JPS5828400A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material which reduces yellow coloring degree on a developer surface and which prevents the color developing capacity due to ageing from decreasing by coating a developer composition which contains phenol resin, acid treated active clay and polyoxyalkylene oxide compound on a support. CONSTITUTION:(A) An acid treated active clay, (B) 2-50wt% (with respect to (A) component) of phenol resin, (C) 0.2-5wt% of polyoxyalkylene oxide compound having 200-5,000 of molecular weight, and (D) 1-6wt% of Mg compound, as required, (E) a binder (e.g., PVA) are dispersed in water so that the concentration of solid components becomes 10-70wt%. The mixture is treated at a temperature lower than 30 deg.C by a dispersing machine, thereby obtaining a developer composition having less than 10um of diameter. Then, the composition is coated on the support so that the solid content becomes 4-10g/m<2>. In this manner, a recording material which has excellent watertight and solvent resistant properties can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a brass material, and more particularly to a brass material using a phenolic resin, an acid-treated activated clay, and a compound in a polyol.

Conventionally, Yuki brass materials have been well known, which utilize a coloring reaction between a coloring agent and a compound that develops a color upon contact with the coloring agent (hereinafter referred to as a toning agent). For example, pressure-sensitive complex,
There are heat-sensitive paper, electrically conductive paper, etc. Eii41I Co., Ltd., 7/J, No. 107, Co.

7JO, No. 4114, J, 7JO, ≠ No. J7, J.

Reference/I, No. 210, J, #J2, No. 127, J.

ft/, 1ko 1, J, Dede J # I J / No., J
.

No. 224.114, J, Tade 4. #tJz issue and #.

As detailed in No. 000.017, etc., these color developers include acid clay, bentonite, kaolin-based clay minerals, phenol-formalin Nomirac, metal-treated Novo 2 Tsuku, Ziro rt-butylsalicylic acid zinc salt and the like are disclosed.

In addition, color formers are usually colorless and have partial skeletons such as lactones, lactams, sultones, spiropyrans, esters, and adendos, and these partial skeletons undergo waml or cleavage upon contact with a color developer. Compounds have been used.

Specifically, crystal violet tuctone, penzoyl leucomethylene/blue, pine chloride lactam, rhodamine B2 lactam, /, J, J-trimethyl-4/-ethyl-l'-butoxylindolinobenzosviropyran, and 4c/-bisdimethylanodiphenylmethyl-p-dodecylphenylsulfo 7.

What are the uses of these coloring agents? Type J or higher may be used in combination.

By the way, when the above-described electrochromic developer is used, when the developer sheet is left in the air, the color developing ability decreases over time. Since such a decrease in color developing ability has a negative effect on commercial value, improvements are desired.

Furthermore, the image on the color developer layer disappears due to the influence of organic detergent vapor, lubricant, etc. This is also an undesirable phenomenon as a recording material and is one of the points for which improvement is required.

Furthermore, when the color forming agent layer and the color developer layer are in good contact with each other and wet with water, the image on the surface of the color developer disappears.

This is also the point that has been revised.

The present inventors have discovered that by using a phenol resin and an acid #&acid clay in combination, an lining material with a small decrease in color developing ability over time and excellent *m* and water resistance can be obtained. I found out.

L, Cal,,,7! /-Although the brass material used in combination with the acid-treated activated clay chamber has the above-mentioned advantages,
Over time, it was recognized that the copper surface was susceptible to yellowing due to sunlight or ultraviolet irradiation, and improvements were needed.9.

Therefore, the objects of the present invention are to reduce the yellowing caused by a color developer in a liquid crystal, to prevent a decrease in color developing ability due to JIIJK, to improve the solvent resistance of a liquid crystal, and to improve solvent resistance of a liquid crystal. An object of the present invention is to provide a lining material having improved water resistance.

The above object can be achieved by using a phenolic resin, an acid-treated activated clay, and a polyalkylene oxide compound as a tinting agent.

The phenol 1111 used in the present invention is known as a so-called Novo2 resin.
A Laphenylphenol resin, Parater 7 Yaripudelphenol 8111, A) Octylphenol resin, A Lanonylphenol resin, Parachlorophenol resin, A
There are rough-textured phenol resins and metal salts thereof, but special KA phenyl phenol resins are preferred because of their high color developing ability.

The active clay used in this study is J611L, Bentonite clay, or Bentonite clay.
used.

The phenolic resin used in the present invention is preferably used in co-powt with respect to the acid-treated activated clay. -JOwt- is more preferably used.

The polyalkylene oxide compound in the present invention refers to a polymer of one or two types of alkylene oxide.

The type of alkylene oxide is not particularly limited, but fullylene oxide with an IR wood number of 1 to 1 is preferred, and ethylene oxide and propylene oxide are particularly preferred.

The molecular weight of polyalkylene oxide is 200 Nj.

000 is preferred, and JOO~l is more preferred.

It is 000.

The amount of these polyalkylene oxide compounds added is 0.00% relative to the acid-treated activated clay. -~jWt5E, preferably 7 to 7w1%. Addition amount is 0. If the amount is less than 1, there will be no #1 effect in preventing noble coloring, and on the other hand, if the amount is less than 1,
%, the color developing ability decreased.

In order to produce the monochromatic agent composition of the present invention, it is necessary to treat the above-mentioned phenolic resin with a dispersing machine.

During dispersion, it is advantageous to coexist with the above-mentioned acid-treated activated clay and a magnesium compound such as magnesium carbonate, magnesium hydroxide, magnesium oxide, etc., from the viewpoint of preventing aggregation and improving color developing ability.

The preferred amount of the magnesium compound added is /-%-4W based on the acid-treated activated clay.

Dispersing machines include those that use media and those that do not, but the object of the present invention can be effectively accomplished by processing with a dispersing machine that uses media.

An example of a disperser using media is -? y domil,
There are various types such as dyno ξl, attritor, ball oar, etc. Among the dispersion machines that use media, Nando mill,
A type that disperses by using electricity and high-speed rotation of a dynoil and can be processed continuously is suitable for the purpose of the present invention in that the mixture can be processed continuously and sent to a tank for coating. Most advantageous.

Various media are used during dispersion, but typically flint, ottawa sand, steel balls, ceramics, high aluna balls, zircon, and glass beads are used. Among these media, spherical ones are
Excellent in handling and maintainability. 1. In order to prevent the product from sticking, it is desirable that the dispersing machine be used at a temperature below JOoC.

During treatment with a disperser, metal oxides, hydroxides, calcium oxides, etc. selected from zinc, aluminum and calcium are further added. When a metal compound such as a salt or carbonate is used in combination, more desirable effects such as a reduction in the viscosity of the coating liquid and an improvement in the color developing ability can be obtained. A desirable combined amount is 10 to 10 parts of IDO per ioo parts of acid-treated activated clay.

The above treatment is preferably performed by wet dispersion in the presence of water, and the solid content during the dispersion treatment is 70 to 7 degrees, preferably JO-10-. Also, the particle size of m* is i
0 μ or less, preferably 4 μ or less.

The binder is selected from the viewpoints of adhesion between the recording layer and the support, surface strength of the recording layer, etc.

Examples of water-soluble binders include proteins (e.g., gelatin, albumin, casein, etc.), cellulose (e.g., carboxylic acid, dimethyl cellulose, hydroxyethyl cellulose), sucrose (e.g., agar, sodium alginate, carbohydrate, etc.). water-soluble natural polymers and molecular compounds such as methyl starch, gum arabic, etc.; polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid,
Charged water-soluble synthetic polymer compounds such as polyacrylic acid latex, styrene-butadiene-methacrylic acid latex, acrylonitrile-butadiene acrylic acid latex, styrene-maleic anhydride copolymer, and other latexes are used. Among these, carboxy-modified latex is particularly preferred.

The recording sheet of the present invention is obtained by applying a coating liquid onto a support such as paper, synthetic paper, film, etc. and drying it.

As for the coating method, a method used among those skilled in the art is used, such as an air knife coater, a roll coater, a flade coater, a size press coater, a curtain coater, etc., and one layer or multiple layers can be coated simultaneously. Can be applied.

The coating amount is 3~/Di/ly'', preferably !~g7m2, more preferably 4~if/ly in solid terms.
rpt” is appropriate.

The color former that reacts with the color developer used in the recording sheet of the present invention is not particularly limited, but examples of these color formers include triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, Examples include spiro compounds or mixtures thereof, and among these compounds, the effects of the present invention are greatest when triarylmethane compounds, especially crystal violet lactone, are used.

The color former is dissolved in a solvent and encapsulated, or dispersed in a binder solution and applied to the support.

As a solvent, natural or synthetic oils can be used alone or in combination. As examples of solvents, mention may be made of cottonseed oil, kerosene, paraffin, naphthenic oil, alkylated biphenyls, alkylated terphels, alkylated naphthalenes, diarylethanes, triarylmethanes, chlorinated, 1-loughine, and the like. Regarding the method for manufacturing capsules, see US Pat. ≠Method using core cell page development of electrophilic colloid sol described in No. JR, British Patent No. 147,727, Dede/,
There are interfacial polymerization methods such as those described in No. 074.

The effects obtained by the present invention are listed below.

Seventh, yellowing of the developer sheet is reduced.

[lambda]th, the deterioration of the color developing ability of the color developer sheet over time is prevented.

Jth, the solvent resistance of the color developer sheet is improved.

Most importantly, the water resistance of the color developer sheet is improved.

The effects of the recording material of the present invention were confirmed using the following color forming agent sheet.

10 parts of mortar-processed pork skin gelatin and 70 parts of gum arabic ≠
o Dissolved in 0.00 parts of water and 0.00 parts of funnel oil as an emulsifier. 10 parts of color former oil were emulsified and dispersed therein. The coloring agent oil was prepared by dissolving crystal violet lactone #1 in diisoprobylna 7-talene.

When the size of the oil droplets became 1 micron on average, emulsification was stopped, and 0.0 c of water was added to the mixture to make a total of 200 parts, and stirring was continued. Next, add 10wt of acetic acid,
The liquid 9H was added to the mackerel flakes, and the mackerel flakes to -06 were added to cause coacervation. Stirring was further continued, and after 20 minutes had elapsed, the mixture was cooled with ice water to gel the coacervate film deposited around the circumference of the oil droplets.

When the liquid temperature reaches O@C, add 77W19g formalin 7
Add 10 parts to 10 IIC, and add /jwt-caustic soda aqueous solution to pHfVC11 to 9.

Next, heat for 20 minutes while stirring, and zooc
I made it.

Jo'C
After cooling to a temperature of 49/111'' (coating amount D), the coating amount was applied to paper with ≠Ol/*''.

Crystal as a coloring agent? (A microcapsule sheet containing iolet lactone was obtained.

Example 1 100 parts of acid-treated active sauce, 20s of aluminum hydroxide
% rose phenylphenol VA fat and 3 s of magnesium oxide were dispersed in 200 parts of water using a Keddy mill.

This dispersion liquid was processed in a sand mill (Igarashi Kikai I1132G type) at a discharge rate of J 00 l/hr to obtain a dispersion m having a volume average particle diameter of 3.4 μm. Polypropylene oxide (molecular weight 〇〇) 2 was added to the obtained dispersion.
910 parts of 10-# starch water and 0 parts of carboxy-modified 88R latexco (refer to solids content) were added.

The mixture was stirred and mixed uniformly, and water was added to adjust the solid content concentration to 0qIIK. This ischemic blood was dried on a 41-0117 m'' base paper using an air knife coater so that a solid content of 4.0/m'' was coated on a -cm cloth to obtain a recording sheet.

Example 2 Borietele/Oquindo (molecular weight 600) and the same binder as in Example 1 were added to the same dispersion as in Example 1, and the same binder as in Example 1 was added, followed by ischemia in the same manner to obtain a recording sheet.

Comparative Example 1 The same binder as in Example 1 was added to a dispersion prepared in the same manner as in Example 1 except that polypropylene oxide was not used, and the same binder as in Example 1 was applied in the same manner to obtain an ml receipt.

Comparative Example 2 Example/In 1.・T-raphenylphenol resin
A dispersion t-
Obtained. Then, the same binder as in Example 1 was added and 1! [Wrap it and get the record sheet.

Comparative Test A comparative test of the recording sheets obtained in Examples and Comparative Examples was conducted as follows. Microcapsule 7 is a microcapsule sheet containing the above-mentioned crystal violet lactone.

1) The recording sheets obtained in the comparative examples and comparative examples of coloring were 1) irradiated with sunlight for 1 week; b) the reflectance after being posted in a room not exposed to direct sunlight for a moss month (≠ 〇nm, Hitachi Cafu Analyzer 107); (type). The smaller the value, the more yellow the coloring.

II) Comparison of 11 color performance The microcapsule sheet and the recording sheets obtained in the above Examples and Comparative Examples were pressure-printed with a breast typewriter, and the color development strength after 1 day (4/On m, Hitachi Color) Analyzer Joym) was used for measurement.

■) - Comparison of changes in color ability over time After displaying the recording sheets obtained in Examples and Comparative Examples in a 100 lux room for 7 days, press printing with a typewriter in the same manner as in l)/Nikkei Features:! A color area was measured.

1v) Solvent Resistance O Comparison 11) The resistance of the colored body to dioctyl phthalate was visually determined.

(2) Comparison of Water Resistance The degree of decolorization τ when the colored body of 11) was wetted with water was determined by visual observation.

The results of the comparative tests are shown in Table 1 below.

From the above MC, it can be seen that the recording sheet of the present invention has less yellowing, less change in color ability over time, and is superior in fastness than the comparative recording sheet.

Claims (1)

[Claims] (a) Phenolic resin, -) Sunsho ring activated clay and (C
) - A material characterized in that a color developer composition containing a polyalkylene oxide compound is wrinkled on a support.