JP3099444B2 - Active energy ray-curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an active energy ray-curable resin composition. More specifically, the present invention relates to an active energy ray-curable resin composition which is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam and is particularly useful as a vehicle for an offset ink.

[0002]

2. Description of the Related Art Conventionally, active energy ray-curable resin compositions containing a resin and a reactive diluent as main components have been used in various fields such as printing inks, paints and adhesives. Particularly in offset inks, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like are widely used as such reactive diluents because of their excellent curability and coating film hardness. On the other hand, various resins have been proposed as resins, but few resins having good compatibility with the reactive diluent and excellent suitability for offset printing are known.

[0003] As a resin having good compatibility with the reactive diluent, diallyl phthalate resin can be cited, and is used exclusively as an active energy ray-curable ink binder. However, the diallyl phthalate resin has poor emulsification resistance and adhesion to various substrates, and its curing property is not sufficient. In addition, since diallyl phthalate resin does not have a functional group suitable for aluminum chelation, aluminum chelation cannot be performed, and it is difficult to impart the viscoelasticity required for offset ink, and printability is not always sufficient. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which can be a new vehicle replacing diallyl phthalate resin. That is, the present invention shows good compatibility with reactive diluents commonly used in active energy ray-curable offset inks such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, and has excellent curability and emulsification resistance. In addition, an object of the present invention is to provide a novel resin composition capable of imparting the viscoelasticity required for offset inks and an active energy ray-curable resin composition containing the resin composition.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a novel resin composition in which bisphenol type epoxy resin is modified with stabilized rosin and a specific functional group. The inventor has found that an object can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention provides a compound represented by the following general formula (1):

[0007]

Embedded image

A stabilized rosin or a stabilized rosin is reacted with at least one monobasic acid, and then a diketene or diketene is reacted with at least one monobasic acid. And an active energy ray-curable resin composition containing the resin composition, a reactive diluent and, if necessary, a photoinitiator.

In the present invention, first, a stabilized rosin is reacted with a bisphenol-type epoxy resin to produce a stabilized rosin-modified epoxy resin having an epoxy group opened.

Here, as the bisphenol type epoxy resin, various known ones can be used, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol A type brominated epoxy resin. The number of skeleton units of bisphenol is 1 to 6, preferably 2 to 5. If the number of skeletal units in the epoxy resin exceeds 6, the viscosity increases and it is difficult to form an ink, which is not preferable.

Examples of the stabilized rosin include a disproportionated rosin, a hydrogenated rosin, and a so-called colorless rosin obtained by optionally passing a natural rosin through a disproportionation step, a hydrogenation step, and a purification step. Here, the stabilized rosin is used for improving the printing characteristics and the like of the obtained resin composition (Formula 1).

The amount of the stabilized rosin used for the epoxy resin is based on 1 equivalent of the epoxy group of the epoxy resin.
Usually about 0.3 to 1.2 mol, preferably 0.5 to 0.1 mol.
9 moles. If it is less than 0.3 mol, the printability is not sufficient, and if it is more than 1.2 mol, unreacted rosin remains in a large amount, which is not preferable. At the time of the reaction, a monobasic acid described later may be used in combination with the stabilizing rosin or charged sequentially, but the use amount is 0.7 to 1 equivalent of the epoxy group of the epoxy resin. It is preferable that the content be about mol or less.

The method of the above reaction is not particularly limited, and may be, for example, a method in which an epoxy resin and a stabilized rosin are simultaneously charged. The reaction temperature is usually about 180 to 240 ° C., and the reaction time is usually about 8 to 18 hours. The reaction is performed so that the esterification reaction rate is sufficient. Insufficient reaction is not preferred because the presence of unreacted rosin causes a problem that the resin composition has poor emulsification resistance.

[0014] In the present invention, the epoxy resin modified with the stabilized rosin is then reacted with diketene or diketene and at least one monobasic acid. Here, diketene is used to introduce an acetoacetyl group into the resin composition by reacting with the hydroxy group of the modified epoxy resin, and to improve the compatibility with the reactive diluent of the resin composition. It is intended to improve the performance and seal off the hydroxyl groups which have an adverse effect on the emulsification resistance.

R ² in Chemical Formula 1 in the obtained resin composition
The ratio (molar ratio) of the acetoacetyl group to the monobasic acid residue introduced into the polymer is usually about 65 to 100: 35 to 0, preferably 70 to 100: 30 to 0. If the ratio of the acetoacetyl group is less than 65, the compatibility with the reactive diluent becomes poor, which is not preferable.

When diketen alone is used to introduce such an acetoacetyl group into the resin composition, the amount of the diketene is usually 0.8 to 1.2 with respect to 1 equivalent of the hydroxy group of the modified epoxy resin. About equivalent, preferably 1.
The equivalent is preferably 0 to 1.1 equivalents.

When diketene and at least one monobasic acid are used, the order of charging is not particularly limited, and they may be charged at the same time, but they may be charged at the same time. It is preferable to use a method of charging and reacting diketene. Specifically, first, 0.35 equivalent to 1 equivalent of the hydroxy group of the modified epoxy resin is usually used.
After reacting about 1 equivalent or less, preferably 0.30 equivalent or less of the monobasic acid, usually about 0.8 to 1.2 equivalents, preferably 1.
It is preferable to react 0 to 1.1 equivalents of diketene.

The monobasic acid may be a saturated or unsaturated aliphatic carboxylic acid having 1 to 18 carbon atoms, 6 to 11 carbon atoms.
At least one of a saturated or unsaturated alicyclic carboxylic acid and an aromatic carboxylic acid. Specifically, acetic acid, propionic acid, butyric acid, octylic acid, lauric acid, stearic acid, benzoic acid, t-butyl benzoic acid,
Examples include hexahydrobenzoic acid, phenylacetic acid, oleic acid, and palmitic acid.

In the above reaction, the conditions for the esterification reaction of the monobasic acid may be the same as those for the esterification of the epoxy resin and the stabilized rosin, and may be carried out following the esterification reaction with the rosin. The temperature at which diketene is reacted is usually about 40 to 80 ° C., and the reaction time is usually 1 to 30 ° C.
It is preferable to set it to about 3 hours.

Since the esterification reaction is a high-temperature reaction in any case, it is preferable to carry out the reaction under an atmosphere of an inert gas such as nitrogen. The use of a coloring inhibitor, an antioxidant, etc., the use of a catalyst in each reaction step, etc. are all optional. It is also optional to carry out the reaction in an inert solvent such as toluene or xylene.

When the thus obtained resin composition of the present invention is used as an active energy ray-curable resin composition, it is usually used in an amount of about 5 to 60 parts by weight, preferably 10 to 40 parts by weight. , Reactive diluent 95-4
It is good to use it at a ratio of about 0 parts by weight, preferably 90 to 60 parts by weight. When a photoinitiator is used, it is used in an amount of about 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total of the resin composition and the reactive diluent.

Examples of the reactive diluent include pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, bisphenol A tetraethoxydiacrylate and the like. Examples of the photoinitiator include benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid methyl ester, p-dimethylacetophenone, thioxanthone, and alkylthioxanthone. Specific examples of commercially available products include Darocure 1173.
(Merck), Irgacure 651, Irgacure 184, Irgacure 907 (Ciba Geigy)
And the like.

If necessary, a polymerization inhibitor, a pigment,
Depending on the purpose, various known additives such as coloring agents and fillers,
It can be appropriately selected and used.

[0024]

According to the present invention, the compound has good compatibility with widely used reactive diluents such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, and has excellent curability and emulsification resistance. In addition, it is possible to provide a novel resin composition and an active energy ray-curable resin composition that can impart the viscoelasticity required for the offset ink. These resin compositions are printing inks,
It can be applied to various uses such as metal inks, paints and adhesives.

[0025]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, in each example, parts and% are based on weight.

Example 1 A 1-liter flask equipped with a stirrer, a thermometer, a cooler equipped with a water separator and a nitrogen inlet tube was purged with nitrogen gas, and then a bisphenol A type epoxy resin (trade name: Epototo YD- 011, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 45
(0 to 500) 300 parts (0.33 mol), disproportionated rosin 188.6 parts (0.53 mol), and xylene 30 parts were charged and gradually heated under a nitrogen stream. Raw material is dissolved 150
When the temperature reached ° C, a dropping funnel was provided, and 1.8 parts of a 5.8% aqueous sodium hydrogen carbonate solution was slowly dropped. After completion of the dropwise addition, the mixture was heated again and refluxed at 230 to 235 ° C. for 1 hour, and then 23.8 parts (0.13 mol) of t-butylbenzoic acid was charged and continuously refluxed for 6 hours. The reaction was terminated at a point where the amount of generated water reached the theoretical value and the acid value became 3 or less, and the mixture was cooled to 130 ° C. or less, and 260 parts of toluene was gradually added and dissolved. After cooling the solution below room temperature,
Remove the water separator and N, N-dimethylbenzylamine 3.2
Of diketene 12 from the dropping funnel with stirring.
3.4 parts (1.47 mol) were added dropwise over 15 minutes.
At this time, the temperature of the reaction solution did not exceed 50 ° C. because heat was generated. After completion of the dropwise addition, 1 hour at 50 ° C. and 1 hour at 80 ° C.
Incubated for hours. The organic solvent was distilled off by performing a reduced pressure operation while continuously heating to obtain 567.8 parts of a brown hard resin (A).

Example 2 In the same manner as in Example 1, except that 47.6 parts (0.27 mol) of t-butylbenzoic acid and 111.0 parts (1.32 mol) of diketene were used. As a result, 586.0 parts of a brown resin (B) was obtained.

Example 3 The procedure of Example 1 was repeated, except that 83.2 parts (0.47 mol) of t-butylbenzoic acid and 92.6 parts (1.10 mol) of diketene were used. This gave 589.6 parts of a brown resin (C).

Example 4 In Example 1, a bisphenol A type epoxy resin (trade name: Epototo YD-011, manufactured by Toto Kasei Co., Ltd.)
300 parts (0.33 mol) of an epoxy equivalent of 450 to 500 were mixed with a bisphenol A type epoxy resin (trade name: Epototo YD-014, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 9).
(00 to 1000) 420 parts (0.26 mol), 147.3 parts (0.42 mol) of disproportionated rosin, 2.5 parts of a 5.8% aqueous sodium hydrogencarbonate solution, t-butylbenzoic acid 37.1 parts (0.21 mol) of acid and 36 parts of toluene
A brown resin (D) was prepared in the same manner as in Example 1 except that 0 parts, 3.7 parts of N, N-dimethylbenzylamine and 134.7 parts (1.60 mol) of diketene were used. 66
5.2 parts were obtained.

Comparative Example 1 The procedure of Example 1 was repeated, except that t-butylbenzoic acid was replaced with 190.1 parts (1.07 mol) and diketene was not used. (E) 619.
Six parts were obtained.

Example 5 A 500 ml flask equipped with a stirrer, thermometer and cooler was charged with 60 parts of resin (A) and pentaerythritol tetraacrylate (trade name: Beam Set 710, manufactured by Arakawa Chemical Industries, Ltd. "Bs-710") 14
0 parts and 0.2 part of methquinone as a polymerization inhibitor were charged, dissolved by stirring at 100 ° C., and then cooled to room temperature. Next, 4 parts of ethyl acetate aluminum diisopropylate (trade name ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was added to this solution with bisphenol A tetraethylene glycol diacrylate (trade name Beam Set 7).
50, manufactured by Arakawa Chemical Industries, Ltd .; hereinafter, referred to as "Bs-750"). A diluent diluted with 20 parts was slowly added, and the mixture was further kept at 80 ° C for 1 hour to obtain a gel varnish. 80 parts of this gel varnish and a pigment (trade name Rio Noble K-LH,
20 parts of Toyo Ink Mfg. Co., Ltd., a photopolymerization initiator (trade name: Irgacure 651, manufactured by Nippon Ciba Geigy Co., Ltd.)
Then, 8 parts of Irg651) and 2 parts of N-methyldiethanolamine (hereinafter, referred to as MDA) were roll-kneaded to obtain a UV ink (1).

Examples 6 to 8 In Example 5, resin (B) was used instead of resin (A).
Except that (C) or (D) was used,
V inks (2), (3) and (4) were obtained.

Comparative Example 2 60 parts of diallyl phthalate resin (trade name: Isodap, manufactured by Daiso Co., Ltd.), 140 parts of "Bs-710", "Bs
-750 "and 20 parts of methoquinone were weighed into a beaker and dissolved by stirring at 110 ° C. This varnish 8
0 parts, 20 parts of pigment, 8 parts of “Irg651”, and 2 parts of MDA were roll-kneaded to obtain a UV ink (5).

(Various Performance Test Methods) Performance tests were performed on the resins and UV inks obtained in the above Examples and Comparative Examples using the following methods. The results are shown in Tables 1 and 2.

1. Curing speed (varnish) Forty parts of each of the resins (A) to (E) and the diallyl phthalate resin used in Comparative Example 2 were converted to 60 parts of trimethylolpropane triacrylate (trade name: Biscoat 295, manufactured by Osaka Organic Chemical Co., Ltd.). Dissolve, Darocur 1173
(Merck Japan K.K.) 3 parts were added to form a varnish. The varnish was applied using an applicator of 1.5 MILs, one 80 W / cm high pressure mercury lamp, irradiation distance 10
Irradiation was performed under the condition of cm, and the irradiation dose (mj) was measured until the cured film was rubbed with the toe and no damage was caused inside. The evaluation results are shown in Table 1.

2. Solubility Resins (A) to (E) and 50 parts of the diallyl phthalate resin used in Comparative Example 2 were each dissolved in 50 parts of "Bs-710", and the varnish transparency at room temperature was visually determined.
The evaluation results are shown in Table 1.

3. Emulsification Resistance (Water Separability) 2.5 g parts of each of the resins (A) to (E) and the diallyl phthalate resin used in Comparative Example 2 were dissolved in 7.5 parts of xylene. Glass test tube (inner diameter 18mm x height 180mm
X 1.2mm thick) (PYREX TEST1)
8, Iwashiro Glass Co., Ltd.), 7.5 parts of distilled water, 7.5 parts of a xylene solution, and stoppered. This was shaken up and down 20 times to emulsify it, and then allowed to stand to measure the time until the aqueous phase and the organic phase were completely separated. Table 1 shows the evaluation results.
Shown in

4. Viscosity (ink) The viscosity was measured for the UV inks obtained in Examples 5 to 8 and Comparative Example 2. Table 2 shows the evaluation results.

5. Fluidity (spreading) For the UV inks obtained in Examples 5 to 8 and Comparative Example 2,
The spread radius of the ink one minute after falling from the glass plate was measured using a spread meter. Table 2 shows the evaluation results.

6. Curing speed (ink) RI tester (Akira Seisakusho Co., Ltd., roll width 115)
mm), the UV inks obtained in Examples 5 to 8 and Comparative Example 2 were printed on carton paper under the condition of 0.25 parts of ink coverage. One 80W / cm high-pressure mercury lamp, irradiation distance 10c
Irradiation was performed under the conditions of m, and the irradiation dose (mj) was measured until the cured film was rubbed with the toe and no damage was caused inside. Table 2 shows the evaluation results.

[0041]

[Table 1] In the table, DAP resin represents diallyl phthalate resin.

[0042]

[Table 2]

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Claims (3)

(57) [Claims] 1. General formula (1): A resin composition represented by 2. A resin composition obtained by reacting a bisphenol-type epoxy resin with stabilized rosin or stabilized rosin and at least one monobasic acid, and then reacting diketene or diketene with at least one monobasic acid. 3. An active energy ray-curable resin composition comprising the resin composition according to claim 1 or 2, a reactive diluent and, if necessary, a photoinitiator.