JPH0217566B2 - - 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 of 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, 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, low pollution, 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 properties of its 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
This results in disadvantages such as poor gloss of the resulting cured printed surface or painted surface, poor adhesion to the substrate, and poor secondary processability such as bending. 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 advantages, in addition to a decrease in curing speed, there are often problems with the surface hardness and chemical resistance of the cured product.
Solvent resistance etc. tend to decrease. This is considered to be because the oil-modified resin has poor reactivity 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. It would be highly desirable if a method could be found that would allow a relatively inexpensive oil-modified resin to be used as it is without any additional treatment and subjected to a crosslinking reaction using active energy rays or a copolymerization reaction with other reactive monomers or oligomers. It is. 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 relates to an active energy ray-curable composition comprising as essential components an oil-modified resin (A) consisting of a urethanized oil and/or a urethanized alkyd resin and a maleimide compound (B). The urethanized oil or urethanized alkyd resin used in the present invention is an air-drying or semi-drying resin selected from the group consisting of drying oil, semi-drying oil, polymerized oil, drying oil fatty acid and semi-drying oil fatty acid. In addition to the oil and fat components and polyhydric alcohols or epoxy resins, or in addition to the oil and fat components and polyhydric alcohols or epoxy resins, further polybasic acids,
After performing a known transesterification reaction or dehydration condensation reaction,
It is obtained by reacting residual hydroxyl groups in the reaction product with polyisocyanate. In the above reaction, when polybasic acids are not used, it is called urethanized oil, and when polybasic acids are used, it is called urethanized alkyd resin. In addition, when reacting the residual hydroxyl group with the polyisocyanate, it is free to use known catalysts for promoting the urethanization reaction, such as organic tin compounds such as di-n-butyltin dilaurate, tertiary amines, etc. It is. The drying oil or semi-drying oil used here is a vegetable oil that is air-drying and generally has an iodine value of 100 or more, such as linseed oil, tung oil, safflower oil, castor oil, dehydrated castor oil, soybean oil, tall oil, There are rice bran oil, etc. 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. Furthermore, drying oil fatty acids or semi-drying oil fatty acids are fatty acid components that constitute drying oils or semi-drying oils. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, glycerin,
Examples of epoxy resins include 1,3-butylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol. Type epoxy resins, phenol novolak type epoxy resins, alicyclic type epoxy resins, etc. Examples of polybasic acids used in obtaining the urethanized alkyd resin include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, phthalic anhydride, tetrahydrophthalic anhydride, and 2,6-endomethylene tetrahydrophthalic anhydride. , adipic acid, glutaric acid, sebacic acid, trimellitic acid, pyromellitic acid, and dicarboxylic acids such as polyethylene glycol or polypropylene glycol. Furthermore, as polyisocyanate, at least 2
There are no particular restrictions on the compound as long as it has isocyanate groups, such as ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,10-decamethylene Diisocyanate, octadecamethylene diisocyanate, lysine diisocyanate, o-, m-
or p-phenylene diisocyanate, 4-
Isopropyl-1,3-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, m- or p-tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 2,4-diisocyanate diphenyl ether, 3,3'-dimethyl -4,
4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, triphenylmethane triisocyanate, tris-(p-isocyanatophenyl) thiophosphite, polymethylene polyphenylisocyanate (novolac type) polyisocyanate), 1,4
-Cyclohexylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, diphenylsulfone diisocyanate,
Examples include isocyanate polymers such as 1,6-hexamethylene diisocyanate dimer and 2,4-tolylene diisocyanate dimer, and crude products of tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate. The maleimide compound (B) used in the present invention includes maleimide, its α-substituted derivatives, N-substituted derivatives, and all polymaleimides, but in particular N-alkyl or N-aryl substitutions or their halogen or functional Bonded with a divalent hydrocarbon group such as a maleimide substituted with a maleimide group or a monocyclic or polycyclic arylene group, or a divalent bonding group containing a divalent atomic group such as methylene, ketone, sulfone, or amide. Examples include polymaleimides such as bismaleimides and poly(phenylmethylene) polymaleimide. The ratio of the maleimide compound (B) to the oil-modified resin (A) is not particularly limited, except that it falls 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 the maleimide compound (B) per 100 parts by weight of the oil-modified resin (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 has an oil-modified resin (A) and a maleimide compound (B) as essential components, and is composed only of the oil-modified resin (A) and the maleimide compound (B), or is composed of only the oil-modified resin (A) and the maleimide compound (B). Conventionally known stabilizers, photopolymerization initiators, reactive diluents, reactive oligomers, and other resins can be added to both components of the maleimide compound (B), depending on the purpose of use. Various colorants, modifiers, solvents, etc., regardless of whether they are inorganic or inorganic, can 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, penzophenone type, halogenated sulfonyl type, quinone type, ketone type, azo type and peroxide type. As the reactive diluent, all conventionally known 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. and allyl compounds such as methacrylates, diallyl phthalate, and triallyl isocyanurate. As the reactive oligomer, known monoacrylates or polyacrylates such as unsaturated polyester, polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, diallyl phthalate prepolymers, etc. can be used. Examples of other resins include known diene rubbers, acrylic polymers, saturated polyesters, butyral resins, polystyrene, rosin resins, oil-modified alkyd resins, oil-modified epoxy ester resins, oil-modified phenol resins, etc. You can use everything you get. Examples of the coloring agent include known inorganic pigments such as titanium white, red iron oxide, 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, if necessary, please ask a person skilled in the art to add additives such as drying oils, semi-drying oils, polymerized oils, waxes, driers, dispersants, wetting agents, thickeners, fluidity regulators, etc. can be blended by a well-known method. The total amount of the oil-modified resin (A) and maleimide compound (B) in the composition of the present invention is not particularly limited, but is at least 10% by weight, more preferably at least 30% by weight. . If the amount is less than 10% by weight, it cannot be considered as a substantially effective amount. The composition comprising the oil-modified resin (A) and the maleimide compound (B) of the present invention 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 anti-corrosion, as well as for surface finishing and adhesives. Colorant-containing compositions are useful for various printing inks and paints. There are no particular restrictions on the substrate that can be applied, as long as it can be printed, painted, and pasted, but paper,
These include plastics, metals, 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 1 440 parts of dehydrated castor oil, trimethylolpropane
68 parts and 0.2 parts of lithium hydroxide were placed in a 4-necked flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen suction tube, and the temperature was raised to 250°C with stirring under a nitrogen gas atmosphere, followed by transesterification for 30 minutes. The reaction was carried out. Next, it was cooled to 50°C, 98 parts of tolylene diisocyanate was added, the temperature was gradually raised to 90°C, and the temperature was maintained for 1 hour, and then dilauric acid di-n
-0.2 part of butyltin was added and the reaction was carried out at 90°C for 4 hours to obtain urethanized oil (1) with a Gardner viscosity of _Z8 . Production Example 2 189 parts of soybean oil, 100 parts of dehydrated castor oil, 53 parts of pentaerythritol and 0.1 part of lithium hydroxide,
The mixture was charged into a four-necked flask similar to that used in Production Example 1, and the temperature was raised to 250° C. with stirring under a nitrogen gas atmosphere, and the transesterification reaction was carried out for 1 hour. The mixture was then cooled to 180°C, 60 parts of phthalic anhydride was added, and the temperature was gradually raised to 220°C and maintained at that temperature to carry out an esterification reaction for 4 hours. Then 50℃
503 parts of toluene, 18 parts of propylene glycol, and 90 parts of tolylene diisocyanate were added, and the temperature was gradually raised to 100°C and reacted for 3 hours to form a urethanized alkyd with a nonvolatile content of 50%, an acid value of 5.0, and a Gardner viscosity of Z. A resin solution (2) was obtained. Examples 1 to 4 and Comparative Examples 1 to 2 The oil-modified resins, maleimide compounds, and photopolymerization initiators obtained in Production Examples 1 to 2 were mixed in the proportions shown in Table 1, and the Ultraviolet curable overprint varnish compositions (1) to (4) were prepared. 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 20 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 (4) of the present invention. Examples 5 to 6 and Comparative Examples 3 to 4 Ultraviolet curable overprint varnish compositions (1) to (2) of the present invention obtained in Examples 1 to 2 and comparative ultraviolet rays obtained in Comparative Examples 1 to 2 The curable overprint varnish compositions (1) and (2) were applied to commercially available art paper, coated paper, offset printing paper, and aluminum vapor-deposited polyester film to a film thickness of 3 μm, respectively, 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) and (2) of the present invention had excellent adhesion and hardness. Examples 7 to 9 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 then kneaded with light. UV-curable blue ink compositions (7) to (9) of the present invention were prepared by mixing a polymerization initiator. For comparison, comparative ultraviolet curable blue ink compositions (5) to (6) without using a maleimide compound were prepared as shown in Table 4. 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 composition of the present invention (7)
Although cured films with excellent adhesion and hardness were obtained from the ink compositions (5) to (9), no cured films were obtained from the comparative ink compositions (5) to (6). Examples 10 to 12 The oil-modified resins, maleimide compounds, and titanium dioxide obtained in Production Examples 1 to 2 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 (10) to (12) 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 Oil modified resin (A) consisting of urethanized oil and/or urethanized alkyd resin and maleimide compound (B)
An active energy ray-curable composition comprising as essential ingredients.