JPS6268808A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition, obtained by polymerizing an alpha,beta-ethylenically unsaturated monomer in the presence of a rosin-modified phenolic resin in a specific composition ratio, useful as a vehicle for lithographic printing ink, capable of satisfying gloss and drying property at the same time and having improved printability. CONSTITUTION:A resin composition obtained by polymerizing (B) 10-80pts.wt. alpha,beta-ethylenically unsaturated monomer, e.g. methyl (meth)acrylate, in the presence of (A) 90-20pts.wt. rosin-modified phenolic resin normally obtained by addition and condensation reaction of rosin with phenol, substance supplying formaldehyde and polyhydric alcohol, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel resin composition that can be used for applications such as paints and printing inks. The present invention relates to a novel and useful resin composition suitable for use as a resin for printing inks, particularly as a resin for lithographic printing inks.

[Prior art and problems to be solved by the invention] Phenolic resins have been used as resins for paints and printing inks.
Rosin-modified phenolic resins are often used for lithographic printing inks.

Of course, alkyd resins, rosin esters, petroleum resins, etc. are sometimes used in conjunction with lithographic printing inks, but basically, this rosin-modified phenolic resin is combined with a drying oil such as linseed oil, and a high boiling point petroleum solvent is used. Solvents and varnishes have been used as vehicles for inks.

However, when such a vehicle is used, it is difficult to simultaneously satisfy high levels of gloss and dryness (cent), which are particularly important factors for a lithographic printing ink.

In other words, raising the softening point of the rosin-modified phenolic resin in the ink vehicle component described in F and also increasing the blending amount of this resin will speed up the setting process, but On the other hand, increasing the amount of drying oil in the ink vehicle component improves the wettability of the pigment. Although it gives a glossy finish, the ink softens and printing becomes slower.

However, in recent years, printed matter has become more and more sophisticated, and at the same time there has been a growing trend toward faster printing, and there has been a strong desire for a lithographic printing ink that is good in both cent and gloss. There is a growing demand for ink with excellent printability that does not cause printing problems such as staining, and there is an urgent need to improve such ink vehicles.

Various resins have been developed to meet these demands, and these can be roughly divided into one type, which attempts to improve the molecular structure of rosin-modified phenolic resin to meet the needs, and the second type. These are so-called vinyl resins such as acrylic resins and/or styrene resins, and the third type includes blends of rosin-modified phenolic resins and vinyl resins.

Among them, as a method for improving the molecular structure of rosin-modified phenolic resin, for example, the present inventors have disclosed in Japanese Patent Application Laid-open Nos. 57-61071 and 57-61072, which are related to gloss and set. As a result of analyzing various factors, we found that animal and vegetable oil-modified rosin phenol resins are extremely superior as resins that can simultaneously satisfy these gloss and set properties. However, as printing speeds have increased since then, Even in the case of lithographic printing inks containing the resin as an active ingredient, it can no longer be said that Cera I~ and gloss are 1 min, and further improvements are required.

Next, as a method for using the second vinyl resin, a copolymer of isobutyl methacrylate, isobornyl methacrylate, and methacrylic acid is used as a fatty acid, as disclosed in JP-A-53-98385, for example. Examples include printing inks that are soluble in high-boiling point solvents, and that contain this copolymer as a main component and do not contain drying oil.However, inks that use a darkening copolymer as a vehicle component are not satisfactory in terms of gloss and set. Although it is within the acceptable range, it has the drawbacks of not only deterioration of ink fluidity but also frequent printing problems such as misting and poor transfer.

Furthermore, as a third method, JP-A-57-14662
A printing ink prepared by dispersing a conventional ink resin such as a rosin-modified phenolic resin, a petroleum-based resin, or a rosin-modified alkyd resin and a vinyl copolymer in a paraffinic hydrocarbon, as disclosed in the above publication. Examples include methods using vehicles.

Lithographic printing inks containing such vehicles have the characteristic of producing strong, dry ink films, and can be said to have virtually no problems with printability. There were drawbacks such as the compatibility of the copolymer itself, poor pigment dispersibility, and poor gloss. □ [Means for solving the problem] However, as a result of intensive research in view of the various shortcomings in the prior art as described above, the present inventors have found that styrene and methyl methacrylate can be dissolved in the presence of a specific modified phenolic resin. The resin composition obtained by polymerizing α,β-unsaturated ethylenically unsaturated monomers such as ethyl acrylate and n-butyl acrylate is of course superior in both shine and gloss, and is suitable for printing. We have completed the present invention by discovering that virtually no troubles occur.

That is, the present invention provides 10 to 80 parts by weight of α, β in the presence of 90 to 20 parts by weight of rosin-modified phenolic resin (A).
- It can be used as a resin for paints and printing inks, especially lithographic printing inks, obtained by polymerizing the ethylenically unsaturated monomer (B), which could not be achieved by conventional techniques. The object of the present invention is to provide a resin composition which has particularly excellent set and gloss, and which is less likely to cause printing troubles such as misting, poor transfer, and plate staining even when applied to high-speed printing.

Here, the above-mentioned rosin-modified phenolic resin (A
) is, for example, ``
As described in "Printing Ink Engineering", page 483, it is already known as a vehicle for printing ink, and contains rosins, phenols, formaldehyde-supplying substances, and polyhydric alcohols, and, if necessary, -basic acid and/or It also refers to a solid resin obtained by addition-condensation reaction of a polybasic acid using a known and commonly used method.
(Dainippon Ink Chemical Industry special product), etc.

In addition, rosin-modified phenolic resins subjected to an addition reaction with an unsaturated dibasic acid may also be used.

On the other hand, the above-mentioned α,β-ethylenically unsaturated monomer (B)
as methyl(meth)acrylate, ethyl(meth)acrylate
Alkyl (meth)acrylates such as acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate or stearyl (meth)acrylate; methoxyethyl Often ether esters such as (meth)acrylate, ethoxyethyl (meth)acrylate or tetrahydrofurfuryl (meth)acrylate; dimethyl fumarate, diethyl fumarate, dibutyl itaconate or di-2-ethylhexyl itaconate or monomethyl itaconate, monoethyl Commonly esters or dialkyl esters of unsaturated dibasic acids such as maleate or monobutyl fumarate; unsaturated dibasic acids or their anhydrides such as maleic anhydride, fumaric acid or itaconic acid; (meth)acrylic acid or unsaturated-basic acids such as crotonic acid; hydroxyalkyl (meth)acrylates such as β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate or γ-hydroxybutyl (meth)acrylate;
Glycidyl (meth)acrylate or (meth)acrylic containing epoxy groups such as β6-methylglycidyl(meth)acryle-1[i or styrene, vinyltoluene, vinyl acetate, vinyl propionate, (meth)acrylonitrile Typical examples include vinyl chloride, ethylene (meth)acrylamide, vinylpyrrolidone, cyclohexyl (meth)acrylate, and cyclopentenyloxyethyl meth)acrylate, among which styrene, vinyltoluene or methyl It is preferable to copolymerize a hard fluorophore such as methacrylate as a main component with a plastic V-isomer such as ethyl acrylate or butyl acrylate.

Each of these monomers is appropriately selected depending on the characteristics such as the softening point and solubility of the rosin-modified phenolic resin (A) that is the graft base.

The resin composition of the present invention can be prepared by a known and commonly used polymerization method using the raw materials listed in 1- below.

That is, for example, a rosin-modified phenolic resin (A) is dissolved in a solvent, a polymerization initiator and an α,β-ethylenically unsaturated monomer) are added thereto, and the mixture is heated at 60 to 150°C.
Alternatively, a method may be used in which the reaction is carried out at a reaction temperature of 1 to 15 hours, or a rosin-modified phenolic resin (A
) may be previously added with an unsaturated dibasic acid to obtain a different type of rosin-modified phenolic resin (A), then dissolved in the same manner as described above for -F, and then reacted.

Here, typical unsaturated dibasic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and succinic acid. The amount is preferably 3 parts by weight or less per 100 parts by weight of the modified phenol resin.

Further, the addition reaction of the unsaturated dibasic acid to the rosin-modified phenolic resin is carried out in the temperature range of 80 to 180° C. in the presence or absence of a solvent.

By the way, in the presence of the rosin-modified phenolic resin itself, that is, in the presence of the rosin-modified phenolic resin (A>) without undergoing the addition reaction with the unsaturated dibasic acid, α,
When the β-ethylenically unsaturated monomer (B) is solution-polymerized, it is thought that a graft polymer is produced by radical chain transfer, and this method is originally sufficient to produce the desired resin composition. However, when polymerization is carried out in the presence of the rosin-modified phenolic resin (A) that has undergone an addition reaction with the unsaturated dibasic acid, rather than the rosin-modified phenolic resin itself, not only chain transfer but also the chain transfer occurs. , it is thought that a graph I polymer is also produced by radical copolymerization with this unsaturated dibasic acid.

The desired resin composition can be obtained by any of these methods.

In this case, the polymerization initiator and the α,β-ethylenically inert saturated monomer) may be charged separately, or they may be mixed and divided into two parts (split charge). Of course, it may be carried out either by continuous addition (continuous addition and preparation) or continuously (continuous addition/preparation).

Typical polymerization solvents include aromatic hydrocarbons such as xylene and toluene, esters, ketones, aliphatic hydrocarbons, and petroleum-based high boiling point solvents for ink. Typical agents include benzoin peroxide, methyl ethyl ketone peroxide, tart-butyl perbenzoate, and tart-butyl perbenzoate.
Organic peroxides such as t-butyl peroxide or cumene hydroperoxide; or azo compounds such as azobisisobutyronitrile or azobisvaleronitrile.

The amount of the polymerization initiator used is 0.5 based on the α,β-ethylenically unsaturated polymer (+1) baking soda.
A range of ~10% is appropriate, and a chain transfer agent such as lauryl mercaptan or thioglycolic acid ester can also be used at the same time as the polymerization initiator, but in the present invention, it is necessary to use this chain transfer agent. There isn't.

Therefore, in order to achieve the desired effects of the present invention, the above-mentioned rosin-modified phenolic resin (A) and α,
The amount of rosin-modified phenol resin (A> used is 90 to 20 parts by weight, preferably 70 to 30 parts by weight, when the total amount of β-ethylenically unsaturated monopole (B) is 100 parts).
On the other hand, the amount of α,β-ethylenically unsaturated monomer) used is 10 to 80 parts by weight, preferably 30 to 70 parts by weight.
Parts by weight are appropriate.

The amount of α, β-ethylenically unsaturated monomer (B) used is 10
If the amount is less than 80 parts by weight, it will not be possible to obtain a resin composition that has both high gloss and quick cleaning properties, which are the first objectives of the present invention, and conversely, if it exceeds 80 parts by weight, misting will occur. , printing problems such as poor transfer and plate staining are likely to occur, making it unusable.

In terms of -a, rosin-modified phenolic resin and vinyl resin are not compatible, so even if they are melt-mixed, a cloudy separation will occur. The resin composition of the invention is uniformly transparent,
This can be said to be one of the noteworthy effects.

However, although the details of the formation mechanism and structure of the composition of the present invention that lead to these remarkable effects are unknown, some of the α,β-ethylenically inert saturated monomers contain rosin. He 1 suspects that the modified phenol resin (A) is graft polymerized by a chain transfer reaction.
6.

The product form of the resin composition of the present invention thus obtained can be changed as appropriate depending on the desired use.

That is, it is possible to make a solid resin by removing the solvent after the polymerization reaction is completed, or it is of course possible to provide the resin in a solution state without removing the solvent.

Incidentally, when used for lithographic printing ink, after the polymerization reaction is completed, the solvent is removed to form a solid resin, and then
After adding drying oil and cumming, it is diluted with a high boiling point petroleum solvent for ink, gelling treatment is performed using aluminum and root, and then the viscosity is adjusted to prepare the desired ink face. Conventional methods may be followed, but the composition of the present invention is prepared in a high-boiling petroleum solvent for ink, and after the polymerization reaction is completed, drying oil is added to perform cuckooing, and if necessary, gelation treatment with aluminum chelate is performed. It is more reasonable to follow the method of preparing the intended ink wash after adjusting the viscosity.

A lithographic printing ink can be prepared by mixing pigments, additives, drying accelerators (ink drier), etc. with the thus obtained face, and then kneading and curing with a triple roll or the like.

Although the resin composition of the present invention can be used as a paint or as a printing ink, it is particularly desirable to use it as a lithographic printing ink.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, Application Examples, and Comparative Application Examples. In the following, parts and percentages are all based on weight unless otherwise specified.

Example 1 [Penkasite F-17
200 parts of 5J and 200 parts of toluene were charged, the temperature was further raised to uniformly dissolve, and the temperature was maintained at 110°C.

Next, 200 parts of styrene and [Perbutyl ZJ
A mixed solution consisting of 4 parts of [tert-butyl peroxybenzoate manufactured by NOF ■] was added dropwise over 30 minutes, and after the addition was completed, the same temperature was maintained for 7 hours to increase the polymerization rate of the monomer. After confirming that it had reached 98%, the solvent was removed under reduced pressure to obtain the desired resin composition.

The resin composition obtained here was a light brown transparent solid having a softening point of 154° C. as measured according to the ring and ball method of JIS-2531.

In parallel with the above example, first, “Penkasite F-17
The same operation as in Example 1 was repeated with no use of 5J, and the monomer was polymerized until the polymerization rate reached 98%.
When the resulting resin solution was collected and dried in the form of a film, the film became cloudy.

From this, a resin composition made by simply blending a vinyl resin and a rosin-modified phenolic resin is non-uniform, and in the resin composition of the present invention, a vinyl resin and a rosin-modified phenolic resin are mixed together. It is known to be a homogeneous composition in an integrated form.

Example 2 In a flask similar to Example 1, [Penkasite F-18
770 parts of 1J, 475 parts of xylene, and 8 parts of maleic anhydride were charged, and the temperature was raised to 140°C to dissolve the maleic anhydride to [Betsukasai] F-181J through ring opening, and then the temperature was lowered to 130°C. 16 of styrene
A mixed solution consisting of 5 parts, 165 parts of n-butyl methacrylate, and 4 parts of "Perbutyl Z" was dropped over 30 minutes, and even after the dropwise addition was completed, it was maintained at this 130 ° C. for 10 hours,
After confirming that the polymerization rate of the school body had reached 99%, the solvent was removed under reduced pressure and the desired resin composition was taken out.

The resin composition obtained here had a softening point of 147° C. and was a light brown transparent solid.

In parallel with this, first, the same operation as in Example 2 was repeated without using Penkasite F-181J to polymerize the monomer until the polymerization rate reached 98%,
Next, 770 parts of this [Penkasite F-181J] was charged and dissolved, and the resulting resin solution was collected and dried in the form of a film, but the film became cloudy.

Example 3 The α,β-ethylenically unsaturated monomers were changed to 165 parts of vinyltoluene and 165 parts of lauryl methacrylate, and the holding time (polymerization reaction time) after completion of the dropwise addition was 12 hours. Except for the following changes, the same procedure as in Example 2 was carried out, and when it was confirmed that the monomer polymerization rate had reached 97%, the solvent was removed under reduced pressure to obtain the desired resin composition.

The resin composition thus obtained was a light brown transparent solid having a softening point of 20°C.

In parallel with this, first, [Example 3 except for the change to completely eliminate the use of Penkasite F-181J]
After polymerizing in the same manner as above until the polymerization rate reached 98%, 770 parts of this [Penkasite F-1811 was charged and dissolved, and the solution was collected and dried into a film, which became cloudy. reached.

Example 4 In a reactor similar to Example 1, ``[Veracasite F-17
72 parts of 5,1 and 200 parts of toluene were charged, the temperature was raised by 1-1 to dissolve them uniformly, and the mixture was heated to 72 parts by 1
259 parts of styrene, 29 parts of methacrylic acid and [
A mixed solution consisting of 9 parts of Perbutyl Z-1 was added dropwise in 1 hour, and even after the addition was completed, the same temperature was maintained for 11 hours to continue the polymerization reaction, and the polymerization rate of the monomer reached 98%. After confirming that this was the case, solvent removal under reduced pressure was carried out to obtain the desired resin composition, which was obtained as a pale yellow transparent solid having a Monoke softening point of 136°C.

In parallel with this, first of all, "Verakasite F -1' 7
The same operation as in Example 4 was repeated except that no 5J was used, and the polymerization was carried out until the polymerization rate reached 98%. Then, 72 parts of this "Pesosai"F'-175J was charged. After dissolving the solution, the solution was collected, dried and soaked into a film, and a cloudy white film was obtained.

Example 5 [Veracasite F-181] was placed in the same reactor as in Example 1.
388 parts of J, No. 15 solvent] [240 parts of [petroleum-based high boiling point solvent for ink manufactured by 1bon Petroleum ■] and 4 parts of maleic anhydride were charged, dissolved at 140°C, and reacted. A mixed solution consisting of 83 parts of styrene, 83 parts of n-butyl methacrylate, and 4 parts of [Percyl HJ (cumene hydroperoxide manufactured by NOF ■) was added dropwise over 30 minutes, and the temperature was maintained at the same temperature even after the addition was completed. to 1
The reaction was held for 5 hours, and the reaction was terminated when it was confirmed that the polymerization rate of the monomers had reached 96%, and the solid content was approximately 69%.
% liquid resin composition was obtained.

In parallel with this, first [Becca Sai] F-'181J
In the case of a sequence in which no use was made, the same operation as in Example 5 was repeated to polymerize until the polymerization rate reached 98%, and then 388 parts of this [Veracasite F-181J] was charged and dissolved, and then the solution was The sample was collected and dried into a film, resulting in a cloudy white film.

Application Examples 1 to 5 and Comparative Application Example 1.2 A four-eye flask equipped with a stirrer, a thermometer, and a nitrogen blowing tube was prepared according to the composition ratio shown in Table 1. The solid resin compositions or liquid resin compositions obtained in Examples and the comparative application examples used F-175J (softening point -165°C, acid value
16) or "24 by preparing Veracasite F-181J (softening point -152°C, acid value = 17) and linseed oil.
The temperature was raised to 0° C., and the product was kneaded for 1 hour.

In the next step, [No. 5 Solvent-1 and [Calcol 40
Add J [higher alcohol manufactured by Kao Soap■] and heat to 160℃.
The temperature was lowered and maintained until

After that, 1 kilogram of aluminum chelate (manufactured by Hope Pharmaceutical ■) was added, and the varnish was gelled by keeping it at the same temperature for 1 hour.

The respective varnish thus obtained is then used to prepare a lithographic printing ink and then to carry out printing tests.

Next, 60 parts of each varnish and 125 parts of a red pigment [Carmine 6BJ (manufactured by Dainippon Ink and Chemicals, Ltd.)] were kneaded three times using three rolls, and then kneaded with a metal dryer (drying acceleration rule for inks). Each lithographic printing ink was obtained by adding 1 part of "Solvent No. 5" and the apparatus and adjusting the viscosity of the ink so that the tack value was within the range of 9 to 11.

Afterwards, the gloss and contrast were evaluated using the "rRI Tester" manufactured by Mei Seisakusho, and the item misting was performed using the "Incometer" manufactured by Twin Albert in the United States for another 9 days. Various printing tests were conducted using a light offset printing machine R2800cDJ manufactured by Co., Ltd., by evaluating water stains and plate stains, as well as evaluating the storage stability of each ink.

The results are summarized in Table 2. First, the outline of each printing test is as follows.

First, the gloss was determined by printing on art paper using an rR1 tester-1 at an ink setting of 0.15 mj/two curls, and drying it for 24 hours at 20°C and 65% RH. The 60 degree/60 degree reflection specular gloss was measured, and the next set was an ink placement of 0.15 mJ using an rRI tester! After first printing on art paper using the /Two-Cantrol, we then pressed the printed surface of the art paper onto high-quality paper using the same rRI tester and observed the transfer of the ink. The set time was defined as the time until there was no transfer.

In addition, misting, which is one of the printing troubles, uses 1.3mβ ink in the "incometer" and 800rp+
This is done by rotating the roll at a speed of m and observing the difficulty of ink scattering. Similarly, water rod smudges and plate stains, both of which are printing problems, are detected using a light offset printing machine, and among them, water smudges and plate stains are detected using a light offset printing machine. This is done by conducting a lithographic printing test with R2800cDJ and observing how easily the water fontaine roller and water duct roller are smeared by ink during the test.
This is done by conducting a lithographic printing test at J and observing the stains on the plate caused by ink.

Furthermore, the storage stability of the ink was determined by observing changes in the state of the ink after storing the ink in a tin can at room temperature for three months.

〔Effect of the invention〕

As is clear from the results in Table 2, the resin composition of the present invention is known to have extremely effective performance, especially when used as a vehicle for lithographic printing ink. That is, the resin composition of the present invention provides a lithographic printing ink that simultaneously satisfies high levels of gloss and drying properties, which are unmatched by conventional techniques or conventional resins, and also provides excellent high-speed printing. It is known to have surprising performance in that it exhibits printability and is less likely to cause printing troubles such as misting, poor transfer, and plate staining.

Claims (1)

[Claims] In the presence of 90 to 20 parts by weight of rosin-modified phenolic resin (A), 10 parts of α,β-ethylenically unsaturated monomer (B)
A resin composition obtained by polymerizing ~80 parts by weight.