KR930002205B1 - Salicylic acid copolymers and their metal salts, production process thereof, color developing agents and sheets - Google Patents

Abstract

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Description

Salicylic acid copolymer and metal salts thereof, preparation method thereof, color developing agent of metal salt of the copolymer and color developing sheet using the color developing agent

1 is an illustration of a pressure sensitive sheet of radiation paper.

* Explanation of symbols for main parts of the drawings

1: CB sheet 2: CF / CB sheet

3: CF sheet 4: microcapsules

5: colorant 6: pen

The present invention relates to a novel salicylic acid resin, a metal salt thereof, and a coloring sheet containing a metal salt as an active ingredient and suitable for use in pressure sensitive radiation papers, as well as a colorant using a colorant used for pressure sensitive radiation papers.

Pressure sensitive copy paper sheets are also referred to as carbon free copy paper sheets. They can be colored by mechanical or impact pressure, for example by writing strokes or typewriter notation, and thus can be copied in multiple sheets at the same time. Among such pressure sensitive copy papers, there are ones called "transfer copy papers" and "own copy papers". Their coloration mechanism is based on the colorimetric reaction between the colorless dye precursor that gives the electron and the colorant that attracts the electron. Taking a transfer type pressure sensitive copy paper as an example, a description will be given with reference to FIG. 1-1, which is a schematic cross-sectional view showing the structure of the pressure sensitive copy paper.

The back of the CB sheet (1) and CF / CB sheet (2) has a diameter of several μm, which is somewhat larger than 10 μm, and the solution obtained after dissolving a colorless pressure sensitive precursor precursor in a nonvolatile oil is encapsulated in a polymer membrane such as gelatin membrane. It is apply | coated with the microcapsule 4 obtained by putting in. On the other hand, the front of the F / CB sheet 2 and the CF sheet 3 is in contact with the pressure sensitive dye precursor so that the colorant 5 reacts with the dye precursor, whereby the dye precursor makes its color. It is applied with a coating agent containing a coloring agent having the property of 5. To make a copy, they are coated with a dye precursor which is brought into contact with the application side of the coloring agent, (CB sheet, (CF / CB sheet), ( CF / CB sheet) and CF sheet in the order CF / CB sheet is optional When the pressure is locally applied by a ballpoint pen 6 or typewriter, the capsule 4 bursts there. A solution containing sensitive dye precursors is transferred to the color developer to obtain one or more duplicated records.

As a color developing agent for attracting electrons, (l) U.S. Patent Nos. 2,712 and 507 include inorganic solid acids such as acidic clay and attapulgite; (2) Japanese Patent Publication No. 9309/1965 describes substituted phenols and diphenols: (3) Japanese Patent Publication No. 20l44 / 1967 describes p-substituted phenol-formaldehyde polymers: (4) Japanese Patent Publication Nos. 1 056 / l974 and 1327 / l977 propose metal salts of aromatic carboxylic acids and the like. Some of them are already in use.

As a performance condition of the coloring sheet which is considered satisfactory, it has excellent color developing ability not only immediately after its manufacture but also after long time storage, and it is almost yellowed during exposure and storage such as sunlight and radiation, It is also possible to mention good color fixing which is not easily erased or desired by water or plasticizers.

The colorants proposed in recent years and sheets coated with such conventional colorants have both benefits and losses. For example, inorganic solid acids are aging but adsorb atmospheric gases and moisture during storage. Thus they yellow the ground and result in a decrease in color performance. Substituted phenols have insufficient coloration ability, and the colored color traces have low color work. Para-phenylphenol-novolak resins commonly used as p-substituted phenol-formaldehyde polymers have excellent color development, but the paper coated thereon is yellowed and the color-coded color indicators are exposed to sunlight or during storage (especially Seriously fading due to nitric oxide in the atmosphere. Moreover, metal salts of aromatic carboxylic acids are excellent in yellowing resistance but still insufficient in color development at low temperatures, resistance to water or plasticizers and light resistance.

A first object of the present invention is to provide a novel copolymer capable of forming a polyvalent metal salt excellent as a color developing agent for pressure sensitive radiation paper having excellent properties in flexibility, oxidation resistance, moldability and the like.

A second object of the present invention is to provide an excellent color developing agent for pressure sensitive radiation paper, which is a metal modified product composed of a molten mixture containing the polyvalent metal salt of the copolymer or the polyvalent metal salt of the copolymer.

It is a third object of the present invention to provide excellent pressure sensitive radiation paper using the above coloring agent.

Therefore, it consists of 5 to 35 mol% of the structural unit (I) of the present invention, 10 to 85 mol% of the structural unit (II) and 4 to 85 mol% of the structural unit (IlI). Copolymer having a weight average molecular weight, [each of the structural unit (I) is defective with the one benzene ring of the structural unit (II) via the α-carbon of one of the structural unit (II), the structure Optionally bonded to a benzene ring or another ring or other structural unit (II) via one or more of its α-carbons or α-carbons of unit (II), wherein at least one of the structural units (III) via α-carbons to one or more rings of the benzene ring or structural unit (II) and / or to the rings of the other structural unit (III), wherein the structural units (I), (II) and (1II) It is represented by (I), (II), and (lII), respectively.

Formula (I):

Formula (II):

General formula (III):

Wherein R₁, R₂ independently represent a hydrogen atom or a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group, R₃ means a hydrogen atom or a C _1-4 alkyl group, R₄ is a hydrogen atom or a methyl group, R One of ₅ and R ₆ is a hydrogen atom, the other is hydrogen or a C _1-4 alkyl group and R ₇ is a methyl or ethyl group]: or a polyvalent metal salt of the copolymer, wherein at least one polyvalent metal atom is Forming the polyvalent metal salt between the carboxyl groups in the same molecule of the copolymer or between the carboxyl groups of other molecules of the copolymer) and: in the form of a melt mixture containing the polyvalent metal salt, as is or suitable for pressure sensitive radiation paper As well as colorants containing polyvalent metal salts; It is suitable for pressure sensitive radiation paper to provide a color sheet containing a colorant distributed almost uniformly on one or more sides thereof.

Copolymers and their polyvalent metal salts, which fall within the scope of the present invention, are novel polymeric compounds and salts that have not been prepared in recent years. Therefore, the color developing agent of the present invention is also a novel color developing agent.

The coloring sheet using the novel coloring agent of the present invention has comparable or better coloring properties compared to the coloring sheet using inorganic solid acid or p-phenylphenol novolak resin. Compared with the coloring sheet using the metal salt of aromatic carboxylic acid, the coloring sheet using the novel coloring agent of the present invention has better coloring properties at low temperatures. In addition, the color traces rendered by the colorant sheets using the novel colorants of the present invention have high resistance that is not easily faded by water, plasticizers or light rays.

The yellowing tendency following exposure to sunlight of the present invention, in particular, yellowing resistance to nitrogen oxides in the air has been greatly improved, and the coloring sheet which is extremely advantageous for use and storage can also be provided at low cost.

The salicylic acid resin (copolymer) of the present invention is a novel resin that has never been produced in recent years. That is, the resins of the present invention are structural units represented by the general formula (I) by reacting a cocondensation resin obtained by reacting salicylic acid with benzyl alcohol and / or benzyl ether in the presence of an acidic catalyst with a styrene derivative in the presence of an acidic catalyst. ˜35 mol%, containing 10 to 85 mol% of structural units represented by formula (II), and 4 to 85 mol% of structural units represented by formula (III), and having a weight average molecular weight of 500 to 10,000 Salicylic acid resins (each of formula (I) is bonded to the benzene ring of the above of the structural unit (II) via α-carbon of one of the general formula (II), and at least one of the structural unit (II) -Via carbon or its α-carbon to a benzene ring or other rings or the remaining structural units (II), each of which is via one of its α-carbons one of the structural units (II) Benzyl ring).

Hereinafter, the manufacturing method of the salicylic acid resin will be described in detail.

The salicylic acid resin of the present invention, as the first step reaction, benzyl alcohol and / or benzyl ether represented by the following formula (IV) with salicylic acid in the presence of an acidic catalyst

Wherein R₁ and R₂ are the same or different and independently represent a hydrogen atom or a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group, R₃ is a hydrogen atom or a C _1-4 alkyl group, R ₉ is a hydrogen atom, C _1-4 alkyl group or

Co-condensation resin obtained by the reaction of

It is obtained by reacting with the styrene derivative represented by (wherein R 'and R ₈ independently mean a hydrogen atom or a methyl group, and R ₆ is a hydrogen atom or a C _1-4 alkyl group).

First, the first stage reaction will be described.

(A) -1. Condensation of Salicylic Acid with Benzyl Alcohol:

The condensation of benzyl alcohol which is a hydrogen atom of R ₉ in the formula (IV) will be described.

Conventionally, various alcohols and salicylic acid are reacted and alkylated to obtain alkyl-substituted salicylic acid, and various methods are known.

For example, reacting isobutanol and salicylic acid to obtain t-butyl salicylic acid ["Kimchi Kazu (Experimental Chemistry Handbook)", 18, 30 (1958), Maruzen Publishing Co., Ltd.], 5- [α- Reaction of 2 mol of phenylethanol and 1 mol of salicylic acid to obtain methyl-4 '-(α-methylbenzyl) -benzyl] -salicylic acid (Japanese Patent Laid-Open Nos. 100493/1986 and 96449/1987) Belongs to:

These conventional methods relate to the preparation of substituted salicylic acid compounds. As in the present invention, a method of preparing a co-condensation resin of salicylic acid using alcohol has not been known. In the method of the present invention, benzyl alcohol is present in excess in order to obtain a novel cocondensation resin of benzyl alcohol and salicylic acid.

That is, the present inventors believe that when benzyl alcohol is present at 1.5 mol or more per mole of salicylic acid and reacts with salicylic acid in a molten state at a reaction temperature of 80 ° C. or higher by an acid catalyst, both positions of the ortho position and / or the para position with respect to the hydroxyl group of salicylic acid are It has been found that more than one benzyl group can be introduced at one of these positions, and that excess benzyl alcohol can produce a resin material by causing continuous condensation with the benzyl group introduced into salicylic acid while undergoing simultaneous self-condensation. .

When the salicylic acid composition obtained as such a resin is modified with a metal and used as a color developing agent, excellent mixing property with oil in the microcapsules on CB-sheet is exhibited, and the coloration speed is greatly improved at low temperatures compared with conventional products. Due to the lack of water solubility, the waterproofness of the manufactured color display is very good.

In such a useful salicylic acid resin and a method for producing a metal modification thereof, various starting benzyl alcohols are those in which R ₉ represents H in general formula (IV).

Although a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms is bonded at the α-position of the benzyl group, a hydrogen atom or a methyl group is preferable. The nucleus of the benzyl group is unsubstituted or substituted in the o-, m- and / or p-positions with at least one C _1-12 alkyl, aralkyl, aryl or cycloalkyl group.

Benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, o-ethylbenzyl are various benzyl alcohols used in the practice of the present invention for providing the co-condensation resin in the first stage reaction. Alcohol, m-ethylbenzyl alcohol, p-ethyl benzyl alcohol, o-isopropyl benzyl alcohol, p-n-propyl benzyl alcohol, p-tert-butyl benzyl alcohol, p-nonyl benzyl alcohol, o-phenyl benzyl 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-dimethyl Benzyl 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-ethyl Vaginal 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-phenyl-α-methylbenzyl alcohol, p (α-methylbenzyl) -α -Methyl benzyl alcohol, p-(α, α-dimethyl benzyl)-α-methyl benzyl alcohol, 2, 3-dimethyl-α-methyl benzyl alcohol, 2, 4-dimethyl-α-methyl benzyl alcohol, 2, 5- Dimethyl-alpha-methyl benzyl alcohol, 3, 4- dimethyl-alpha-methyl benzyl alcohol, 2-methyl- 5-tert- butyl- alpha-methyl benzyl alcohol, etc. can be mentioned.

However, the method of the present invention is not necessarily limited to the use of the specific benzyl alcohols. Preferred benzyl alcohols include benzyl alcohol, p-methylbenzyl alcohol, α-methylbenzyl alcohol, p-methyl-α-methylbenzyl alcohol and the like.

In the first stage reaction according to the present invention, benzyl alcohol may use 1 to 10 moles per mole of salicylic acid.

The reaction temperature is at least 80 ° C or higher, and the reaction rate is very slow at temperatures lower than 80 ° C. The temperature range of 100-240 degreeC is preferable in order to reduce reaction time as much as possible. The reaction time can be 1 to 20 hours.

Examples of acid catalysts include organic acids such as inorganic acids and organic acids, particularly inorganic acids such as Friedel-Crafts catalysts such as hydrochloric acid, phosphoric acid and sulfuric acid, formic acid, zinc chloride, tin tin chloride and ferric chloride, methanesulfonic acid, and p-toluene sulfonic acid. Sulfonic acid can be used alone or in combination. The catalyst may be used in an amount of about 0.01 to 20% by weight, preferably 0.5 to 5% by weight, based on the total amount of salicylic acid and benzyl alcohol.

As a conventional method for preparing a resin used in the first step of the present invention, salicylic acid, benzyl alcohol and a catalyst are simultaneously added in predetermined amounts, and then heated to proceed with the reaction at a predetermined temperature, or a part of benzyl alcohol is reacted during the reaction. The reaction proceeds while being added dropwise. The water formed as a result of the reaction is extracted out of the reaction system with nitrogen gas.

After completion of the reaction, the contents are taken out and cooled to obtain the intended product. When benzyl alcohol is used in a small molar ratio for the purpose of obtaining a resin having a relatively low molecular weight composition, unreacted salicylic acid remains. As a method of removing the remaining salicylic acid, for example, the resin is washed with hot water as it is, or after dissolving the resin in an organic solvent such as methyl isobutyl ketone or cyclohexanone and washing with hot water.

(A) -2. Condensation of salicylic acid with benzyl ether:

Benzyl ether is other than those in which R ₉ is a hydrogen atom in general formula (lV).

Benzyl ether can introduce a benzyl group into an aromatic compound. For example, in the case of benzyl propyl ether, it is known to introduce the benzyl group into benzene, naphthalene, phenol, etc. ["Kimji Kagaku (Experimental Handbook)", 18, 30 (1985), Maruzen Publishing Co., Ltd.) . These reactions use very strong acidic catalysts such as boron fluoride and also select compounds which are relatively prone to nucleophilic substitution.

However, no method of reacting salicylic acid and benzyl ether as in the present invention is known. This reaction has not yet been contemplated because of the difficulty in introducing benzyl or substituted benzyl groups by reacting benzyl ether with a compound that is somewhat resistant to nucleophilic substitution resulting from the inclusion of carboxylic acids such as salicylic acid.

In the production of the resin of the above invention, alcohol is formed through a de-alcohol reaction. One of the reactants, salicylic acid, can be expected to produce a mixture of salicylic acid esters and their resins through reaction with alcohols formed in the presence of an acid catalyst, which will confront many difficulties in obtaining the intended product.

The present inventors have overcome this difficult situation by reacting various benzyl ethers with salicylic acid at a reaction temperature of 80 ° C. or higher in the presence of an acidic catalyst without inducing substantial aspects of reactions such as the corresponding esterification reaction and ortho to salicylic acid and hydroxyl groups. It has been surprisingly found that various benzyl groups can be introduced into the position and / or para position. It was also found that when an excess amount of benzyl ether is used, an excess of benzyl ether causes a condensation reaction with the benzyl group introduced into salicylic acid while undergoing a simultaneous self-condensation reaction to form a resin material.

In order to explain in more detail the condensation with benzyl ether mentioned above, it divides into four cases.

(a) Benzylalkyl ethers:

These benzyl alkyl ethers are represented by the general formula (IV), wherein R ₃ represents a hydrogen atom and R ₉ represents a C _1-4 alkyl group. [However, p-methylbenzyl alkyl ethers are described in the following section (b). will be]. As long as R ₉ contains 4 or less carbon atoms and the reaction is carried out at the temperature described below, the reaction is rapid and no esterification occurs, thereby facilitating the supply of a good resin. When R ₉ contains four carbon atoms, that is, when R ₉ is a butyl group, the t-butyl group tends to cause a slow reaction rate.

As a representative example of the benzyl alkyl ether used in the first stage reaction of the present invention which provides the cocondensation resin, benzyl methyl ether, benzyl ethyl ether, benzyl isopropyl ether, benzyl n-butyl ether, o-methylbenzyl ether, o- Methyl benzyl ethyl ether, o-methyl benzyl isobutyl ether, m-methibenzyl methyl ether, m-methyl benzyl ethyl ether, m-methyl benzyl isopropyl ether, o-methyl benzyl methyl ether, o-ethyl benzyl ethyl ether, o Ethyl benzyl isopropyl ether, p-ethyl benzyl methyl ether, p-ethyl benzyl ethyl ether, p-ethyl benzyl isopropyl ether, p-ethyl benzyl n-butyl ether, o-isopropyl benzyl ethyl ether, p-isopropyl Benzylethyl ether, p-n-propylbenzylethyl ether, p-tert-butylbenzylethyl ether, p-tert-butylbenzylisopropylether, p-tert-octylbenzylethyl ether, p-dodecylbenzylmethyl ether, p Phenylbenzylmethyl ether, o-phenylbenzylisopropyl ether, p-cyclohexyl benzyl ether, p-(α-methylbenzyl) benzyl methyl ether, p-(α-methylbenzyl) benzyl ethyl ether, p-(α, α-dimethylbenzyl) benzyl Methyl ether, 2,3-dimethylbenzylmethylether, 2,4-dimethylbenzylmethylether, 2,5-dimethylbenzylmethylether, 2,6-dimethylbenzylmethylether, 3,4-dimethylbenzylether, 3, 5 Dimethylbenzylmethyl ether, 2,4-diethylbenzylmethylether, 3,4-dimethylbenzylethylether, 3,5-dimethylbenzylmethylether, 2,4-diethylbenzylmethylether, 2,3-dimethylbenzyl Isopropyl ether, 2,4-dimethylbenzyl n-propylether, 3,4-dimethylbenzyl n-butylether, 2,4-dimethylbenzyl sec-butylether, 3,5-dimethylbenzyl n-amylether, 2, 4-diethylbenzylmethyl ether, 3, 5-diethylbenzylisopropyl ether; 2,3-diethylbenzyl n-butylether, 2,4-diisopropylbenzylmethylether, 3,5-diisopropylbenzylethylether, 3-methyl-4-ethylbenzylmethylether, 3-methyl-5 -tert- butylbenzyl methyl ether, 2-methyl- 4-((alpha)-methyl benzyl) benzyl methyl ether, etc. can be mentioned. However, the present invention is not necessarily limited to using the benzyl alkyl ethers exemplified above.

(b) p-methylbenzylalkyl ethers:

Representative p-methylbenzylalkyl ethers are preferably p-methylbenzylmethyl ether, p-methylbenzylethyl ether, p-methylbenzyl n-propylether, p-methylbenzylisopropyl ether, p-methylbenzyl n -Butyl ether, p-methylbenzyl sec-butyl ether, p-methylbenzyl isobutyl ether, etc. can be mentioned.

(c) α-alkylbenzylalkyl ethers:

These α-alkylbenzylalkyl ethers are represented by general formula (IV), wherein R ₃ and R ₉ independently represent a C _1-4 alkyl group.

As long as the carbon number of the o-bonded alkyl group in various α-alkylbenzylalkyl ethers is 4 or less and the reaction is carried out at the temperature described below, the reaction proceeds at a high speed and no esterification occurs, so that a good resin is obtained. . When the o-bonded alkyl group contains four carbon atoms, i.e., if the o-bonded alkyl group is a butyl group, the tert-butyl group tends to cause a slow reaction rate.

On the other hand, the alkyl group bonded to the α-position of the benzyl group is a C _1-4 alkyl group, and from an industrial point of view, a methyl group or an ethyl group is preferable.

Representative examples of α-alkylbenzylalkyl ethers used in the practice of the present invention for providing co-condensation resins include α-methylbenzylmethyl ether, α-methylbenzylethyl ether, α-methylbenzylisopropyl ether, and α-methylbenzyl n -Propyl ether, α-methylbenzyl n-butyl ether, α-ethylbenzylmethyl ether, α-ethylbenzylethyl ether, α-ethylbenzyl isopropyl ether, α-ethylbenzyl n-butyl ether, α-n-propylbenzylmethyl Ether, α-isopropylbenzylethyl ether, α-n-butylbenzylisopropyl ether, o-methyl-α-methylbenzylmethylether, p-methyl-α-methylbenzylmethylether, m-methyl-α-methylbenzyl Methyl ether, p-methyl-α-methylbenzylethylether, p-methyl-α-methylbenzylisopropylether, p-methyl-α-methylbenzyl n-propylether, p-methyl-α-methylbenzyl n-butyl Ether, p-methyl-α-ethylbenzylmethylether, p-methyl-α-ethylbenzylethylether, p-methyl- α-ethylbenzylisopropyl ether, p-methyl-α-ethylbenzyl n-butyl ether, o-methyl-α-ethylbenzylmethyl ether, o-methyl-α-ethylbenzylisopropyl ether, m-methyl-α- Ethylbenzylmethylether, p-ethyl-α-methylbenzylmethylether, O-ethyl-α-benzylether-m-ethyl-α-propylbenzylmethylether, p-isopropyl-α-methylbenzylmethylether, o- Isopropyl-α-methylbenzylmethylether, p-sec-butyl-α-methylbenzylmethylether, p-tert-butyl-α-methylbenzylmethylether, p-nonyl-α-methylbenzylmethylether, p-dode Sil-α-methylbenzylmethylether, p-phenyl-α-methylbenzylmethylether, o-phenylbenzyl-α-ethylbenzylmethylether, p-cyclohexyl-α-methylbenzylmethylether, p- (α-methyl Benzyl) -α-methylbenzylmethylether, p- (α, α-dimethylbenzyl) -α-methylbenzylmethylether, 2, 3-dimethyl-α-methylbenzylmethylether, 2, 4-dimethyl-α-methyl Benzilme Butyl ether, 2, 5-dimethyl-α-methylbenzylmethylether, 2,6-dimethyl-α-methylbenzylmethylether, 3,4-dimethyl-α-methylbenzylmethylether, 3, b-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-butylether, 3,4-dimethyl-α-methylbenzyl Sec-butylether, 2,3-dimethyl-α-ethylbenzylmethylether, 2,4-dimethyl-α-ethylbenzyl Methyl ether, 2,5-dimethyl-α-ethylbenzylethylether, 2,6-dimethyl-α-ethylbenzyl n-propylether, 3,4-dimethyl-α-ethylbenzylisopropylether, 3, 5-dimethyl -α-ethylbenzyl-n-butylether, 2,4-dimethyl-α-propylbenzylmethylether, 2,4-diethyl-α-methylbenzylmethylether, 2,6-diethyl-α'-methylbenzyl Methyl ether, 3,4-diethylbenzyl-α-ethylbenzylmethyl Ether, 3,5-diethylbenzyl-α-propylbenzylisopropylether, 2,4-diisopropyl-α-methylbenzylmethylether, 2,4-diisopropyl-α-ethylbenzylmethylether, 2, 6-diisopropyl-α-propylbenzylmethylether, 3,5-diisopropyl-α-butylbenzylmethylether, 2-methyl-4-ethyl-α-methylbenzylmethylether, 2-methyl-4-tert -Butyl-alpha-methylbenzyl methyl ether, 2-methyl-4-(alpha -methylbenzyl)-alpha-methylbenzyl methyl ether, 2-methyl-4-(alpha, alpha-dimethylbenzyl)-alpha-methylbenzylmethyl Ethers and the like. However, the present invention is not necessarily limited to the use of the specific α-alkylbenzylalkyl ethers.

(d) dibenzyl ethers:

These dibenzyl ethers are represented by general formula (IV), wherein R ₉ is Indicates. This substituent bonded to the α-position of the benzyl group is a hydrogen atom or a lower alkyl group of C _1-4 . Among these, a hydrogen atom or an ethyl group is preferable.

Various dibenzyl ethers which can provide cocondensation resins according to the present invention 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 (pn-propylbenzyl) ether, di ( p-tert-butyl benzyl) 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-di Ethylbenzyl) ether, di (3-methyl-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-n-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, di (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. However, the present invention is not necessarily limited to the use of the specific dibenzyl ethers.

Among these representative dibenzyl ethers, dibenzyl ether, di (p-methylbenzyl) ether, di (?-Methylbenzyl) ether, di (p-methyl-? '-Methylbenzyl) ether and the like are preferable. In the first stage of reaction, dibenzyl ether is used at 0.5 to 5 moles per mole of sillylic acid.

When dibenzyl ether is used in a small molar ratio for the purpose of obtaining a resin having a relatively low molecular weight composition, unreacted salicylic acid remains. As a method of removing the remaining salicylic acid, for example, the resin is washed with hot water as it is or dissolved in benzene, toluene, monochlorobenzene, methyl isobutyl ketone or cyclohexanone and then with hot water. Next, the second stage reaction will be described.

The cocondensation resin produced by the first step reaction is represented by Formula (VII).

In the formula, R 'and R ₈ independently represent a hydrogen atom or a methyl group, and R ₆ represents a hydrogen atom or a C _1-4 alkyl group. The reaction is carried out in the presence of an acid catalyst with a styrene derivative.

In this reaction, the styrene derivative acts at the α-position on the aromatic substituent of the salicylic acid resin obtained in the first step reaction to introduce a corresponding number of benzyl groups in the resin. That is, the styrene derivative reacts with the at least one benzene ring other than the skeletal benzene ring of silicic acid at the α-position.

In addition, the excess of the styrene derivative reacts with the aromatic substituent of the salicylic acid resin, and the molecular weight increases by reacting with the benzene ring of the styrene derivative bonded to such an aromatic substituent.

Examples of cannons for the styrene derivatives used in the second stage reaction include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, and m-iso. Propyl styrene, p-isopropylstyrene, p-tert-butylstyrene, (alpha) -methylstyrene, p-methylstyrene, etc. can be mentioned. However, this field name is not necessarily limited to using the specific styrene derivative. Styrene is economical from an industrial point of view.

The styrene derivative may be used in an amount of 0: 2 to 20 mol, preferably 0.5 to 10 mol, per mol of the silicic acid contained in the resin obtained in the first step reaction. When the styrene derivative is used in an amount less than the specific lower limit in the present invention, the coloring agent containing the metal modified product of the obtained resin is mixed with nonvolatile oil and water in the microcapsules on the CB-sheet of the above-mentioned copy paper. Insolubility is somewhat insufficient. On the other hand, if the amount is higher than the upper limit, the relative proportion of salicylic acid decreases and the color density created is not obtained to the desired level. The weight average molecular weight produced using the styrene derivative in the specific range is in the range of 500 to 10,000, preferably 500 to 5000.

In this second stage reaction, an acid catalyst is also used.

Representative examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, ferric chloride, zinc chloride, aluminum chloride, tin chloride, Friedel-Crafts catalysts such as titanium tetrachloride and boron trifluoride, methanesulfonic acid and trifluoromethanesulfonic acid. And the like.

Particularly preferred among these exemplified strong acid catalysts is cheap sulfuric acid. The catalyst may be used in the range of 0.05 to 200% by weight based on the total amount of the salicylic acid resin and the styrene derivative obtained in the first step reaction, and from 1 to 100% by weight is preferable from an economical point of view.

In addition, a solvent may be used in the second stage reaction. Typical examples of the solvent include, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, n-pentane and cyclohexane; ethers such as ethyl ether and ethylene glycol dimethyl ether: methylene chloride 1, 2-dichloroethane, Halogenated hydrocarbon solvents such as 1, 1, 2-trichloroethane, carbon tetrachloride, chloroform and monochlorobenzene: ketones such as organic acids, acetone and methyl ethyl ketone such as acetic acid and propionic acid; Carbon insulfur disulfide, nitromethane, acetonitrile, tetrahydrofuran and the like can be listed. From an economic point of view, it is preferable to use such a solvent at 30 volume / weight times or less with respect to the total amount of starting material.

The reaction temperature at the time of the second stage reaction is -20 to 180 ° C, preferably 0 to 120 ° C, and the reaction time is 1 to 30 hours.

As a method for producing a resin by a second step reaction, a catalyst is added to the organic solvent solution of the salicylic acid resin obtained in the first step, and a starting material, that is, a styrene derivative and a salicylic acid resin is added dropwise by adding dropwise styrene derivative at a predetermined temperature. React. Here, the dropping addition time is preferably 50% or more of the total reaction time, and generally 1 to 20 hours. If the solvent used is insoluble in water, water may be added to the reaction mixture after the reaction. The reaction mixture was washed with water and the resulting mixture was separated into two layers, and then the solvent was distilled off to obtain a resin. Alternatively, the resin can be extracted with a dilute aqueous alkaline solution for use in the next step. If the solvent is soluble in water, the reaction mixture can be poured into water to obtain a resin as a precipitate.

In addition, a coloring agent composed of a polyvalent metal modified product of a copolymer formed of structural units represented by the general formulas (I), (II) and (III), respectively, is a colorless pressure dissolved in a nonvolatile oil under application of pressure. Immediate reaction with sensitive dye precursors brings the advantage of instant formation of vivid pressure-sensitive labels.

The polyvalent metal modified product of the salicylic acid resin mentioned above is demonstrated. As described above, "polyvalent metal modified product of salicylic acid resin" as used herein means a molten mixture containing a polyvalent metal salt or a polyvalent metal salt of salicylic acid resin.

Various known methods can be used to prepare the polyvalent metal salt of salicylic acid resin described above. For example, the alkali metal salt and the water-soluble polyvalent metal salt of the resin can be prepared by reacting in water or in a solvent capable of dissolving the alkali metal salt and the water-soluble polyvalent metal salt. That is, an alkoxide, carbonate or hydroxide of an alkali metal may be reacted with a resin to obtain an alkali metal salt, an aqueous solution, an alcohol solution or a water-alcohol mixture solution of the resin, followed by reaction with a water-soluble polyvalent metal salt to form a polyvalent metal salt. More specifically, the copolymer is dispersed in an amount corresponding to the amount of the carboxyl group in the copolymer in a water-alcohol solution, an alcohol solution, an aqueous solution containing an alkali metal alkoxide, carbonate or hydroxide, and the copolymer is dissolved at 100 ° C. . Next, the water-soluble polyvalent metal salt is added as it is or as an aqueous solution, an alcohol solution or a water-alcohol solution, and reacted at 0 to 100 ° C to obtain a metal salt of the copolymer as a precipitate. It is preferable to react the water-soluble polyvalent metal salt at about 0.5 to 1 equivalent with respect to the carboxyl group in the copolymer.

In order to obtain a molten mixture containing a polyvalent metal salt of salicylic acid resin, the resin is mixed with an organic carboxylic acid such as formic acid, acetic acid, propionic acid, valeric acid, caproic acid, stearic acid or benzoic acid, heated in a molten state and reacted, and then the mixture is mixed. Cool. In some cases, basic substances such as ammonium carbonate, ammonium bicarbonate, ammonium acetate or ammonium benzoate may be added to perform heating and reaction in the molten state.

In addition, the carbonate, oxide or hydroxide of the resin and the polyvalent metal is heated together with the ammonium salt of an organic carboxylic acid such as a basic substance such as ammonium formate, ammonium acetate, ammonium caproate, ammonium stearate or ammonium benzoate, and the resulting mixture is melted. It can be made to react in a state and to cool.

When the metal modified product of the resin is prepared by heating and melting the resin and the polyvalent metal salt, the melting is generally performed at 100 to 180 ° C., although the reaction depends on the resin composition, the melting temperature, and the type and amount of the polyvalent metal used. The time is 1 to several hours. It is also preferable to use the polyvalent metal salt as an organic carboxylate or carbonate of the polyvalent metal, an oxide or hydroxide of the polyvalent metal in an amount of 1 to about 20% by weight based on the total weight of the resin.

Although there is no specific limitation imposed on the amount of basic material used, it can generally be used in an amount of 1 to 15% by weight based on the total weight of the resin, and it is more preferable to use after mixing with the polyvalent metal salt in advance.

The softening point (measured by the ring and ball softening point measurement method described in JIS K-2548) of the metal modified resin produced by the heating and melting method is in the range of 50 to 120 ° C.

Representative examples of the metal of the metal modified product of the salicylic acid cocondensation resin of the present invention include metals other than alkali metals such as lithium, sodium and potassium. Preferred polyvalent metals include calcium, magnesium, aluminum, copper, zinc, tin, barium, cobalt, nickel and the like. Of these, zinc is particularly effective. Each of these polyvalent metals forms a polyvalent metal salt between carboxyl groups in the same molecule of salicylic acid resin or a polyvalent metal salt between carboxyl groups of other molecules of salicylic acid resin.

The coloring agent of the present invention can be used in combination with one or more of known coloring agents, that is, organic polymers such as inorganic solid acids, such as activated clay, phenol formaldehyde resins and aromatic carboxylic acid metal salts.

In addition, the color developer of the present invention can be used in combination with one or more of carbonates, oxides and hydroxides of polyvalent metals selected from the group consisting of zinc, magnesium, aluminum, lead, titanium, calcium, cobalt, nickel, manganese and barium.

As the method for producing the coloring sheet of the present invention suitable for use of pressure sensitive copy paper, any one of the following methods can be used.

(1) Aqueous coatings using aqueous suspensions of metal-modified products, applied to base materials such as paper webs. (2) When the base paper webs are prepared, the metal modified products are mixed into the base paper web: (3) Organic The base material is applied with a suspension or solution of the metal modified product in a solvent.

In the preparation of the coating agent, kaolin or its similar clay, calcium carbonate, starch, synthetic or natural latex and the like are added to obtain a coating agent having a suitable viscosity and coating property. The proportion of colorants in the coating formulations is preferably 10 to 70% of the total solid. If the proportion of the coloring agent is less than 10%, it is impossible to exhibit sufficient coloring ability. A ratio of more than 70% results in a coloring sheet having a deteriorated surface property of the paper. The coating agent may be applied at a dry weight of 0.5 g / m ² or more, preferably 1 to 10 g / m ³ .

In the coloring sheet of the present invention suitable for pressure sensitive radiation paper, it is possible to use a small amount of the coloring agent and the coating agent.

In addition, the concentration, viscosity, etc. of the coating agent may change in a relatively wide range. Therefore, the on-machine and off-machine coating operation can be performed. Therefore, it brings great advantages not only in terms of implementation of pressure sensitive copy paper, but also in terms of manufacturing.

According to the present invention, a coloring sheet containing a coloring agent suitable for pressure sensitive radiation paper as well as a coloring agent composed of a novel salicylic acid resin, a polyvalent metal salt thereof, and a polyvalent metal modified resin of salicylic acid resin suitable for pressure sensitive radiation paper Is provided.

The coloring sheet of the present invention is substantially free of yellowing due to light and gases in the atmosphere such as nitric oxide. The toned color display is stable to light plasticizers, does not have low color density, and has excellent water resistance. Therefore, the present invention can extend the practicality of pressure sensitive copy paper even in a field where conventional coloring sheets are not suitable due to long-term storage stability requirements. Therefore, the present invention has a very practical meaning.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

The following methods were used to determine the viability of the color sheet of pressure sensitive radiation paper.

1. Coloring Speed and Coloring Density:

Low temperature color production was carried out in an air-conditioned room at a relative humidity of 65% and 20 ° C, with the exception of those specifically indicated (5 ° C, 60% relative humidity). In the case of blue tint or black tint, (I) a commercially available blue tint CB-sheet containing "Crystal Violet Lactone (CVL) based on pressure-sensitive dye precursors (" NW-40T "trade name, manufactured by Jujo paper Cp. LTd. Or (2) a commercially available blackish CB-sheet ("KW-40T") containing 3-diethylamino-6-methyl-7-phenyl-aminofuran (0DB) based on a pressure sensitive dye precursor; , A sample coating sheet (CF-sheet) doped with an aqueous coating agent using Jujo paper CO.LTd., Was deposited onto their coated surfaces maintained in contact.

Thus, the pressure sensitive radiation paper was typed with an electronic typewriter to calculate the color.

The reflectance of the sample color sheet was twice with a "∑-80 color difference meter" (trade name: serial measurement was performed with the same color difference meter manufactured by Tokyo Denshoku Kogyo KK), that is, 1 minute 30 seconds after typing and 24 hours after die The result is represented by Y value.

The Y value is a value obtained according to the dual range display method established by the Commission Internationale de l'Eelairage (CIE). This is represented by the following equation (the same definition applies to the Y value of successive measurement tests):

JIS Z8722 may be referred to for P (λ) and Y (λ).

2. Light Resistance of Toning Marks:

Each sample-colored sheet made by the method described in Test Method 1 was exposed to light for 2 hours (and 4 hours) on a carbon arc fading tester (Suga Testing Machine Co. 1 Td, manufactured). After exposure, the reflectance was measured with a "-80 color difference meter". The result is expressed as a Y value. The smaller the value of Y, the smaller the difference from the value of Y before the test, the less discoloration caused by light, and the more preferable.

3. Fireproof:

It contains dioctyl phthalate (DOP) as a key substance and has an average capsule size of 5 μm, microcapsules with melamine-formaldehyde resin capsule walls, small amounts of starch-type binders, and 5 g / m ² dry coating. In order to obtain the weight, a coating agent prepared as described above was applied to the high-quality paper web with an air-knife spreader, and the paper web thus applied was dried to prepare a paper sheet coated with DOP microcapsules. One of the paper sheets coated with DOP microcapsules and the coloring agent with color marks calculated in Test Method 1 above were bonded to each other on the coated surfaces thereof. Thereafter, the DOP was uniformly infiltrated into the colored surface by passing through a super calender roll under a linear pressure of 100 kg / cm.

One hour after the test, the reflectance of the color development sheet was measured with a "-80 color difference meter". Output this result as Y. The smaller the Y value, and the smaller the difference from the Y value before the test, the better the flame resistance of the toning marks.

4. Water Resistance of Toning Marks:

Each sample-colored sheet colored in Test Method 1 was immersed in a rule for 2 hours, and the density change of the color traces was visually observed.

5. Yellowing of Color Sheet:

(5-1) Yellowing with NOx:

According to JIS L-1055 (Test method of NOx gas fastness of dyestuffs and dyes), each sample color sheet was sealed in NOx atmosphere generated by reaction of NaNO ₂ (sodium sulfite) and H ₃ PO ₄ (phosphate). 1 hour storage in the container was checked for yellowness.

After 1 hour of storage, the reflectance of the color sheet was measured with a "∑-80 color difference meter". The measurement result is expressed by WB value. The smaller the difference from the WB value before the test is, the less yellowing is in the NOx atmosphere.

(5-2) Yellowing by light:

Each sample color sheet was exposed to light for 4 hours on a carbon arc fading tester (manufactured by Suga Testing Machine Co., Ltd.). After the test, the reflectance of the sample coloring sheet was measured with a "-80 color difference meter". The measurement result is represented by WB value.

The larger the WB value, the smaller the difference from the WB value before the test, and the less yellowing is when exposed to light.

Example 1

a. Synthesis of Salicylic Resin and Polyvalent Metal Modified Products

Into the glass reactor, 27.6 g (0.2 mol) of salicylic acid, 44.8 g (0.4 mol) of benzyl methyl ether, and 0.76 g of p-toluene sulfonic acid and 0.76 g of zinc anhydrous chloride are added as catalysts. It is condensed under nitrogen stream for 3 hours at 125 to 135 ° C. Then, the reaction temperature is raised to 145 ° C, and the reaction is further proceeded at that temperature for 2 hours. After cooling the internal temperature to 70 ° C, 150m1 of 1,2-dichloroethane was added. The resulting mixture is cooled to room temperature. Then, 7.5 g of 96% sulfuric acid was added, and 83.2 g (0.8 mole) of styrene was added dropwise with vigorous stirring at 20 to 30 ° C. over 5 hours. After the addition, the reaction mixture is aged for 5 hours at the same temperature to terminate the reaction. 60 g of water is added to the reaction mixture under stirring, and the obtained mixture is left to stand to separate into layers. The weight average molecular weight of the obtained condensation resin is 1380. The lower layer, ie, the solvent layer, is placed in another glass reactor and 20 g of 28% aqueous ammonia and 8.1 g (0.1 mol) of zinc oxide are added. The resulting mixture is stirred at room temperature for 1 hour. The reaction mixture is heated and reacted at 60 to 70 ° C. for 1 hour. The reaction mixture is then heated to distill off the solvent. After raising the internal temperature to 150 ° C., the reaction product was degassed in a vacuum of 20 mmHg for 30 minutes and then taken out of the reactor, thereby obtaining 156 g of a reddish-brown transparent zinc-modified salicylic acid resin (stoichiometric yield).

The softening point of the zinc-modified resin was measured by a ring and ball softening point measuring instrument according to the method specified in JIS K-2548, and found to be 85 ° C.

b. Use of Zinc Modified Products as Coloring Agents and Their Performance:

A zinc modified product of salicylic acid resin is used as a color developing agent, and is dispersed by a sand grinding mill according to the following ingredients to prepare a suspension.

Next, a coating agent of the next composition is prepared using the above color developer suspension.

The coating agent is coated on a high quality paper plate to have a dry coating weight of 5.0 to 5.5 g / m ² and dried to obtain a color developing sheet. The performance of the color sheet for pressure sensitive coated papers is determined by the above-described measuring method.

Example 2

27.6 g (0.2 mol) of salicylic acid, 40.8 g (0.3 mol) of p-methyl-α-methyl-benzyl alcohol, 100 ml of monochlorobenzene and 0.7 g of anhydrous zinc chloride as a catalyst were added and reacted under reflux for 5 hours. Water distilled during the reaction is removed by a water separator. After the reaction, 300 ml of warm water is added, the obtained mixture is stirred at 90 ° C or higher for 20 minutes, and the upper moisture is removed. The warm water washing and separation process was repeated two more times to remove unreacted salicylic acid. The monochlorobenzene solution was cooled to 5 ° C., and then 10 g of concentrated sulfuric acid was added. To the obtained mixture, 31.2 g (0.3 mol) of styrene were added dropwise at 5 to 10 DEG C for 7 hours. After the reaction, the reaction mixture is aged at the same temperature for 3 hours. The weight average molecular weight of the formed resin is 1150. After 1500 ml of water was added to the resin, 36 g (0.4 mol) of 45% aqueous sodium hydroxide solution was added dropwise. The reaction mixture is heated to azeotropically remove the solvent, thereby obtaining an aqueous solution somewhat cloudy. The solution is cooled to 40 ° C, and 29 g (0.1 mol) of zinc monohydrate sulfate is dissolved in 200 ml of water, and a previously formed aqueous solution is added dropwise thereto. White precipitates formed. The precipitate is collected by filtration, washed with water and dried in vacuo, thereby obtaining 92 g of zinc salt of salicylic acid resin. As a result of elemental analysis, the zinc content was found to be 6.8%. Using a zinc-modified salicylic acid resin, a color sheet was obtained in the same manner as in Example 1.

EXAMPLES 3-16

Various polyvalent metals in the same manner as in Example 1 except for changing the kind of benzyl alcohol or benzyl alkyl ether, the molar ratio to salicylic acid, the kind and amount of styrene, the amount and type of catalyst used, and the reaction conditions as shown in Table 1. A modified salicylic acid resin is prepared. The softening point of the obtained metal modified product is shown in Table 1.

Using a polyvalent metal-modified salicylic acid resin, a color sheet was prepared in the same manner as in Example 1.

Table 1-1

Table 1-1 (continued)

TABLE 1-2

Table 1-2 (continued)

[Examples 17 and 18]

Using the colorant suspensions obtained in Examples 1 and 6, respectively, coating formulations of the following compositions were prepared.

Each of these coating agents is applied to a high quality paper to obtain a dry coating weight of 5.0 to 5.5 g / m ² to obtain a color developing agent.

The color development sheets obtained in Examples 1 to 18 are subjected to the performance test together with the color development sheets of Comparative Examples 1 and 2. The results are shown in Table 2.

Comparative Example 1

170 g of p-phenylphenol, 80 g of paraformaldehyde 22.5 g-p-toluenesulfonic acid, and 200 g of benzene were added to the glass reaction vessel. The contents are heated with stirring, and at the same time, water obtained as an azeotrope with benzone is removed from the reaction system in a middle stream, and these are reacted at 70 to 80 ° C for 2 hours. After the reaction, 320 g of 10% sodium hydroxide solution was added, and benzene was distilled off by steam distillation. The reaction mixture is then cooled and dilute sulfuric acid is added dropwise. The precipitated p-phenolphenol-formaldehyde polymer is collected by filtration, washed with water and dried to give 176 g of white powder.

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

Comparative Example 2

9.4 g of phenol and 0.2 g of sulfuric acid were added to a reaction vessel equipped with a thermometer, a reflux bed accumulator, a dropping funnel and a stirrer. Next, 23.6 g of α-methyl styrene was added dropwise from the dropping funnel with stirring at 50 ° C. After completion of the dropwise addition, the reaction mixture is aged for 5 hours and placed in a dilute aqueous solution of sodium carbonate. The obtained mixture is separated to obtain an oil layer. The oil layer is distilled in vacuo. At a vacuum of 3-4 mmHg, 22 g of oil having a breaking point of at least 220 ° C. are obtained. Next, 7.5 g of a 40% aqueous solution of caustic soda was added to the oil and dehydrated under reflux of xylene. After dehydration, the xylene mixture is transferred to an autoclave and the carbon oxide is introduced at 160 ° C. at 30 kg / cm ² . The contents are reacted for 5 hours at the same temperature. After the reaction, the autoclave is cooled, the remaining gas is removed, the reaction mixture is extracted with hot water, and the extract is neutralized with dilute sulfuric acid solution. The crystals are collected by filtration and recrystallized from an aqueous acetic acid solution to obtain 8 g of 3, 5-di (α, α'-dimethylbenzyl) salicylic acid. Zinc salt was produced from salicylic acid in the same manner as in Example 1. Using 3, 5-di (?-?-Dimethylbenzyl) zinc salicylate, a color sheet was obtained in the same manner as in Example 1.

Example 19

TABLE 2

(a) Synthesis of salicylic acid resin and polyvalent metal modified product thereof: 27.6 g (0.2 mole) of salicylic acid, 39.7 g (0.2 mole) of dibenzyl ether and 0.7 g of p-toluenesulfonic acid as catalyst and 0.7 g of zinc chloride Put it. The reactants are condensed at 125-135 ° C. for 3 hours under a stream of nitrogen. Then, the reaction temperature is raised to 145 ° C and the reaction proceeds for another 2 hours. The internal temperature was cooled to 70 ° C, and 150 ml of 1, 2-dichloroethane was added thereto. The reaction mixture is cooled to room temperature. Subsequently, 7.59 of 96% hoaic acid was added, followed by dropwise addition of 83.29 (0.8 mole) of styrene at 20 to 30 ° C. over 5 hours with vigorous stirring. 60 g of water is added to the reaction mixture by stirring, and the obtained mixture is left standing to separate into each layer. The weight average molecular weight of the obtained condensation resin is 1100. One layer, that is, the solution layer, is added to another glass reactor, to which 10 g of 28% aqueous ammonia and 8.19 (0.1 mol) of zinc oxide are added. The resulting mixture is stirred at room temperature for 1 hour. The reaction mixture is heated and reacted at 60 to 70 ° C. for 1 hour. The reaction mixture is then heated to distill off the solvent. After raising the internal temperature to 150 ° C., the reaction product was degassed for 30 minutes at 20 mmHg vacuum and then taken out of the reactor, thereby obtaining 155 g of reddish brown transparent zinc-modified salicylic acid resin. (Stoichiometric yield)

The softening point of the zinc-modified resin was measured by a ring and a softening point measuring instrument according to the method specified in JIS K-2548, and found to be 78 ° C.

(b) Use of zinc modified resins as colorants:

Using a zinc-modified salicylic acid resin as a coloring agent, a coloring sheet was obtained in the same manner as in the process (b) of Example 1.

Into the reactor, 27.6 g (0.2 mol) of salicylic acid, 31.8 g of di (p-methyl-α-methylbenzyl) ether, 100 ml of monochlorobenzene and 0.7 g of anhydrous zinc chloride were added as a catalyst. These are reacted for 5 hours under reflux of the solvent. Water distilled off during the reaction is removed by a water separator. After the reaction, a temperature of 300 ml is added, and the obtained mixture is stirred at 90 ° C or higher for 20 minutes to remove the upper moisture. The hot water washing and separation process is repeated two more times to remove unreacted salicylic acid. After cooling the monochlorobenzene solution to 5 ° C, 10 g of concentrated sulfuric acid was added. 31.2 g (0.3 mol) of styrene is added dropwise to the obtained mixture at 5 to 10 ° C over 7 hours. After the reaction, the reaction mixture is aged at the same temperature for 3 hours. The weight average molecular weight of the formed resin is 85. After adding 1500 ml of water to the resin, 36 g (0.4 mol) of 45% aqueous caustic soda was added dropwise. The reaction mixture is heated to azeotropically remove the solvent, thereby obtaining an aqueous solution somewhat cloudy. The solution is cooled to 40 ° C, and 29 g (0, 1 mol) of zinc hexahydrate sulfate is dissolved in 200 ml of water, and a pre-formed aqueous solution is added dropwise thereto. White precipitates formed. The precipitate was collected by filtration, washed with water and dried in vacuo to thereby obtain 90 g of zinc salt of salicylic acid resin. As a result of elemental analysis, the zinc content was found to be 6.50%. Using a zinc-modified salicylic acid resin, a color sheet was obtained in the same manner as in Example 19.

[Examples 21 to 24]

Various polyvalent metal-modified salicylic acid resins were prepared in the same manner as in Example 19 except for changing the type of dibenzyl ether, the molar ratio to salicylic acid, the type and amount of styrene, the type and amount of catalyst used, and the reaction conditions as shown in Table 3. do. The softening point of the obtained metal modified product is also shown in Table 3.

Using such a polyvalent metal-modified salicylic acid resin, a color sheet was prepared in the same manner as in Example 1.

TABLE 3

Table 3 (continued)

[Examples 25 and 26]

The colorant suspensions obtained in Examples 19 and 24, respectively, were prepared with the coating agents of the composition used in Examples 17 and 18, respectively, and the colorimetric sheets were obtained correspondingly. The color development sheets obtained in Examples 19 to 26 were subjected to the performance test together with the color development sheets of Comparative Examples 1 and 2. The results are shown in Table 4.

TABLE 4

Claims (20)

The following general formulas (I), (II) and (III) Formula (I) Formula (II) General formula (III) Wherein R₁ and R₂ independently represent a hydrogen atom or a C _1-12 alkyl group, an aralkyl group, an aryl group or a cycloalkyl group, R₃ independently means a hydrogen atom or a C _1-4 alkyl group, and R₄ is a hydrogen atom or ₅ to 35 mole% of the structural unit (I) represented by the group represented by methyl, one of R ₅ and R ₆ is a hydrogen atom, the other is hydrogen or a C _1-4 alkyl group, and R ₇ is a methyl or ethyl group. It consists of 10-85 mol% of unit (II) and 4-85 mol% of structural unit (II), the weight average molecular weight is 500-100,000, and each of structural unit (I) is a structural unit (II) Through one α-carbon of one of the structural units (II) and the benzene ring of one or more structural units (II), and through one or more α-carbons or α-carbons of the structural unit (II) Optionally bound to II) and to each benzene ring of structural unit (II) via each α-carbon of structural unit (III) Wherein the one or more polyvalent metal atoms form a valent metal salt between carboxyl groups in the same molecule of the copolymer or between carboxyl groups of other molecules of the copolymer. Salicylic acid and the following formula (IV) Wherein R₁ and R2 are the same or different and independently represent a hydrogen atom or a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group, where R₃ is a hydrogen atom or a C _1-4 alkyl group, R₄ is a hydrogen atom, C _1-4 alkyl group or to be) The cocondensate obtained by reacting benzyl alcohol and / or benzyl ether represented by the following in the presence of an acidic catalyst is represented by the following formula (VII) Wherein the molar ratio of styrene derivative / salicylic acid in the presence of an acidic catalyst in the styrene derivative represented by (wherein R₄ and R ₈ independently mean a hydrogen atom or a methyl group and R ₆ is a hydrogen atom or a C _1-4 alkyl group) General formula (I), (II) and (III) which consist of making it react with 0 at 120-120 degreeC. Formula (I) Formula (II) General formula (III) Wherein R₁ and R₂ independently represent a hydrogen atom or a C _1-12 alkyl group, an aralkyl group, an aryl group or a cycloalkyl group, R₃ independently means a hydrogen atom or a C _1-4 alkyl group, and R₄ is a hydrogen atom or ₅ to 35 mole% of the structural unit (I) represented by the group represented by methyl, one of R ₅ and R ₆ is a hydrogen atom, the other is hydrogen or a C _1-4 alkyl group, and R ₇ is a methyl or ethyl group. It consists of 10-85 mol% of unit (II) and 4-85 mol% of structural unit (III), the weight average molecular weight is 500-100,000, and each structural unit (I) is a structural unit (II) Through one α-carbon of one of the structural units (II) and the benzene ring of one or more structural units (II), and through one or more α-carbons or α-carbons of the structural unit (II) Is optionally bonded to II), and each of the structural units (III) is bound to the benzene ring of one of the structural units (II) via α-carbon. Method for producing a copolymer. A color developing agent for pressure-sensitive coating paper containing the polyvalent metal salt of the copolymer according to claim 1 as an active ingredient. The coloring agent according to claim 3, wherein the at least one polyvalent metal atom is a metal atom selected from the group consisting of magnesium aluminum, copper, zinc, tin barium, cobalt and nickel atoms. 5. A color developing agent according to claim 4, wherein said at least one polyvalent metal atom is a zinc atom. (i) dispersing and dissolving the copolymer according to claim 1 in an aqueous solution, an alcohol solution or an aqueous-alcohol solution containing an alkali metal hydroxide or carbonate or alcohol citrate in an amount of 0 to 100 ° C. or more of the carboxyl groups of the copolymer. Thereby obtaining a substantial solution of the alkali salts of the copolymer: (ii) a water-soluble polyvalent metal salt as such or in an amount of 0.5 to 19 equivalent to the carboxyl groups of the copolymer in the form of an aqueous solution, an alcohol solution or a water-alcohol solution. A method for producing a color-sensing agent for pressure-sensitive coating paper, comprising the step of adding and reacting to a real solution of an alkali salt of a copolymer at 0 to 100 ° C., thereby obtaining a metal salt of the copolymer as a precipitate. (i) The copolymer according to claim 1, wherein the polyvalent metal salt contains the polyvalent metal in an amount of 1 to 20% by weight of the weight of the copolymer, and optionally, in the coexistence of inorganic base salts, with the polyvalent metal salt of organic carboxylic acid. Heating, melting and reacting at 100 to 180 DEG C: (ii) cooling the reaction mixture to obtain a metal salt-containing melt mixture of the copolymer. (i) The copolymer according to claim 1, wherein the carbonate, oxide or hydroxide is contained in an amount of 1 to 20% by weight of the weight of the copolymer. Heating, melting and reacting with an organic base salt in an amount equal to by weight: (ii) cooling the reaction mixture to obtain a molten mixture containing metal spirits of the copolymer. The method of claim 6, wherein the at least one polyvalent metal is a metal selected from the group consisting of magnesium, aluminum, copper, zinc, tin, barium, cobalt and nickel. The method of claim 7, wherein the at least one polyvalent metal is a metal selected from the group consisting of magnesium, aluminum, copper, zinc, tin, barium, cobalt and nickel. The method of claim 8, wherein the at least one polyvalent metal is a metal selected from the group consisting of magnesium, aluminum, copper, zinc, tin, barium, cobalt and nickel. 10. The method of claim 9, wherein the polyvalent metal is zinc. Coloring agent for pressure sensitive applicator paper, wherein the coloring agent containing the polyvalent metal salt of the copolymer according to claim 1 is almost evenly distributed on at least one side as an active ingredient, The color sheet according to claim 13, wherein the at least one polyvalent metal is a metal selected from the group consisting of magnesium, aluminum, copper, zinc, tin, barium, cobalt and nickel. The chromosome sheet according to claim 14, wherein the polyvalent metal is zinc. A method for producing a coloring sheet for pressure sensitive use paper comprising coating a coating agent comprising an aqueous suspension of a coloring agent containing a polyvalent metal salt of a copolymer according to claim 1 as an active ingredient on a basic paper web. A method for producing a coloring sheet for pressure-sensitive coating paper comprising the step of incorporating a coloring agent containing a polyvalent metal salt of a copolymer according to claim 1 as an active ingredient into a basic paper web during production of a basic paper web. A method for producing a coloring sheet for pressure sensitive paper, comprising applying to a basic paper a solution or suspension in which a coloring agent containing a polyvalent metal salt of a copolymer according to claim 1 is dissolved in an organic solvent as an active ingredient. The method of claim 10, wherein the polyvalent metal is zinc. 12. The method of claim 11, wherein the polyvalent metal is zinc.