JPH11286529A - Rosin-modified phenol resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin having high viscosity and high solubility and useful as a resin, for printing ink, or the like, by adding a metal compound to a reaction product obtained after reaction with rosins and reacting the mixture. SOLUTION: This rosin-modified phenol resin is obtained by reacting (A) rosins with (B) resol type phenols and (C) polyols and then further, adding (D) a metal compound (preferably a metal hydroxide, a metal oxide or an acetic acid metal salt, e.g. zinc acetate) thereto and reacting the mixture. Furthermore, it is preferable that the components B, C and D are respectively used in amounts of 20-120 pts.wt., 3-20 pts.wt. and 0.05-5 pts.wt. based on 100 pts.wt. charging amount of the component A and the component A is reacted with the component B and then, the component D is added to the reaction product and further, the reaction product is reacted with the component D is production of the objective resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a rosin-modified phenol resin and a method for producing the same. The rosin-modified phenolic resin obtained according to the present invention is useful as a resin for printing inks, particularly as a resin for offset printing inks.

[0002]

2. Description of the Related Art Conventionally, a method for producing a rosin-modified phenol resin includes a method for reacting a rosin ester obtained by previously reacting a metal compound with a resole-type phenol.
Alternatively, a production method is known in which a rosin is reacted with a resol-type phenol, and then a metal compound is reacted with a polyol. However, in such a method for producing a rosin-modified phenol resin, the viscosity of the system is significantly increased during the production, so that it is often difficult to control the reaction, and it is difficult to produce a high-viscosity resin. Also,
In the design of rosin-modified phenolic resin, when using a catalyst or additive that forms a metal and a salt in a metal compound, insoluble matter may be generated in the obtained rosin-modified phenolic resin. However, there are many design restrictions. In recent years, this is not only disadvantageous in terms of high viscosity printing and high solubility required for printing ink resins in which rosin-modified phenolic resins are mainly used from the viewpoint of high-speed printing and environmental protection, It is disadvantageous from the viewpoint of designing and obtaining a rosin-modified phenol resin having an arbitrary viscosity and solubility.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a rosin-modified phenol resin having high viscosity and high solubility and a method for easily producing the rosin-modified phenol resin.

[0004]

Means for Solving the Problems In view of the above problems, the present inventors have intensively studied various production conditions for producing a rosin-modified phenolic resin, particularly focusing on the timing of addition of a metal compound. As a result, when a metal compound is added and reacted after reacting rosins, resole-type phenols and polyols, a reaction having a relatively low viscosity is performed in a step before the addition of the metal compound. The system can be maintained, and finally, a high-viscosity rosin-modified phenolic resin can be produced, and the rosin-modified phenolic resin thus obtained has a higher solubility than that produced by the conventional process. It was found that it was a rosin-modified phenol resin. The present invention has been completed based on these new findings.

That is, the present invention provides (a) rosins,
(B) a rosin-modified phenolic resin obtained by reacting (b) a resole-type phenol and (c) a polyol and then adding and reacting a metal compound; a resin for a printing ink using the rosin phenolic resin; Relates to a method for producing a rosin-modified phenol resin in which (a) rosins, (b) resole-type phenols and (c) polyols are reacted, and then (d) a metal compound is added and reacted.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in order to obtain a target rosin-modified phenol resin, first, rosins (hereinafter referred to as rosins) are used.
(Referred to as component (a)), resole type phenol resin (hereinafter referred to as component (b)) and polyols (hereinafter referred to as component (b)).
(Referred to as component (c)).

The rosins as the component (a) include:
Examples thereof include gum rosin, tall oil rosin, wood rosin, disproportionated rosin, hydrogenated rosin, polymerized rosin, modified products thereof, and salts of these with metals. The component (a) may be one obtained by modifying a part of the rosins with a carboxylic acid other than rosin, if necessary. Specific examples of rosins modified with carboxylic acids include rosin-modified maleic resin and rosin-modified fumaric resin.

As the component (b), phenols (P) and formaldehyde (F) are mixed with F / P (molar ratio).
In the range of usually 1 to 3, and various known condensates obtained by addition and condensation in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide and calcium hydroxide. As the component (b), a component obtained by neutralizing and washing with water as necessary can be used. The phenols include phenol, cresol, amylphenol, bisphenol-A, p-butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol and the like. The amount of the component (b) to be used per 100 parts by weight of the component (a) is not particularly limited, but is usually 2 parts.
It is preferably from 0 to 120 parts by weight. More preferably, the lower limit of the component (b) is 40 parts by weight, and the upper limit is 100 parts by weight.

Examples of the component (c) include various components conventionally known as a polyol component of a rosin-modified phenol resin such as pentaerythritol and glycerin. (C) based on 100 parts by weight of component (a)
Although the use amount of the component is not particularly limited, it is usually 20 to 120.
It is preferred to use parts by weight. More preferably, the lower limit of the component (c) is 40 parts by weight, and the upper limit is 100 parts by weight.

The above components (a), (b) and (c)
The order in which the components are reacted is not particularly limited. For example,
A method in which the components (a), (b) and (c) are simultaneously charged and reacted, a method in which the components (a) and (b) are reacted and then the component (c) is reacted, and a method in which the components (a) and (a) are reacted. Any method such as a method of reacting the component (b) and then reacting the component (c) can be employed. In addition, before and after reacting these components (a), (b) and (c), other components such as maleic anhydride can be reacted if necessary.

The above components (a), (b) and (c)
The reaction conditions of the components can be employed without substantially changing the conventionally known method for producing a rosin-modified phenol resin. For example, in the case of the method of reacting the component (a) and the component (b) and then reacting the component (c),
The component (a) is heated and melted at 120 to 250 ° C., and a predetermined amount of the component (b) is allowed to react dropwise for about 1 to 10 hours, and then a predetermined amount is added in the presence or absence of a conventionally known catalyst. (C) component and add
Let react for about 20 hours. At this time, in the presence of a conventionally known acidic catalyst, the catalyst is distilled off under reduced pressure, and then the addition of the component (b) can prevent generation of insolubles in the resin. In the case of a method in which the components (a) and (b) are reacted, and then the component (c) is reacted, the component (a) and a predetermined amount of the component (c) are mixed with a known acid catalyst. After allowing the reaction to proceed at about 230 to 300 ° C for about 2 to 20 hours in the absence or absence of the catalyst, the catalyst is distilled off under reduced pressure, and then the component (b) is added. The reaction is added dropwise at 120 to 270 ° C for about 1 to 10 hours.

In the present invention, (a)
After reacting the components, component (b) and component (c),
A metal compound (hereinafter, referred to as component (d)) is added and reacted. If the component (d) is added at a stage prior to the reaction of the component (b) and / or the component (c) with the component (a), gelation or non-uniformity occurs, and the stirring state in the reaction system is reduced. In some cases, the rosin-modified phenol resin is not good, and it becomes difficult to increase the viscosity, and a rosin-modified phenol resin having high solubility cannot be obtained.

The component (d) is preferably a metal compound such as a metal hydroxide, a metal oxide, a metal acetate, a metal formate, a metal oxalate, or a chloride. Metal compounds such as calcium, zinc, magnesium, nickel, potassium, aluminum and barium are preferred. The component (d) includes metal hydroxides such as lithium hydroxide, magnesium hydroxide and calcium hydroxide, metal oxides such as zinc oxide and magnesium oxide, metal acetates such as zinc acetate and calcium acetate, and calcium formate. Metal formate such as potassium formate,
Nickel chloride, magnesium chloride and the like can be mentioned.

The amount of the component (d) used is not particularly limited with respect to 100 parts by weight of the component (a).
5 to 5 parts by weight are preferred. If the amount is less than 0.05 part by weight, the effect of increasing the viscosity is small, and if the amount is more than 5 parts by weight, the final rosin-modified phenol resin may become non-uniform and may cause adverse effects such as turbidity. The lower limit of component (d) is more preferably 0.1 part by weight or more and the upper limit is 3 parts by weight or less.

After the components (a), (b) and (c) are reacted, the reaction conditions when the component (d) is added and reacted are not particularly limited. It is about 30 minutes to 10 hours.

The rosin-modified phenolic resin of the present invention thus obtained can be used as a resin for printing ink. As for the type of printing ink, it can be used especially for offset printing ink, and can also be suitably used for letterpress printing ink and gravure printing ink.

[0017]

According to the present invention, a rosin-modified phenol resin having high viscosity and high solubility can be easily produced,
It is possible to reduce disadvantages to various properties required for a resin for printing ink, such as high viscosity and high solubility. In addition, restrictions on catalysts, additives, and the like during production of the rosin-modified phenolic resin are eased.

[0018]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but it is needless to say that the present invention is not limited to these Examples. In the following, "part",
“%” Is based on weight.

Example 1 A flask equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1000 parts of gum rosin, and stirred under stirring.
The temperature was raised to 20 ° C. to be melted. Then, resol type p
857 parts of a 70% xylene solution of nonylphenol (600 parts of solid content) were dropped into the system over 6 hours. After completion of the dropwise addition, 93 parts of glycerin was charged, and the temperature was 220 to 260 ° C.
The reaction was carried out until the acid value became 25 in the temperature range described above. Further, 10 g of zinc acetate was added thereto and reacted for 1 hour. Then, the pressure was reduced at 160 mmHg for 10 minutes. After cooling, 1600 parts of a solid resin was obtained. The rosin-modified phenolic resin thus obtained has a 33% linseed oil viscosity of 250 seconds,
No. 0 solvent (manufactured by Nippon Oil Co., Ltd.) has a tolerance of 3.
It was 0 g / g.

Example 2 The same flask as in Example 1 was charged with 1000 parts of gum rosin, and heated to 220 ° C. with stirring to melt. Then, 1143 parts (800 parts of solid content) of a 70% xylene solution of resol-type p-nonylphenol was dropped into the system over 6 hours. After completion of the dropwise addition, 93 parts of glycerin were charged and reacted until the acid value became 25 in a temperature range of 220 to 260 ° C. Further, 10 g of zinc acetate was added thereto and reacted for 1 hour. Then, the pressure was reduced at 160 mmHg for 10 minutes, and after cooling, 1800 parts of a solid resin was obtained. The rosin-modified phenol resin thus obtained has a 33% flaxseed oil viscosity of 400 seconds and a No. 0 solvent tolerance of 2 g.
/ G.

Example 3 The same flask as in Example 1 was charged with 1000 parts of gum rosin and heated to 230 ° C. with stirring to melt. Then, 90 parts of pentaerythritol was added, and the mixture was heated to 260 ° C. with stirring, and reacted until the acid value became 25 or less. Further, after cooling to 230 ° C, 714 parts (solid content: 500 parts) of a 70% xylene solution of resol-type p-nonylphenol was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C in a warm state. I let it. After completion of the dropping, 10 g of zinc oxide was added and reacted for 1 hour.
The pressure was reduced at 160 mmHg for 10 minutes, and after cooling, 1500 parts of a solid resin was obtained. The rosin-modified phenol resin thus obtained had a 33% linseed oil viscosity of 150 seconds and a No. 0 solvent tolerance of 3.5 g / g.

Example 4 The same flask as in Example 1 was charged with 1000 parts of gum rosin, and heated to 230 ° C. with stirring to melt. Then, 90 parts of pentaerythritol was added, and the mixture was heated to 260 ° C. with stirring, and reacted until the acid value became 25 or less. Further, after cooling to 230 ° C., 857 parts (600 parts solids) of a 70% xylene solution of resol-type p-nonylphenol was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C. while keeping the temperature kept. I let it. After completion of the dropping, 10 g of zinc oxide was added and reacted for 1 hour.
The pressure was reduced at 160 mmHg for 10 minutes, and after cooling, 1600 parts of a solid resin was obtained. The rosin-modified phenol resin thus obtained had a 33% linseed oil viscosity of 300 seconds and a No. 0 solvent tolerance of 3 g / g.

Example 5 The same flask as in Example 1 was charged with 1000 parts of gum rosin and heated to 220 ° C. with stirring to melt. Then, 1143 parts (800 parts of solid content) of a 70% xylene solution of resol-type p-nonylphenol was dropped into the system over 6 hours. After completion of the dropwise addition, 93 parts of glycerin and 0.5 part of paratoluenesulfonic acid were charged, and 220 to 2 parts were added.
The reaction was carried out in a temperature range of 60 ° C. until the acid value became 25. Further, 10 g of zinc acetate was added thereto and reacted for 1 hour. Then, the pressure was reduced at 160 mmHg for 10 minutes, and after cooling, 1800 parts of a solid resin was obtained. The rosin-modified phenolic resin thus obtained had a 33% linseed oil viscosity of 420 seconds and a No. 0 solvent tolerance of 3.5 g / g.

Comparative Example 1 Into the same flask as in Example 1, 1000 parts of gum rosin were charged and heated to 220 ° C. under stirring to melt. Next, 857 parts (600 parts of solid content) of a 70% xylene solution of resole-type p-nonylphenol was dropped into the system over 6 hours to cause a reaction. After completion of the dropwise addition, 93 parts of glycerin and 10 g of zinc acetate were charged and reacted until the acid value became 25 within a temperature range of 220 to 260 ° C. This is 16
The pressure was reduced at 0 mmHg for 10 minutes, and after cooling, the solid resin 16
00 parts were obtained. The rosin-modified phenol resin thus obtained had a 33% linseed oil viscosity of 210 seconds and a No. 0 solvent tolerance of 1.5 g / g.

Comparative Example 2 1000 parts of gum rosin was charged into the same flask as in Example 1, and the temperature was raised to 220 ° C. with stirring to melt. Then, 1143 parts (800 parts of solid content) of a 70% xylene solution of resole-type p-nonylphenol was dropped into the system over 6 hours to cause a reaction. After dropping, glycerin 93
And 10 g of zinc acetate were charged and the reaction was allowed to proceed within a temperature range of 220 to 260 ° C., but when the acid value reached 32, the whole became a gel-like substance, so that stirring was impossible and the reaction was interrupted.

Comparative Example 3 1000 parts of gum rosin were charged into the same flask as in Example 1, and the temperature was raised to 230 ° C. with stirring to melt. Then, 90 parts of pentaerythritol and 10 g of zinc oxide
Was added, and the mixture was heated to 260 ° C. with stirring, and reacted until the acid value became 25 or less. Further, after cooling to 230 ° C., 714 parts (solid content: 500 parts) of a 70% xylene solution of resole-type p-nonylphenol was added while keeping the temperature warm.
It was dropped into the system over a period of 4 hours within a temperature range of 30 to 260 ° C. to cause a reaction. After completion of the dropwise addition, the pressure was reduced at 160 mmHg for 10 minutes, and after cooling, 1500 parts of a solid resin was obtained. The rosin-modified phenol resin thus obtained has a 33% linseed oil viscosity of 117 seconds and a No. 0 solvent tolerance of 1.
It was 5 g / g.

Comparative Example 4 Into the same flask as in Example 1, 1000 parts of gum rosin were charged and heated to 230 ° C. under stirring to melt. Then, 90 parts of pentaerythritol and 10 g of zinc oxide
Was added, and the mixture was heated to 260 ° C. with stirring, and reacted until the acid value became 25 or less. Further, after cooling to 230 ° C., 857 parts (600 parts solid content) of a 70% xylene solution of resol-type p-nonylphenol were added while keeping the temperature warm.
The solution was dropped within a temperature range of 30 to 260 ° C, but when 750 parts were dropped, a gel-like substance was generated and became insoluble in linseed oil, so the reaction was stopped.

Comparative Example 5 The same flask as in Example 1 was charged with 1000 parts of gum rosin, and heated to 220 ° C. with stirring to be melted. Then, 1143 parts (800 parts of solid content) of a 70% xylene solution of resole-type p-nonylphenol was dropped into the system over 6 hours to cause a reaction. After dropping, glycerin 93
Parts, 0.5 parts of paratoluenesulfonic acid and 1 part of zinc acetate
0 g was charged and reacted in a temperature range of 220 to 260 ° C. until the acid value became 25. This at 160 mmHg
The pressure was reduced for 0 minutes, and after cooling, 1800 parts of a solid resin was obtained.
The rosin-modified phenolic resin thus obtained was precipitated in the form of an insoluble salt, and was not a uniform resin but had turbidity.

Claims (19)

[Claims] 1. A rosin-modified phenolic resin obtained by reacting (a) a rosin, (b) a resole type phenol and (c) a polyol, and further adding (d) a metal compound to react. 2. A composition obtained by reacting (a) a rosin and (b) a resol-type phenol, then reacting (c) a polyol, and further adding (d) a metal compound to react. The rosin-modified phenol resin according to the above. 3. The method according to claim 1, wherein (a) a rosin and (c) a polyol are reacted, (b) a resole-type phenol is reacted, and then (d) a metal compound is added and reacted. The rosin-modified phenol resin according to the above. 4. The metal compound (d) is at least one metal compound selected from metal hydroxides, metal oxides, metal acetates, metal formates, metal oxalates and chlorides. Item 4. The rosin-modified phenolic resin according to any one of Items 1 to 3. 5. The metal compound (d) is a metal compound of at least one metal selected from lithium, magnesium, calcium zinc, magnesium, nickel, potassium, aluminum and barium.
5. The rosin-modified phenol resin according to any one of items 1 to 4. 6. The rosin-modified phenolic resin according to claim 1, wherein the amount of the component (b) is from 20 to 120 parts by weight based on the amount of the component (a) charged to 100 parts by weight. 7. The rosin-modified phenolic resin according to claim 1, wherein the amount of the component (c) is 3 to 20 parts by weight based on 100 parts by weight of the component (a). 8. The rosin-modified phenol according to claim 1, wherein the amount of the component (d) is 0.05 to 5 parts by weight with respect to the amount of the component (a) 100 parts by weight. resin. 9. The rosin-modified phenol according to claim 1, wherein the amount of the component (d) is 0.1 to 3 parts by weight based on 100 parts by weight of the component (a). resin. 10. A resin for printing ink using the rosin phenol resin according to claim 1. 11. A method for producing a rosin-modified phenol resin, which comprises reacting (a) a rosin, (b) a resole type phenol and (c) a polyol, and further adding (d) a metal compound. 12. The rosin according to claim 11, wherein (a) a rosin and (b) a resole-type phenol are reacted, (c) a polyol is reacted, and then (d) a metal compound is added and reacted. Production method of modified phenolic resin. 13. The rosin according to claim 11, wherein (a) a rosin and (c) a polyol are reacted, (b) a resole-type phenol is reacted, and then (d) a metal compound is further added and reacted. Production method of modified phenolic resin. 14. (d) the metal compound is a metal hydroxide,
The rosin-modified phenol resin according to any one of claims 11 to 13, which is at least one metal compound selected from metal oxides, metal acetates, metal formates, metal oxalates and chlorides. (D) the metal compound is lithium, magnesium, calcium zinc, magnesium, nickel,
The rosin-modified phenolic resin according to any one of claims 11 to 14, which is a metal compound of at least one metal selected from potassium, aluminum, and barium. 16. The rosin-modified phenolic resin according to claim 11, wherein the amount of the component (b) is 20 to 120 parts by weight based on the amount of the component (a) 100 parts by weight. 17. The rosin-modified phenol resin according to claim 11, wherein the amount of the component (c) is 3 to 20 parts by weight based on 100 parts by weight of the component (a). 18. The rosin-modified phenol according to claim 11, wherein the amount of the component (d) is 0.05 to 5 parts by weight based on 100 parts by weight of the component (a). resin. 19. The rosin-modified phenol according to claim 11, wherein the amount of the component (d) is 0.1 to 3 parts by weight based on 100 parts by weight of the component (a). resin.