JP2882214B2 - Active energy ray-curable water-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable water-containing resin composition having water miscibility. More specifically, the present invention relates to an active energy ray-curable hydrous resin composition containing no surfactant and comprising a nonionic vehicle.

[0002]

2. Description of the Related Art Active energy ray-curable resin compositions are
In addition to being excellent in safety because it does not contain a solvent, it is generally recognized as having excellent characteristics in terms of productivity and energy saving because of its excellent curability. In view of such properties, active energy ray-curable resin compositions have been employed in various applications such as various plastic film overcoating agents, woodwork paints, and printing inks.

[0003] In recent years, however, there has been an increasing demand for water-based compositions from the viewpoints of air pollution prevention, regulations under the Fire Service Law, occupational safety and health, and the like. Various aqueous active energy ray-curable resin compositions have already been developed, but these contain surfactants in the composition, or have strong hydrophilic groups such as carboxyl, sulfone, and amino groups. Since a vehicle component having the following is introduced, the composition generally has a higher viscosity as compared with the non-aqueous active energy ray-curable resin composition, and is inferior in water resistance, curability, and storage stability of the composition when containing water ( However, there are disadvantages such as the phenomenon of separation of water and a vehicle), and at present, satisfactory characteristics have not always been achieved.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances regarding an aqueous active energy ray-curable resin composition,
To obtain a water-based active energy ray-curable resin composition having curability and water resistance comparable to that of a non-aqueous active energy ray-curable resin composition, and having relatively low viscosity and excellent storage stability. With the goal.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have focused on the water mixing ratio of the vehicle components in the composition, and have conducted intensive studies on the types of the components and their usage ratios. As a result, it was surprisingly found that by selecting a composition comprising the following specific vehicle component and a specific amount of water, an excellent water-based active energy ray-curable resin composition satisfying the above objects can be obtained. Obtained. The present invention has been completed based on such findings.

That is, the present invention provides an active energy ray-curable water-containing resin composition comprising a vehicle and water as essential components, wherein the vehicle component has (A) a water miscibility of 10 to 10.
A nonionic monomer and / or oligomer having at least one radically polymerizable unsaturated bond in a molecule of 50% by weight, 15 to 50% by weight, and (B) a water polymerization rate of 100% by weight or more. Nonionic monomers and / or oligomers having at least one possible unsaturated bond in the molecule: 15 to 50% by weight; and (C) a radically polymerizable unsaturated bond having a water miscibility of 5% by weight or less. A nonionic monomer and / or oligomer having at least one
40% by weight and the total of these components is 100% by weight, characterized in that the composition contains no surfactant and contains 5 to 20 parts by weight of water with respect to 100 parts by weight of the vehicle. The present invention relates to an active energy ray-curable water-containing resin composition.

[0007] The vehicle in the active energy ray-curable water-containing resin composition of the present invention comprises the components (A), (B) and (C) as described above. The component (A) is a nonionic monomer and / or nonionic oligomer having at least one radically polymerizable unsaturated bond in the molecule and having a water miscibility of 10 to 50% by weight. In addition,
In the present specification, “water mixing ratio” means each vehicle component 1
It refers to a value in which the number of parts by weight of water that can be mixed in a uniform transparent state per 100 parts by weight is expressed in percentage. The component (A) can be defined as having a water miscibility of 10 to 50% by weight based on the above definition, and has a hydroxyl group in the molecule and usually has a hydroxyl value of 220 to 320, preferably 250 to 280. Is applicable. Specific examples thereof include, for example, dipropylene glycol mono (meth) acrylate, glycerin diepoxy (meth) acrylate, glycerin triepoxy (meth) acrylate, 1,6-hexanediol diepoxy (meth) acrylate, and neopentyl glycol diepoxy. (Meth) acrylates and the like can be mentioned, and these can be used alone or in combination. The amount of the component (A) used is usually 15% based on the total amount of the vehicle in the composition.
-50% by weight, preferably 25-50% by weight. When the amount of the component (A) is out of the range, the composition having the performance of the present invention even if the amounts of the components (B) and (C) described below are appropriately adjusted. Cannot be prepared.

The component (B) is a nonionic monomer and / or nonionic oligomer having at least one radically polymerizable unsaturated bond in the molecule and having a water miscibility of 100% by weight or more. This component is an essential component for imparting a desired water miscibility to the obtained composition. The component (B), unlike the component (A), need not necessarily have a hydroxyl group in the molecule as long as the water miscibility is 100% by weight or more. Specific examples of the component (B) include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, morpholine acrylamide, hexaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and the like. These can be used alone or in combination. Component (B) is used in an amount of 15 to 50% by weight, preferably 20 to 50% by weight, based on the total amount of the vehicle in the composition. When the amount of the component (B) is less than 15% by weight, a stable water-containing composition cannot be obtained. On the other hand, when the amount exceeds 50% by weight, the composition has good shelf stability but has a cured film. In any case, a composition having the performance intended for the present invention cannot be prepared because of a decrease in water resistance.

The component (C) is a nonionic monomer and / or nonionic oligomer having at least one radically polymerizable unsaturated bond in the molecule and having a water miscibility of 5% by weight or less. The component is an essential component because it affects various physical properties such as the curability of the composition obtained and the adhesion of the cured film to the substrate. The component (C) does not necessarily have to have a hydroxyl group in the molecule, similarly to the component (B). Specific examples of the component (C) include, for example, polyurethane (meth) acrylate, epoxy (meth) acrylate, and ester (meth) acrylate, and these can be used alone or in combination.
Component (C) has a higher hydrophobicity than component (A) or component (B) and thus tends to decrease the stability of the resulting composition when it contains water. It is 15 to 40% by weight, preferably 20 to 30% by weight based on the total amount.

The active energy ray-curable water-containing resin composition of the present invention contains water in an amount of 5 to 20 parts by weight based on 100 parts by weight of the vehicle comprising the components (A), (B) and (C). It is mandatory to do so. By containing the above specific amount of water, the composition exhibits an effect of having a lower viscosity and excellent curability as compared with the non-water-containing resin composition. Therefore, when the water content of the composition is less than 5% by weight, the viscosity of the composition is not sufficiently reduced, and the effect of improving the curability cannot be obtained. On the other hand, when the water content of the composition exceeds 20% by weight, the vehicle content in the composition becomes considerably small, and the film thickness obtained by one coating operation is reduced, and the curability and the water-containing composition are reduced. The stability of the material tends to decrease.

The active energy ray-curable water-containing resin composition of the present invention contains, in addition to the essential components vehicle and water, a hydrophilic solvent such as a lower alcohol, a coloring agent, a photoinitiator, and the like, if necessary. Additives such as a leveling improver may be appropriately used within a range not departing from the purpose and effect of the present invention. However, a surfactant must not be contained in consideration of the water resistance of the cured film, in particular, the prevention of the film whitening phenomenon during immersion.

[0012] The optimum viscosity of the active energy ray-curable water-containing resin composition of the present invention cannot be uniquely determined because it varies depending on the application, but it is usually preferably about 50 to 500 cP.

The active energy ray-curable water-containing resin composition of the present invention obtained as described above has excellent curability and water resistance, and has relatively low viscosity and good stability over time. The known non-aqueous active energy ray-curable resin composition can be similarly applied to various uses in which it has been used, for example, various plastic film overcoating agents, woodwork paints, printing inks, and the like.

[0014]

According to the present invention, it has curability and water resistance comparable to those of non-aqueous active energy ray-curable resin compositions, and has relatively low viscosity and good stability over time. An aqueous active energy ray-curable resin composition printed material can be provided.

[0015]

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, "parts" and "%" are based on weight unless otherwise specified.

Example 1 35 parts of a mixture of glycerin diepoxy acrylate and triglycerin diepoxy acrylate as the component (A) was placed in a 200 ml flask equipped with a stirrer, a thermometer and a cooling tube, and protected from light, (B) 35 parts of hexaethylene glycol diacrylate as a component, 30 parts of rosin epoxy acrylate (manufactured by Arakawa Chemical Industries, Ltd., trade name “Beamset 101”) and a photoinitiator (Ciba Geigy, trade name “Irga” as a component (C)) Cure 184 ”), and then warm to 50-60 ° C. while stirring,
Stirring was continued for 30 minutes. After cooling to room temperature, distilled water 1
0 parts were added and stirred to obtain a homogeneous water-containing composition.

The composition has a viscosity under the following conditions:
The stability, curability, and water resistance of the cured film were measured and evaluated, respectively. (Viscosity) The viscosity was measured at 25 ° C. using an E-type viscometer (3 degree cone). (Stability) After the composition was prepared and left for one day, the appearance change of the varnish was visually observed and evaluated according to the following criteria. Evaluation criteria: ○ Uniformly transparent or translucent with almost no change × Vehicle layer and aqueous layer separated into two layers (curable) The composition was applied on a black glass plate so that the film thickness after curing became 10 μm, Then, after irradiating with ultraviolet rays under the following curing conditions, the degree of tackiness of the film was judged by touch with a finger according to the following criteria. Curing conditions: Ultraviolet lamp 80W / cm x 1 Belt speed 55m / min, Irradiation distance 10cm Irradiation intensity per irradiation 10mJ, Irradiation 1 to 4 times Evaluation criteria: ○ No tackiness △ Slight tackiness × Equivalent Strong tack (water resistance of cured film)
The composition was applied so as to have a thickness of 00 μm, and then irradiated with ultraviolet rays so that the irradiation intensity was about 500 mJ, and then the film was completely cured. The cured film was peeled off from the glass plate, and the film was immersed in distilled water for 24 hours at room temperature. Evaluation criteria: ○ No swelling, almost no decrease in film strength × Swelled considerably, and embrittlement of film observed

Examples 2 to 4 The same procedures as in Example 1 were carried out except that at least one of the types of components (A) to (C) and their use ratio was changed as shown in Table 1. Various uniform compositions were obtained in the same manner as in Example 1. These compositions were similarly evaluated for performance according to the evaluation method of Example 1. The results are shown in Table 1. The beam set 551B used in Example 4 is a bifunctional polyester polyurethane acrylate having a molecular weight of 900 manufactured by Arakawa Chemical Industries, Ltd.

Comparative Examples 1 to 5 In Example 1, at least one of the types of the components (A) to (C) or the proportion of the components used was
Various compositions were obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 1. These were similarly evaluated for performance according to the evaluation method of Example 1. The results are shown in Table 1. In Comparative Example 4, the measurement and evaluation on viscosity, curability and water resistance of the cured film were abandoned because the stability was poor.

[0020]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 2/00 C08F 2/46-2/56 C09D 4/00-4/06

Claims (1)

(57) [Claims] 1. An active energy ray-curable water-containing resin composition containing a vehicle and water as essential components, wherein the vehicle component is (A) a water-mixable ratio of 10 to 50% by weight, and a radical polymerizable unsaturated. Nonionic monomers and / or oligomers having at least one bond in the molecule 15 to 50% by weight, (B) at least one radically polymerizable unsaturated bond in the molecule having a water miscibility of 100% by weight or more. Nonionic monomer and / or oligomer having 15 to 50% by weight, and (C) nonionic monomer and / or having at least one radically polymerizable unsaturated bond in a molecule having a water miscibility of 5% by weight or less. Oligomer comprising from 15 to 40% by weight and the sum of these components being 100% by weight, wherein the composition contains a surfactant. An active energy ray-curable water-containing resin composition comprising 5 to 20 parts by weight of water with respect to 100 parts by weight of the vehicle.