JPS6264813A - Actinic energy ray-curable composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in flow, affinity for pigments, etc., adhesion to substrates, etc., and useful for inexpensive printing inks, overprint varnishes and paints, by using an oil-modified resin and a maleimide compound as essential components. CONSTITUTION:The titled composition essentially consisting of an oil-modified resin (A) comprising urethanized oil and/or urethanized alkyd resin (one obtained by transesterifying and dehydratively condensing an oil component such as a drying or semidrying oil with a polyalcohol or an epoxy resin and reacting the remaining OH groups in the reaction product with a polyisocyanate) and a maleimide compound (B). This composition is excellent in flow, affinity for pigments, etc., and adhesion to substrates such as paper, plastic, metal, glass, ceramic and wood, can be obtained by using a relatively inexpensive oil-modified resin as such, can be crosslinked by irradiation with actinic energy rays, or can be copolymerized with other reactive monomers or oligomers and can be suitably used for printing inks, overprint varnishes and paints.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition intended for coating or adhesion of active energy ray-curable printing inks, paints, gloss varnishes, etc., and more specifically, the present invention relates to a composition containing a specific oil component and a maleimide compound as essential components. The present invention relates to active energy ray-curable compositions that can be suitably used as printing inks, paints, acid varnishes, adhesives, and the like.

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, plastics, metals, glass, ceramics, 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, printing,
Considering not only paint suitability, quick curing properties, and physical properties of the cured product, but also cost, there is still no composition that can satisfy all of these requirements, and the emergence of such printing inks and paints is a major challenge. The current situation is that

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 optionally contain Although it contains a sensitizer, a colorant, and other additives, the properties of this composition and the properties of its cured product largely depend on the vehicle in the composition. Various unsaturated compounds are blended as the reactive vehicle, and it is well known that mono- or polyhydric acrylates and methacrylates or oligomers 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 also has problems with viscosity control, 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, in addition to the above-mentioned reactive hexamers or oligomers, various resins, such as fats and oils such as animal and vegetable oils, and so-called oil-modified resins using these as starting materials are blended as a vehicle. There is an attempt. However, in this case, although there are improvements in fluidity, adhesion, pigment compatibility, etc. and cost benefits, there is also a decrease in the speed of processing, and there are often problems with the surface hardness of the cured product, chemical resistance, and solvent resistance. There is a tendency for sexual performance to decrease. This is considered to be because the oil-modified resin has poor reactivity with the reactive hetamine 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, is added to the oil-modified resin, thereby copolymerizing it with a reactive heptamer or oligomer. There is a method of causing this to occur, and this method can have some effect in improving the above-mentioned disadvantages. however,
Introducing reactive groups into such oil-modified resins is
The additive manufacturing process requires careful handling to eliminate the risk of gelation and is not only expensive as a result, but the reaction can also lead to extreme discoloration due to the use of catalysts, e.g. via epoxidation reactions. Problems may occur, such as the appearance of dirt or the contamination of impurities.

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 urethane low oil or urethanized alkyd resin used in the present invention is an air-drying or semi-drying resin, and is a drying oil,
An oil component selected from the group consisting of semi-drying oils, polymerized oils, drying oil fatty acids, and semi-drying oil fatty acids and polyhydric alcohols or epoxy resins, or the oil component and polyhydric alcohols or epoxy resins. In addition, after performing a known transesterification reaction or dehydration condensation reaction with polybasic acids,
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 urethane low oil,
When polybasic acids are used, it is called - 0 - urethanized alkyd resin. In addition, when reacting the residual hydroxyl group with the polyisocyanate, it is free to use a known catalyst for promoting the urethanization reaction, such as an organic tin compound such as di-n-butyltin dilaurate or a tertiary amine. be.

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, 1°3-butylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol,
Examples of epoxy resins include dipentaerythritol, and commonly available commercially available epibis type epoxy resins, phenol novolak type epoxy resins, alicyclic type epoxy resins, and the like. In addition, examples of polybasic acids used in obtaining the urethanized alkyd resin include maleic anhydride,
Fumaric acid, itaconic acid, citraconic acid, phthalic anhydride, tetrahydrophthalic anhydride, 2,6-nindomethylene tetrahydrophthalic anhydride, adipic acid, glutaric acid, cepatic acid, trimellitic acid, pyromellitic acid, polyethylene glycol or polypropylene Examples include glycol dicarboxylic acids. Further, the polyisocyanate is not particularly limited as long as it is a compound having at least two isocyanate groups in one molecule; for example, dilene diisocyanate, trimethylene diisocyanate, 1.4
-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,10-decamethylene diisocyanate, octadecamethylene diisocyanate, lysine diisocyanate, o-lm- or p-phenylene diisocyanate, 4-isopropyl- 1,3-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 2,4- or 2,6-t-lylene 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-
Cyclohexylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate,
Hydrogenated 4,4'-diphenylmethane diisocyanate, 1,5-tetrahydronaphthalene diisocyanate,
Isophorone diisocyanate, diphenylsulfone diisocyanate, isocyanate polymers such as 1,6-hexamethylene diisocyanate dimer and 2,4-tolylene diisocyanate dimer, crude products of tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate etc.

The maleimide compound (B) used in the present invention includes all maleimides, their α-substituted derivatives, N-substituted derivatives, and polymaleimides, but especially N-alkyl or N-aryl substituted 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 bismaleimides and polymaleimides such as poly(phenylmethylene) polymaleimide.

The ratio of the maleimide compound (B) to the oil-modified resin (A) 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 substantial proportion is 0.1 parts 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 (8) 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 (8) 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). Depending on the purpose of use, conventionally known stabilizers, photopolymerization initiators, reactive diluents, reactive oligomers, and other resins can be added to both components of the maleimide compound (8). Various colorants, modifiers, solvents, etc., whether organic or inorganic, can be blended.

Examples of stabilizers include thermal polymerization inhibitors and anti-skinning agents that are released during storage of the composition.

Examples of the photopolymerization initiator include various known photopolymerization initiators such as benzoin type, benzophenone type, halogenated sulfonyl type, quinone type, ketone type, azo type and peroxide type.

As the reactive diluent, all conventionally known vinyl thread additives and polyfunctional monomers can be used, such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylatrile, 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 such resins include known diene rubbers, acrylic polymers, saturated polyesters, butyral resins,
Anything that can be dissolved in the composition can be used, such as polystyrene, rosin resin, oil-modified alkyd resin, oil-modified epoxy ester resin, and oil-modified phenol resin.

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.

Additionally, if necessary, oils and fats such as drying oil, semi-drying oil, and polymerized oil, waxes, dryers, dispersants, wetting agents, thickeners, fluidity regulators, and other additives can be added to those skilled in the art. If so, they 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 wt ω%, it cannot be considered as a substantially effective amount.

The composition comprising the oil-modified resin (8) 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 nature of the substrate to which the composition is applied, the thickness of the applied coating layer, the atmospheric oxygen concentration, temperature, etc. The composition can also be cured (set) 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. Colorant-containing compositions are useful for 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.

The present invention will be explained below with reference to examples, but the present invention is not limited to these examples.

In addition, unless otherwise specified in the examples, all parts are parts by weight.
All percentages refer to percentages by weight.

Production Example 1 440 parts of dehydrated castor oil, 68 parts of trimethylolpropane, and 0.2 parts of lithium hydroxide were placed in a 4-ton flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen suction tube, and stirred under a nitrogen gas atmosphere. The mixture was heated to 250° C. and transesterification was carried out for 30 minutes.

Then, it was cooled to 50°C, and tolylene diisocyanate 9
After adding 8 parts, gradually warm the stomach to 90℃ and reduce the temperature to 1.
hold for an hour and then di-n-butyltin dilaurate 0
．． 2 parts were added and the reaction was carried out at 90°C for 4 hours to obtain a low urethane oil (1) having 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 were charged into a 4-tubular flask similar to that used in Production Example 1, and the mixture was stirred under a nitrogen gas atmosphere. The temperature was raised to 250°C, and the transesterification reaction was carried out for 1 hour.

Next, it was cooled to 180°C, 60 parts of anhydrous phthalate M was added, and the temperature was gradually raised to 220°C and maintained at that temperature for 44 hours.
A time esterification reaction was carried out. Next, it was cooled to 50°C, 503 parts of toluene, 18 parts of propylene glycol, and 90 parts of tolylene diisocyanate were added, and the stomach was gradually warmed to 100°C and reacted for 3 hours, resulting in a non-volatile content of 50% and an acid value of 5.
0, urethanized alkyd resin solution with Gardner viscosity Z (
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. In addition, for comparison, as shown in Table 1, comparative ultraviolet curable overprint varnish compositions (1) to (2) that do not use maleimide compounds were used.
) was prepared.

Each of the obtained ultraviolet curable overprint varnish compositions was applied to a tin plate to a film thickness of 5μ, and 1
20m at 10ctn under 20W/CIR high pressure mercury lamp
The sample was placed on a conveyor at a speed of 1/min, and was irradiated and dried.

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 5-6 and Comparative Examples 3-4 Ultraviolet curable overprint varnish compositions (1)-(2) of the present invention obtained in Examples 1-2 and Comparative Examples 1-
Comparative ultraviolet curable overprint varnish compositions (1) and (2) obtained in step 2 were applied to commercially available art paper, coated paper, offset printing paper, and aluminum-deposited polyester film to a film thickness of 3 μm, respectively. One pass of ultraviolet light was applied in the same manner as described in Example 1.

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. The ultraviolet curable blue ink composition (7) of the present invention is prepared by mixing a polymerization initiator.
(9) was prepared.

In addition, for comparison, as shown in Table 4, comparative ultraviolet curable blue ink compositions (5) to
(6) was prepared. Each of the obtained ink compositions was applied to a 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. Cured films with excellent adhesion and hardness were obtained from the ink compositions (7) to (9) of the present invention, whereas cured films were obtained from the comparative ink compositions (5) to (6). There wasn't.

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 Hrad using a curtain beam type electron beam irradiation device. The obtained cured film had excellent adhesion and hardness.

*) Performance evaluation method Curability: A coating sample was repeatedly passed through a 120 W/cm high-pressure mercury lamp at a distance of 10 cm at a conveying speed of 20 m/min, and evaluated by the number of passes until the sample was cured.

Adhesion: Using a cutter knife, cut 100 gongs in an area of 10 m x 10 mm at intervals of 11Nn on the cured coating film obtained in the curing test, press cellophane tape, and then peel it off vigorously. Observe the peeling condition,
It was expressed as 100-(number of peeled gobbins)/100.

Shine: The cured coating film was visually evaluated.

Solvent resistance: Under the same ultraviolet irradiation conditions as the curing test, the coating sample was cured by passing it under a high-pressure mercury lamp 5 times, and then immersed in acetone for 10 minutes to observe the condition of the coating. ○: No abnormality. A three-level evaluation was performed: Δ: Abnormalities such as blistering were observed. ×: Dissolution.

Flexibility: Flexibility of the cured coating film obtained in the curability test was evaluated according to JIS K 5400.

Table 3 *) Performance evaluation method Adhesion: A cellophane tape peeling test was performed on the coating film obtained by UV irradiation, and those with no interlayer peeling from the base were evaluated as ○, and those with interlayer peeling were evaluated as ×.

Pencil hardness: Evaluated according to JIS K-5400 pencil scratch test.

Table 4 Chapter 5 Table Patent applicant: Nippon Shokubai Chemical Co., Ltd.-26=

Claims (1)

[Claims] 1. An active energy ray-curable composition comprising an oil-modified resin (A) comprising a urethanized oil and/or a urethanized alkyd resin and a maleimide compound (B) as essential components.