JP7281218B2 - Polymerizable composition using hydroxyalkyl (meth)acrylamide, its polymer, and molded article made of them - Google Patents

Description

The present invention exhibits extremely little coloring or discoloration even when exposed to heat or light, does not cause corrosion when in contact with metal, and uses hydroxyalkyl (meth)acrylamide as an N-substituted (meth)acrylamide. The present invention relates to a polymerizable resin composition used, a polymer obtained by polymerizing the composition, and a molded article comprising the composition and the polymer.

In recent years, N-substituted (meth)acrylamides have been used in adhesives for optical components, active energy curable adhesives for polarizing plates, stereolithography resin compositions and inkjet 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 cohesive strength of the amide group is high, the adhesion to various substrates is excellent, and there is no corrosiveness 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 prone to yellowing due to light irradiation or heating, and if it contains an acidic component such as (meth)acrylic acid, it may cause corrosion to metals over a long period of time. I was afraid. Therefore, in applications such as electronic materials and optical materials, there have been cases where the blending amount of N-substituted (meth)acrylamide is reduced (Patent Document 8), or not used completely (Patent Documents 9 and 10).

Therefore, when N-substituted (meth)acrylamide is used as a resin composition component, in order to suppress the yellowing of the cured film over time, the present inventors reduce amine impurities (Patent Document 11) and oxidize It has been proposed to add an inhibitor, an ultraviolet absorber, and the like (Patent Documents 12 and 13). These proposals have certainly improved heat yellowing, but the cost has 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. , and there remains concern about the impact of additives on final products.

On the other hand, N-substituted (meth)acrylamide is often used as a constituent component of active energy ray-curable resins, but methods for suppressing coloring and discoloration due to light irradiation such as ultraviolet rays and visible light have not yet been reported.

JP 2008-287207 A JP 2011-122013 A JP-A-2001-310918 JP 2010-155889 A Japanese Unexamined Patent Application Publication No. 2011-137181 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 to contain hydroxyalkyl (meth)acrylamide as an industrial grade N-substituted (meth)acrylamide produced by a general production method without requiring a special purification process, A polymerizable resin composition that does not require the addition of additives of concern, exhibits extremely little coloration or discoloration (yellowing) when exposed to heat or light, and is useful as various functional materials including optical applications. offer things. In addition, a polymer obtained by polymerizing the polymerizable resin composition and having excellent wet heat yellowing resistance, light yellowing resistance and corrosion resistance, and a molded article manufactured using these polymerizable resin compositions and polymers are provided. It is to be.

The present inventors have made intensive studies to solve this problem, and found that the content of basic components and acidic components in a polymerizable resin composition using hydroxyalkyl (meth)acrylamide as the N-substituted (meth)acrylamide As a result of paying attention to, the total base number is 12.0 KOH mg / g or less, the total acid value is 8.0 KOH mg / g or less, and the difference between the total base number and the total acid number (total base number - total acid value) is Polymerizable resin excellent in yellowing resistance and corrosion resistance using hydroxyalkyl (meth)acrylamide as N-substituted (meth)acrylamide by controlling within the range of -1.0 to 5.0 KOHmg/g It has been found that a composition, a polymer of the composition, and a molded article made of them having excellent yellowing resistance and corrosion resistance can be obtained.

（式中、Ｒ_１は水素原子またはメチル基を示し、Ｒ_２及びＲ_３は、一方が水素原子、他方が水酸基で置換された、炭素数１乃至６の直鎖状或いは分岐鎖状のアルキル基を示す。）
（２）前記単官能モノマー（ヒドロキシアルキル（メタ）アクリルアミドを除く）は、アミド基を含有するモノマーを含むことを特徴とする前記（１）に記載の熱重合性樹脂組成物、
（３）前記単官能モノマー（ヒドロキシアルキル（メタ）アクリルアミドを除く）は、（メタ）アクリル酸エステルを含むことを特徴とする前記（１）又は（２）に記載の熱重合性樹脂組成物、
（４）前記アミド基を含有するモノマー（ヒドロキシアルキル（メタ）アクリルアミドを除く）が、（メタ）アクリロイルモルホリン、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－メチル－Ｎ－ヒドロキシエチル（メタ）アクリルアミド、ダイアセトンアクリルアミドから選ばれる１種以上であることを特徴とする前記（２）に記載の熱重合性樹脂組成物、
（５）前記（１）～（４）のいずれか一項に記載の熱重合性樹脂組成物を熱により重合して得られる重量平均分子量が１０００～９５万の重合物、
（６）前記（１）～（４）のいずれか１項に記載の熱重合性樹脂組成物の重合物又は前記（５）に記載の重合物、及び架橋剤からなる粘着剤組成物であって、
架橋剤の含有量は、重合物１００重量部に対して０．１～１５重量部であり、
該粘着剤組成物の、全塩基価は１２．０ＫＯＨｍｇ／ｇ以下であり、全酸価は８．０ＫＯＨｍｇ／ｇ以下であり、かつ、該粘着剤組成物の全塩基価と全酸価の差は－１．０～５．０ＫＯＨｍｇ／ｇであることを特徴とする粘着剤組成物、
（７）前記（６）に記載の粘着剤組成物であって、該粘着剤組成物の、全塩基価は３．０ＫＯＨｍｇ／ｇ以下であり、全酸価は２．０ＫＯＨｍｇ／ｇ以下であり、かつ、該粘着剤組成物の全塩基価と全酸価の差は－０．２～１．０ＫＯＨｍｇ／ｇであることを特徴とする光学用粘着剤組成物、
（８）前記（１）～（４）のいずれか１項に記載の熱重合性樹脂組成物の重合物又は前記（５）に記載の重合物、多官能モノマー及び光重合開始剤からなる活性エネルギー線硬化性粘着剤組成物であって、
多官能モノマーの含有量は重合物１００重量部に対して０．０５～５０重量部であり、
光重合開始剤の含有量は該粘着剤組成物中の０．１～１０重量％であり、
該粘着剤組成物の、全塩基価は１２．０ＫＯＨｍｇ／ｇ以下であり、全酸価は８．０ＫＯＨｍｇ／ｇ以下であり、かつ、該粘着剤組成物の全塩基価と全酸価の差は－１．０～５．０ＫＯＨｍｇ／ｇであることを特徴とする活性エネルギー線硬化性粘着剤組成物、
（９）前記（８）に記載の活性エネルギー線硬化性粘着剤組成物であって、該粘着剤組成物の、全塩基価は３．０ＫＯＨｍｇ／ｇ以下であり、全酸価は２．０ＫＯＨｍｇ／ｇ以下であり、かつ、該粘着剤組成物の全塩基価と全酸価の差は－０．２～１．０ＫＯＨｍｇ／ｇであることを特徴とする光学用活性エネルギー線硬化性粘着剤組成物
（１０）金属基材の片面若しくは両面、又は２以上の金属基材の間に配置された、前記（１）～（４）のいずれか１項に記載の熱重合性樹脂組成物及び／又は前記（６）～（９）のいずれか１項に記載の粘着剤組成物を硬化させてなる粘着剤層。
を提供することである。 That is, the present invention
(1) Contains 1 to 90% by weight of hydroxyalkyl(meth)acrylamide represented by general formula [1], 10 to 99% by weight of monofunctional monomers (excluding hydroxyalkyl(meth)acrylamide), and a thermal polymerization initiator A thermopolymerizable resin composition that
The content of the thermal polymerization initiator is 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of polymerizable monomer components,
The total base number of the thermopolymerizable resin composition is 12.0 KOHmg/g or less,
The total acid value of the thermopolymerizable resin composition is 8.0 KOHmg/g or less, and
A thermopolymerizable resin composition, wherein the difference between the total base number and the total acid number (total base number - total acid number) of the thermopolymerizable resin composition is -1.0 to 5.0 KOHmg/g. ,

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are linear or branched alkyl having 1 to 6 carbon atoms, one of which is a hydrogen atom and the other is a hydroxyl group. indicates the group.)
(2) The thermopolymerizable resin composition according to (1) above, wherein the monofunctional monomer (excluding hydroxyalkyl (meth)acrylamide) contains a monomer containing an amide group;
(3) The thermopolymerizable resin composition according to (1) or (2) above, wherein the monofunctional monomer (excluding hydroxyalkyl (meth)acrylamide) contains a (meth)acrylic acid ester,
(4) the amide group-containing monomer (excluding hydroxyalkyl(meth)acrylamide) is (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N- (2) above, characterized in that it is one or more selected from isopropyl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-methyl-N-hydroxyethyl (meth)acrylamide, and diacetoneacrylamide The thermopolymerizable resin composition described,
(5) a polymer having a weight average molecular weight of 1,000 to 950,000 obtained by thermally polymerizing the thermopolymerizable resin composition according to any one of (1) to (4);
(6) A pressure-sensitive adhesive composition comprising the polymer of the thermopolymerizable resin composition according to any one of (1) to (4) or the polymer according to (5), and a cross-linking agent. hand,
The content of the cross-linking agent is 0.1 to 15 parts by weight with respect to 100 parts by weight of the polymer,
The adhesive composition has a total base number of 12.0 KOHmg/g or less, a total acid number of 8.0 KOHmg/g or less, and a difference between the total base number and the total acid number of the adhesive composition. is -1.0 to 5.0 KOHmg / g adhesive composition,
(7) The pressure-sensitive adhesive composition according to (6) above, wherein the pressure-sensitive adhesive composition has a total base number of 3.0 mg KOH/g or less and a total acid value of 2.0 mg KOH/g or less. and an optical pressure-sensitive adhesive composition, wherein the difference between the total base number and the total acid number of the pressure-sensitive adhesive composition is -0.2 to 1.0 KOHmg/g;
(8) The polymer of the thermopolymerizable resin composition according to any one of (1) to (4) above or the polymer according to (5) above, an activity comprising a polyfunctional monomer and a photopolymerization initiator An energy ray-curable pressure-sensitive adhesive composition,
The content of the polyfunctional monomer is 0.05 to 50 parts by weight with respect to 100 parts by weight of the polymer,
The content of the photopolymerization initiator is 0.1 to 10% by weight in the adhesive composition,
The adhesive composition has a total base number of 12.0 KOHmg/g or less, a total acid number of 8.0 KOHmg/g or less, and a difference between the total base number and the total acid number of the adhesive composition. is -1.0 to 5.0 KOHmg/g, an active energy ray-curable pressure-sensitive adhesive composition,
(9) The active energy ray-curable pressure-sensitive adhesive composition according to (8) above, wherein the pressure-sensitive adhesive composition has a total base number of 3.0 KOHmg/g or less and a total acid number of 2.0 KOHmg. /g or less, and the difference between the total base number and the total acid number of the adhesive composition is -0.2 to 1.0 KOHmg/g. Composition (10) The thermopolymerizable resin composition according to any one of (1) to (4), disposed on one or both sides of a metal substrate, or between two or more metal substrates; and / Or a pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition according to any one of (6) to (9).
is to provide

The polymerizable resin composition using hydroxyalkyl (meth)acrylamide as the N-substituted (meth)acrylamide of the present invention has low viscosity and high curability, and is excellent in heat resistance, adhesion and transparency. can be suitably used as adhesives, adhesives, sealants, coating agents, anti-fogging agents, and inks in the It is. The resin composition of the present invention, including optical applications, does not require a special purification process or compounding of additives of concern, and industrial hydroxyalkyl (meth)acrylamide can be used as a raw material monomer or a constituent component. . In addition, it is possible to incorporate a large amount of hydroxyalkyl (meth)acrylamide into the resin composition, and improvement in weather resistance, heat resistance, scratch resistance, and chemical resistance can be expected.

The present invention will now be described in detail.
Hydroxyalkyl (meth)acrylamide as N-substituted (meth)acrylamide, which is a component of the polymerizable resin composition of the present invention, is represented by general formula [1] (wherein R ₁ represents a hydrogen atom or a methyl group, One of R ₂ and R ₃ represents a linear or branched C 1-6 alkyl group substituted with a hydrogen atom and the other with a hydroxyl group.

N-substituted (meth)acrylamides specifically include, for example, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl (Meth)acrylamide, N-isobutyl (meth)acrylamide, N-hexyl (meth)acrylamide, N-alkoxy (linear or branched structure with 1 to 6 carbon atoms) alkyl (linear or branched structure with 1 to 6 carbon atoms) ) (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)acrylamide, 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. These are not limited to one type, and a plurality of types may be used in combination. In addition, from the viewpoint of easy availability as industrial products and high curability, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, (meth)acryloylmorpholine, N-hydroxyethylacrylamide, N-methyl-hydroxyethyl acrylamide, diacetone acrylamide, N-isopropyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam are preferred.

The resin composition of the present invention has a total base number of 12.0 KOHmg/g or less and a total acid number of 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 preferably -1.0 to 5.0 mg/g. Here, the total base number of the composition is the sum of base numbers derived from basic constituents and basic impurities contained in N-substituted (meth)acrylamide and other neutral components. The basic constituents and impurities are not particularly limited as long as they are alkaline compounds, but from the viewpoint of the yellowing resistance of the present invention, the reduction of the base number derived from amines is most preferable. Since amines have a lone pair of electrons on the nitrogen atom, they are easy to color, and at the same time, the vinyl group contained in the composition, the amide group of N-substituted (meth)acrylamide, and the (meth)acrylate polyfunctional, monofunctional monomer The present inventors presume that the effect on ester groups and the like is large.

In the present invention, the total acid value of the composition is the sum of the acid values derived from the acidic constituents and the acidic impurities contained in the N-substituted (meth)acrylamide and other neutral components. Here, the acidic constituents and impurities are not particularly limited as long as they are acidic compounds. The acid value of has a large effect on the vinyl group contained in the composition, the amide group of N-substituted (meth)acrylamide, the (meth)acrylate polyfunctional, the ester group of a monofunctional monomer, etc., and their reduction is most preferable. The inventors think that

If the total base number, the total acid number, and the difference between them are outside the above ranges, the molded article using the resin composition may turn yellow over time due to heat or light, and contact with metals or metal oxides may result in yellowing. It can lead to corrosion.

The resin composition of the present invention can be produced by uniformly mixing various components including the N-substituted (meth)acrylamide in predetermined proportions. If the total base value of the composition, the total acid value, and the difference between them are not within the above range, a method of neutralizing by adding an acidic or basic component, or a specific acidity or It may be adjusted by ordinary means such as a method of removing basic components and purifying.

When adjusting the total base number of the resin composition of the present invention, the total acid number and the difference between them, as a method of neutralizing by adding an acidic or basic component, an acidic or basic gas is added to the resin composition. and a method of adding an acidic or basic liquid or solid into the resin composition. Both inorganic and organic compounds can be used as the acidic component and the basic component. As solid acids or bases, powders, particles such as ion-exchange resins, and chelating agents immobilized on carriers can also be used. Depending on the state, type and amount of the neutralizing agent used, the product of the neutralization reaction may remain in the composition, but it is preferable to remove it by an ordinary method such as filtration, distillation or centrifugation. . Furthermore, it is particularly preferable to use a polymerizable acid or base because the product after neutralization becomes a component of the composition.

When adjusting the total base number, the total acid number, and the difference between the total base number and the total acid number of the resin composition of the present invention, as a method for purifying by removing the acidic or basic component contained in the composition, distillation by boiling point difference or ionic Examples thereof include adsorption using exchange resins, separation using osmotic membranes based on differences in molecular size and osmotic pressure, reverse osmosis membranes, and electrophoretic separation. Both batch and continuous flow systems can be used. From the viewpoint of ensuring high yield and removal, the method of passing through a packed column or cartridge of ion exchange resin is preferable.

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

The resin composition of the present invention can be used as a pressure-sensitive adhesive for optical members, a pressure-sensitive adhesive sheet, an active energy-curable adhesive for polarizing plates, a resin composition for stereolithography, an inkjet ink, and glass, which have conventionally been problematic in terms of coloring and corrosion. It can be used for modifying coating agents for resin moldings, sealing agents for organic EL elements, and the like. The resin composition at this time has a total base value of 3.0 KOHmg / g, a total acid value of 2.0 KOHmg / g or less, and a difference between the total base value and the total acid value (total base value - total acid value) -0 .2 to 1.0 KOHmg/g is more preferred. If the total base number, total acid number, and their difference are within these ranges, the molded product will not deteriorate in performance due to yellowing, reddish discoloration, or corrosion over a long period of time, and transparency will be maintained. can.

The resin composition of the present invention may contain 100% by weight of N-substituted (meth)acrylamide as a monomer unit, but preferably contains 1 to 90% by weight. Further, the N-substituted (meth)acrylamide content in the resin composition is more preferably 5 to 70% by weight. By blending the N-substituted (meth)acrylamide, it is possible to dilute the resin and improve performance such as adhesion, compatibility and curability of the resin composition. If the content is less than 1%, the properties of the N-substituted (meth)acrylamide cannot be exhibited sufficiently, 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 adding a photopolymerization initiator and a monomer having an unsaturated bond to N-substituted (meth)acrylamide. In addition, depending on the purpose of viscosity adjustment, a monofunctional monomer having one unsaturated bond, a polyfunctional monomer for the purpose of adjusting the cross-linking rate, a monofunctional or polyfunctional oligomer, a non-polymerizable polymer, etc. for improving flexibility. Can be used together. These combined components may be added singly to the N-substituted (meth)acrylamide, or two or more of them may be combined. The amount of each compound may be appropriately adjusted according to the specific application, but 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 acrylic, etc.

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, (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 (meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified diphosphoric acid (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, tricyclodecanedimethanol di(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 di(meth)acrylate, alkoxylated cyclohexanedimethanol di(meth)acrylate, epoxy (meth)acrylate, urethane (meth) Examples include monomers and oligomers such as acrylates and urethane (meth)acrylamides. In addition, from the viewpoint of easy commercial availability, urethane acrylates, for example, manufactured by Nippon Synthetic Chemical Co., Ltd., trade names UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-3310B, UV-7000B and new Nakamura Chemical Co., Ltd., trade names U-4HA, U-200PA, Daicel Cytec Co., Ltd., trade names EBECRYL245, EBECRYL1259, EBECRYL8210, EBECRYL284, EBECRYL8402, SARTOMER, trade names CN944, CN969, CN9002, CN9029, root upper industry manufactured by KJ Chemicals, KJSA5100, KJSA6100, etc. can be used as urethane (meth)acrylamide. Epoxy resins such as EBECRYL1259, EBECRYL605 and EBECRYL1606 manufactured by Daicel Cytec, and CN110, CN120 and CN153 manufactured by SARTOMER can be used as epoxy resins. As the acrylic resin, products such as SARTOMER trade names CN2203 and CN2270 and Toagosei Co. trade names M-6100 and M-8060 can be used. Further, 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 type of these polyfunctional (meth)acrylates may be used alone, or two or more types may be used in combination.

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

Monofunctional monomers used in the resin composition of the present invention include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, unsaturated nitrile monomers, styrene, amide group-containing monomers, methylol group-containing monomers, and alkoxymethyl group-containing monomers. , vinyl esters, olefins, and other radically polymerizable compounds having a reactive double bond in the molecular chain.

The monofunctional (meth)acrylates include, for example, 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, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) ) acrylate, 2-(2-ethoxyethoxy) ethyl acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene 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.

The monofunctional (meth)acrylamides include, for example, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, 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. mentioned.
One of these monofunctional monomers may be used alone, or two or more thereof may be used in combination.

Oligomers and polymers used in the resin composition of the present invention include linear and/or branched oligomers and polymers having skeletons such as acrylic, ester, ether, urethane, and amide. Oligomers composed of the 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. Acrylate, bifunctional polyester (meth)acrylate, multifunctional polyester (meth)acrylate, bifunctional polyether (meth)acrylate, multifunctional polyether (meth)acrylate, bifunctional polyamide (meth)acrylate, multifunctional polyamide (meth)acrylate Acrylate, bifunctional poly(meth)acrylate (meth)acrylate, multifunctional poly(meth)acrylate (meth)acrylate, bifunctional poly(meth)acrylate (meth)acrylamide, multifunctional poly(meth)acrylate) Acrylic acid ester (meth)acrylamide, bifunctional poly(meth)acrylamide (meth)acrylate, multifunctional poly(meth)acrylamide (meth)acrylate, bifunctional polystyrene (meth)acrylate, multifunctional polystyrene (meth)acrylate, bifunctional Examples include 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 coated or molded on a substrate and then cured by irradiation with an active energy ray. Molded articles can be produced having membranes and adhesives, adhesives, sealants, and the like.

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

The active energy ray irradiation is preferably performed in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or in an atmosphere with a reduced oxygen concentration, but the resin composition of the present invention contains N-substituted (meth)acrylamide. Therefore, it has good curability, and both thin and thick films 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 curing the active energy ray-curable resin composition of the present invention, a photopolymerization initiator may be added as necessary, but it is not particularly necessary when electron beams are used. The photopolymerization initiator may be appropriately selected from ordinary ones such as acetophenone series, benzoin series, benzophenone series, and thioxanthone series. Commercially available products manufactured by BASF, trade names: Darocur 1116, Darocur 1173, Irgacure 184, Irgacure 369, Irgacure 500, Irgacure 651, Irgacure 754, Irgacure 819, Irgacure 907, Irgacure 1300, Irgacure 1800, Irgacure 1870, Irgacure 2959, Darocur 4265, Darocur TPO, manufactured by UCB, trade name Uvecryl P36, and the like can be used. These photoinitiators can be used singly or in combination of two or more.

The amount of these photopolymerization initiators to be used is not particularly limited, but generally 0.1 to 10% by weight, preferably 1 to 5% by weight, is added to the active energy ray-curable resin composition. 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 deteriorate.

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

Examples of the monomer capable of introducing the cross-linking point include hydroxyl group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers, amino group-containing (meth)acrylic monomers, and acetoacetyl group-containing (meth)acrylic monomers. system monomers, isocyanate group-containing (meth)acrylic monomers, glycidyl group-containing (meth)acrylic monomers, oxazoline group-containing (meth)acrylic monomers, and the like.

Examples of the hydroxyl group-containing (meth)acrylic monomers 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 others, 2- Acryloyloxyethyl 2-hydroxyethyl phthalate, primary hydroxyl group-containing (meth) acrylic monomers such as N-methylol (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Secondary hydroxyl group-containing (meth) acrylic monomers such as hydroxy 3-phenoxypropyl (meth) acrylate, 3-chloro 2-hydroxypropyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, 2,2- Tertiary hydroxyl group-containing (meth)acrylic monomers such as dimethyl 2-hydroxyethyl (meth)acrylate can be mentioned. Among them, 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; etc., among which (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, N,N-di-t-butylaminoethyl (meth)acrylates, aminoalkyl (meth)acrylates such as N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N, Aminoalkyl (meth)acrylamides such as N-dimethylaminopropyl (meth)acrylamide can be mentioned.

Examples of the acetoacetyl group-containing (meth)acrylic monomer include 2-(acetoacetoxy)ethyl (meth)acrylate.

Examples of the isocyanate group-containing (meth)acrylic monomers 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, allylglycidyl (meth)acrylate, and (meth)acrylamidoglycidyl.

Examples of the oxazoline group-containing (meth)acrylic monomer 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. . Also, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline, which have high reactivity, are preferred, and 2-vinyl-2- Oxazolines are 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 thermally polymerizable resin composition can be carried out 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 are used. When a solution polymerization method in an organic solvent is employed for solution polymerization, there is no particular limitation as long as the solvent dissolves the polymer obtained by polymerization. Examples of the polymerization solvent include benzene, toluene, ethylbenzene, and xylene. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane, esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc. ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetonitrile, N,N-dimethylformamide and the like. These organic solvents can be used alone or in combination of two or more. In particular, it is preferable to use low boiling point ethyl acetate, methyl ethyl ketone, acetone, etc., because they are easy to remove when forming a molded article.

As thermal radical polymerization initiators, azo compound catalysts such as azobisisobutyronitrile and azobisvaleronitrile, peroxide catalysts such as benzoyl peroxide and hydrogen peroxide, ammonium persulfate and sodium persulfate. persulfate-based catalysts such as The amount of the polymerization initiator to be used is usually about 0.001 to 10% by weight based on the total weight of the polymerizable monomer components. Furthermore, usual radical polymerization techniques such as adjustment of molecular weight with a chain transfer agent are applied.

The weight average molecular weight of the polymer of the present invention is 1,000 to 3,000,000, preferably 5,000 to 2,500,000, more preferably 10,000 to 2,000,000. If the weight-average molecular weight is within the range of 1,000 to 3,000,000, the viscosity of the solution when dissolved in a solvent is neither too high nor too low, so that it can be suitably handled, and the processing accuracy of coating films, sheets, etc. is high. expensive. When such a polymer is diluted with ethyl acetate to 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. , and particularly preferably 2000 to 5000 mPa·s/25°C. 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, adhesive strength, adhesion to various substrates, heat resistance, and durability, so that it can be used as it is. Furthermore, by cross-linking with a cross-linking agent, it is possible to obtain a product having more excellent heat resistance and durability. Examples of the cross-linking method include (1) a method of cross-linking using a cross-linking agent, and (2) a method of cross-linking by incorporating an unsaturated group-containing compound and a polymerization initiator and using active energy rays and/or heat. be done. One of these crosslinking methods may be used, or both may be used in combination.

The (1) method of cross-linking using a cross-linking agent includes a compound having a functional group capable of reacting with the functional group contained in the (meth)acrylic resin, such as an isocyanate compound, an epoxy compound, an aziridine compound, or a carboxyl group compound. is added and allowed to react.

Among them, isocyanate compounds 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, isocyanate compounds include, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; - Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, aromatic diisocyanates such as xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate L), tri Isocyanate adducts such as methylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HL), isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX) etc. These isocyanate compounds may be used alone or in combination of two or more.

Examples of epoxy compounds include polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerin diglycidyl ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, 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 commercially available products such as HDU, TAZM, and TAZO (manufactured by Sogo Pharmaceutical Co., Ltd.). These compounds may be used alone or in combination of two or more.

Carboxyl group compounds such as L-lactic acid, D-lactic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxyl group, 2,6-naphthalenedicarboxyl group, diphenyldicarboxyl group, diphenoxyethanedicarboxyl group, diphenyl ether Dicarboxyl group, aromatic dicarboxyl group such as diphenylsulfonedicarboxyl group, alicyclic dicarboxyl group such as 1,3-cyclopentanedicarboxyl group, 1,3-cyclohexanedicarboxyl group, 1,4-cyclohexanedicarboxyl 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 and other aliphatic dicarboxylic acids, glycolic acid, 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxyl groups, and their ester-forming properties A compound having a dicarboxyl group derived from a derivative or the like can be mentioned. These compounds may be used alone or in combination of two or more.

The amount of these cross-linking agents to be used can be appropriately selected depending on the balance between the amount of functional groups contained in the polymer to be cross-linked and the molecular weight, and further depending on the purpose of use. On the other hand, the content is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight. If the content is less than 0.1% by weight, the cross-linking formation by the cross-linking agent may be insufficient, and the cohesion of the molded product such as the pressure-sensitive adhesive may be insufficient, resulting in insufficient heat resistance. It tends to cause sticky residue. On the other hand, when the content exceeds 15% by weight, the cohesive force of the resin composition after cross-linking is large, the flexibility and elasticity are lowered, and the conformability (wettability) to the adherend tends to be insufficient. .

Furthermore, together with the cross-linking agent, it is possible to use an acid catalyst, for example, a cross-linking accelerator such as p-toluenesulfonic acid, phosphoric acid, hydrochloric acid, ammonium chloride, etc., in order to promote cross-linking. The amount is preferably 10-50% by weight relative to the cross-linking agent.

(2) The method of incorporating an unsaturated group-containing compound and a polymerization initiator and cross-linking with active energy rays and/or heat includes two or more active energy rays and/or heat-reactive unsaturated bonds as a cross-linking agent. A method of adding a polyfunctional monomer and a polymerization initiator and cross-linking with an active energy ray and/or heat can be mentioned.

Examples of polyfunctional monomers having two or more active energy rays and/or heat-reactive unsaturated bonds include vinyl groups, acryloyl groups, methacryloyl groups, vinylbenzyl groups, and cross-linking treatment by irradiation with active energy rays and/or heat. A polyfunctional monomer component having one or more active energy rays and/or two or more heat-reactive unsaturated bonds capable of (curing) is used. In general, one having 10 or less active energy rays and/or thermally reactive unsaturated bonds is 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. Specific 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, 1,6-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, phthalate diglycidyl ester Monomers such as di(meth)acrylates, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylates, ethylene oxide isocyanurate-modified diacrylates, and 2-(meth)acryloyloxyethyl acid phosphate diesters can be mentioned.

Examples of the trifunctional or higher 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 dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, and succinic acid-modified pentaerythritol tri(meth)acrylate.

The amount of the polyfunctional monomer used is preferably 0.05 to 50% by weight based on the polymer to be crosslinked, and more preferably 0.05% from the viewpoint of flexibility and adhesiveness (adhesion). 1 to 30% by weight. If the content is less than 0.05% by weight, cross-linking by the cross-linking agent may be insufficient, resulting in insufficient cohesion and insufficient heat resistance when used in pressure-sensitive adhesives or adhesives. On the other hand, if the content exceeds 50% by weight, for example, the cohesive strength of the polymer becomes too high, the flexibility and adhesive strength are reduced, and the wettability to the adherend becomes insufficient, causing peeling. Tend.

Pigments, dyes, surfactants, antiblocking agents, leveling agents, dispersants, antifoaming agents, antioxidants, UV sensitizers, as long as they do not impair the properties of the resin composition of the present invention and the molded articles produced therefrom. Other optional ingredients such as agents and preservatives may be used in combination.

The resin composition of the present invention can be applied to substrates such as paper, cloth, non-woven fabric, glass, polyethylene terephthalate, diacetate cellulose, triacetate cellulose, acrylic polymers, polyvinyl chloride, cellophane, celluloid, polycarbonate, polyimide and other plastics and metals. A high-performance coating layer, ink layer, pressure-sensitive adhesive layer, sealant layer, or adhesive layer can be obtained by coating and curing the surface or interstices. 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 coating materials for optical films It can be preferably used as. Methods for applying these resin compositions onto substrates include spin coating, spray coating, dipping, gravure roll, knife coating, reverse roll, screen printing, bar coater and the like. can be used. Moreover, the lamination method, the roll-to-roll method, etc. are mentioned as a method of apply|coating between base materials.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The abbreviations of the components described in Examples and Comparative Examples are as follows.
(1) N-substituted (meth)acrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademark “Kohsylmer”)
"DEAA": N,N-diethylacrylamide (registered trademark "DEAA")
"DMAA": N,N-dimethylacrylamide (registered trademark "DMAA")
"ACMO": acryloylmorpholine (registered trademark "ACMO")
"NIPAM": N-isopropylacrylamide (registered trademark "NIPAM")
"HEAA": N-hydroxyethyl acrylamide (registered trademark "HEAA")
MHEAA: N-methyl-N-hydroxyethylacrylamide HEMAA: N-hydroxyethylmethacrylamide "DMAPAA": N,N-dimethylaminopropylacrylamide (registered trademark "DMAPAA")
(2) Polyfunctional monomers, oligomers, polymers PETA: Pentaerythritol triacrylate DPHA: Dipentaerythritol hexaacrylate HDDA: 1,6-hexanediol diacrylate TPGDA: Tripropylene glycol diacrylate UV6640B: Urethane acrylate (Nippon Synthetic Chemical Co., Ltd. ) made)
U200-PA: urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
KJSA-6100: urethane acrylamide (manufactured by KJ Chemicals Co., Ltd.)
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) Others 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) (manufactured by 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 is expressed in mg of potassium hydroxide equivalent to hydrochloric acid or perchloric acid required to neutralize all basic components contained in 1 g of the resin composition. K7237-1995 was referred to, and measured with a potentiometric automatic titrator. As a measurement solvent, one or a mixture of two or more selected from deionized water, methanol, ethanol, isopropanol, and tetrahydrofuran was used according to the solubility of the resin composition. The procedure is described below.
10 g of the resin composition was accurately weighed into a 200 mL beaker, and 50 mL of a measurement solvent (special grade product) was added and uniformly dissolved to obtain a sample solution. 50 mL of the measurement solvent was added to a 200 mL beaker to prepare a blank solution. Each of the sample liquid and the blank liquid 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 by Equation 1 to determine the total base number (KOH mg/L) (F indicates the factor of the titrant determined using standard hydrochloric acid solution, where F=1.000). Composite glass electrode C-173 (manufactured by Horiba, Ltd.) was used for the measurement.

formula 1

（６）全酸価
全酸価は樹脂組成物１ｇに含まれる酸性成分を中和するのに要する水酸化カリウムのｍｇ数で表し、本発明はＪＩＳ Ｋ００７０－１９９２を参考に、電位差自動滴定装置により測定した。測定溶媒は樹脂組成物の溶解性と酸性成分の解離能に合わせて脱イオン水、メタノール、エタノール、イソプロパノール、テトラヒドロフランの中から選べる１種また２種以上の混合物を用いた。以下に手順を述べる。
２００ｍＬ容量のビーカーに樹脂組成物２０ｇと測定溶媒（特級品）（例えば、テトラヒドロフラン／脱イオン水＝５／１、ｖ／ｖ）１２０ｍＬを入れて均一に溶解させ、サンプル液とした。測定溶媒１２０ｍＬを２００ｍＬのビーカーに加え、ブランク液とした。サンプル液とブランク液それぞれを自動電位差滴定装置により、濃度０．０４２５ｍｏｌ／Ｌの 水酸化カリウム水溶液（又はエタノール溶液）にて滴定した。滴定結果を式２により計算し、全酸価（ＫＯＨｍｇ/Ｌ）を求めた（Ｆは標準塩酸溶液を用いて求めた滴定液のファクターを示す。ここでＦ＝１．０００）。なお、測定には複合ガラス電極Ｃ－１７１（（株）堀場製作所製）を用いた。

(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. Measured by As the measurement solvent, one or a mixture of two or more selected from deionized water, methanol, ethanol, isopropanol, and tetrahydrofuran was used according to the solubility of the resin composition and the ability to dissociate the acidic component. The procedure is described below.
20 g of the resin composition and 120 mL of a measurement solvent (special grade) (eg, tetrahydrofuran/deionized water = 5/1, v/v) were placed in a 200 mL beaker and uniformly dissolved to obtain a sample solution. 120 mL of the measurement solvent was added to a 200 mL beaker to prepare a blank solution. Each of the sample liquid and the blank liquid was titrated with an aqueous potassium hydroxide solution (or ethanol solution) having a concentration of 0.0425 mol/L using an automatic potentiometric titrator. The titration result was calculated by Equation 2 to determine the total acid value (KOH mg/L) (F indicates the factor of the titrant determined using standard hydrochloric acid solution, where F=1.000). Composite glass electrode C-171 (manufactured 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 uniformly mixed at room temperature to measure the total base number and total acid number. As shown in Table 1, confirm that the total base number of the mixture is 1.0 KOHmg / g, the total acid number is 1.2 KOHmg / g, and the difference between the total base number and the total acid number is -0.2 KOHmg / 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 constituents were accurately measured in proportions 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 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. 0 to 5.0 KOHmg/g, and the polymerizable resin composition of the present invention was obtained without reprocessing.

Example A-11
70 g of "DMAA", 15 g of EBECRY 112, 5 g of TPGDA, 5 g of HEA and 5 g of THFA were weighed out, mixed uniformly at room temperature, and the total base number and total acid number were measured. and 3.3 KOH mg/g. The mixed solution was passed through a glass column packed with 10 g of a strongly acidic ion exchange resin (manufactured by Mitsubishi Chemical Corporation, trade name Diaion SK1B). The mixture after passing the liquid was analyzed again, and the total base number was 11.5 KOHmg/g, the total acid number was 7.2 KOHmg/g, and the difference between the total base number and the total acid number was 4.3 KOHmg/g. and the polymerizable resin composition of the present invention.

Example A-12
10 g of HEMAA, 20 g of UV-6640B, 40 g of HDDA, 20 g of HEA, 20 g of THFA, 1 g of AAc and 10 g of CHA were weighed and uniformly mixed at room temperature to measure the total base number and total acid number. 1.5 KOH mg/g and 25.8 KOH mg/g. 1.28 g of sodium hydroxide was added to the mixture, slowly stirred for 10 minutes, and further cooled with ice water for 1 hour. After that, a white solid precipitated in the mixed liquid was removed by filtration. The obtained transparent liquid mixture was analyzed again, and the total base number was 7.0 KOH mg/g, the total acid number was 8.0 KOH mg/g, and the difference between the total base number and the total acid number was -1.0 KOH mg/g. This fact was confirmed, and the polymerizable resin composition of the present invention was prepared.

Comparative Examples A-13 to A-17
In the same manner as in Example A-1, the constituent components such as N-substituted (meth)acrylamide were accurately measured in proportions 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 mg KOH/g, the total acid number exceeds 8.0 mg KOH/g, or the difference between the total base number and the total acid number is -1. Although it was confirmed that it was outside the range of 0 to 5.0 KOH mg/g, it was used as a comparative polymerizable resin composition of the present invention without reprocessing.

Add 3 parts by weight of D-1173 as a photopolymerization initiator to 100 parts by weight of the various polymerizable resin compositions obtained in Examples A-1 to A-12 and Comparative Examples A-13 to A-17. , and mixed uniformly to prepare an active energy ray-curable resin composition. Using these resin compositions, active energy ray-cured films were produced and their properties were evaluated by the following methods.

Using a desktop coater (coater TC-1, manufactured by Mitsui Electric Seiki Co., Ltd.), the mixed solutions of Examples A1 to A12 and Comparative Examples A13 to A17 were coated on an aluminum substrate (Al, A5052), then irradiated with ultraviolet rays (equipment: eye graphics inverter type conveyor device ECS-4011GX, metal halide lamp: eye graphics M04-L41, UV illuminance: 700 mW/cm ² , integrated light intensity: 3000 mJ/cm ² ) to obtain a cured film. The obtained cured film was slowly peeled off from the aluminum substrate, and the initial transparency (transparency) and yellowing resistance (yellowing degree b value) were measured according to the following methods. In addition, an accelerated test for wet heat yellowing resistance and light yellowing resistance was performed as described below, and the transparency and yellowing resistance after the test were similarly evaluated. Furthermore, using an amyl substrate and a copper foil as metal materials, corrosion resistance was evaluated by the following method, and the results are shown in Table 2.

(7) Transparency (Transmittance)
Using the obtained cured film at the initial stage or after the accelerated yellowing resistance test, it was left still for 24 hours in an atmosphere of a temperature of 23° C. and a relative humidity of 50%. Thereafter, the transmittance of the cured film was measured with a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the transparency was evaluated according to the following four stages.
◎: Transmittance is 90% or more ○: Transmittance is 85% or more and less than 90% △: Transmittance is 50% or more and less than 85% ×: Transmittance is less than 50% (8) Humidity and heat resistance to yellowing Using the initial cured film obtained, the film was allowed to stand still for 24 hours in an atmosphere of 23° C. and 50% relative humidity. After that, the transmission spectrum of the cured film was measured using a dedicated transmission color measuring machine (TZ-6000, manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain the initial b value. The cured film was allowed to stand in a thermo-hygrostat set at 85° C. and a relative humidity of 85% for 500 hours to conduct an accelerated test of yellowing resistance to moisture and heat. Similarly, the cured film after the test was left still for 24 hours in an atmosphere of 23° C. and 50% relative humidity, and the transmission color was measured, and the b value was obtained after wet heating. 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). The wet heat yellowing resistance was evaluated by dividing into four stages as follows.
◎: Both the initial b value and the b value after moist heat are 0.2 or less, and Δb is 0.1 or less ○: Either one or both of the initial b value and the b value after moist heat exceeds 0.2 , Both are 0.5 or less, and Δb is 0.2 or less △: Either one of the initial b value and the b value after moist heat exceeds 0.5, but both are 1.0 or less and Δb is 0.3 or less ×: Either one of the initial b value and the b value after moist heat or both exceeds 1.0, or Δb exceeds 0.3 (9) Light yellowing resistance above An accelerated test of light yellowing resistance was performed in the same manner as in the wet heat yellowing resistance evaluation, and the b value before and after the test and Δb, which is the difference between them, were measured and calculated. In the accelerated test of light yellowing resistance, an ultraviolet fade meter (U48, manufactured by Suga Test Instruments Co., Ltd.) was used, the black panel temperature was set to 63° C., and irradiation was performed for 168 hours under the conditions of 500 W/m 2 . Evaluation was performed by dividing into four levels in the same manner as the wet heat yellowing resistance.
(10) Corrosion resistance An active energy ray-cured film was prepared by the above method, and the cured film was slowly removed from the test piece (for evaluation of Al corrosion resistance) in which the obtained cured film was attached to the aluminum substrate, and the aluminum substrate. Using a test piece (for Cu corrosion resistance evaluation) that was peeled off and attached to a copper foil (thickness 80 μm), it was left for 168 hours in a constant temperature and humidity machine set at a temperature of 60° C. and a relative humidity of 95%. Thereafter, the cured film was peeled off from the aluminum substrate or copper foil, and the surfaces of the aluminum substrate and copper foil were visually observed to evaluate the corrosion resistance of the cured film.
◎: No corrosion ○: Slightly corroded △: Slightly corroded ×: Significant corrosion

Example B-1
40 g of "DEAA", 40 g of BA, 15 g of 2EHA, 5 g of 4HBA and 0.2 g of AIBN were weighed out and uniformly mixed at room temperature to measure the total base number and total acid number. As shown in Table 3, 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. Then, without reprocessing, the thermopolymerizable resin composition of the present invention was obtained.
200 g of ethyl acetate and 100 g of the thermopolymerizable resin composition were added to a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, and nitrogen gas was introduced while stirring to remove air from the apparatus. After purging with nitrogen, the temperature was raised to the reflux temperature, and the reaction was carried out for 7 hours while passing nitrogen. After completion of the reaction, ethyl acetate was added to obtain a polymer solution with a solid content of 30%. Using a cone-plate viscometer (manufactured by Toki Sangyo Co., Ltd., model RE550), the solution viscosity was measured at 25° C. according to JIS K5600-2-3 and was 3500 mPa·s.
Further, 30 parts of the polymer solution was taken out and the volatile components in the solution were completely removed to obtain a polymer. Then, it was dissolved in tetrahydrofuran (THF) to prepare a polymer solution having a concentration of 0.5% by weight, and allowed to stand overnight. The THF solution of the polymer was filtered through a 0.45 μm membrane filter, and the filtrate was subjected to gel permeation chromatography (GPC) measurement (Shimadzu Prominence GPC system, Shodex KF-806L column, eluent THF), The weight-average molecular weight (Mw) of the polymer was calculated to be 1,160,000 based on polystyrene conversion values.

Examples B-2 to B-6 and Comparative Examples B-7 to B-9
Examples B-2 to B-6 and Comparative Examples B-7 to B-9 of thermopolymerizable resin compositions in the same manner as in Example B-1, except for changing to the polymerizable composition shown in Table 3. was prepared and the total base number and total acid number were measured. Further, thermal polymerization was performed in the same manner, 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, 2 and Comparative Example C-11
The polymer solutions obtained in Examples B-1 and B-4 and Comparative Example B-7 were applied to a polyethylene terephthalate (PET) film having a thickness of 100 μm so that the thickness after drying was 25 μm, and the temperature was maintained at 90°C. and dried for 2 minutes to form an adhesive layer. Then, it was placed in an environment with a temperature of 23° C. and a relative humidity of 50% for one day to obtain a pressure-sensitive adhesive sheet for testing (type a).

Examples C-3, 4 and Comparative Example C-12
Further, 100 g of the 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 added. After adding and uniformly mixing, it was similarly coated on a PET film having a thickness of 25 μm after drying and dried at 90° C. for 2 minutes to form an adhesive layer. After that, it was aged in a constant temperature bath at 40° C. for 3 days, and placed in an environment with 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, 6 and Comparative Example C-13
100 g of the polymer solution with a solid content of 30% obtained in Examples B-2 and B-6 and 70 g of the polymer solution with a solid content of 30% obtained in Comparative Example B-9 were weighed, respectively, and polyfunctional 5 g of a 50% ethyl acetate solution of DPHA as a monomer and 1 g of a photopolymerization initiator I-184 were added and uniformly mixed, and then similarly applied to a PET film having a thickness of 25 μm after drying. It was dried for a minute to form an adhesive layer. After that, it is irradiated with ultraviolet rays (equipment: eye graphics inverter type conveyor device ECS-4011GX, metal halide lamp: eye graphics M04-L41, ultraviolet illuminance: 700 mW/cm ² , integrated light intensity: 1000 mJ/cm ² ) to cure. and placed in an environment with a temperature of 23° C. and a relative humidity of 50% for one day to obtain a pressure-sensitive adhesive sheet for testing (type c).

Examples C-7-9
The polymerizable 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. After weighing and mixing uniformly, apply it to a heavy release separator (silicone coated PET film), and apply it to a light release separator (silicone coated PET film) with a desktop roll laminator (Royal Sovereign) so as not to bite air bubbles. RSL-382S), the adhesive layer is laminated to a thickness of 25 μm, and irradiated with ultraviolet rays (equipment: eye graphics inverter type conveyor device ECS-4011GX, metal halide lamp: eye graphics M04-L41, UV illuminance: 700 mW/cm ² , integrated light quantity: 1000 mJ/cm ² ) to prepare an optical transparent pressure-sensitive adhesive sheet (type d).

Example C-10 and Comparative Example C-14
The polymerizable compositions obtained in Example A-4 and Comparative Example A-15, HDI as a cross-linking agent, DPHA as a polyfunctional monomer, and I-184 as a photopolymerization initiator were weighed in predetermined amounts shown in Table 4. , After uniformly mixing, a pressure-sensitive adhesive sheet was produced in the same manner as type c, and cured with ultraviolet rays. After that, it was aged in a constant temperature bath at 40° C. for 3 days and placed in an environment with 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 properties of the pressure-sensitive adhesive sheets produced were evaluated by the following methods, and the results are shown in Table 4.
(11) Transparency The prepared pressure-sensitive adhesive sheet was allowed to stand still for 24 hours in an atmosphere with a temperature of 23°C and a relative humidity of 50%. After that, the transparency was evaluated by measuring the transmittance with a haze meter in the same manner as described above.
(12) Adhesive strength Transferred to a 100 μm thick PET film or glass substrate as an adherend under conditions of a temperature of 23° C. and a relative humidity of 50%, and applied by reciprocating twice using a pressure roller weighing 2 kg. It was pressed and left for 30 minutes under the same atmosphere. After that, using a tensile tester (device name: Tensilon RTA-100 manufactured by ORIENTEC), the 180° peel strength (N/25 mm) was measured at a peel speed of 300 mm/min.
◎: 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) A stain-resistant adhesive sheet is attached to the adherend in the same manner as in the measurement of adhesive strength described above, left at 80 ° C. for 24 hours, and then the adhesive sheet is peeled off. Observed visually.
⊚: No contamination ◯: Slightly contaminated.
Δ: Slightly contaminated.
x: There is a glue (adhesive) residue.
(14) The light-yellowing resistance adhesive sheet was evaluated for light-yellowing resistance 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 polymerizable composition obtained in Example A and the polymer obtained in Example B, the predetermined amounts shown in Table 5 are weighed out together with other components, mixed uniformly, and an ultraviolet curable sealant is obtained. was prepared. After that, using the obtained encapsulant, production of a cured encapsulant resin by ultraviolet curing and evaluation of physical properties were performed by the following methods.

Method for preparing UV curable sealant resin cured product Set a silicon spacer (30 mm long x 15 mm wide x 3 mm thick) on a glass plate (50 mm long x 50 mm wide x 5 mm thick), and place the spacer inside the spacer. A copper foil (length 5 mm×width 50 m×thickness 80 μm) was placed, and the UV-curing sealant prepared above was injected. After sufficient degassing, it is irradiated with ultraviolet rays (equipment: eye graphics inverter type conveyor device ECS-4011GX, metal halide lamp: eye graphics M04-L41, ultraviolet illuminance: 700 mW/cm2, integrated light intensity: 1000 mJ/cm2). Then, a sealant resin cured product was produced. The properties of the obtained cured product were evaluated by the following methods, and the results are shown in Table 5.

(15) Transparency The prepared cured product was allowed to stand still for 24 hours in an atmosphere with a temperature of 23°C and a relative humidity of 50%. After that, the transparency was evaluated by measuring the transmittance with a haze meter in the same manner as described above.
(16) Humidity and heat yellowing resistance The obtained cured product was evaluated for humidity and heat yellowing resistance in the same manner as described above, and the results are shown in Table 5.
(17) Water absorption test Cut 1 g from the obtained cured product, set it as a test piece in a constant temperature and humidity machine at a temperature of 85 ° C. and a relative humidity of 95%, and after standing for 48 hours, measure the weight of the test piece again. Then, the water absorption rate was calculated by Equation 3.

Formula 3

◎：吸水率は１．０％未満
○：吸水率は１．０％以上、かつ２．０％未満
△：吸水率は２．０％以上、かつ３．０％未満
×：吸水率は３．０％以上
（１８）アウトガス試験
得られた硬化物から１ｇを切り取って、試験片として温度１００℃に設定した恒温槽に静置し、乾燥窒素気流を２４時間流して、その後再び試験片の重量を測定し、式４によりアウトガスの発生率を算出した。

◎: 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% or more (18) Outgassing test Cut 1 g from the obtained cured product, leave it as a test piece in a constant temperature bath set at a temperature of 100 ° C., let dry nitrogen stream flow for 24 hours, and then repeat the test piece. The weight was measured, and the outgassing rate was calculated by Equation 4.

formula 4

◎：発生率は０．１％未満
○：発生率は０．１％以上、かつ０．３％未満
△：発生率は０．３％以上、かつ１．０％未満
×：発生率は１．０％以上
（１９）耐ヒートサイクル性
得られた硬化物を－４０℃で３０分間、次に１００℃で３０分間放置を１サイクルとして１００回繰り返し、硬化物の状態を目視によって観察した。
◎：全く変化が見られない
〇：わずかに気泡の発生が見られるが、クラックの発生が見られない。透明である。
△：多少の気泡或いはクラックの発生が見られ、わずかな曇である。
×：気泡又はクラックが全面的に発生し、半透明状態である。
（２０）耐腐食性
耐湿熱黄変性試験後、銅箔の表面を目視で観察し、前記と同様に硬化膜の耐腐食性を評価し、結果を表５に示す。

◎: Incidence rate is less than 0.1% ○: Incidence rate is 0.1% or more and less than 0.3% △: Incidence rate is 0.3% or more and less than 1.0% ×: Incidence rate is 1 0% or more (19) Heat Cycle Resistance The resulting cured product was left at −40° C. for 30 minutes and then at 100° C. for 30 minutes as one cycle, which was repeated 100 times, and the state of the cured product was visually observed.
⊚: No change was observed ◯: Slight air bubbles were observed, but cracks were not observed. Transparent.
Δ: A few bubbles or cracks are observed, and slight fogging is observed.
x: Bubbles or cracks are generated on the entire surface, and the film is in a semi-transparent state.
(20) Corrosion Resistance After the wet heat yellowing resistance test, the surface of the copper foil was visually observed and the corrosion resistance of the cured film was evaluated in the same manner as described above.

Examples E-1 to 8 and Comparative Examples E-9 to 12
Using the polymerizable composition obtained in Example A and the polymer obtained in Example B, a UV-curable adhesive having the composition shown in Table 6 was prepared, and a polarizing plate was produced and a polarizing plate was manufactured by the following method. Physical properties were evaluated and the results are shown in Table 6.

Preparation of polarizing plate by ultraviolet irradiation Using a tabletop roll laminator (RSL-382S manufactured by Royal Sovereign), a polarizing film is sandwiched between two transparent films, and a polarizing film is placed between the transparent film and the polarizing film. The adhesive of the comparative example was pasted together so as to have a thickness of 10 μm. Irradiate ultraviolet rays from the upper surface of the laminated transparent film (equipment: eye graphics inverter type conveyor device ECS-4011GX, metal halide lamp: eye graphics M04-L41, ultraviolet illuminance: 700 mW / cm2, integrated light intensity: 1000 mJ / cm2 ) to prepare a polarizing plate having transparent films on both sides of the polarizing film. As the transparent film, an acrylic protective film (Sunduren SD-014 manufactured by Kaneka Corporation) was used.

(21) Observation of surface shape The surface of the obtained polarizing plate was visually observed and evaluated according to the following criteria.
◎: No fine streaks or irregularities can be observed on the surface of the polarizing plate. Clear streaks and uneven unevenness can be observed on the surface of the polarizing plate. It was attached to a test plate attached to 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 grip, and peeled at a peel speed of 300 mm / min at a 90 ° peel strength (N / 20 mm) was measured.
◎: 3.0 (N / 20 mm) or more ○: 1.5 (N / 20 mm) or more, less than 3.0 (N / 20 mm) △: 1.0 (N / 20 mm) or more, 1.5 (N / 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 between the retardation film and the optical compensation film was checked. Judgment was made according to the following criteria.
◎: No peeling at the interface between the polarizer and the protective film (less than 1 mm)
○: Peeling at part of the interface between the polarizer and the protective film (1 mm or more, less than 3 mm)
△: peeling at part of the interface between the polarizer and the protective film (3 mm or more, less than 5 mm)
×: peeling at the interface between the polarizer and the protective film (5 mm or more)
(24) Durability The obtained polarizing plate was cut to 150 mm x 150 mm, placed in a thermal shock device (TSA-101L-A manufactured by Espec Co., Ltd.), and heat-shocked from -40 ° C. to 80 ° C. 100 times for 30 minutes each. and evaluated according to the following criteria.
A: No crack O: A short crack of 5 mm or less occurred only at the edge △: A short linear crack occurred at a location other than the edge. However, the line does not separate the polarizing plate into two or more parts. ×: Cracks occur in places other than the edges, and the line separates the polarizing plate into two or more parts ( 25) Heat-resistant yellowing The resulting polarizing plate was cut into pieces of 30 mm x 30 mm, and the a-value and b-value of the transmitted hue were measured (using an ultraviolet-visible spectrophotometer UV-2450 manufactured by Shimadzu Corporation, wavelength 380). The parallel transmission hue a value and the cross transmission hue b value at ~780 nm were measured, and the transmission hue ab value (ab = (a2 + b2) 1/2) was calculated.Then, the polarizing plate was placed in a constant temperature bath at 90°C for 48 hours. The ab value after the test was similarly calculated, and the value of Δab (Δab = ab value after the test - ab value before the test) was used as an index of yellowing. A value of 0 means no yellowing, and the greater Δab is, the greater the yellowing.
◎: 0 <= Δab <= 2
○: 2<Δab<=6
△: 6<Δab<=10
×: 10<Δab

Examples F-1 to 8 and Comparative Examples F-9 to 12
Using the polymerizable composition obtained in Example A and the polymer obtained in Example B, a photocurable ink composition having the composition shown in Table 7 was prepared, and then inkjet printing was performed by the following method. , the resulting prints were evaluated. The clear ink composition did not contain the pigment and the pigment dispersant, and the black ink composition contained the pigment Pigment Black 7 (abbreviated as PMB-7) and the pigment dispersant Azysper PB821 (abbreviated as PB821) in predetermined amounts shown in Table 7. It is compounded with

(26) Viscosity The viscosity of the obtained ink composition was measured according to JIS K5600-2-3 using a cone-plate type viscometer (device name: RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.). Considering inkjet printing, the viscosity of the ink composition at 20° C. is preferably 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 preferable that it is s (double-circle evaluation). If the viscosity is less than 2 mPa·s (x evaluation), the ejection followability is deteriorated due to print blurring and printing misalignment after ejection. Therefore, it is not preferable.
(27) Compatibility Compatibility of the ink composition prepared by the above method was visually confirmed.
◎: No insoluble matter in the ink composition ○: Slight insoluble matter is observed in the ink composition △: Insoluble matter is observed in the entire ink composition ×: Precipitates are present in the ink composition

Preparation of printed material by UV irradiation The obtained ink composition was applied to a PET film having a thickness of 100 μm using a bar coater (RDS 12) (film thickness after drying: 10 μm), and irradiated with ultraviolet rays (device: inverter type conveyor manufactured by igraphics). A printed matter was produced by curing with an apparatus ECS-4011GX and a methhalide lamp: M04-L41 manufactured by Eyegraphics.

(28) Curability When printed matter was prepared by the above method, the cumulative amount of light until the ink composition was completely cured (non-sticky state) was measured to evaluate curability.
◎: Completely cured at 1000 mJ/cm2 ○: Completely cured at 1000 to 2000 mJ/cm2 △: Completely cured at 2000 to 5000 mJ/cm2 ×: 5000 mJ/cm2 or more is required for complete curing (29) Surface drying by the above method The printed material was placed in an environment with a room temperature of 23°C and a relative humidity of 50% for 5 minutes. A high-quality paper was placed on the printed surface, and a load of 1 kg/cm2 was applied for 1 minute to evaluate the degree of ink transfer to the paper. bottom.
⊚: The ink was dried and there was no transfer to the paper.
◯: The ink was dried and slightly transferred to the paper.
C: The ink was almost dried and there was some transfer to the paper.
x: The ink was hardly dried, and there was much transfer to the paper.

Inkjet printing and printability evaluation The ink composition prepared above was filled in a commercially available inkjet printer (LuxelJet UV350GTW, manufactured by Fujifilm Corporation), and a solid image was printed using coated paper. It was evaluated by the method of

(30) Ejection Stability The printing condition of the obtained prints was visually evaluated.
⊚: Good printing without missing nozzles.
◯: Slight missing nozzle.
Δ: Nozzle missing in a wide range.
x: There is ejection failure.
(31) Clarity The image clarity of the printed matter obtained from the ink composition containing the pigment was visually observed.
⊚: No ink bleeding was observed, and the image was clear.
◯: There was almost no ink bleeding, and the image was good.
Δ: Slight bleeding of ink was observed.
x: Remarkable ink bleeding was observed.
(32) Heat Resistant Yellowing The obtained clear ink composition was applied to a 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 above. The hue of the resulting coating film was measured by Spectrolino (manufactured by GretagMacbeth) and left in a constant temperature bath maintained at 60° C. for 1 week. Thereafter, the hue of the coating film was measured again, and the yellowing resistance was evaluated by the change in hue value before and after heating (ΔE=hue after heating−hue before heating).
◎: 0 <= ΔE <= 0.2
○: 0.2 < ΔE <= 0.5
△: 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, test pieces for evaluating three-dimensional objects were prepared as follows, and strength, shrinkage resistance, heat resistance, etc. were measured.

A 75 μm thick heavy release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is adhered to a horizontally placed glass plate, a spacer with a thickness of 1 mm and an inside of 20 mm × 40 mm is placed, and the inside of the spacer is activated. After filling the energy ray curable resin composition, a 50 μm thick light release PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) is layered thereon and irradiated with ultraviolet rays (equipment: eye graphics, inverter type Conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by Eyegraphics, UV illumination of 300 mW/cm2, integrated light intensity of 900 mJ/cm2) to obtain a cured product of the composition. After that, the cured product is left stationary for 24 hours in an atmosphere of 23 ° C. and 50% relative humidity, and the peeled PET films on both sides are removed, and mechanical properties such as tensile properties and bending properties, thermal properties, and three-dimensional objects The shrinkage rate, surface strength, etc. were measured.

(33) Tensile test According to 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), tensile strength, tensile elongation and tensile elasticity. rate was measured. Each measured value obtained was evaluated based on the following criteria.
Tensile strength ◎: Maximum point stress is 40 MPa or more ○: Maximum point stress is 30 to 40 MPa
△: Maximum point stress is 15 to 30 MPa
×: Maximum point stress is 15 MPa or less Tensile elongation ◎: Elongation at break is 100% or more ○: Elongation at break is 80 to 100%
△: elongation at break is 50% to 80%
×: Elongation at break is 50% or less Tensile modulus ◎: 1500 MPa or more ○: 1000 to 1500 MPa
△: 500 to 1000 MPa
×: 500 MPa or less (34) Bending test Using the obtained cured test piece, it was processed into a bar shape according to JIS K-7171 and used as a test piece for the bending test. According to JIS K-7171, a bending test was performed on the cured test piece using a precision universal testing machine (AG-X 500N manufactured by Shimadzu Corporation) to measure the bending strength and bending elastic modulus of the test piece. Each measured value obtained was evaluated based on the following criteria.
Bending strength ◎: Maximum bending stress is 80 MPa or more ○: Maximum bending stress is 50 to 80 MPa
△: Maximum bending stress is 30 to 50 MPa
×: Maximum bending stress is 30 MPa or less bending elastic modulus ◎: 1500 MPa or more ○: 1000 to 1500 MPa
△: 500 to 1000 MPa
×: 500 MPa or less (35) Surface hardness Using the above cured test piece, the surface hardness was measured by the durometer method of "Asker D type hardness tester (manufactured by Kobunshi Keiki Co., Ltd.)" in accordance with JIS K6253. Evaluation was made based on
◎: Exceeding D80 〇: Exceeding D60 ~ D80
△: Over D40 ~ D60
x: D40 or less (36) Heat distortion temperature Using the cured test piece described above, the heat distortion temperature was measured according to JIS K7207 and evaluated according to the following criteria.
◎: Over 50°C ○: Over 40°C to 50°C
△: Over 25°C to 40°C
x: 25° C. or less (37) Photo-yellowing resistance Using the obtained cured test piece, photo-yellowing resistance was evaluated in the same manner as described above.

Using the above clear ink composition, an ultra-high-speed stereolithography system (SOLIFORM500B, manufactured by Nabtesco) is used with a semiconductor laser (manufactured by Spectra Physics, semiconductor-excited solid-state laser BL6 type, wavelength 355 nm), and the liquid surface irradiation amount is 100 mJ / cm 2 , a slice pitch of 0.10 mm, and three-dimensional modeling was performed for 2 minutes per layer to produce a three-dimensional model having a rectangular parallelepiped shape.

(38) Curing shrinkage resistance The curing shrinkage rate 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 product obtained after curing, and the curing shrinkage resistance is measured as follows. was evaluated based on
Curing shrinkage rate (%) = {(d1-d0)/d1} x 100
◎: Less than 2% ○: 2% to less than 5% △: 5% to less than 10% ×: 10% or more

Examples H-1 to 6 and Comparative Examples H-7 to 10
Using the polymerizable composition obtained in Example A and the polymer obtained in Example B, four types (b, c, d, and e) of antifogging coating compositions described in Example C are shown. 9 was prepared and applied to glass, aluminum, PET and PC substrates so that the film thickness after drying would be 1 μm. After that, depending on each type, curing was performed by heat curing, active energy ray curing, or a combination thereof.

(39) Transparency The transparency and hue of the evaluation specimen coated with the antifogging paint were visually observed and evaluated on a 4-point scale.
⊚: Excellent (colorless, transparent and with good glossiness)
○: Good (colorless and transparent, but slightly inferior in glossiness)
△: Slightly bad (slightly cloudy and poor glossiness)
×: Poor (almost opaque, cloudiness observed)
(40) The coating film surface of the test piece for tack resistance evaluation was directly touched with a finger, and the degree of stickiness was evaluated on a 4-point scale.
◎: excellent (no stickiness at all)
◯: Good (slightly sticky, but fingers do not stick to the surface of the coating film.)
△: Somewhat bad (there is stickiness, fingers stick to the surface of the coating film.)
x: Poor (severe stickiness, fingers stick to the surface of the coating film.)
(41) Adhesion According to JIS K5400, after making a grid with a cutter knife and sticking cellophane tape, peel off the cellophane tape at an angle of 90 degrees, and the degree of peeling of the coating film from the substrate is graded in 4 stages. evaluated.
A: Excellent (no peeling at all)
○: good (slightly peeled, but less than 10%)
△: Somewhat bad (10% or more and less than 50% peeled off.)
x: Poor (50% or more peeled off)
(42) Anti-fogging properties Anti-fogging properties were evaluated by the breath anti-fogging method using test pieces for evaluation coated with anti-fogging paints. In a constant temperature and constant humidity room at 23° C. and a relative humidity of 50%, breath was blown for 1 second from a distance of 15 cm to a glass plate with an anti-fogging film, and the cloudy state was visually observed and evaluated on a 4-point scale.
◎: Excellent (not cloudy at all)
○: Good (Slightly cloudy for a moment, but the cloudiness clears up soon.)
△: Slightly bad (slightly cloudy)
×: Bad (clearly cloudy.)
(43) A mixed solution of antifouling oil/carbon pigment = 1/1 is applied as a contaminant to the coating film of the test piece for evaluation in a streak shape, and after 3 hours, running water is poured from above for 1 minute to clean the mixed solution. The performance was visually confirmed and evaluated in four stages.
⊚: 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 traces of dirt flow are slightly observed.)
△: Slightly bad (a small amount of dirt remains on the surface of the test piece.)
×: Poor (a considerable amount of dirt remains on the surface of the test piece.)
(44) A test piece for water resistance evaluation was immersed in hot water at 40°C for 240 hours, dried at room temperature, and the appearance of the coating film was visually observed. The appearance was compared with the appearance before the test and evaluated on a 4-point scale.
◎: excellent (no change)
○: Good (Slightly rough coating film surface)
△: Slightly bad (The surface of the coating film is rough, or slight whitening or stains are observed.)
x: Poor (Part or all of the coating film is dissolved, or whitening or stains are clearly observed.)
(45) The test piece for durability evaluation was allowed to stand in a thermo-hygrostat at 60°C and a relative humidity of 90% for 5 minutes, and then dried at 90°C for 5 minutes. This was regarded as one cycle, and after 5 cycles, the antifogging property was evaluated by the exhalation antifogging method in the same manner as described above.
(46) Humidity and heat resistance to yellowing Using the antifogging film-coated test piece thus obtained, the humidity and heat resistance to yellowing was evaluated in the same manner as described above.
(47) Corrosion Resistance After the wet heat yellowing resistance test, the surface of the aluminum substrate was visually observed to evaluate the corrosion resistance of the cured film in the same manner as for the copper foil.

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

Method for preparing active energy ray coating film The obtained hard coating composition was applied to a 100 µm thick PET film anchor coat surface with a bar coater (RDS 1) so that the thickness of the dry coating film was 3 µm. to prepare a coating film. When a solvent was contained, the resulting coating film was dried at 80°C for 2 minutes in an explosion-proof dryer. The obtained coating film was irradiated with a UV-LED irradiator (HOYA CANDEO OPTRONICS Co., Ltd. EXECURE-H-1VC2, sport type ) to prepare a UV-LED cured film. The UV-LED curability was evaluated by the following methods, and the adhesion, pencil strength and scratch resistance of the cured film were evaluated by the following methods.

(48) Curability Using the dried coating film, the resin composition was cured by the above UV-LED irradiation, the time required for complete curing was measured, and the integrated amount of light was calculated. Complete curing refers to a state in which no trace is left when the surface of the cured film is traced with silicone rubber.
(49) Adhesion Adhesion was evaluated in the same manner as described above using the obtained test piece with a coating film.
(50) Scratch Resistance #0000 steel wool was rubbed against the surface of the obtained coating film 10 times while applying a load of 200 g/cm ² , and the presence or absence of scratches was visually evaluated.
(double-circle): Almost no peeling or scratching of the film is observed.
◯: Slight fine scratches are observed in part of the film.
Δ: streak-like scratches are observed on the entire surface of the film.
x: Peeling of the film occurs.
(51) Pencil Hardness Evaluation was made based on JIS K 5400 8.4 hand scratching method (1990 edition) using the obtained test piece with a coating film.
(52) Light Yellowing Resistance A hard coating composition was used in the same manner as described above to prepare a coating film on a PC substrate instead of a PET film. Using the obtained PC board with the coating film as a test piece, the light yellowing resistance evaluation was performed in the same manner as described above.

As shown in the evaluation results of each of the 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, a total acid By controlling the value to 8.0 KOH mg / g or less, and the difference between the total base number and the total acid number (total base number - total acid number) within the range of -1.0 to 5.0 KOH mg / g, It has been confirmed that it is suitable for use in various fields such as adhesives, adhesives, sealants, inks, anti-fogging agents, hard coating agents, etc. 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 for each application. - The energy ray curability of substituted (meth)acrylamide is extremely high, and both thin and thick films can be easily cured, and the resulting cured product has low shrinkage, high transparency, and excellent corrosion resistance, heat resistance and strength , elongation, etc., and can be widely used in electronic materials, optical parts, semiconductors, solar cells, etc.

As has been explained above, the polymerizable resin composition of the present invention can be prepared by using a special purification process or additions that may cause concern as long as the total base number, the total acid number, and the difference between them are within the limits of the present invention. Industrial grade N-substituted (meth)acrylamide produced by a general production method without compounding agents is preferably used. In addition, it is possible to provide a polymerizable resin composition thereof and a resin composition which does not substantially cause yellowing or coloration and which does not corrode metal using a polymer comprising them. In addition, since there is no concern about yellowing, it becomes possible to incorporate a large amount of N-substituted (meth)acrylamide in the resin composition, and the adhesiveness to the substrate, weather resistance, heat resistance, scratch resistance ( coating film hardness), chemical resistance, etc. can be improved.

Claims (8)

A thermally polymerizable resin composition comprising a hydroxyalkyl (meth)acrylamide represented by the general formula [1] , a monofunctional monomer ( excluding hydroxyalkyl (meth)acrylamide ), and a thermal polymerization initiator,
The content of hydroxyalkyl (meth)acrylamide is 1 to 90% by weight of the total amount of polymerizable monomer components,
Monofunctional monomers are monomers containing amide groups and (meth)acrylic acid esters, the content of which is 10 to 99% by weight of the total amount of polymerizable monomer components,
The content of the thermal polymerization initiator is 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of polymerizable monomer components,
The total base number of the thermopolymerizable resin composition is 3.0 KOHmg/g or less,
The total acid value of the thermopolymerizable resin composition is 2.0 KOHmg/g or less, and
A thermopolymerizable resin composition, wherein the difference between the total base number and the total acid number (total base number - total acid number) of the thermopolymerizable resin composition is -0.2 to 1.0 KOHmg/g. thing.

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are linear or branched alkyl groups having 1 to 6 carbon atoms, one of which is a hydrogen atom and the other of which is a hydroxyl group. indicates the group.) The amide group-containing monomers (excluding hydroxyalkyl (meth)acrylamide ) are (meth)acryloylmorpholine, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth) 2.) The thermopolymerizable resin composition according to claim 1, wherein the resin composition is one or more selected from acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, and diacetone acrylamide. 3. A polymer having a weight-average molecular weight of 1,000 to 950,000 obtained by thermally solution-polymerizing the thermopolymerizable resin composition according to claim 1 or 2. A pressure-sensitive adhesive composition comprising the solution polymerization polymer of the thermopolymerizable resin composition according to claim 1 or 2 or the polymer according to claim 3 and a cross-linking agent,
The content of the cross-linking agent is 0.1 to 15 parts by weight with respect to 100 parts by weight of the polymer,
The adhesive composition has a total base number of 3.0 KOHmg/g or less and a total acid number of 2.0 KOHmg/g or less, and the total base number and the total acid number of the adhesive composition is -0.2 to 1.0 KOHmg/g. 5. The pressure-sensitive adhesive composition according to claim 4, wherein the pressure-sensitive adhesive composition has a total base number of 3.0 mg KOH/g or less and a total acid number of 2.0 mg KOH/g or less, and A pressure-sensitive adhesive composition for optics, wherein the difference between the total base number and the total acid number of the pressure-sensitive adhesive composition is -0.2 to 1.0 KOHmg/g. A solution polymerization polymer of the thermopolymerizable resin composition according to claim 1 or 2 or an active energy ray-curable pressure-sensitive adhesive composition comprising the polymer according to claim 3, a polyfunctional monomer and a photopolymerization initiator. There is
The content of the polyfunctional monomer is 0.05 to 50 parts by weight with respect to 100 parts by weight of the polymer,
The content of the photopolymerization initiator is 0.1 to 10% by weight in the adhesive composition,
The adhesive composition has a total base number of 3.0 KOHmg/g or less and a total acid number of 2.0 KOHmg/g or less, and the total base number and the total acid number of the adhesive composition difference is −0.2 to 1.0 KOHmg/g, an active energy ray-curable adhesive composition. 7. The active energy ray-curable pressure-sensitive adhesive composition according to claim 6, wherein the pressure-sensitive adhesive composition has a total base value of 3.0 KOHmg/g or less and a total acid value of 2.0 KOHmg/g or less. and a difference between the total base number and the total acid number of the adhesive composition is -0.2 to 1.0 KOHmg/g. The thermopolymerizable resin composition according to claim 1 or 2 and/or any one of claims 4 to 7, disposed on one or both sides of a metal substrate, or between two or more metal substrates. An adhesive layer obtained by curing the described adhesive composition.