CN1057103C - Graft copolymer of modified phenolic resin and metallic carboxylate - Google Patents

Abstract

The present invention relates to a graft copolymer of modified phenolic resin and a metal salt of carboxylic acid, which belongs to the field of color-developing agent. The graft copolymer is prepared by the following steps: (1) melting the mixture of p-substituted phenol, organic carboxylic acid, metal oxide and a catalyst; (2) making the mixture react with aldehyde to carry out refluxing; (3) adding organic carboxylate in the mixture to carry out a reaction; (4) dewatering the reaction product. The color-developing agent prepared by the present invention has the advantages of high speed of colour development and high color-developing value.

Description

Modified phenolic resin and carboxylate metal salt graft copolymer

The invention belongs to the field of organic color developers, in particular to a graft copolymer of modified phenolic resin and carboxylic acid metal salt. This resin with a linear structure and the emulsion made of the resin are mainly used as a color developer for carbonless copy paper.

In previous patents, the European patent EP066519A ₂ , the US patent US4604436 and the Japanese patent Ping 4-118280 all described the preparation method of modified phenolic resin, but when the resin is used as a color developer, its color development speed and color development strength are both Not ideal. Although the Chinese patent CN1040543A applied by Japan's Mitsui East Asia Chemical Co., Ltd. has proposed a preparation method for a salicylic acid copolymer and metal salt thereof, it is difficult to produce because of its complex process, labor and time-consuming, and high product cost, which affects its industrial maturity. Accepted by carbonless copy paper manufacturers.

The object of the present invention is to provide a new organic color developer—a graft copolymer of modified phenolic resin and carboxylate metal salt. The color developer made of the copolymer has fast color development speed and high color development value.

For reaching above-mentioned object, the present invention adopts following technical scheme: modified phenolic resin and carboxylate metal salt graft copolymer, this copolymer is made through following steps: 1. melt p-substituted phenol, organic carboxylic acid, metal oxide, catalyst ②The above mixture reacts with aldehydes at 90-110°C and refluxes for 1-6 hours; ③Adds organic carboxylate to the above reaction mixture and reacts at 80-120°C for 10-120 minutes; ④The product is at 0.02-0.06MP . Dehydration under vacuum degree and temperature of 110-130°C; the molar ratio of carboxylic acid to p-substituted phenol in the reactant is 0.05-1.55:1.0, the molar ratio of aldehyde to p-substituted phenol is 0.06-1.22:1.0, the molar ratio of metal oxide to carboxylic acid The ratio is 0.02-1.30:1.0, and the molar ratio of metal organic carboxylate to p-substituted phenol is 0.01-1.10:1.0.

The molar ratio of reactants in the preparation process is: phenol=0.1-1.0:1.0, metal oxide: carboxylic acid=0.2-0.8:1.0, metal organic carboxylate: p-substituted phenol=0.05-1.0:1.0, reacted in _N2 Carried out under the protection of an inert atmosphere.

The p-substituted phenols used in the preparation include alkylphenols, arylphenols, aralkylphenols or mixtures thereof, such as p-cresol, p-ethylphenol, p-propylphenol, p-butylphenol, p-tert-butylphenol, p-amylphenol, p-hexylphenol, p-heptylphenol, p-octylphenol, p-tert-octylphenol, p-nonylphenol, p-decylphenol, p-dodecylphenol, p-chlorophenol, p-bromophenol, p-phenylphenol, p-phenylalkylphenol, etc.

The aldehydes used in the preparation include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde, etc., the most commonly used formaldehyde solution is 37% and 50% formaldehyde by weight.

The carboxylic acids used in the preparation include alkyl carboxylic acids, cycloalkyl carboxylic acids, halogenated carboxylic acids, aryl carboxylic acids, phenylalkyl substituted acids, phenoxy substituted acids, and the like.

The metal oxides used in the preparation include oxides of Mg, Ca, Cu, Cd, Al, Zn, Cr, In, Sn, Co, Ni, Ti, Ba and other metals.

The metal organic carboxylates used in the preparation include metal organic carboxylates formed with the organic carboxylic acids of the present invention and the metal oxides of the present invention, preferably zinc salts.

The catalysts used in the preparation are generally acidic or basic catalysts.

The resin of the present invention is made into the CF coating and the CF coating (the reference substance 1) made by the resin of a company in the United States and the CF coating (the reference substance 2) made by the resin of a company in Taiwan are compared and measured For its color effect, CB uses the products of Jiangxi Lida Special Paper Co., Ltd. The color rendering value was measured with an SC-80 color difference meter produced by Beijing Kangguang Instrument Co., Ltd. The results are shown in the table below:

Table 1, Color Rendering Value of Pure Resin Type CF Formula, RH50%, 19.5°C

Table 2, color development value of resin + clay mixed CF formula, RH50%, 19.5°C

Table 3, the color rendering value of the pure resin CF formula after photoaging RH43%, 19°C, photoaging conditions: 40W ultraviolet lamp, 4h.

Table 4, the color development value of pure resin type CF formula after heat aging, RH43%, 19°C, heat aging condition: 65°C, 4h

Table 5, photoaging after color development of pure resin CF formula, RH43%, 19°C, photoaging conditions: 40W UV lamp, 4h sample ΔE before photoaging ΔE after photoaging this invention 85.02 79.25 Reference substance 1 81.03 71.59 Control substance 2 77.33 64.16

Table 6, the whiteness of pure resin CF coating and the effect of light aging on whiteness, light aging conditions: outside 40W purple lamp, 4h sample Raw paper whiteness Coating whiteness Whiteness after photoaging this invention 91.6 88.1 78.5 Reference substance 1 91.6 88.4 77.1 Control substance 2 91.6 88.1 76.5 Note: CF-chromogen layer, CB-microcapsule layer, RH-humidity, ΔE-color value, ΔE _10s , ΔE _1min , ΔE _5min , ΔE _24h are 10 seconds, 1 minute, 5 minutes, Color development value at 24 hours.

As can be seen from Table 1 and Table 2, the CF formula color value of the product of the present invention is significantly higher than that of reference substance 1 and reference substance 2; 2 large.

It can be seen from Table 3 and Table 4 that the CF formula color value of the product of the present invention after photoaging and heat aging is higher than that of reference substance 1 and reference substance 2, and has better color rendering property.

Table 5 shows that before and after photoaging, the change in the color value of the CF formula of the product of the present invention is much smaller than that of reference substance 1 and reference substance 2.

Table 6 shows that the impact of photoaging on the whiteness of the CF formula of the product of the present invention is lower than that of the control substance 1 and the control substance 2 brightness.

Below by embodiment the present invention will be further described.

Example 1, add 700Kg of p-cresol, 200Kg of salicylic acid, 50Kg of zinc oxide, and 2.5Kg of toluenesulfonic acid to the reactor, heat up and melt. After the material is completely melted, add 100Kg of formaldehyde, keep the temperature of the kettle at 90°C, reflux for 6 hours, then add 100Kg of organic carboxylate (zinc salicylate), react for 2 hours, and then dehydrate under a vacuum of 0.06MPa. Maintain at 110°C, discharge after completion of dehydration, cool and pulverize to obtain the product of the present invention.

Example 2, add 700Kg of p-cresol, 130Kg of salicylic acid, 30Kg of zinc oxide, and 2.0Kg of hexylbenzenesulfonic acid to the reactor, heat up and melt. After the material is completely melted, add 90Kg of formaldehyde, keep the temperature of the kettle at 100°C, reflux for 4 hours, then add 80Kg of organic carboxylate (zinc salicylate), react for 1 hour, and then dehydrate under a vacuum of 0.04MPa. Maintain at 120°C, discharge after completion of dehydration, cool and pulverize to obtain the product of the present invention.

Example 3, add 700Kg of p-phenylphenol, 40Kg of salicylic acid, 25Kg of zinc oxide, and 1.5Kg of dodecylbenzenesulfonic acid into the reactor, heat up and melt. After the material is completely melted, add 50Kg of formaldehyde, keep the temperature of the kettle at 110°C, reflux for 2 hours, then add 30Kg of organic carboxylate (zinc salicylate), react for 30 minutes, and then dehydrate under a vacuum of 0.02MPa. Maintained at 130°C, discharged after dehydration, cooled and crushed to obtain the product of the present invention.

Example 4, add 700Kg of p-chlorophenol, 25Kg of salicylic acid, 1.5Kg of zinc oxide, and 1.0Kg of undecylbenzenesulfonic acid into the reaction kettle, heat up and melt. After the material is completely melted, add 30Kg of formaldehyde, keep the temperature of the kettle at 100°C, reflux for 2 hours, then add 5Kg of organic carboxylate (zinc salicylate), react for 10 minutes, and then dehydrate under a vacuum of 0.02MPa. Maintained at 130°C, discharged after dehydration, cooled and crushed to obtain the product of the present invention.

Claims (10)

1, modified phenolic resin and carboxylic acid metal salt graft copolymer, the present invention is characterized in that, this copolymer is made through following steps: 1. melt the mixture of p-substituted phenol, organic carboxylic acid, metal oxide, catalyst; 2. above-mentioned The mixture reacts with aldehydes at 90-110°C and refluxes for 1-6 hours; ③Add organic carboxylate to the above reaction mixture and react at 80-120°C for 10-120 minutes; ④The product is vacuumed at 0.02-0.06MPa, 110- Dehydration at 130°C; the molar ratio of carboxylic acid to p-substituted phenol in the reactant is 0.05-1.55:1.0, the molar ratio of aldehyde to p-substituted phenol is 0.06-1.22:1.0, and the molar ratio of metal oxide to carboxylic acid is 0.02-1.30 : 1.0, the molar ratio of metal organic carboxylate to p-substituted phenol is 0.01-1.10: 1.0. 2. The copolymer according to claim 1, wherein the molar ratio of the reactants during the preparation is: carboxylic acid: p-substituted phenol=0.1-0.6: 1.0, formaldehyde: p-substituted phenol=0.1-1.0: 1.0, Metal oxide: carboxylic acid 0.2-0.8: 1.0, metal organic carboxylate: p-substituted phenol = 0.05-1.0: 1.0, the reaction is carried out under the protection of an inert atmosphere such as _N2 . 3. The polymer according to claim 1 or 2, characterized in that the p-substituted phenols used in the preparation include alkylphenols, arylphenols, aralkylphenols or mixtures thereof. 4. The polymer according to claim 1 or 2, characterized in that the aldehydes used in the preparation include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde. 5. The polymer according to claim 4, characterized in that the aldehyde used in the preparation is an aqueous formaldehyde solution with a weight percentage of 37% and 50% formaldehyde. 6. The polymer according to claim 1 or 2, wherein the carboxylic acid used in the preparation comprises alkyl carboxylic acid, cycloalkyl carboxylic acid, halogenated carboxylic acid, aryl carboxylate, phenylalkyl substituted acid , Phenoxy substituted acid. 7. The polymer according to claim 1 or 2, wherein the metal oxides used in the preparation include Mg, Ca, Cu, Cd, Al, Zn, Cr, In, Sn, Co, Ni, Ti, Ba oxide. 8. The polymer according to claim 1 or 2, wherein the metal organic carboxylate used in the preparation comprises the metal organic carboxylate formed from the organic carboxylic acid in the present invention and the metal oxide in the present invention. 9. Polymers as claimed in claim 8, characterized in that the organometallic carboxylates used in the preparation are zinc salts. 10. The polymer according to claim 1 or 2, characterized in that the catalyst used in the preparation is a general acidic or basic catalyst.