.5 0.5 6 8 5

I. 0. 6 4 0. 5 6 8 8

(J) 0, 5 9 0. 1 2 3 1

() 0.6 5 0 0.2 0 3 2

(L) 0.4 8 0.1 0.1 9 4 0

Note: (i) Samples with (:) in the sample symbol are comparative examples outside the present invention.

(ii) ① is a calendar roll niff. E 450 k ^ ½2 2 Net color density after 4 hours.

(Ex.) ②, a commercially available polychlorinated vinyl chloride resin film containing dioctynolephthalate as a plasticizer is superimposed on the colored paper piece measured in the column of ②. The net density of the colored surface after 24 hours at ° 0 ° G with the weight placed.

(IV) Therefore, (2) Z①X100 (%) represents the residual ratio of the bleaching density of the plasticized image to the plasticized image.

From Table 2, it can be seen that in the examples (D, E, F, G, .H, I) according to the present invention, i? In any of the cases where the color developer is alone (A, C, J JK ゝ L) Furthermore, it has been found that the fastness of the formed image with respect to the plasticizer is remarkably improved as compared with the case of adding the phenolic compound having a specific chemical structure proposed in the prior application by the present applicant (B). .

Example 2

Cristal / Diorectolacton 3.5 part Pergus Cliff. Toda Rau S-RB 3.5 copy Nich compound.ヽ

Described in the detail book

93 A solution of a basic rho dye, consisting of 3 parts of 1-phenyl-1 xylyl ethane, was treated in the same manner as in Example 1 to form a micro-layer of the melamine resin film. H. In the same way, a basic loco dye sheet (Π) was prepared.

Combining the developer sheet prepared in Example 1 with the basic loco-material sheet (I) or (II), the developer is subjected to a calendar press to perform the developer. After the sheet surface was fully colored, the color image was tested for fastness to sunlight and for plasticizers. Table 3 shows the test results.

Table 3 Results of color image fastness test Basic color dye

Sample (I) Basic silicone dye sheet (π) Material υ ife degree Sunlight resistance Concentration before test Sunlight resistance Plasticizer ratio

(A) 0.65 5 1% 0.72 7 9% 7 4%

(B) 0.ό8ό5% 0.75 8 1% 6 8%

(C) 0.6695.4% 0.70.779% 7.4%

D 0.ό 2 5 5% 0.79 8 4% 7 ό%

E 0.67 5 2% 0.78 8 1 8 1%

P 0.ό 25 3% 0.7 3 8 2% 7 5%

G 0.58 ό 2% 0.7 1 8 7 ° 8 2%

H 0. ό ό 5 7% 0.74 9 0% 7 8%

I 0.64 ό 8% 0.70 9 5 ° 8 9%

(J) 0.3 9 5 4 ° 0.5 6 7 1% 5 9%

() 0. ό 5 ό 0% 0.75 7 4% 4 4%

(L) 0.4 8 5 1% 0.ό 5 ό 6% 5 4%

Note: ('Ι) Sunlight resistance is the ratio (%) of the color image density to the pre-test density after a 2-hour exposure test to direct sunlight.

(ii) Refer to Table 2 for the rate of plasticizer resistance.

Table 3 shows that when a caliperylmethane compound is contained as a basic rho dye, both the fastness to sunlight of a color image and the fastness to a plasticizer are extremely high in the system of the present invention. It is recognized that it is suitable for writing. Availability on

As is clear from the results of the examples, the present invention shows that, as a developer, (1) a solid acid represented by the above definition is used as a main component, and (2) a sodium acid is used as an auxiliary component. By using a combination developer containing a polyvalent metal salt of a formic acid derivative to form an acid-base type recording material and a developing layer of a non-carbon-based pressure-sensitive recording material, Therefore, the color shift is higher than when (1) or (2) is used alone. It is noticeable that the improvement of the image quality and the remarkable improvement of the color image

Therefore, by applying the present invention, it is possible to provide an acid-base type recording material with high reliability, particularly in terms of the durability of a color image.

Claims

The scope of the claims

1- In acid-base type recording materials that utilize the color development phenomena due to the interaction between a basic rho dye and an acidic head coloring agent for image formation, the acid head coloring agent is (1) a regular tetrahedron of silica It is derived from a clay mineral having a layered structure consisting of a layered structure. According to X-ray diffraction, the diffraction pattern based on the crystal having the above layer structure is not substantially exhibited according to X-ray diffraction. (2) a polyvalent metal salt of a salicylic acid derivative and, if desired, a metal compound; and (2) a solid acid containing cesium and Z or aluminum. An acid-base type recording material characterized by being contained as a component.

2. The acid-base recording material according to claim 1, wherein the basic π-ico dye contains at least one calpa or lilmethan compound.