JPS61287919A - Resin for printing ink - Google Patents

Abstract

PURPOSE:To raise the m.p. and paraffin solvent solubility of the obtained resin, by reacting a novolak phenolic resin with a specified carboxylic acid by heating in the presence of an acid catalyst to a specified acid value or below. CONSTITUTION:A resin obtained by reacting a novolak phenolic resin with at least one carboxylic acid selected from among rosin, its derivatives, 6C or higher fatty acids or their derivatives and acid-modified alkyd resins at a temperature >=150 in the presence of an acid catalyst to an acid value <=30. The amount of the novolak phenolic resin is preferably 20-70wt% based on the total of the novolak phenolic resin and said carboxylic acid. Examples of the novolak phenolic resins include those prepared by using at least one phenol selected from among p-t-butylphenol, p-octylphenol and p-nonylphenol as a principal component.

Description

Detailed Description of the Invention "Object of the Invention" (Industrial Field of Application) The present invention provides an ink with a dilution ratio of 70% by weight or more at 25°C by an ink solvent, particularly a solvent mainly composed of an aliphatic hydrocarbon solvent. The present invention relates to a printing ink resin that does not become cloudy and has high solubility and a high melting point of 130° C. or higher (capillary method).

(Prior Art) In recent years, aliphatic hydrocarbon-based solvents, that is, paraffin-based solvents have become the main solvents used in printing inks and paints. The main reasons for this are that there is little risk of air pollution, there is little odor, and there is good releasability from the film when drying. On the other hand, this paraffinic solvent has the drawback of extremely poor dissolving power.

Therefore, the resins that can be used in combination with paraffinic solvents are severely limited and cannot be fully utilized.

Especially for printing inks, many of the widely used rosin-modified phenolic resins have poor compatibility with paraffinic solvents, and large amounts of higher alcohols and drying oils are used to maintain ink stability. However, if large amounts of these higher alcohols or drying oils are used, the drying oils deteriorate, leading to a decrease in printing efficiency and an increase in fuel consumption during heat drying.

(Problems to be Solved by the Invention) From this point of view, it is desirable to increase the compatibility with paraffinic solvents such as rosin-modified phenolic resins and reduce the amount of higher alcohols and drying oils used. A high softening point is advantageous for drying properties. Such a resin for printing ink has been desired.

"Structure of the Invention" (Means for Solving the Problems) Among printing inks and even offset inks, the present inventors have developed a heat-set type offset rotary ink (hereinafter referred to as "off-set rotary ink"), which often uses paraffin solvents, among printing inks and even offset inks. A modified phenol that is particularly suitable for use in ink (abbreviated as ink), which does not become cloudy even at a dilution rate of 70% or more at 25°C with the solvent, has a high solubility with a melting point of 130°C (capillary method) or higher, and has a high melting point. This led to the invention of resin.

That is, a novolac type phenolic resin as a polyol component, one or more carboxylic acids selected from rosin or its derivative, a fatty acid having 6 or more carbon atoms or its derivative, and an acid-modified alkyd resin are combined in an acid-catalyzed manner. A printing ink resin obtained by reacting at a temperature of at least 150° C. in the presence of an acid value of 30 or less, preferably 20 or less, wherein the carboxylic acid is rosin, polymerized rosin, maleated rosin, fumarated rosin, carbon number 6～
18 fatty acids, polymerized drying oil fatty acids, maleated fatty acids,
Printing that is one or more selected from fumarated fatty acids, rosin-modified alkyd resins, maleated rosin-modified alkyd resins, fumarated rosin-modified alkyd resins, fatty acid-modified alkyd resins, maleated fatty acid-modified alkyd resins, and fumarated fatty acid-modified alkyd resins It is a resin for ink, and furthermore, it is a resin for printing ink using a novolac type phenolic resin mainly containing at least one selected from pt-butylphenol, p-octylphenol, and p-nonylphenol. This is a resin for printing ink in which the ratio of novolak type phenolic resin to the above carboxylic acid is 20 to 70% by weight.

In particular, at 25°C in a paraffinic solvent having 13 to 14 carbon atoms.
This is a printing ink resin that does not become cloudy even at a dilution rate of 70% (% by weight in the solution) or more. This printing ink resin is particularly useful for offset printing inks that have strict physical properties requirements, and is suitable for two-sheet offset printing inks.

Of course, it can also be used for letterpress ink, gravure ink, etc.

Resins for offset inks have undesirable residual free carboxyl groups in terms of printability, and the acid value is 3.0.
Hereinafter, carboxyl groups are blocked with some kind of functional group so that the number of carboxyl groups is preferably 20 or less. Most of them are due to esterification with alcohols, especially polyhydric alcohols. In addition, reactions using isocyanate groups, epoxy groups, etc. may also be used for this purpose. However, all of the rosin-modified phenolic resins produced by these reactions have deteriorated compatibility with paraffinic solvents. Further, Japanese Patent Publication No. 59-191776 describes a rosin phenol resin that has good compatibility with paraffinic solvents. Although the resin produced by this method has good compatibility with paraffinic solvents, it is difficult to control the molecular weight distribution of the resol type phenolic resin used as a raw material because a self-condensation reaction occurs simultaneously during the esterification reaction with the rosin.

In order to avoid this problem, we use novolak type phenolic resin, which is a thermoplastic resin, and the above carboxylic acid (rosin, polymerized rosin, maleated rosin, fumarated rosin, acid value 10).
0-300 rosin modified alkyd resin, acid value 100-
As a result of studying the reaction with 300 maleated or fumarated rosin alkyd resins, it was found that the esterification reaction progressed in the presence of a strong acid catalyst such as sulfuric acid or sulfonic acid, and that it was faster than when using a resol type phenolic resin. It was also discovered that it is very easy to control the molecular weight distribution of the resulting modified phenolic resin.2 In order to obtain the modified phenolic resin of the present invention, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and methanesulfone were used. It is necessary to heat to 150° C. or higher using an acid, sulfonic acids such as ethanesulfonic acid, or mineral acids such as sulfuric acid or hydrochloric acid as a catalyst. However, under such conditions, the reaction product is easily colored, so it is preferable to use a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, etc. in combination.

The proportion of novolak type phenolic resin in this modified phenolic resin is 20% to 70% by weight, and the phenolic O
H group/C○OH group = 1.0/1.0-2.571
．． A range that satisfies 0 is preferable.

In addition, the phenolic components of the novolak type phenolic resin include carbolic acid, cresol, tertiary or secondary butylphenol, amylphenol, cyclohexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol, catechol, resorcinol, hydroquinone, bisphenol, etc. Among these, long-chain alkylphenols such as butylphenol, octylphenol, and nonylphenol are preferred from the viewpoint of solubility. Furthermore, the present invention is not necessarily limited to long-chain alkylphenols, and other phenols can also be used in combination with long-chain alkylphenols. However, if these phenols are used together in too large an amount, the solubility often deteriorates.

Examples of the aldehyde component include formaldehyde, p-formaldehyde, etc., and 0.2 to 4 moles per mole of the phenol component are used under known acid catalysts such as phosphoric acid, p-)luenesulfonic acid, repair, hydrochloric acid, and sulfuric acid. You can react with

Next, carboxylic acid components include rosin, fatty acids, acid-modified alkyd resins, and the like. Examples of rosin or derivatives thereof include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, or mixtures thereof, and polymers thereof, and examples of carboxylic acid-modified rosin include maleic acid, fumaric acid, itaconic acid, Examples include rosin derivatives to which unsaturated carboxylic acids such as crotonic acid are added.

Next, examples of fatty acids having 6 or more carbon atoms or derivatives thereof include monopolymerized drying oil fatty acids having 6 to 18 carbon atoms, maleated drying oil fatty acids, fumarized drying oil fatty acids, and the like.

Fatty acids with 6 to 18 carbon atoms include caproic acid, caprylic acid, capric acid, lauric acid, tridecanoic acid, valmitic acid, stearic acid, nonadecaic acid, laurolenic acid, myristoleic acid, seamaric acid, oleic acid, linoleic acid, and linolenic acid. acids, eleostearic acid, lylunic acid, etc. and mixtures thereof.

Furthermore, for example, coconut oil fatty acids, rice bran oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, cottonseed oil fatty acids, tung oil fatty acids, fish oil fatty acids, etc. are used.

Next, the acid-modified alkyd resin includes rosin-modified alkyd resin, fatty acid-modified alkyd resin, maleated rosin-modified alkyd resin, fumarated rosin-modified alkyd resin, maleated fatty acid-modified alkyd resin, fumarated fatty acid-modified alkyd resin, etc. Preferably, it is an acid-modified alkyd resin having an acid value of 100 to 300.

Further, as rosin-modified alkyd resins, gum rosin, wood rosin, tall oil rosin, disproportionated rosin, and mixtures thereof are modified with the following polyols and polycarboxylic acids, and preferably alkyd resins with residual carboxylic acid having an acid value of 100 to 300 are used. Can be mentioned. Here, the polyols include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and neopentyl glycol, glycerin, trimethylolethane, and tris-2hydroxyethyl isocyanurate.

Examples include one kind of polyols such as pentaerythritol, diglycerin, dipentaerythritol, and tripentaerythritol, or a mixture thereof.

Examples of polycarboxylic acids include benzene polycarboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, and aliphatic dicarboxylic acids such as adipic acid and azelaic acid. Furthermore, an alkyd resin having an acid value of 100 to 300, which is synthesized by replacing part or all of the rosin part of the above alkyd resin with maleated or fumarized rosin, is also used as the carboxylic acid component of the printing ink resin of the present invention. be able to.

Further, a fatty acid-modified alkyd resin with an acid value of 100 to 300 and a residual carboxylic acid can be used as the carboxylic acid component of the resin for printing ink of the present invention by reacting the aforementioned fatty acid with a polycarboxylic acid if necessary. can.

Furthermore, the resin for printing ink of the present invention may include a rosin-modified phenolic resin, which has been conventionally used for printing ink.
It is also possible to use it in combination with alkyd resins, oil resins, etc., and to modify some petroleum resins, acrylics, urethanes, etc.

To make a varnish for printing ink using the resin of the present invention 2
50 to 150 parts by weight of a solvent and/or a drying oil (or a modified drying oil such as a polymerized oil or a drying oil alkyd resin) are dissolved in 100 parts by weight of the resin of the present invention. In actual use, gel varnishes are made using gelling agents such as aluminum octylate, aluminum stearate, zirconium octylate, aluminum triisopropoxide, and aluminum diproboxide monoacetylacetonate, and are colored yellow, red, and indigo. , or by dispersing pigments such as black ink, adding compounds such as anti-friction improvers, ink dryers, and drying inhibitors as necessary, and adjusting the viscosity to the appropriate viscosity. It becomes an off-cent ink such as ink.

It can also be used as newspaper ink or letterpress ink. Furthermore, in order to make a varnish for gravure or flexographic ink using the resin of the present invention, 2. For 1.0 parts by weight of the resin of the present invention, 100% of aliphatic and alicyclic hydrocarbons having a boiling point of 140°C or less at normal pressure are added. What is necessary is to melt it in ~200 parts by weight.

Next, the present invention will be explained using specific examples. "Parts" and "%" refer to parts by weight of 1M.

Production example 1 (Production of novolac type phenolic resin) In a 4-hole flask equipped with a stirrer, reflux condenser, and temperature needle,
Prepare 1500 parts of p-t-butylphenol, 570 parts of formalin (37%), 300 parts of water, and 2 parts of oxalic acid.
After heating to 90°C, react for 90 minutes, add 4 parts of hydrochloric acid, further react for 120 minutes, add 2000 parts of water,
The mixture was stirred for 0 minutes and left for 1 hour. After removing the condensate, add another 2000 parts of water and stir for 20 minutes.
After leaving it for 0 minutes, remove the water, heat it, and enter the dehydration process.
The mixture was stirred at 120° C. for 3 hours, and 1,800 parts of xylene was added dropwise and dissolved to obtain about 3,600 parts of a novolac type phenol resin solution with a nonvolatile content of 50%. This is called A novolac.

Production Example 2 In the process shown in Production Example 1, pt-butylphenol 15
To part 0! The same procedure was carried out except that a mixture of 1,850 parts of p-octylphenol and 23 parts of bisphenol A was used to obtain about 3,600 parts of a resin solution with a non-volatile content of 52%. This is designated as B novolak.

Production Example 3 1030 parts of p-octylphenol and 80% purity in a 4-bottle flask equipped with a stirrer, a reflux device with a water separator, and a thermometer.
300 parts of formaldehyde and 600 parts of l-toluene were added, and while stirring at 60°C, 185 parts of a catalyst prepared by dissolving 5 parts of p-toluenesulfonic acid in 180 parts of water were added.
After reacting at 90t' for 5 hours.

After removing the water and raising the temperature to 115℃ and reacting for 2 hours,
400 parts of toluene was added and cooled to obtain about 2000 parts of a resin solution with a non-volatile content of 50%. This is called C novolac.

Example 1 (Production of highly soluble rosin-modified phenolic resin) 200 parts of Chinese gum rosin was charged into a four-bottle flask equipped with a stirrer, a water separator, a condenser, and a thermometer, heated while blowing nitrogen gas, and melted at 200°C or less. , stir and raise the temperature to 260°C. Esterification catalyst mixed with 400 parts of A novolak liquid and sulfuric acid/hypophosphorous acid = 3/7 1.
5 parts are mixed well and added dropwise over 2 hours. During this time, xylene and water (reactive dehydration due to esterification) were collected through a condenser with a water separator, and the temperature was maintained at 260°C.

It was pumped out when the acid value reached 12 6 hours after dropping. This rosin-modified phenolic resin has an acid value of 12. The melting point (capillary method) was 152°C, and the dilution rate with 28koku No. O Solvent H (Normal paraffin, C=13 to 14, manufactured by Yakkoku Kagaku) was stable at 80% at 25°C. The yield of this rosin-modified phenol resin was 385 parts. FIG. 1 shows the infrared absorption spectrum of this resin obtained. In this Figure 1, the absorption at 1700 cm (due to the ketone of carboxylic acid) is small, and the absorption at 1700 cm due to the ester bond is small.
A large peak can be seen at 0 cm.

Example 2 415 parts of B novolac liquid and 200 parts of Chinese gum rosin were charged into a reaction apparatus similar to that in Example 1, and while blowing nitrogen gas, the temperature was raised to 150°C to dissolve the rosin, and the mixture was stirred.
A mixed solution of 0.2 parts of p-)luenesulfonic acid and 0.2 parts of hypophosphorous acid was added as a catalyst, and while removing xylene, the mixture was heated to 240 DEG C., stirred for 5 hours, and pumped out. The acid value of this resin is 15.5 and the melting point is 155°C.
The dilution rate with H was stable at 90%.

Example 4 In a reactor similar to Example 1, 180 parts of Chinese gum rosin, Malquid 3003 (maleated rosin modified alkyd resin manufactured by Arayo Kagaku Kogyo, acid value 115), and PS-2851 were added.
(Gun-ei Chemical p-octylphenol novolac resin)
160 parts and 80 parts of toluene were added, and while blowing gas, the temperature was raised to 80°C and stirred.

1 of the dissolved catalyst mixed with sulfuric acid/hypophosphorous acid = 3/7
．． Two parts were added, the temperature was raised to 240°C, the mixture was reacted for 4 hours, and then pumped out. This resin has an acid value of 16.4. Melting point is 138℃
The dilution rate with H was stable at 90%.

Example 5 In a reactor similar to Example 1, 190 parts of Chinese gum rosin and 10 parts of distilled oleic acid were charged, dissolved at 185°C while blowing nitrogen gas, and heated to 260°C with stirring.

After thoroughly mixing 405 parts of A novolak liquid and 1.5 parts of esterification catalyst mixed with sulfuric acid/hypophosphorous acid = 3/7,
The mixture was added dropwise over a period of 15 minutes.

During this time, xylene and water were collected through a condenser with a water separator and the temperature was maintained at 260°C. It was pumped out when the acid value reached 13, 4 hours and 30 minutes after dropping. This resin has an acid value of 12. The melting point was 138°C, and the dilution rate with No. 0 Solvent H at 25°C was stable at 95% or more.

Comparative Example 1 (Conventional production of rosin-modified ferrite and nol resin) 200 parts of Chinese gum rosin was charged into the same reactor as in Example 1, heated while blowing nitrogen gas, and stirred at 200°C, then further heated to 260°C. Raise the temperature and add 250 hytanol
1 (resol type phenol resin of p-octylphenol manufactured by Hitachi Chemical Co., Ltd.) was added over 2 hours and reacted at the same temperature for 2 hours. The acid value was 83, and no esterification occurred. Thereafter, 16 parts of glycerin was added and the mixture was reacted for 8 hours, and the acid value decreased to 16. The melting point of this resin was 143°C, and the dilution rate with No. 18 Solvent H at 25°C was 54%, at which point it started to become cloudy.

[Inking evaluation]

The six types of rosin-modified phenolic resins obtained were made into varnishes using the following two types of formulations, and after being made into inks, the printing was evaluated.

a. Making varnish. Fesification A - 200 parts of each resin synthesized in Examples 1 to 4 and Comparative Example 1, No. OO polymerized oil 4
8 parts 9 days Stone No. 0 turben) H1 part 2 parts were put into a flask and heated to 180℃ while blowing nitrogen gas.
Varnishing B-Example 1 kept warm for 30 minutes while stirring
200 parts of each resin synthesized in ~4 and Comparative Example 1, 0
Four 48 parts of No. 0 polymerized oil and 152 parts of Maggi 470 solvent (ink solvent manufactured by Maggi Oil) were put into a Lof flask and varnished in the same manner as varnishing A.

b. Preparation of gel varnish. Gel varnish A - 188 parts of each varnish obtained in varnishing A were charged into a Lof flask, stirred and heated to 100°C while blowing nitrogen gas, and 3 parts of ALCH (gelling agent made by Yoken Fine Chemicals) and 8 Add a mixture of 6 parts of stone O turben) H, 180
The mixture was allowed to rest at ℃ and kept warm for 1 hour to obtain gel varnish A.

Gel varnish B - In the same manner as gel varnish A, a gel varnish was formed using a mixture of the varnish obtained in varnishing B, ALCH, and Maggi 470.

C. Preparation of Ink Ink A-Ink A was prepared using each of the gel varnishes obtained in A-gel varnish A. That is, disperse 18 parts of Carmine 6BA (red pigment manufactured by Toyo Ink Manufacturing Co., Ltd.) in 60 parts of gel varnish A using a three-roll mill, and use 18 stone No. O Solvent H and varnish and/or gel varnish to make a total of 100 parts. Also tank value 5.5-6.0. Flow value 19.
It was adjusted to be 0 to 20.0 (at 25°C).

Inking B - 8 used in Inking A in the same way as Inking A
Ink was made in the same manner by replacing Stone No. 0 Turupen L-H with Magee 470.

These 10 types of inks were spread on Mitsubishi Pearl Coat 66.5 kg (off-export coated paper) using an R1 tester, and then immediately placed in an oven at 100℃ for 4 seconds to dry. Glossy GM26D (60
Gloss was measured at 60°-60°.

The drying property was expressed as the drying time in an oven at 160° C. to eliminate aftertack caused by finger touch.

The evaluation results are shown in Table-1.

Table 1 (Ink evaluation results) As shown in Table 1, the resin of the present invention is a novel resin that has the ability to simultaneously satisfy the gloss and drying properties of the ink when used in printing ink.

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of the rosin-modified phenolic resin according to the present invention.

Claims (1)

[Claims] 1. A novolac type phenolic resin and one or more carboxylic acids selected from rosin or its derivative, a fatty acid having 6 or more carbon atoms or its derivative, and an acid-modified alkyd resin. At least 15 in the presence of a catalyst
A resin for printing ink, characterized in that it reacts at a temperature of 0°C to give an acid value of 30 or less. 2. The carboxylic acid is rosin, polymerized rosin, maleated rosin, fumarated rosin, fatty acid having 6 to 18 carbon atoms,
Polymerized drying oil fatty acids, maleated fatty acids, fumarated fatty acids, rosin modified alkyd resins, maleated rosin modified alkyd resins, fumarated rosin modified alkyd resins, fatty acid modified alkyd resins, maleated fatty acid modified alkyd resins and fumarated fatty acid modified alkyd resins The printing ink resin according to claim 1, which is one or more selected from the following. 3. The resin for printing ink according to claim 1 or 2, which uses a novolac type phenol resin mainly containing at least one selected from pt-butylphenol, p-octylphenol, and p-nonylphenol. 4. The ratio of novolac type phenol resin to novolac type phenol resin and the above carboxylic acid is 20 to 7.
The resin for printing ink according to any one of claims 1 to 3, which has a content of 0% by weight. 5. The printing according to any one of claims 1 to 4, which has a melting point measured by a capillary method of 130°C or higher and does not become cloudy even if the dilution rate at 25°C with an ink solvent having a boiling point of 200°C or higher is 70% by weight or higher. Resin for ink.