JP2016204597A - Polymerizable composition using n-substituted (meth)acrylamide, copolymer thereof and molded article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable resin composition extremely low in yellow discoloration when exposed to heat or light without using an adhesive with anxiety even when containing industrial product grade N-substituted (meth)acrylamide and suitably used for special applications such as optical or electronic materials, a polymer manufactured by polymerizing the same and excellent in wet heat yellow discoloration resistance, light yellow discoloration resistance and corrosion resistance and a molded article manufactured by using the polymerizable resin composition and the polymer.SOLUTION: There is provided a polymerizable resin composition having total base value of 12.0 KOHmg/g or less, total acid value of 8.0 KOHmg/g or less and difference between total base value and total acid value (total base value-total acid value) in a range of -1.0 to 5.0 KOHmg/g as a result of paying attention to a basic component in the polymerizable resin composition using N-substituted (meth)acrylamide, especially the content of amine and the content of an acidic component. There is provided a polymerizable resin composition containing N-substituted (meth)acrylamide of 1 to 90 wt.% as a monomer unit.SELECTED DRAWING: None

Description

  The present invention is a polymerizable resin composition using N-substituted (meth) acrylamide, which is very little colored or discolored even when exposed to heat or light, and does not corrode even when contacted with metal. The present invention relates to a polymer obtained by polymerizing the composition, and a molded article comprising the composition and the polymer.

  In recent years, N-substituted (meth) acrylamides are adhesives for optical members, active energy curable adhesives for polarizing plates, resin compositions for optical modeling and ink-jet inks, sealing materials for semiconductors and electronic materials, glass and resin molding. It has come to be widely applied as a raw material monomer for coating agents for products (Patent Documents 1 to 4). In particular, the amide group has high cohesive strength, excellent adhesion to various substrates, and is not corrosive to metals or metal oxides, so it is often used as a substitute for (meth) acrylic acid. (Patent Documents 5 to 7). However, it has been pointed out that N-substituted (meth) acrylamide is likely to be yellowed by light irradiation or heating, and when an acidic component such as (meth) acrylic acid is contained, corrosion of metals over a long period of time is caused. There was a fear. For this reason, in applications such as electronic materials and optical materials, there are cases where the amount of N-substituted (meth) acrylamide is reduced (Patent Document 8), or cases where it is not used completely (Patent Documents 9 and 10).

  Therefore, when N-substituted (meth) acrylamide is used as a resin composition component, the present inventors have reduced amine impurities (Patent Document 11) and oxidation in order to suppress the heat-resistant heat and heat yellowing of the cured film over time. It has been proposed to add an inhibitor or an ultraviolet absorber (Patent Documents 12 and 13). These proposals certainly improved the yellowing of the heat, but the cost increased due to the addition of a purification process to obtain high-purity N-substituted (meth) acrylamide and the addition of additives to suppress yellowing. There are also concerns about the effects of additives on the final product.

  On the other hand, N-substituted (meth) acrylamide is often used as a component of the active energy ray-curable resin, but no method for suppressing coloring or discoloration by irradiation with light such as ultraviolet rays or visible light has been reported yet.

JP 2008-287207 A JP 2011-121203 A JP 2001-310918 A JP 2010-155889 A JP 2011-137181 A JP 2010-235646 A JP 2013-256552 A JP 2008-24818 A JP 2005-255877 A JP 2005-015524 A JP 2012-025675 A JP 2013-035893 A JP 2013-057020 A

  The problem to be solved by the present invention is that it does not require a special purification step, contains industrial grade N-substituted (meth) acrylamide produced by a general production method, and blends additives with concern. The present invention provides a polymerizable resin composition that is very little colored or discolored (yellowing) when exposed to heat or light, and is also useful as various functional materials including optical applications. Also provided are polymers that are excellent in wet heat yellowing resistance, light yellowing resistance and corrosion resistance obtained by polymerizing a polymerizable resin composition, and further, these polymerizable resin compositions and molded articles produced using the polymer. It is to be.

  As a result of intensive studies to solve such problems, the present inventors focused on the contents of the basic component and the acidic component in the polymerizable resin composition using N-substituted (meth) acrylamide, The total acid value is 12.0 KOHmg / g or less, the total acid value is 8.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total base number-total acid value) is -1.0 to 5. By controlling it within the range of 0 KOH mg / g, N-substituted (meth) acrylamide is used, a polymerizable resin composition excellent in yellowing resistance and corrosion resistance, a polymer of the composition, and a resistance of them. It has been found that a molded article excellent in yellowing and corrosion resistance can be obtained.

That is, the present invention
(1) General formula [1] (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are the same or different and are substituted with a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, or a carbonyl group. A linear or branched alkyl group having 1 to 6 carbon atoms, an aliphatic or aromatic ring having 3 to 6 carbon atoms, and R ₂ and R ₃ are nitrogen atoms supporting them. Together with the atoms, a saturated or unsaturated 5- to 7-membered ring which may further contain an oxygen atom or a nitrogen atom may be formed, provided that R ₂ and R ₃ are simultaneously hydrogen atoms. The total base number is 12.0 KOH mg / g or less, the total acid number is 8.0 KOH mg / g or less, and the total base number and the total base number The difference in acid value (total base number-total acid value) is -1. A polymerizable resin composition of 0 to 5.0 KOHmg / g,
(2) The polymerizable resin composition as described in (1) above, which contains 1 to 90% by weight of N-substituted (meth) acrylamide as a monomer unit,
(3) The compound represented by the general formula [1] is (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N 1 selected from vinylpyrrolidone, N, N-dimethylaminopropyl (meth) acrylamide, N-vinylcaprolactam, N-hydroxyethyl (meth) acrylamide, N-methyl-N-hydroxyethyl (meth) acrylamide and diacetone acrylamide The polymerizable resin composition according to (1) or (2), wherein the polymerizable resin composition is a monomer of at least one species,
(4) The active energy ray curable, wherein the polymerizable resin composition according to any one of (1) to (3) further includes a monomer having a photopolymerization initiator and an unsaturated bond. Resin composition,
(5) A polymer obtained by curing the composition according to (4) by irradiation with active energy rays,
(6) The polymerizable resin composition according to any one of (1) to (3), further including a monomer having a thermal polymerization initiator and an unsaturated bond. object,
(7) A polymer obtained by polymerizing the composition according to (6) with heat,
(8) The pressure-sensitive adhesive composition comprising the composition according to (4) or (5) and / or the polymer according to (6) or (7),
(9) The pressure-sensitive adhesive composition according to (8), wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, the total base number and the total acid number The difference (total base number-total acid number) is -0.2 to 1.0 KOHmg / g, an optical pressure-sensitive adhesive composition,
(10) A coating composition comprising the composition according to (4) or (5) and / or the polymer according to (6) or (7),
(11) The coating composition according to (10), wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number The coating composition for optical members, wherein (total base number-total acid number) is -0.2 to 1.0 KOHmg / g,
(12) The coating composition according to (10), wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (Total base number-total acid number) is -0.2 to 1.0 KOHmg / g, a coating composition for a metal substrate,
(13) An ink composition comprising the composition according to (4) or (5) and / or the polymer according to (6) or (7),
(14) The ink composition according to (13), wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (Clear ink composition, wherein (total base number-total acid number) is -0.2 to 1.0 KOHmg / g,
(15) The resin composition for optical three-dimensional modeling characterized by containing the composition as described in said (4) or (5), and / or the polymer as described in said (6) or (7),
(16) An adhesive composition comprising the composition according to (4) or (5) and / or the polymer according to (6) or (7),
(17) The adhesive composition according to (16), wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, the total base number and the total acid number The difference (total base number-total acid number) is -0.2 to 1.0 KOHmg / g, an optical adhesive composition,
(18) The adhesive composition according to (16), wherein the total base number is 3.0 KOH mg / g or less, the total acid number is 2.0 KOH mg / g or less, the total base number and the total acid number The difference (total base number-total acid number) is -0.2 to 1.0 KOHmg / g, an adhesive composition for electronic materials,
(19) A sealant composition comprising the composition according to (4) or (5) and / or the polymer according to (6) or (7),
(20) The sealant composition according to (19), wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, the total base number and the total acid number The difference (total base number-total acid number) is -0.2 to 1.0 KOHmg / g, a sealing agent composition for organic EL devices,
(21) An antifogging agent composition comprising the composition according to (4) or (5) and / or the polymer according to (6) or (7),
(22) Using one or more compositions according to (9), (11), (14), (17) and (20), the composition is applied to one or both sides of an optical film or sheet and activated. An object of the present invention is to provide an optical molded article obtained by energy ray irradiation, heat curing or lamination curing.

  The polymerizable resin composition using the N-substituted (meth) acrylamide of the present invention has low viscosity and high curability, and is excellent in heat resistance, adhesion, and transparency. It can be suitably used as a sealing agent, a coating agent, an antifogging agent, and an ink. Further, the obtained molded product is hardly yellowed over a long period of time, and does not corrode against metals or metal oxides. The resin composition of the present invention does not require special purification processes and optical additives, including optical applications, and uses industrial N-substituted (meth) acrylamide as a raw material monomer or component. it can. Moreover, it is possible to mix | blend N-substituted (meth) acrylamide in a resin composition in large quantities, and the improvement of a weather resistance, heat resistance, a flaw resistance, and chemical resistance can be anticipated.

Hereinafter, the present invention will be described in detail.
The N-substituted (meth) acrylamide which is a constituent component of the polymerizable resin composition of the present invention has the general formula [1] (wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are the same or Differently, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an amino group, an alkoxy group or a carbonyl group, an aliphatic group having 3 to 6 carbon atoms or R ₂ and R ₃ represent a saturated or unsaturated 5- to 7-membered ring which may contain an oxygen atom or a nitrogen atom together with a nitrogen atom supporting them, and represents an aromatic ring. Provided that R ₂ and R ₃ are simultaneously hydrogen atoms).

    Specific examples of N-substituted (meth) acrylamide include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-butyl. (Meth) acrylamide, N-isobutyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-alkoxy (C 1-6 linear or branched structure) alkyl (C 1-6 linear or branched structure) ) (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-diisobutyl (meth) Kurylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-methylethyl (meth) acrylamide, N, N-methylpropyl (meth) acrylamide, N, N-methylbutyl (meth) acrylamide, N, N-ethylpropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N- (2-hydroxyethyl) acrylamide, N- (meth) acryloylmorpholine, allyl (meth) acrylamide, 2-ethylhexyl (meth) acrylamide and the like can be mentioned. These are not limited to one type, and a plurality of types may be used in combination. In addition, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, N-hydroxyethylacrylamide, from the point of being easily available as an industrial product and having high curability. N-methyl-hydroxyethyl acrylamide, diacetone acrylamide, N-isopropyl (meth) acrylamide, N-vinyl pyrrolidone and N-vinyl caprolactam are preferable.

  The resin composition of the present invention has a total base number of 12.0 KOHmg / g or less, a total acid value of 8.0 KOHmg / g or less, and a difference between the total base number and the total acid number (total base number-total acid The value is preferably -1.0 to 5.0 mg / g. Here, the total base number of the composition is the sum of the base numbers derived from basic components, N-substituted (meth) acrylamide and other basic impurities contained in other neutral components. Although it will not specifically limit if it is an alkaline compound as a basic structural component and an impurity, From the viewpoint of the yellowing resistance of this invention, reduction of the base number derived from amines is the most preferable. Since amines have an unshared electron pair on the nitrogen atom, they are easy to color, and at the same time, vinyl groups, N-substituted (meth) acrylamide amide groups, (meth) acrylate polyfunctional, monofunctional monomers The present inventors speculate that the influence on the ester group and the like is great.

  In the present invention, the total acid value of the composition is the sum of acid values derived from acidic constituents, acidic impurities contained in N-substituted (meth) acrylamide and other neutral components. Here, the acidic component or impurity is not particularly limited as long as it is an acidic compound, but from the viewpoint of yellowing resistance and corrosion resistance of the present invention, it is derived from carboxylic acids having an unsaturated bond such as acrylic acid and methacrylic acid. The acid value has a large influence on the vinyl group, N-substituted (meth) acrylamide amide group, (meth) acrylate polyfunctional, monofunctional monomer ester group, etc. contained in the composition, and their reduction is most preferable. The present inventors think.

  If the total base number, the total acid number, and the difference between them are out of the above ranges, the molded product using the resin composition may be yellowed over time by heat or light, and further contact with a metal or metal oxide It can lead to corrosion.

  The resin composition of the present invention can be produced by uniformly mixing various components including N-substituted (meth) acrylamide in a predetermined proportion. If the total base number of the composition, the total acid number and the difference between them do not fall within the above range, a method of neutralizing by adding an acidic or basic component, a specific acidic or What is necessary is just to adjust by normal means, such as the method of removing and refine | purifying a basic component.

  When adjusting the total base number, the total acid number and the difference between them in the resin composition of the present invention, as a method of neutralizing by adding an acidic or basic component, an acidic or basic gas is used in the resin composition. And a method of adding an acidic or basic liquid or solid into the resin composition. The acidic component and the basic component can be either inorganic or organic. In the solid acid or base, a powder form, a particulate form such as an ion exchange resin, a chelating agent fixed on a carrier, or the like can also be used. Depending on the state of the neutralizing agent used, the type and the amount added, the product of the neutralization reaction may remain in the composition, but it is preferable to remove it by a normal method such as filtration, distillation, or centrifugation. . Furthermore, it is particularly preferable to use a polymerizable acid or base because the neutralized product becomes a constituent of the composition.

  When adjusting the total base number, the total acid number, and the difference between them in the resin composition of the present invention, as a method of purifying by removing acidic or basic components contained in the composition, distillation or ion due to boiling point difference Examples of the method include adsorption by an exchange resin, separation by a osmosis membrane by a difference in molecular size and osmotic pressure, separation by a reverse osmosis membrane, and separation by electrophoresis. Moreover, a batch or a continuous flow type can be used. From the viewpoint of reliable removal at a high yield, a method of passing through a packed column of ion exchange resin or a cartridge is preferable.

  The total base number and total acid number of the resin composition in the present invention are measured by an automatic potentiometric titrator. Details will be described in Examples.

  The resin composition of the present invention is a pressure-sensitive adhesive for optical members, a pressure-sensitive adhesive sheet, an active energy curable adhesive for polarizing plates, a resin composition for optical modeling, an ink-jet ink, glass, and the like, which have been problems with coloring and corrosion. It can be used for modifying coating agents for resin molded products, sealing agents for organic EL elements, and the like. The resin composition at this time has a total base number of 3.0 KOHmg / g, a total acid number of 2.0 KOHmg / g or less, and a difference between the total base number and the total acid number (total base number-total acid number) is -0. More preferably, it is 2 to 1.0 KOHmg / g. If the total base number, total acid number, and the difference between them are within these ranges, the molded product will not deteriorate in color due to yellowing, redness, corrosion, etc. and will remain transparent over a long period of time. it can.

  The resin composition of the present invention may contain 100% by polymerization of N-substituted (meth) acrylamide as a monomer unit, but preferably 1 to 90% by weight. The N-substituted (meth) acrylamide content in the resin composition is more preferably 5 to 70% by weight. While diluting the resin by blending N-substituted (meth) acrylamide, it is possible to improve the performance of the resin composition such as adhesion, compatibility and curability. When the content is less than 1%, the characteristics of N-substituted (meth) acrylamide cannot be fully exhibited, and the blending effect may not be obtained.

  The resin composition of the present invention can be suitably used as an active energy ray-curable resin composition by further adding a photopolymerization initiator and a monomer having an unsaturated bond to N-substituted (meth) acrylamide. Depending on the purpose of adjusting the viscosity, a monofunctional monomer having one unsaturated bond, a polyfunctional monomer for adjusting the crosslinking rate, a monofunctional or polyfunctional oligomer for improving flexibility, a non-polymerizable polymer, etc. Can be used together. These combined components may be added singly to N-substituted (meth) acrylamide, or two or more types may be combined. The amount of each compound may be appropriately adjusted according to the specific application. In the total amount of the resin composition, the monofunctional monomer is 1 to 70% by weight, the polyfunctional monomer is 1 to 50% by weight, and the oligomer. Is preferably 1 to 50% by weight, and the polymer is preferably 0.1 to 10% by weight.

  Examples of the polyfunctional monomer used in the resin composition of the present invention include polyfunctional (meth) acrylates and polyfunctional (meth) acrylamides having two or more unsaturated bonds, and from the main chain structure to urethane type and epoxy type. And acrylic.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ditetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8- Kutandiol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate , Ethylene oxide-modified phosphoric acid di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethano Rudi (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated hexanediol Examples include monomers and oligomers such as di (meth) acrylate, alkoxylated cyclohexanedimethanol di (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and urethane (meth) acrylamide. In addition, from the viewpoint of easy availability as a commercial product, examples of urethane acrylate include Nippon Synthetic Chemical Co., Ltd., trade names UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-3310B, and UV-7000B. Nakamura Chemical Co., Ltd., trade names U-4HA, U-200PA, Daicel Cytec, trade names EBECRYL245, EBECRYL1259, EBECRYL8210, EBECRYL284, EBECRYL8402, SARTOMER, trade names CN944, CN969, CN900, CN900, CN900, CN900, CN900, CN900 Product names UN1255, UN-5507, Kyoeisha, product names AH-600, UA-306I, and the like can be used, and urethane (meth) acrylamide may be KJ Chemicals, KJS. It used the 5100, KJSA6100 like, as the epoxy resin, Daicel-Cytec Co., Ltd., trade name EBECRYL1259, EBECRYL605, EBECRYL1606 and SARTOMER Co., trade name CN110, CN120, CN153 and the like can be used. As the acrylic resin, SARTOMER, trade names CN2203, CN2270, Toagosei Co., Ltd., trade names M-6100, M-8060, and the like can be used. Furthermore, urethane acrylate UV-6640B or U-200PA is more preferable from the viewpoint of the viscosity of the resin composition and ease of handling.
One kind of these polyfunctional (meth) acrylates may be used alone, or two or more kinds may be used in combination.

  Examples of the polyfunctional (meth) acrylamide include methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, diallyl (meth) acrylamide and the like.

  Monofunctional monomers used in the resin composition of the present invention include monofunctional (meth) acrylates, monofunctional (meth) acrylamides and unsaturated nitrile monomers, styrene, amide group-containing monomers, methylol group-containing monomers, alkoxymethyl group-containing monomers. And radical polymerizable compounds having a reactive double bond in the molecular chain such as vinyl ester and olefin.

  Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxy Ethyl acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, Methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxydiethyleneglycol (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy Tetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentanyl (meth ) Acrylate, dicyclopentenyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl (meth) acrylate, allyl (meth) acrylate, hydroxyethyl (meth) ) Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and the like.

Examples of the monofunctional (meth) acrylamide include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-methoxyethyl ( (Meth) acrylamide, N-ethoxyethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N- (2-hydroxy) Ethyl) acrylamide, N- [3- (dimethylamino)] propylacrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-acryloylmorpholine, hydroxyalkyl (meth) acrylamide, etc. And the like.
These monofunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the oligomer or polymer used in the resin composition of the present invention include linear and / or branched oligomers and polymers having a skeleton such as acrylic, ester, ether, urethane, and amide. Examples include oligomers composed of the above polyfunctional (meth) acrylates and / or polyfunctional (meth) acrylamides having an average molecular weight of less than 10,000, and / or curable resins having a weight average molecular weight of 10,000 or more. .

  Examples of the curable resin having a weight average molecular weight of 10,000 or more include bifunctional polyurethane (meth) acrylate, polyfunctional polyurethane (meth) acrylate, bifunctional polyester (meth) acrylate, and polyfunctional urethane (meth). Acrylate, bifunctional polyester (meth) acrylate, polyfunctional polyester (meth) acrylate, bifunctional polyether (meth) acrylate, polyfunctional polyether (meth) acrylate, bifunctional polyamide (meth) acrylate, polyfunctional polyamide (meth) Acrylate, Bifunctional poly (meth) acrylate (meth) acrylate, Multifunctional poly (meth) acrylate (meth) acrylate, Bifunctional poly (meth) acrylate (meth) acrylamide, Multifunctional poly (meth) acrylic Ester (meth) acrylamide, bifunctional poly (meth) acrylamide (meth) acrylate, polyfunctional poly (meth) acrylamide (meth) acrylate, bifunctional polystyrene (meth) acrylate, polyfunctional polystyrene (meth) acrylate, bifunctional polyacrylonitrile (Meth) acrylate, polyfunctional polyacrylonitrile (meth) acrylate, bifunctional epoxy acrylate (bisphenol A type), polyfunctional epoxy acrylate (bisphenol A type) and the like. Moreover, these polymers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The active energy ray-curable resin composition of the present invention is applied or molded to a substrate, and then cured by irradiation with active energy rays, and a three-dimensionally shaped article, hard coating film, antifogging obtained by an adhesive sheet or a three-dimensional molding method. A molded product having a film and a pressure-sensitive adhesive, an adhesive, a sealant, and the like can be manufactured.

  The active energy rays are defined as energy rays that can generate active species by decomposing a compound (photopolymerization initiator) that generates active species. Examples of such active energy rays include optical energy rays such as visible light, electron rays, ultraviolet rays, infrared rays, X rays, α rays, β rays, and γ rays. Among them, it is preferable to use ultraviolet rays from the balance of the active energy ray generator, the curing speed and the safety. Examples of the ultraviolet ray source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an ultraviolet LED lamp, and a microwave excimer lamp.

  The active energy ray irradiation is preferably performed in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is reduced, but the resin composition of the present invention has N-substituted (meth) acrylamide. Therefore, the curability is good, and both a thin film and a thick film can be sufficiently cured even in a normal air atmosphere. The irradiation temperature of the active energy ray is preferably 10 to 200 ° C., and the irradiation time is preferably 1 second to 60 minutes.

  When the active energy ray-curable resin composition of the present invention is cured, a photopolymerization initiator can be added as necessary, but is not particularly necessary when an electron beam is used. The photopolymerization initiator may be appropriately selected from ordinary ones such as acetophenone, benzoin, benzophenone, and thioxanthone. Commercially available products include BASF Corporation, trade names Darocur 1116, Darocur 1173, Irgacure 184, Irgacure 369, Irgacure 500, Irgacure 651, Irgacure 754, Irgacure 719, Irgacure 819, Irgacure 9019 4265, Darocur TPO, UCB, trade name Ubekrill P36, etc. can be used. These photopolymerization initiators can be used alone or in combination of two or more.

  Although the usage-amount of these photoinitiators is not restrict | limited in particular, Generally 0.1 to 10 weight% with respect to an active energy ray-curable resin composition, and 1 to 5 weight% in it being added Is preferred. If it is less than 0.1% by weight, sufficient curability cannot be obtained, and if it exceeds 10% by weight, performance such as strength of the cured product may be deteriorated.

  The resin composition of the present invention can be suitably used as a polymerizable resin composition by adding a monomer having a thermal polymerization initiator and an unsaturated bond to N-substituted (meth) acrylamide. The monomer having an unsaturated bond referred to here is the above-mentioned various monofunctional and polyfunctional monomers and oligomers, and has one unsaturated bond in order to obtain a thermoplastic polymer that easily adjusts the physical properties. Monofunctional monomers are preferred, and monomers that can introduce crosslinking points to increase the cohesive strength of the resulting polymer are particularly preferred. The above monofunctional monomers may be added alone or in combination of two or more. The blending amount thereof may be arbitrarily adjusted according to the specific application, but is preferably 10 to 99% by weight in total in the total amount of the resin composition.

  Examples of the monomer capable of introducing the crosslinking point include a hydroxyl group-containing (meth) acrylic monomer, a carboxyl group-containing (meth) acrylic monomer, an amino group-containing (meth) acrylic monomer, and an acetoacetyl group-containing (meth) acrylic. Examples thereof include a system monomer, an isocyanate group-containing (meth) acrylic monomer, a glycidyl group-containing (meth) acrylic monomer, and an oxazoline group-containing (meth) acrylic monomer.

  Examples of the hydroxyl group-containing (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. , Hydroxyalkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylate, hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, and the like, 2- Primary hydroxyl group-containing (meth) acrylic monomers such as acryloyloxyethyl 2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Secondary hydroxyl group-containing (meth) such as butyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, 3-chloro 2-hydroxypropyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate There can be mentioned tertiary hydroxyl group-containing (meth) acrylic monomers such as acrylic monomers and 2,2-dimethyl-2-hydroxyethyl (meth) acrylate. Of these, hydroxyalkyl (meth) acrylates are preferably used.

  Examples of the carboxyl group-containing (meth) acrylic monomer include monocarboxylic acids such as (meth) acrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid, Among them, (meth) acrylic acid is preferably used.

  Examples of the amino group-containing (meth) acrylic monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-di-t-butylaminoethyl. Aminoalkyl (meth) acrylates such as (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, Examples include aminoalkyl (meth) acrylamides such as N-dimethylaminopropyl (meth) acrylamide.

  As said acetoacetyl group containing (meth) acrylic-type monomer, 2- (acetoacetoxy) ethyl (meth) acrylate etc. are mentioned, for example.

  Examples of the isocyanate group-containing (meth) acrylic monomer include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

  Examples of the glycidyl group-containing (meth) acrylic monomer include glycidyl (meth) acrylate, allyl glycidyl (meth) acrylate, and (meth) acrylamide glycidyl.

  Examples of the (meth) acrylic monomer containing oxazoline group include 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2 -Vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5 -Dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl 2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl 2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, 4 , 5-diethyl-2-isopropenyl-2-oxazoline and the like. Further, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline having high reactivity are preferable, and 2-vinyl-2- Oxazoline is most preferred. These functional group-containing (meth) acrylic monomers are not limited to one type, and a plurality of types may be used in combination.

  Thermal polymerization of the thermopolymerizable resin composition can be performed by a known method in the presence of a radical polymerization initiator. For example, methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be used. In the case of employing a solution polymerization method in an organic solvent, the solution polymerization is not particularly limited as long as it is a solvent that dissolves a polymer obtained by polymerization, and examples of the polymerization solvent include benzene, toluene, ethylbenzene, and xylene. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, esters such as ethyl acetate, butyl acetate, 2-hydroxyethyl acetate, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc. Aliphatic alcohols, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, N, N-dimethylformamide, and the like. These organic solvents can be used alone or in admixture of two or more. In particular, the use of ethyl acetate, methyl ethyl ketone, acetone or the like having a low boiling point is preferable because it is easy to remove when forming a molded product.

  Thermal radical polymerization initiators include azo compound catalysts such as azobisisobutyronitrile and azobisvaleronitrile, peroxide catalysts such as benzoyl peroxide and hydrogen peroxide, ammonium persulfate, and sodium persulfate. A persulfate-based catalyst such as can be used. The usage-amount of a polymerization initiator is about 0.001 to 10 weight% normally with respect to the polymerizable monomer component total amount. Furthermore, usual radical polymerization techniques such as adjustment of molecular weight by a chain transfer agent are applied.

  The molecular weight of the polymer of the present invention is 1,000 to 3,000,000 on a weight average, preferably 5,000 to 2,500,000, and more preferably 10,000 to 2,000,000. If the weight average molecular weight is in the range of 1,000 to 3,000,000, the solution viscosity when dissolved in a solvent is not too high and not too low, so that it can be suitably handled, and the processing accuracy of coating films, sheets, etc. is high high. When diluted with ethyl acetate so that such a polymer becomes 30%, the solution viscosity is usually 100,000 to 100,000 Pa · s / 25 ° C., more preferably 500 to 10,000 mPa · s / 25 ° C. Especially preferably, it is 2000-5000 mPa * s / 25 degreeC. The viscosity can be measured according to the cone plate viscometer method of JIS K5600-2-3 (1999).

  Since the polymer of the present invention contains N-substituted (meth) acrylamide as a constituent component, it has sufficient cohesive strength and adhesive strength, adhesion to various substrates, heat resistance, and durability, so it can be used as it is. In addition, by being cross-linked by a cross-linking agent, a product having more excellent heat resistance and durability can be obtained. Examples of the crosslinking method include (1) a method of crosslinking using a crosslinking agent, (2) a method of incorporating an unsaturated group-containing compound and a polymerization initiator, and a method of crosslinking by active energy rays and / or heat. It is done. One of these crosslinking methods may be used, or both may be used in combination.

  (1) As a method of crosslinking using a crosslinking agent, a compound having a functional group capable of reacting with a functional group contained in the (meth) acrylic resin, such as an isocyanate compound, an epoxy compound, an aziridine compound, or a carboxyl group compound The method of adding and making it react is mentioned.

  Among these, examples of the isocyanate compound include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. More specifically, as the isocyanate compound, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2, 4 -Tolylene diisocyanate, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), tri Methylolpropane / hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HL), hexamethylene diisocyanate Isocyanurate (product name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.). These isocyanate compounds may be used alone or in combination of two or more.

  Examples of the epoxy compound include polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerin diglycidyl ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetra. Glycidyl-m-xylenediamine (manufactured by Mitsubishi Gas Chemical Company, trade name: TETRAD-X) and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, trade name: TETRAD-C) ) And the like. These compounds may be used alone or in combination of two or more.

  Examples of the aziridine compound include a commercial product name: HDU, a trade name: TAZM, and a trade name: TAZO (manufactured by Mutual Pharmaceutical Co., Ltd.). These compounds may be used alone or in combination of two or more.

  As carboxyl group compounds, L-lactic acid, D-lactic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxyl group, 2,6-naphthalenedicarboxyl group, diphenyldicarboxyl group, diphenoxyethanedicarboxyl group, diphenyl ether Alicyclic dicarboxyl groups such as dicarboxyl group and diphenylsulfone dicarboxyl group, 1,3-cyclopentane dicarboxyl group, 1,3-cyclohexane dicarboxyl group and 1,4-cyclohexane dicarboxyl group Carboxyl group, malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid , Sebacic acid, suberic acid Dihydroxy acids derived from aliphatic dicarboxylic acids, glycolic acid, 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid, hydroxybenzoic acid and the like, and ester-forming derivatives thereof. The compound which has a carboxyl group is mentioned. These compounds may be used alone or in combination of two or more.

  The amount of these crosslinking agents to be used can be appropriately selected according to the purpose of use depending on the balance between the amount of the functional group contained in the polymer to be crosslinked and the molecular weight, and is usually 100% by weight of the polymer. On the other hand, it is preferable to contain 0.1 to 15 weight%, and it is more preferable to contain 0.5 to 10 weight%. When the content is less than 0.1% by weight, the cross-linking by the cross-linking agent is insufficient, the cohesive strength of the molded product such as the pressure-sensitive adhesive may be insufficient, and sufficient heat resistance may not be obtained, It tends to cause glue residue. On the other hand, when the content exceeds 15% by weight, the cohesive force of the resin composition after crosslinking is large, the flexibility and elasticity are lowered, and the conformability (wetting property) to the adherend tends to be insufficient. .

  Furthermore, in addition to the crosslinking agent, an acid catalyst, for example, a crosslinking accelerator such as p-toluenesulfonic acid, phosphoric acid, hydrochloric acid, ammonium chloride can be used in combination with the crosslinking agent. The amount is preferably 10 to 50% by weight with respect to the crosslinking agent.

  As the method of (2) containing an unsaturated group-containing compound and a polymerization initiator and crosslinking by active energy rays and / or heat, two or more active energy rays and / or thermally reactive unsaturated bonds are used as a crosslinking agent. The polyfunctional monomer which has, and the polymerization initiator are added, and the method of bridge | crosslinking with an active energy ray and / or heat is mentioned.

  The polyfunctional monomer having two or more active energy rays and / or heat-reactive unsaturated bonds is crosslinked by irradiation with active energy rays such as vinyl group, acryloyl group, methacryloyl group, vinylbenzyl group and / or heat. A polyfunctional monomer component having two or more active energy rays and / or two or more thermally reactive unsaturated bonds that can be (cured) is used. In general, those having 10 or less active energy rays and / or thermally reactive unsaturated bonds are preferably used. Two or more polyfunctional monomers can be used in combination.

  As the polyfunctional monomer, a bifunctional monomer or a trifunctional or higher monomer can be used. As specific examples, examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1, -Hexanediol di (meth) acrylate, 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, Diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, 2- (meth) acryloyloxyethyl And monomers such as acid phosphate diesters.

  Examples of the tri- or higher functional monomer include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri ( (Meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipenta Risuri Tall hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate.

  The polyfunctional monomer is preferably used in an amount of 0.05 to 50% by weight based on the polymer to be crosslinked, and more preferably from the viewpoint of flexibility and adhesiveness (adhesion). 1 to 30% by weight. When the content is less than 0.05% by weight, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force when used in the pressure-sensitive adhesive or the adhesive is insufficient, and sufficient heat resistance may not be obtained. On the other hand, when the content exceeds 50% by weight, for example, the cohesive strength of the polymer becomes too high, the flexibility and the adhesive strength are lowered, the wetness to the adherend is insufficient, and peeling is caused. Tend.

  The pigment, dye, surfactant, anti-blocking agent, leveling agent, dispersant, antifoaming agent, antioxidant, ultraviolet sensitization as long as the properties of the resin composition of the present invention and the molded product produced therefrom are not impaired. You may use together other arbitrary components, such as an agent and a preservative.

  The resin composition of the present invention is made of paper, cloth, non-woven fabric, glass, polyethylene terephthalate, diacetate cellulose, triacetate cellulose, acrylic polymer, polyvinyl chloride, cellophane, celluloid, polycarbonate, polyimide, and other base materials such as metal and metal. A high-performance coating layer, ink layer, pressure-sensitive adhesive layer, sealant layer or adhesive layer can be obtained by applying and curing between the surfaces. In particular, since the active energy ray-curable resin composition of the present invention has a highly transparent urethane oligomer, optical resin compositions such as optical pressure-sensitive adhesives, optical adhesives and sealants, and optical film coating materials. Can be suitably used. In addition, as a method for applying these resin compositions on a substrate, spin coating, spray coating, dipping, gravure roll, knife coating, reverse roll, screen printing, bar coater, etc. are usually used. The coating film forming method can be used. Moreover, as a method of apply | coating between base materials, the laminating method, the roll-to-roll method, etc. are mentioned.

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. Abbreviations of each constituent component described in Examples and Comparative Examples are as follows.
(1) N-substituted (meth) acrylamide (manufactured by KJ Chemicals)
“DEAA”: N, N-diethylacrylamide “DMAA”: N, N-dimethylacrylamide “ACMO”: acryloylmorpholine “NIPAM”: N-isopropylacrylamide “HEAA”: N-hydroxyethylacrylamide MHEAA: N-methyl-N -Hydroxyethylacrylamide HEMAA: N-hydroxyethylmethacrylamide "DMAPAA": N, N-dimethylaminopropylacrylamide (2) Polyfunctional monomer, oligomer, polymer PETA: Pentaerythritol triacrylate DPHA: Dipentaerythritol hexaacrylate HDDA: 1 , 6-hexanediol diacrylate TPGDA: tripropylene glycol diacrylate UV6640B: urethane acrylate (Nippon Go Chemical Co., Ltd.)
U200-PA: Urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
KJSA-6100: Urethane acrylamide (manufactured by KJ Chemicals)
EBECRYL 112: Aliphatic epoxy acrylate (manufactured by Daicel Cytec Co., Ltd.)
(3) Monofunctional monomer PEA: phenoxyethyl acrylate BZA: benzyl acrylate HEA: hydroxyethyl acrylate 4HBA: 4-hydroxybutyl acrylate EEA: 2- (2-ethoxyethoxy) ethyl acrylate THFA: tetrahydrofurfuryl acrylate IBOA: isobornyl Acrylate CHA: cyclohexyl acrylate M-106: o-phenylphenol EO modified acrylate (manufactured by Toagosei Co., Ltd.)
LA: lauryl acrylate DMAEA: N, N-dimethylaminoethyl acrylate AAc: acrylic acid BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate (4) Other I-184: IRGACURE 184 (photopolymerization initiator, manufactured by BASF Japan Ltd.) )
D-1173: Darocur 1173 (photopolymerization initiator, manufactured by BASF Japan Ltd.)
D-TPO: Darocur TPO (photopolymerization initiator, manufactured by BASF Japan Ltd.)
KE-359: Hydrogenated rosin (Tacky Fire) (Arakawa Chemical Industries)

Various physical properties of the resin composition of the present invention were determined according to the following measuring methods.
(5) Total base number The total base number represents hydrochloric acid or perchloric acid required for neutralizing all basic components contained in 1 g of the resin composition in terms of mg of potassium hydroxide equivalent to the present invention. Measured with an automatic potentiometric titrator with reference to K7237-1995. As the measurement solvent, one or a mixture of two or more selected from deionized water, methanol, ethanol, isopropanol, and tetrahydrofuran was used in accordance with the solubility of the resin composition. The procedure is described below.
10 g of the resin composition was accurately weighed into a 200 mL capacity beaker, and 50 mL of measurement solvent (special grade) was added and dissolved uniformly to obtain a sample solution. 50 mL of measurement solvent was added to a 200 mL beaker to obtain a blank solution. Each of the sample solution and the blank solution was titrated with an acetic acid solution of perchloric acid having a concentration of 0.01 mol / L using an automatic potentiometric titrator (AT-510N, manufactured by Kyoto Electronics Industry Co., Ltd.). The titration result was calculated according to Formula 1 and the total base number (KOHmg / L) was determined (F represents the factor of the titrant determined using a standard hydrochloric acid solution, where F = 1.000). In addition, the composite glass electrode C-173 (made by Horiba, Ltd.) was used for the measurement.

Formula 1

(6) Total acid value The total acid value is represented by the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin composition, and the present invention refers to JIS K0070-1992 and is an automatic potentiometric titrator. It was measured by. The measurement solvent used was one or a mixture of two or more selected from deionized water, methanol, ethanol, isopropanol, and tetrahydrofuran in accordance with the solubility of the resin composition and the dissociation ability of the acidic component. The procedure is described below.
In a 200 mL beaker, 20 g of the resin composition and 120 mL of a measurement solvent (special grade) (for example, tetrahydrofuran / deionized water = 5/1, v / v) were added and uniformly dissolved to obtain a sample solution. 120 mL of measurement solvent was added to a 200 mL beaker to obtain a blank solution. Each of the sample liquid and the blank liquid was titrated with an automatic potentiometric titrator with a potassium hydroxide aqueous solution (or ethanol solution) having a concentration of 0.0425 mol / L. The titration result was calculated according to Formula 2, and the total acid value (KOHmg / L) was determined (F represents the factor of the titrant determined using a standard hydrochloric acid solution, where F = 1.000). In addition, the composite glass electrode C-171 (made by Horiba, Ltd.) was used for the measurement.

Formula 2

Example A-1
50 g of “DEAA” and 50 g of UV6640B were weighed and mixed uniformly at room temperature, and the total base number and total acid number were measured. As shown in Table 1, it was confirmed that the total base number of the mixture was 1.0 KOH mg / g, the total acid number was 1.2 KOH mg / g, and the difference between the total base number and the total acid number was -0.2 KOH mg / g. Then, the polymerizable resin composition of the present invention was obtained without reprocessing.

Examples A-2 to A-10
In the same manner as in Example A-1, N-substituted (meth) acrylamide and other components were accurately measured and mixed at the ratios shown in Table 1, and the total base number and total acid number were measured. As shown in Table 1, the total base number of these mixtures is 12.0 mgKOH / g or less, the total acid number is 8.0 mgKOH / g or less, and the difference between the total base number and the total acid number is −1. It confirmed that it was 0.0-5.0KOHmg / g, and it was set as the polymeric resin composition of this invention, without reprocessing in particular.

Example A-11
“DMAA” 70 g, EBECRY 112 15 g, TPGDA 5 g, HEA 5 g and THFA 5 g were weighed and mixed uniformly at room temperature to measure the total base number and total acid number, but each was 18.8 KOH mg / g. And 3.3 KOH mg / g. The mixed solution was passed through a glass column filled with 10 g of a strongly acidic ion exchange resin (trade name Diaion SK1B, manufactured by Mitsubishi Chemical Corporation). The mixture after passing through was analyzed again, and it was confirmed that the total base number was 11.5 KOH mg / g, the total acid number was 7.2 KOH mg / g, and the difference between the total base number and the total acid number was 4.3 KOH mg / g. Thus, a polymerizable resin composition of the present invention was obtained.

Example A-12
HEMAA 10g, UV-6640B 20g, HDDA 40g, HEA 20g, THFA 20g, AAc 1g and CHA 10g were weighed and mixed uniformly at room temperature to measure the total base number and total acid number. They were 1.5 KOH mg / g and 25.8 KOH mg / g. 1.28 g of sodium hydroxide was added to the mixture, and the mixture was stirred slowly for 10 minutes and further cooled with ice water for 1 hour. Thereafter, the white solid precipitated in the mixed solution was removed by filtration. The clear liquid mixture thus obtained was analyzed again. The total base number was 7.0 KOHmg / g, the total acid number was 8.0 KOHmg / g, and the difference between the total base number and the total acid number was -1.0 KOHmg / g. It confirmed that there was and it was set as the polymeric resin composition of this invention.

Comparative Examples A-13 to A-17
In the same manner as in Example A-1, components such as N-substituted (meth) acrylamide were accurately measured at the ratios shown in Table 1, mixed, and the total base number and total acid number were measured. As shown in Table 1, the total base number of these mixtures exceeds 12.0 mgKOH / g, the total acid number exceeds 8.0 mgKOH / g, or the difference between the total base number and the total acid number is −1. Although it confirmed that it was out of the range of 0.0-5.0 KOHmg / g, it did not reprocess in particular and was set as the comparative polymerizable resin composition of this invention.

  To 100 parts by weight of various polymerizable resin compositions obtained in Examples A-1 to A-12 and Comparative Examples A-13 to A-17, 3 parts by weight of D-1173 was added as a photopolymerization initiator. The active energy ray-curable resin composition was prepared by mixing uniformly. And using these resin compositions, preparation of an active energy ray cured film and characteristic evaluation were performed by the following method.

Using a tabletop coating machine (Coater TC-1, manufactured by Mitsui Denki Co., Ltd.), the mixed solution of Examples A1 to A12 and Comparative Examples A13 to 17 was made of an aluminum substrate (Al, A5052) is irradiated with ultraviolet rays (apparatus: Inverter type conveyor device ECS-4011GX made by Eye Graphics, metal halide lamp: M04-L41 made by Eye Graphics, ultraviolet illuminance: 700 mW / cm ² , integrated light quantity: 3000 mJ / cm ² ) to obtain a cured film. The obtained cured film was slowly peeled from the aluminum substrate, and initial transparency (transparency) and yellowing resistance (yellowing degree b value) were measured according to the following methods. Moreover, the accelerated test of moisture heat yellowing resistance and light yellowing resistance was performed as follows, and the transparency and yellowing resistance after the test were similarly evaluated. Furthermore, using an amyl substrate and copper foil as a metal material, corrosion resistance was evaluated by the following method, and the results are shown in Table 2.

(7) Transparency (transmittance)
The obtained cured film after the initial or yellowing resistance acceleration test was used for 24 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. Then, the transmittance | permeability of the cured film was measured with the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH-2000), and transparency was divided into four steps as follows and evaluated.
◎: Transmittance is 90% or more ○: Transmittance is 85% or more and less than 90% Δ: Transmittance is 50% or more and less than 85% X: Transmittance is less than 50% (8) Moisture and heat yellowing resistance The initial cured film thus obtained was allowed to stand for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. After that, the transmission spectrum of the cured film was measured by a transmission color measurement dedicated machine (TZ-6000, manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain an initial b value. The cured film was allowed to stand for 500 hours in a thermo-hygrostat set at 85 ° C. and a relative humidity of 85%, and an accelerated test for heat and heat yellowing resistance was performed. Similarly, the cured film after the test was allowed to stand for 24 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and the transmitted color was measured. The difference between the b value after wet heat and the initial b value was defined as a change value Δb (Δb = b value after wet heat−initial b value). Wet heat and yellowing resistance was evaluated in four stages as follows.
A: Both the initial b value and the b value after wet heat are 0.2 or less, and Δb is 0.1 or less. ○: Either the initial b value or the b value after wet heat exceeds 0.2 or both. Both are 0.5 or less and Δb is 0.2 or less. Δ: Either the initial b value or the b value after wet heat exceeds 0.5, but both are 1.0 or less. And Δb is 0.3 or less. X: The initial b value and the b value after wet heat exceed 1.0 or both, or Δb exceeds 0.3. (9) Light yellowing resistance In the same manner as in the evaluation of heat-and-humidity yellowing resistance, an accelerated test of light yellowing resistance was performed, and the b value before and after the test and Δb which was the difference between them were measured and calculated. The accelerated test for light yellowing resistance was performed by using an ultraviolet fade meter (U48 manufactured by Suga Test Instruments Co., Ltd.), setting the black panel temperature to 63 ° C., and irradiating for 168 hours under the condition of 500 W / m 2. The evaluation was divided into four stages in the same manner as the heat and heat yellowing resistance.
(10) Corrosion resistance An active energy ray cured film is prepared by the above method, and the cured film thus obtained is adhered to the aluminum substrate (for Al corrosion resistance evaluation), and the cured film is slowly removed from the aluminum substrate. Using a test piece (for evaluation of Cu corrosion resistance) peeled off and bonded to a copper foil (thickness 80 μm), the sample was allowed to stand for 168 hours in a constant temperature and humidity chamber set at a temperature of 60 ° C. and a relative humidity of 95%. Thereafter, the cured film is peeled off from the aluminum substrate or the copper foil, the surfaces of the aluminum substrate and the copper foil are visually observed, the corrosion resistance of the cured film is evaluated, and the results are shown in Table 2.
◎: No corrosion ○: Slight corrosion △: Slight corrosion ×: Significant corrosion

Example B-1
“DEAA” 40 g, BA 40 g, 2EHA 15 g, 4 HBA 5 g and AIBN 0.2 g were weighed and mixed uniformly at room temperature to measure the total base number and the total acid number. As shown in Table 3, it was confirmed that the total base number of the mixture was 1.80 KOHmg / g, the total acid number was 2.0 KOHmg / g, and the difference between the total base number and the total acid number was -0.2 KOHmg / g. And it was set as the thermopolymerizable resin composition of this invention, without reprocessing in particular.
In a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introduction tube, 200 g of ethyl acetate and 100 g of the thermopolymerizable resin composition are added, and nitrogen gas is introduced while stirring to evacuate the air in the apparatus. After substituting with nitrogen, the temperature was raised to the reflux temperature, and the reaction was allowed to proceed for 7 hours while passing nitrogen. After completion of the reaction, ethyl acetate was added to obtain a polymer solution having a solid content of 30%. Using a cone plate viscometer (RE550, manufactured by Toki Sangyo Co., Ltd.), the solution viscosity was measured at 25 ° C. according to JIS K5600-2-3 and found to be 3500 mPa · s.
Further, 30 parts were taken out from the polymer solution, and the polymer was obtained by completely removing volatile components in the solution. Then, it melt | dissolved in tetrahydrofuran (THF), the polymer solution with a density | concentration of 0.5 weight% was prepared, and it left still overnight. The polymer THF solution was filtered through a 0.45 μm membrane filter, and gel permeation chromatography (GPC) measurement was performed using the filtrate (Prominence GPC system manufactured by Shimadzu Corporation, Shodex KF-806L column, eluent THF). The weight average molecular weight (Mw) of the polymer was calculated to be 1.16 million from the polystyrene equivalent value.

Examples B-2 to B-6 and Comparative Examples B-7 to B-9
Except changing to the polymerizable composition shown in Table 3, Examples B-2 to B-6 and Comparative Examples B-7 to B-9 of the thermopolymerizable resin composition were performed in the same manner as Example B-1. Were prepared, and the total base number and total acid number were measured. Moreover, thermal polymerization was performed in the same manner, and the solid content of the obtained polymer solution was adjusted to 30%, and the viscosity of the solution was measured. Furthermore, each polymer was obtained by completely removing the volatile components in the solution in the same manner as in Example B-1, and the weight average molecular weight was measured. Table 3 shows the results of various evaluations.

Examples C-1 and 2 and Comparative Example C-11
The polymer solution obtained in Examples B-1 and B-4 and Comparative Example B-7 was applied to a polyethylene terephthalate (PET) film having a thickness of 100 μm so that the thickness after drying was 25 μm, and 90 ° C. And dried for 2 minutes to form an adhesive layer. Subsequently, it was placed in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test pressure-sensitive adhesive sheet (type a).

Examples C-3, 4 and Comparative Example C-12
Further, 100 g of a polymer solution having a solid content of 30% obtained in Examples B-3 and B-5 and Comparative Example B-8 was weighed, and 3 g of a 50% ethyl acetate solution of hexamethylene diisocyanate (HDI) was obtained. After adding and mixing uniformly, it was similarly applied to a PET film having a thickness after drying of 25 μm and dried at 90 ° C. for 2 minutes to form an adhesive layer. Thereafter, the film was aged in a constant temperature bath at 40 ° C. for 3 days and placed in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test pressure-sensitive adhesive sheet (type b).

Examples C-5 and 6 and Comparative Example C-13
100 g of the polymer solution having a solid content of 30% obtained in Examples B-2 and B-6 and 70 g of the polymer solution having a solid content of 30% obtained in Comparative Example B-9 were respectively weighed to obtain a polyfunctional product. After adding 5 g of a DPHA 50% ethyl acetate solution and 1 g of a photopolymerization initiator I-184 as monomers and mixing them uniformly, it was similarly applied to a PET film having a thickness of 25 μm after drying. It was made to dry for minutes and the adhesive layer was formed. Thereafter, irradiation with ultraviolet rays (apparatus: Inverter type conveyor device ECS-4011GX made by Eye Graphics, metal halide lamp: M04-L41 made by Eye Graphics, ultraviolet illuminance: 700 mW / cm ² , integrated light amount: 1000 mJ / cm ² ) and curing And placed in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test pressure-sensitive adhesive sheet (type c).

Examples C-7-9
Polymeric compositions obtained in Examples A-1, A-7 and A-10, DPHA as a polyfunctional monomer, KE-359 as a polymer, and I-184 as a photopolymerization initiator in predetermined amounts shown in Table 4 Weigh out and mix uniformly, then apply to heavy release separator (silicone-coated PET film) and make it a table roll laminator machine (Royal Sovereign) so as not to bite air bubbles with light release separator (silicone-coated PET film) RSL-382S) was used to bond the adhesive layer to a thickness of 25 μm and irradiated with ultraviolet rays (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics) UV intensity: 700mW / cm ^2, the accumulated amount of light: 1000mJ cm ^2), and to produce an optical transparent pressure-sensitive adhesive sheet (type d).

Example C-10 and Comparative Example C-14
The polymeric composition obtained in Example A-4 and Comparative Example A-15, HDI as a crosslinking agent, DPHA as a polyfunctional monomer, and I-184 as a photopolymerization initiator were weighed in predetermined amounts shown in Table 4. After mixing uniformly, a pressure-sensitive adhesive sheet was prepared in the same manner as in type c, and cured with ultraviolet rays. Thereafter, the film was aged in a constant temperature bath at 40 ° C. for 3 days and placed in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test pressure-sensitive adhesive sheet (type e).

The characteristics of the produced adhesive sheet were evaluated by the following method, and the results are shown in Table 4.
(11) Transparency The produced pressure-sensitive adhesive sheet was allowed to stand still for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the transmittance was measured with a haze meter in the same manner as described above, and the transparency was evaluated.
(12) Adhesive strength Under conditions of a temperature of 23 ° C. and a relative humidity of 50%, the substrate is transferred as an adherend to a PET film or glass substrate having a thickness of 100 μm, and added by reciprocating twice using a pressure roller having a weight of 2 kg. The film was pressed and left under the same atmosphere for 30 minutes. Thereafter, 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min using a tensile tester (device name: Tensilon RTA-100 ORIENTEC).
◎: 30 (N / 25 mm) or more ○: 15 (N / 25 mm) or more, less than 30 (N / 25 mm) △: 8 (N / 25 mm) or more, less than 15 (N / 25 mm) ×: 8 (N / 25 mm ) Less than (13) Contamination resistance Adhering the adhesive sheet to the adherend in the same manner as the measurement of the adhesive force described above, leaving it at 80 ° C. for 24 hours, and then removing the adhesive sheet from the adherend surface. It was observed visually.
◎: No contamination ○: Very slight contamination
Δ: Slightly contaminated
X: There exists adhesive (adhesive) remainder.
(14) Light yellowing resistance The light yellowing resistance of the pressure-sensitive adhesive sheet was evaluated in the same manner as described above, and the results are summarized in Table 4.

Examples D-1 to 8 and Comparative Examples D-9 to 12
Using the polymer composition obtained in Example A and the polymer obtained in Example B, together with other components, weighed out in a predetermined amount shown in Table 5 and mixed uniformly to prepare an ultraviolet curable sealant. Was prepared. Then, preparation and physical property evaluation of the sealing agent resin hardened | cured material by ultraviolet curing were performed with the following method using the obtained sealing agent.

Preparation method of UV curable encapsulant resin cured product Set a silicon spacer (length 30 mm x width 15 mm x thickness 3 mm) on a glass plate (length 50 mm x width 50 mm x thickness 5 mm), and place it inside the spacer. Copper foil (length 5 mm × width 50 m × thickness 80 μm) was put, and the ultraviolet curable sealant prepared above was injected. After sufficiently deaerated, irradiated with ultraviolet rays (apparatus: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm2, integrated light amount: 1000 mJ / cm2) Then, an encapsulant resin cured product was produced. The characteristics of the obtained cured product were evaluated by the following methods, and the results are shown in Table 5.

(15) Transparency The produced cured product was allowed to stand still for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the transmittance was measured with a haze meter in the same manner as described above, and the transparency was evaluated.
(16) Humidity and heat yellowing resistance The cured product thus obtained was evaluated for moisture and heat yellowing resistance in the same manner as described above, and the results are shown in Table 5.
(17) Water absorption test 1 g of the obtained cured product was cut out and set as a test piece in a thermo-hygrostat with a temperature of 85 ° C. and a relative humidity of 95%. After standing for 48 hours, the weight of the test piece was measured again. The water absorption was calculated according to Equation 3.

Formula 3

◎: Water absorption is less than 1.0% ○: Water absorption is 1.0% or more and less than 2.0% △: Water absorption is 2.0% or more and less than 3.0% ×: Water absorption is 3 0.0% or more (18) Outgas test 1 g of the obtained cured product was cut out and left as a test piece in a thermostatic bath set at a temperature of 100 ° C., and a dry nitrogen stream was allowed to flow for 24 hours. The weight was measured, and the outgas generation rate was calculated according to Equation 4.

Formula 4

◎: The incidence is less than 0.1% ○: The incidence is 0.1% or more and less than 0.3% △: The incidence is 0.3% or more and less than 1.0% ×: The incidence is 1 0.0% or more (19) Heat cycle resistance The obtained cured product was repeated 100 times with one cycle of standing at −40 ° C. for 30 minutes and then at 100 ° C. for 30 minutes, and the state of the cured product was visually observed.
A: No change is observed. O: Bubbles are slightly generated, but no cracks are observed. It is transparent.
Δ: Some bubbles or cracks are observed, and it is slightly cloudy.
X: Bubbles or cracks are generated over the entire surface, and the film is translucent.
(20) Corrosion resistance After the moisture and heat yellowing test, the surface of the copper foil was visually observed, the corrosion resistance of the cured film was evaluated in the same manner as described above, and the results are shown in Table 5.

Examples E-1 to 8 and Comparative Examples E-9 to 12
Using the polymer composition obtained in Example A and the polymer obtained in Example B, an ultraviolet curable adhesive was prepared with the composition shown in Table 6, and the polarizing plate was prepared and the polarizing plate was prepared by the following method. The physical properties were evaluated and the results are shown in Table 6.

Production of Polarizing Plate by UV Irradiation Using a table-top roll laminator (RSL-382S manufactured by Royal Sovereign), a polarizing film is sandwiched between two transparent films, and the examples or The adhesive of the comparative example was bonded so as to have a thickness of 10 μm. Irradiate ultraviolet rays from the upper surface of the laminated transparent film (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, UV illuminance: 700 mW / cm2, integrated light amount: 1000 mJ / cm2 And a polarizing plate having a transparent film on both sides of the polarizing film was prepared. An acrylic protective film (Sanduren SD-014 manufactured by Kaneka Corporation) was used as the transparent film.

(21) Surface shape observation The obtained polarizing plate surface was observed visually and evaluated on the following reference | standard.
◎: No minute streaks or uneven unevenness can be confirmed on the surface of the polarizing plate ○: Minute streaks can be partially confirmed on the surface of the polarizing plate Δ: Minute streaks or uneven unevenness can be confirmed on the surface of the polarizing plate ×: Clear stripes and irregularities can be confirmed on the surface of the polarizing plate. (22) Peeling strength A polarizing plate (test piece) cut to 20 mm × 150 mm under the conditions of a temperature of 23 ° C. and a relative humidity of 50% is subjected to a tensile tester (Shimadzu). It was affixed on the test plate attached to the autograph AGXS-X 500N) manufactured by Seisakusho using a double-sided adhesive tape. One piece of the transparent protective film and the polarizing film to which the double-sided adhesive tape is not attached is peeled off in advance by about 20 to 30 mm, chucked on the upper gripping tool, and peeled at 90 ° peel strength (N / 20 mm).
A: 3.0 (N / 20 mm) or more B: 1.5 (N / 20 mm) or more, less than 3.0 (N / 20 mm) Δ: 1.0 (N / 20 mm) or more, 1.5 (N / Less than 20 mm) ×: Less than 1.0 (N / 20 mm) (23) Water resistance The obtained polarizing plate was cut into 20 × 80 mm and immersed in warm water at 60 ° C. for 48 hours. The presence or absence of peeling at the interface with the phase difference film and the optical compensation film was confirmed. The determination was made according to the following criteria.
A: No peeling at the interface between the polarizer and the protective film (less than 1 mm)
○: There is peeling at a part of the interface between the polarizer and the protective film (1 mm or more and less than 3 mm)
Δ: There is peeling at a part of the interface between the polarizer and the protective film (3 mm or more and less than 5 mm)
X: Peeling at the interface between the polarizer and the protective film (5 mm or more)
(24) Durability The obtained polarizing plate was cut into 150 mm × 150 mm, put into a thermal shock device (TSA-101L-A manufactured by Espec), and subjected to a heat shock of −40 ° C. to 80 ° C. for 30 minutes for 100 times. And evaluated according to the following criteria.
A: No crack occurred. O: A short crack of 5 mm or less occurred only at the end. Δ: A crack occurred in a short line at a place other than the end. However, the polarizing plate is not separated into two or more parts by the line. X: Cracks are generated in places other than the end portions, and the polarizing plate is separated into two or more parts by the line ( 25) Heat-resistant yellowing The obtained polarizing plate was cut into 30 mm × 30 mm, and the a value and b value of the transmitted hue were measured (with a UV-visible spectrophotometer UV-2450 manufactured by Shimadzu Corporation, wavelength 380) The parallel transmission hue a value and the orthogonal transmission hue b value of ˜780 nm were measured, and the ab value (ab = (a2 + b2) 1/2) of the transmission hue was calculated, and then the polarizing plate was placed in a thermostat at 90 ° C. for 48 hours. The ab value after the test was calculated in the same manner, and the value of Δab (Δab = ab value after the test−ab value before the test) was used as an index of yellowing. In the case of 0, yellowing does not occur, and yellowing increases as Δab increases. It means the door.
A: 0 <= Δab <= 2
○: 2 <Δab <= 6
Δ: 6 <Δab <= 10
×: 10 <Δab

Examples F-1 to 8 and Comparative Examples F-9 to 12
Using the polymer composition obtained in Example A and the polymer obtained in Example B, a photocurable ink composition was prepared with the composition shown in Table 7, and ink jet printing was performed by the following method. The obtained printed matter was evaluated. The clear ink composition does not contain a pigment and a pigment dispersant, and the black ink composition contains pigment pigment black 7 (abbreviated as PMB-7) and pigment dispersant Addisper PB821 (abbreviated as PB821) in predetermined amounts shown in Table 7. It is blended with.

(26) Viscosity The viscosity of the obtained ink composition was measured using a cone plate viscometer (device name: RE550 viscometer manufactured by Toki Sangyo Co., Ltd.) according to JIS K5600-2-3. In consideration of ink jet printing, the viscosity of the ink composition at 20 ° C. is 2 to 50 mPa · s (Δ evaluation), or preferably 3 to 30 mPa · s (◯ evaluation), and more preferably 5 to 20 mPa · s. It is preferably s (◎ evaluation). If it is less than 2 mPa · s (× evaluation), bleeding after printing is observed, and discharge followability is deteriorated due to printing misalignment, and if it exceeds 50 mPa · s (× evaluation), discharge stability is reduced due to clogging of the discharge nozzle. Therefore, it is not preferable.
(27) Compatibility The compatibility of the ink composition prepared by the above method was confirmed visually.
A: Insoluble matter is not present in the ink composition. O: Insoluble matter is slightly observed in the ink composition. Δ: Insoluble matter is observed in the entire ink composition. X: Precipitation is present in the ink composition.

Preparation of printed matter by ultraviolet irradiation The obtained ink composition was applied to a PET film having a thickness of 100 μm by a bar coater (RDS 12) (after drying, a film thickness of 10 μm), and then irradiated with ultraviolet rays (apparatus: an inverter made by Eye Graphics) Cured with an apparatus ECS-4011GX, a metahalide lamp: M04-L41 manufactured by Eye Graphics, to produce a printed matter.

(28) Curability When the printed material was prepared by the above method, the integrated light amount until the ink composition was completely cured (non-sticky state) was measured to evaluate the curability.
A: Completely cured at 1000 mJ / cm 2 ○: Completely cured at 1000 to 2000 mJ / cm 2 Δ: Completely cured at 2000 to 5000 mJ / cm 2 ×: 5000 mJ / cm 2 or more is required until complete curing (29) Surface drying property By the above method The produced printed matter is allowed to stand in an environment of room temperature 23 ° C. and relative humidity 50% for 5 minutes, and high-quality paper is stacked on the printing surface, and a load of 1 kg / cm 2 is applied for 1 minute to evaluate the degree of ink transfer to the paper. did.
A: The ink was dried and there was no transfer to paper.
◯: The ink was dried and there was a slight transfer to paper.
Δ: The ink was almost dried and transferred to paper.
X: The ink was hardly dried and there was much transfer to paper.

Inkjet printing and printability evaluation The ink composition prepared above is filled into a commercially available inkjet printer (LuxelJet UV350GTW, manufactured by Fuji Film Co., Ltd.), and a solid image is printed using a coated paper. The method was evaluated.

(30) Discharge stability The printed state of the obtained printed matter was visually evaluated.
A: Printed satisfactorily without nozzle missing.
◯: Slightly missing nozzle
Δ: Nozzle missing over a wide range.
X: There is no ejection.
(31) Sharpness The image sharpness of the printed matter obtained from the ink composition containing the pigment was visually observed.
A: No ink bleeding was observed, and the image was clear.
○: There was almost no ink bleeding and the image was good.
Δ: Some ink bleeding was observed.
X: The ink was noticeably blurred.
(32) Heat-resistant yellowing Using the obtained clear ink composition, it was applied to a substrate substrate (# 125-E20) with a bar coater so as to have a film thickness of 10 μm, and cured with a metal halide lamp in the same manner as described above. The hue of the obtained coating film was measured with Spcetrolino (manufactured by GretagMacbeth) and left in a thermostatic bath maintained at 60 ° C. for 1 week. Thereafter, the hue of the coating film was measured again, and yellowing resistance was evaluated by a change in hue value before and after heating (ΔE = hue after heating−hue before heating).
A: 0 <= ΔE <= 0.2
A: 0.2 <ΔE <= 0.5
Δ: 0.5 <ΔE <= 1.0
×: 1.0 <ΔE

Examples G-1 to 4 and Comparative Examples G-5 and 6
Using the clear ink composition obtained in Example F, a three-dimensional molded object evaluation test piece was prepared as follows, and the strength, shrinkage resistance, heat resistance and the like were measured. The results are shown in Table 8.

  A 75 μm thick heavy peeled PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is adhered to a horizontally placed glass plate, and a spacer with a thickness of 1 mm and an inside of 20 mm × 40 mm is installed, and active inside the spacer. After filling the energy ray curable resin composition, a 50 μm thick lightly peeled PET film (Toyobo Co., Ltd., polyester film E7002) is further laminated thereon and irradiated with ultraviolet rays (apparatus: made by Eye Graphics, inverter type) Conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance of 300 mW / cm2, integrated light quantity 900 mJ / cm2), and a cured product of the composition was obtained. After that, the cured product is allowed to stand for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, and the peeled PET film on both sides is removed to obtain tensile properties, bending properties such as mechanical properties and thermal properties, three-dimensional shaped products. The shrinkage ratio, surface strength, etc. of the film were measured.

(33) Tensile test In accordance with JIS K-7113, a tensile test was performed on a cured test piece obtained using a precision universal testing machine (manufactured by Shimadzu Corporation, AG-X 500N), and tensile strength, tensile elongation, and tensile elasticity were measured. The rate was measured. Each measurement value obtained was evaluated based on the following criteria.
Tensile strength A: Maximum point stress is 40 MPa or more. O: Maximum point stress is 30-40 MPa.
Δ: Maximum point stress is 15-30 MPa
X: Maximum point stress is 15 MPa or less Tensile elongation ◎: Elongation at break is 100% or more O: Elongation at break is 80 to 100%
Δ: Elongation at break 50% to 80%
X: Elongation at break is 50% or less Tensile elastic modulus A: 1500 MPa or more O: 1000-1500 MPa
Δ: 500 to 1000 MPa
X: 500 MPa or less (34) Bending test Using the obtained cured test piece, it was processed into a bar shape in accordance with JIS K-7171 to obtain a test piece for a bending test. In accordance with JIS K-7171, a bending test was performed on the cured specimen using a precision universal testing machine (AG-X 500N manufactured by Shimadzu Corporation), and the bending strength and the flexural modulus of the specimen were measured. Each measurement value obtained was evaluated based on the following criteria.
Bending strength A: Maximum bending stress is 80 MPa or more. O: Maximum bending stress is 50 to 80 MPa.
Δ: Maximum bending stress is 30 to 50 MPa
X: Maximum bending stress is 30 MPa or less Bending elastic modulus A: 1500 MPa or more O: 1000-1500 MPa
Δ: 500 to 1000 MPa
×: 500 MPa or less (35) Surface hardness Using the above-mentioned cured test piece, the surface hardness is measured by the durometer method of “Asker D-type hardness meter (manufactured by Kobunshi Keiki Co., Ltd.)” in accordance with JIS K6253. Based on the evaluation.
: Over D80 O: Over D60 to D80
Δ: Over D40 to D60
X: D40 or less (36) Thermal deformation temperature Using the above-mentioned curing test piece, the thermal deformation temperature was measured according to JIS K7207, and the evaluation was performed based on the following criteria.
A: Over 50 ° C. O: Over 40 ° C. to 50 ° C.
Δ: 25 ° C to 40 ° C
X: 25 ° C. or less (37) Light yellowing resistance Light yellowing resistance was evaluated in the same manner as described above using the obtained cured test piece.

  Using the above clear ink composition, using a super-high-speed stereolithography system (manufactured by Nabtesco, SOLIFORM 500B) with a semiconductor laser (Spectra Physics, semiconductor-excited solid laser BL6 type, wavelength 355 nm), a liquid surface irradiation amount of 100 mJ / Three-dimensional modeling was performed in a time of 2 minutes per slice with a slice pitch of 0.10 mm under the condition of cm2, and a three-dimensional molded object having a rectangular parallelepiped shape was produced.

(38) Curing shrinkage resistance Curing shrinkage is obtained from the following formula from the specific gravity (d0) of the ink composition before photocuring and the specific gravity (d1) of the molded article obtained after curing, and the curing shrinkage resistance is based on the following criteria: Based on the evaluation.
Curing shrinkage (%) = {(d1-d0) / d1} × 100
A: Less than 2% O: 2% to less than 5% Δ: 5% to less than 10% ×: 10% or more

Examples H-1 to 6 and Comparative Examples H-7 to 10
Using the polymer composition obtained in Example A and the polymer obtained in Example B, the four types (b, c, d, e) of antifogging coating compositions described in Example C are shown. 9 was applied to glass, aluminum, PET and a PC substrate so that the film thickness after drying was 1 μm. Thereafter, curing was performed by thermosetting, active energy ray curing or a combination thereof according to each type, and the performance of the obtained antifogging film was evaluated by the following method. The results are shown in Table 10.

(39) Transparency The transparency and hue of the test piece for evaluation coated with an antifogging paint were visually observed and evaluated in four stages.
A: Excellent (colorless, transparent and glossy)
○: Good (colorless and transparent but slightly inferior in gloss)
Δ: Slightly bad (slightly cloudy and poor gloss)
X: Poor (almost opaque and cloudy)
(40) Tack resistance The coating surface of the test piece for evaluation was directly touched with a finger, and the stickiness was evaluated in four stages.
A: Excellent (no stickiness)
○: Good (although there is some stickiness, fingers do not stick to the surface of the coating film)
Δ: Slightly bad (there is stickiness and fingers stick to the surface of the coating film)
X: Bad (stickiness is severe and fingers stick to the surface of the coating film)
(41) Adhesion In accordance with JIS K5400, after putting a grid with a cutter knife and pasting the cellophane tape, the cellophane tape is peeled off at an angle of 90 degrees, and the degree of peeling from the base material of the coating film in four stages evaluated.
A: Excellent (no peeling at all)
○: Good (slightly peeled, but less than 10%)
Δ: Slightly bad (10% or more and less than 50% peeled)
X: Poor (50% or more peeled off)
(42) Antifogging property The antifogging property was evaluated by the breath antifogging method using an evaluation test piece coated with an antifogging paint. In a constant temperature and humidity room at 23 ° C. and a relative humidity of 50%, exhaled air was sprayed from a distance of 15 cm on a glass plate with an antifogging coating for 1 second, and the cloudy state was visually observed and evaluated in four stages.
A: Excellent (not cloudy at all)
○: Good (slightly cloudy for a moment, then cloudy soon)
Δ: Slightly bad (slightly cloudy)
×: Poor (clear cloudiness is confirmed)
(43) Antifouling property A mixed liquid of oil / carbon pigment = 1/1 is used as a contaminant to cause streaks to adhere to the coating film of the test piece for evaluation. After 3 hours, running water is applied for 1 minute from above to clean the mixed liquid. The performance was visually confirmed and evaluated in four stages.
A: Excellent (no dirt remains on the surface of the test piece, and no trace of dirt is observed)
○: Good (no dirt remains on the surface of the test piece, but a trace of dirt flow is slightly recognized.)
Δ: Slightly bad (slight dirt remains on the surface of the test piece)
X: bad (contamination remains considerably on the surface of the test piece)
(44) Water resistance After the test specimen for evaluation was immersed in warm water at 40 ° C. for 240 hours, it was dried at room temperature, and the appearance of the coating film was visually observed. Compared with the appearance before the test, it was evaluated in four stages.
A: Excellent (no change)
○: Good (the coating film surface is slightly rough)
Δ: Slightly bad (the surface of the coating film is rough or slightly whitened or stained)
X: Poor (part or all of the coating film is dissolved, or whitening or spots are clearly observed)
(45) Durability The test specimen for evaluation was allowed to stand in a thermostat at 60 ° C. and 90% relative humidity for 5 minutes, and then dried at 90 ° C. for 5 minutes. This was defined as 1 cycle, and after 5 cycles, the antifogging property was evaluated by the breath antifogging method as described above.
(46) Humidity and heat yellowing resistance Using the obtained test pieces with an antifogging film, the resistance to moisture and heat yellowing was evaluated in the same manner as described above.
(47) Corrosion resistance After the moisture and heat yellowing test, the surface of the aluminum substrate was visually observed, and the corrosion resistance of the cured film was evaluated in the same manner as described above and the copper foil.

Examples I-1 to 8 and Comparative Examples I-9 to 12
Using the polymer composition obtained in Example A and the polymer obtained in Example B, an active energy ray-curable hard coating composition having the composition shown in Table 11 was prepared. A coating layer having a thickness of 3 μm was formed on the film and cured by irradiating with an ultraviolet LED lamp (UV-LED) to evaluate UV-LED curability and physical properties of the obtained hard coat. The evaluation results are shown in Table 11.

Method for producing active energy ray coating film Using the obtained hard coating composition, a 100 μm-thick PET film anchor coat surface is coated with a bar coater (RDS 1) so that the thickness of the dry coating film becomes 3 μm. A coating film was prepared. When the solvent was contained, the obtained coating film was dried at 80 ° C. for 2 minutes with an explosion-proof dryer. The UV-LED irradiator in which the distance between the coating film and the lamp was adjusted so that the ultraviolet energy of the obtained coating film was 2.7 mJ / cm 2 per second (HOYA CANDEO OPTRONICS Co., Ltd. EXERCURE-H-1VC2, sport type) ) To prepare a UV-LED cured film. The UV-LED curability was evaluated by the following method, and the adhesion of the cured film, the pencil strength and the scratch resistance were evaluated by the following method, and the results are shown in Table 11.

(48) Curability Using the dried coating film, the resin composition was cured by the above-mentioned UV-LED irradiation, and the time required for complete curing was measured, and the integrated light amount was calculated. Complete curing is a state in which no trace is left when the surface of the cured film is traced with silicon rubber.
(49) Adhesiveness Using the obtained test piece with a coating film, adhesiveness evaluation was performed in the same manner as described above.
(50) Scratch resistance Using a # 0000 steel wool, while applying a load of 200 g / cm ² , the surface of the obtained coating film was rubbed 10 times, and the presence or absence of scratches was visually evaluated.
A: The film is hardly peeled or scratched.
○: Slight thin scratches are observed on a part of the film.
Δ: Streaky scratches are observed on the entire surface of the film.
X: Peeling of the film occurs.
(51) Pencil hardness It evaluated based on JISK54008.4 hand-drawing method (1990 version) using the obtained test piece with a coating film.
(52) Light yellowing resistance In the same manner as described above, a hard coating composition was used to prepare a coating film on a PC substrate instead of a PET film. Using the obtained PC board with a coating film as a test piece, evaluation of light yellowing resistance was performed in the same manner as described above.

  As shown in the evaluation results of the respective examples and comparative examples described above, the polymerizable resin composition containing the N-substituted (meth) acrylamide of the present invention has a total base number of 12.0 KOHmg / g or less, total acid By controlling the difference between the total base number and the total acid number (total base number-total acid number) within the range of -1.0 to 5.0 KOHmg / g As a result, it was confirmed that yellowing did not occur with respect to light and that it was suitably used in various fields such as pressure-sensitive adhesives, adhesives, sealants, inks, antifogging agents, and hard coating agents. In addition, N-substituted (meth) acrylamide has good compatibility with various organic solvents, general-purpose monomers, and oligomers, and can easily prepare an optimal polymerizable resin composition according to each application. -Substituted (meth) acrylamide has extremely high energy ray curability, both thin and thick films can be cured easily, and the resulting cured product has low shrinkage, high transparency and excellent corrosion resistance, heat resistance and strength. It can be used widely for electronic materials, optical components, semiconductors, solar cells, etc.

  As described above, the polymerizable resin composition of the present invention is a special purification step or a worrisome addition as long as the total base number, total acid number and the difference thereof are within the range limited to the present invention. An industrial grade N-substituted (meth) acrylamide produced by a general production method is preferably used without blending the agent. In addition, it is possible to provide a resin composition that does not cause yellowing or coloration and does not cause corrosion of a metal using the polymerizable resin composition or a polymer composed thereof. Further, since there is no concern about yellowing, a large amount of N-substituted (meth) acrylamide can be blended in the resin composition, and adhesion to the substrate, weather resistance, heat resistance, scratch resistance ( Coating film hardness) and chemical resistance can be improved.

Claims (22)

General formula [1] (wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ may be the same or different and may be substituted with a hydrogen atom, a hydroxyl group, an amine group, an alkoxy group, or a carbonyl group). A linear or branched alkyl group having 1 to 6 carbon atoms, an aliphatic or aromatic ring having 3 to 6 carbon atoms, and R ₂ and R ₃ together with the nitrogen atom supporting them. And may form a saturated or unsaturated 5- to 7-membered ring which may further contain an oxygen atom or a nitrogen atom, except that R ₂ and R ₃ are simultaneously hydrogen atoms. The total base number is 12.0 KOHmg / g or less, the total acid number is 8.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total Base number-total acid number) is -1.0 to 5.0 KOHm g / g polymerizable resin composition
2. The polymerizable resin composition according to claim 1, comprising 1 to 90% by weight of N-substituted (meth) acrylamide as a monomer unit. The compound represented by the general formula [1] is (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-vinylpyrrolidone. Or at least one monomer selected from N-vinylcaprolactam, N-hydroxyethyl (meth) acrylamide, N-methyl-N-hydroxyethyl (meth) acrylamide, and diacetone acrylamide. Item 3. The resin composition according to Item 2 The active energy ray-curable resin composition further comprising a monomer having an unsaturated bond with a photopolymerization initiator in the polymerizable resin composition according to any one of claims 1 to 3. Polymer obtained by curing the composition according to claim 4 by irradiation with active energy rays The polymerizable resin composition according to any one of claims 1 to 3, further comprising a monomer having a thermal polymerization initiator and an unsaturated bond. A polymer obtained by polymerizing the composition according to claim 6 with heat. A pressure-sensitive adhesive composition comprising the composition according to claim 4 or 5 and / or the polymer according to claim 6 or 7. The pressure-sensitive adhesive composition according to claim 8, wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total base number -Total acid value) is -0.2 to 1.0 KOHmg / g. A coating composition comprising the composition according to claim 4 or 5 and / or the polymer according to claim 6 or 7. The coating composition according to claim 10, wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total base number -Total acid value) is -0.2 to 1.0 KOHmg / g, Coating composition for optical members The coating composition according to claim 10, wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total base number -Total acid value) is -0.2 to 1.0 KOHmg / g, coating composition for metal substrates, An ink composition comprising the composition according to claim 4 or 5 and / or the polymer according to claim 6 or 7. 14. The ink composition according to claim 13, wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total base number). -Total acid value) is -0.2 to 1.0 KOHmg / g. A resin composition for optical three-dimensional modeling, comprising the composition according to claim 4 or 5 and / or the polymer according to claim 6 or 7. An adhesive composition comprising the composition according to claim 4 or 5 and / or the polymer according to claim 6 or 7. The adhesive composition according to claim 16, wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total base number) -Total acid value) is -0.2 to 1.0 KOHmg / g, an optical adhesive composition characterized in that The adhesive composition according to claim 16, wherein the total base number is 3.0 KOHmg / g or less, the total acid number is 2.0 KOHmg / g or less, and the difference between the total base number and the total acid number (total base number) -Total acid value) is -0.2 to 1.0 KOHmg / g, the adhesive composition for electronic materials An encapsulant composition comprising the composition according to claim 4 or 5 and / or the polymer according to claim 6 or 7. 20. The sealant composition according to claim 19, wherein the total base number is 3.0 KOH mg / g or less, the total acid number is 2.0 KOH mg / g or less, and the difference between the total base number and the total acid number (total Base number-total acid number) is -0.2 to 1.0 KOHmg / g, and is a sealing agent composition for organic EL devices An antifogging composition comprising the composition according to claim 4 or 5 and / or the polymer according to claim 6 or 7. Using any one or more of the compositions according to claims 9, 11, 14, 17 and 20, an optical film, applied to one or both sides of a sheet, and obtained by active energy ray irradiation, heat curing or lamination curing. Optical molded products