KR100728664B1 - resin composition for offset ink and method of manufacturing the same - Google Patents

Abstract

Provided are a photocurable resin composition for offset ink and a method of manufacturing the same. The photocurable resin composition for offset ink is a polyester resin by reacting with 0.5 to 0.95 equivalents of polyhydric basic acid to 1 equivalent of polyhydric alcohol, and 0.005 to 0.5 weight% of polymerization inhibitor to 25 to 60 weight% of the polyester resin. Adding a step, diluting the mixture with 40 to 70% by weight of a polyfunctional acrylate monomer, adding 0.1 to 5% by weight of an aluminum chelate compound to the diluted mixture and reacting for 30 to 60 minutes under 50 to 100 ° C. It is prepared through the step of. The photocurable resin composition for offset inks is used in offset UV inks to exhibit excellent printability, transferability, emulsification resistance, and the like.

Description

Photocurable resin composition for offset ink and a method of manufacturing the same {resin composition for offset ink and method of manufacturing the same}

The present invention relates to a photocurable resin composition and a method for producing the same. More specifically, the present invention relates to a photocurable resin composition and a method for producing the same, which can be used for preparing offset UV inks to exhibit excellent physical properties.

In the conventional offset UV ink, polyester acrylate resin, epoxy acrylate resin and the like were used, but in the ultraviolet curable resin without gelling agent, the viscoelasticity was very low, resulting in poor emulsification resistance, printability, and gas phase stability. In particular, print transferability is very poor in the recent high speed printing environment.

In order to solve this problem of conventional viscoelasticity reduction, a composition and a gelling agent prepared by dissolving a rosin-modified phenolic resin in vegetable oil were used as varnishes used in offset inks. However, there is a problem that the gelling agent must be reacted at a high temperature in order to use the gelling agent, and when applied to an ultraviolet curable resin, there is a problem of gelation due to thermal polymerization.

The present invention provides a photocurable resin composition for offset ink having improved physical properties such as printability, transferability, and emulsion resistance.

This invention also provides the manufacturing method of the said photocurable resin composition for offset inks.

The photocurable resin composition for offset ink according to one aspect of the present invention comprises 100 parts by weight of a polyester acrylate resin made of a repeating unit of a polyester resin and a polyfunctional acrylate monomer, and hydroquinone, p-benzoquinone, t- 0.005 to 0.5 parts by weight of an anti-polymerization agent composed of at least one compound selected from the group consisting of butylhydroquinone and methylhydroxyquinone. The carboxyl group and the hydroxy group of the polyester resin are combined with 0.1 to 5 parts by weight of a naphthalene oil-containing aluminum chelate compound. The polyester resin has a weight average molecular weight of 1000 to 8000.

Method for producing a photocurable resin composition for offset ink according to one aspect of the present invention,

Synthesizing a polyester resin by reacting with 0.5 to 0.95 equivalents of polyhydric base acid per 1 equivalent of polyhydric alcohol, adding 0.005 to 0.5 wt% of a polymerization inhibitor to 25 to 60 wt% of the polyester resin, Diluting with 40 to 70% by weight of a functional acrylate monomer, adding 0.1 to 5% by weight of an oil-containing aluminum chelate compound to the diluted mixture and reacting for 30 to 60 minutes at 50 to 100 ° C.

Hereinafter, the present invention will be described in detail.

In order to manufacture the photocurable resin composition for offset ink, a polyester resin must first be synthesized. The polyester resin is synthesized by condensation reaction between a polyhydric alcohol and a polyvalent basic acid. The polybasic base acid is allowed to react with 0.5 to 0.95 equivalents based on 1 equivalent of the polyhydric alcohol. If the equivalent weight of the polyhydric base acid reacted with respect to 1 equivalent of the polyhydric alcohol is less than 0.5, the hardness becomes poor, whereas if it exceeds 0.95, the emulsion resistance is poor.

The synthesis reaction is carried out under a catalyst and nitrogen atmosphere. As the catalyst, tin compounds, organic lead, manganese compounds and the like are used. More specifically, examples of the catalyst include tetra phenyl tin, tetra octyl tin, diphenyl tin laurate, dimethyl tin oxide, dibutyl tin oxide and lead acetate, magnesium acetate and the like. The compounds may be used alone or in combination of two or more.

The catalyst is used in an amount of 0.01 to 1.0% by weight based on the total amount of polyhydric alcohol and polyvalent basic acid. If the amount of the catalyst used is less than 0.01% by weight relative to the total amount of the polyhydric alcohol and the polybasic acid, the promoting effect of the dehydration reaction is insufficient. On the other hand, if the amount of the catalyst exceeds 1.0% by weight, the side reactions may proceed.

The condensation reaction is allowed to proceed for 6 hours to 10 hours under 200 to 260 ° C. When the reaction proceeds and the acid value of the resin reaches 15 or less, the polyester resin is obtained by cooling the internal temperature to 180 to 200 ° C and decompressing the vacuum to remove the dehydrated product.

Examples of the polyhydric alcohols include glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, diethylene glycol, neopentyl glycol, diglycerol, sorbitol, 1,6-hexanediol, and the like. The alcohols may be used alone or in combination of two or more. As said polyhydric alcohol, in order to improve hardness, toughness, etc., it is preferable to use the polyhydric alcohol more than trifunctional group.

Examples of the polybasic base acid include phthalic anhydride, phthalic acid, maleic anhydride, adipic acid, isophthalic acid, benzoic acid, citric acid, lauryl acid, sebacic acid, and oleic acid. The polyvalent basic acids may be used alone or in combination of two or more.

The polyester resin is included in the 25 to 60% by weight for the production of the photocurable resin composition for offset ink according to an aspect of the present invention.

If the content ratio of the polyester resin is less than 25% by weight, the transferability is poor, while if the content ratio of more than 60% by weight there is a problem that the emulsion resistance is poor. In particular, the content of the polyester resin is preferably 35 to 55% by weight.

The weight average molecular weight of the synthesized polyester resin is 1000 to 8000. If the weight average molecular weight is less than 1000, the viscoelasticity cannot be sufficiently improved. On the other hand, if the weight average molecular weight exceeds 8000, a large network structure is formed and transferability is poor.

In addition, the synthesized polyester resin has a hydroxyl value of 20 to 100 and an acid value of 5 to 15. If the hydroxyl value is less than 20, the hydroxyl group is insufficient and the viscoelasticity is lowered. On the other hand, if the hydroxyl value is more than 100, the gelation degree is increased and the oil resistance is poor. If the acid value is less than 5, the carboxyl group capable of reacting with the gelling agent is insufficient, and if the acid value exceeds 15, emulsification resistance is poor.

As the polymerization inhibitor, hydroquinone, p-benzoquinone, t-butylhydroquinone, methylhydroxyquinone and the like are used. The polymerization inhibitor is included in the total photocurable resin composition 0.005 to 0.5% by weight. If the content of the polymerization inhibitor is less than 0.005% by weight, there is a problem in storage properties, while if the content exceeds 0.5% by weight, the curability may be poor.

Such polyester resin is diluted with a polyfunctional acrylate monomer in the presence of the polymerization inhibitor. At this time, the multifunctional acrylate monomer added for the production of the photocurable resin composition for offset ink is included in the content of 40 to 70% by weight in the total photocurable resin composition. If the content of the multifunctional acrylate monomer is less than 40% by weight, physical properties such as hardness and abrasion resistance are lowered. On the other hand, if the content is more than 70% by weight, the emulsification resistance is poor. In particular, the content of the multifunctional acrylate monomer is preferably 55 to 65% by weight.

Examples of the polyfunctional acrylate monomers include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, 1,4 butanediol diacrylate, neopentyl glycol diacrylate. Acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ditrimethylolpropane Tetraacrylate, dipentaerythritol hexaacrylate, and the like. The polyfunctional acrylate monomers may be added alone or in combination of two or more.

Photocurable for offset ink according to an aspect of the present invention by reacting the mixed solution diluted with the multifunctional acrylate monomer as described above by adding the aluminum chelate compound for about 30 to 60 minutes at a temperature of about 50 to 100 ℃ A resin composition can be manufactured.

 The aluminum chelate compound functions as a gelling agent in the photocurable resin composition for offset ink. The gelling agent used in the present invention is an organoaluminum compound, in which an aluminum alkoxide of naphthalene oil is present as a chelate, which can gel at 100 ° C. or less and has a high yield value. The aluminum compound contains oil so that the reaction with oxygen in the air is suppressed to form a dihydroxyaluminum which causes a seed and can be protected from moisture. In the case of using aluminum alkoxides conventionally used as an organoaluminum compound, hydrolysis occurs easily due to moisture and oxygen, resulting in aluminum hydroxide, difficult to handle, and thickening and gelling during storage.

As said aluminum chelate compound which concerns on one characteristic of this invention, organoaluminum compounds, such as an aluminum alcoholate and an aluminum alkyl acetate, can be used.

Examples of the aluminum alcoholate include aluminum isopropylate, aluminum tri-n-butylate, aluminum tri-sec-butylate, aluminum tri-tert-butylate, mono-sec-butoxy aluminum diisopropylate, and the like. have.

Moreover, as said aluminum alkyl acetate, ethyl aceto acetate aluminum diisopropylate, aluminum tris (ethyl aceto acetate), aluminum monoacetyl acetate bis (ethyl aceto acetate), aluminum aceto acetate ester, aluminum octoate isopropyl ethyl hexano And aluminum tris (acetyl acetate), aluminum monoisopropoxy monooleoxyethyl acetate, aluminum acetyl acetate, aluminum acylate and the like.

As the aluminum alcoholate and the aluminum alkyl acetate, the aluminum compounds listed above may be used alone or in combination of two or more thereof.

The aluminum chelate compound is contained in an oil so that 0.1 to 5% by weight of the total photocurable resin composition is included. When the content of the aluminum chelate compound is less than 0.1% by weight, the gelling agent may not be able to perform a smooth function, and thus, viscoelasticity may not be improved. On the other hand, when the content is more than 5% by weight, side reactions may occur to form seeds. have.

The oil-containing aluminum chelate compound reacts with the carboxyl group and the hydroxyl group of the polyester resin. When the reaction temperature exceeds 100 ° C., there is a fear that seeds are generated by excessive reaction of the organoaluminum compound.

The photocurable resin composition for offset ink prepared above includes a polyester acrylate resin and a polymerization inhibitor polymerized using a polyester resin and a polyfunctional acrylate monomer as each repeating unit. The carboxyl and hydroxy groups of the polyester acrylate resin in the final composition have a form combined with the oil-containing aluminum chelate compound.

The polymerization inhibitor is preferably included in an amount of 0.005 to 0.5 parts by weight based on 100 parts by weight of the polyester acrylate resin. If the polymerization inhibitor is less than 0.005 parts by weight, there is a problem in storage properties, while if it exceeds 0.5 parts by weight, the curability may be poor.

In addition, the oil-containing aluminum chelate compound bonded to the carboxyl group and the hydroxyl group of the polyester acrylate resin is preferably bonded to 0.1 to 5 parts by weight based on 100 parts by weight of the polyester acrylate resin. When the oil-containing aluminum chelate compound is combined at less than 0.1 part by weight, the gelling agent may not be able to smoothly function as a gelling agent, and thus, viscoelasticity cannot be improved. On the other hand, when the amount of the oil-containing aluminum chelate compound is greater than 5 parts by weight, side reactions are formed and seeds are generated. .

Hereinafter, the present invention will be described in more detail with reference to specific embodiments. However, the technical spirit of the present invention is not limited by the following embodiments.

Synthesis Example 1

Into a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a water separator, pentaerythritol 136.0 g, isophthalic acid 99.7 g, benzoic acid 238.1 g and 0.15 g of dibutyl tin oxide were added as a catalyst and nitrogen gas was injected to 160 ° C. It heated up. Since the dehydration reaction proceeds from 160 ° C., the temperature is gradually increased to 230 ° C. While the acid value was measured, cooling was started at 10 or less, vacuum reduced pressure at 200 ° C., and dehydration was removed to synthesize a polyester resin.

Synthesis Example 2-4

Polyester resins were synthesized from the components shown in Table 1 by the same method as in Synthesis Example 1.

ingredient Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Pentaerythritol (g) 136 136 136 99.4 Trimethylol propane (g) 36.3 Isophthalic acid (g) 99.7 74.5 83.1 83.1 Benzoic acid (g) 238.1 183.2 280.1 207.6 Lauryl acid (g) 44.1 44.1 Adipic acid (g) 58.5 16.1 Dibutyl tin oxide 0.15 0.15 0.15 0.15 Polyester resin characteristic value Hydroxyl value 90 90 37 60 Acid value 9.5 12.0 9.0 9.0 Molecular Weight 2400 6800 4500 6000

Example 1

40 g of polyester resin composition obtained in Synthesis Example 1 and 0.2 g of hydroquinone, a polymerization inhibitor, were added and stirred well, followed by diluting 40 g of ditrimethylolpropane tetraacrylate and 20 g of trimethylolpropane triacrylate, and containing oil. 1.0 g of ethyl acetoacetate aluminum diisopropylate was added and reacted at 80 ° C. for 40 minutes to prepare a photocurable resin composition for offset ink.

Example 2-4

It was carried out in the same manner as in Example 1 but shown in Table 2 to carry out the reaction according to the conditions. In addition, the viscosity after the gelling agent of the prepared photocurable resin composition for offset ink is shown in Table 2.

Example 1 Example 2 Example 3 Example 4 Polyester resin Synthesis Example 1 40 Synthesis Example 2 40 Synthesis Example 3 35 Synthesis Example 4 45 Ditrimethylolpropane Tetraacrylate 40 30 30 35 Dipentaerythritol hexaacrylate 15 25 Trimethylolpropane triacrylate 20 15 10 20 Hydroquinone 0.2 0.2 0.2 0.2 Viscosity before adding gelling agent (Poise / 25 ℃) 890 1400 1050 1250 Oil-containing ethyl acetoacetate aluminum diisopropylate 1.0 Oil-containing aluminum octoate isopropyl ethylhexanoate 1.0 Oil-containing aluminum acylate 1.0 1.5 Viscosity after adding gelling agent (Poise / 25 ℃) 1920 2800 2300 2700

Comparative Example 1

30 g of diallyl phthalate polymer and 0.3 g of hydroquinone as polymerization inhibitors were added to the same apparatus as in Example 1, and stirred well, followed by dilution of 70 g of trimethylolpropane triacrylate and 1.0 g of aluminum isopropylate. Reaction was carried out to prepare a curable resin composition.

Comparative Example 2

A curable resin composition was prepared in the same manner as in Example 1 except for using ethylacetoacetate aluminum diisopropylate containing oil differently from Comparative Example 1.

Comparative Example 3

A curable resin composition was prepared in the same manner as in Example 2 except for using aluminum monoisopropoxy monooleoxyethyl acetate containing oil differently from Comparative Example 1.

In order to perform the physical property test of the resin compositions prepared in the above Examples and Comparative Examples, 45% by weight of the resin composition, 25% by weight of the pigment component consisting of cyanine blue, calcium carbonate, 22% by weight of the reactive monomer, 5% by weight of the photopolymerization initiator, As an additive, a wax and a dispersant were 3% by weight and ground on a 3 roll mill to prepare an offset UV ink composition. The physical properties were compared with the offset UV ink composition thus prepared.

1. Printability Test

The print aptitude test evaluated the problems of ink yogure, width of water, and long-term printing.The printing test equipment (RYOBI 3200, Japan) supplied 120 g of sample ink to ink turbo and 7000 sheets / hr using the specified water. Printed at a speed, the damp gauge was reduced until the yogure occurred, and the roll state and the damp state were evaluated.

2. Oil resistance

After weighing the ink sample to 100 ± 0.01g in a clean sample container, take the water with a graduated cylinder, add it to the sample container, and test the test time every 3 minutes on the DUKE test machine (Model: D-10, DUKE CUSTOM USA). When the tester stopped, the sample was scraped with a spatula, placed in the sample container, and the amount of damp water in the sample container was weighed with a graduated cylinder, and then the degree of the curve was evaluated.

3. High speed printing test

High speed printing test equipment (PM-901PT, Samjeong Electric Regular Co., Ltd.) Set the temperature to 32 ℃ and the water supply to 40 microliters, transfer 0.2cc of the sample ink to the roller with an ink dropper to transfer to 3.6m / sec printing speed. The ink state was evaluated.

Test results evaluated by the test method as described above are shown in Table 3.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Printability ◎ ◎ ◎ ◎ ○ △ △ Oil resistance ◎ ◎ ◎ ◎ △ × △ High speed printability ○ ◎ ○ ◎ △ △ ×

Evaluation standard ; ◎: Excellent, ○: Good, △: Normal, ×: Poor

When the photocurable resin composition for offset ink is applied to the offset ink, the viscoelasticity of the offset ink can be increased, and printability, transferability, and emulsion resistance can be greatly improved. In particular, it can exhibit very good performance even at high speed printing.

As described above, although described with reference to the preferred embodiment of the present invention, those skilled in the art will be variously modified without departing from the spirit and scope of the invention described in the claims below. And can be changed.

Claims (20)

100 weight part of polyester acrylate resin which consists of a polyester resin and a polyfunctional acrylate monomer which have a weight average molecular weight of 1000-8000 as a repeating unit, respectively; And It contains 0.005 to 0.5 parts by weight of an anti-polymerizing agent composed of at least one compound selected from the group consisting of hydroquinone, p-benzoquinone, t-butylhydroquinone and methylhydroxyquinone, and the carboxyl group and hydroxy of the polyester acrylate resin. The group is combined with 0.1 to 5 parts by weight of the naphthalene-based oil-containing aluminum chelate compound, the photocurable resin composition for offset ink. The photocurable resin composition for offset ink according to claim 1, wherein the polyester resin has a hydroxyl value of 20 to 100 and an acid value of 5 to 15. delete delete The method of claim 1, wherein the aluminum chelate compound is aluminum isopropylate, aluminum tri-n-butylate, aluminum tri-sec- butyrate, aluminum tri-tert- butyrate, mono-sec-butoxy aluminum diisopropyl Ethyl Acetoacetate Aluminum Diisopropylate, Aluminum Tris (ethyl Aceto Acetate), Aluminum Aceto Acetate Ester, Aluminum Octoate Isopropyl Ethyl Hexate, Aluminum Monoacetyl Acetate Bis (ethyl Aceto Acetate), Aluminum Tris (acetyl Acetate) ), At least one compound selected from the group consisting of aluminum monoisopropoxy monooleoxy ethyl acetate, aluminum acetyl acetate, aluminum acylate, and the like. Synthesizing the polyester resin by reacting 0.5 to 0.95 equivalents of polyvalent basic acid with respect to 1 equivalent of polyhydric alcohol; Adding 0.005 to 0.5 wt% of a polymerization inhibitor to 25 to 60 wt% of the polyester resin; Diluting the mixture with 40 to 70 wt% of a multifunctional acrylate monomer; Method for producing a photocurable resin composition for offset ink comprising the step of adding 0.1 to 5% by weight of an oil-containing aluminum chelate compound to the diluted mixture for 30 to 60 minutes under 50 to 100 ℃. delete The method of manufacturing a photocurable resin composition for offset ink according to claim 6, wherein the step of synthesizing the polyester resin is performed under nitrogen gas injection. The method of manufacturing a photocurable resin composition for offset ink according to claim 8, wherein the step of synthesizing the polyester resin is performed under a temperature of 200 to 260 ° C. 10.  10. The method of claim 9, wherein the step of synthesizing the polyester resin includes cooling to a temperature of 180 to 200 ℃ at the time when the acid value is 15 or less during the reaction, and then removing the dehydrated under vacuum pressure The manufacturing method of the photocurable resin composition for offset ink characterized by the above-mentioned. The method of manufacturing a photocurable resin composition for offset ink according to claim 6, wherein the step of synthesizing the polyester resin is performed so that the weight average molecular weight of the polyester resin is 1000 to 8000. The method of claim 6, wherein the step of synthesizing the polyester resin, the photoresist of the offset ink photocurable resin composition, characterized in that for reacting so that the hydroxyl value of the polyester resin is 20 to 100, the acid value is 5 to 15 Manufacturing method. According to claim 6, wherein the polyhydric alcohol is at least one selected from the group consisting of glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, diethylene glycol, neopentyl glycol, diglycerol, sorbitol, 1,6-hexanediol Method for producing a photocurable resin composition for offset ink comprising a compound of. The method of claim 6, wherein the polybasic acid comprises at least one compound selected from the group consisting of phthalic anhydride, phthalic acid, maleic anhydride, adipic acid, isophthalic acid, benzoic acid, citric acid, lauryl acid, sebacic acid and oleic acid. The manufacturing method of the photocurable resin composition for offset ink characterized by the above-mentioned. The method of claim 6, wherein the multifunctional acrylate monomer is ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, 1,4 butanediol diacrylate, neo Pentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, di A method for producing a photocurable resin composition for offset ink, comprising at least one monomer selected from the group consisting of trimethylolpropane tetraacrylate and dipentaerythritol hexaacrylate. 7. The photocurable resin for offset ink according to claim 6, wherein the polymerization inhibitor comprises at least one compound selected from the group consisting of hydroquinone, p-benzoquinone, t-butylhydroquinone and methylhydroxyquinone. Method of Preparation of the Composition. The method of manufacturing a photocurable resin composition for offset ink according to claim 6, wherein the oil is naphthalene oil. 18. The method of claim 17, wherein the aluminum chelate compound is aluminum isopropylate, aluminum tri-n-butylate, aluminum tri-sec-butylate, aluminum tri-tert-butylate, mono-sec-butoxyaluminum diisopropyl Ethyl Acetoacetate Aluminum Diisopropylate, Aluminum Acetoacetate Ester, Aluminum Octoate Isopropylethylhexanoate, Aluminum Tris (ethyl Aceto Acetate), Aluminum Monoacetyl Acetate Bis (ethyl Aceto Acetate), Aluminum Tris (acetyl Acetate ), At least one compound selected from the group consisting of aluminum monoisopropoxy monooleoxyethyl acetate, aluminum acetyl acetate, aluminum acylate and the like. 10. The method of claim 9, wherein the step of synthesizing the polyester is at least one selected from the group consisting of tetraphenyl tin, tetra octyl tin, diphenyl tin laurate, dimethyl tin oxide, dibutyl tin oxide, lead acetate and magnesium acetate A method for producing a photocurable resin composition for offset ink, comprising a catalyst atmosphere. 20. The method of claim 19, wherein the catalyst is used in an amount of 0.01 to 1.0 wt% based on the total weight of the polyhydric alcohol and the polybasic acid.