JPH0479362B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to active energy ray-curable printing inks, paints, compositions for coating or adhesion with glossy varnishes, etc., and more specifically, printing inks containing specific oil and fat components and maleimide compounds as essential components,
The present invention relates to active energy ray-curable compositions that can be suitably used as paints, gloss varnishes, adhesives, etc. The present invention is a novel active energy ray-curable composition useful for printing inks, overprint varnishes, and various paints intended for printing or painting on substrate surfaces such as paper, plastic, metal, glass, ceramic, and wood. It is something that provides something. In recent years, in the fields of printing inks, paints, and adhesives, active energy ray curing systems such as electron beams and ultraviolet rays have been adopted for reasons such as resource saving, pollution resistance, and improved productivity due to rapid curing. It is well known that compositions have been proposed and have achieved some success. However, as exemplified in the following description, if we consider not only printing, paint suitability, quick curing properties, physical properties of the cured product, but also cost, there is still no composition that can satisfy all of these requirements. At present, the appearance of such printing inks, paints, etc. is awaited. As is well known, active energy ray-curable compositions used for this purpose generally contain a vehicle having an unsaturated group capable of causing a radical polymerization reaction or a crosslinking reaction by the energy rays as a main reaction component, and
Although a sensitizer, a colorant, and other additives are blended as necessary, the properties of this composition and the characteristics of the cured product largely depend on the vehicle in the composition. Various unsaturated compounds can be blended as the reactive vehicle, and it is well known that monomers or oligomers of mono- or polyhydric acrylates and methacrylates are often used. When more rapid curing is intended in the composition, a compound having a high concentration of reactive unsaturated groups, such as diethylene glycol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, etc., is incorporated into the vehicle component. However, although this method is very advantageous in that it ensures rapid curing, it has problems such as difficulties in controlling the viscosity, poor compatibility with pigments, and significant volumetric shrinkage during curing. In addition, the resulting cured product is hard and brittle. This not only tends to cause problems with fluidity related to printability and painting suitability, but also causes drawbacks such as poor gloss of the resulting cured printed surface and painted surface, adhesion to the substrate, and secondary processability such as bending. I will invite you. In order to overcome these drawbacks, attempts have been made to blend various resins, such as oils and fats such as animal and vegetable oils, and so-called oil-modified resins using these as starting materials in addition to the above-mentioned reactive monomers or oligomers as vehicles. be. However, in this case, although there are improvements in fluidity, adhesion, pigment compatibility, etc. and cost benefits, there is also a decrease in the curing speed, and the surface hardness and chemical resistance of the cured product are affected accordingly.
Solvent resistance etc. tend to decrease. This is thought to be due to the poor reactivity of the resin with the reactive monomer or oligomer. Even if the resin has an unsaturated group based on drying oil or semi-drying oil, the reactivity of the unsaturated group with energy rays is very poor. In addition, as another attempt, a reactive group capable of causing a polymerization reaction with active energy rays, such as an acryloyl group or a methacryloyl group, was added to the oil-modified resin to cause copolymerization with a reactive monomer or oligomer. There is a method of tightening, which can be somewhat effective in improving the above-mentioned disadvantages. However, the introduction of reactive groups into such oil-modified resins requires careful handling to eliminate the risk of gelation during the additive manufacturing process, and is not only expensive as a result; This reaction, for example, occurs via an epoxidation reaction, which causes problems such as extreme coloration and contamination of impurities due to the use of catalysts. Considering the above points, it is preferable to use a material that is highly reliable in terms of fluidity, affinity with pigments, etc., adhesion to various substrates, etc., and which has been generally used in conventional room-temperature or thermosetting types. Relatively inexpensive drying oils, semi-drying oils, polymerized oils or oil-modified resins derived from these oils can be used as they are without any additional treatment, and can be used for crosslinking reactions with active energy rays or with other reactive monomers or oligomers. It would be highly desirable if a method could be found to effect the copolymerization reaction. The present inventors focused on the fact that maleimide compounds have photosensitized polymerizability, and after conducting various studies, they discovered that maleimide compounds can be copolymerized with fatty acids having unsaturated groups, thereby completing the present invention. It is. That is, the present invention provides at least one compound selected from the group consisting of a drying oil, a semi-drying oil, a polymerized oil, an oil-modified resin having a drying oil fatty acid as a constituent, and an oil-modified resin having a semi-drying oil fatty acid as a constituent. This invention relates to an active energy ray-curable composition containing (A) and a maleimide compound (B) as essential components. Drying oil, semi-drying oil, polymerized oil used in the present invention,
At least one compound (A) selected from the group consisting of an oil-modified resin containing a drying oil fatty acid as a constituent and an oil-modified resin containing a semi-drying oil fatty acid as a constituent.
I will explain about it. Drying oils or semi-drying oils are vegetable oils that are air-dryable and generally have an iodine value of 100 or more, such as linseed oil, tung oil, safflower oil, castor oil,
Examples include dehydrated castor oil, soybean oil, tall oil, and rice sugar oil. Polymerized oil is, for example, what is called boiled oil, which is obtained by polymerizing drying oil or semi-drying oil by a well-known method such as heating. In addition, oil-modified resins containing drying oil fatty acids or semi-drying oil fatty acids are:
It is obtained by subjecting the fatty acid, polybasic acid, polyhydric alcohol, etc. to a dehydration condensation or transesterification reaction using a known method, or by subjecting the fatty acid to an ester reaction with an epoxy resin. Examples of polybasic acids used here include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, phthalic anhydride, tetrahydrophthalic anhydride, 2,6-endomethylene,
Examples include dicarboxylic acids such as tetrahydrophthalic anhydride, adipic acid, glutaric acid, sebacic acid, trimellitic acid, pyromellitic acid, polyethylene glycol or polypropylene glycol, and examples of polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, 1,3- There are butylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Epoxy resins include, for example, commercially available Epibis type epoxy resins, There are phenol novolac type epoxy resins, alicyclic type epoxy resins, etc., and these can be effectively used to produce desired oil-modified resins such as oil-modified alkyd resins and oil-modified epoxy ester resins, as well as oil varnishes and oil-modified phenolic resins. etc. can be obtained. The maleimide compound (B) used in the present invention includes all maleimides, their α-substituted derivatives, N-substituted derivatives, and polymaleimides, but especially N
- Divalent hydrocarbon groups such as alkyl or N-aryl substitutions or their halogen or functional group-substituted maleimides, monocyclic to polycyclic arylene groups, or divalent atomic groups such as methylene, ketones, sulfones, or amides. Polymaleimides such as bismaleimide and poly(phenylmethylene)polymaleimide bonded with a divalent bonding group comprising: The ratio of the maleimide compound (B) to the compound (A) to be used is not particularly limited, except that it is within the effective substantial ratio to the extent that it can be dissolved in the resulting composition.
The effective effective proportion is 0.1 part by weight of maleimide compound (B) per 100 parts by weight of compound (A). When blended in a proportion smaller than this, it is difficult to recognize any substantial crosslinking reaction. Furthermore, if the maleimide compound (B) is used in a composition in a range exceeding its solubility, the cured product obtained therefrom will be non-uniform, which is unfavorable in terms of surface gloss, adhesion, etc. The composition of the present invention contains the compound (A) and the maleimide compound (B) as essential components, and may be composed only of the compound (A) and the maleimide compound (B), or may contain only the compound (A) and the maleimide compound (B).
and maleimide compound (B), depending on the purpose of use, conventionally known stabilizers, photopolymerization initiators,
Reactive diluents, reactive oligomers, other resins, etc. can be blended, and various colorants, modifiers, solvents, etc., whether organic or inorganic, can also be blended. Examples of stabilizers include thermal polymerization inhibitors and anti-skinning agents during storage of the composition. Examples of the photopolymerization initiator include various known photopolymerization initiators such as benzoin type, penzophein type, halogenated sulfonyl type, quinone type, ketone type, azo type and peroxide type. As the reactive diluent, conventionally known all-vinyl monomers and polyfunctional monomers can be used, such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and various other acrylates. Examples include methacrylates. As the reactive oligomer, known monoacrylates or polyacrylates such as unsaturated polyester, polyester acrylate, epoxy acrylate, urethane acrylate, and polyether acrylate can be used. As other resins, any resin that can be dissolved in the composition can be used, such as known diene rubbers, acrylic polymers, saturated polyesters, petitral resins, polystyrene, and rosin resins. Examples of the coloring agent include known inorganic pigments such as titanium white, Benkara, and carbon black, organic pigments such as azo pigments, phthalocyanine pigments, and lake pigments, and dyes. Examples of the solvent include ketones, esters, aliphatic and aromatic hydrocarbons, cellosolves, and alcohols. Furthermore, additives such as waxes, driers, dispersants, wetting agents, thickeners, fluidity regulators, etc. can be added as required by methods well known to those skilled in the art. The total amount of compound (A) and maleimide compound (B) in the composition of the present invention is not particularly limited, but is preferably 10% by weight or more, more preferably
It is 30% by weight or more. If the amount is less than 10% by weight, it cannot be considered as a substantially effective amount. A composition comprising the compound (A) of the present invention and the maleimide compound (B) as essential components can be cured by irradiation with electron beams, ultraviolet rays, etc. by a known method. The irradiation time is determined to be an appropriate amount to ensure the effect. The energy dose to be irradiated is appropriately determined depending on the type and amount of each component in the composition, the properties of the substrate to which the composition is applied, the thickness of the applied coating layer, the atmospheric oxygen concentration, temperature, etc. Further, the composition can be semi-cured (setting) by energy ray irradiation and then cured at room temperature or by heating. The composition of the present invention has various adaptability by changing the composition depending on its use.
For example, if the composition does not contain a colorant or contains only a small amount of colorant, it is useful as an undercoat, overcoat, or overprint material for various substrates, and can be used to seal, smooth, and modify the surface properties of various substrates. It is useful for treatments such as quality and rust prevention, polishing surface finishing, and adhesives. In compositions containing colorants, they are useful as various printing inks and paints. Applicable substrates are not particularly limited as long as they can be printed, painted, and pasted, and include paper, plastic, metal, and inorganic materials. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. In the examples, unless otherwise specified, all parts are by weight, and all percentages are by weight. Production Example 1 656 parts of linseed oil, 131 parts of pentaerythritol and 0.2 parts of lithium hydroxide were mixed in a stirrer, a cooler,
Pour into a 4-necked flask equipped with a thermometer and nitrogen blowing tube, and heat to 250 ml while stirring under nitrogen gas atmosphere.
The temperature was raised to ℃ and the transesterification reaction was carried out for 1 hour. Next, it was cooled to 180°C, 249 parts of phthalic anhydride was added, and then the temperature was gradually raised to 230°C and maintained at that temperature to carry out an esterification reaction for 5 hours, resulting in an acid value of 8.0,
Gardner clay Z8 alkyd resin (1) was obtained. Production example 2 1117 parts of Epon 1004 (Epivis type epoxy resin manufactured by Ciel Chemical Co.) and 744 parts of dehydrated castor oil fatty acid
of the mixture was placed in a four-necked flask similar to that used in Production Example 1, and heating the mixture to 140°C under a nitrogen gas atmosphere until it became a fluid.
After raising the temperature to 24℃ and maintaining this temperature for 5 hours until the acid value reached 4.0, it was cooled to 140℃ and xylene
1218 parts were added to obtain an epoxy ester resin solution (2) having a Gardner viscosity of Z ₁ . Production example 3 Soybean oil fatty acid 1016 parts, ethylene glycol 228 parts
parts, 408 parts of pentaerythritol, phthalic anhydride
924 parts of maleic anhydride and 4 parts of maleic anhydride were placed in a 4-necked flask, and the temperature was gradually raised to 180°C while stirring under a nitrogen gas atmosphere. After maintaining this temperature for 1 hour, the temperature was further raised to 220°C to determine the acid value. This temperature was maintained for 7 hours until the temperature reached 8. The mixture was then cooled to 140° C. and 1720 parts of xylene was added to obtain an alkyd resin solution (3) having a Gardner viscosity of L ₁ to V. Examples 1 to 6 and Comparative Examples 1 to 2 Each of the oil-modified resins, oils and fats, maleimide compounds, and photopolymerization initiators obtained in Production Examples 1 to 3 was
UV-curable overprint varnish compositions (1) to (6) of the present invention were prepared by mixing in the proportions shown in the table. For comparison, comparative ultraviolet curable overprint varnish compositions (1) and (2) without using a maleimide compound were prepared as shown in Table 1. Each of the obtained UV-curable overprint varnish compositions was applied to a tin plate to a film thickness of 5 μm, placed 10 cm under a 120 W/cm high-pressure mercury lamp on a conveyor at a speed of 30 m/min, and irradiated and dried. I let it happen. The performance evaluation results of the obtained coating films are shown in Table 2. Cured films with excellent curability, adhesion, and flexibility were obtained from the UV-curable overprint varnish compositions (1) to (6) of the present invention. Examples 7 to 9 and Comparative Examples 3 to 4 Ultraviolet curable overprint varnish compositions (1) to (3) of the present invention obtained in Examples 1 to 3 and comparative ultraviolet rays obtained in Comparative Examples 1 to 2 The curable overprint varnish compositions (1) to (2) were applied to commercially available art paper, coated paper, offset printing paper, and aluminum evaporated polyester film to a film thickness of 3 μm, respectively, and the compositions were prepared as described in Example 1. One pass of ultraviolet light was irradiated using the same method. The performance evaluation results of the obtained coating films are shown in Table 3. The cured films obtained from the varnish compositions (1) to (3) of the present invention had excellent adhesion and hardness. Examples 10 to 12 and Comparative Examples 5 to 6 The oil-modified resins, maleimide compounds, and phthalocyanine blue obtained in Production Examples 1 to 2 were kneaded using three rolls in the proportions shown in Table 4, and further kneaded with light. UV-curable blue ink compositions (10) to (12) of the present invention were prepared by mixing a polymerization initiator. or,
For comparison, a comparative ultraviolet curable blue ink composition that does not use a maleimide compound as shown in Table 4
(5)-(6) were prepared. Each of the obtained ink compositions was applied to commercially available coated paper to a film thickness of 3 μm, and irradiated with ultraviolet rays for one pass in the same manner as described in Example 1. Ink compositions (10) to (12) of the present invention
A cured film with extremely excellent adhesion was obtained from Comparative Ink Compositions (5) to (6), whereas no cured film was obtained from Comparative Ink Compositions (5) to (6). Examples 13 to 15 Each oil-modified resin, maleimide compound, and titanium dioxide obtained in Production Examples 1 to 3 were kneaded using three rolls in the proportions shown in Table 5, and the electron beam curable white color of the present invention was prepared. Ink compositions (13) to (15) were prepared. Each of the obtained ink compositions was applied to an aluminum plate to a film thickness of 50 μm, and irradiated at 10 Mrad using a curtain beam type electron beam irradiation device. The obtained cured film had excellent adhesion and hardness.

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Claims (1)

[Claims] 1 At least one compound (A) selected from the group consisting of drying oils, semi-drying oils, polymerized oils, oil-modified resins containing drying oil fatty acids, and oil-modified resins containing semi-drying oil fatty acids as constituents; An active energy ray-curable composition containing a maleimide compound (B) as an essential component.