JPS6372588A - Color developing sheet for pressure-sensitive copying paper - Google Patents

Abstract

PURPOSE:To obtain a color developing sheet having color forming properties (color forming speed and density) sufficient from a practical aspect and imparting a color image not easily generating browning by water, a plasticizer and light, by containing a metallic compound of a co-condensation resin using salicylic acid and alpha, alpha'-dialkoxy- p-xylene as main monomer components and higher fatty acid. CONSTITUTION:Salicylic acid and alpha,alpha'-dialkoxy-p-xylene being main monomer components or said main monomer components and mesitylene and/or p-substituted phenol being other monomer component are reacted at 110 deg.C or more in the presence of an acid catalyst to obtain a salicylic acid/phenol co-condensation resin without almost generating side-reaction such as the corresponding esterifying reaction. Then, the metallic compound of the above mentioned co-condensation resin and higher fatty acid are contained. The metal compound of the salicylic acid co-condensation resin can be prepared by reacting the alkali metal salt of said resin and a water-soluble multivalent salt in water or a solvent capable of dissolving both of them. As the higher fatty acid, straight chain fatty acids such as capric acid, undecanoic acid, lauric acid or the like are designated as representative examples.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a color developing sheet for pressure-sensitive copying paper, and more specifically to a color developing sheet containing a novel metallized salicylic acid cocondensation resin and streak fatty acid. This invention relates to a color developing sheet for pressure-sensitive copying paper.

(Prior Art) Pressure-sensitive copying paper is also called carbonless paper, and is a copying paper that develops color by mechanical or impact pressure, such as when writing or using a typewriter, and can make multiple copies at the same time. There are some that are called transfer-type papers and others that are called single color-forming papers, but their color development is based on a color-forming reaction between an electron-donating colorless dye and an electron-accepting color developer. As an electron-accepting color developer, fl) LISP
Inorganic solid acids such as acid clay and Akpal guide disclosed in 2,712.507, (2) Japanese Patent Publication No. 1986-1993
Substituted phenols and diphenols disclosed in 09, (3) p-1tA phenol-formaldehyde polymer disclosed in Japanese Patent Publication No. 42-20144, (4
) Special Publication No. 49-10856 and Special Publication No. 52-1327
Aromatic carboxylic acid metal salts disclosed in et al. have been proposed and some have been put into practical use.

The properties that a color developer sheet containing such a color developer for pressure-sensitive copying paper should have include excellent color development that remains unchanged immediately after the sheet is manufactured and after long-term storage, and excellent color development properties that remain unchanged during storage and when exposed to radiation such as sunlight. Examples include low yellowing and a solid colored image that does not easily disappear or fade due to radiation, water or plasticizers.

Conventional sheets coated with color developers have advantages and disadvantages in terms of performance.For example, inorganic solid acids are inexpensive, but they absorb gas and moisture in the air during storage, resulting in yellowing of the paper surface. Substituted phenols have insufficient color-forming properties and low density of colored images. p-phenylphenol novolak resin, which is most commonly used as p-2tA phenol formaldehyde polymer, has poor color-forming properties. However, the coated paper turns yellow when exposed to sunlight or during storage (particularly due to nitrogen oxides in the air), and the colored image fades significantly.Additionally, metal salts of aromatic carboxylic acids have poor color-forming properties. , yellowing, and fading due to light are good, but resistance to water or plasticizers is still not sufficient, and the color development rate tends to decrease after the color developer sheet is stored for a long time or at high temperatures. A solution was also required.

(Problems to be Solved by the Invention) An object of the present invention is to provide a pressure-sensitive copying paper developer sheet that improves the above-mentioned drawbacks.

(Means for Solving the Problems) The present inventors have conducted intensive studies to achieve the above object, and as a result, have completed the present invention.

That is, the present invention provides a pressure-sensitive copying paper comprising: (1) a metallized product of a co-condensed resin using salicylic acid and α, α°-dialkoxy p-xylene as main monomers, and a higher resin acid; This is a color developing sheet for use.

The novel color developing sheet for pressure-sensitive copying paper of the present invention has practical properties equivalent to or better than conventional inorganic solid acid or p-phenylphenol novolak resin, Zn-modified p-octylphenol novolak resin, etc. It has sufficient color development (color development speed and intensity), and the color image has resistance to browning easily due to water, plasticizers, and light.

Furthermore, the resistance to yellowing due to light irradiation is greatly improved, and there is no tendency for the paper surface to yellow in the surrounding environment, including oxidizing gases such as NOx, which are a problem in the process of using pressure-sensitive copying paper. Has characteristics.

Furthermore, the color developer sheet of the present invention has improved color development ability (in particular, color development speed) after long-term storage or high-temperature storage, which is a common problem with color developer sheets using Rename's resin-based color developer. ) has the excellent feature of significantly improving the decreasing tendency of

The salicylic acid cocondensation resin used in the present invention is a novel resin that has never been produced before.

α, α′, which are essential components of the cocondensation resin used in the present invention
-Dialkoxy-p-xylene gives the corresponding phenolic resin by reaction with a phenolic compound, and this resin is further reacted with a basic compound such as hexamethylenetetramine to cure it, a so-called thermosetting polymeric composition. It is used as a product (Special Publication No. 47-15111)
.

However, these thermosetting polymer compositions use carbolic acid, alkylphenols, phenylphenols, para-aminophenol, pyrogallol, and phloroglycitol as phenolic compounds;
Nothing is known about those reacted with salicylic acid. This means that when a phenol compound and α,α′-dialkoxy-ρ-xylene are reacted under an acidic catalyst,
Alcohol is produced by the dealcoholization reaction, but when a phenol compound containing an organic carboxylic acid, i.e., salicylic acid, which is a component of the present invention, reacts with the alcohol produced under an acidic catalyst, salicylic acid esters and a mixture of these resins are produced. It is thought that this has not been considered yet because it is easily expected that it would be difficult to obtain the intended target product.

However, the present inventors surprisingly found that in addition to salicylic acid and α,α9-dialkoxy p-xylene, or their main monomer components, mesitylene and/or
Alternatively, when p-substituted phenol is further reacted as a monomer component in the presence of an acid catalyst at a reaction temperature of 110°C or higher, almost no side reactions such as esterification reactions occur, and a salicylic acid phenol cocondensation resin is produced. I found out what I can get.

α,α′-dialkoxy p-xylene as the main monomer component of the cocondensation resin used in the present invention is preferably α,α′-dimethoxy-p-xylene, α,α1-jetoxy p-xylene, α , α'-di-n-propoxy p-xylene, α, α1-isopropoxy p-xylene, α, α1-di-n-butoxy p-xylene,
α, α1-di-5ec-butoxy p-xylene, α,
Examples include α°-diisobutyl-p-xylene.

The other major monomer component is salicylic acid.

When obtaining a cocondensation resin consisting of these main Mffi components, the amount of these components to be used is 0.1 to 1 mol of α,α"-dialkoxy-p-xylene per mol of salicylic acid.
．． The ratio is 0 mol.

In addition to the above-mentioned main monomer components, a co-condensation resin containing mesitylene and/or p-substituted phenol as a monomer component can also be used.

The p-substituted phenols used in such cocondensation resins include p-alkylphenols having 1 to 12 carbon atoms, p-cycloalkylphenols,
Examples include p-aralkylphenols and p-phenylphenol.

Examples of p-alkylphenol include p-cresol, p-
-ethylphenol, p-isopropylphenol, p
-5ee-butylphenol, p-tert-butylphenol, p-tert-octylphenol, p-nonylphenol and the like. Examples of p-cycloalkylphenol include p-cyclopentylphenol and p-cycloalkylphenol.
- Cyclohexylphenol. Examples of p-aralkylphenol include p-benzylphenol and p-benzylphenol.
-α-methylbenzylphenol, p-α, α-dimethylbenzylphenol, and the like.

These phenols may be used alone or in combination of two or more.

Such salicylic acid and α,α”-dialkoxy-
In addition to the main monomer component of p-xylene, when mesitylene and p-substituted phenol are used to produce a cocondensation resin containing p-substituted phenol and/or mesitylene as the ttHit component, mesitylene may be used. The amount is 0.1 to 15 molar ratio, preferably 0.5 to 10 molar ratio per mol of salicylic acid, and the amount of p-substituted phenol used is 0.1 to 15 molar ratio to 1 mol of salicylic acid.
The molar ratio is preferably 0.5 to 10 molar ratio. In addition, the amount of α, α′-dialkoxy p-xylene used is:
The molar ratio is 0.1 to 1.0, preferably 0.3 to 0.8 molar relative to 1 mole of the combination of the three components of salicylic acid, mesitylene and p-substituted phenol.

Further, when only mesitylene is used, the amount of mesitylene used is 0.1 to 20 molar ratio, preferably 0.5 to 10 molar ratio per 1 mole of salicylic acid.

Further, the amount of α,α'-dialkoxy p-xylene to be used is 0.1 to 1.0 molar ratio, preferably 0.1 to 0.0 molar ratio of the combination of two components of salicylic acid and mesitylene.
The molar ratio is 3 to 0.8.

Furthermore, when only p-substituted phenol is used, p-
The amount of substituted phenol used is 0.1 to 50 molar ratio, preferably 0.5 to 20 molar ratio per mole of salicylic acid. The amount of α,α'-dialkoxy p-xylene to be used is 0.1 to 1.0 molar ratio, preferably 0.3 to 0.0 molar ratio to 1 mole of the combination of two components of salicylic acid and p-substituted phenol. .8 molar ratio.

The reaction temperature needs to be 110° C. or higher; if it is lower than 110° C., the reaction will be extremely slow and side reactions such as esterification reactions will increase. Further, in order to shorten the reaction time as much as possible, a temperature range of about 130 to 240°C is desirable. Reaction time is 1 to 20 hours.

Inorganic or organic acids are suitable as acid catalysts, especially! ! Acids such as hydrochloric acid, phosphoric acid, sulfuric acid or formic acid, or free sol co-fluorocatalysts such as zinc chloride, stannic chloride, ferric chloride, organic acids such as methanesulfonic acid or P-)luenesulfonic acid. Sulfonic acid may be used alone or in combination, and the amount of catalyst used is as follows: salicylic acid, α, α0
The amount may be about 0.01 to 5% by weight of the total weight of -dialkoxy p-xylene, and optionally mesitylene and/or p-substituted phenol.

A general method for producing the resin used in the present invention is as follows:
Predetermined amounts of salicylic acid and α,α′-dialkoxy p
- If xylene or mesitylene and/or p-substituted phenol are used as monomer components in addition to these main monomer components, add these, and then add them when the catalyst is opened, and then heat up to a predetermined temperature. React 6
The alcohol produced as the reaction progresses is trapped outside the system. If necessary, trace amounts of alcohol remaining in the system are removed from the thread using nitrogen.

After the reaction is completed, the contents are discharged, cooled, and then pulverized to obtain the desired product. In addition, if unreacted salicylic acid remains in the resin, it can be removed by washing the resin with hot water or using benzene, toluene, xylene, monochlorobenzene,
A method of dissolving it in a polyhydric solvent such as methyl isobutyl ketone or cyclohexanone and washing with hot water is used.

Several known methods can be applied to produce the metallized product from the salicylic acid cocondensation resin thus produced.

For example, it can be produced by reacting the alkali metal salt of the present resin with a water-soluble polyvalent metal salt in water or a solvent in which both are soluble.

That is, after reacting an alkali metal hydroxide, carbonate, alkoxide, etc. with a resin to obtain an alkali metal salt of the resin or an aqueous solution, alcohol solution, or water-alcohol mixed solution of the alkali metal salt, a water-soluble polyhydroxide is prepared. This is a method of producing it by reacting valent metal salts. It is desirable to react about 0.5 to 1 gram equivalent of water-soluble polyvalent metal salt per mole of salicylic acid in the resin.

It can also be produced by mixing a resin with a polyvalent metal salt of an organic carboxylic acid such as formic acid, acetic acid, propionic acid, valeric acid, caproic acid, stearic acid or benzoic acid, and heating and melting the mixture. Depending on the case, a basic substance such as ammonium carbonate, ammonium bicarbonate, ammonium acetate, or ammonium benzoate may be added and heated. 8 may be melted. Furthermore, by using resins and polyvalent metal carbonates, oxides, hydroxides, and halides, organic carboxylic acid ammonium or ammonia such as ammonium formate, ammonium acetate, ammonium caproate, ammonium stearate, ammonium benzoate, etc. It can be produced by heating and melting it with a basic substance.

When producing a metallized resin by heating and melting, the melting temperature is usually 100 to 180°C, and the reaction time depends on the resin composition, melting temperature, type of polyvalent metal salt, and amount used.
It takes about 1 to several hours. Regarding the amount of polyvalent metal salt used, the amount of metal is 1% to about 20% by weight based on the total weight of the resin.
% of organic carboxylates, carbonates, oxides, hydroxides, halides of polyvalent metals.

There is no particular restriction on the amount of the basic substance used, but it is usually used in an amount of 1 to 15% by weight based on the total weight of the resin. When using a basic substance, it is more preferable to mix it with a polyvalent metal salt beforehand.

The metal of the metal compound of the salicylic acid cocondensation resin used in the present invention includes metals excluding alkali metals such as lithium, sodium, and potassium. Preferred polyvalent metals include magnesium, aluminum, calcium, copper, zinc, and tin. , barium, cobalt and nickel. Among these, zinc is particularly effective.

If necessary, a component having ultraviolet absorbing ability such as a benzotriazole derivative may be added to and mixed with the above color developer composition.

Specifically, the higher fatty acids used in the color developing sheet of the present invention include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, hehenic acid, lignocetic acid, cerotic acid, and montanic acid. ,
Typical examples include straight chain saturated fatty acids such as melisic acid.

These higher fatty acids may be synthetic products or those obtained by hydrolysis from vegetable or animal oils.Higher fatty acids obtained from animal and vegetable oils are mixtures of straight chain fatty acids with an even number of carbons. and may contain some unsaturated carboxylic acids, but these are of course included in the higher fatty acids referred to in the present invention. Further, a cured product of unsaturated fatty acid (so-called 12-hydroxystearic acid) is also included in the higher fatty acid referred to in the present invention.

In the present invention, fat salicylic acid cocondensation resin and (1
)) Methods for preparing a color developing sheet containing higher fatty acids include a method in which (A) fat salicylic acid co-condensed resin metallized product and a higher fatty acid are dissolved and mixed in advance as a homogeneous resinous composition, and CB) HJI. One example is a method in which fa) salicylic acid cocondensation resin metallization and (bl higher fatty acid) are separately added to a coating solution for producing a colored sheet.

In the manufacturing process of a pressure-sensitive copying paper developer sheet by coating with an aqueous coating liquid, (AO) an aqueous coating of a resinous composition in which a metalized salicylic acid co-condensed resin and a higher fatty acid are mixed in advance. A method of applying an aqueous coating solution using a suspension onto a support such as paper, and (b) a method of applying an aqueous coating solution using an aqueous suspension of a salicylic acid co-condensed resin and an aqueous suspension of a higher fatty acid, respectively. Although there are methods of coating it on a support, the former method is more commonly used.

When creating a color developing sheet, (1) white i-free pigments (e.g. calcium carbonate, clay minerals, aluminum hydroxide, etc.) (2) adhesives (synthetic rubber latex, starch, polyvinyl alcohol) (3) ) Others (anti-dusting agents, fluorescent whitening agents, viscosity property modifiers, antifoaming agents), etc. are mixed with the aqueous suspension of the salicylic acid co-condensed resin metallization and higher fatty acids of the present application, and added to the coating method used. A method is used in which an aqueous coating liquid with a suitable viscosity and solid content is prepared in advance and coated on a support such as paper and dried.

As a coating method, an air knife coater, a bar coater, a blade coater, a gravure coater, a roll coater, etc. are generally used.

In the present application, the usage ratio of (2) (a) salicylic acid co-condensed resin metallized resin and middle) higher fatty acid is expressed as a weight ratio (at:
(b) is generally 100:1 to 100:100, and the salicylic acid cocondensation resin metallization in the aqueous coating solution is generally 5 to 50% of the total solid content.

The coating amount of the aqueous coating liquid is 1 g/m'' or more in terms of dry weight, preferably 2 to 10 g/crystal 2.

The color developing sheet of the present invention requires only a small amount of color developer component and coating liquid to be applied, and also allows the concentration, viscosity, etc. of the coating liquid to be changed over a relatively wide range, and has thermal and mechanical resistance to water-based coating liquids. Due to its excellent stability, it can be applied both on-machine and off-machine, which brings great benefits not only in terms of performance but also in the pressure-sensitive paper manufacturing process.

(Action and Effect) The present invention provides salicylic acid and α,α′-dialkoxy-
A color developing sheet for pressure-sensitive copying paper containing a metallized product of a co-condensed resin containing p-xylene as a main monomer component and a higher fatty acid and having excellent performance and coating suitability is provided.

The color developer sheet for pressure-sensitive copying paper of the present invention does not have a tendency to yellow due to light or gases such as nitrogen oxides in the air, and its color image is extremely stable against light, solvents such as plasticizers, water, etc. be.

In addition, even if coated paper is stored for a long period of time, or even after being stored at high temperatures, which is expected during the drying, storage, or transportation process of coated paper, there is extremely little decline in coloring ability, and overall it has a long shelf life. It is an excellent color developing sheet, and it has become possible to expand the use of pressure-sensitive paper to applications that were previously not used due to its instability, and its practical significance is extremely large.

Prior to working examples, a method for producing a color developer sheet and a method for evaluating its performance as a pressure-sensitive copying paper will be described below.

The color developer used on each side was wet-pulverized in the presence of a small amount of anionic polymeric surfactant to form an aqueous suspension with a solid content of 40 times (average particle size 2.5 μm).

Next is this! ! ! An aqueous coating solution (solid content: 30% by weight) having the following composition is prepared using the suspension.

Standard aqueous coating liquid composition Solid content weight ratio Pigment 100 Color developer 17 Synthetic rubber latex 8 Oxidized starch 12 Dusting prevention agent 1.5 Notes Pigment Calcium carbonate (TP-123
) Synthetic rubber latex Mitsui Toatsu Polyrank 52-A Oxidized starch Egg cornstarch Ace B Anti-dusting agent Nissin Chemical DEF-922F This aqueous coating liquid was coated at 40 g/m using a Meyer bar coater.
A pressure-sensitive copying paper developer sheet is prepared by coating and smoking so that the dry coating amount is 6 g/m2 on high-quality paper.

The method for evaluating the performance of the color developing sheet thus obtained as a pressure-sensitive paper is as follows.

(1) 8 color development rate and density (conducted in a thermostatic chamber at 20°C and 65χRH) Commercial blue coloring paper containing crystal bioleft lactone (CVL) as the main pressure-sensitive dye (N-40 manufactured by Jujo Paper Co., Ltd.)
7), overlap the two coated surfaces of the color developing sheet (lower paper) obtained in the example with facing each other, and write on an electronic typewriter.
Emboss and color.

The reflectance 30 seconds and 24 hours after stamping is measured using a TSS type Hunter colorimeter (using an amber filter) and displayed as a Y value.

(2) Light fastness of 1 color image (The color developer sheet developed using method 11 was irradiated with light for 4 hours using a carbon arc fade meter (Model FAL-5 manufactured by Suga Test Instruments), and the color image after the test was Hunter colorimeter (
The color was measured and displayed using an amber filter. The smaller the difference before and after the test, the less fading of the colored image due to light, which is preferable.

(3) Melamine/formaldehyde resin membrane microcapsules with an average particle size of 5.0 μm containing dioctyl phthalate (DOP) as a core 1iW were prepared, and a small amount of starch-based binder was added. DOP microcapsule-coated paper is prepared by coating and drying the solution on high-quality paper using an air knife coater so that the dry coating amount is 5 g/e. After facing them, they are passed through a super calender roll having a linear pressure of 100 kg/cmO to uniformly infiltrate the coloring surface with the oop.

Y
Display by value. The lower the Y value and the smaller the difference from the pre-test value, the better the plasticizer resistance of the colored image.

(4) Water resistance of 1 colored image The color developing sheet developed by the method of (1) was immersed in water for 2 hours, and changes in the density of the colored image were observed with the naked eye.

i5), Yellowing of 8N color sheet (5-1) Yellowing due to NO, based on JIS L-1055 (nitrogen oxide gas fastness test method for dyed products and dyes)
The sample was stored for 1 hour in a sealed container in an atmosphere of NOx gas generated by the reaction between sodium nitrite (sodium nitrite) and 1hPO4 (phosphoric acid), and the degree of yellowing was examined.

One hour after the end of the test, the WB value is displayed using a Σ-80 color difference meter. A large WB value and a small difference from the same value of an untested sheet means that there is little yellowing in an NOx atmosphere.

(5-2) Yellowing caused by light The developer sheet is irradiated with a carbon arc fade meter (manufactured by Suga Test Instruments) for 4 hours, and after the test, the same value is displayed using a Σ-80 color difference meter. - The larger the B value (and the smaller the difference from the WB value of the untested sheet, the smaller the yellowing caused by light irradiation.

(6) Heat resistance of color developer sheet Evaluation was made by measuring the tendency for color development ability to decrease during long-term storage or high-temperature storage (particularly, color development immediately after color development? change in production level).

Each color developing sheet was stored at a constant temperature fH of 50°C for 100 hours, and a commercially available upper paper for blue color development (Jujo N
W-407) and passed through a calender roll with a linear pressure of 50 kg/■ to develop color.

10 seconds after color development, the color density at the mouth is displayed as a Y value using a Σ-80 color difference meter. The smaller the change compared to the color density of an untreated color developer sheet, which was similarly subjected to a color development test, the better the long-term storage and heat stability.

Synthesis Example 1 In a reactor, 138 g (1.0 mol) of salicyl H, 361 g (3.0 mol) of mesitylene, α, α°-dimethoxy p
- Charge 332 g (2.0 mol) of xylene and charge the catalyst with p
-2.0g of toluenesulfonic acid and 2.0g of anhydrous zinc chloride
added. Next, heat while stirring until the temperature reaches 150~
When the reaction was carried out at 160°C for 4 hours, 133g of methanol was distilled out.After the 9 reactions were completed, 2000 g of toluene
m I! was added to dissolve the reaction product. After adding 4000 mff of warm water to this and stirring under reflux for 30 minutes, the lower aqueous layer was separated and removed. After repeating this extraction and separation operation of unreacted monomers with hot water two more times,
The solvent toluene was distilled off under reduced pressure. The molten resin was then discharged to obtain a pale brown transparent resin.

100 g of the obtained co-condensed resin was placed in a flask and heated to 7 ml at a temperature of 150-160°C, and then 21 g of zinc oxide and 2 ammonium bicarbonate, OR
The mixture was gradually added over 30 minutes while stirring. Thereafter, the mixture was stirred at 160 to 170°C for 1 hour to complete the reaction. 2-(2゛-hydroxy-3', 5'-di-L-butylphenyl)-5- was melted onto the spun yarn.
Add, dissolve and mix 3.0g of chlorohencitriazole,
A pale yellow and transparent Zn compound of salicylic acid cocondensation resin (color developer [A]) was obtained.

Synthesis Example-2 Stearic acid (NOF NAA-180) 1 per 50 parts of the salicylic acid cocondensation resin Zn compound obtained in Synthesis Example-1
Three parts were melt-mixed to obtain color developer CB).

Synthesis Example 3 In a reactor, 138 g (1.0 mol) of salicylene a, 240 g (2.0 mol) of mesitylene, 206 g (1.0 mol) of p-tert-octylphenol, and 332 g (2,0 mol) of α,α'-dimethoxy p-xylene were added. 0 mol),
3.0 g of p-toluenesulfonic acid was added to the catalyst. Then, the reaction mixture was heated with stirring to carry out a reaction at a temperature of 150 to 160° C. for 4 hours, and 112 g of methanol was distilled out.

After the reaction was completed, 2000 mf of toluene was added to dissolve the reaction composition. After adding warm water 4000II11 to this and stirring under reflux for 30 minutes, the lower aqueous layer was separated and removed. After repeating this extraction and separation operation of unreacted monomers with hot water two more times, the solvent toluene was distilled off under reduced pressure. The molten resin was then discharged to obtain a pale brown transparent resin.

100 g of the obtained salicylic acid-mesitylene-p-tert-octylphenol cocondensation resin was placed in a flask and heated to melt at a temperature of 150 to 160°C. Next, a mixture of 14 g of zinc benzoate and 8.5 g of ammonium bicarbonate was added to the molten resin for 30 minutes while stirring.
Added slowly over a period of minutes.

After this, the reaction was completed by stirring for 1 hour at a temperature of 155 to 165°C.After the reaction was completed, 2
- 4 parts by weight of (2'-hydroxy-5'-methylphenyl)benzotriazole were mixed and mixed and heated to 180°C to obtain a pale yellow and transparent salicylic acid cocondensation resin Zn compound (color developer [C]). Ta.

Synthesis Example-4 Nippon Oil & Fats A-1760 (beef tallow stearic acid) per 50 parts by weight of the salicylic acid cocondensation resin Zn compound obtained in Synthesis Example-3
10 parts were melt-mixed to obtain a color developer (D).

Synthesis Example 5 A color developer (E) was obtained by melt-mixing 20 parts of Myristicin rJ (NOF ^-1400) per 50 parts of the salicylic acid cocondensation resin Zn compound obtained in Synthesis Example 1.

The color developer (composition) obtained in the above Synthesis Examples 1 to 5 is wet-pulverized in advance in the presence of a small amount of anionic polymeric surfactant to produce a 40% solid powder before producing a color developer sheet. It was made into an aqueous suspension solution having a minute concentration (average particle size 2.5μ).

Example-1 A color developer sheet was obtained using the aforementioned standard aqueous coating liquid using the color developer CB obtained in Synthesis Example-2 as a color developer and calcium carbonate (Okutama Kogyo TP-123) as an IF agent. Ta.

Example 2 A color developing sheet was obtained in the same manner as in Example 1 except that the color developer CD obtained in Synthesis Example 4 was used as the color developer.

Example 3 A color developing sheet was obtained in the same manner as in Example 1 except that the color developer (E) obtained in Synthesis Example 5 was used as the color developer.

Example 4 Using the color developer (A) obtained in Synthesis Example 1 as a color developer, an aqueous suspension of stearic acid (Cellosol 920---manufactured by Ichchuso Yushi Co., Ltd.) was added to the standard aqueous coating composition. The solid content ratio is developer: 1
An aqueous coating solution was prepared by adding 10 parts per 0.00 parts by weight, and a color developing sheet was obtained.

Example-5 Using the color developer (C) obtained in Synthesis Example-3 as a color developer, add 20 parts of an aqueous suspension of behenic acid to the standard water-based paint composition per 100 parts of the color developer in terms of solid content. An aqueous coating liquid was prepared with the addition of the above ingredients, and a color developing sheet was obtained.

Comparative Example-1 Using the color developer (A) obtained in Synthesis 1-1 as a color developer,
A color developer sheet was obtained using a standard aqueous coating solution.

Comparative Example 2 A developer sheet was obtained using a standard aqueous coating solution using the developer CB obtained in Synthesis Example 2 as a developer.

Comparative Examples-3 to 5 As a color developer, p-phenylphenol formaldehyde condensate (Comparative Example-3), Zn-modified salicylic acid nonylphenol formaldehyde co-condensate (Comparative Example-4), or 2,5-di-α - Zn methylbenzyl salicylate and low molecular weight polystyrene (Sanyo Kasei Hymer 5
A color developer sheet was obtained using a standard aqueous coating solution using a molten mixture (Comparative Example-5) with a weight ratio of 100:50 and T-95).

As the pressure-sensitive copying paper of the color developing sheet of the examples of the present invention and comparative examples,
The performance evaluation results are summarized in Table 1.

As is clear from Table 1, it is clear that the color developing sheet containing the novel metallized salicylic acid co-condensed resin and higher fatty acid of the present invention exhibits excellent quality.

Claims (3)

[Claims] (1) It is characterized by containing (a) a metalized product of a co-condensation resin using salicylic acid and α,α′-dialkoxy-p-xylene as main monomer components, and (b) a higher fatty acid. Color developer sheet for pressure-sensitive copying paper. (2) A patent claim that is a molten mixture of (a) a metallized co-condensed resin using salicylic acid and α,α'-dialkoxy-p-xylene as main monomer components, and (b) a higher fatty acid. A color developer sheet for pressure-sensitive copying paper according to item 1. (3) The color developer according to claim 1 or 2, wherein the metallized cocondensation resin is a polyvalent metallization of salicylic acid-mesitylene-α,α'-dimethoxy-p-xylene cocondensation resin. sheet.