JPS63182181A - Color developer sheet for pressure-sensitive paper - Google Patents

Abstract

PURPOSE:To obtain a color developer sheet for a pressure sensitive paper having excellent performance, coating properties and printability, by incorporating a polyvalent metal compound of a co-condensation resin comprising salicylic acid and an alpha,alpha'- dialkoxy-p-xylene as main monomeric components and a calcium salt of a higher fatty acid. CONSTITUTION:A color developer sheet for a pressure-sensitive paper comprises a polyvalent metal compound of a co-condensation resin comprising salicylic acid and an alpha,alpha'-dialkoxy-p-xylene as main monomers and a calcium salt of a higher fatty acid. The color developer sheet has color developing properties (color developing speed and developed color density) satisfactory for practical use, and developed color images obtained have such resistance as not to be easily faded by water, plasticizers or rays. In addition, resistance to after yellowing upon irradiation with light is markedly enhanced, and a tendency toward after-yellowing of a paper surface in an oxidizing gas atmosphere represented by NOx which is the problem in use of the pressure sensitive paper, is not observed at all. The color developer sheet shows a marked improvement in the tendency toward lowering in color developing performance (particularly, color developing speed) after long-time preservation or after preservation at high temperature.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color developer sheet for pressure-sensitive copying paper, and more specifically, it relates to a color developer sheet for pressure-sensitive copying paper, and more specifically, a novel color developer sheet containing a metal compound of a new salicylic acid cocondensation resin and a higher fatty acid. This invention relates to a color developing sheet for pressure-sensitive copying paper.

[Conventional technology]

Pressure-sensitive copying paper is also called carbonless paper, and is a type of copying paper that develops color under mechanical or impact pressure, such as when used in writing or typewriting, and is capable of making multiple copies at the same time, and is called a transfer type copying paper. , or single-coloring paper, the coloring mechanism of which is based on a coloring reaction between an electron-donating colorless dye and an electron-accepting color developer. ' as a child-receptive color developer, (1) USP
2,712,507, inorganic solid acids such as acid clay and Akpal guide;
Substituted phenol and diphenol [, (3) p-substituted phenol-formaldehyde polymer disclosed in Japanese Patent Publication No. 42-20144, (4)
Aromatic carboxylic acid metal salts and the like disclosed in Japanese Patent Publication No. 49-10856 and Japanese Patent Publication No. 52-1327 have been proposed, and some of them 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.

Conventionally proposed 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, causing yellowing of the paper surface and a decline in coloring performance, while substituted phenols have insufficient coloring properties and the density of colored images is reduced. Low p-W, which is mostly used as a p-W substituted phenol-formaldehyde polymer,
Although phenylphenol-novolac resins have excellent coloring properties, the coated paper turns yellow when exposed to sunlight or during storage (particularly due to nitrogen oxides in the air), and the colored images significantly fade.

Further, although aromatic carboxylic acid metal salts have good coloring properties, yellowing properties, and fading properties due to light, their resistance to water or plasticizers is still not sufficient. Additionally, a solution has been sought regarding the tendency of the color development rate to decrease after the color developer sheet is stored for a long period of time or at high temperatures.

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

[Means for solving 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) a polyvalent metallized product of a cocondensation resin using salicylic acid and α1 α°-dialkoxy p-xylene as main monomers, and (b) a Ca
This is a color developing sheet for pressure-sensitive copying paper, characterized in that it contains a salt.

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 properties (color development speed and density), and the color image is resistant to browning easily due to water, plasticizers, and light.Furthermore, the yellowing resistance due to light irradiation is greatly improved, and , NOx is a problem in the process of using pressure-sensitive copying paper.
The paper has a characteristic that there is no tendency for the paper surface to turn yellow in an oxidizing gas atmosphere, such as that represented by .

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 has been a common problem with color developer sheets using resin-based color developers up to now. ) 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, α1, which are essential components of the cocondensation resin used in the present invention
- Dialkoxy p-xylene is reacted with a phenolic compound to give the corresponding phenolic resin, and this resin is further reacted with a basic compound such as hexamethylenetetramine to cure it, as a so-called thermosetting polymeric composition. Used (Special Publication No. 47-15111)
.

However, these thermosetting polymer compositions use carbolic acid, alkylphenols, phenylphenols, baraminophenol, pyrogallol, and phloroglycitol as phenolic compounds;
Nothing is known about those reacted with salicylic acid. When this word is reacted with a phenol compound under an acidic catalyst of α1 α゛-dialkoxy p-xylene,
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, surprisingly, the present inventors discovered that salicylic acid and α,α'-dialkoxy p-xylene, or their main monomer components, polyalkylbenzene and/or p-W phenol, were further monomerized. It has been found that when the reaction is carried out in the presence of an acid catalyst as a component at a reaction temperature of 110'C or higher, a salicylic acid phenol cocondensation resin can be obtained with almost no corresponding side reactions such as esterification reactions occurring. 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,α°-jetoxy p-xylene , α, α
ゝ-Di-n-propoxy=p-xylene, α, α°-isopropoxy p-xylene, α, α′-di. -butoxy-p-xylene, α, α, millet-di-di-5ec-butoxy-p-xylene, α, α1. Examples include α-isobutyl-p-xylene.

The other major monomer component is salicylic acid.

When obtaining a cocondensation resin consisting of these main monomer components, the amount of these components used is α per mole of salicylic acid.
, α1-dialkoxy p-xylene from 0.1 to 1.0
It is a molar ratio.

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

Polyalkylbenzenes used in such co-condensation resins include m-xylene, mesitylene, pseudocumene, durene, indulene, diethylbenzene,
Typical examples include triethylbenzene, and mesitylene is preferred.

Examples of the p-W substituted phenol include p-alkylphenols having 1 to 12 carbon atoms, p-cycloalkylphenols, p-aralkylphenols and p-phenylphenol. Examples of p-alkylphenol include p-cresol, p-ethylphenol, p-isopropylphenol, p-5ec-butylphenol/p4ert-butylphenol, p-
Examples include tert-octylphenol and p-nonylphenol. Examples of p-cycloalkylphenol include p-cyclopentylphenol and p-cyclohexylphenol. Examples of p-aralkylphenol include P-benzylphenol, P-α-methylbenzylphenol, p-α, α-dimethylbenzylphenol, and the like.

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

In addition to the main monomer components of salicylic acid and α8 α1-dialkoxy-p-xylene, polyphenol is When alkylbenzene and p-W substituted phenol are used together, the amount of polyalkylbenzene used is 0.1 to 15 molar ratio, preferably 0.5 to 10 molar ratio, per mole of salicylic acid, and The amount used is 0.1 to 15 molar ratio, preferably 0.5 to 1 mol of salicylic acid.
~lO molar ratio, α, α8. The amount of α-alkoxy p-xylene used is 0.1 to 10 molar ratio, preferably 0.3 to 0.1 molar ratio, per 1 mole of the combination of the three components of salicylic acid, polyalkylbenzene, and P-substituted phenol.
The molar ratio is 8.

Furthermore, in the production of a cocondensation resin using only polyalkylbenzene, preferably mesitylene, the amount of polyalkylbenzene used is 0.1 to 2 mol per mol of salicylic acid.
0 molar ratio, preferably 0.5 to 10 molar ratio, α,
The amount of α゛-dialkoxy p-xylene to be used is 0.1 to 10 molar ratio, preferably 0.3 to 1 mole of the combination of two components of salicylic acid and polyalkylbenzene.
The molar ratio is ~0.8.

Furthermore, in the production of a cocondensation resin using only P-substituted phenol, the amount of p-substituted phenol used is 0.1 to 50 mol, preferably 0.5 to 20 mol, per 1 mol of salicylic acid. The amount of α, α゛-dialkoxy p-xylene to be used is 0.0000000000000 yen per mole of the combination of salicylic acid and p-substituted phenol.
The molar ratio is 1 to 1.0, preferably 0.3 to 0.8.

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. In addition, in order to shorten the reaction time as much as possible, approximately 130 to 24
A temperature range of 0°C is preferred. Reaction time is 1 to 20 hours. Acid catalysts include inorganic or organic acids, in particular mineral acids, such as hydrochloric acid, phosphoric acid, sulfuric acid or formic acid, or Friedel-Crach type catalysts such as zinc chloride, stannic chloride, ferric chloride. , methanesulfonic acid or p-toluenesulfonic acid may be used alone or in combination. The amount of the catalyst used is determined by the amount of salicylic acid, α,α1-dialkoxy p-xylene, and polyalkylbenzene and/or p-xylene used as necessary.
It may be about 0.01 to 5% by weight of the total weight of the -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, ρ
- Add xylene or these main monomer components, polyalkylbenzene and/or pH-changed rough phenol when used as a monomer component, add a catalyst at the same time, raise the temperature as it is, and react at a predetermined temperature. .

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 such as dissolving in an organic 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. In some cases, a basic substance such as ammonium carbonate, ammonium bicarbonate, ammonium acetate, or ammonium benzoate may be further added and melted by heating. 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 a few hours. Regarding the amount of polyvalent metal salt used, organic carboxylates, carbonates, oxides, and hydroxides of polyvalent metals should be used so that the metal is present at 1% to about 20% by weight based on the total weight of the resin. , it is desirable to use halides.

There is no particular restriction on the amount of the basic substance used, but it is usually 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.

Examples of the metal of the polyvalent metal compound of the salicylic acid cocondensation resin used in the present invention include magnesium, aluminum, calcium, copper, zinc, tin, barium, cobalt, and nickel. Among these, zinc is particularly effective.

If necessary, components such as salicylic acids, penzotriazole derivatives, and benzophenone derivatives may be added to and mixed with the above polyvalent metallized salicylic acid cocondensation resin.

The Ca salt of higher fatty acids, which is the other essential component in the color developing sheet of the present invention, specifically refers to Ca salts of straight chain fatty acids having 8 or more carbon atoms, such as caprylic acid, capric acid, lauric acid, etc. Representative examples include Ca salts of linear saturated fatty acids such as myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignocetic acid, cerotic acid, montanic acid, and melisic acid.

The higher fatty acids constituting these may be synthetic products or those obtained by hydrolysis from vegetable oils or animal oils. Higher fatty acids obtained from animal and vegetable oils are a mixture of straight chain fatty acids with an even number of carbon atoms, and may also contain some unsaturated carboxylic acids, but these are of course included in the higher fatty acids as used 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.

These higher fatty acids are used as Ca salts by a known method.

In the present invention, as a method for preparing a color developing sheet containing (a) a polyvalent metallized product of a salicylic acid cocondensation resin and (b) a Ca salt of a higher fatty acid, (A) A method of using a polyvalent metal compound of a co-condensed resin and (b) a Ca salt of a higher fatty acid as a homogeneous resinous composition;
and CB) a method in which (a) a polyvalent metal compound of a salicylic acid cocondensed resin and (a) a Ca salt of a higher fatty acid are separately added to a coating solution for producing a color developing sheet.

In the manufacturing process of the anger pressure copying color developing sheet by coating with a water-based coating solution, which is generally carried out, (a'') a salicylic acid co-condensed resin metallized compound and a C of higher fatty acid are preliminarily applied.
(a) A method of applying an aqueous coating solution using an aqueous suspension of a resinous composition mixed with a salt to a support such as paper, and (bo) a method of applying an aqueous suspension of a salicylic acid cocondensation resin and a higher fatty acid Ca. Examples include a method of coating a support with an aqueous coating solution using an aqueous suspension of a salt, and any method is preferably used.

Ca salts of higher fatty acids are readily available commercially as aqueous suspensions with a solids content of 20-50% by weight.

When creating a color developing sheet, (1) white inorganic pigments (e.g. calcium carbonate, clay minerals, aluminum hydroxide, etc.) (2) adhesives (synthetic rubber latex, starch, polyvinyl alcohol) (3) Coatings that are used by mixing other substances (anti-dusting agents, fluorescent whitening agents, viscosity property modifiers, antifoaming agents), etc. with the salicylic acid co-condensed resin metallization of the present application and an aqueous suspension of Ca salts of higher fatty acids. A method is used in which an aqueous coating liquid with a viscosity and solid content depending on the method is prepared in advance, and then applied to 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 (a) salicylic acid co-condensed resin metallized product and (b) Ca salt of higher fatty acid is (a) by weight.
): (b) -100:1 to 100:100 is common, 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 20 g/m''.

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 relates to salicylic acid and α,α°-dialkoxy-
Provided is a color developing sheet for pressure-sensitive copying paper which contains a metallized co-condensed resin containing p-xylene as a main monomer component and a Ca salt of a higher fatty acid and has excellent performance, coating suitability, and printability.

The color developing sheet of the present invention can be used in combination with a microcapsule-coated paper (top paper) using a dye precursor such as triphenylmethane phthalide, diisodylmethane phthalide, or fluoran to quickly and intensify the color development. It has excellent color-forming performance, and the color image obtained is stable against light, water, and solvents.

Furthermore, the color developing sheet of the present invention has an extremely small tendency to yellow due to light or gases such as nitrogen oxides in the air.

In addition, even if coated paper is stored for a long period of time, there is very little decline in coloring ability after high-temperature storage, which is expected during the drying, storage, or transportation process of coated paper, and overall it has a long shelf life. It is a color developing sheet with excellent color development properties, 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.

In addition, the color developing sheet of the present invention reduces the adhesiveness of the binder during production, prevents dusting problems on the calendered surface, and prevents dusting on the coated paper surface. The smoothness of the paper increases, and the effect of improving printability is recognized.

〔Example〕

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 milled in the presence of a small amount of anionic polymeric surfactant to form an aqueous suspension with a solids content of 40% by weight (average particle size 2.5μ).

Next, using this suspension, an aqueous coating liquid (solid content: 30% by weight) having the following composition is made of steel.

Standard aqueous coating liquid composition Solid content/weight ratio Pigment 100 Color developer 17 Synthetic rubber latex 8 Oxidized starch 12 Notes Pigment Light calcium carbonate (Okutama Kogyo TP-123) Synthetic rubber latex Mitsui Toatsu Polylac 52-A Oxidized starch Egg corn starch ace B. Apply 40g7 of this aqueous coating liquid using a Meyer bar coater.
A pressure-sensitive copying paper developer sheet was prepared by applying and drying the mixture to a dry coating amount of 6 g/m'' on high-quality paper having a size of 100 mm.

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

(1) 0 color development speed and density (71fli in a constant temperature and humidity room at 20°C and 165χRH) Commercially available blue coloring paper containing crystal violet lactone (CVl) as the main pressure-sensitive dye (NW-
407), the two fabric surfaces of the color-developing sheet (lower sheet) obtained in the example were placed one on top of the other, facing each other, and the color was developed by stamping with an electronic typewriter.

The reflectance after 30 seconds and 24 hours of imprinting was measured using a Σ-80 color difference meter (manufactured by Nippon Denshoku ■) and displayed as a Y value.

(2) Light fastness of 0 color image The color developer sheet developed using the method in (1) was irradiated with light for 4 hours using a carbon arc fade meter (Suga Test Instruments Model FAL-5), and the color image after the test was The color was measured using a Σ-80 color difference meter and expressed as a Y value. 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 plasticizer-resistant dioctyl phthalate (DOP) as a core material and a small amount of starch-based binder were prepared. 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/m. After facing each other, they are passed through a super calender roll having a linear pressure of 100 Kg/c+n to uniformly infiltrate the coloring surface with 110P.

The concentration one hour after the test is expressed as a Y value using a Σ-80 color difference meter. 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 0 color image The color developer sheet developed by the method of (1) was immersed in water for 2 hours, and changes in density of the color image were observed with the naked eye.

(5) Yellowing of developer sheet (5-1) Yellowing due to NOx Jrst, -1055 (Based on the nitrogen oxide gas fastness test method for dyed products and dyes, the developer sheet was
The sample was stored for 1 hour in a sealed container in an atmosphere of NOx gas generated by the reaction between (sodium nitrite) and HsPOa (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. The larger the same value and the smaller the difference from the WB value of the untested sheet, the less yellowing in the NOx atmosphere.

(5-2) Yellowing due to light The color developing sheet is irradiated with a carbon arc fade meter (manufactured by Suga Test Instruments) for 4 hours, and after the test, it is displayed as a WB value using a Σ-80 color difference meter. The larger the WB 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 (in particular, changes in color density immediately after color development).

Each color developing sheet was stored in a constant temperature bath at 105°C for 2 hours, and then a commercially available upper paper for blue color development (Jujo NW-
407) and passed through a calender roll with a linear pressure of 50 kg/cm 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 salicylic acid, 361 g (3.0 mol) of mesitylene, α,α'-dimethoxy-p
- 332 g (2.0 mol) of xylene was charged, and 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 reaction is completed, 200 g of toluene
Oaf was added to dissolve the reaction product. Add 4 warm water to this
After adding 000d and stirring for 30 minutes under reflux, 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 charged into a flask and heated to melt it at a temperature of 150 to 160°C, and then a mixture of 21 g of zinc oxide and 2.0 g of ammonium bicarbonate was mixed in advance with stirring. Added gradually over 30 minutes. Thereafter, the mixture was stirred at 160 to 170°C for 1 hour to complete the reaction. 3.0 g of 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole was added and mixed to the system while melting, and a pale yellow transparent salicylic acid cocondensation resin was obtained. Zn compound (color developer)
A]) was obtained.

Synthesis Example 2 5 parts of Ca stearate (NOF ■, Calcium Stearate G) were melt-mixed per 50 parts of the Zn compound of the salicylic acid cocondensation resin obtained in Synthesis Example 1 to obtain a color developer CB).

Synthesis Example-3 In a reactor, 138 g (1.0 mol) of salicylic acid, 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 placed in a reactor. ,0 mol) and 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 mN of toluene was added to dissolve the reaction composition. After adding 4000 d of warm water to this and stirring under reflux for 30 minutes, the lower aqueous layer was separated and removed.

This extraction and separation operation of unreacted monomers using warm water is carried out for two more times.
After repeating this process several 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 charged into 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 while stirring.
Added gradually over 0 minutes. After this, 155-1
The reaction was completed by stirring at a temperature of 65"C for 1 hour. After the reaction was completed, 4 parts by weight of 2-(2'-hydroxy-5-methylphenyl)benzotriazole was mixed with 100 parts by weight of this zincide, and the mixture was heated at 180°C. The mixture was heated and mixed until a pale yellow transparent salicylic acid cocondensation resin Zn compound (color developer [C]) was obtained.

Synthesis Example 4 8 parts of 5-α,α-dimethylbenzyl salicylic acid were melt-mixed per 50 parts of the salicylic acid cocondensation resin Zn compound obtained in Synthesis Example 3 to obtain a color developer (E).

The color developer (composition) obtained in the above synthesis examples 1 to 4 is wet-pulverized in the presence of a small amount of anionic polymeric surfactant to produce a 40% solid powder before producing a color developer sheet. (average particle size 2.5 μm).

Example 1 A color developer sheet was obtained using the color developer CB obtained in Synthesis Example 2 as a color developer and an aqueous coating solution.

Example 2 The color developer (C) obtained in Synthesis Example 3 was used as a color developer to add Ca stearate (manufactured by NOF ■, Calcium Stearate S1) to a standard aqueous coating composition, which was pre-contained with an anionic polymer surface active agent. A color developer sheet was obtained using an aqueous coating solution using 2 parts of aqueous suspension (used as an aqueous suspension dispersed in the presence of a pigment) per 100 parts of pigment calcium carbonate.

Example 3 A color developing sheet was obtained in the same manner as in Example 2 except that the color developer CD obtained in Synthesis Example 4 was used as the color developer.

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

Comparative Example 1 A color developer sheet was obtained using the color developer (A) obtained in Synthesis Example 1 and a standard aqueous coating composition.

Comparative Example 2 A color developing sheet was obtained in the same manner as in Comparative Example 1, except that the color developer (C) obtained in Synthesis Example 3 was used as the color developer.

Comparative Example-3 Example-1 except that a Zn-modified product of salicylic acid nonylphenol formaldehyde cocondensate was used as the color developer.
A color developing sheet was obtained in the same manner as above.

Table 1 summarizes the performance evaluation results of Examples and Comparative Examples of the present invention using pressure-sensitive copying paper as developer sheets.

As is clear from Table 1, the novel color developer sheet containing the polyvalent metallized salicylic acid cocondensation resin and the Ca salt of higher fatty acid of the present invention is a color developer sheet that exhibits excellent quality and is suitable for coating.

Claims (1)

[Claims] 1) (a) salicylic acid and α,α'-dialkoxy-
1. A color developer sheet for pressure-sensitive copying paper, characterized in that it contains a polyvalent metal compound of a co-condensed resin using p-xylene as a main monomer component, and (b) a Ca salt of a higher fatty acid. 2) (a) Salicylic acid and α,α'-dialkoxy-
The pressure-sensitive copying paper microscope according to claim 1, wherein the polyvalent metallized cocondensation resin using p-xylene as the main monomer component and (b) a Ca salt of a higher fatty acid are a molten mixture. color sheet. 3) The color developer according to claim 1 or 2, wherein the metallized co-condensed resin is a polyvalent metalized co-condensed resin of salicylic acid, mesitylene and α,α'-dimethoxy-p-xylene. sheet. 4) The color developing sheet for pressure-sensitive copying paper according to any one of claims 1 to 3, wherein the Ca salt of higher fatty acid is a Ca salt of stearic acid.