KR20020093916A - Resin composition for printing ink and process for producing the same - Google Patents

Abstract

The present invention provides a resin composition for a toluene-free printing ink having good high temperature stability.

The resin composition for printing ink comprises a graft copolymer in which an acrylic monomer having an ethylenically unsaturated bond is reacted with an oxidized chlorinated polyolefin having a weight average molecular weight of 3000 to 50000 in the presence of a polar solvent, and an alicyclic solvent. do.

Description

Resin composition for printing ink and process for producing same

Chlorinated polyolefins, which are the raw materials for printing inks, are difficult to dissolve other than aromatic solvents such as toluene. In addition, chlorinated polyolefins are poorly miscible with urethane resins, and are rarely miscible in a system in which toluene, which is a good solvent of chlorinated polyolefins, does not exist. Moreover, in printing ink, aromatic solvents, such as toluene, are favorably used for the printing ink using resin which urethane-modified chlorinated polyolefin and chlorinated polyolefin for the reason that it is excellent in the drying property and the solubility of binder resin.

In recent years, the working environment has been a major problem, and the use of aromatic solvents, which are frequently used in printing inks, has been crying out. In particular, regarding the film printed matter for food packaging, the solvent remaining in the printing ink is also attracting attention, and a reduction in the amount of aromatic solvents such as toluene is strongly desired. In addition, since the use of toluene has a problem in high temperature stability, development of a resin for a toluene-free printing ink having good high temperature stability is urgently needed.

Accordingly, urethane-modified products of chlorinated polyolefins have been proposed as resins for printing ink having high versatility that do not select a base film (Japanese Patent Application Laid-Open No. 1-252606, Japanese Patent Application Laid-Open No. 4). -4148, Japanese Patent Application Laid-Open No. 11-61024, etc.). However, these use an amine resin as a chain extender at the time of urethane modification, and it is because a chlorinated resin is made to react, or color number rises with time. As a result, when used for ink, there was a problem that the color tone change was large, and in some cases, the formulation should be changed.

This invention is a resin composition for printing inks which does not use aromatic solvents, such as toluene, and is excellent in solution property and high temperature stability, and excellent in miscibility with ink resins, such as a urethane resin, a polyamide resin, and nitrocellulose, and It is an object to provide a method for producing the same.

The present invention relates to a resin composition for printing ink and a method for producing the same. More specifically, the present invention relates to a resin composition for printing inks, which is not only useful for coating for various plastic films, plastic sheets or synthetic resin moldings, but also contains no aromatic solvents such as toluene, and a method for producing the same.

The present invention does not use any aromatic solvents such as toluene, and has a good solution property and high temperature stability, and a resin composition for printing inks excellent in compatibility with resins for inks such as urethane resins, polyamide resins, nitrocellulose, and the like. It is an object to provide a method for producing the same.

The present inventors earnestly examined, and the graft copolymer which made the acrylic monomer which has ethylenically unsaturated bond react with the oxidation-treated chlorinated polyolefin whose weight average molecular weights are 3000-500000 and chlorine content 10-50 weight%, and non-aromatic polarity The said problem was solved by using the resin composition for printing inks containing the mixed solvent of a solvent and an alicyclic solvent.

Oxidation treatment chlorinated polyolefin used for this invention is a component for providing adhesiveness with respect to a polyolefin base film, and is obtained by oxidizing a chlorinated polyolefin.

Oxidized chlorinated polyolefins are readily obtained by conventional chlorination reactions. For example, the α-olefin copolymer is dissolved in a chlorine solvent such as chloroform, and then irradiated with ultraviolet rays or simultaneously blown one or more selected from gaseous chlorine and air, oxygen, and ozone in the presence of an organic peroxide. Is obtained. In the oxidation-treated chlorinated polyolefin, hydroxyl groups, carboxyl groups, peracids, and the like are formed, so that various polymer reactions can be performed. Therefore, reaction with the acryl-type monomer which has ethylenically unsaturated bond is possible.

The progress of oxidation can be judged by the increase in absorption in the vicinity of 1730 cm ^-1 measured with an infrared spectrophotometer. In addition, the degree of oxidation can be confirmed by the functional group index measured according to the scale of Equation (1). In order to improve the reactivity of the oxidized chlorinated polyolefin and the monomer, the functional group index is preferably 5 to 30%. More preferably, it is 10 to 25%.

Crystalline polypropylene, amorphous polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-propylene-α-olefin copolymer, etc. can be used for the polyolefin which is a raw material of an oxidizing process chlorinated polyolefin.

The oxidation treatment chlorinated polyolefin can use a chlorine content of 10 to 50% by weight, preferably a 15 to 40% by weight. If the chlorine content is lower than 10% by weight, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alicyclic solvents such as cyclohexane, methyl cyclohexane, ethyl cyclohexane, and the like When the solubility in solvents other than the aromatic solvent is reduced, and the chlorine content exceeds 50% by weight, the adhesion with the polypropylene base film is reduced. In addition, the chlorine content rate in this invention is the value measured based on JIS-K7229.

In addition, the oxidation-treated chlorinated polyolefin can use what has a weight average molecular weight 3000-500000. If the weight average molecular weight is less than 3000, the cohesion force of the resin is weak and the adhesion to the substrate is reduced, and if it is more than 50000, the miscibility with other resins is poor, which is undesirable. In addition, the weight average molecular weight in this invention is a value measured by gel permeation chromatography (GPC) using polystyrene resin as a standard.

Oxidized chlorinated polyolefins are usually treated as toluene solutions, but toluene is not used at all in the present invention. The chloroform solution of the oxidized chlorinated polyolefin obtained by chlorination in a chloroform solvent is added to a screw shaft portion, and then supplied to an extruder with an outlet equipped with a desorbing suction portion for solidification. The solidification method can be performed by a well-known method, for example using the extruder with an outlet equipped with the underwater cutting pelletizer in the outlet part of an extruder, the extruder with an outlet, the pelletizer which cut | disconnects strand type resin, etc.

An epoxy compound is added to chlorinated resin as a stabilizer. Although an epoxy compound is not specifically limited, It is preferable that it is miscible with chlorinated resin. The epoxy equivalent is about 100-500, The compound which has one or more epoxy groups per molecule can be illustrated. For example, Epoxidized soybean oil and Epoxidized linseed oil which epoxidized the vegetable oil which has a natural unsaturated group with peracid, such as peracetic acid; Moreover, epoxidized fatty acid ester which epoxidized unsaturated fatty acids, such as oleic acid, tall oil fatty acid, and soybean oil fatty acid; Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate; For example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycides condensed with bisphenol A or polyhydric alcohol and epichlorhydrin Dill ether and the like are exemplified. In addition, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether monoepoxy compounds represented by tert-butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether and the like are exemplified. Moreover, metal soaps, such as calcium stearate and lead stearate, organometallic compounds, such as dibutyl tin dilaurate and dibutyl maleate, and hydrotalcite compounds which are used as stabilizers of polyvinyl chloride resins can also be used. These may be used alone or in combination. It is preferable to add 1 to 5 weight% (solid content conversion) with respect to an oxidizing process chlorinated polyolefin.

In the present invention, the graft copolymer is obtained by reacting the oxidized chlorinated polyolefin obtained by the above method with an acrylic monomer having an ethylenically unsaturated bond using a polymerization initiator in the presence of a non-aromatic polar solvent.

As a non-aromatic polar solvent used for this invention, an ester solvent or a ketone solvent is mentioned. Ethyl acetate, butyl acetate, etc. are mentioned as ester solvent. Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned as a ketone solvent. These may be used alone or in combination of two or more. The amount of the polar solvent during the reaction is preferably such that the solid concentration of the oxidized chlorinated polyolefin is in the range of 40 to 80% by weight. If it is out of this range, the graft efficiency of the acryl-type monomer which has an ethylenically unsaturated bond will become low, and there exists a fault that solution property is bad.

Moreover, in this invention, you may perform reaction using the mixed solvent which mixed the alicyclic solvent with the said polar solvent in the range of 30 weight% or less. Examples of the alicyclic solvents include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, cyclopentane, methylcyclopentane, ethylcyclopentane, and p-mentane. If the alicyclic solvent exceeds 30% by weight of the mixed solvent, the graft efficiency of the acrylic monomer having an ethylenically unsaturated bond is low, not only the solution properties are poor, but also the miscibility with other resins such as urethane is used. Not desirable

Although the polymerization initiator used for reaction can be selected suitably from well-known things, Organic peroxide is preferable. For example, benzoyl peroxide, dialkyl peroxide, ketone peroxide, peroxy ester, diacyl peroxide, etc. are mentioned. In addition, reaction temperature can be implemented in the range below normal temperature-the boiling point of a solvent, and reaction time is suitable for 1 to 10 hours.

The acryl-type monomer which has an ethylenically unsaturated bond used by this invention is an acryl-type monomer which has one ethylenically unsaturated bond in 1 molecule, For example, glycidyl acrylate, glycidyl methacrylate, 2-hydride Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid or methacrylic acid, and the like. These may be used alone or in combination of two or more.

In the present invention, the ratio of the acrylic monomer having an ethylenically unsaturated bond to the oxidized chlorinated polyolefin is preferably in the range of 1 to 50% by weight. If it is less than 1 weight%, miscibility with other resin, such as a urethane resin, with respect to the said solvent is poor. If it exceeds 50% by weight, not only the solubility in the solvent is poor, but also an insoluble homopolymer is formed and sometimes precipitated, which is not preferable as a resin for printing ink.

The resin composition for printing inks of this invention mix | blends an alicyclic solvent further with the graft polymer obtained by the said method. As an alicyclic solvent, said thing can be used. It is preferable to mix | blend the resin composition for ink of this invention so that an alicyclic solvent may be 10 to 90 weight% with respect to the total solvent amount. If the alicyclic solvent is less than 10% by weight or more than 90% by weight, the solution properties become poor, which is not preferable.

It is preferable that the resin solid content concentration of a printing ink of this invention is 30 to 70 weight% from a viewpoint of the handling at the time of ink manufacture. Although the resin composition for printing inks of the present invention may be used as an ink as it is, resins such as polyurethane resins, polyamide resins, polyester polyols, cellulose acetate butylate, nitrocellulose, etc., within the range of not impairing the effects of the present invention, You may add and use a pigment, a solvent, and other additives.

The present invention is characterized in that a urethane resin is used by using a non-aromatic polar solvent or a mixed solvent of the polar solvent and an alicyclic solvent in the solvent when reacting the oxidized chlorinated polyolefin with an acrylic monomer having an ethylenically unsaturated bond. It is a point which can obtain the resin composition for ink which is excellent in miscibility with resin for ink, such as polyester resin and nitrocellulose, and is excellent in high temperature stability.

In addition, in order to increase the miscibility of the oxidized chlorinated polyolefin with urethane resin, polyamide resin, nitrocellulose, etc., it is important to introduce an acrylic monomer having an ethylenically unsaturated bond into the oxidized chlorinated polyolefin to increase the polarity of the resin. I think. The graft copolymer obtained by graft polymerization of an oxidized chlorinated polyolefin and an acrylic monomer having an ethylenically unsaturated bond in the presence of a non-aromatic polar solvent or a mixed solvent of the polar solvent and an alicyclic solvent is dissolved in an alicyclic solvent. It is thought that making it become one cause to raise miscibility with each resin.

<Example>

Next, although an Example demonstrates this invention still in detail, this invention is not limited to this.

(Test Production Example-1)

300 g of isotactic polypropylene having a melt viscosity of about 4000 mPa · s at 160 ° C. is introduced into a glass lined reactor. 5 L of chloroform is added, and under the pressure of 2 kg / cm 2, chlorine gas and oxygen gas are blown while irradiating ultraviolet rays, and chlorinated until the functional group index is 20% and the chlorine content is 32% by weight. After the reaction was completed, 18 g of an epoxy compound (e.g., Eposizer W-100EL, manufactured by Dainippon Ink and Chemicals, Inc.) was added as a stabilizer to remove the screw shaft. It is supplied to an extruder equipped with an outlet equipped with a solvent suction part (Twin screw extruder KZW40-34MG, manufactured by Technovel Corp.), desolventized and solidified. The weight average molecular weight of the obtained oxidation treated chlorinated polypropylene is 11000.

(Test Production Example-2)

300 g of isotactic polypropylene having a melt viscosity of about 4200 mPa · s at 160 ° C. was introduced into a glass-lined reactor, 5 L of chloroform was added, and chlorine gas and oxygen gas were irradiated under ultraviolet light at a pressure of 2 kg / cm 2. Blown and chlorination until the functional group index is 23% and the chlorine content is 39% by weight. After the completion of the reaction, 18 g of an epoxy compound (Epiol SB, manufactured by Nippon Oil and Fats Co., Ltd.) was added as a stabilizer, and the solvent was removed in the same manner as in Test Production Example 1. Solidify. The weight average molecular weight of the obtained oxidation treated chlorinated polypropylene is 18000.

(Test Production Example-3)

300 g of isotactic polypropylene having a melt viscosity of about 4200 mPa · s at 160 ° C. was introduced into a glass-lined reactor, 5 L of chloroform was added, and chlorine gas and oxygen gas were irradiated under ultraviolet light at a pressure of 2 kg / cm 2. Blown and chlorination until the functional group index is 18% and the chlorine content is 68% by weight. After the completion of the reaction, 18 g of an epoxy compound (Epiol SB, manufactured by Nippon Yushi Co., Ltd.) is added as a stabilizer, and is subjected to desolvation and solidification as in Test Production Example 1. The weight average molecular weight of the obtained oxidation treated chlorinated polypropylene is 10000.

(Example-1)

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 380 g of the oxidized polychlorinated polypropylene obtained in Test Production Example-1 and 200 g of ethyl acetate were charged and dissolved at 70 ° C by heating. Next, 3.8 g of benzoyl peroxide (hereinafter abbreviated as BPO) were added and held for 10 minutes, followed by 20 g of 2-hydroxyethyl methacrylate (hereinafter abbreviated as 2-HEMA) over 3 hours. Add. Then, post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. In addition, 200 g of methylcyclohexane (hereinafter abbreviated as MCH) is added to obtain a resin composition having a solid content concentration of 50% by weight.

(Example-2)

Into the reactor used in Example 1, 400 g of oxidized chlorinated polypropylene obtained from Test Production Example 2, 40 g of MCH, and 360 g of ethyl acetate were added and dissolved in a heating at 70 ° C. Next, 3.8 g of BPO are added and held for 10 minutes, then 20 g of 2-HEMA is added over 3 hours. Then, post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. Moreover, 20 g of MCH is added and it is set as the resin composition of 50 weight% of solid content concentration.

(Example-3)

Into the reactor used in Example-1, 320 g of oxidized polychlorinated polypropylene obtained in Test Production Example-2, 20 g of MCH, and 150 g of ethyl acetate were added and dissolved in a heat at 70 ° C. Next, 3.8 g of BPO are added and held for 10 minutes, followed by 80 g of 2-HEMA over 3 hours. Then, the post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. Moreover, 230 g of MCH is added and it is set as the resin composition of 50 weight% of solid content concentration.

(Example-4)

Into the reactor used in Example 1, 380 g of the oxidized polychlorinated polypropylene obtained in Test Production Example 2, 20 g of MCH, and 150 g of ethyl acetate were added and dissolved in a heating at 70 ° C. Next, 3.8 g of BPO is added and held for 10 minutes, and then 20 g of glycidyl methacrylate (hereinafter abbreviated as GMA) is added over 3 hours. Then, the post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. Moreover, 230 g of MCH is added and it is set as the resin composition of 50 weight% of solid content concentration.

Example-5

Into the reactor used in Example-1, 400 g of oxidized polychlorinated polypropylene obtained in Test Production Example-1, 40 g of ethylcyclohexane (hereinafter abbreviated as ECH), and 200 g of ethyl acetate were added and dissolved at 70 ° C by heating. Next, 3.8 g of BPO are added and held for 10 minutes, then 20 g of 2-HEMA is added over 3 hours. Then, the post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. Moreover, 180 g of ECH is added and it is set as the resin composition of 50 weight% of solid content concentration.

(Comparative Example-1)

Into the reactor used in Example 1, 380 g of the oxidation-treated chlorinated polypropylene obtained in Test Production Example-1 and 400 g of MCH were added and heated to be dissolved at 70 ° C. Next, 3.8 g of BPO are added and held for 10 minutes, then 20 g of 2-HEMA is added over 3 hours. Then, post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. Solid content concentration of the obtained graft copolymer solution is 50 weight%, making this a resin composition.

(Comparative Example-2)

Into the reactor used in Example 1, 380 g of the oxidized polychlorinated polypropylene obtained in Test Production Example 2 and 400 g of ethyl acetate were added and dissolved in a heating at 70 ° C. Next, 3.8 g of BPO are added and held for 10 minutes, then 20 g of 2-HEMA is added over 3 hours. Then, post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. Solid content concentration of the obtained graft copolymer solution is 50 weight%, making this a resin composition.

(Comparative Example-3)

Into the reactor used in Example 1, 380 g of the oxidized polychlorinated polypropylene obtained in Test Production Example 3, 200 g of MCH, and 200 g of ethyl acetate were added and dissolved in a heat at 70 ° C. Next, 3.8 g of BPO are added and held for 10 minutes, then 20 g of 2-HEMA is added over 3 hours. Then, post-reaction is performed for 3 hours while maintaining at 70 degreeC, and the graft copolymer solution is obtained. Solid content concentration of the obtained graft copolymer solution is 50 weight%, making this a resin composition.

(Comparative Example-4)

Into the reactor used in Example 1, 400 g of oxidized chlorinated polypropylene, 200 g of MCH and 200 g of ethyl acetate obtained in Test Production Example 1 were added, heated and dissolved at 70 ° C, and oxidized chlorinated polypropylene having a solid content of 50 wt%. Obtain a solution. Let this be a resin composition.

(Comparative Example-5)

Into the reactor used in Example 1, 400 g of oxidized polychlorinated polypropylene obtained by Test Production Example 2, 47 g of MCH, and 267 g of ethyl acetate were added and dissolved in a heating at 60 ° C. Subsequently, 71 g of a polyester polyol having a hydroxyl value of 112 KOHmg / g and 31 g of isophorone diisocyanate obtained by condensation polymerization of 2,2,4-trimethylhexanediol and adipic acid were added and reacted for 8 hours. Next, 6 g of isophoronediamine, 85 g of MCH, and 101 g of isopropyl alcohol (hereinafter abbreviated as IPA) are added, and the mixture is reacted at 40 ° C. for 2 hours under stirring. Solid content concentration of the obtained urethane modified oxidation-treated chlorinated polypropylene solution is 50 weight%, and this is set as the resin composition.

Table 1 shows the raw materials and reaction conditions used in Examples 1 to 5 and Comparative Examples 1 to 4.

Resin Weight (g) Type Solution composition at the time of reaction ^{※ 1} (rate (%) of alicyclic solvent) Acrylic monomer type weight (g) (ratio to resin (%)) Addition amount of alicyclic solvent to graft copolymer (g) Percentage of alicyclic solvents in all solvents Example 1 Trial Production Example 1 380 200/0 (0) 2 HEMA 20 (5.3) 200 50.0 Example 2 Trial Production Example 2 400 360/40 (10.0) 2HEMA 20 (5.0) 20 14.3 Example 3 Trial Production Example 2 320 150/20 (11.8) 2HEMA 80 (25.0) 230 62.5 Example 4 Trial Production Example 2 380 150/20 (11.8) GMA 20 (5.3) 230 62.5 Example 5 Trial Production Example 1 400 200/40 (16.7) 2HEMA 20 (5.0) 180 52.4 Comparative Example 1 Trial Production Example 1 380 0/400 (100) 2 HEMA 20 (5.3) 0 100 Comparative Example 2 Trial Production Example 2 380 400/0 (0) 2 HEMA 20 (5.3) 0 0 Comparative Example 3 Trial Production Example 3 380 200/200 (50.0) 2 HEMA 20 (5.3) 0 50.0 Comparative Example 4 Trial Production Example 1 400 200/200 (50.0) -(0) 0 50.0 Solution composition during the reaction ^{* 1} : Polar solvent / alicyclic solvent (weight ratio)

Next, the following tests are performed about the resin composition obtained by each Example.

High temperature stability

Regarding the resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 5, the change over time of the color number (Gardner color number) immediately after the preparation and after storage for 1 month at 50 ° C is investigated. The results are shown in Table 2.

Miscibility test

The resin composition obtained in Examples 1-5 and Comparative Examples 1-5, and urethane resin for ink (Sanprene IB-422, Sanyo Chemical Industries, Ltd.) or poly An ester resin (Desmophene 670, Sumitomo Bayurethane Co., Ltd.) is mixed at a solids weight ratio of 1/9 and prepared with ethyl acetate at a total resin concentration of 30% by weight. The state of the obtained mixed resin solution is visually determined. The results are shown in Table 2. In Table 2, evaluation criteria are?: Clear (no separation), x: poor (with precipitation).

High temperature stability and miscibility test results 50 degrees * 1 month Miscibility Urethane resin Polyester resin Example 1 No change ◎ ◎ Example 2 No change ◎ ◎ Example 3 No change ◎ ◎ Example 4 No change ◎ ◎ Example 5 No change ◎ ◎ Comparative Example 1 No change × × Comparative Example 2 No change × × Comparative Example 3 No change × × Comparative Example 4 No change × × Comparative Example 5 5 (initial) → 10 ◎ ◎

Adhesive test

The following materials are mixed using a mixed resin solution (30% by weight solution) used in the miscibility test, kneaded with a paint shaker, and then the white printing ink is adjusted.

40 parts of mixed solution

Pigment (titanium white) 30 parts

20 parts ethyl acetate

IPA15 Part

The obtained white printing ink is applied to a stretched polypropylene film (OPP), polyester film (PET) or nylon film (NY) with a # 10 Meyer bar. The cellophane tape is affixed on a coating surface, and the state of the coating surface at the time of peeling this rapidly is observed. The results are shown in Table 3. In Table 3,?: Very good,?: Good,?: Slightly defective, x: defective.

Adhesive test results Mixture with urethane resin for inks Mixture with polyester resin OPP PET NY OPP PET NY Example 1 ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 1 △ O O △ O O Comparative Example 2 △ O O △ O O Comparative Example 3 × O O × O O Comparative Example 4 ◎ × × ◎ × × Comparative Example 5 ◎ ◎ ◎ ◎ ◎ ◎

From the results of Tables 2 and 3, the resin composition for printing inks of the present invention is excellent in high temperature stability and also excellent in compatibility with ink urethane resins or polyester resins. Moreover, it turns out that it is useful industrially from the point which is excellent in adhesiveness to various films, such as OPP, PET, and NY.

Moreover, since the resin composition for printing inks of this invention does not use aromatic solvents, such as toluene, at all also in a manufacturing process, it is excellent also environmentally.

Claims (8)

A graft copolymer in which an acrylic monomer having an ethylenically unsaturated bond is reacted with an oxidized chlorinated polyolefin having a weight average molecular weight of 3000 to 50000 and a chlorine content of 10 to 50% by weight, a mixed solvent of a non-aromatic polar solvent and an alicyclic solvent Resin composition for a printing ink comprising a. The resin composition for printing ink according to claim 1, wherein the resin solid content concentration is 30 to 70% by weight. The resin composition for printing inks according to claim 1 or 2, wherein 10 to 90% by weight of the alicyclic solvent is contained in the mixed solvent. The resin composition for printing ink according to any one of claims 1 to 3, wherein the ratio of the acrylic monomer having an ethylenically unsaturated bond to the oxidized chlorinated polyolefin is 1 to 50% by weight. Graft copolymer obtained by reacting an acrylic monomer having an ethylenically unsaturated bond with an oxidized chlorinated polyolefin having a weight average molecular weight of 3000 to 50000 and a chlorine content of 10 to 50% by weight in the presence of a non-aromatic polar solvent. A method for producing a resin composition for printing ink, comprising mixing an food solvent. The manufacturing method of the resin composition for printing inks of Claim 5 which mixes alicyclic solvent so that it may become 10 to 90weight% of a range with respect to the total solvent amount. The manufacturing method of the resin composition for printing inks of Claim 5 or 6 whose ratio of the acryl-type monomer which has ethylenically unsaturated bond with respect to oxidized chlorinated polyolefin is 1-50 weight%. The manufacturing method of the resin composition for printing in any one of Claims 5-7 which makes it react in presence of the mixed solvent of a non-aromatic polar solvent and 30 weight% or less of an alicyclic solvent.