JPH0770269A - Rosin-modified phenolic resin - Google Patents

Abstract

PURPOSE:To obtain a new resin for ink having well-balanced gloss and dryability and especially excellent ink stability unattainable by conventional rosin-modified phenolic resins even by using an AF solvent. CONSTITUTION:This improved rosin-modified phenoltic resin having an acid value of <=40 is produced by using a rosin-modified phenolic resin composed of (A) a rosin, (B) a resol-type phenolic resin or a phenolic resin converted to novolak and then to resol and (C) a polyhydric alcohol and carrying out Friedel-Crafts reaction of the remaining phenolic OH group with turpentine oil using an acid catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink resin having excellent ink performance and printing workability in offset printing, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the solvent used for offset printing ink has been mainly composed of a solvent obtained by hydrogenating an aromatic component of a conventional solvent to form a non-aromatic component. The main reasons are that there is little danger of air pollution and a good printing environment with less odor can be obtained. However, this aroma-free (hereinafter referred to as AF) solvent has a drawback that its solubility is poor as compared with conventional ink solvents. As a standard for measuring the solubility of the rosin-modified phenolic resin in the AF solvent, there is the solubility in AF6 solvent (trade name of Nippon Petrochemical Co., Ltd.). As a measuring method, for example, the resin% in the solution when the solution becomes cloudy at 25 ° C. is expressed. The lower the resin%, the better the solubility of the rosin-modified phenolic resin in the AF solvent. The AF6 solvent solubility is specifically described in Examples.

As the resin to be combined with the AF solvent, only those having good solubility in a solvent can be used. Most of the conventional rosin-modified phenolic resins having good solubility have a large proportion of the resole-type phenolic resin used to increase the number of condensation nuclei of the resole-type phenolic resin. The rosin-modified phenol resin having such a composition has a high acid value, and when it is used as an offset ink, the emulsification amount is large and water marks are likely to occur. Further, when an ink is formed by using an AF solvent, there is a new problem that the drying time on paper is extremely long even if the set is the same as the ink using the conventional solvent.

The above problem can be solved by using a conventional rosin-modified phenol resin having poor solubility in the ink using AF solvent. However, if such a low-solubility component is included in the ink, it is necessary to maintain the stability of the ink by using a large amount of higher alcohol or drying oil. If a large amount of these higher alcohols and drying oils are used, the drying property will be slow. If the drying property becomes slow, the sheet-fed ink will lack the amount of sticking, and the off-wheel ink will result in poor drying during heating and drying, and only high-speed printing suitability will be obtained.

[0005]

As described above, as long as the ink is designed by using the AF solvent using the rosin-modified phenolic resin thus far, it is possible to obtain satisfactory performance in the drying property even if the gloss appears. I can't. In addition, the stability is poor and the ink will be aged over time, or the ink will have a strong temperature dependency and the state will change easily on the machine. In view of such circumstances, the inventors of the present invention have developed a novel ink having a good balance of gloss and drying property, which is not obtained by a conventional rosin-modified phenol resin using AF solvent, and particularly excellent ink stability. The present invention has reached the present invention after earnestly investigating for a resin for use.

[0006]

The present invention relates to a rosin-modified phenol resin comprising a rosin (a), a phenol resin (b) which is a resole type or novolak and then resole, and a polyhydric alcohol (c). The present invention relates to an improved rosin-modified phenolic resin characterized in that the residual phenolic OH group having an acid value of 40 or less is subjected to Friedel-Crafts reaction with turpentine oil using an acid catalyst.

In the present invention, a rosin-modified phenolic resin,
In particular, in a phenol resin containing a resole-type phenol resin component in an amount of 30 to 80 parts by weight with respect to 50 parts by weight of rosins, unreacted phenolic OH groups that are not involved in the formation of rosin and chroman rings are present in the presence of an acid catalyst. Then, the Friedel-Crafts reaction is performed to form a terpene phenol ether, thereby modifying the structure of the phenolic OH group. That is, the structure of the phenol moiety in the rosin-modified phenolic resin is 2,6-di-t-butyl-4-
Similar to methylphenol and the like, the effect of antioxidants is known. Phenolic compounds with weak O- and H-bonds of phenolic OH are the peroxide radicals that are first generated in the process of drying the vehicle. Radical reaction in the drying step is hindered because it reacts with. The phenolic OH group, which is an inhibitory component of this drying step, is converted into turpentine phenol ether.

Examples of the rosin component (a) include gum rosin, wood rosin, tall oil rosin, polymerized rosin, and asymmetric rosin. At least 220 ° C. or higher, preferably 2 ° C. or higher, by adding at least trinuclear or higher resole type or phenol resin (b) that has been resolized after novolak to rosin component (a)
By the ester reaction at 40 to 275 ° C, a rosin-modified phenol resin having good solubility in AF solvent can be produced. This manufacturing method is disclosed in JP-A-58.
It is not necessary to use a special method as described in Japanese Patent Laid-Open No. -65233, and it is possible to sufficiently manufacture by a known method.

Rosin component (a) and polyhydric alcohol (c)
When esterifying, it is not possible to use an alkaline substance as a catalyst. The reaction is preferably carried out in the absence of catalyst or in an acidic atmosphere. This is because, in the Friedel-Crafts reaction of residual phenolic OH groups and turpentine oil, which will be described later, the presence of an alkali catalyst neutralizes the acid catalyst and significantly inhibits the formation of terpene phenol ether, and is a neutralization product of both catalysts. This is because the product may become cloudy.

The resol type phenolic resin (b) used in the present invention must be a resole type phenolic resin having at least 3 or more nuclei after resolization or novolak formation and then resolization. In the case of a mononuclear or binuclear resol-type phenol resin, it is possible that most of the phenolic OH groups have been consumed in the formation of chroman rings with rosin. If there is no unreacted phenolic OH group in the system, the turpentine oil component does not react and evaporates out of the reaction system, resulting in corrosion of the device by the acid catalyst and severe coloring of the resin. As the phenols used in the resol type phenol resin, alkylphenol having a C _{4 to} C ₁₂ substituent at the para position is most preferable. As the aldehyde component, paraformaldehyde and formalin aqueous solution are used. An alkali catalyst is used to synthesize the above components with the rosin (a) to synthesize a resol type phenol resin (b). Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, zinc oxide, aqueous ammonia solution and the like. The alkali catalyst used in the resol reaction also needs to be sufficiently neutralized and washed so as not to impair the effect of the acid catalyst in the Friedel-Crafts reaction between turpentine oil and residual phenolic OH groups. This is because if the neutralization washing is insufficient, the acid catalyst is neutralized and the production of terpene phenol ether is significantly inhibited, and the product is turbid due to the neutralization products of both catalysts.

Examples of the polyhydric alcohol (c) used in the present invention include glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, pentaerythritol and dipentaerythritol. The amount of the polyhydric alcohol used is closely related to the solubility of the resulting rosin-modified phenolic resin and is therefore limited to some extent, usually 1 molar equivalent or less, preferably 0.6 or less, relative to the carboxylic acid of the rosin component (a). ~ 0.85 molar equivalents are added. Addition of an amount larger than that lowers the solubility of the resin, which is not preferable. Excessive alcoholic OH groups increase the emulsification amount of the ink and have a harmful effect that water marks are easily generated during printing.

The turpentine oil component to be reacted with the phenolic OH groups of the rosin-modified phenol resin in the present invention includes raw turpentine oil and refined turpentine oil. Preferably, the use of refined turpentine oil having an α-pinene content of 80% by weight or more is effective in reactivity. The amount of turpentine oil component added is equimolar to the phenol nucleus containing residual phenolic OH groups. If the input amount is large, the molecular weight does not grow and misting increases, resulting in a defective set. If the amount is too small, the residual phenolic OH groups cannot be sufficiently modified to improve the drying property.

The use of an acid catalyst is an essential component in the Friedel-Crafts reaction of residual phenolic OH groups with an acid value of 40 or less with turpentine oil. The amount of the acid catalyst used is usually relative to the weight of the rosin-modified phenolic resin before addition,
0.01-1.0% by weight, preferably 0.05-0.5
Add weight%. When the input amount is less than the above specified amount, the reaction becomes insufficient, and when the input amount is more than the above specified amount, abnormal heat generation or the like is dangerous and the apparatus is corroded severely. Examples of the acid catalyst include boron trifluoride, anhydrous aluminum chloride, hydrochloric acid, sulfuric acid, phosphoric acids, paratoluenesulfonic acid,
Dodecylbenzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, etc. are mentioned. Among them, the terpene phenol ether structure is preferentially obtained over the terpene phenol structure, and paratoluene sulfonic acid, dodecylbenzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, concentrated sulfuric acid, etc., which can be added at the production temperature of the above-mentioned rosin-modified phenol resin The sulfuric acid compounds of are preferred. When using boron trifluoride or anhydrous aluminum chloride, there is a danger of abnormal heat generation and explosion unless the reaction system is kept below 30 ° C. This catalyst is effective when the rosin-modified phenolic resin is varnished into a liquid form and used.

Further, the rosin-modified phenol resin of the present invention is a rosin which has been conventionally used for printing inks, such as unsaturated dibasic acid modification of rosins (a), petroleum resin modification, acrylic modification, urethane modification. It is also possible to use in combination with modified phenol resin, alkyd resin, petroleum resin.

To make a varnish for printing ink using the resin of the present invention, a solvent and / or a drying oil (or a modified drying oil such as a polymerized oil or a drying oil alkyd resin) is added to 100 parts by weight of the resin of the present invention. Is dissolved in 50 to 150 parts by weight. In actual use, use a gelling agent such as aluminum octylate, zirconium octylate, aluminum triisobropoxide, aluminum dipropoxide monoacetylacetonate to make a gel varnish, and use yellow, red, indigo or black Dispersing pigments, adding compounds such as friction resistance improvers, ink dryers, drying inhibitors, etc. as necessary, and adjusting to an appropriate viscosity, dampening water for sheet-fed inks, off-wheel inks, etc. It becomes the offset ink which uses or the waterless offset ink.

It can also be used as newspaper ink or letterpress ink. Furthermore, in order to prepare a varnish for gravure or flexo ink using the resin of the present invention, the resin 100 of the present invention is used.
100 parts by weight to 200 parts by weight of aliphatic and alicyclic hydrocarbons having a boiling point of 140 ° C. or less at normal pressure may be dissolved in parts by weight. Next, the present invention will be described with reference to specific examples. "Part"
"%" Represents parts by weight and% by weight.

[0017]

【Example】

Production Example 1 (Production of Resol-Type Reactant) In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer,
Charge 1640 parts of p-t-amylphenol, 652 parts of 92% paraformaldehyde and 1260 parts of toluene,
After heating to 60 ° C to dissolve, calcium hydroxide 8.2
Throw in a section. After heating to 90 ° C. and reacting for 4 hours to adjust the resole having an average number of nuclei of 2 nuclei, the temperature is further raised to 110 ° C. and dehydrated at the same temperature until a resole-type phenol resin having an average number of nuclides of 4 to 6 is obtained. I went. After the resin is neutralized with an acid, it is washed with water until the pH of the washing water becomes 6 to 7 and used for the reaction with rosin.

Production Example 2 In a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer,
pt-amylphenol 1640 parts, 92% paraformaldehyde 326 parts, toluene 1260 parts and oxalic acid 8.
2 parts and 4.1 parts of 17% sulfuric acid were charged, and dehydration was performed at 110 ° C. at the same temperature until a novolac type phenol resin having an average number of nuclides of 4 to 6 was obtained. 60 ° C after confirmation of phenol nucleus
It was cooled to pH 7, and washed with water until the pH of the wash water became 6-7.
Then, 326 parts of 92% paraformaldehyde and 8.2 parts of calcium hydroxide were added at the same temperature, and the mixture was heated to 90 ° C. and reacted for 2 hours to add a methylol group to the phenol nucleus. After neutralizing the resin with an acid, the pH of the washing water is 6 to 7
Wash with water and use for reaction with rosin.

Example 1 (Production of rosin-modified phenolic resin) In a four-necked flask equipped with a stirrer, a reflux condenser equipped with a water separator, and a thermometer, 660 parts of gum rosin was charged and heated while blowing nitrogen gas at 200 ° C. After 670 parts of the resol type phenol resin (solid content 65%) and 57 parts of glycerin produced by Production Example 1 were added by melting and stirring below, the temperature was raised to 265 ° C. while observing the state of the inside of the system successively. On this occasion,
Toluene and water (reaction dehydration by esterification) were collected by a reflux condenser equipped with a water separator, reacted at the same temperature for 6 hours, and when the acid value reached 36, 126 parts of turpentine oil and paratoluenesulfonic acid were collected. After adding 0.8 parts, the product was reacted at 265 ° C. for 4 hours. The obtained product has an acid value of 16, a softening point of 178 ° C., an AF6 solvent solubility of 17%, and a MW of 7.
It was good.

Example 2 The same operation as in Example 1 was carried out except that a part of the gum rosin used in Example 1 was replaced with gum rosin / tall oil rosin = 50/50. When the acid value reached 39 after reacting at 260 ° C. for 6 hours, 126 parts of turpentine oil and 0.8 part of paratoluenesulfonic acid were added, and then the mixture was reacted at 265 ° C. for 8 hours to obtain a product. The product obtained has an acid value of 20, and a softening point of 172.
C., AF6 solvent solubility was 7%, and MW was 40,000.

Example 3 The same operation as in Example 1 was carried out except that the resol type phenol resin used in Example 1 was replaced with the resolized phenol resin of Production Example 2 after the novolac conversion. 260 ° C
When the acid value reached 39 after reacting for 6 hours, 189 parts of turpentine oil and 0.8 part of paratoluenesulfonic acid were added, and the mixture was reacted at 265 ° C. for 8 hours to obtain a product. The obtained product had an acid value of 21, a softening point of 174 ° C., an AF6 solvent solubility of 10%, and a MW of 50,000. Example 4 The same operation as in Example 1 was carried out except that 57 parts of glycerin used in Example 1 was replaced with 45 parts of pentaerythritol. When the acid value reached 39 after reacting at 270 ° C. for 9 hours,
126 parts turpentine oil and 0.8 parts paratoluenesulfonic acid
After the addition of parts, reaction was carried out at 265 ° C. for 8 hours to obtain a product.
The obtained product had an acid value of 17, a softening point of 182 ° C., an AF6 solvent solubility of 12%, and a MW of 70,000.

Example 5 In Example 1, 900 parts of xylene was added at an acid value of 36 and cooled to a reaction temperature of 30 ° C., then 0.4 parts of boron trifluoride phenol complex was added, and turpentine oil 126 was used.
While maintaining the reaction temperature at 30 ° C. or less, the mixture was added dropwise. When the acid value of the resin solid content becomes 25 or less, the temperature starts to be raised, xylene and reaction water are collected by a reflux condenser with a water separator, and the temperature is raised to 260 ° C and then kept at the same temperature for 2 hours. Other than that, the same operation as in the example was performed. The product obtained has an acid value of 8, a softening point of 169 ° C. and an AF6 solvent solubility of 7
% And MW was 50,000.

Comparative Example 1 The same operation as in Example 1 was carried out except that 0.8 part of paratoluenesulfonic acid was added and reacted without adding turpentine oil when the acid value was 36 in Example 1. After reacting at 260 ° C. for 14 hours, the obtained product has an acid value of 29, a softening point of 168 ° C. and an AF6.
No. solvent solubility was 22% and MW was 50,000.

Comparative Example 2 Using the same composition as in Comparative Example 1, 0.8 parts of zinc acetate was used as an esterification catalyst when the resin was heated to 265 ° C.,
The same operation as in Comparative Example 1 was carried out except that the acid value was 40 or less and no paratoluenesulfonic acid was added. After reacting at 260 ° C for 10 hours, the obtained product has an acid value of 30 and a softening point of 172.
C., AF6 solvent solubility was 25%, and MW was 60,000. Comparative Example 3 The same operation as in Comparative Example 1 was carried out except that the resol type phenolic resin used in Comparative Example 1 was replaced with the novolac-converted phenolic resin which was resolated in Production Example 2. 260 ° C
After 18 hours of reaction, the resulting product had an acid value of 33, a softening point of 169 ° C., an AF6 solvent solubility of 12%, and a MW of 40,000.

Next, the ink evaluation results of the resins obtained in Examples and Comparative Examples are shown.

A. Preparation of Inks Each resin obtained in Examples 1 to 5 and Comparative Examples 1 and 3 was dissolved in linseed oil and AF6 solvent, and the amount (0.3 to 1.5 parts) of each resin was adjusted. A gel varnish was prepared by adding AlCH (a gelling agent manufactured by Kawaken Fine Chemicals Co., Ltd.). 60 parts of each obtained gel varnish and 18 parts of Carmine 6B (red pigment manufactured by Toyo Ink Mfg. Co., Ltd.) were dispersed using a three-roll mill, and AF6 solvent and gel varnish were added so that the total amount became 100 parts. Then, 0.5 part of a 6% manganese naphthenate solution (Harima Kasei Co., Ltd. dryer) was added, and the tack at 25 ° C. was 8.5 to 10.0 and the flow was 17.0 to 18.0. To obtain a sheet-fed ink.

C. Printing test evaluation Gloss: Ink O. 15 cc of the RI tester (manufactured by Akira Seisakusho Co., Ltd.) was rolled on the art paper with a full roll, and the gloss value after 24 hours was measured by a 60 ° -60 ° gloss meter. Set: Ink O. After 15cc was developed with a 4 cut roll of RI tester (Myo Seisakusho Co., Ltd.), the colored product was cut and stuck to another art paper, and the ink was attached to the art paper using the roll of RI tester. The time (minutes) until it stopped was measured. Dryability on paper: After 0.2 cc of ink was spread on sulfuric acid paper with a RI tester 4-cut roll, the sulfuric acid paper was overlaid and set on a Choyokai type drying tester, and the drying time was compared under the condition of 0.1 rpm. Dryability on machine: After the ink was spread on a glass plate with an applicator of 75 μm, the humidity was 6 at 25 ° C.
Finger touch dry time was examined every 30 minutes under 5% conditions.

The test results are shown in Table 1. Table-1 ─────────────────────────── Gloss set Paper drying On-machine drying Example 1 68 12 minutes 9 hours 4 hours Example 2 75 15 minutes 10 hours 6 hours Example 3 68 12 minutes 10 hours 5 hours Example 4 67 6 minutes 7 hours 3 hours Example 5 6 7 9 minutes 10 hours 6 hours Comparative example 1 70 15 minutes 15 hours 9 hours Comparative example 2 64 9 minutes 12 hours 7 hours Comparative Example 3 68 15 minutes 18 hours 10 hours ────────────────────────────

Evaluation As is clear from Table 1, in the ink system using the AF solvent, the rosin-modified phenol resin obtained by the present invention has a gloss and set balance as a resin for printing ink, which is higher than that of the comparative example. A significant improvement is seen in the improvement of the drying property when the value is adjusted.

[0030]

INDUSTRIAL APPLICABILITY As described above, the rosin modification obtained by reacting the rosin component (a) with the resol type or the resol type phenolic resin (b) which has been resolized after novolak formation and the polyhydric alcohol obtained according to the method of the present invention A resin obtained by modifying the residual phenolic OH of a phenolic resin with terpine oil into a terpene phenol ether in the presence of an acid catalyst is used for inks, especially for odorless and pollution-free lithographic printing inks using AF solvent. When used, the ink has a good balance between gloss and set and can be dried well. Since the sheet-fed ink increases the amount of sticking and the off-wheel ink can increase the printing press speed, it has exceptionally high-speed printing suitability and has a very practical effect.

Claims (3)

[Claims] 1. A rosin-modified phenolic resin comprising a rosin (a), a resol type or novolac-forming phenolic resin (b) which is then resolized, and a polyhydric alcohol (c) having an acid value of 40 or less. An improved rosin-modified phenolic resin characterized in that the phenolic OH groups are reacted with turpentine oil using a Friedel-Crafts reaction using an acid catalyst. 2. The rosin-modified phenolic resin according to claim 1, wherein the number of condensed nuclei of the phenolic resin (b), which is resol type or novolak and then resolizes, is 3 or more. 3. The rosin-modified phenolic resin according to claim 1, which has an acid value of 25 or less.