KR920010143B1 - Process for preparing saliccylic acid copolymer - Google Patents

Abstract

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Description

Method for preparing salicylic acid copolymer

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

* Explanation of symbols for the 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 using a coloring agent, which contains a metal salt as an active ingredient and is suitable for pressure sensitive radiation paper, and is suitable for use in pressure sensitive radiation paper.

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 stroke or typewriter notation, and thus can be copied in multiple sheets at the same time. Such pressure sensitive copy papers are called "transcription copy papers" and "own self-use 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, 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 micrometers, which is somewhat larger than 10 μm, and dissolves the colorless pressure sensitive precursor precursor in a nonvolatile oil, and then the obtained solution is separated into a polymer membrane such as a gelatin membrane. It is applied with a microcapsule 4 obtained in a capsule. On the other hand, the front of the CF / CB sheet 2 and the CF sheet 3 is in contact with the pressure sensitive dye precursor, so that the coloring agent 5 reacts with the dye precursor, thereby causing the dye precursor to make its color. It is apply | coated with the coating agent containing the coloring agent 5 which has a characteristic. To make a copy, they are stacked in the order of CB sheets, (CF / CB sheets), (CF / CB sheets) and CF sheets on the side coated with the dye precursor which comes into contact with the side to which the coloring agent is applied. CF / CB sheet is arbitrary. When pressure is locally applied by a ballpoint pen 6 or typewriter, the capsule 4 bursts there. As a result, a solution containing the pressure sensitive dye precursor is transferred to the color developer to obtain one or more duplicated records.

As a color developing agent for attracting electrons, (1) U.S. Patent No. 2,712,507 discloses inorganic solid acids such as acidic clay and attapulsasheet; (2) Japanese Patent Laid-Open No. 9313/1965 includes substituted phenols and diphenols; (3) Japanese Patent Publication No. 20144/1967 discloses P-substituted phenol-formaldehyde polymers; (4) Japanese Patent Publication Nos. 10856/1974 and 1327/1977 have proposed metal salts of aromatic carboxylic acids and the like. Some of them are already in use.

As a performance condition of the color sheet which is considered to be satisfactory, it has excellent color developing ability not only immediately after its manufacture but also after long time storage, as well as almost no yellowing during exposure and storage of radiation such as sunlight, and the color display made Mention may be made of good color fixation 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 inexpensive 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 density.

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.

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

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, the present invention consists of 5 to 35 mol% of the structural unit (I), 10 to 85 mol% of the structural unit (II) and 4 to 85 mol% of the structural unit (III), and has a weight average molecular weight of 500 to 10,000. A copolymer having: [Each of the structural unit (I) is bonded to the one benzene ring of the structural unit (II) via? -Carbon of one of the structural unit (II), and the structural unit (II) At least one of which is optionally bonded to the benzene ring or another ring or other structural unit (II) via its α-carbon or α-carbons, and at least one of said structural units (III) is the α-carbon or α- Via carbon to a ring of at least one of the benzene ring or structural unit (III) and / or a ring of another structural unit (III), wherein the structural units (I), (II) and (III) are represented by the following formula (I) And (II) and (III), respectively.

Wherein R ₁ and R ₂ independently represent a hydrogen atom or a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group, R ₃ is a hydrogen atom or a methyl group, one of R ₅ and R ₆ is a hydrogen atom and the other One 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 forms the polyvalent metal salt between carboxyl groups in the same molecule of the copolymer or between carboxyl groups of other molecules of the copolymer; Coloring agents containing polyvalent metal salts as they are suitable for pressure sensitive radiation paper or in the form of molten mixtures containing polyvalent metal salts; It provides a color sheet which is suitable for pressure sensitive radiation paper and which contains a colorant which is distributed almost uniformly on at least one side 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 than the coloring sheet using an 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 stimulus toned by the coloring agent sheet using the new coloring agent of the present invention has a high resistance that is not easily faded by water, plasticizer or light.

The present invention has also improved the yellowing tendency due to the old iron to sunlight, in particular, the yellowing resistance to nitrogen oxides in the atmosphere, and also has the advantage that the coloring sheet which is very advantageous for use and storage can 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 preferably structural units represented by the general formula (I) by reacting a cocondensate obtained by reacting salicylic acid with benzyl alcohol or benzyl ether in the presence of an acidic catalyst with benzyl halide in the presence of an acidic catalyst. Salicylic acid number containing 5-35 mol%, 10-85 mol% of structural units represented by general formula (II), and 4-85 mol% of structural units represented by general formula (III), and having 500-10,000 weight average molecular weight. Tributary (each structural formula (I) is bonded to the benzene ring of said one of said structural unit (II) via the α-carbon of said general formula (II), wherein at least one of said structural unit (II) Or through its α-carbon to a benzene ring or other rings or to the remaining structural unit (II), each of which is bonded to the benzene ring of one of the structural units (II) via its α-carbon. )to be.

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

Salicylic acid resin belonging to the present invention is a first step reaction, benzyl alcohol and / or benzene ether represented by the following formula (IV) and salicylic acid in the presence of an acidic catalyst

Wherein R ₁ and R ₂ are the same or different and independently represent a hydrogen atom or a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group, R ₃ is a hydrogen atom or a C _1-4 alkyl group, R ₉ is hydrogen An atom, a C _1-4 alkyl group or

The co-condensation resin obtained by the reaction is benzyl halide represented by the following general formula (VI) in the presence of an acidic catalyst by the second stage reaction.

Wherein R ₄ is a hydrogen atom or a methyl group, one of R ₅ and R ₆ is a hydrogen atom, the other is hydrogen or a C _1-4 alkyl group, and X represents a halogen atom. First, the first stage reaction will be described.

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

In formula (IV), the condensation of benzyl alcohol in which R ₉ is a hydrogen atom 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, the reaction of isobutanol and salicylic acid to obtain t-butyl salicylic acid, and the "[Kimji Kyushu (Experimental Chemistry Handbook)", 18, 30 (1958), Maruzen Publishing Co., Ltd., 5- [α- Reaction of 2 moles of phenyl ethanol and 1 mole 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 process of the 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, when benzyl alcohol is present at 1.5 mol or more per mole of salicylic acid and reacted 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 and / or para positions with respect to the hydroxyl group of salicylic acid It has been found that one or more benzyl groups can be introduced at one of these positions, and that excess benzyl alcohol can undergo continuous condensation with benzyl groups introduced into salicylic acid to produce resinous materials. .

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 modified product 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 substituted or unsubstituted 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 step reaction. Alcohol, m-ethylbenzyl alcohol, P-ethylbenzyl alcohol, O-isopropyl benzyl alcohol, Pn-propylbenzyl alcohol, P-tert-butylbenzyl alcohol, p-nonylbenzyl alcohol, O-phenylbenzyl alcohol, P-cyclo Hexylbenzyl 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-4ethylbenzyl alcohol , 3- (α-methylbenzyl) -4-methylbenzyl alcohol, 2,5- (dimethylbenzyl) benzyl alcohol, α-methylbenzyl alcohol, α-ethylbenzyl alcohol α-n-propylbenzyl alcohol, α-isopro Benzyl 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-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- Methyl benzyl alcohol, 2-methyl-5-tert-butyl-α-methyl benzyl alcohol, and the like.

However, the method of the present invention is not necessarily limited to those using the above 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 extremely 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 inorganic acids and organic acids, particularly inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, tin tin chloride, ferric chloride, such as ferric chloride, methanesulfonic acid, and P-toluene sulfonic acid. May 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 during the reaction of benzyl alcohol. The reaction proceeds while dropwise addition of a portion. 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 R ₉ in the general formula (IV).

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 this benzyl group into benzene, naphthalene, phenol, etc. [“To develop a chemical (experimental chemical handbook)”, 18, 30 (1985), Maruzen Publishing Co., Ltd.) . These reactions use very strong acidic catalysts, such as boron fluoride, and also select compounds that are relatively prone to nucleophilic substitution.

However, no method of reacting salicylic acid with 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 invention, alcohol is formed through the de-alcohol reaction. One of the reactants, salicylic acid, can be predicted to produce a mixture of salicylic acid esters and their resins through reaction with alcohols formed in the presence of an acid catalyst and will face 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, ortho to the hydroxyl group of salicylic acid without inducing substantial side reactions such as the corresponding ester and the reaction. It has been found surprising that various benzyl groups can be introduced from 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 benzylalkyl 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-methylbenzylalkyl ethers will be described in the next section (b)]. 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 benzylalkyl 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-methyl benzyl ether, O- Methylbenzylethyl ether, O-methylbenzyl isobutyl ether, m-methylbenzylmethyl ether, m-methylbenzylethyl ether, m-methylbenzylisopropyl ether, O-ethylbenzylmethyl ether, o-ethylbenzylethyl ether, O Ethylbenzyl isopropyl ether, P-ethylbenzylmethyl ether, p-ethylbenzylethyl ether, P-ethylbenzylisopropyl ether, P-ethylbenzyl, n-butyl ether, O-isopropylbenzylethyl ether, P-iso Propylbenzylethyl ether, Pn-propylbenzylethyl ether, P-tert-butylbenzylethyl ether, P-tert-butylbenzylisopropyl ether, P-tert-octylbenzylethyl ether, P-dodecylbenzylmethyl ether, P- Phenylbenzylmethyl ether, O-phenylbenzyl isopropyl Ether, P-cyclohexylbenzyl ether, P- (α-methylbenzyl) benzylmethyl ether, P- (α-methylbenzyl) benzylethyl ether, P- (α, α-dimethylbenzyl) benzylmethyl ether, 2,3 -Dimethylbenzyl methyl ether, 2,4-dimethylbenzyl methyl ether, 2,5-dimethylbenzylmethyl ether, 2,6-dimethylbenzylmethyl ether, 3,4-dimethylbenzylmethyl ether, 3,5-dimethylbenzylmethyl ether , 2,4-dimethylbenzylmethyl ether, 3,4-dimethylbenzylethyl ether, 3,5-dimethylbenzylmethyl ether, 2,4-dimethylbenzylmethyl ether, 2,3-dimethylbenzylisopropyl ether, 2,4 -Dimethylbenzyl n-propylether, 3,4-dimethylbenzyl, n-butylether, 2,4-dimethylbenzyl, Sec-butylether, 3,5-dimethylbenzyl n-amylether, 2,4-diethylbenzyl Methyl ether, 3,5-diethylbenzylisopropyl ether, 2,3-diethylbenzyl n-butyl ether, 2,4-diisopropylbenzylmethyl ether, 3,5-diisopropylbenzyl ethyl ether, 3- Methyl-4-ethylbenzylmethyl ether, 3-meth -5-tert- butyl-benzyl ether, 2-methyl -4- (α- methylbenzyl) can be exemplified such as a benzyl ether. 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-methylenezylethyl 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 the general formula (IV), wherein R ₃ and R ₃ independently represent a C _1-4 alkyl group.

As long as the number of carbon atoms 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 rapid rate and no esterification occurs so that a good resin is obtained. . When the O-linked alkyl group contains four carbon atoms, that is, when the O-linked 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 the industrial point of view, a methyl group or an ethyl group is preferable.

Representative examples of the α-alkylbenzenealkyl ether used in the practice of the present invention for providing the co-condensation resin include α-methylbenzylmethyl ether, α-methylbenzylethyl ether, α-methylbenzylisopropyl ether and α-methylbenzyl n -Propyl ether, α-methylbenzyl n-butyl ether, α-ethylbenzyl methyl ether, α-ethylbenzylethyl ether, α-ethylbenzylisopropylether, α-ethylbenzyl n-butylether, α-n-propylbenzyl Methyl ether, α-isopropylbenzylethyl ether, α-n-butylbenzyl isopropyl ether, O-methyl-α-methylbenzyl ether, P-methyl-α-methylbenzylmethyl ether, m-methyl-α-methylbenzyl Methyl ether, P-methyl-α-methylbenzylethyl ether, P-methyl-α-methylbenzylisopropyl ether, P-methyl-α-methylbenzyl n-propylether, P-methyl-α-methylbenzyl n-butyl Ether, P-methyl-α-ethylbenzylmethyl ether, P-methyl-α-ethylbenzylethyl ether, 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-ethylbenzylmethyl ether, P- Ethyl-α-methylbenzylmethylether, O-ethyl-α-ethylbenzylether, m-ethyl-α-n-propylbenzylmethylether, P-isopropyl-α-methylbenzylmethylether, O-isopropyl-α -Methylbenzylmethyl ether, P-sec-butyl-α-methylbenzylmethyl ether, P-tert-butyl-α-methylbenzylmethyl ether, P-nonyl-α-methylbenzylmethyl ether, P-dodecyl-α- Methylbenzylmethyl ether, P-phenyl-α-methylbenzylmethyl ether, O-phenylbenzyl-α-ethylbenzylmethyl ether, P-cyclohexyl-α-methylbenzylmethyl ether, P- (α-methylbenzyl) -α -Methylbenzylmethyl ether, P- (α, α-dimethylbenzyl) -α-methylbenzylmethylether, 2,3-dimethyl-α-methylbenzylmethylether, 2,4-dimethyl-α-methylbenzylmethylether, To 2,5-dimethyl-α-methylbenzylmethylether, 2,6-dimethyl-α-methylbenzylmethyl Ter, 3,4-dimethyl-α-methylbenzylmethylether, 3,5-dimethyl-α-methylbenzylmethylether, 2,3-dimethyl-α-methylbenzylethylether, 2,4-dimethyl-α-methyl Benzylisopropyl ether, 2,5-dimethyl-α-methylbenzyl n-propylether, 2,6-dimethyl-α-methylbenzyl n-butylether, 3,4-dimethyl-α-methylbenzyl Sec-butylether, 2,3-dimethyl-α-ethylbenzylmethylether, 2,4-dimethyl-α-ethylbenzylmethylether, 2,5-dimethyl-α-ethylbenzylmethylether, 2,4-dimethyl-α-ethylbenzyl n -Propyl ether, 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-methyl benzylethylether, 3,4-diethylbenzyl-α-ethylbenzylmethylether, 3,5-diethylbenzyl-α- Propylbenzylisopropylether, 2,4-diisopropyl-α-methylbenzylmethylether, 2,4-diisopropyl-α-ethylbenzyl Butyl ether, 2,6-diisopropyl-α-propylbenzylether, 3,5-diisopropyl-α-butylbenzylmethylether, 2-methyl-4-ethyl-α-methylbenzylmethylether, 2-methyl 4-tert-butyl-α-methylbenzylmethylether, 2-methyl-4- (α-methylbenzyl) -4-methylbenzylmethylether, 2-methyl-4- (α, α-dimethylbenzyl) -α -Methyl benzyl methyl ether, 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 a methyl group is preferable.

Various debenzyl ethers which can provide the cocondensation resin according to the present invention include dibenzyl ether, di (O-methylbenzyl) ether, di (m-methylbenzyl) ether and di (P-methylbenzyl) ether. , Di (O-ethylbenzyl) ether, di (m-ethylbenzyl) ether, di (P-ethylbenzyl) ether, di (O-isopropylbenzyl) ether, formula (Pn-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-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-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 (3,4-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-meth Benzyl) can be exemplified an ether. 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.

Dibenzyl ether is used in the first stage of reaction with 0.5 to 5 moles per mole of salicylic 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, direactive 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 is described. That is, this reaction is a general formula (VI) of the co-condensation resin produced in the first step reaction

Wherein R ₄ represents a hydrogen atom or a C ₁ -C ₄ alkyl group and R ₅ and R ₆ independently represent a hydrogen atom, a C ₁ -C ₁₂ alkyl group, an aralkyl, aryl or cycloalkyl group, and X represents a halogen atom It is condensed again in the presence of benzyl halide and acid catalyst.

In the second stage reaction, the benzyl halide represented by the formula (VI) is reacted with the cocondensate resin obtained in the first stage reaction in the presence of a Friedel-Krafts catalyst.

In this reaction, the aromatic substituent of the salicylic acid resin obtained by the first stage reaction is substituted with a benzyl group. That is, the benzyl halide reacts with at least one benzene ring other than the skeletal benzene ring of salicylic acid.

In addition, the excess of the halide reacts with the aromatic substituent of the salicylic acid resin to increase the molecular weight.

In the starting benzyl halide, the nuclei of the benzyl groups are substituted or unsubstituted with at least one of a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group in the O-, m- or P-position, and the α-position Contains a hydrogen atom or a C _1-4 lower alkyl group. Halogens include chlorine, bromine and fluorine, with dichlorine being preferred.

Typical examples of benzyl halide include benzyl chloride, benzyl bromide, O-methylbenzyl chloride, m-methylbenzyl chloride, P-methylbenzyl chloride, O-ethylbenzyl chloride, m-ethylbenzyl chloride, P-ethylbenzyl chloride and O- Isopropylbenzyl, Pn-propylbenzyl, brominated P-tert-butylbenzyl, P-nonylbenzyl chloride, fluorinated O-phenylbenzyl, P-cyclohexylbenzyl chloride, P- (benzyl) benzyl chloride, P- (α -Methylbenzyl) benzyl chloride, P- (α, α-dimethyl) benzyl, fluorinated 2,3-dimethylbenzyl, 2,4-dimethylbenzyl, 2,5-dimethylbenzyl, 2,6-dimethylbenzyl , 3,4-dimethylbenzyl chloride, 3,5-dimethylbenzyl chloride, 2,4-diethylbenzyl chloride, 3-methyl-4-ethylbenzyl chloride, 3- (α-methylbenzyl) -4-methylbenzyl 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, m-methyl-α-methyl Vaginal, 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, P- (α, α-dimethylbenzyl) -α-methylbenzyl, 2,3-dimethyl-α-methylbenzyl, 2,4-dimethyl-α-methylbenzyl, 2,5-dimethyl-α-methylbenzyl chloride, 3,4-dimethyl-α-methylbenzyl chloride, 2-methyl-5-tert-butyl-α-methylbenzyl chloride and the like. However, the present invention does not necessarily limit the use of such specific halogenated dibenzyl.

Among these representative halogen-substituted benzyls, benzyl chloride, P-methylbenzyl chloride, α-methylbenzyl chloride, P-methyl-α-methylbenzyl chloride and the like are preferable. Benzyl halide may be used at 0.2 to 20 moles, preferably 0.5 to 10 moles per mole of salicylic acid used in the first stage reaction.

Fundamental advantages derived from the use of such benzyl halides include the low cost of benzyl halides compared to alcohols and / or ethers used in the first stage reaction, in addition to improvements carried out as colorants. Only attempts to use benzyl halides in high proportions for economic reasons will reduce the relative proportions of salicylic acid, and the density of colors created will not be achieved at the desired level. In the case where the starting material is used in a substantial amount in the above-mentioned range, it is within the range of 500-10000, preferably 500-5000, of the weight average molecular weights obtained.

As a representative example of the catalyst used in the second step reaction, there may be mentioned freetel krafts catalysts such as ferric chloride, zinc chloride, aluminum chloride, tin tin chloride, titanium tetrachloride and boron trifluoride. Of these, zinc chloride is particularly preferred. The catalyst can be used at 0.05 to 200 mol% based on the salicylic acid obtained in the first step reaction. However, 1-100 mol% is preferable from an economic point of view. In this method of the present invention, when the catalyst is neutralized with a base after the reaction, the metal type of the catalyst used in the reaction is reacted with the salicylic acid resin to obtain the metal type of the catalyst as the metal modified product of the salicylic acid resin. This is a beneficial feature of the method of the invention. It is economical because the catalyst is effectively used so that the process and treatment as waste material is unnecessary.

In the second step reaction, a solvent can also be used. As such a typical solvent, For example, aliphatic hydrocarbons, such as n-hexane, n-heptane, n-pentane, and cyclohexane; Ethers such as ethyl ether and ethylene glycol dimethyl ether; Halogenated hydrocarbon solvents such as methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride, chloroform and monochlorobenzene; Organic acids such as acetic acid and propionic acid; Carbon sulfide, 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 or less with respect to the total amount of starting materials.

The reaction temperature at the time of carrying out the second stage reaction is 20 to 180 캜, preferably 50 to 160 캜. The reaction time is 1 to 30 hours.

As a method for producing the resin by the second step reaction, a catalyst is added to the salicylic acid resin obtained in the first step, and the starting materials, that is, the benzyl halide and the salicylic acid resin are added dropwise and the benzyl halide is reacted at a predetermined temperature.

Here, the dropping addition time is preferably 50% or more of the total reaction time, and generally 1 to 20 hours. If a solvent is used and the solvent is insoluble in water, water may be added to the reaction mixture after the reaction. The reaction mixture is washed with water and the resulting mixture is separated into two layers, and then the solvent is distilled off to obtain a resin. Alternatively, the resin can be extracted with a dilute aqueous alkaline solution for use in another 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 general formulas (I), (II) and (III), respectively, was subjected to colorless pressure dissolved in nonvolatile oil under the application of pressure. The immediate reaction with sensitive dye precursors brings the advantage of the immediate 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 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 the water-alcohol solution containing the alkoxide, carbonate or hydroxide of an alkali metal and an aqueous solution in an amount equivalent to or greater than the carboxyl group in the copolymer to dissolve the copolymer at 0 to 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, a basic substance 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 carboxylate, ammonium stearate or ammonium benzoate, and the resulting mixture is heated. It can be obtained by reacting in a molten state and cooling.

The metal modified product of the resin is generally prepared by heating and melting the resin and the polyvalent metal salt at 100 to 180 DEG C, and the reaction is performed depending on the resin composition, the melting temperature, and the type and amount of the polyvalent metal used. The time is 1 to several hours. In addition, it is 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 measuring 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 without any problem or inconvenience in combination with a known coloring agent, i.e., one or more organic polymers such as inorganic solid acids such as activated clay, phenolformaldehyde 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 a method for producing the coloring sheet of the present invention suitable for use of pressure sensitive copy paper, any of the other methods can be used.

(1) an aqueous coating agent using an aqueous suspension of a metal modified product applied to a base material such as paper web; (2) mixing the metal modified product in the base paper web when the base paper web was produced; (3) Apply the base material with a suspension or solution of metal modified product in organic solvent.

In the preparation of the coating agent: Kaolin or similar clays thereof, calcium carbonate, starch, synthetic or natural latex is added to obtain a coating agent having a suitable viscosity and coating properties. The proportion of colorants in the coating formulations is preferably from 10 to 70% of the total solids. If the proportion of the coloring agent is less than 10%, it is impossible to exhibit sufficient coloring ability. A ratio of 70% or more results in a color sheet in which the surface property of the paper is lowered. The coating agent may be applied at a dry weight of 0.5 g / m 2 or more, preferably 1 to 10 g / m 2.

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, and the like of the coating agent may change over a relatively wide range. Therefore, the on-machine and off-machine coating operation can be performed. Therefore, pressure sensitive brings great advantages not only in terms of the performance of copy paper, but also in terms of manufacturing.

According to the present invention, there is provided a coloring sheet containing a coloring agent suitable for pressure-sensitive copying 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 copying paper. do.

The coloring sheet of the present invention is substantially free from yellowing due to light and gases of atmospheric species such as nitric oxide. It is stable in toned light, plasticizer, etc., does not have low color density, and has excellent water resistance. Therefore, the present invention can extend the practicality of pressure-sensitive radiation 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 color density; [Except for those specially indicated as low temperature color preparation (5 ° C., 60% RH), it was performed in an air-conditioned room at 65 ° C. and 20 ° C. In the case of blue tint or black tint (1) A commercially available blue tint CB-sheet (“NW-40T” trade name, Jujopaper Co., Ltd.) containing crystal violet lene lactone (CVL) based on a pressure sensitive dye precursor. Or (2) a commercially available black toned CB-sheet (“KW-40T”) containing 3-diethylamino-6-methyl-7-phenyl-aminofuran (0DB) based on a pressure-sensitive dye precursor; A sample coloring sheet (CF-sheet) coated with an aqueous coating agent using the trade name, manufactured by Jujo paper Co., Ltd., was deposited onto their coated surfaces held in contact.

Thus, the pressure sensitive radiation paper was typed with an electronic typewriter and the color was ejected.

The reflectance of the sample color sheet was repeated twice with a “∑-80 color difference meter” (trade name: a series of measurement tests performed with the same color difference meter manufactured by Tokyo Denshoku Koqyo KK), that is, 11 minutes 30 seconds after typing and 24 hours after typing. Was measured. This result is represented by Y value.

The Y value is a value obtained according to the dual range display method established by the CIE (Commision Internaionale de L'Eelairage). This is expressed as:

In the formula: P (λ): standard light source distribution, (λ): Color matching function in double range, τ (λ): JIS Z8722 can be referred for the spectral characteristics of each sample, P (λ) and Y (λ).

2. Light resistance of color stimulation: Each sample color 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 (manufactured by Suga Testing machine Co., Ltd.). . After exposure, the reflectance was measured with a ∑-80 colorimeter. 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 by light, and the more preferable.

3. Fire resistance: It contains dioctyl phthalate (DOP) as the core material, has an average capsule size of 5㎛, and makes microcapsules with the capsule wall of methamine-formaldehyde resin, and adds a small amount of starch binder. In order to obtain a dry coating weight of 5g / ㎡, coating the coating agent prepared as described above with an air-knife spreader on a high-quality paper web, and dried the paper web so applied to the paper sheet coated with DOP microcapsule Prepared. One of the paper sheets coated with DOP microcapsules and the color developing agent having the color marks calculated in Test Method 1 were bonded to each other on the coated surfaces. 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 sheet was measured with a ∑-80 color difference meter. This result is represented by Y value.

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. Waterproofing of the color traces: Each sample color sheet colored by Test Method 1 was immersed in water for 2 hours, and the density change of the color traces was visually observed.

5. Yellowing of the color sheet: (5-1) Yellowing with NOx: Each sample color sheet was treated with NaNO ₂ (sodium sulfite) and according to JIS L-1055 (Test method of NOx gas fastness of dyestuff and dye). The yellowness was investigated by storing for 1 hour in a closed container of NOx atmosphere generated by the reaction of H ₃ PO ₄ (phosphoric acid).

After 1 hour of storage, the reflectance of the color sheet was measured with a ∑-80 colorimeter. 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 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 acid resin and polyvalent metal modified product thereof: 27.6 g (0.2 moles) of salicylic acid, 44.8 g (0.4 moles) of benzyl methyl ether, 0.76 g of P-toluenesulfonic acid and 0.76 g of zinc anhydride in a glass reactor Put it. The reactants are condensed under nitrogen stream at 125-135 ° C. for 3 hours. Then, the reaction temperature is raised to 145 ° C and the reaction proceeds for 2 hours. After cooling the internal temperature to 100 ° C. and adding 1.3 g of anhydrous aluminum chloride, 112.5 g (0.8 mol) of P-methylbenzyl chloride was added dropwise over 5 hours at the same temperature. Then, the reaction mixture is aged at the same temperature for 5 hours to complete the reaction. Under stirring, 60 g of water and 200 ml of toluene are added to the reaction mixture, and the obtained mixture is raised to separate each side. The weight average molecular weight of obtained resin is 1420. Into the glass reactor in which the upper solvent was separated, 20 g of 28% aqueous ammonia and 8.1 g (0.1 mol) of zinc oxide were added. The resulting mixture is stirred at room temperature for 1 hour. The reaction mixture is heated to distill off the solvent. The internal temperature is raised to 150 ° C and the reaction product is aged for 2 hours. The reaction product was degassed in a vacuum of 20 mmHg for 30 minutes and then taken out of the reactor to obtain 153.5 g of reddish brown transparent zinc-modified salicylic acid resin (stoichiometric yield).

It was found that the softening point of the zinc modified resin was measured by a ring and bowl softening point measuring instrument according to the method specified in JIS K-2548, and was found to be 92 ° C.

(b) Use of zinc modified resin as a color developing agent: 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 applied to 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

In the glass reactor, 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 were added as a catalyst. These are reacted for 5 hours under reflux of the solvent. 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 conflicting water is removed. The warm water washing and separation process is repeated two more times to remove unreacted salicylic acid. The monochlorobenzene solution was dried with a salt gate, and 0.5 g of anhydrous chloride was added and placed under reflux of monochlorobenzene, and 38 g (0.3 mol) of benzyl chloride was added dropwise over 5 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 970. The resin is added with 1500 ml of water and 36 g (0.4 mole) of caustic soda 45% solution is added dropwise. The reaction mixture is heated to azeotropically remove the solvent, thereby obtaining an aqueous solution somewhat cloudy. The solution was cooled to 40 ° C, 29 g (0.1 mol) of zinc hexahydrate sulfate was dissolved in 200 ml of water, and a previously formed aqueous solution was added dropwise to the solution. White precipitates formed. The precipitate was collected by filtration, washed with water and vacuum dried to obtain 85 g of a zinc salt of salicylic acid resin. As a result of elemental analysis, zinc content was found to be 7.56%. Using a zinc-modified salicylic resin, a color sheet was obtained in the same manner as in Example 1.

Example 3

27.6 g (0.2 mol) of salicylic acid, 86.4 g (0.8 mol) of benzyl alcohol and 1.2 g of zinc chloride were added to the reactor. These are condensed under nitrogen stream at 125 to 135 DEG C for 5 hours. The reaction temperature then rises to 145 ° C. and the reaction proceeds further for 2 hours. Next, 13.5 g of anhydrous zinc chloride is added to the reaction mixture. At the same temperature, benzyl chloride 76k (0.6 mol) was added dropwise for 5 hours. After the dropwise addition, the reaction mixture is aged for 2 hours at the same temperature to terminate the reaction. The weight average molecular weight of the obtained condensation resin was 2250.

To the reaction mixture, 150 ml of toluene is added to dissolve it. The pH of the reaction mixture is adjusted to 6 by dropwise addition of dilute aqueous ammonia solution at 70-80 ° C. The mixture is then stirred at 70-80 ° C. for 1 hour to complete the reaction. After completion of the reaction, the lower layer, that is, the aqueous layer, is removed and the organic layer is heated and concentrated. The obtained molten resin is taken out of the reactor, cooled and pulverized to obtain 148 g of zinc-modified acid ratio of the salicylic acid resin of the powder. The softening point of the zinc-modified product was found to be 91 DEG C as measured by the ring and the softening point measuring instrument according to the method specified in JIS K-2548.

Using a zinc-modified salicylic resin, a color sheet was obtained in the same manner as in Example 1.

Example 4

27.6 g (0.2 moles) of salicylic acid, 59.5 g (0.3 moles) of dibenzyl ether and 1.2 g of aluminum hexachloride are added as a catalyst. The first stage reaction is carried out at 125-150 ° C. for 8 hours. Next, 14.8 g of anhydrous zinc chloride is added to the reaction mixture. At the same temperature, 76 g (0.6 mol) of benzyl chloride was added dropwise over 5 hours, and aged at the same temperature for 2 hours. The weight average molecular weight of the obtained condensation resin is 1640. The reaction mixture was zinc-modified in the same manner as in Example 75, whereby 135 g of a zinc-modified product having a softening point of 96 ° C was obtained. Using a zinc-modified salicylic acid resin, a color sheet was obtained in the same manner as in Example 1.

[Examples 5-10]

Various polyvalent metal-modified salicylic acid resins, benzyl alcohol, benzyl alkyl ether or dibenzyl ether, their molar ratio to salicylic acid, benzyl halide type and amount, catalyst usage and type and reaction conditions are shown in Table 1, respectively. Each of them is obtained in the same manner as in Example 1 except for changing. The softening point of the obtained metal modified product is shown in Table 1.

Using such a polyvalent metal modified salicylate resin, a color sheet is obtained in the same manner.

TABLE 1

[Examples 11 and 12]

The coating agent of the following composition is manufactured using the suspension of the polyvalent metal modified salicylic acid resin obtained respectively in Example 1 and Example 7, and a coloring sheet is corresponded and obtained.

Parts by weight

Suspension 10

Zinc Oxide 2

Calcium Carbonate 8

Starch 0.8

Synthetic Rubber Latex 0.8

Water 32.5

The color developing sheets obtained in Examples 1 to 12 were subjected to the performance test together with the color developing sheets of Comparative Examples 1 and 2. The results are shown in Table 2.

Comparative Example 1

170 g of P-phenylphenol, 22.5 g of 80% para-formaldehyde, 2.0 g of P-toluene sulfonic 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 benzene from the reaction system is distilled off, and they are reacted at 78 to 80 캜 for 2 hours. After the reaction, 320 g of 10% aqueous sodium hydroxide solution is added and benzene is distilled off by steam distillation. The reaction mixture is then cooled and dilute sulfuric acid is added dropwise. The precipitated P-phenylphenol-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 manner as in Example 1.

Comparative Example 2

In a reaction vessel equipped with a thermometer, a reflux condenser, a dropping funnel and a stirrer, 9.4 g of phenol and 0.2 g of sulfuric acid were added. Next, 23.6 g of α-methylstyrene 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 to 4 mm Hg, 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 fraction and dehydrated under reflux of xylene. After dehydration, the xylene mixture is transferred to an autoclave and carbon dioxide is introduced at 160 ° C. at 20 kg / cm 2. The contents are reacted at the same temperature for 5 hours. 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 (α, α-dimethylbenzyl) salicylic acid zinc, a color sheet was obtained in the same manner as in Example 1.

TABLE 2

Claims (1)

Salicylic acid and the following formula (Ⅳ) Wherein R ₁ and R ₂ may be the same or different and each represents a hydrogen atom or a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group, and R ₃ represents a hydrogen atom or a C _1-4 alkyl group R ₉ is a hydrogen atom, a C _1-4 alkyl group or The co-condensation resin obtained by reacting benzyl alcohol and / or benzyl ether represented by (R ₁ , R ₂ and R ₃ in the same meaning as defined above) in the presence of a nova catalyst is represented by the following formula (VI) Benzyl halide (VI) represented by (wherein R ₄ is a hydrogen atom or a methyl group, one of R ₅ and R ₆ is a hydrogen atom, the other is a hydrogen or a C _1-4 alkyl group, and X represents a halogen atom) 5-35 mol% of structural unit (I) and 10 of structural unit (II) which consist of making it react at 50-160 degreeC by making the molar ratio of benzyl halide (VI) / salicylic acid (1) into 0.2-20 in presence of a catalyst. A process for producing a copolymer consisting of -85 mol% and 4-85 mol% of the structural unit (III), and having a weight average molecular weight of 500-10,000. [Each structural unit (I) is bonded to the one benzene ring of the structural unit (II) via one α-carbon of the structural unit (II), and at least one of the structural units (II) optionally a bond of benzene ring or another ring or other structural unit (II) via α-carbon or α-carbon, each of the structural units (III) being one of the structural units (II) Combined with a benzene ring, and the structural units (I), (II) and (III) are represented by the following general formulas (I) and (II). Wherein R ₁ and R ₂ independently represent a hydrogen atom or a C _1-12 alkyl, aralkyl, aryl or cycloalkyl group, R ₃ represents a hydrogen atom or a C _1-4 alkyl group, R ₄ represents a hydrogen atom or One of the methyl groups, 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)