JPS5941451B2 - UV curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ultraviolet curable composition that is rapidly cured and dried by ultraviolet rays, and more specifically to a composition comprising a higher fatty acid having 8 or more carbon atoms alone or a mixture with an unsaturated monobasic acid and a polyisocyanate. Ultraviolet light produced by reacting a reaction product (a) of a compound, an unsaturated monobasic acid alone or a mixture of a higher fatty acid having 8 or more carbon atoms, and a reaction product (b) of at least one epoxy compound. Polymerizable unsaturated compound (1) 5-2
UV-polymerizable unsaturated compound (
■) 10-60% by weight, polymerizable vinyl monomer (■) 5
~50% by weight, UV polymerization initiator (W) 1-15% by weight
It is an ultraviolet curable composition containing other additives as necessary.

The ultraviolet curable composition of the present invention is particularly advantageously used as an ultraviolet curable overprint varnish or an ultraviolet curable ink for paperboard.

Generally, in the case of UV-curable overprint varnish, overprinting is performed with a considerable film thickness, and in the case of UV-curable ink for paperboard, the film is usually thick and heavy paper is used. Therefore, it is necessary to have faster curing properties that are superior to that of general UV-curable sheet-fed printing, and it must also have a corresponding gloss. Among various compositions that can be cured by ultraviolet rays, those whose products are esters of unsaturated monobasic acids such as acrylic esters or methacrylic esters have a fast curing rate. The reaction product of an unsaturated monobasic acid such as methacrylic acid and an epoxy resin has a fast curing speed even in air and has excellent storage stability. UV-curable coating compositions have also been proposed (Japanese Patent Laid-Open No. 49-212
No. 05).

However, although such compositions dry well, when used alone as an overprint varnish or a vehicle for printing inks, they exhibit a marked lack of gloss;
Furthermore, when used in offset printing, it has poor affinity with pigments, and therefore has a negative effect on the consistency of the ink, causing problems such as water loss'7 and poor transfer'5. ing. For this reason, the present inventors conducted various studies on ultraviolet curable compositions and found that
We first developed an ultraviolet curable printing ink and filed a patent application (Japanese Patent Application No. 10033/1983), but as a result of further research, we completed the present invention.

That is, the present invention provides a reaction product (4) of a polyisocyanate compound with a higher fatty acid having 8 or more carbon atoms or a mixture thereof with an unsaturated monobasic acid, and an unsaturated monobasic acid alone or a mixture with an unsaturated monobasic acid having 8 or more carbon atoms. Ultraviolet polymerizable unsaturated compound obtained by reacting a mixture with a higher fatty acid and a reaction product (b) of at least one epoxy compound 1) 5 to 20% by weight, unsaturated monobasic acid or carbon number 8 UV-polymerizable unsaturated compounds () 10 to 60 obtained by reacting the above higher fatty acids or mixtures thereof with at least one epoxy compound
It is an ultraviolet curable composition containing 5 to 50% by weight of a polymerizable vinyl monomer (), 1 to 15% by weight of an ultraviolet polymerization initiator (IV), and other additives as necessary. The ultraviolet curable composition of the present invention uses a higher fatty acid having 8 or more carbon atoms as the ultraviolet polymerizable unsaturated compound (1),
Furthermore, by incorporating this through urethane bonding, it is possible to provide good performance as an offset printing ink or the like.

That is, it can have good gloss, affinity with pigments, and good ink consistency. However, when the ratio of higher fatty acids used increases, gloss increases and excellent performance is obtained for general UV-curable sheet-fed printing, but fast-curing properties are particularly required for UV-curable overprint varnishes or paperboard inks. becomes worse. Therefore, by using 5 to 20% by weight of the UV-polymerizable unsaturated compound (1) as in the present invention, it is possible to achieve a good balance between the required hardenability and gloss, and to use the UV-curable overprint varnish or paperboard. It can give excellent properties to inks for printing. That is, if the usage ratio of the UV-polymerizable unsaturated compound (1) is less than 556%, even if the curability is excellent, the necessary gloss cannot be obtained, and if it is more than 20%, the curability will be poor. The present invention will be explained in detail below.

The ultraviolet polymerizable unsaturated compound 1) is the reaction product a)
and (b) in the presence of a suitable organic solvent, preferably a polymerizable vinyl monomer, usually at a temperature of 70° C. or lower.

Here, the reaction product (a) is a higher fatty acid having 8 or more carbon atoms alone or a mixture with an unsaturated monobasic acid, and a polyisocyanate compound having two or more isocyanate groups in the molecule, usually acid groups: Isocyanate group = 1:1.6-3
Using a catalyst such as a tertiary amine compound such as triethylamine, an organometallic compound, or a metal salt, etc., an appropriate organic solvent or polymerizable vinyl monomer and hydroquinone are used at a molar ratio of 70°C or less under mild conditions. , 2-methylhydroquinone, P-benzoquinone, etc., by reacting in the presence of a thermal polymerization inhibitor, and the reaction product (b) is an unsaturated monobasic acid alone or an unsaturated monobasic acid having 8 carbon atoms.
A mixture of the above-mentioned higher fatty acids and an epoxy compound having two or more epoxy groups in the molecule are usually mixed at a molar ratio of acid group:epoxy group=1:0.8-1.2 of 80-150.
Triethylamine, triethanolamine, at a temperature of °C
It is synthesized by reacting a catalyst such as hexamethylphosphoramide or P-toluenesulfonic acid in the presence of a thermal polymerization inhibitor such as hydroquinone, 2-methylhydroquinone, or P-benzoquinone.

The ultraviolet polymerizable unsaturated compound (4) is an unsaturated monobasic acid, a higher fatty acid having 8 or more carbon atoms, or a mixture thereof,
An epoxy compound having two or more epoxy groups in the molecule is usually mixed with triethylamine, triethanolamine, hexane at a molar ratio of acid group:epoxy group = 1:0.8-1.2 at a temperature of 80-150°C. Methylphosphoramide, P
-Catalyst such as toluenesulfonic acid and hydroquinone, 2-
It is synthesized by reaction in the presence of a thermal polymerization inhibitor such as methylhydroquinone or P-benzoquinone.

The higher fatty acids having 8 or more carbon atoms used in the present invention include hydrofuric acid, nonanoic acid, lauric acid, valmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, and linseed oil containing these. Fatty acids mainly obtained from animal and vegetable oils and fats such as tung oil, dehydrated castor oil, soybean oil, safflower oil, bean oil, and beef tallow are mentioned. Further, examples of unsaturated monobasic acids include acrylic acid, methacrylic acid, and tarotonic acid. Examples of epoxy compounds include the reaction of epichlorohydrin or methylepichlorohydrin with bisphenol A1 resorcinol, aniline, oxybenzoic acid, m-hydroxyaniline, o-cresol novolak, glycols, polyhydric alcohols, halogenated phenols, etc. Examples include di- or triglycidyl-type epoxy compounds synthesized by Furthermore, examples of polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-xylylene diisocyanate, 2,6-tolylene diisocyanate, and 2,4-tolylene diisocyanate.
-xylylene diisocyanate, lysine diisocyanate, diphenylmethane-4,4'-diisocyanate,
Examples include hexamethylene diisocyanate, isoborone diisocyanate, dimer acid diisocyanate, and the like.

Examples of organic solvents include acetone, ethers, benzene, toluene, and tetrahydrofuran. Examples of polymerizable vinyl monomers include trimethylolproban triacrylate or methacrylate, tri- or tetraacrylate or methacrylate of pentaerythritol, and diethylene glycol. diacrylate or methacrylate, neopentyl glycol diacrylate or methacrylate, polyethylene glycol diacrylate or methacrylate, styrene,
Examples include divinylbenzene, 2,2bis(4-acryloxypropyloxyphenyl)propane, 2,2bis(4-acryloxydiethoxyphenyl)propane, and the like.
Examples of ultraviolet polymerization initiators include benzoin-based, benzophenone-based, halogenated sulfonyl-based, quinone-based, ketone-based polymerization initiators, and mixtures thereof. Further, the ultraviolet curable composition of the present invention optionally contains additives such as colorants and other resins depending on the purpose and use, but the amount thereof is generally 30% by weight or less. .

As examples of colorants, all conventionally used pigments and dyes can be used.

Examples of resins include conventionally used vegetable oils and their polymers, rosin-modified phenolic resins, rosin-modified ester resins, various modified alkyd resins, P-toluenesulfonic acid amide formalin resins, acrylated melamine resins, Examples include unsaturated polyester resins, ultraviolet polymerizable resins such as various petroleum resins, and non-polymerizable resins. Further, as other additives, waxes, anti-set-off agents, plasticizers, dryers, and other additives conventionally used for printing inks can all be used.

The present invention will be specifically explained below using synthesis examples and examples.

Synthesis example 1 (1) 500 with cooling pipe, thermometer, and drip load installed
Trimethylolproban triacrylate 1939 and P-benzoquinone 0.199 were charged in an m14 Turow flask and stirred.

Furthermore, tolylene diisocyanate (2,4 monoisomer 80
%, 20% of 2,6 monoisomer) and 0.439% of triethylamine were charged, and heated with stirring to reach 45°C in about 30 minutes. Lunatsk O-A (manufactured by Kao Soap Co., Ltd., oleic acid) 1409 was mixed in advance while maintaining this temperature.
, triethylamine (0.869 g) was added dropwise over a period of about 2 hours. Thereafter, the temperature was maintained at 50° C., stirring was continued for about 1 to 2 hours, and the reaction was terminated when the free isocyanate groups reached 6%. This is designated as compound (a-1). (2)
Sumiepoxy ELA-12 in 500m14 flask
8 (Epoxy resin obtained by reaction of Sumitomo Chemical bisphenol A and epichlorohydrin, epoxy equivalent: 1
84-194), 0.179 g of 2-methylhydroquinone, and 94 y of acrylic acid were sequentially charged and stirred thoroughly. Furthermore, 1.79 g of triethylamine is added, and the temperature is raised to 110° C. while being careful not to generate heat. Stirring was continued at this temperature for about 4 hours, and the reaction was terminated when the oxidation reached 7 or less.
Rapidly cool to about 6°C, 2 methyl hydroquinone 0.06
6g, trimethylolproban triacrylate 133
9 was added and diluted. Approximately 72% of the reaction product as solid matter
Slightly yellow transparent viscosity Z6 to Z7 (Cardner viscometer 25
A liquid of °C) was obtained. This is designated as compound (b-1). (3) Next, compound (a-1) 2259 and compound (b-1) 200 synthesized earlier were placed in a 500 m1 Mitsuro flask.
9. Add 0.29 g of P-benzoquinone and stir and mix thoroughly.

Thereafter, the temperature was gradually raised to 5'C, the reaction was carried out at the same temperature for about 30 minutes, and dibutyltin diacetate was added as a catalyst in an amount of 0.15% based on the total amount, and the same amount was further added 30 minutes later. Stirring was then continued at this temperature for about 2 to 3 hours, and the reaction was terminated when free isocyanate reached 0.3%. A light brown transparent liquid with a viscosity of Z7 was obtained, containing about 62% of the ultraviolet polymerizable unsaturated compound (1). This is compound (1
−1). Synthesis Example 2 (1) In Synthesis Example 1-(1), trimethylolpropane triacrylate 1379, P-benzoquinone 0.1
49. Perform the same procedure except using triethylamine 0.319, and use Lunatsuku 8 instead of Lunatsuku O-A.
The same operation was carried out except that 72 g of -95 (manufactured by Kao Soap Co., Ltd.) and 0.629 g of triethylamine were used, and the reaction was terminated when the free isocyanate groups reached 9%.

This is designated as compound (a-2). (2) In a 11-Yotsuro flask, add 1149 Sumiepoxy ELA-1128, Denacol EX-810 (manufactured by Nagase Sangyo Co., Ltd., ethylene glycol type epoxy resin) 161f1, 0.21 g of 2-methylhydroquinone, 1459 acrylic acid, and tetramethylammonium chloride. 2.1g was charged, and Synthesis Example 1-(2
), the reaction was terminated when the acid value became 13 or less, and the reaction was rapidly cooled to about 60°C, and 2-methylhydroquinone 0.099, trimethylolproban triacrylate 181f! was added and diluted.

A pale yellow, transparent liquid with a viscosity of W-X was obtained, containing about 70% of the reaction product as a solid. This is designated as compound (b-2). (3) Next, compound (a-2) 2 was added to the 11 Mitsuro flask.
509, compound (b-2) 2509 and P-benzoquinone 0.259.

Thereafter, the same operation as in Synthesis Example 1-(3) was performed to obtain a light brown transparent liquid with a viscosity of Z6 to Z7 containing about 62% of the ultraviolet polymerizable unsaturated compound UI). This is designated as compound (1-2). Synthesis Example 3 The same reaction was carried out except that n-nonanoic acid 799 was used in place of Lunatuk 8-95 in Synthesis Example 2, and a light brown transparent product containing about 61% of the light brown transparent UV polymerizable unsaturated compound (1) was obtained. A liquid with a viscosity of Z6 to Z7 was obtained.

This is designated as compound (1-3). Synthesis Example 4 (1) Trimethylolpropane triacrylate 1639, P-benzoquinone 0.1 in Synthesis Example 1-(1)
69, the same operation was performed except that triethylamine 0.369 was used, and the free isocyanate group was converted to 7 ( The end point of the reaction was when Fb was reached.

This is designated as compound (a-3). (2) In a 11-Yotsuro flask, add 2669 of Sumiepoxy ELA-128, Denacol EX-810 (manufactured by Nagase Sangyo Co., Ltd., ethylene glycol type epoxy resin) 69f1, 2-methylhydroquinone 0.249, acrylic acid 1459, and tetramethylammonium chloride. Prepare 2.4g, Synthesis Example 1-(2)
The same operation as above was carried out, and the reaction was terminated when the acid value reached 3.5. Cooled to about 60°C, 2-methylhydroquinone 0.19, trimethylolproban triacrylate 2
069 was added and diluted.

A light brown transparent liquid with a viscosity of Z5 to Z6 was obtained containing about 70 (fl) of the reaction product as a solid. This is converted into compound (b-
3). (3) Next, add the compound (
Charge a-3) 2509, compound (b-3) 2509, and 0.25 f1 of P-benzoquinone.

Thereafter, the same operation as in Synthesis Example 1-(3) was performed to obtain a light brown transparent liquid having a viscosity of Z6 to Z7 and containing about 61% of the ultraviolet polymerizable unsaturated compound (1). This is compound (1-4)
shall be. Synthesis Example 5 (1) Trimethylolproban triacrylate 1709, P-benzoquinone 0.
29. Perform the same operation except using tolylene diisocyanate 879 and triethylamine 0.359, and also use Lunatsuk O-A (manufactured by Kao Soap Co., Ltd., oleic acid) 709,
The same procedure was carried out except that 14f1 of acrylic acid and 0.7 g of triethylamine were used, and the end point of the reaction was determined when the amount of free isocyanate groups reached 7%.

This is designated as compound (a-4). (2) Next, compound (a-4) 2709 and compound (b-3) were added to the 11 Mitsuro flask.
) 2509 and P-benzoquinone 0.259.

After that, the same operation as in Synthesis Example 1-(3) was carried out, and about 61% of the light brown transparent ultraviolet polymerizable unsaturated compound (1) was obtained.
A liquid containing viscosity Z6 to Z7 was obtained. This is compound (1
−5). Synthesis Example 6 (1) Acetone 3659 and hexamethylene diisocyanate 1419 were charged into a 11-fourth flask equipped with a cooling tube, a thermometer, and a dropping load, and heated while stirring.
Bring to 45°C in about 30 minutes.

Pre-mixed flaxseed oil fatty acids 2 while maintaining this temperature
249, 2 g of triethylamine is added dropwise over a period of about 2 hours. Thereafter, stirring was continued for about 1 to 2 hours at the same temperature, and the reaction was terminated when the amount of free isocyanate reached 5.5%. This is designated as compound (a-5). (2) Synthesis example 1
- In reaction (2), replace 2-methylhydroquinone with P-benzoquinone and perform the same operation, add trimethylolprobane triacrylate and 2-methylhydroquinone, and take it out as it is without diluting to obtain a high viscosity liquid. Ta.

This is designated as compound (b-4). (3) Next, compound (a-5) 3409 and compound (b-4) were added to Mitsuro flask 11.
) 2009 and 0.29 of P-benzoquinone were added and thoroughly stirred and mixed.

After that, the same operation as in Synthesizer 1-(3) was carried out, and when the free isocyanate became 0.3% or less, the reaction was deemed to end, and trimethylolproban triacrylate 247
g, 0.2 g of P-benzoquinone was added and diluted. Next, the volatile content contained in this compound was removed under reduced pressure until it became 3% or less. Light brown transparent UV polymerizable unsaturated compound (1
) was obtained, containing approximately 60 (Fb) and a viscosity of Z6 to Z7. This is referred to as compound (1-6). Synthesis Example 7 (1) A 500-liter liquid containing a cooling pipe, a thermometer, and a dripping load was obtained.
2,2-bis(4-acryloxydiethoxyphenyl)proban [Shin-Nakamura Chemical Co., Ltd.] in a m1 four-piece flask
acrylic acid ester compound] 2329, P-benzoquinone, and 0.23 f1 were added and stirred.

Furthermore, tolylene diisocyanate (2,4 monoisomer 80
%, 20% 2,6 monoisomer) and 0.519% of triethylamine were added, heated with stirring, and heated to about 30%
Bring to 45°C in minutes. Lunatsk O-A (manufactured by Kao Soap Co., Ltd., oleic acid) 169 was mixed in advance while maintaining this temperature.
9. Add 1.01 liters of triethylamine dropwise over about 1.5 hours. Thereafter, the temperature was maintained at 50° C., stirring was continued for about 1 to 2 hours, and the reaction was terminated when the free isocyanate groups reached 5.5%. This is referred to as compound (a-6).
(2) In the reaction of Synthesis Example 2-(2), 0.18 g of 2-methylhydroquinone was used, and 2,2-bis(4-acryloxydiethoxyphenyl)proban 1819 was used instead of trimethylolprobane triacrylate. The same operation was performed except that a light brown transparent liquid having a viscosity of Z6 to Z7 and containing about 700 t of ultraviolet polymerizable unsaturated compound (2) was obtained.

This is designated as compound (b-5). (3) Next 500m1
Compound (a-6) 2509 and compound (
b-5) Add 180g and 0.29g of P-benzoquinone.

Thereafter, the same operation as in Synthesis Example 1-(3) was performed to obtain a light brown transparent liquid having a viscosity of Z6 to Z7 and containing about 61% of the ultraviolet polymerizable unsaturated compound (1). This is compound (1-7)
shall be. Example 1 The compounds obtained in Synthesis Examples 1 to 7, polymerizable vinyl monomers, extender pigments, resins, additives, etc., were thoroughly mixed and kneaded using a three-roll mill at 60°C or lower, and then exposed to ultraviolet light. A polymerization initiator was further mixed to prepare ultraviolet curable overprint varnishes 1 to 8.

In addition, Comparative Examples Buddha 1 to Rei 3 were prepared in the same manner. name of the compound,
The blending ratios are as shown in Table 1. Furthermore, using each UV-curable overprint varnish, apply conventional offset ink to art paper using an RI tester and 1Z roll, then immediately perform overprinting, and immediately apply irradiation from a height of 5 CTIL using Iwasaki Electric's U device. The curability and gloss were compared. The gloss value was measured by the 60 degree reflection method. Next, printing was performed using a PS plate under normal printing conditions using a conventional paperboard ink using an offset sheet-fed monochrome machine (manufactured by Color Metal Co., Ltd., model name: Baru), and then the above-mentioned overlay was printed in the same manner. The printing varnish was overprinted on top of the paperboard ink, and the printing suitability of each was compared. The results are shown in Table 2. Example 2 The compounds obtained in Synthesis Examples 1 to 7, polymerizable vinyl monomers, colorants, resins, additives, etc. were thoroughly mixed and kneaded using a three-roll mill at 60°C or lower, and then exposed to ultraviolet light. A polymerization initiator is further mixed to make ultraviolet curing ink paper for paperboard 9~▲
16 was created.

Claims (1)

[Claims] 1 Reaction product (a) of a polyisocyanate compound with a higher fatty acid having 8 or more carbon atoms or a mixture with an unsaturated basic acid, and a reaction product (a) of a higher fatty acid having 8 or more carbon atoms or a mixture with an unsaturated basic acid and a higher fatty acid having 8 or more carbon atoms Ultraviolet polymerizable unsaturated compound (I) obtained by reacting the mixture with the reaction product (b) of at least one epoxy compound (I) 5 to 20% by weight, unsaturated basic acid or higher fatty acid having 8 or more carbon atoms or 10 to 60% by weight of an ultraviolet polymerizable unsaturated compound (II) obtained by reacting a mixture thereof with at least one epoxy compound;
An ultraviolet curable composition comprising 5 to 50% by weight of a polymerizable vinyl monomer (III), 1 to 15% by weight of an ultraviolet polymerization initiator (IV), and other additives as necessary.