JP3225095B2 - Developer composition and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel developer composition comprising a salicylic acid resin polyvalent metal, a developer sheet for pressure-sensitive copying paper provided with this developer composition layer, and this developer. It relates to an aqueous suspension of the composition. This developer composition can be used for pressure-sensitive paper, heat-sensitive paper, copy ink composition, transfer type developer for copy paper, and the like.

[0002]

2. Description of the Related Art Pressure-sensitive copying paper is also referred to as carbonless paper, and is a copying paper that can be colored by mechanical or impact pressure such as writing or a typewriter and can make a plurality of copies at the same time. There is a type referred to as a type or a type referred to as a single color developing paper. The color forming mechanism is based on a color forming reaction between an electron-donating colorless dye and an electron-accepting color developer.

In general, a pressure-sensitive copying paper contains a sheet (CB paper) coated with microcapsules of a nonvolatile organic solvent containing an electron-donating organic compound (pressure-sensitive dye), and a sheet containing an electron-accepting developer. The sheet (CF paper) to which the aqueous coating composition to be applied is applied, the application surfaces thereof are opposed to each other,
Breaking the microcapsules by the printing pressure,
The pressure-sensitive dye solution that has flowed out is brought into contact with a developer so as to give a color. Therefore, by changing the combination of the microcapsule layer having the pressure-sensitive dye and the color developer layer, it is possible to copy a large number of sheets, and it is also possible to manufacture pressure-sensitive copying paper (SC paper) that develops a single leaf. It is.

A transfer-type pressure-sensitive copying paper will be described below with reference to FIG. 1 as an example.

A colorless color-forming pressure-sensitive dye is dissolved in a non-volatile oil to form a pressure-sensitive dye solution on the back surface of the upper paper 1 and the middle paper 2 to form a pressure-sensitive dye solution. Microcapsules 4 of several microns are applied. The surface of the middle paper 2 and the lower paper 3 is coated with a paint containing a color developing agent 5 which has a property of reacting and developing a color when it comes into contact with the above-mentioned pressure-sensitive dye. In order to make a copy, the layers are superimposed in the order of top- (medium)-(medium) -bottom (the dye-containing surface and the developer-coated surface are opposed to each other), and the pen pressure is 6
When a local pressure such as pressure or pressure is applied, the capsule 4 at that portion is broken and the pressure-sensitive dye solution is transferred to the developer 5 to obtain a copy record.

The colorless or pale-color dye precursors used in such pressure-sensitive copying paper include: triarylmethanephthalide compounds such as crystal violet lactone; and 3-dibutylamino-6-methyl-7-aniline. Fluoran compounds such as linofluorane, pyridylphthalide compounds, phenothiazine compounds, leuco auramine compounds, etc., one or more of which are dissolved in a hydrophobic high-boiling solvent and microencapsulated Being used.

As an electron-accepting developer, (1) USP
4,173,684, and inorganic solid acids such as acid clay, attapull guide and the like; (2) JP-B-40-930.
9 and (3) p-type compounds disclosed in JP-B-42-20144.
-Substituted phenol-formaldehyde polymers; (4) metal salts of aromatic carboxylic acids disclosed in JP-B-49-10856, JP-B-51-25174 and JP-B-52-1327, etc. have been proposed and partially put into practical use. ing.

The performance conditions to be provided for the color developing sheet include (1) that the density of the color image at room temperature is high;
(2) The decrease in the density of the color image due to long-term storage is small, (3) the color development speed of the color image particularly at low temperatures is high, and (4) the yellowing of the paper surface due to storage and exposure to radiation such as sunlight. (5) that the color image does not easily disappear or fade due to water or a plasticizer, (6) that the color image does not fade due to exposure to radiation such as sunlight, etc.
No.

Conventionally-developed developers and sheets coated with them have the following advantages and disadvantages.

[0010] 1. Inorganic Solid Acids For example, inorganic solid acids are inexpensive, but adsorb gas and moisture in the air during storage and cause yellowing of the paper surface and deterioration of color development performance. In addition, inorganic solid acids cause large discoloration of a color image due to exposure to radiation such as sunlight.

2. Substituted phenols Substituted phenols have insufficient color developability and low color image density and low color development speed.

[0012] 3. p-Substituted phenol formaldehyde polymer p-phenylphenol-novolak resin, which is used exclusively as a p-substituted phenol formaldehyde polymer, is excellent in the density of a color image, the color development speed at low temperature, and the resistance to water or a plasticizer. However, the coated paper yellows due to exposure to radiation such as sunlight or storage (especially nitrogen oxides in air), and the color-developed image is significantly faded.

4. Aromatic Carboxylic Acid Metal Salts In order to improve the drawbacks of the conventional color developers, some metal salts of aromatic carboxylic acids, especially metal salts of salicylic acid derivatives, have been proposed in recent years.

4-1.3. Mixture containing 3,5-di (α-methylbenzyl) salicylic acid metal salt For example, (i) JP-A-61-100493 and JP-A-62
5- [α-methyl-4 ′-(α-methylbenzyl) -benzyl] -salicylic acid metal salt obtained from salicylic acid and phenylethanols or styrenes disclosed in JP-084045 and JP-A-62-096449. ,
A mixture of 5-di (α-methylbenzyl) salicylic acid metal salt, (ii) JP-A-2-91042, JP-A-2-9104
3-alpha-methylbenzyl-5- (1,3) obtained from salicylic acid, styrene and derivatives thereof disclosed in US Pat.
-Diphenylbutyl) salicylic acid metal salt and 3,5-di (α-methylbenzyl) salicylic acid metal salt.

The color developer comprising the salicylic acid compound according to the proposed production method usually comprises a mixture of two kinds of components from which a resin component containing no salicylic acid component is extracted and separated. Such a mixture of salicylic acid derivatives,
It contains the metal salt of 3,5-di (α-methylbenzyl) salicylic acid disclosed and put to practical use in the above-mentioned JP-B-51-25174, and the other salicylic acid components have the same or similar molecular weights. Compound.

When these developers are used in copy recording paper, the yellowing resistance of the coated paper surface is improved, but the color development at low temperatures and the resistance to water or plasticizer, which have been conventionally problematic, are improved. It is hard to say that the stability to light and the like have been improved.

4-2. Mixture of salicylic acid compound and resin compatible therewith For the purpose of improving the stability to light and the resistance to water or plasticizer, (iii) Japanese Patent Publication No. 55-1195 discloses that a resin compatible with salicylic acid compound is mixed. Methods have been proposed. Although such a method is surely effective for improving water resistance and light resistance, there are still insufficient points regarding the color developing speed at low temperature, the density of a color developed image, and the stability over a long period of time.

Further, since the effect of the salicylic acid compound as a color developer depends on the substituent, even if, for example, a simple metal salt of salicylic acid is used by mixing with a compatible resin, the color developing ability is generally high. small. Therefore, in the salicylic acid compound used in such a method, it is a necessary condition to introduce an aromatic substituent into the salicylic acid skeleton.
However, it has been pointed out that 3,5-di (α-methylbenzyl) salicylic acid, which is conventionally known as a compound having an aromatic substituent introduced into the salicylic acid skeleton, is expensive because it is produced by a high-temperature, high-pressure reaction. Have been.

4-3. Metallized Resinized Salicylic Acid As an attempt to improve the color development at low temperatures and the resistance to water or plasticizers, a method has been proposed in which salicylic acid is resinified to utilize this metallized product.

For example, (iv) JP-A-63-132857
(V) a metalized product of salicylic acid resin obtained from salicylic acid and styrene disclosed in JP-A-63-112537; (Vi) Japanese Patent Application Laid-Open No. 63-186
729, JP-A-63-254124, JP-A-63-28
9017, JP-A-64-56724 and JP-A-64-7
7575 is a metal product of a salicylic acid resin composed of salicylic acids and various benzylated products.

It is described that when these salicylic acid resin metallized products are used as a color developer, the color development speed and water resistance at low temperatures are generally greatly improved.

However, in the disclosed examples of the polyvalent metal compound of the salicylic acid resin, the existence of a compatible organic high molecular compound is not recognized, and such a developer does not have a light resistance or a color image. Solutions for long-term stability are not yet satisfactory.

Generally, in order to produce a pressure-sensitive copying paper using a developer, the developer is wet-pulverized in the presence of a surfactant to form an aqueous suspension as fine particles having a particle diameter of 1 to 10 μm. . At this time, a dispersant is used, but the selection of the combination of the particles to be dispersed and the dispersant to obtain a good dispersion system is often empirical, and there is no general rule. Also,
When selecting dispersants, it is necessary to consider not only the dispersibility but also the effects of them on the interaction with the particles to be dispersed. For example, a phenol-formaldehyde condensate which has been used as a developer for pressure-sensitive copying paper usually contains a polycarboxylic acid type anionic polymer surfactant, specifically, maleic anhydride / diisobutylene copolymer. The combined sodium salt is utilized as a dispersant. However, when these are used in aqueous suspension of the developer composition comprising the above-mentioned salicylic acid resin polyvalent metal compound, undesirable complex salt formation occurs between the polyvalent metal and the carboxylate, and the dispersion performance And significant reduction in dispersion stability, formation of foam that is difficult to defoam,
Changes in the properties of the color developer due to alteration of the polyvalent metal compound of the salicylic acid resin, which is the substance to be dispersed, occur, making it impossible to obtain a practically usable aqueous suspension. Further, a salt of a formaldehyde condensate of naphthalenesulfonic acid, which was once used as a phenol-formaldehyde condensate-based color developer,
Lignin sulfonic acid salts and the like also exhibit dispersing performance with respect to a color developer composition comprising a salicylic acid resin polyvalent metal, but when they are used in pressure-sensitive copying paper, they are based on the dispersing agent itself. It has drawbacks such as coloring of the paper surface or photoyellowing, and is extremely lacking in practicality.

Therefore, a water-based composition having good performance in various aspects such as dispersibility, stability and color development is obtained by combining the color developer composition comprising the salicylic acid resin polyvalent metallization and a dispersant suitable therefor. Creating a suspension is not easy.

[0025]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a color-developed sheet having a water-resistant image, a plasticizer resistance, a light-fastness, a long-term stability, a low-temperature colorability, and the like. And to provide a color developer that can be manufactured at low cost.

A second object of the present invention is to provide a color-developing sheet for pressure-sensitive copying paper provided with a layer of the color developer.

A third object of the present invention is to provide an aqueous suspension which has good dispersibility, storage stability, coating stability and the like, and can be used very conveniently in the production of pressure-sensitive copying paper. That is. In addition, it has excellent color image stability (light, water, solvent, writing utensils, plasticizers, etc.) and can produce high quality pressure-sensitive copy paper that does not change during storage, such as coloration of the paper surface or light yellowing. Is to provide an aqueous suspension.

[0028]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above-mentioned object, and as a result, have mixed a salicylic acid resin polyvalent metal compound with a polycondensation resin containing no salicylic acid component as a developer composition. By doing so, it was discovered that the water resistance, plasticizer resistance, light resistance, long-term stability, color development at low temperature, and the like of a color-developed image in a color developing sheet were significantly improved, and the present invention was completed. It is a thing.

That is, the present invention provides (1) Formula (I),
(II), (III)

[0030]

Embedded image(Wherein, Z represents M / m, and M is an m-valent metal ion.
Where m is an integer. R ₁ , R_Two Is a hydrogen atom or carbon
Alkyl, aralkyl, aryl groups of 1 to 12
Or a cycloalkyl group;_Three , R₆ Is hydrogen field
Or an alkyl group having 1 to 4 carbon atoms, R_Four , R_Five Is hydrogen field
Shows a child or a methyl group. From the structural unit represented by)
The structural unit (I) is 5 to 35 mol%, and the structural unit (I
At least one of I) is 65 to 95 mol% or a structural unit (II)
One or more of which is combined with one or more of structural units (III) is 6
5 to 95 mol%, and the weight average molecular weight is
Polyvalent metalization of salicylic acid resin of 350-5,000
(Resin A) and the structural unit (II) and / or the structural unit
(III) and has a weight average molecular weight of 350 to 5,
000 and a polycondensation resin (resin B).
Color development where the weight ratio of the resin and the resin B is 90-30: 10-70
Agent composition.

Further, the present invention relates to the above-mentioned color developing composition, wherein (a) a polyvinyl alcohol derivative having a sulfonic acid group in a molecule or a salt thereof, (b) a styrene sulfonate represented by the general formula (IV)

[0032]

Embedded image (Wherein R ₇ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, M ′ is Na ⁺ , K ⁺ , Cs ⁺ , Fr ⁺ , or NH ₄
⁺ ) In the presence of one or more compounds selected from the group of anionic water-soluble polymers consisting of a polymer or a copolymer consisting essentially of a salicylic acid resin polyvalent metallized product in the presence of one or more compounds. It is an aqueous suspension of a coloring composition.

Further, the present invention is a color developing sheet for pressure-sensitive copying paper obtained by applying an aqueous paint using the above aqueous suspension to high quality paper.

The color developing sheet using the color developing agent composition of the present invention has a color developing property equal to or higher than that of the color developing sheet using inorganic solid acid or p-phenylphenol novolak resin. Further, the yellowing resistance of the coated paper surface, particularly the yellowing resistance due to nitrogen oxides in the air, is greatly improved, which is extremely advantageous for handling and storage.

On the other hand, when compared with a metal salt of a salicylic acid-based compound, which is a typical metal salt of an aromatic carboxylic acid, resistance of a color image to water and a plasticizer, light resistance, stability over a long period of time, and color development at a low temperature And the like, and it has become possible to provide a useful developer at low cost.

A feature of the developer composition of the present invention is that the polyvalent metallized salicylic acid resin contains a polycondensation resin containing no salicylic acid component in the range of 10 to 70% by weight based on the total weight of the resin.

In such a developer composition, styrenes are further reacted with the resin composition obtained in the first reaction (I) or the first reaction (I) in which salicylic acids are reacted with a benzyl compound. The salicylic acid resin obtained in the first-stage reaction (II) can be obtained by mixing it with a polycondensation resin (resin B) and then reacting it with a polyvalent metal salt. Further, as another method, the resin (resin A) after the second step of reacting the salicylic acid resin obtained in the first step reaction (I) or the reaction (II) with a polyvalent metal salt is used. ) And a polycondensation resin (resin B).

Further, in the first step reaction (I) and / or the first step reaction (II) for producing a salicylic acid resin, a method of intentionally allowing a polycondensation resin to be present is also possible.

The ratio of the metallized salicylic acid resin component (resin A) to the polycondensation resin component (resin B) in the resin composition of the present invention is in the range of 30 to 90/70 to 10 (weight ratio). .

If the polycondensation resin component is more than the above range relative to the metallized salicylic acid resin component, the color development performance of the color developing sheet will be remarkably reduced, and the desired light resistance and long-term stability of the color image will be reduced. On the contrary, it is damaged. Also,
When the amount is small, the coloring performance is good, but the light fastness and the long-term stability of the coloring image deteriorate.

The advantage of mixing such a polycondensation resin with a salicylic acid resin polyvalent metal compound has not heretofore been recognized. That is, the production method disclosed for the salicylic acid resin polyvalent metallized product does not disclose a method for positively producing a polycondensation resin in order to utilize the polycondensation resin, but rather discloses a method for removing the polycondensation resin.

For example, JP-A-61-100493 and JP-A-62-84045 disclose a step of extracting and separating a resin component containing no salicylic acid component. This step removes the polycondensation resin in such a step. It means that.

In the color developer composition of the present invention, by appropriately mixing such a polycondensation resin, the performance as a copy recording sheet such as the light resistance of a color image and the long-term storage stability is more preferable. And

The reason why this type of polycondensation resin produces such an effect is not only that the polycondensation resin does not only play a role as a bulking agent, but also a role of enhancing the compatibility with the pigment or oil in the microcapsules, but also a color development. It is considered that it also plays a role of absorbing ultraviolet rays that decompose the dye.

On the other hand, the method of mixing a resin compatible with the salicylic acid compound disclosed in Japanese Patent Publication No. 55-1195 is to improve the water resistance, and the salicylic acid compound itself is somewhat water-soluble. It discloses an effect of preventing a colored image from disappearing due to water.

The polyvalent metal compound of the salicylic acid resin (resin A) of the present invention has a satisfactory level of color development performance and water resistance performance by itself. In which the stability of the color image over the range is improved.

Next, the method for producing the color developer composition of the present invention will be described in more detail.

The reaction (I) in the first step is carried out by reacting salicylic acid with a compound of the formula (V)

[0049]

Embedded image (Wherein R ₁ , R ₂ and R ₃ represent the atoms or groups defined in the above formula (II), and Y is a halogen atom or OR ₇
(R ₇ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or

[0050]

Embedded image (Wherein R ₁ , R ₂ and R ₃ have the same meaning as described above))) and at least one benzyl derivative represented by the formula (1) in the presence of an acid catalyst.

The following are specifically used as the benzyl derivative represented by the formula (V). 1) Benzyl ethers 2) Benzyl alcohols 3) Mixture of benzyl alcohols and benzyl ethers 4) Benzyl halides Hereinafter, the case where 1) to 4) are used will be described in detail.

(1) Condensation of Salicylic Acid with Benzyl Ethers This is because, in the above formula (V), Y is OR ₇ (provided that R ₇
Is other than hydrogen).

Benzyl ethers can introduce a benzyl group into certain aromatic compounds. For example, when using benzyl propyl ether,
Examples of introducing a benzyl group into benzene, naphthalene, phenol, and the like are known (“Jikken Kagaku Koza”, vol. 18 (II), p. 84 (1956), Maruzen).

However, the reaction between salicylic acid and benzyl ethers of the present invention has been previously found by the present inventors (Japanese Patent Application Laid-Open No. 64-77575).

The amount of the benzyl ether to be used is 1 to 5 mol, preferably 1.5 to 3 mol, as the benzyl group contained per mol of salicylic acid.

In this reaction, the reaction temperature needs to be 80 ° C. or higher. If the temperature is lower than 80 ° C., the reaction becomes extremely slow and the generation of side reactions such as an esterification reaction increases. In order to shorten the reaction time as much as possible,
A temperature range of 00 to 240 ° C is desirable. Reaction time is 1 to
20 hours. As an acid catalyst, an inorganic or organic acid,
Particularly mineral acids, for example hydrochloric acid, phosphoric acid, sulfuric acid or formic acid, or Friedel-Crafts type catalysts such as zinc chloride, stannic chloride, ferric chloride, organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid May be used alone or in combination. The amount of the catalyst used is about 0.01 to 20% by weight, preferably 0.5 to 5% by weight based on the total weight of salicylic acid and benzyl ethers.

As a general method for producing this salicylic acid resin, a predetermined amount of salicylic acid, benzyl ether and a catalyst are simultaneously added, and the mixture is heated at the same temperature and reacted at a predetermined temperature, or a part of the benzyl ether is reacted. The reaction may be performed while dropping during the reaction. The alcohol or water generated as the reaction proceeds is trapped outside the system.
If necessary, a trace amount of alcohol or water remaining in the system is removed from the system with nitrogen.

After the completion of the reaction, the contents are taken out and cooled to obtain the desired product. In addition, in order to obtain a resin having a relatively low molecular weight composition, when the molar ratio of benzyl ethers is reduced, unreacted salicylic acid remains, and as a method of removing this, washing the resin with hot water or benzene, toluene,
A method of dissolving in an organic solvent such as monochlorobenzene, methyl isobutyl ketone, and cyclohexanone and washing with hot water is used.

Examples of the above-mentioned benzyl ethers include benzyl alkyl ethers, α-alkylbenzyl alkyl ethers, and dibenzyl ethers.

Benzyl alkyl ethers are described in the above (V)
In the formula, R ₃ is hydrogen, Y is OR ₇ , and R ₇ is 1
This is the case with the alkyl groups of Nos. 1 to 4. When the number of carbon atoms of the alkyl group of R ₇ is 4 or less under the above reaction conditions, the reaction is fast, and an esterification reaction does not occur, and a good salicylic acid resin is easily obtained. In addition, when the number of carbon atoms is 4, that is, a butyl group, the reaction of the tert-butyl group tends to be slow.

Accordingly, the benzyl alkyl ethers which give the resin of the first stage (I) include benzyl methyl ether, benzyl ethyl ether, benzyl isopropyl ether, benzyl-n-butyl ether, o
-Methylbenzyl methyl ether, o-methylbenzyl ethyl ether, o-methylbenzyl isobutyl ether, m-methylbenzyl methyl ether, m-methylbenzylethyl ether, m-methylbenzylisopropyl ether, p-methylbenzylmethyl ether, p-
Methylbenzyl ethyl ether, p-methylbenzyl-
n-propyl ether, p-methylbenzyl isopropyl ether, p-methylbenzyl-n-butyl ether, p-methylbenzyl-sec-butyl ether, p
-Methylbenzyl isobutyl ether, o-ethylbenzyl methyl ether, o-ethylbenzylethyl ether, o-ethylbenzylisopropyl ether, p-ethylbenzylmethylether, p-ethylbenzylethylether, p-ethylbenzylisopropylether, p- Ethylbenzyl-n-butyl ether, o-isopropylbenzylethyl ether, p-isopropylbenzylethylether, pn-propylbenzylethylether, p-tert-butylbenzylethylether, p-tert-butylbenzylisopropylether, p- tert-octylbenzylethyl ether, p-nonylbenzylmethylether, p-dodecylbenzylmethylether, p-phenylbenzylmethylether, o-fe Le benzyl isopropyl ether, p- cyclohexyl benzyl ethyl ether, p-
(Α-methylbenzyl) benzyl methyl ether, p-
(Α-methylbenzyl) benzyl ethyl ether, p-
(Α, α-dimethylbenzyl) benzyl methyl ether, 2,3-dimethylbenzyl methyl ether, 2,4
-Dimethylbenzyl methyl ether, 2,5-dimethylbenzyl methyl ether, 2,6-dimethylbenzyl methyl ether, 3,4-dimethylbenzyl methyl ether, 3,5-dimethylbenzyl methyl ether, 2,4
-Diethylbenzyl methyl ether, 3,4-dimethylbenzyl ethyl ether, 3,5-dimethylbenzyl ethyl ether, 2,4-diethylbenzyl methyl ether, 2,3-dimethylbenzyl isopropyl ether,
2,4-dimethylbenzyl-n-propyl ether,
3,4-dimethylbenzyl-n-butyl ether, 2,
4-dimethylbenzyl-sec-butyl ether, 3,
5-dimethylbenzyl-n-amyl ether, 2,4-
Diethylbenzyl methyl ether, 3,5-diethylbenzyl isopropyl ether, 2,3-diethylbenzyl-n-butyl ether, 2,4-diisopropylbenzyl methyl ether, 3,5-diisopropylbenzyl ethyl ether, 3-methyl-4-ethyl Examples include, but are not limited to, benzyl methyl ether, 3-methyl-5-tert-butylbenzyl methyl ether, 2-methyl-4- (α-methylbenzyl) benzyl methyl ether, and the like.

The α-alkylbenzylalkyl ethers are those wherein, in the above formula (V), R ₃ is an alkyl group having 1 to 4 carbon atoms, Y is OR ₇ and R ₇ is an alkyl group having 1 to 4 carbon atoms. As in the case of the above-mentioned alkylbenzyl ether, when the number of carbon atoms of the alkyl group of R ₇ is 4 or less under the above-mentioned reaction conditions, the reaction is fast and the ester or the reaction does not occur, and a good salicylic acid resin is obtained. Can be Also,
In the case where the number of carbon atoms is 4, that is, a butyl group,
The t-butyl group tends to react slowly.

R ₃ is industrially preferably a methyl group or an ethyl group.

Therefore, α which gives the first stage resin
-Alkylbenzyl alkyl ethers include α-
Methylbenzyl methyl ether, α-methylbenzyl ethyl ether, α-methylbenzyl isopropyl ether, α-methylbenzyl-n-propyl ether, α-
Methyl benzyl-n-butyl ether, α-ethyl benzyl methyl ether, α-ethyl benzyl ethyl ether, α-ethyl benzyl isopropyl ether, α-ethyl benzyl-n-butyl ether, α-n-propyl benzyl methyl ether, α-isopropyl benzyl Ethyl ether, α-n-butylbenzyl isopropyl ether, o-methyl-α-methylbenzyl methyl ether, p-methyl-α-methylbenzyl methyl ether,
m-methyl-α-methylbenzyl methyl ether, p-
Methyl-α-methylbenzylethyl ether, p-methyl-α-methylbenzylisopropyl ether, p-methyl-α-methylbenzyl-n-propyl ether, p
-Methyl-α-methylbenzyl-n-butyl ether,
p-methyl-α-ethylbenzyl methyl ether, p-
Methyl-α-ethylbenzylethyl ether, p-methyl-α-ethylbenzylisopropyl ether, p-methyl-α-ethylbenzyl-n-butyl ether, o-
Methyl-α-ethylbenzyl methyl ether, o-methyl-α-ethylbenzyl isopropyl ether, m-methyl-α-ethylbenzyl methyl ether, p-methyl-α-methylbenzyl methyl ether, o-ethyl-α
-Ethylbenzylethyl ether, m-ethyl-α-n
-Propylbenzyl methyl ether, p-isopropyl-α-methylbenzyl methyl ether, o-isopropyl-α-methylbenzyl methyl ether, p-sec-
Butyl-α-methylbenzyl methyl ether, p-te
rt-butyl-α-methylbenzyl methyl ether, p
-Nonyl-α-methylbenzyl methyl ether, p-dodecyl-α-methylbenzyl methyl ether, p-phenyl-α-methylbenzyl methyl ether, o-phenylbenzyl-α-methylbenzyl methyl ether, p-
Cyclohexyl-α-methylbenzyl methyl ether,
p- (α-methylbenzyl) -α-methylbenzyl methyl ether, p- (α, α-dimethylbenzyl) -α-
Methylbenzyl methyl ether, 2,3-dimethyl-α
-Methylbenzyl methyl ether, 2,4-dimethyl-
α-methylbenzyl methyl ether, 2,5-dimethyl-α-methylbenzyl methyl ether, 2,6-dimethyl-α-methylbenzyl methyl ether, 3,4-dimethyl-α-methylbenzyl methyl ether, 3,5- Dimethyl-α-methylbenzyl methyl ether, 2,3-
Dimethyl-α-methylbenzylethyl ether, 2,4
-Dimethyl-α-methylbenzylisopropyl ether, 2,5-dimethyl-α-methylbenzyl-n-propyl ether, 2,6-dimethyl-α-methylbenzyl-n-butyl ether, 3,4-dimethyl-α-methyl Benzyl-sec-butyl ether, 2,3-dimethyl-α-ethylbenzyl methyl ether, 2,4-dimethyl-α-ethylbenzyl methyl ether, 2,5-dimethyl-α-ethylbenzyl ethyl ether, 2,6-dimethyl -Α-ethylbenzyl-n-propyl ether,
3,4-dimethyl-α-ethylbenzyl isopropyl ether, 3,5-dimethyl-α-ethylbenzyl-n-
Butyl ether, 2,4-dimethyl-α-propylbenzyl methyl ether, 2,4-diethyl-α-methylbenzyl methyl ether, 2,5-diethyl-α-methylbenzyl methyl ether, 3,4-diethylbenzyl-
α-ethylbenzyl methyl ether, 3,5-diethylbenzyl-α-propylbenzylisopropyl ether, 2,4-diisopropyl-α-methylbenzylmethyl ether, 2,4-diisopropyl-α-ethylbenzylmethyl ether, 2,6 -Diisopropyl-α-propylbenzyl methyl ether, 3,5-diisopropyl-α-butylbenzyl methyl ether, 2-methyl-
4-ethyl-α-methylbenzyl methyl ether, 2-
Methyl-4-tert-butyl-α-methylbenzyl methyl ether, 2-methyl-4- (α-methylbenzyl) -α-methylbenzyl methyl ether, 2-methyl-4- (α, α-dimethylbenzyl)- α-methylbenzyl methyl ether and the like, but are not limited thereto.

In the dibenzyl ethers, R ₃ is hydrogen or an alkyl group having 1 to 4 carbon atoms in the formula (V), Y is OR ₇ and R ₇ is

[0066]

Embedded image Is the case. Therefore, the molar ratio to salicylic acid as dibenzyl ether in the above reaction conditions is 1/2 that in the case of the benzyl ethers.

Various dibenzyl ethers which give the resin of the first stage (I) include dibenzyl ether, di (o-methylbenzyl) ether, di (m-methylbenzyl) ether, di (p-methylbenzyl) )ether,
Di (o-ethylbenzyl) ether, di (m-ethylbenzyl) ether, di (p-ethylbenzyl) ether, di (o-isopropylbenzyl) ether, di (p
-N-propylbenzyl) ether, di (p-tert)
-Butylbenzyl) ether, di (p-nonylbenzyl) ether, di (o-phenylbenzyl) ether,
Di (p-cyclohexylbenzyl) ether, di [(p
-Benzyl) benzyl] ether, di [p- (α-methylbenzyl) benzyl] ether, di [p- (α, α-
Dimethyl) benzyl] ether, di (2,3-dimethylbenzyl) ether, di (2,4-dimethylbenzyl)
Ether, di (2,5-dimethylbenzyl) ether,
Di (2,6-dimethylbenzyl) ether, di (3,4
-Dimethylbenzyl) ether, di (3,5-dimethylbenzyl) ether, di (2,4-diethylbenzyl)
Ether, di (3-ethyl-4-ethylbenzyl) ether, di [3- (α-methylbenzyl) -4-methylbenzyl] ether, di [2,5- (dimethylbenzyl)
Benzyl] ether, di (α-methylbenzyl) ether, di (α-ethylbenzyl) ether, di (α-n-
Propylbenzyl) ether, di (α-isopropylbenzyl) ether, di (α-n-butylbenzyl) ether, di (o-methyl-α-methylbenzyl) ether, di (p-methyl-α-methylbenzyl) ether ,
Di (m-methyl-α-methylbenzyl) ether, di (p-methyl-α-ethylbenzyl) ether, di (p
-Methyl-α-isopropylbenzyl) ether, di (p-methyl-α-n-propylbenzyl) ether,
Di (p-methyl-α-n-butylbenzyl) ether,
Di (p-ethyl-α-methylbenzyl) ether, di (m-ethyl-α-ethylbenzyl) ether, di (o
-Ethyl-α-methylbenzyl) ether, di (p-isopropyl-α-methylbenzyl) ether, di (p-
Phenyl-α-methylbenzyl) ether, di [p-
(Α-methylbenzyl) -α-methylbenzyl] ether, di [p- (α, α-dimethylbenzyl) -α-methylbenzyl] ether, di (2,3-dimethyl-α-methylbenzyl] ether, (2,4-dimethyl-α-
Methylbenzyl) ether, di (2,5-dimethyl-α
-Methylbenzyl) ether, di (3,4-dimethyl-
α-methylbenzyl) ether, di (2-methyl-5-
tert-butyl-α-methylbenzyl) ether and the like, but are not limited thereto. Of these, preferred are dibenzyl ether, di (p-methylbenzyl) ether, di (α-methylbenzyl) ether, di (p-methyl-α-methylbenzyl) ether and the like.

(2) Condensation of Salicylic Acid and Benzyl Alcohol This is the case where Y is OR ₇ and R ₇ is hydrogen in the above formula (V).

Heretofore, there have been general and several known methods for obtaining alkyl-substituted salicylic acids by reacting various alcohols by alkylation of salicylic acid.

For example, a method of reacting salicylic acid with isobutanol to obtain tert-butylsalicylic acid (“Experimental Chemistry Course”, Vol. 18, (II), pp. 30 (1956), Maruzen), 1 mol of salicylic acid and 2 moles of phenylethanol A method of obtaining 5- [α-methyl-4 ′-(α-methylbenzyl) -benzyl] -salicylic acid by a molar reaction (JP-A-61-100493, JP-A-62-96449) and the like.

These are all examples of the production of substituted salicylic acid compounds, and the present inventors have found an example of producing a salicylic acid resin using an alcohol as in the present invention. In the method of the present invention, a co-condensation resin with salicylic acid is obtained in the presence of excess benzyl alcohol.

That is, the present inventors have found that when 2 mols or more of benzyl alcohol is present in 1 mol of salicylic acid and a melt reaction is carried out at a reaction temperature of 80 ° C. or more with an acid catalyst, ortho-position and / or Alternatively, it has been found that various benzyl groups can be introduced into the para-position, and that excess benzyl alcohols are successively condensed into various benzyl groups introduced into salicylic acid while undergoing a self-condensation reaction to form a resin. This condensation reaction is the same as the reaction with benzyl ether except that water is produced instead of alcohol during the progress of the reaction. That is, the amount of benzyl alcohol used, the reaction conditions, the average molecular weight of the obtained salicylic acid resin, the salicylic acid content, and the like are the same as those in the above (1).

The various benzyl alcohols giving the resin of the first stage (I) include benzyl alcohol, o-
Methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, o-ethylbenzyl alcohol, m-ethylbenzyl alcohol, p-
Ethylbenzyl alcohol, o-isopropylbenzyl alcohol, pn-propylbenzyl alcohol, p
-Tert-butylbenzyl alcohol, p-nonylbenzyl alcohol, o-phenylbenzyl alcohol,
p-cyclohexylbenzyl alcohol, p- (benzyl) benzyl alcohol, p- (α-methylbenzyl)
Benzyl alcohol, p- (α, α-dimethyl) benzyl alcohol, 2,3-dimethylbenzyl alcohol,
2,4-dimethylbenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2,6-dimethylbenzyl alcohol, 3,4-dimethylbenzyl alcohol, 3,5
-Dimethylbenzyl alcohol, 2,4-diethylbenzyl alcohol, 3-methyl-4-ethylbenzyl alcohol, 3- (α-methylbenzyl) -4-methylbenzyl alcohol, 2,5- (dimethylbenzyl) benzyl alcohol, α -Methylbenzyl alcohol, α-ethylbenzyl alcohol, α-n-propylbenzyl alcohol, α-isopropylbenzyl alcohol, α-
n-butylbenzyl alcohol, o-methyl-α-methylbenzyl alcohol, p-methyl-α-methylbenzyl alcohol, m-methyl-α-methylbenzyl alcohol, p-methyl-α-ethylbenzyl alcohol, p
-Methyl-α-isopropylbenzyl alcohol, p-
Methyl-α-n-propylbenzyl alcohol, p-methyl-α-n-butylbenzyl alcohol, p-ethyl-α-methylbenzyl alcohol, m-ethyl-α-ethylbenzyl alcohol, o-ethyl-α-methylbenzyl Alcohol, p-isopropyl-α-methylbenzyl alcohol, p-phenyl-α-methylbenzyl alcohol, p- (α-methylbenzyl) -α-methylbenzyl alcohol, p- (α, α-dimethylbenzyl)-
α-methylbenzyl alcohol, 2,3-dimethyl-α
-Methylbenzyl alcohol, 2,4-dimethyl-α-
Methylbenzyl alcohol, 2,5-dimethyl-α-methylbenzyl alcohol, 3,4-dimethyl-α-methylbenzyl alcohol, 2-methyl-5-tert-butyl-α-methylbenzyl alcohol, and the like. However, the present invention is not limited to this. Of these,
Preferable examples include benzyl alcohol, p-methylbenzyl alcohol, α-methylbenzyl alcohol, p-methyl-α-methylbenzyl alcohol and the like.

As described above, the resin of the first stage (I) is obtained by condensation of salicylic acid with various benzyl alcohols or various benzyl ethers, and a mixture of these benzyl derivatives can also be used.

In particular, a mixture of benzyl alcohols and dibenzyl ethers is obtained by hydrolysis of benzyl halides, which will be described below.

(3) Condensation of Salicylic Acid with Hydrolyzate of Benzyl Halides Benzyl halides in which Y is a halogen atom in the above general formula (V) can be converted to alkali metal or alkaline earth metal hydroxides or carbonates. Alternatively, by hydrolysis with an aqueous solution of bicarbonate, benzyl alcohols wherein Y is OH in the above general formula (V),

[0077]

Embedded image A mixture of dibenzyl ethers is obtained. That is, potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, potassium bicarbonate, sodium bicarbonate, etc., per mole of benzyl halides At least 1 mol, preferably 1 mol
About 10 to 10 mol is used.

The concentration of the above alkali compound in the aqueous solution is 1
-40% by weight, preferably 3-20% by weight. The higher the concentration of the alkali compound, the higher the ratio of dibenzyl ethers in the obtained mixture, and conversely, the lower the concentration of the alkali compound, the higher the ratio of benzyl alcohols.

Further, apart from the concentration of the aqueous solution, the composition ratio of the mixture varies depending on the kind of the alkali compound.
For example, when potassium hydroxide and sodium hydroxide, which are strongly alkaline hydroxides, are used, the mixing ratio of dibenzyl ethers is increased as compared with the case where relatively weakly alkaline sodium carbonate and sodium bicarbonate are used. .

The reaction temperature in this hydrolysis reaction is from room temperature to about 100 ° C. In order to accelerate the reaction,
In some cases, the heating is further performed under increased pressure. The reaction time is 1 to 40 hours, usually 5 to 20 hours.
This reaction is usually performed without using an organic solvent, but an organic solvent inert to the reaction may be used.

In order to accelerate the reaction, a phase transfer catalyst such as crown ether, cryptate, quaternary ammonium salt, quaternary phosphonium salt and the like may be used.

After completion of the reaction, the reaction solution is allowed to stand, and the separated oil is separated to obtain a mixture of benzyl alcohol and dibenzyl ether. This may be further purified by distillation, but can be used as it is. The composition ratio of benzyl alcohol and dibenzyl ether obtained by the above method is in the range of 1:99 to 99: 1 (weight ratio).

The amount of the raw materials used and the reaction conditions in the condensation of the mixture of benzyl alcohols and dibenzyl ethers thus obtained with salicylic acid are as described in (1) and (2) above.
This is the same as the case (2).

(4) Condensation of Salicylic Acid and Benzyl Halides This reaction will be described in more detail. The free radical in salicylic acid in which benzyl halides of the general formula (V) and Y is a halogen atom are collectively described as the acid catalyst The reaction is carried out in the presence of a Del Crafts catalyst to obtain a co-condensation resin.

That is, when 2 moles or more of benzyl halides are present in 1 mole of salicylic acid and reacted at a reaction temperature of 20 ° C. or more with a Friedel-Crafts catalyst, the hydroxyl group of salicylic acid is ortho- and / or para-positioned. It has been found that various benzyl groups can be introduced, and that excess benzyl halides are successively condensed into various benzyl groups introduced into salicylic acid while undergoing a self-condensation reaction to form a resin.

Examples of the kind of halogen in the benzyl halides include chlorine, bromine and fluorine, and chlorine is preferable.

Therefore, the benzyl halide base includes benzyl quinolide, benzyl bromide, o
-Methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, o-ethylbenzyl chloride, m-ethylbenzyl chloride, p
-Ethylbenzyl chloride, o-isopropylbenzyl chloride, pn-propylbenzyl chloride,
p-tert-butylbenzyl bromide, p-nonylbenzyl chloride, o-phenylbenzyl fluoride, p-cyclohexylbenzyl chloride, p- (benzyl) benzyl chloride, p- (α-methylbenzyl) benzyl chloride, p- (α , Α-dimethyl) benzyl chloride, 2,3-dimethylbenzyl fluoride, 2,4-dimethylbenzyl chloride, 2,5-
Dimethylbenzyl chloride, 2,6-dimethylbenzyl chloride, 3,4-dimethylbenzyl chloride,
3,5-dimethylbenzyl dichloride, 2,4-diethylbenzyl chloride, 3-methyl-4-ethylbenzyl chloride, 3- (α-methylbenzyl) -4-methylbenzyl chloride, 2,5- (dimethylbenzyl) benzyl Chloride, α-methylbenzyl chloride, α-ethylbenzyl bromide, α-isopropylbenzyl chloride, α-n-butylbenzyl chloride, o-methyl-α-methylbenzyl chloride, p-
Methyl-α-methylbenzyl chloride, m-methyl-
α-methylbenzyl chloride, p-ethyl-α-methylbenzyl chloride, o-ethyl-α-methylbenzyl chloride, p-isopropyl-α-methylbenzyl chloride, p-phenyl-α-methylbenzyl chloride, p- (α -Methylbenzyl) -α-methylbenzyl chloride, p- (α, α-dimethylbenzyl) -α
-Methylbenzyl chloride, 2,3-dimethyl-α-
Methylbenzyl chloride, 2,4-dimethyl-α-methylbenzyl chloride, 2,5-dimethyl-α-methylbenzyl chloride, 3,4-dimethyl-α-methylbenzyl chloride, 2-methyl-5-tert-butyl- α-methylbenzyl chloride and the like,
It is not limited to these. Of these, benzyl chloride, p-methylbenzyl chloride, α-methylbenzyl chloride, p-methyl-α
-Methylbenzyl chloride and the like.

The amount of various benzyl halides used in the production of the resin of the first stage (I) is 1 to 5 mol, preferably 1.5 to 3 mol, per 1 mol of salicylic acid.

The catalyst used in this reaction is known as a Lewis acid type catalyst such as ferric chloride, zinc chloride, aluminum chloride, stannic chloride, titanium tetrachloride, boron trifluoride or the like, or a super strong acid. Perfluoroalkanesulfonic acids such as trifluoromethanesulfonic acid, Nafion H as a perfluoroalkanesulfonic acid resin
(Trade name: manufactured by Du'pont) can be used. Among them, zinc chloride is particularly preferred. The amount of the catalyst to be used is in the range of 0.05 to 200 mol%, preferably 1 to 100 mol% with respect to salicylic acid, in view of economy.

In this reaction, a solvent may be used. As the solvent, those inert to the reaction, for example,
Examples include ethyl ether, ethylene glycol dimethyl ether, methylene chloride, 1,2-dichloroethane, acetic acid, propionic acid, carbon disulfide, and nitromethane.

The amount of use of these solvents is desirably 30 volumes / weight or less in consideration of economy with respect to the total weight of the raw materials.

The reaction temperature for carrying out this reaction is 20
To 180 ° C, preferably 50 to 160 ° C.
The reaction time is 1 to 30 hours.

As a method for producing a resin by this reaction,
A method in which all the raw materials are charged at once and the temperature is raised to react at a predetermined temperature, or salicylic acid and a catalyst are charged, and the reaction is performed while the benzyl halides of the other raw material are dropped at a predetermined temperature. Is common. At this time, the dropping time is preferably 50% or more of the total reaction time, and usually 1 to 5.
20 hours.

The salicylic acid resin obtained in the first step reaction (I) may be mixed with a polycondensation resin or may be directly transferred to a second step reaction with a polyvalent metal salt. After the washing and liquid separation, the above method may be adopted.

Further, when the first-stage reaction (II) is further carried out on the resin obtained in the first-stage reaction (I), after the first-stage reaction (I), in a method using no solvent, The used catalyst can be used continuously in the first-stage reaction (II), or can be directly transferred to the first-stage reaction (II) if the amount is small, but the catalyst used in the first-stage reaction (I) can be used. When is not used in the first-stage reaction (II), the catalyst is dissolved in a solvent insoluble in water, water is added thereto, and the catalyst is dissolved in the aqueous layer by water washing and separation in two layers to remove the catalyst. In the method using a solvent, similarly, the process directly proceeds to the first-stage reaction (II), or the first-stage reaction (II) is carried out with another catalyst after removing the catalyst by washing or the like.

Next, the first-stage reaction (II) is carried out by adding the compound represented by the general formula (VI) to the co-condensation resin obtained in the first-stage reaction (I).

[0097]

Embedded image (Wherein, R ₄ , R ₅ and R ₆ represent the atoms or groups defined in the above formula (III)) in the presence of a strong acid catalyst.

In this reaction, the α-position of the styrene derivative benzylates the aromatic substituent of the salicylic acid resin obtained in the first reaction (I). That is, it reacts with a benzene ring other than the salicylic acid skeleton.

Further, the excess styrene reacts with the benzene ring of the styrene derivative bonded to the aromatic substituent of the salicylic acid resin to increase the molecular weight.

The styrene derivative used in the reaction (II) of the first step includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, o-isopropyl Examples include, but are not limited to, styrene, m-isopropylstyrene, p-isopropylstyrene, p-tert-butylstyrene, α-methylstyrene, β-methylstyrene, and the like. Industrially preferred is inexpensive styrene.

The amount of the styrene derivative to be used is 0.2 to 20 mol, preferably 0.5 to 10 mol, per 1 mol of salicylic acid in the resin obtained in the first reaction (I).

In the first reaction (II), a strong acid catalyst is used.

For example, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid;
Friedel-Crafts catalysts such as ferric chloride, zinc chloride, aluminum chloride, stannic chloride, titanium tetrachloride, and boron trifluoride, or strong acid catalysts such as methanesulfonic acid and trifluoromethanesulfonic acid can be used. Of these, inexpensive sulfuric acid is particularly preferred. The amount of the catalyst used is 0.05 to 200% by weight, preferably 1 to 100% by weight in consideration of economy, based on the total weight of the salicylic acid resin and the styrene derivative obtained in the first stage reaction (I). Range.

In the reaction (II) of the first step, a solvent may be used. As the solvent, those inert to the reaction, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, n-pentane and cyclohexane, ethers such as ethyl ether and ethylene glycol dimethyl ether, ethyl acetate, acetic acid Esters such as butyl, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride, chloroform, halogenated hydrocarbon solvents such as monochlorobenzene, acetic acid, organic acids such as propionic acid, acetone, Examples thereof include ketones such as methyl ethyl ketone, carbon disulfide, nitromethane, acetonitrile, and tetrahydrofuran.

The amount of use of these solvents is desirably 30 volumes / weight or less in consideration of economy with respect to the total weight of the raw materials.

The reaction temperature for carrying out the first-stage reaction (II) is in the range of -20 ° C to 180 ° C, preferably 0 to 120 ° C. The reaction time is 1 to 30 hours.

As a method for producing a resin by the first-stage reaction (II), a catalyst is charged into an organic solvent solution of the salicylic acid resin obtained in the first stage (I), and the other raw material is heated at a predetermined temperature. The reaction is generally carried out while dropping a styrene derivative. At this time, the dropping time is preferably 50% or more of the total reaction time, and is usually 1 to 20 hours. After the reaction, if the solvent used is insoluble in water, water may be added and the mixture may be washed with two layers and separated, and then the solvent may be distilled off to obtain a resin. When the solvent is dissolved in water, it can be poured into water to obtain a precipitated resin.

The salicylic acid resin in the reaction product thus obtained contains the structural unit (I) in an amount of 5 to 35 mol%, the structural unit (II) or the structural unit (II) and the structural unit (I).
II) comprises 65 to 95 mol%, and the polyvalent metal compound (resin A) has a weight average molecular weight of 350 to 95 mol%.
5,000.

Next, the polycondensation resin (resin B) will be described.

The polycondensation resin of the present invention has the structural unit (II)
And / or at least one of the structural units (III). These two or more types of structural units may be a mere mixture as a resin or a composition in which two or more types of the structural units are reacted and bonded. Good.

Examples of such resins include one or more condensates of various benzylating agents used in the first step reaction (I) and styrene derivatives used in the first step reaction (II). 1
Polymers with more than one nucleus or side chain, first stage reaction (I)
And at least one copolycondensate of a styrene derivative used in the first stage reaction (II) and a mixture of these three resins. In the composition of these polycondensation resins, any proportion of the components of the copolycondensate or mixture comprising two or more raw material components can be selected.

The weight average molecular weight of such a polycondensation resin (resin B) is in the range of 350 to 5,000.

When such a polycondensation resin is used as the color developer composition of the present invention, it is common to separately prepare the resin (A) in advance and mix and use it. Sometimes it is possible to intentionally produce a by-product. That is, in the reaction of the resin (A), a resin of the structural unit (II) and / or the structural unit (III) is formed without adding salicylic acid, and the reaction is carried out while the resin is present when the next salicylic acid resin is produced. You can also.

In the case where the separately prepared polycondensation resin (B) is mixed with the resin (A), it is common to mix by heating and melting after the first-stage reaction (I). There is an advantage that can be transferred to. Further, after completion of the second-stage reaction of the resin (A), the resin (A) can be melt-mixed with the resin B.

Next, the second-stage reaction will be described. The second-stage reaction involves salification of the salicylic acid resin in the resin composition with a polyvalent metal. Several known methods can be applied to salicylic acid resin for polyvalent metal salification. For example, an alkali metal salt and a water-soluble polyvalent metal salt of the present resin,
It can be produced by reacting in water or a solvent in which both are soluble. That is, a salicylic acid resin is reacted with an alkali metal hydroxide, carbonate, or alkoxide to obtain an alkali metal salt of the salicylic acid resin or an aqueous solution, an alcohol solution, or a water-alcohol mixed solution. This is a method of producing a reactive polyvalent metal salt by reacting the same.

That is, the salicylic acid resin is dispersed in an aqueous solution, an alcohol solution or a water-alcohol solution containing a hydroxide, carbonate or alkoxide of an alkali metal in an amount equivalent to or more than the carboxyl group in the salicylic acid resin, Dissolved under a temperature condition of 0 to 100 ° C,
The polyvalent metal salt of the salicylic acid resin is obtained as a precipitate by adding the water-soluble polyvalent metal salt to the solution as it is or as an aqueous solution, an alcohol solution or a water-alcohol solution at 0 to 100 ° C. It is desirable to react about 0.5 to 1 equivalent of a water-soluble polyvalent metal salt to the carboxyl group in the salicylic acid resin.

In this method, a method of melting and mixing a salicylic acid resin polyvalent metal salt with a separately prepared resin (B) is often used.

In order to obtain a molten mixture containing a polyvalent metal salt of a salicylic acid resin, a salicylic acid resin containing a polycondensation resin component is mixed with an organic compound such as formic acid, acetic acid, propionic acid, valeric acid, caproic acid, stearic acid or benzoic acid. It can be produced by mixing with a polyvalent metal salt of a carboxylic acid, heating and melting and then cooling. In some cases, a basic substance, for example, ammonium carbonate, ammonium bicarbonate, ammonium acetate, or ammonium benzoate may be added and the mixture may be heated and melted.

Further, using a salicylic acid resin containing a polycondensation resin component and a carbonate, oxide or hydroxide of a polyvalent metal,
It can be produced by heating and melting reaction with a basic substance such as ammonium ammonium carboxylate such as ammonium formate, ammonium acetate, ammonium caproate, ammonium stearate, ammonium benzoate, and then cooling.

In the case of producing a metal product of a salicylic acid resin containing a polycondensation resin component by heating and melting, the melting temperature is usually 1 to 1.
The reaction is carried out at 00 to 180 ° C., and the reaction time is about 1 to several hours, depending on the resin composition, the melting temperature, the kind of the polyvalent metal salt, and the amount used. The polyvalent metal salt is an organic carboxylate, carbonate, oxide, water, etc. of the polyvalent metal so that the metal is present in an amount of 1% by weight to about 20% by weight based on the total weight of the salicylic acid resin including the polycondensation resin component. It is desirable to use an oxide.

The amount of the basic substance used is not particularly limited, but is usually 1 to 15% by weight based on the total weight of the salicylic acid resin including the polycondensation resin component. When using a basic substance, it is more preferable to use it in advance by mixing it with a polyvalent metal salt.

The softening point (ring and ball softening point measurement method according to JIS-K-2548) of the metallized resin containing the polycondensation resin component produced by this heat melting method (hereinafter the same measurement method)
0-120 ° C.

The metal of the metal salicylic acid resin containing the polycondensation resin component of the present invention includes lithium, sodium,
Includes metals excluding alkali metals such as potassium,
Preferred polyvalent metals include calcium, magnesium, aluminum, copper, zinc, tin, barium, cobalt and nickel. Of these, zinc is particularly effective. These polyvalent metals form polyvalent metal salts with the intramolecular or intermolecular carboxyl groups of the salicylic acid resin.

The developer of the present invention can be used in combination with a known developer, that is, an inorganic solid acid such as activated clay, an organic polymer such as phenol-formaldehyde resin, or a metal salt of an aromatic carboxylic acid. Absent.

The developer of the present invention further comprises a polyvalent metal oxide, hydroxide or carbonate selected from the group consisting of zinc, magnesium, aluminum, lead, titanium, calcium, cobalt, nickel, manganese and barium. And at least one of them.

The method of preparing a color developing sheet for pressure-sensitive copying paper using the salicylic acid resin polyvalent metal material containing the polycondensation resin component of the present invention comprises the steps of (1) using an aqueous suspension of the metal material. A method of applying a water-based paint to a support such as paper, (2)
Any method such as a method of shaking the metallized material during papermaking, and (3) a method of applying a solution obtained by dissolving or suspending the metallized material in an organic solvent to a support, can be used.

In preparing the paint, kaolin clay was used.
, Calcium carbonate, starch, synthetic and natural latex, etc.
To obtain a paint having appropriate viscosity and coating suitability.
The ratio of the developer component in the paint is 1% of the total solid content.
0-70% is desirable, and the ratio of the components of the developer is less than 10%.
When it is full, it cannot exhibit sufficient color developability, and it exceeds 70%
Then, the paper surface characteristics of the color developing sheet deteriorate. The amount of paint applied is dry
0.5g / m in dry weight ^Two Above, preferably 1 to 10 g /
m^Two It is.

The color developing sheet using the novel color developing agent of the present invention has the same or higher color developing property than the color developing sheet using the inorganic solid acid or p-phenylphenol novolak resin. Furthermore, yellowing due to sunlight irradiation is also improved, and especially yellowing resistance due to nitrogen oxides in the air is greatly improved, which is extremely advantageous for handling and storage.

On the other hand, when compared with a typical metal salt of a salicylic acid-based compound as a metal salt of an aromatic carboxylic acid, there is a defect as a color developer of a conventionally known metal salt of an aromatic carboxylic acid. Insufficient compatibility with non-volatile oil in which a colorless color-forming dye is dissolved (b) Somewhat soluble in water (c) Color image disappears due to light (d) Expensive . In addition, as compared with resinous polyvalent metal salts of salicylic acid, light resistance and stability of a color image over a long period of time are improved. As a result, according to the present invention, it has become possible to supply a useful developer composition at low cost, which can eliminate various disadvantages of the conventional developer sheet.

Next, the aqueous suspension of the present invention will be described.

The aqueous suspension of the present invention can be used to prepare a colorant composition comprising a salicylic acid resin polyvalent metallized product having good color developer performance and the like, and which is particularly suitable for the metallized product and has excellent properties. An aqueous suspension using a dispersing agent, which can be suitably used for the production of pressure-sensitive copying paper. Further, the obtained pressure-sensitive copying paper has improved color-forming performance and the like, and has extremely good performance. It shows.

In the present invention, the anionic water-soluble polymers (a) and (b) serving as dispersants will be described.

The anionic water-soluble polymer (a) is an anionic water-soluble polymer comprising a polyvinyl alcohol derivative having a sulfonic acid group in the molecule or a salt thereof,
The polymerization degree is 200-5000, preferably 200-
2000. The sulfonic acid group is used as an alkali metal salt (Na ⁺ , K ⁺ , Cs ⁺ , Fr ⁺ ) or an NH ₄ ⁺ salt. As a method for producing the polymer (a),
(1) a method of copolymerizing vinyl acetate and an α, β-unsaturated monomer containing a sulfonic acid group, followed by saponification,
(2) a method of reacting polyvinyl alcohol with concentrated sulfuric acid, (3) a method of oxidizing polyvinyl alcohol with bromine, iodine, or the like, and then reacting the same with acid sodium sulfite.
(4) A method in which an aldehyde compound having a sulfonic acid group is reacted with polyvinyl alcohol in the presence of an acid catalyst to form a sulfoacetal, and the method (1) is preferable.

Specific examples of the α, β-unsaturated monomer containing a sulfonic acid group used in the method (1) include (i) sulfoalkyl acrylates, for example, sulfoethyl acrylate, sulfoethyl methacrylate, and (ii) vinyl Sulfonic acid, styrenesulfonic acid, allylsulfonic acid (iii) maleimide-N-alkanesulfonic acid (iv) 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid and the like are exemplified. . The polymer (a) generally comprises these monomers in an amount of 0.5 to 20 per 100 moles of vinyl acetate.
Mol, preferably 1 to 10 mol, and then obtained by saponifying (50 to 100%) the vinyl acetate group under alkaline conditions by a conventional method.

The polymer (a) is obtained by copolymerizing vinyl acetate with an aromatic α, β-unsaturated monomer such as styrene,
After sulfonation, it can be obtained by saponification. Further, vinyl acetate is copolymerized with an α, β-unsaturated monomer having a sulfonic acid group in the molecule and another α, β-unsaturated monomer. You can also get.

A typical example of the anionic water-soluble polymer (b) which is a polymer or a copolymer containing the sulfonate represented by the general formula (IV) as an essential component is styrene sulfonic acid or a derivative unit thereof. Is a polymer having in a molecule. Among them, polystyrene sulfonate and poly α-methylstyrene sulfonate having an average degree of polymerization of 5 to 1,000 are mentioned as preferred examples. Such a homopolymer may be synthesized in any manner. That is, the salt of the derivative of polystyrene sulfonic acid may be synthesized by sulfonating polystyrene or polymerizing styrene sulfonic acid (or a salt thereof). The polymerization may be performed by a known method, for example, radical polymerization at 0 to 150 ° C., ionic polymerization, or the like. Specific examples of the polymer (b) which is a copolymer include salts of styrene sulfonic acid and maleic anhydride copolymer, salts of styrene / maleic acid copolymer sulfonate, and styrene and other vinylic monomers. Examples thereof include salts of sulfonated copolymers.

The characteristics of the anionic water-soluble polymers (a) and (b) used as the dispersant in the present invention are as follows. Unlike general completely saponified or partially saponified polyvinyl alcohol, the polymer (a) having a sulfonic acid group has high solubility in water, is easily dissolved, and has a viscosity over a wide pH range. It has little change and is substantially colorless or extremely pale. Therefore, the aqueous suspension of the developer composition comprising the salicylic acid resin polyvalent metallization obtained using the same, less coloring,
Therefore, pressure-sensitive copying paper (CF paper) having high whiteness can be obtained by using the aqueous suspension. As described above, the polyvinyl alcohol derivative having a sulfonic acid group in the molecule itself has the property of not changing or discoloring under severe environmental conditions, and furthermore, a developer comprising a salicylic acid resin polyvalent metal compound. It provides a thermally, mechanically, and chemically stable aqueous suspension having excellent dispersibility for the composition. Furthermore, the polymer (a) is different from commonly used completely saponified or partially saponified polyvinyl alcohol or polyvinyl alcohol modified with a carboxy group or the like, and has a low foaming property and a self-extinguishing property. Since it has excellent foaming properties, it can also eliminate troubles caused by foaming during dispersion work.

The anionic water-soluble polymer (b) used in the present invention can also provide a stable aqueous solution over a wide pH range, and is extremely pale.

As described above, in the present invention, the anionic water-soluble polymers (a) and (b) used as dispersants
Each has an extremely excellent dispersing ability for a developer composition comprising a salicylic acid resin polyvalent metallization, and the aqueous suspension of the present invention has a high concentration and a stable low viscosity. Become. In addition, unlike the case of using general polyvinyl alcohol, there is no problem of intense foaming or difficulty in defoaming.

The anionic water-soluble polymer (a) used in the present invention has not only anionic properties but also nonionic properties, and has excellent dispersing performance and excellent protective colloid ability. Aqueous suspensions have significantly better mechanical and thermal stability than aqueous suspensions using other dispersants.

Next, the aqueous suspension of the present invention was prepared from the above-mentioned anionic water-soluble polymers (a) and (b) and the developer composition comprising the above-mentioned salicylic acid resin polyvalent metallized product. A method for performing the above will be described.

Anionic water-soluble polymers (a), (b)
Are usually obtained as a white powder or an aqueous solution that is easily soluble in water, and are used by dissolving in water as necessary. The pH of the solution is in the range of 4 to 10, preferably 6 Adjust to ~ 9 range. Into the aqueous polymer solution thus prepared, a powder of a developer composition comprising a salicylic acid resin polyvalent metallization is charged, stirred, and slurried, and then wet-milled, for example, a ball mill, an attritor. , Such as a sand grinder, a device for performing wet fine pulverization using a spherical pulverizing measure, an average particle diameter of 1 to 20 μm
to obtain an aqueous suspension. Such wet pulverization can be performed by a batch method or a continuous processing method.
Pulverize to the target particle size and finish the work. If the developer composition comprising the salicylic acid resin polyvalent metallization has a low softening point and easily liquefies below the boiling point of water, it is emulsified by high-speed stirring in warm to hot water and then cooled. To give an aqueous suspension.

The amount of the anionic water-soluble polymer (a) and / or (b) used in the present invention depends on the substance to be dispersed (color developer composition) and the physical properties (concentration, Although it depends on the particle size, viscosity, etc., and is not particularly limited, a practical aqueous suspension (average particle size of 1 to 10
μm) to obtain 0.5 parts by weight or more per 100 parts by weight of the developer composition comprising a salicylic acid resin polyvalent metal
Preferably it is 2 to 30 parts by weight. The concentration of the aqueous suspension is preferably 30 to 80% by weight. As the dispersant, any of the anionic water-soluble polymers (a) and (b) may be used, but it is preferable to use them in combination. By using both in combination, it becomes possible to reduce the amount of the dispersant used when forming an aqueous suspension compared to the case of using alone, and to obtain a more stable aqueous suspension as compared with the case of using alone. Can be. When the anionic water-soluble polymers (a) and (b) are used in combination, 10 parts by weight per 100 parts by weight of the developer composition
At below parts by weight, very stable aqueous suspensions can be obtained. In order to adjust the viscosity rheological properties of the aqueous suspension, other anionic or nonionic surfactants, water-soluble polymers and the like can be used in combination.

The average particle diameter of the color developer composition comprising the salicylic acid resin polyvalent metallization in the aqueous suspension is 10 μm or less, preferably in the range of 0.5 to 10 μm. 10μ
If the number of particles exceeds m, the sedimentation of the aqueous suspension during standing storage increases, and the color-forming performance of the pressure-sensitive copying paper, particularly, the concentration immediately after the coloration is reduced. On the other hand, if there are many particles smaller than 0.5 μm, the aqueous suspension will exhibit a thickening behavior, making it difficult to increase the concentration and handle the aqueous suspension.

When preparing a pressure-sensitive copying paper using the aqueous suspension of the present invention, first, an inorganic or organic pigment, a coating binder, a pigment dispersant, After mixing various other additives and the like, an aqueous paint is prepared according to the coating method. And
This water-based paint is applied to a support and dried to obtain a pressure-sensitive copying paper. As inorganic or organic pigments, kaolin, calcined kaolin, bentonite, talc, calcium carbonate, barium sulfate, aluminum oxide, silica, titanium white,
Titanium oxide, polystyrene emulsion, urea resin emulsion, etc., as a coating binder, oxidized starch, enzymatic starch, urea phosphate starch, modified starch such as alkylated starch, casein, water-soluble proteins such as gelatin,
Styrene-butadiene latex (SBR), methyl methacrylate-butadiene latex (MBR), vinyl acetate polymer emulsion, polyvinyl alcohol,
Synthetic and semi-synthetic binders such as carboxymethylcellulose, hydroxyethylcellulose and methylcellulose, and the like, as pigment dispersants, phosphates such as sodium metaphosphate, sodium hexametaphosphate, sodium tripolyphosphate, and polycarboxylates such as sodium polyacrylate Etc., and as other various additives, a fluorescent whitening agent,
An antifoaming agent, a viscosity controlling agent, an anti-dusting agent, a lubricant, a waterproofing agent and the like are used.

An aqueous suspension prepared by mixing and dispersing the aqueous suspension of the present invention and the above-mentioned various components was applied to an air knife coater.
Blade coater, brush coater, roll coater,
It is coated on a support such as paper or film by a bar coater, gravure coater or the like, and dried to obtain a pressure-sensitive copying paper color developing sheet of the present invention. Generally, the application amount of the water-based paint is 0.5 g / m ² or more by dry weight, preferably 1 to 10 g / m ^2.
Range. The color development performance of the sheet coated with the water-based paint is mainly governed by the concentration of the developer composition composed of the salicylic acid resin polyvalent metal in the water-based paint.
The coating amount of more than m ² is not effective in improving the color performance,
It is also disadvantageous economically.

The fact that the aqueous suspension of the present invention is suitable for producing pressure-sensitive copying paper is specifically confirmed in the following points.
That is, since the aqueous suspension of the present invention has a low tendency to thicken, the workability at the time of applying an aqueous paint containing it as a main component is remarkably improved. In addition, if an air knife coating method using a low-viscosity coating liquid at the time of coating is used for coating these water-based paints, foaming during circulation of the water-based paints is remarkably suppressed, which is advantageous. Further, the aqueous suspension of the present invention, when preparing an aqueous paint used for pressure-sensitive copying paper, other components generally used, for example, kaolin clay, calcium carbonate,
No tendency to increase viscosity (shock) when mixed with white pigments such as zinc oxide and aluminum oxide. Furthermore, these aqueous suspensions have high solid content and excellent thermal stability, and aqueous coatings using them have excellent thermal and mechanical stability. It can be suitably applied to a coating machine for applying a coating material.

The color developing sheet for pressure-sensitive copying paper produced by using the aqueous suspension of the present invention is the same as or similar to the color developing sheet using inorganic solid acid or p-phenylphenol novolak resin. It has a higher color developing property, and furthermore has greatly improved yellowing resistance due to sunlight irradiation, which is extremely advantageous for handling and storage. Further, it is a disadvantage of a metal salt of a salicylic acid-based compound that is a typical metal salt of an aromatic carboxylic acid. (A) Lack of compatibility with a non-volatile oil in which a leuco dye is dissolved (b) Some solubility in water ( C) the color image disappears due to light; and (d) the cost is high. Furthermore, even when compared with the conventional polyvalent metal salt of resinated salicylic acid, the light resistance of the color developing sheet and the stability of the color image over a long period of time are greatly improved.

Hereinafter, the present invention will be described in detail with reference to examples. First, the developer composition will be described with reference to Examples 1 to 4 and Comparative Examples 1 to 4, and then examples of the aqueous suspension will be described with reference to Examples 5 to 12 and Comparative Examples 5 to 8.

[0150]

EXAMPLES The performance of a color developing sheet of a pressure-sensitive copying paper using the color developing composition of the present invention was measured by the following method. The measurement results are collectively shown in Tables 1 and 2.

1. Coloring speed and density (low-temperature coloring (5
(° C, 60% RH) is performed in a constant temperature and humidity room at 20 ° C, 65% RH except where noted.) For blue color, crystal violet lactone (CV
Using a commercially available blue-colored upper paper (NW-40T, manufactured by Jujo Paper Co., Ltd.) which mainly uses L) as a pressure-sensitive dye, and superimposing the developing sheet (lower paper) coated with a water-based paint such that both coated surfaces face each other. Combine and color with an electronic typewriter.

1 minute and 30 seconds after stamping and 2 hours after 24 hours
The reflectance of a point is measured with a $ 80 color difference meter (Tokyo Denshoku Industries Co., Ltd.)
The same applies to the following measurement methods) and is indicated by the Y value.

The Y value is determined by the International Commission on Illumination (CIE, Comm).
issue Internationale de
1'Eclairage) and is a value of the two-degree visual field display method and is represented by the following equation (the same applies to the following measurement methods).

[0154]

(Equation 1) Here, p (λ) = distribution of the standard light source y (λ) = color matching function of 2 degree field τ (λ) = spectroscopic characteristic of sample

It should be noted that p (λ) and y (λ) are JIS Z
8722.

[0156] 2. Lightfastness of Colored Image The developed sheet developed by the method of 1 was exposed to a carbon arc fade meter (manufactured by Suga Test Instruments) for 2 hours (and 4 hours), and the reflectance after irradiation was measured using a Σ-80 color difference meter. And measured and indicated by Y value.

The lower the Y value and the smaller the difference from the value before the test, the less the discoloration due to light is.

[0158] 3. Long-term storage stability of the colored image After displaying the color developing sheet colored by the method of 1 above on the wall surface of the office room (fluorescent lamp 500Lx) for 6 months, the reflectance after irradiation is measured using a Σ-80 color difference meter. Measured and indicated by Y value.

4. Plasticizer resistance A melamine-formaldehyde resin film microcapsule having an average particle diameter of 5.0 μm using dioctyl phthalate (DOP) as a core material is prepared, and a coating solution containing a small amount of a starch-based binder is dried on woodfree paper with an air knife coater. DOP microcapsule coated paper is used after coating and drying so that the coating amount is 5 g / m ² . After making the color-developing surface of the color-developing sheet colored with the DOP microcapsule-coated paper 1 face, the DOP is passed through a super calender roll having a linear pressure of 100 kg / cm to uniformly penetrate the color-developing surface.

The reflectance for one hour after the test is measured using a Σ-80 color difference meter and is indicated by a Y value. The lower the Y value and the smaller the difference from the value before the test, the better the plasticizer resistance of the color image.

5. Water resistance of the color-developed image The color-developed sheet colored by the method of 1 was immersed in water for 2 hours, and the change in density of the color-developed image was visually observed.

6. Yellowing of the color-developing sheet (6-1) on the basis of yellow by NO _X varying JIS L-1055 (nitrogen oxide gas fastness test method for dyeing and dye), NaNO ₂ the color-developing sheet
Save 1 hour in a closed container of the NO _X gas atmosphere generated by the reaction between (sodium nitrite) and H ₃ PO ₄ (phosphoric acid), to examine the extent of yellowing.

At the end of the first hour after storage, the data is displayed as a WB value using a Σ-80 color difference meter. WB value is large and means that there is less yellowing in about NO _X atmosphere a small difference between the WB value of untested sheet. (6-2) Yellowing due to light The developed sheet is irradiated to a carbon arc fade meter (manufactured by Suga Test Instruments) for 4 hours, and after the test, is indicated by 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 due to light irradiation.

Example 1 [First-stage reaction (I)] 13.8 g of salicylic acid (0.1
Mol), 0.2 g of anhydrous zinc chloride and 30 ml of 1,2-dichloroethane were charged into a glass reactor, and the temperature was increased while passing nitrogen gas to keep the temperature at 70 to 80 ° C.

Next, 49.2 g (0.35 mol) of α-methylbenzyl chloride was dropped from the dropping funnel into this reactor over 5 hours. After the completion of dropping, 3
After the aging, the reaction of the first stage (I) was completed. The reaction solution was concentrated in vacuo to give 49.6 g of a pale yellow transparent resin.
I got The weight average molecular weight of this resin was 660.
Next, 20 g (corresponding to 0.04 mol of salicylic acid) of the resin obtained in the first-stage reaction (I) is melted in the range of 140 to 150 ° C., and the mixture having a weight average molecular weight of 5,000 and a softening point of 95 ° C. is stirred with stirring. 30 g of polystyrene was added and melt-mixed.

[Second Stage Reaction] 6.7 g of zinc benzoate and 4 parts of ammonium bicarbonate were added to this molten mixture in advance.
g was gradually added in 30 minutes. Thereafter, stirring was continued at the same temperature for 30 minutes to complete the second-stage reaction. Immediately after discharging and cooling, 55 g of a hard and brittle reddish brown transparent resin was obtained. The softening point of this resin was 91 ° C.

[Use as a color developer] Using a subchloride of a salicylic acid resin containing the above polymer resin component as a color developer,
A suspension was prepared by dispersing with a sand grinding mill according to the following composition.

Developer 6 parts by weight 10% aqueous solution of polyvinyl alcohol (Kuraray # 117) 3 parts by weight Water 22.5 parts by weight Next, a coating material having the following composition was prepared using the suspension.

Suspension 10 parts by weight Light calcium carbonate 10 parts by weight Starch 0.8 parts by weight Synthetic rubber latex 0.8 parts by weight Water 32.5 parts by weight These paints were applied to a high quality paper at a dry coating amount of 5.0. ~ 5.5
g / m ² and dried to obtain a color developing sheet.

Example 2 440 g of a 10% by weight aqueous sodium hydroxide solution (1.
1 mol), and 126.0 g (1 mol) of benzyl chloride was added dropwise over 4 hours while stirring at a temperature of 50 ° C. Thereafter, the temperature was raised and the reaction was carried out at a temperature of 100 ° C. for 7 hours. After the completion of the reaction, the mixture was allowed to cool and left to separate into two layers.
The lower aqueous layer was removed to obtain an upper organic layer. Yield 105
g and composition by gas chromatography were as follows.

Benzyl alcohol 61.2% by weight Dibenzyl ether 36.3% by weight Others 2.5% by weight This benzyl compound was used in this example.

[First-stage reaction (I)] In a reaction vessel, 27.6 g (0.2 mol) of salicylic acid, the above-mentioned benzyl compound 1
05 g and zinc chloride 0.8 as a catalyst were charged, and the temperature was raised while passing nitrogen gas. Distillation of water began at 120 ° C., and the temperature was raised to 150 ° C. while distilling the distilled water out of the system. The reaction was carried out at the same temperature for 7 hours to complete the co-condensation reaction. After finishing, drain immediately.
5 g of resin were obtained. The weight average molecular weight of this co-condensation resin was 890.

Next, 38.3 g of polystyrene having a weight average molecular weight of 5,000 was added to the resin, and the mixture was melted by heating.

[Second-stage reaction] Using 8.1 g (0.1 mol) of zinc oxide with respect to the molten mixed resin, the reaction was carried out in the same manner as in the second-stage reaction of Example 1 to obtain a hard and brittle softening point. 9
158 g of a resin composition containing a zincated salicylic acid resin at 4.5 ° C. as a main component was obtained.

[Use as a developer] A developer sheet was obtained in the same manner as in Example 1 except that the above resin composition was used as a developer.

Example 3 [First-Step Reaction (I)] 13.8 g of salicylic acid (0.1
Mol), 0.2 g of anhydrous zinc chloride and 50 ml of 1,2-dichloroethane were charged into a glass reactor, and the temperature was raised with stirring to maintain the temperature in the range of 70 to 80 ° C. Then, 28.1 g of α-methylbenzyl chloride was added from the dropping funnel.
(0.2 mol) was added dropwise over 3 hours, followed by aging for 2 hours in the same temperature range to complete the reaction of the first stage (I).

[First-stage reaction (II)] The reaction solution obtained in the first-stage reaction (I) was cooled and kept at 0 to 5 ° C. 3.5 g of 96% sulfuric acid was added to this solution, and 20.8 g (0.2 mol) of styrene was added to 5
It was allowed to drip over time. Thereafter, aging was performed for 1 hour in the same temperature range to complete the first-stage reaction (II).

Next, 50 ml of water was added to the reaction solution, and the mixture was neutralized to pH 6 with aqueous ammonia. Thereafter, the mixture was allowed to stand to obtain a lower organic layer, and 1,2-dichloroethane as a solvent was recovered under reduced pressure while heating and raising the temperature. The weight average molecular weight of the obtained resin was 650.

Then, 37 g of polystyrene having a weight average molecular weight of 5,000 and a softening point of 95 ° C. was heated and melt-mixed in a range of 140 to 150 ° C. to 55 g of the salicylic acid resin.

[Second Stage Reaction] 4.1 g of zinc oxide was added to 92 g of the melt-mixed resin composition, and the mixture was added under a nitrogen stream.
The mixture was melted and mixed at a temperature of 140 to 145 ° C. for 1 hour to carry out a second-stage reaction. During the reaction, the cloudy state changed to a transparent state. Immediately after the reaction was completed, the mixture was discharged and cooled to obtain a hard, brittle, pale yellow, transparent resin. The yield was quantitative and the softening point of the resin was 94 ° C.

[Use as a color developer] A color developer sheet was obtained in the same manner as in Example 1 using the above composition as a color developer.

Example 4 0.8 g of p-toluenesulfonic acid was added to 10.8 g (0.1 mol) of benzyl alcohol, and the temperature was raised to 1
The reaction was carried out for 2 hours while removing water generated in a temperature range of 30 to 150 ° C outside the system.

Next, 35.4 g (0.3 mol) of α-methylstyrene was added dropwise to the reaction solution, and the mixture was aged to obtain a viscous resin. This was used as Resin B by mixing with a zincated salicylic acid resin obtained by the following method.

[First Step Reaction (I)] Salicylic acid
8 g (0.1 mol), anhydrous zinc chloride 0.2 g and 1,2
-Dichloroethane (30 ml) was charged into a glass reactor, and the temperature was maintained at 70 to 80 ° C while passing nitrogen gas through.

Next, 46.4 g of p-methyl-α-methylbenzyl chloride was added to the reactor from the dropping funnel.
3 mol) was added dropwise over 5 hours. After completion of the dropwise addition, aging was performed for 3 hours in the same temperature range to complete the first-stage reaction (I). The reaction solution was concentrated in vacuo to obtain a pale yellow transparent resin.

[Second Step Reaction] Next, the first step (I)
Was dispersed in 4.3 g of caustic soda and 500 g of water and heated to a temperature of 70 ° C. to dissolve the resin.

Next, the temperature of this solution was cooled to 30 ° C., and 15.8 g of zinc sulfate heptahydrate was previously added with stirring.
(0.055 mol) in 50 g of water
Dropped in minutes.

A white precipitate was deposited. The mixture was stirred at the same temperature for 2 hours, filtered, washed with water and dried to obtain 51.5 g of a white powder. The zincated salicylic acid resin was melt-mixed with the resin B prepared above under heating to obtain a color developer.

[Use as a color developer] A color developer sheet was obtained in the same manner as in Example 1, except that the zincated salicylic acid resin containing the polycondensation resin component was used as a color developer.

Comparative Example 1 170 g of p-phenylphenol, 22.5 g of 80% paraformaldehyde, 2.0 g of p-toluenesulfonic acid
Then, 200 g of benzene and 200 g of benzene are charged into a glass reaction vessel, heated with stirring, and reacted at 70 to 80 ° C. for 2 hours while distilling off water produced by the reaction azeotropically with benzene. After the reaction, 320 g of a 10% aqueous sodium hydroxide solution was added, and benzene was distilled off by steam distillation. Next, the mixture was cooled and dilute sulfuric acid was added dropwise, and the precipitated p-phenylphenol formaldehyde polymer was collected by filtration, washed with water and dried to obtain 176 g of a white powder.

Using this p-phenylphenol formaldehyde polymer, a color developing sheet was obtained in the same manner as in Example 1.

Comparative Example 2 A color developing sheet was obtained in the same manner as in Example 1 except that zinc 3,5-di (α-methylbenzyl) salicylate was used.

Comparative Examples 3 and 4 20 g of the salicylic acid resin obtained in the reaction (I) of the first stage of Example 1 was dispersed in 1.76 g of caustic soda and 300 g of water and dissolved by heating. From this solution, a zinc salt of salicylic acid resin (resin A) was synthesized using zinc sulfate heptahydrate in the same manner as in the second stage reaction of Example 4. Yield 2
0.5 g.

The zinc salt of the salicylic acid resin was divided, and a part of the zinc salt was used as a developer as in Example 1 to obtain a color developing sheet (Comparative Example 3).

Of the remaining zinc salt of salicylic acid resin, 10
g was heated and melt-mixed with 30 g of polystyrene having a weight average molecular weight of 5,000 to obtain a color developer.

This developer was composed of 25/75 of resin A / resin B.
Is the weight ratio. Using this developer, a developer sheet was obtained in the same manner as in Example 1 (Comparative Example 4).

[0197]

[Table 1]

[0198]

[Table 2] * (): Difference between (WB value) of untested sheet and sheet (WB value) after test Prior to Examples of aqueous suspension of the present invention, various performance test methods are shown below.

A) Properties of Aqueous Suspension • Hue: A sheet (aqueous suspension coated sheet) obtained by applying the aqueous suspension to fine wood at a dry weight of 5 g / m ² using a Meyer bar was prepared. The sheets are superimposed and measured with a # 80 color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.), and displayed as WB values.

[0200] The larger the WB value, the whiter the aqueous suspension, and if the difference is about 1 point, it is possible to distinguish the superiority with the naked eye. Viscosity: After adjusting the solid content of the aqueous suspension obtained by atomization to 40% by weight, the value measured by a B-type viscometer is displayed (measurement conditions: 25 ° C., No. 1 rotor, 60 rpm, unit: cps). -High-temperature storage stability: 2 kg of the aqueous suspension was placed in a stainless steel beaker having an inner volume of 31 and stored at 40 ° C for 1 week while stirring at 100 rpm using a glass stirring blade (squid type, diameter 100 mm). The filterability before and after is compared with the filtration time (sec) of a 200-mesh sieve having a diameter of 7.5 cm.

In a dispersion having poor high-temperature storage stability, a color developer composition comprising a salicylic acid resin polyvalent metal material aggregates in an aqueous suspension, and the sieve filtration speed decreases as the particle size grows.

B) Properties of Aqueous Coating Solution Using the aqueous suspensions of Examples and Comparative Examples, an aqueous coating material (50% solids) for coating a pressure-sensitive copying paper blade having the following composition was prepared. The properties were measured. Ingredients by weight (solid content ratio) (a) Aqueous suspension 18 (as developer composition comprising salicylic acid resin polyvalent metallization in liquid) (b) Light calcium carbonate 100 (c) Styrene butadiene latex 6 ( d) Oxidized starch 6 (e) Sodium polyacrylate (pigment dispersant) 0.5 Viscosity: B-type viscometer (No. 3 rotor, 60 rpm)
Check for thickening with. Preferred viscosity is 300-100
0 cp. -Mechanical stability: Using the water-based paint having a solid content of 50%, the amount of agglomerates generated was measured using a Malon-type mechanical stability tester according to JIS K-8392 (test method for NBR synthetic latex). (Measurement conditions: sample amount 100
g, 1000 rpm, 10 min. Load: 20 kg), which is a measure of the mechanical stability of the water-based paint. After the test, the mixture is filtered through a 200-mesh sieve, and the amount of aggregates (after absolute drying) is weighed.
The indication is expressed in terms of the aggregate formation rate (%).

The water-based paint having a large value of the agglomerate generation rate by this test method may be used to break or agglomerate the dispersed state of the water-based paint during high-speed coating, such as blade coating or gate roll coating, in which a high shear force is applied. Coating troubles are likely to occur.

C) Performance as pressure-sensitive copying paper The water-based paint used for mechanical stability by malon described in the preceding section was applied to a high-quality paper with a Mayer bar so as to have a dry coating amount of 5 g / m ² and dried. Thus, a color developing sheet was prepared. Coloring speed and concentration (implemented in a thermo-hygrostat at 20 ° C. and 65% RH): a commercially available blue coloring paper mainly using crystal violet lactone (N-4 manufactured by Mitsubishi Paper Mills)
Using 0), the ink is combined with the above-described color developing sheet, and the color is applied with an electronic typewriter. 105 seconds after embossing and 2
The reflectivity of two points after 4 hours is measured by a # 80 color difference meter and is indicated by a Y value. Whiteness of the color developing sheet: Four of the above color developing sheets are superimposed, and the reflectance is measured with a # 80 color difference meter, and displayed as a WB value.

The whiteness (whiteness) of the color developing sheet can be determined by the naked eye if the difference is about 1 point. · NO _X by yellowing: same as method (6-1).

Example 5 2-acrylamido-2-methylpropanesulfonic acid N
25 g of a 20% aqueous solution of polyvinyl alcohol having an a unit of 5 mol% (average degree of polymerization 300, degree of saponification 90%) and water 8
5 g of the fine powder of the resin obtained in Example 1 was charged into an aqueous solution in which 5 g had been previously mixed and the pH was adjusted to 8.0, and the mixture was stirred and slurried. Treated for 2 hours to have an average particle size of 2.4
A .mu.m white aqueous suspension (50% solids by weight) was obtained.

Example 6 An ethylenesulfonic acid-vinyl acetate copolymer having an ethylenesulfonic acid content of 3 mol% was saponified with caustic soda.
Polyvinyl alcohol containing sulfonic acid groups equivalent to 3 mol% and acetyl groups 1 mol% (average degree of polymerization 30
0) was obtained.

25 g of a 20% aqueous solution of the polyvinyl alcohol having a sulfonic acid group and 85 g of water were previously mixed, and p
100 g of the resin fine powder obtained in Example 2 was charged into an aqueous solution in which H was adjusted to 8.4, and the mixture was stirred and slurried. Then, an attritor (manufactured by Mitsui Miike Seisakusho Co., Ltd .; Measure) under water cooling for 2 hours and white aqueous suspension having an average particle size of 2.1 μm (solid content: 45% by weight)
I got

Example 7 Sulfonated polyvinyl alcohol obtained by adding and reacting polyvinyl alcohol to 80% sulfuric acid (maintained at 0 ° C.) followed by neutralization and purification (to 5 mol% of all monomer units) 25 g of a 20% aqueous solution of the corresponding sulfone group and 10 mol% of acetyl group) and 85 g of water were previously mixed, heated to 90 ° C. in the aqueous solution, and 100 g of the resin fine powder obtained in Example 3 was charged. Mixer (Special Kiko Co., Ltd.)
), Cooled to room temperature, and cooled to a white aqueous suspension having an average particle diameter of 2.0 µm (solid content: 52%).
% By weight).

Example 8 15 g of a 20% aqueous solution of polyvinyl alcohol (average degree of polymerization: 250, saponification degree: 88%) having an ethylene sulfonic acid content of 5 mol% and polystyrene sulfonic acid sodium salt (Caron 330I, Lion Corporation) 33 4.5% aqueous solution
g was mixed in advance with 109 g of water, and 100 g of the fine resin powder obtained in Example 4 was charged into an aqueous solution whose pH was adjusted to 8.0, stirred, slurried, and then glass beads having a diameter of 1 mm were used. A white aqueous suspension (average particle size: 2.1 μm) treated with a sand grinder for 2 hours (solid content: 50% by weight)
I got

Example 9 Polystyrenesulfonic acid sodium salt (molecular weight: 1000
(0, degree of sulfonation 70%)
g in an aqueous solution adjusted to pH 8.0,
100 g of the resin fine powder obtained in Example 1 was charged, stirred and slurried, and then treated with glass beads having a diameter of 1 mm using a sand grinder for 2 hours to obtain an average particle diameter of 2.2 μm.
A white aqueous suspension (solid content 50% by weight) was obtained.

Example 10 25 g of a 20% aqueous solution of ammonium polystyrene sulfonate (Chemistat 6500, Sanyo Chemical Industries, Ltd.) was previously mixed with 85 g of water, and the mixture was obtained in Example 1 in an aqueous solution whose pH was adjusted to 8.0. 100 g of the obtained resin fine powder was charged, stirred and slurried, and then treated with a sand grinder using glass beads having a diameter of 1 mm for 2 hours to obtain an average particle diameter of 2.
A 4 μm white aqueous suspension (50% solids by weight) was obtained.

Example 11 15 g of a 20% aqueous solution of polyvinyl alcohol having an ethylene sulfonic acid content of 5 mol% (average degree of polymerization: 250, saponification degree: 88%) and sodium polystyrene sulfonate (OKS- 3376) 30% aqueous solution 5
g of water was previously mixed with 89 g of water, and 100 g of the resin fine powder obtained in Example 2 was charged into an aqueous solution whose pH was adjusted to 8.0, stirred, slurried, and then glass beads having a diameter of 1 mm were used. Closed sand grinder (Dynomill)
For 1.5 hours to obtain a white aqueous suspension having an average particle size of 2.1 μm (solid content: 50% by weight).

Example 12 A 30% aqueous solution of a 30% aqueous solution of a sodium salt of a sulfonated styrene-maleic acid copolymer (Arco, SMA-1000) and 93 g of water were mixed in advance, and the mixture was added to an aqueous solution whose pH was adjusted to 8.0. Then, 100 g of the resin fine powder obtained in Example 3 was charged, stirred and slurried, and treated with a sand grinder using glass beads having a diameter of 1 mm for 2 hours to obtain a white aqueous suspension having an average particle diameter of 2.5 μm. A turbid liquid (solid content 50% by weight) was obtained.

Comparative Example 5 Instead of polyvinyl alcohol having a sulfonic acid group,
The treatment was carried out in the same manner as in Example 5, except that the sodium salt of formaldehyde condensate of naphthalenesulfonic acid was used, but the dispersion was impossible at a solid content of 50%. After dilution with water, a white aqueous suspension having a solid content of 40% and an average particle size of 3.1 μm was obtained.

Comparative Example 6 Instead of polyvinyl alcohol having a sulfonic acid group,
Except for using partially saponified polyvinyl alcohol (manufactured by Kuraray, Poval 117), the treatment was carried out in the same manner as in Example 5. However, in several tens of minutes after the sand grinder treatment, dispersion was impossible due to vigorous foaming and thickening. Was. Diluted with water,
A white aqueous suspension having an average particle size of 2.8 μm was obtained with a solid content of 40%. Even after the treatment, it took a day and night until the bubbles disappeared, and the working efficiency was extremely poor.

Comparative Example 7 100 g of the fine resin powder obtained in Example 2 was mixed with ligninsulfonic acid sodium salt (ITT Leonia, Ozan CD).
Dispersed and slurried in 134 g of water in which 10 g was dissolved,
A brown aqueous suspension obtained by sand grinder treatment in the same manner as in Example 5 (average particle size: 2.5 μm, solid content: 45% by weight)
I got

Comparative Example 8 Instead of polyvinyl alcohol having a sulfonic acid group,
When the same amount of sodium polycarboxylate (Nippon Oil & Fats Co., Ltd., Polystar OM) was used and treated in the same manner as in Example 5, the dispersion was poor and the whole became a hard paste, and an aqueous suspension was obtained. Did not.

The aqueous suspensions obtained in the above Examples and Comparative Examples, the aqueous coating solution prepared by the above method using this aqueous suspension, and the pressure-sensitive copying paper obtained by applying the aqueous coating solution Table 3 and Table 4 show the results of the evaluation of the above-mentioned test methods.

[0220]

[Table 3]

[0221]

[Table 4] As is clear from Tables 3 and 4, according to the present invention, when an aqueous suspension of the developer composition is obtained, by using the anionic aqueous polymer of the present invention as a dispersant, It has become possible to produce aqueous suspensions of developer compositions having excellent characteristics. Less coloring. It is extremely stably dispersed and has little aggregation and precipitates even after long-term storage at high temperatures. Less thickening and foaming during aqueous suspension work. Coatings for the production of pressure-sensitive copying paper have excellent thermal and mechanical stability. The dispersant itself discolors to yellow upon exposure to light or during storage, and provides an excellent pressure-sensitive paper without lowering the quality.

As described above, according to the present invention, there is provided an aqueous suspension having good dispersibility, storage stability, coating stability and the like, and which can be used very conveniently in the production of pressure-sensitive copying paper. It became possible.

Furthermore, by using the aqueous suspension of the present invention, the color image stability (light, water, solvent, writing implement, plasticizer, etc.) is excellent, and the coloration of paper surface, light yellowing, etc. It has become possible to produce high-quality pressure-sensitive copying paper that does not sometimes change.

[Brief description of the drawings]

FIG. 1 is a diagram showing a structure of a pressure-sensitive copying paper.

[Explanation of symbols]

 1 Upper paper 2 Medium paper 3 Lower paper 4 Microcapsule 5 Developer 6 Pen pressure

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd. (56) References JP-A-2-653 (JP, A) JP-A-49 -55410 (JP, A) JP-A-2-194990 (JP, A) JP-A-64-56724 (JP, A) JP-A-63-289017 (JP, A) JP-A-64-77575 (JP, A) JP-A-63-132857 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/155

Claims (3)

(57) [Claims] 1. A compound of the general formula (I), (II) or (III)(Wherein, Z represents M / m, and M is an m-valent metal ion.
Where m is an integer. R ₁ , R_Two Is a hydrogen atom or carbon
1 to 12 alkyl groups, aralkyl groups, aryl groups
Or a cycloalkyl group;_Three , R₆ Is a hydrogen atom
Or an alkyl group having 1 to 4 carbon atoms, R_Four , R_Five Is a hydrogen atom
Or a methyl group. )
The structural unit (I) is 5 to 35 mol%, and the structural unit (II)
Is at least 65 to 95 mol% or 1 of the structural unit (II)
Those in which one or more of the structural units (II) are combined with 65 to 65
95 mol% and a weight average molecular weight of 35
Polyvalent metal salt of salicylic acid resin having a molecular weight of 0 to 5,000 (tree
A) and the structural unit (II) and / or the structural unit (II
I) and having a weight average molecular weight of 350 to 5,000
And a resin A and a resin
Developer composition wherein the weight ratio of B is 90-30: 10-70
object. 2. A color developing sheet for pressure-sensitive copying paper, comprising the color developing agent composition layer according to claim 1. (3) a polyvinyl alcohol derivative having a sulfonic acid group in the molecule and a salt thereof, and (b) a general formula (I)
Styrene sulfonate represented by V) (Wherein, R ₇ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, M is Na ⁺ , K ⁺ , Cs ⁺ , Fr ⁺ , or NH ₄ ⁺
A) a developer composition comprising a polyvalent metal salt of a salicylic acid resin in the presence of one or more compounds selected from the group of anionic water-soluble polymers consisting of a polymer or a copolymer having an essential component The aqueous suspension of the developer composition according to claim 1, which is wet-milled.