JPH02286749A - Resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the title transparent and uniform composition useful as a binder component of a gravure printing ink by mixing an alpha,beta-ethylenically unsaturated carboxylic acid/rosin adduct into which a plurality of metal compounds are introduced with a rosin into which a single metal compound is introduced. CONSTITUTION:The title composition is obtained by mixing an alpha,beta-ethylenically unsaturated carboxylic acid/rosin adduct, into which at least two metal compounds are introduced desirably by reacting a mixture of rosin with an alpha,beta-ethylenically unsaturated carboxylic acid (e.g. fumaric acid)/rosin adduct with at least two kinds of metal compounds [e.g. Ca(OH)2, MgO or ZnO] in at least two stages by adding at least 2wt.% water based on the total amount of the above two rosins and an organic solvent (e.g. toluene) with a rosin into which at least one metal compound is introduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new and useful resin composition and a method for producing the same. More specifically, the present invention provides a resin composition comprising an addition rosin and a rosin in which a metal compound is introduced into each molecule, as well as a resin composition comprising an addition rosin and a rosin, and a resin composition comprising the addition rosin and the rosin, which are combined by making full use of a multi-step reaction. An extremely useful resin composition that is used in large quantities as a binder component in gravure printing inks, etc. It relates to products and their manufacturing methods.

[Conventional technology]

This type of resin composition obtained from rosin and/or its derivatives and metal compounds has a high melting point.

Moreover, because it forms an ink film with excellent gloss, it is currently used in large quantities as a binder component in gravure printing inks and the like.

By the way, this type of resin composition is prepared by melting rosin and/or its derivatives, then adding a metal compound to the resin composition.
It is obtained by reacting at a temperature of 00°C or higher.

In addition, as a method for preparing quick-drying varnish, a high-temperature reaction of 250°C or higher is particularly adopted;
In particular, methods have been adopted in which a large amount of a metal compound in the form of a calcium compound is used for reaction.

However, when the various conventional methods as described above are followed, the melting point inevitably reaches 200° C. or higher, and the viscosity of the system also becomes abnormally high, making stirring difficult.

In addition, the metal compound tends to remain unreacted, and moreover, it is difficult to use a rosin derivative, especially an α,β-ethylenically unsaturated carboxylic acid addition rosin, and to react the addition rosin with the metal compound. In such cases, it is inevitable that a large amount of glucide that is insoluble in organic solvents will be generated, and therefore, even filtration of the target resin composition obtained will be difficult.
You will end up in a situation where you will no longer be able to do so.

[Problem to be solved by the invention]

As described above, there are many unresolved problems in the prior art, and the problems that the present invention attempts to solve are exactly the unresolved problems in the prior art.

That is, the problems to be solved by the present invention are as follows: - It itself has a high melting point, has excellent gloss and drying properties of printed matter, and is easy to stir during the reaction. Another object of the present invention is to provide a practical resin composition that contains no unreacted metal compounds or dulled substances and is therefore extremely easy to filter, as well as a method for producing the same.

[Means to solve the problem]

Therefore, as a result of extensive research along the lines of these problems, the present inventors not only used an organic solvent, but also created a system in which water was present, and rosin and α, β-
A mixture with ethylenically unsaturated cargenic acid addition rosin (hereinafter also referred to as addition rosin) is subjected to a so-called multi-step reaction of two or more steps, that is, a reaction by dividing the addition of two or more metal compounds. By making full use of these techniques, I was able to discover that all of the above problems, K and R, could be solved using examples, and thus I was able to complete the present invention.

In this way, the present invention has finally been completed in line with the above-mentioned problem, and is equipped with the solution means as specifically shown below.

Tsumashi 1 The present invention relates to an addition rosin in which two or more metal compounds are introduced into the molecule, that is, an α,β-ethylenically unsaturated cargenic acid addition rosin, and a rosin in which one metal compound is introduced into the molecule. The present invention aims to provide a resin composition comprising rosin and α, β-
To a mixture of this rosin and an addition rosin obtained through an addition reaction with an ethylenically unsaturated carboxylic acid, an organic solvent and further water in an amount of 2 parts by weight or more based on the total amount of both rosins are added, 2 or more metal compounds are introduced into the molecule of the rosin, and one metal compound is introduced into the rosin molecule through at least two reaction steps. Added rosin in which a metal compound is introduced into the molecule;
It is also an object of the present invention to provide a method for producing a resin composition comprising a rosin in which one type of metal compound is introduced into the molecule.

First of all, let's talk about the rosin mentioned above.

Any of the commonly used ones can be used, but
Among them, wood rosin, f-mulosin, tall oil rosin, Indonesian rosin, and dimer rosin are just a few examples.

As the α,β-ethylenically unsaturated carboxylic acid used to prepare the above-mentioned addition rosin, any of the commonly used ones can be used, but among them, particularly representative ones can be used. If I only exemplify it,
(Anhydrous) unsaturated socargenic acids such as maleic fumaric acid or itaconic acid; the use of such unsaturated socargenic acids is particularly desirable in order to introduce as many types of metal compounds as possible without gluing. .

Further, as the above-mentioned metal compounds, any of those normally used in this type of introduction reaction can be used, but among them, only the most representative ones are exemplified: calcium, magnesium, Oxides of various metals such as zinc, barium manganese, tin or aluminum,
In order to introduce as many kinds of metal compounds as possible, such as hydroxides or organic acid salts, without causing dullness, it is particularly desirable to use such divalent or trivalent metal compounds. Among these, oxides or hydroxides of divalent metals such as calcium, magnesium or zinc are preferably used.

Therefore, the appropriate amount of the metal compound to be used is within the range of 5 to 15% by weight based on the total amount of rosin and additional rosin.

Furthermore, the above-mentioned organic solvents are not particularly limited as long as they do not dissolve in water, but only the most representative ones will be exemplified.
These include aromatic hydrocarbons such as toluene or xylene, esters such as ethyl acetate or n-tutyl acetate, or ketones such as methyl ethyl ketone or methyl isobutyl ketone. desirable.

Furthermore, as the above-mentioned water, it is desirable to use ion-exchanged water, and the amount used is 2% by weight or more, preferably 5 to 20% by weight based on the total amount of rosin and added rosin.
It is appropriate that the amount of M be within the range.

If the weight is less than 2, the reactivity of the reaction for introducing the metal compound is likely to be poor, and unreacted metal compounds will remain, resulting in a loss of product quality and subjectivity. Undesirable.

The reaction temperature for the reaction of introducing the metal compound into the rosin and the addition rosin, respectively, is suitably 100°C or less, preferably within the range of 50 to 80°C.

When carried out at temperatures higher than 100°C.

Inevitably, water and other coexisting organic solvents tend to evaporate without the reaction progressing sufficiently, and unreacted metal compounds tend to remain), and furthermore, the introduction of metal compounds. As a reaction method to be carried out under such conditions, which is undesirable since the continuation of the reaction itself is dangerous, a two-step or more multi-step reaction method is adopted.

The first step of the reaction is usually carried out using a calcium compound or two or three types of metal compounds mainly consisting of a calcium compound.
It is carried out for 0.5 to 5 hours at a temperature below 100°F.

In this way, in the present invention, the first stage reaction includes:
The use of calcium compounds is desirable and such reactions are recommended.

Next, in the second and subsequent reactions, it is desirable to use one or two divalent metal compounds other than the calcium compound, so that the metal compounds used in the first reaction are duplicated. However, it is desirable that only this calcium compound be used in the first stage, and if it is to be used redundantly in the second and subsequent stages, It is easy to introduce only a calcium compound, and as long as there is no such bias, it is of course permissible to use the same metal compound in the first stage and in the second and subsequent stages. That's true.

For example, a calcium compound is placed in the first row, and 4! is placed in the second and subsequent rows. , and if you want to arrange this compound,
In each stage of the reaction after the second stage, respectively,
For convenience, two or more types of metal compounds may be used, and this calcium compound may be placed as one of them, and the calcium compound and magnesium compound may be placed in the first stage. Continue to make noise using the compound,
The use of calcium compounds and magnesium compounds in the second and subsequent stages does not contradict the purpose of the present invention, which is to introduce as many types of metal compounds as possible, and there is no problem. However, even so, it is unavoidable that there is a bias toward compounds of all these genera, and therefore, the use of these fungal compounds can be limited to at most the second stage of each stage after the second stage. It may be discontinued and no longer used in the third and subsequent stages, or in addition to these calcium compounds and magnesium compounds, during the first and/or second stage reactions. As another type of compound, for example, a divalent metal compound such as a zinc compound should also be used, and in this way, the same metal compounds should be unevenly distributed. is essential.

The most preferred embodiment is one in which a calcium compound and a zinc compound or a magnesium compound are introduced during the first reaction step, and a magnesium compound or a zinc compound is introduced in the second and subsequent steps.

Thus, the reactions in the second and subsequent stages also use one or more metal compounds, as in the first stage, and
at a temperature of 50 to 80 °C, preferably 50 to 80 °C,
This is carried out over a period of 0.5 to 5 hours, preferably 1 to 3 hours.

Particular attention should be paid to the problem of controlling the heat of reaction in the reaction of introducing such metal compounds into rosin and adduct rosin.

It goes without saying that the reaction between rosin and the additional rosin metal compound in the presence of water is accompanied by intense heat generation, and therefore sufficient care must be taken to prevent bumping of the reaction contents.

7.The acid value of the resin composition in the present invention is 5.
It is necessary to fall within the range of 0 to 150.

〔Effect of the invention〕

According to the present invention, the target resin composition obtained through the multi-step reaction of rosin and rosin addition with a metal compound is generally free of unreacted metal compounds, is transparent and uniform, and has excellent gloss. Prints can be provided.

In addition, by following the method examples of the present invention, there is no generation of rulides that are insoluble in solvents, and therefore the resulting resin composition can be filtered very easily, thereby ensuring improved productivity.

Furthermore, according to the present invention, in the presence of an organic solvent,
All you have to do is set the temperature below and then continue the reaction below 100°C.Therefore, there is less heat loss, and it also has the advantage of being easy to stir. .

In this way, according to the present invention, it is possible to obtain a truly practical and versatile resin composition in which not only one type of metal compound but many types of metal compounds are introduced.

As described above, the resin composition of the present invention has a number of excellent characteristics, so it is expected that it will play a role in the development of new applications. The production method can also be said to be a truly useful technology that will form the basis of this type of reaction method in the future.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, "parts" means "parts by weight" unless otherwise specified. It shall be.

Example 1 500 parts of tall oil rosin and 40 parts of fumaric acid were charged into 21 four-way flasks equipped with a stirrer, a thermometer, and a decanter, and the mixture was kept at 250°C for 1 hour to conduct a reaction. A mixture with 7 malic acid added rosin was obtained.

Subsequently, 540 parts of toluene are added to this mixture and 7
While maintaining the temperature at 0° C., 80 parts of ion-exchanged water, 10 parts of calcium hydroxide, and 15 parts of magnesium oxide were added over 3 hours to carry out the reaction.

Next, 35 parts of zinc oxide was added and the reaction was carried out for 3 hours, and then maintained at 110°C for 3 hours, and water was removed using a decanter.

During this time, stirring was easy, and the objective resin composition obtained had a transparent appearance and an acid value of 100.

In addition, there were no glucides insoluble in toluene, and filtration was easy.

The various characteristic values of the resin composition were as follows.

Viscosity (Pluckfield viscosity at 25°C; same below): 600 cps Weight average molecular weight (polystyrene equivalent; same below): 480 Non-volatile content: 51% Example 2 In a reaction vessel similar to Example 1, 450 parts of gum rosin was added. ,
50 parts of dimer rosin and 30 parts of maleic anhydride were charged, and a reaction was carried out at 150° C. for 1 hour to obtain a mixture of rosin and maleic anhydride-added rosin.

Next, 530 parts of toluene was added to this mixture, and 8 parts of ion-exchanged water, which had been previously dispersed at 80°C, was added.
0 parts and 12.5 parts of calcium hydroxide and 16 parts of zinc oxide
A mixture consisting of 1 and 2 parts was added over 2 hours and the reaction was carried out at the same temperature.

Thereafter, 30 parts of magnesium oxide was added over 1 hour to carry out a reaction, and the mixture was maintained at 110 DEG C. for 3 hours, and the water was removed in a decanter.

During this time, stirring was easy, and the resulting resin composition had a transparent appearance and an acid value of 9o.

In addition, there was no glucide insoluble in toluene, and filtration was easy.

The various characteristic values of the resin composition were as follows.

Viscosity: 1,030cI) 8° Weight average molecular weight: 530 Nonvolatile content: 51% Example 3 In a reaction vessel similar to Example 1, 500% of tall oil rosin was added.
and 34 parts of maleic anhydride and heated to 170°C.
The reaction mixture was maintained for 1 hour to obtain a mixture of rosin and maleic anhydride-added rosin.

Subsequently, 540 parts of toluene are added to this mixture,
While maintaining the temperature at 70° C., 80 parts of ion-exchanged water, 10 parts of lithium hydroxide, and 15 parts of calcium hydroxide were added over 3 hours to carry out the reaction.

25 parts of magnesium oxide were then added over a period of 1 hour and the reaction was carried out for 2 hours before being heated to 110°C.
The mixture was kept for 3 hours and water was removed using a decanter.

During this time, stirring was easy, the target resin composition obtained had a transparent appearance, and the acid value of this resin composition was 100.

In addition, no gluides insoluble in toluene were observed.
Filtration was also easy.

The various characteristic values of the resin composition were as follows.

Viscosity: 350cps.

Weight average molecular weight: 430 Non-volatile content: 50.5 Comparative Example 1 Into the same reaction vessel as in Example 1, 500% of tall oil rosin was added.
and 50 parts of maleic anhydride and heated to 150°C.
The reaction was carried out for 1 hour to obtain a mixture of rosin and maleic anhydride-added rosin.

Next, 550 parts of toluene, 11 parts of calcium hydroxide, 33 parts of magnesium oxide, and 28 parts of zinc oxide were added to this mixture while maintaining the temperature at 70°C to perform a one-step reaction. Various unreacted metal compounds remained in the resulting resin composition, and the appearance of the resin composition was opaque and non-uniform.

Comparative Example 2 Into the same reaction vessel as in Example 1, 500 g of tall oil rosin was added.
1 part and 40 parts of fumaric acid were charged, and the reaction was carried out at 250°C for 1 hour to obtain a mixture of rosin and fumaric acid-added rosin.

Next, 540 parts of toluene was charged, kept at 70°C, 5 parts of ion exchange water, 10 parts of calcium hydroxide,
15 parts of magnesium oxide and 35 parts of zinc oxide,
After 5 minutes of addition for a single step reaction, the mixture was kept at 110 DEG C. for 3 hours and water was removed using a decanter.

The resulting resin composition contained a large amount of gluides insoluble in toluene, and therefore was unable to be subjected to p-filtration.

Comparative Example 3 550 parts of the mixture of Kuchi-Shin and maleic anhydride-added rosin obtained in Comparative Example 1 were charged into the same reaction vessel as in Example 1, and 35 parts of calcium hydroxide and 35 parts of calcium hydroxide were added at 270°C.
When 20 parts of magnesium oxide and 30 parts of zinc oxide were added to carry out a one-step reaction, the viscosity became abnormally high during this reaction, making stirring extremely difficult.

Therefore, it was decided to stop the reaction, but the resulting resin composition contained a large amount of various unreacted metal compounds.

Weight ratio to yield of resin composition in Table 1 As is clear from the results in Table 1, according to the present invention,
The amount of glucide insoluble in organic solvents is negligible.
Moreover, since the resulting resin composition is extremely easy to pass through, the present invention contributes to improving productivity in many ways.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] α, β in which one or more metal compounds are introduced into the molecule
- A resin composition comprising an ethylenically unsaturated carboxylic acid addition rosin and a rosin in which one type of metal compound is introduced into the molecule. 2. An organic solvent is added to the mixture of rosin and α, β-ethylenically unsaturated carboxylic acid addition rosin, and further,
Conveniently, two or more metal compounds are added to the molecules of the α,β-ethylenically unsaturated carboxylic acid addition rosin by adding 2% by weight or more of water based on the total amount of both rosins and carrying out at least two steps of reaction. α,β-ethylenically unsaturated carboxylic acid addition in which two or more metal compounds are introduced into the molecule of the rosin, characterized in that one metal compound is introduced into the molecule of the rosin. Rosin and
A method for producing a resin composition comprising a rosin in which one type of metal compound is introduced into the molecule. 3. Addition of rosin and α,β-ethylenically unsaturated compound A dispersion of two or more metal compounds and water is added to the rosin and an organic solvent in portions, and through at least two steps of reaction, 2. α, β-ethylenic compound in which two or more kinds of metal compounds are introduced into the molecule, characterized in that more than one kind of metal compound is introduced into the molecule of the α, β-ethylenically unsaturated carboxylic acid addition rosin. A method for producing a resin composition comprising an unsaturated carboxylic acid-added rosin and a rosin in which one type of metal compound is introduced into the molecule. 4. Claims 2 and 3, wherein the mixture of the rosin and the α,β-ethylenically unsaturated carboxylic acid addition rosin is obtained by an addition reaction between the rosin and the α,β-ethylenically unsaturated carboxylic acid. A method for producing the resin composition described above. 5. The method for producing a resin composition according to claims 2 and 3, wherein the at least two-step reaction is performed by adding two or more metal compounds in portions.