JP6948077B2 - A polymerizable composition using N-substituted (meth) acrylamide, a polymer thereof, and a molded product comprising them. - Google Patents

Description

The present invention is a polymerizable resin composition using N-substituted (meth) acrylamide, which has very little coloring or discoloration even when exposed to heat or light, does not cause corrosion even when in contact with a metal. The present invention relates to a polymer obtained by polymerizing the composition, and a molded product composed of the composition and the polymer.

In recent years, N-substituted (meth) acrylamide has been used as an adhesive for optical members, an active energy curable adhesive for polarizing plates, a resin composition for stereolithography, an ink for inkjet, a sealing material for semiconductors and electronic materials, and glass and resin molding. It has come to be widely applied as a raw material monomer for coating agents of products (Patent Documents 1 to 4). In particular, it is often reported that it is used as a substitute for (meth) acrylic acid because it has high cohesiveness of amide groups, excellent adhesion to various substrates, and does not have corrosiveness to metals or metal oxides. (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 when acidic components such as (meth) acrylic acid are contained, corrosion of metals occurs over a long period of time. I was afraid. Therefore, in applications such as electronic materials and optical materials, there are cases where the blending amount of N-substituted (meth) acrylamide is reduced (Patent Document 8), or cases where it is not completely used (Patent Documents 9 and 10).

Therefore, when N-substituted (meth) acrylamide is used as a resin composition component, the present inventors reduce amine-based impurities and oxidize in order to suppress the time-dependent heat-resistant heat denaturation of the cured film. It has been proposed to add an inhibitor, an ultraviolet absorber, or the like (Patent Documents 12 and 13). These proposals did improve heating yellowing, but the cost increased due to the addition of a purification process to obtain high-purity N-substituted (meth) acrylamide and the addition of additives to suppress yellowing. In addition, there remains concern about the impact of additives on the final product.

On the other hand, N-substituted (meth) acrylamide is often used as a constituent component of an active energy ray-curable resin, but a method for suppressing coloring or discoloration by light irradiation such as ultraviolet rays and visible light has not yet been reported.

Japanese Unexamined Patent Publication No. 2008-287207 Japanese Unexamined Patent Publication No. 2011-12203 Japanese Unexamined Patent Publication No. 2001-310918 Japanese Unexamined Patent Publication No. 2010-155889 Japanese Unexamined Patent Publication No. 2011-137181 Japanese Unexamined Patent Publication No. 2010-235646 Japanese Unexamined Patent Publication No. 2013-256552 Japanese Unexamined Patent Publication No. 2008-24818 Japanese Unexamined Patent Publication No. 2005-255877 Japanese Unexamined Patent Publication No. 2005-015524 Japanese Unexamined Patent Publication No. 2012-0256775 Japanese Unexamined Patent Publication No. 2013-035893 Japanese Unexamined Patent Publication No. 2013-057020

The problem to be solved by the present invention is the formulation of an additive of concern, which contains industrial grade N-substituted (meth) acrylamide produced by a general manufacturing method without requiring a special purification step. Provided is a polymerizable resin composition which is not required to be used, has extremely little coloring or discoloration (yellowing) when exposed to heat or light, and is also useful as various functional materials including optical applications. Further, a polymer having excellent moisture-heat yellowing resistance, photoyellowing resistance and corrosion resistance obtained by polymerizing a polymerizable resin composition, and a molded product produced by using these polymerizable resin compositions and polymers are provided. It is to be.

The present inventors have conducted diligent studies to solve this problem, and as a result of paying attention to the contents of the basic component and the acidic component in the polymerizable resin composition using N-substituted (meth) acrylamide, all the bases are used. The valence 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 value and the total acid value (total base value-total acid value) is -1.0 to 5. By controlling within the range of 0 KOH mg / g, a polymerizable resin composition having excellent yellowing resistance and corrosion resistance using N-substituted (meth) acrylamide, a polymer of the composition, and resistance to the same. It has been found that a molded product having excellent yellowing 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は同一または異なって、水素原子、水酸基、アミン基、アルコキシ基、カルボニル基で置換されていてもよい炭素数１乃至６の直鎖状または分岐鎖状のアルキル基、炭素数３乃至６の脂肪族または芳香環を示し、また、Ｒ_２及びＲ_３は、それらを担持する窒素原子と一緒になって、さらに酸素原子または窒素原子を含まれていてもよい飽和あるいは不飽和の５〜７員環を形成してもよい。但し、Ｒ_２及びＲ_３が同時に水素原子の場合を除く。）
（２）Ｎ−置換（メタ）アクリルアミドが、（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−ヒドロキシエチル（メタ）アクリルアミド、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（１）に記載の樹脂組成物、
（３）光重合開始剤を０．１〜１０重量％と不飽和結合を有するモノマーを１〜７０重量％さらに含有することを特徴とする前記（１）又は（２）に記載の樹脂組成物、
（４）不飽和結合を有するモノマーは単官能モノマー及び／又は多官能モノマーであることを特徴とする前記（１）〜（３）の何れか一項に記載の樹脂組成物、
（５）前記（１）〜（４）の何れか一項に記載の樹脂組成物を含有する活性エネルギー線硬化性粘着剤組成物であって、粘着剤組成物の全塩基価は１２．０ＫＯＨｍｇ／ｇ以下、全酸価は８．０ＫＯＨｍｇ／ｇ以下、かつ、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、
（６）前記（５）に記載の粘着剤組成物であって、粘着剤組成物の全塩基価は３．０ＫＯＨｍｇ／ｇ以下、全酸価は２．０ＫＯＨｍｇ／ｇ以下、かつ、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、
（７）前記（１）〜（４）の何れか一項に記載の樹脂組成物を含有する活性エネルギー線硬化性コーティング組成物であって、コーティング組成物の全塩基価は１２．０ＫＯＨｍｇ／ｇ以下、全酸価は８．０ＫＯＨｍｇ／ｇ以下、かつ、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コーティング組成物、
（８）前記（７）に記載のコーティング組成物であって、コーティング組成物の全塩基価は３．０ＫＯＨｍｇ／ｇを超え且つ１２．０ＫＯＨｍｇ／ｇ以下、全酸価は２．０ＫＯＨｍｇ／ｇを超えかつ８．０ＫＯＨｍｇ／ｇ以下、全塩基価と全酸価の差は−１．０〜−０．２ＫＯＨｍｇ／ｇ未満或いは１．０ＫＯＨｍｇ／ｇを超え〜５．０ＫＯＨｍｇ／ｇ以下であることを特徴とする金属基材用エネルギー線硬化性コーティング組成物。
（９）前記（１）〜（４）の何れか一項に記載の樹脂組成物を含有する活性エネルギー線硬化性インク組成物であって、インク組成物の全塩基価は１２．０ＫＯＨｍｇ／ｇ以下、全酸価は８．０ＫＯＨｍｇ／ｇ以下、かつ、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インク組成物、
（１０）前記（９）に記載のインク組成物であって、インク組成物の全塩基価は３．０ＫＯＨｍｇ／ｇ以下、全酸価は２．０ＫＯＨｍｇ／ｇ以下、かつ、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立体造形用インク組成物、
（１１）前記（１）〜（４）の何れか一項に記載の樹脂組成物を含有する活性エネルギー線硬化性接着剤組成物であって、接着剤組成物の全塩基価は１２．０ＫＯＨｍｇ／ｇ以下、全酸価は８．０ＫＯＨｍｇ／ｇ以下、かつ、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接着剤組成物、
（１２）前記（１１）に記載の接着剤組成物であって、かつ、全塩基価は３．０ＫＯＨｍｇ／ｇ以下、全酸価は２．０ＫＯＨｍｇ／ｇ以下、全塩基価と全酸価の差（全塩基価−全酸価）は−０．２〜１．０ＫＯＨｍｇ／ｇであることを特徴とする電子材料用接着剤組成物、
（１３）前記（１）〜（４）の何れか一項に記載の樹脂組成物を含有する活性エネルギー線硬化性封止剤組成物であって、封止剤組成物の全塩基価は１２．０ＫＯＨｍｇ／ｇ以下、全酸価は８．０ＫＯＨｍｇ／ｇ以下、かつ、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封止剤組成物、
（１４）前記（１）〜（４）の何れか一項に記載の樹脂組成物を含有する活性エネルギー線硬化性防曇剤組成物であって、防曇剤組成物の全塩基価は１２．０ＫＯＨｍｇ／ｇ以下、全酸価は８．０ＫＯＨｍｇ／ｇ以下、かつ、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防曇剤組成物
を提供することである。 That is, the present invention
(1) An active energy ray-curable resin composition containing 1 to 90% by weight of N-substituted (meth) acrylamide represented by the general formula [1], wherein the total base value of the composition is 12.0 KOH mg /. It is characterized in that it is g or less, the total acid value is 8.0 KOHmg / g or less, and the difference between the total base value and the total acid value (total base value-total acid value) is -1.0 to 5.0 KOHmg / g. Active energy ray-curable resin composition,

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are the same or different, and may be substituted with a hydrogen atom, a hydroxyl group, an amine group, an alkoxy group, or a carbonyl group. It exhibits a linear or branched alkyl group of 6, an aliphatic or aromatic ring having 3 to 6 carbon atoms, and R ₂ and R ₃ together with a nitrogen atom carrying them further oxygen. A saturated or unsaturated 5- to 7-membered ring may be formed, which may contain an atom or a nitrogen atom, except when R ₂ and R ₃ are hydrogen atoms at the same time.)
(2) N-substituted (meth) acrylamide is (meth) acryloylmorpholin, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-vinylpyrrolidone. , N- vinyl caprolactam, N- hydroxyethyl (meth) acrylamide, N- methyl -N- hydroxyethyl (meth) acrylamide, according to (1), wherein the at least one selected from diacetone acrylamide Resin composition,
(3) The resin composition according to (1) or (2) above, which further contains 0.1 to 10% by weight of a photopolymerization initiator and 1 to 70% by weight of a monomer having an unsaturated bond. ,
(4) The resin composition according to any one of (1) to (3) above, wherein the monomer having an unsaturated bond is a monofunctional monomer and / or a polyfunctional monomer.
(5) An active energy ray-curable pressure-sensitive adhesive composition containing the resin composition according to any one of (1) to (4) above, wherein the total base value of the pressure-sensitive adhesive composition is 12.0 KOH mg. Active energy ray-curable adhesive characterized by having a total acid value of 8.0 KOH mg / g or less and a difference between the total base value and the total acid value of -1.0 to 5.0 KOH mg / g. Agent composition,
(6) The pressure-sensitive adhesive composition according to (5) above, wherein the total base value of the pressure-sensitive adhesive composition is 3.0 KOH mg / g or less, the total acid value is 2.0 KOH mg / g or less, and the total base value is 2.0 KOH mg / g or less. An active energy ray-curable pressure-sensitive adhesive composition for optics, wherein the difference between the total acid value and the total acid value is −0.2 to 1.0 KOH mg / g.
(7) An active energy ray-curable coating composition containing the resin composition according to any one of (1) to (4) above, wherein the total base value of the coating composition is 12.0 KOH mg / g. Hereinafter, the active energy ray-curable coating composition is characterized in that the total acid value is 8.0 KOH mg / g or less, and the difference between the total base value and the total acid value is −1.0 to 5.0 KOH mg / g. ,
(8) The coating composition according to (7 ) above, wherein the total base value of the coating composition exceeds 3.0 KOH mg / g and is 12.0 KOH mg / g or less, and the total acid value is 2.0 KOH mg / g. Exceeding and less than 8.0 KOH mg / g, the difference between total base value and total acid value is -1.0 to less than -0.2 KOH mg / g or more than 1.0 KOH mg / g to 5. An energy ray-curable coating composition for a metal substrate, which is characterized by being 0 KOH mg / g or less.
(9) An active energy ray-curable ink composition containing the resin composition according to any one of (1) to (4) above, wherein the total base value of the ink composition is 12.0 KOH mg / g. Hereinafter, the active energy ray-curable ink composition is characterized in that the total acid value is 8.0 KOH mg / g or less, and the difference between the total base value and the total acid value is −1.0 to 5.0 KOH mg / g. ,
(10) The ink composition according to (9 ) above, wherein the total base value of the ink composition is 3.0 KOH mg / g or less, the total acid value is 2.0 KOH mg / g or less, and the total base value and the total. An ink composition for three-dimensional modeling, characterized in that the difference in acid value is −0.2 to 1.0 KOH mg / g.
(11) An active energy ray-curable adhesive composition containing the resin composition according to any one of (1) to (4) above, wherein the total base value of the adhesive composition is 12.0 KOH mg. Active energy ray-curable adhesion characterized in that the total acid value is 8.0 KOHmg / g or less, and the difference between the total base value and the total acid value is -1.0 to 5.0 KOHmg / g. Agent composition,
(12) The adhesive composition according to (11) above, having a total base value of 3.0 KOH mg / g or less, a total acid value of 2.0 KOH mg / g or less, and a total base value and a total acid value. An adhesive composition for electronic materials, wherein the difference (total base value-total acid value) is -0.2 to 1.0 KOH mg / g.
(13) An active energy ray-curable encapsulant composition containing the resin composition according to any one of (1) to (4) above, wherein the total base value of the encapsulant composition is 12. Active energy ray curing characterized in that the total acid value is 8.0 KOH mg / g or less, and the difference between the total base value and the total acid value is −1.0 to 5.0 KOH mg / g. Sex sealant composition,
(14) An active energy ray-curable antifogging agent composition containing the resin composition according to any one of (1) to (4) above, wherein the total base value of the antifogging agent composition is 12. Active energy ray curing characterized in that the total acid value is 8.0 KOH mg / g or less, and the difference between the total base value and the total acid value is −1.0 to 5.0 KOH mg / g. To provide a sex antifogging agent composition.

The polymerizable resin composition using N-substituted (meth) acrylamide of the present invention has low viscosity and high curability, and is excellent in heat resistance, adhesion, and transparency. It can be suitably used as a sealing agent, a coating agent, an antifogging agent, and an ink, and the obtained molded product does not easily turn yellow for a long period of time and does not corrode to metals or metal oxides. The resin composition of the present invention does not require a special purification process including optical applications or the addition of additives of concern, and the industrial product N-substituted (meth) acrylamide can be used as a raw material monomer or a constituent component. can. Further, N-substituted (meth) acrylamide can be blended in a large amount in the resin composition, and improvement in weather resistance, heat resistance, scratch resistance and chemical resistance can be expected.

Hereinafter, the present invention will be described in detail.
The N-substituted (meth) acrylamide, which is a constituent of the polymerizable resin composition of the present invention, has the general formula [1] (in the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are the same or Differently, a linear or branched alkyl group having 1 to 6 carbon atoms, which may be substituted with a hydrogen atom, or a hydroxyl group, an amino group, an alkoxy group, or a carbonyl group, an aliphatic group having 3 to 6 carbon atoms, or Aroma rings are shown, and R ₂ and R ₃ together with the nitrogen atoms carrying them form a saturated or unsaturated 5- to 7-membered ring which may further contain oxygen or nitrogen atoms. It may be formed, except when R ₂ and R ₃ are hydrogen atoms at the same time).

Specific examples of N-substituted (meth) acrylamide include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-butyl. (Meta) 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) ) (Meta) 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) Examples thereof include 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, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholin, N-hydroxyethylacrylamide, because they are easily available as industrial products and have high curability. N-Methyl-hydroxyethyl acrylamide, diacetone acrylamide, N-isopropyl (meth) acrylamide, N-vinylpyrrolidone, and N-vinylcaprolactam are preferred.

The resin composition of the present invention has a total base value of 12.0 KOH mg / g or less, a total acid value of 8.0 KOH mg / g or less, and a difference between the total base value and the total acid value (total base value-total acid). The value) is preferably −1.0 to 5.0 mg / g. Here, the total base value of the composition is the total of the base values derived from the basic constituents, N-substituted (meth) acrylamide and other basic impurities contained in the neutral component. The basic constituents and impurities are not particularly limited as long as they are alkaline compounds, but from the viewpoint of yellowing resistance of the present invention, reduction of the base value derived from amines is most preferable. Since amines have an unshared electron pair at the nitrogen atom, they are easy to color, and at the same time, vinyl groups, N-substituted (meth) acrylamide amide groups and (meth) acrylate-based polyfunctional and monofunctional monomers contained in the composition. The present inventors presume that the effect on the ester group and the like is large.

In the present invention, the total acid value of the composition is the total acid value derived from the acidic constituents, N-substituted (meth) acrylamide and other acidic impurities contained in the neutral component. Here, the acidic constituents and impurities are not particularly limited as long as they are acidic compounds, but are derived from carboxylic acids having unsaturated bonds such as acrylic acid and methacrylic acid from the viewpoint of yellowing resistance and corrosion resistance of the present invention. The acid value of the acid has a large effect on the vinyl group contained in the composition, the amide group of N-substituted (meth) acrylamide, the (meth) acrylate-based polyfunctionality, the ester group of the monofunctional monomer, etc., and its reduction is most preferable. The present inventors think.

If the total base value, total acid value, and their differences are out of the above ranges, the molded product using the resin composition may turn yellow over time due to heat or light, and if it comes into contact with a metal or metal oxide. It may cause corrosion.

The resin composition of the present invention can be produced by uniformly mixing various constituent components including N-substituted (meth) acrylamide in a predetermined proportion. If the total base value, total acid value of the composition and their differences do not fall within the above range, a method of adding an acidic or basic component to neutralize the composition, or a specific acidic or specific acid contained in the composition or It may be adjusted by ordinary means such as a method of removing basic components and purifying.

An acidic or basic gas is added to the resin composition as a method for neutralizing by adding an acidic or basic component when adjusting the total base value, the total acid value and their differences in the resin composition of the present invention. Examples include a method of blowing into a resin composition, a method of adding an acidic or basic liquid or solid to the resin composition, and the like. Further, the acidic component and the basic component can be either inorganic or organic. For solid acids or bases, powders, particles such as ion exchange resins, and chelating agents immobilized on a carrier can also be used. Depending on the state of the neutralizing agent used, the type and the amount of the neutralizing agent added, the product of the neutralization reaction may be left in the composition, but it is preferable to remove it by a usual method such as filtration, distillation, or centrifugation. .. Further, it is particularly preferable to use a polymerizable acid or base because the product after neutralization becomes a constituent component of the composition.

When adjusting the total base value, total acid value, and their differences in the resin composition of the present invention, as a method for purifying by removing acidic or basic components contained in the composition, distillation or ions due to a difference in boiling point can be used. Examples thereof include adsorption with an exchange resin and the like, separation with a osmosis membrane due to a difference in molecular size and osmotic pressure, separation with a reverse osmosis membrane, and separation with electrophoresis. In addition, both batch and continuous distribution type can be used. From the viewpoint of high yield and reliable removal, a method of passing an ion exchange resin packed bed or a cartridge is preferable.

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

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

The resin composition of the present invention may contain 100% of polymerization 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. The resin can be diluted by blending N-substituted (meth) acrylamide, and the performance of the resin composition such as adhesion, compatibility, and curability can be improved. If the content is less than 1%, the characteristics of N-substituted (meth) acrylamide cannot be sufficiently exhibited, and the compounding effect may not be obtained.

The resin composition of the present invention can be suitably used as an active energy ray-curable resin composition by further adding a monomer having an unsaturated bond with a photopolymerization initiator to N-substituted (meth) acrylamide. Further, depending on the purpose of adjusting the viscosity, a monofunctional monomer having one unsaturated bond, a polyfunctional monomer for the purpose of adjusting the crosslink rate, a monofunctional or polyfunctional oligomer for improving flexibility, a non-polymerizable polymer, etc. Can be used together. These concomitant components may be added alone to 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) acrylate and polyfunctional (meth) acrylamide having two or more unsaturated bonds, and from the main chain structure, urethane-based and epoxy-based. And acrylic type etc. are separated.

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, and ditetraethylene glycol di. (Meta) 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 (Meta) 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-Nonandiol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified di-phosphate (Meta) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Trimethylol ethanetri (meth) acrylate, trimethylolpropantri (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 thereof include monomers and oligomers such as acrylate and urethane (meth) acrylamide. From the viewpoint of easy availability of commercially available products, urethane acrylates include, for example, UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-3310B, UV-7000B, and new products manufactured by Nippon Synthetic Chemical Co., Ltd. Nakamura Chemical Industry Co., Ltd., product name U-4HA, U-200PA, Daicel Cytec Co., Ltd., product name EBECRYL245, EBECRYL1259, EBECRYL8210, EBECRYL284, EBECRYL8402, SARTOMER, product name CN944, CN969, CN9002 Product names UN1255, UN-5507, Kyoei Co., Ltd., product names AH-600, UA-306I, etc. can be used, and as the urethane (meth) acrylamide, KJSA5100, KJSA6100, etc. manufactured by KJ Chemicals Co., Ltd. can be used. As the epoxy resin, EBECRYL1259, EBECRYL605, EBECRYL1606, SARTOMER, trade names CN110, CN120, CN153, etc. manufactured by Daicel Cytec Co., Ltd. can be used. As the acrylic resin, SARTOMER's trade names CN2203 and CN2270, Toagosei's trade names M-6100, M-8060 and the like can be used. Further, urethane acrylate UV-6640B or U-200PA is more preferable from the viewpoint of viscosity of the resin composition, ease of handling, and the like.
One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

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

The monofunctional monomer used in the resin composition of the present invention includes monofunctional (meth) acrylate, monofunctional (meth) acrylamide, unsaturated nitrile monomer, styrene, amide group-containing monomer, methylol group-containing monomer, and alkoxymethyl group-containing monomer. , Vinyl ester, olefin, etc. Examples thereof include radically polymerizable compounds having a reactive double bond in the molecular chain.

The monofunctional (meth) acrylate includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 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 (Meta) 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) acrylamide is, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-methoxyethyl ( Meta) 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-acrylloylmorpholin, hydroxyalkyl (meth) acrylamide, etc. Can be mentioned. One of these monofunctional monomers may be used alone, or two or more thereof may be used in combination.

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

Examples of the curable resin having a weight average molecular weight of 10,000 or more include bifunctional polyurethane (meth) acrylate, polyfunctional polyurethane (meth) acrylate, bifunctional polyester (meth) acrylate, and polyfunctional urethane (meth). Acrylate, bifunctional polyester (meth) acrylate, polyfunctional polyester (meth) acrylate, bifunctional polyether (meth) acrylate, polyfunctional polyether (meth) acrylate, bifunctional polyamide (meth) acrylate, polyfunctional polyamide (meth) Acrylate, bifunctional poly (meth) acrylic acid ester (meth) acrylate, polyfunctional poly (meth) acrylic acid ester (meth) acrylate, bifunctional poly (meth) acrylic acid ester (meth) acrylamide, polyfunctional poly (meth) Acrylate ester (meth) acrylamide, bifunctional poly (meth) acrylamide (meth) acrylate, polyfunctional poly (meth) acrylamide (meth) acrylate, bifunctional polystyrene (meth) acrylate, polyfunctional polystyrene (meth) acrylate, bifunctional Examples thereof include polyacrylonitrile (meth) acrylate, polyfunctional polyacrylonitrile (meth) acrylate, bifunctional epoxy acrylate (bisphenol A type), and polyfunctional epoxy acrylate (bisphenol A type). In addition, these polymers may be used alone or in combination of two or more.

The active energy ray-curable resin composition of the present invention is coated or molded on a substrate and then cured by irradiation with active energy rays to obtain a pressure-sensitive adhesive sheet, a hard coating film, and an antifogging agent obtained by a three-dimensional molding method. A molded product having a film, an adhesive, an adhesive, a sealing agent, and the like can be produced.

The active energy ray is defined as an energy ray capable of decomposing a compound (photopolymerization initiator) that generates an active species to generate an active species. Examples of 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. Above all, it is preferable to use ultraviolet rays from the viewpoint of the balance between the active energy ray generator, the curing speed and the safety. Examples of the ultraviolet source include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet LED lamps, microwave excimer lamps, and the like.

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

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

The amount of these photopolymerization initiators used is not particularly limited, but generally 0.1 to 10% by weight, of which 1 to 5% by weight is added to the active energy ray-curable resin composition. Is preferable. 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 further adding a monomer having an unsaturated bond with a thermal polymerization initiator to N-substituted (meth) acrylamide. The monomer having an unsaturated bond referred to here is the above-mentioned various monofunctional and polyfunctional monomers and oligomers, and also has one unsaturated bond in order to obtain a thermoplastic polymer whose physical properties can be easily adjusted. A monofunctional monomer is preferable, and a monomer capable of introducing a cross-linking point in order to enhance the cohesiveness of the obtained polymer is particularly preferable. The above-mentioned monofunctional monomer may be added alone, or two or more kinds may be combined. The blending amount thereof may be arbitrarily adjusted according to the specific use, but is preferably 10 to 99% by weight in total in the total amount of the resin composition.

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

Examples of the hydroxyl group-containing (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. , Hydroxyalkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylates, hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, and others 2- Primary hydroxyl group-containing (meth) acrylic monomers such as acryloyloxyethyl 2-hydroxyethylphthalic acid and N-methylol (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Secondary hydroxyl group-containing (meth) acrylic monomers such as hydroxy3-phenoxypropyl (meth) acrylate, 3-chloro2-hydroxypropyl (meth) acrylate, 2-hydroxy3-phenoxypropyl (meth) acrylate, 2,2- Examples thereof include tertiary hydroxyl group-containing (meth) acrylic monomers such as dimethyl2-hydroxyethyl (meth) acrylate. Of these, hydroxyalkyl (meth) acrylates are preferably used.

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

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

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

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

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

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, and 4-ethyl-2. -Vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5 -Dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl -2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline , 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, 4,5-diethyl-2-isopropenyl-2-oxazoline and the like. .. Further, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline having high reactivity are preferable, and 2-vinyl-2- 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.

The thermal polymerization of the thermopolymerizable 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 the solution polymerization method in an organic solvent is adopted for solution polymerization, there is no particular limitation as long as it is a solvent that dissolves the polymer obtained by polymerization. For example, the polymerization solvent includes benzene, toluene, ethylbenzene, xylene and the like. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, esters such as ethyl acetate, butyl acetate, 2-hydroxyethyl acetate, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc. Examples thereof include aliphatic alcohols, 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 admixture of two or more. In particular, it is preferable to use ethyl acetate, methyl ethyl ketone, acetone, etc. having a low boiling point because they can be easily removed when forming a molded product.

Examples of the thermal radical polymerization initiator include azo compound-based catalysts such as azobisisobutyronitrile and azobisvaleronitrile, peroxide-based catalysts such as benzoylperoxide and hydrogen peroxide, ammonium persulfate, and sodium persulfate. Persulfate-based catalysts such as, etc. can be used. The amount of the polymerization initiator used is usually about 0.001 to 10% by weight based on the total amount of the polymerizable monomer components. Further, ordinary radical polymerization techniques such as adjustment of molecular weight by a chain transfer agent are applied.

The molecular weight of the polymer of the present invention is, on average, 10 to 3 million, preferably 50 to 2.5 million, and particularly preferably 10,000 to 2 million. When the weight average molecular weight is in the range of 10 to 3 million, the solution viscosity when dissolved in a solvent is neither too high nor too low, so that it can be handled favorably and the processing accuracy of the coating film, sheet, etc. is improved. high. When such a polymer is diluted with ethyl acetate so as to be 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. Particularly preferably, it is 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 and adhesive strength, adhesion to various substrates, heat resistance, and durability, and thus can be used as it is. Further, 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 with a cross-linking agent, (2) a method of containing an unsaturated group-containing compound and a polymerization initiator and cross-linking with active energy rays and / or heat. Be done. One of these cross-linking methods may be used, or both may be used in combination.

As a method of cross-linking using the (1) cross-linking agent, a compound having a functional group capable of reacting with a functional group contained in the (meth) acrylic resin, such as an isocyanate compound, an epoxy compound, an aziridine compound, and a carboxyl group compound. Can be mentioned as a method of adding and reacting.

Among these, examples of the isocyanate compound include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. More specifically, examples of the isocyanate compound include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2,4 -Aromatic diisocyanates such as -tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 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 trimeric adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HL) and isocyanurates of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX). And so on. These isocyanate compounds may be used alone or in combination of two or more.

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

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

Carboxyl group compounds include L-lactic acid, D-lactic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxyl group, 2,6-naphthalenedicarboxyl group, diphenyldicarboxyl group, diphenoxyetane dicarboxyl group, diphenyl ether. Aromatic dicarboxyl groups such as dicarboxyl group and diphenylsulfone dicarboxyl group, alicyclic dicarboxyl group such as 1,3-cyclopentane dicarboxyl group, 1,3-cyclohexanedicarboxyl group and 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, trimethyladiponic acid, pimeric acid, azelaic acid , Aliphatic dicarboxylic acids such as sebacic acid and suberic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid, hydroxycarboxyl groups such as hydroxybenzoic acid, and their ester-forming properties. Examples thereof include compounds having a dicarboxyl group derived from a derivative or the like. These compounds may be used alone or in combination of two or more.

The amount of these cross-linking agents used can be appropriately selected depending on the balance with the amount of functional groups and the molecular weight contained in the polymer to be cross-linked and further depending on the purpose of use, but is usually 100% by weight of the polymer. On the other hand, it is preferably contained in an amount of 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 by the cross-linking agent may be insufficient, the cohesive force of the molded product such as the adhesive may be insufficient, and sufficient heat resistance may not be obtained. It tends to cause adhesive residue. On the other hand, when the content exceeds 15% by weight, the cohesive force of the crosslinked resin composition is large, the flexibility and elasticity are lowered, and the adaptability (wetting property) to the adherend tends to be insufficient. ..

Further, it is also possible to use an acid catalyst such as paratoluene sulfonic acid, phosphoric acid, hydrochloric acid, ammonium chloride or the like in combination with the cross-linking agent in order to promote the cross-linking, and the addition of the cross-linking accelerator The amount is preferably 10 to 50% by weight based on the cross-linking agent.

As a method of (2) containing an unsaturated group-containing compound and a polymerization initiator and cross-linking with active energy rays and / or heat, two or more active energy rays and / or thermally reactive unsaturated bonds are used as the cross-linking agent. Examples thereof include a method in which a polyfunctional monomer having a substance and a polymerization initiator are added and crosslinked with active energy rays and / or heat.

As the polyfunctional monomer having two or more active energy rays and / or heat-reactive unsaturated bonds, cross-linking treatment is performed by irradiation with active energy rays and / or heat such as a vinyl group, an acryloyl group, a methacryloyl group, and a vinylbenzyl group. A polyfunctional monomer component having one or more active energy rays and / or two or more thermally reactive unsaturated bonds that can be (cured) is used. Generally, those having 10 or less active energy rays and / or thermoreactive unsaturated bonds are preferably used. It is also possible to use two or more kinds of polyfunctional monomers in combination.

As the polyfunctional monomer, a bifunctional monomer and a trifunctional or higher functional monomer can be used. Specific examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and 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, phthalic acid diglycidyl ester Examples thereof include monomers such as di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2- (meth) acryloyloxyethyl acid phosphate diester.

Examples of the trifunctional or higher functional monomer include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylpropanthry (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol tetra (dipentaerythritol tetra (meth) acrylate. Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylol propane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanurate ethylene oxide-modified tri (meth) acrylate Meta) 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, Examples thereof include 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. It is 1 to 30% by weight. If the content is less than 0.05% by weight, the cross-linking by the cross-linking agent may be insufficient, the cohesive force when used as an adhesive or an adhesive may be insufficient, and sufficient heat resistance may not be obtained. On the other hand, when the content exceeds 50% by weight, for example, the cohesive force of the polymer becomes too high, the flexibility and adhesive force decrease, and the wettability to the adherend becomes insufficient, which causes peeling. Tend.

Pigments, dyes, surfactants, blocking inhibitors, leveling agents, dispersants, defoamers, antioxidants, UV sensitizers, as long as they do not impair the properties of the resin composition of the present invention and the molded products produced from it. Other optional ingredients such as agents and preservatives may be used in combination.

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

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The abbreviations of the constituents 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": Acryloyl morpholine (registered trademark "ACMO")
"NIPAM": N-isopropylacrylamide (registered trademark "NIPAM")
"HEAA": N-Hydroxyethyl acrylamide (registered trademark "HEAA")
MHEAA: N-Methyl-N-Hydroxyethyl acrylamide HEMAA: N-Hydroxyethyl methacrylamide "DMAPAA": N, N-dimethylaminopropyl acrylamide (registered trademark "DMAPAA")
(2) Polyfunctional Monomer, Oligomer, Polymer PETA: Pentaerythritol Triacrylate DPHA: Dipentaerythritol Hexacrylate 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 Industry 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 Toa Synthetic 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 Industry Co., Ltd.)

The physical characteristics of the resin composition of the present invention were determined according to the following measuring methods.
(5) Total base value The total base value represents hydrochloric acid or perchloric acid required to neutralize all the basic components contained in 1 g of the resin composition by the equivalent number of mg of potassium hydroxide, and the present invention relates to JIS. It was measured by a potential difference automatic titrator with reference to K7237-1995. As the measurement solvent, one type or a mixture of two or more types that can be 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 in a 200 mL beaker, 50 mL of the measurement solvent (special grade product) was added, and the mixture was uniformly dissolved to prepare 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 solution and the blank solution was titrated with an acetic acid solution of perchloric acid having a concentration of 0.01 mol / L by an automatic potentiometric titrator (AT-510N, manufactured by Kyoto Denshi Kogyo Co., Ltd.). The titration result was calculated by Equation 1 and the total base value (KOHmg / L) was determined (F indicates the factor of the titration solution determined using a standard hydrochloric acid solution, where F = 1.000). A composite glass electrode C-173 (manufactured by HORIBA, Ltd.) was used for the measurement.

Equation 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, which can be selected from deionized water, methanol, ethanol, isopropanol, and tetrahydrofuran, was used according to the solubility of the resin composition and the dissociation ability of the acidic component. The procedure is described below.
20 g of the resin composition and 120 mL of a measurement solvent (special grade) (for example, tetrahydrofuran / deionized water = 5/1, v / v) were placed in a 200 mL beaker and dissolved uniformly to prepare 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 solution and the blank solution was titrated with an aqueous potassium hydroxide solution (or ethanol solution) having a concentration of 0.0425 mol / L by an automatic potentiometric titrator. The titration result was calculated by Equation 2 and the total acid value (KOHmg / L) was determined (F indicates the factor of the titration solution determined using the standard hydrochloric acid solution, where F = 1.000). A composite glass electrode C-171 (manufactured by HORIBA, Ltd.) was used for the measurement.

Equation 2

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

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 and mixed at the ratios shown in Table 1, and the total base value and total acid value were measured. As shown in Table 1, the total base value of these mixtures is 12.0 mgKOH / g or less, the total acid value is 8.0 mgKOH / g or less, and the difference between the total base value and the total acid value is -1. It was confirmed that the content was 0 to 5.0 KOH mg / g, and the polymerizable resin composition of the present invention was obtained without any particular retreatment. In addition, Examples A-1, A-2, A-6, A-7, A-9 to A-11 are reference examples.

Example A-11
70 g of "DMAA", 112 15 g of EBECRY, 5 g of TPGDA, 5 g of HEA and 5 g of THFA were weighed and mixed uniformly at room temperature, and the total base value and total acid value 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 solution was analyzed again, and it was confirmed that the total base value was 11.5 KOH mg / g, the total acid value was 7.2 KOH mg / g, and the difference between the total base value and the total acid value was 4.3 KOH mg / g. The polymerizable resin composition of the present invention was obtained.

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

Comparative Examples A-13 to A-17
Similar to Example A-1, constituent components such as N-substituted (meth) acrylamide were accurately measured at the ratios shown in Table 1, mixed, and the total base value and total acid value were measured. As shown in Table 1, the total base value of these mixtures exceeds 12.0 mgKOH / g, the total acid value exceeds 8.0 mgKOH / g, or the difference between the total base value and the total acid value is -1. Although it was confirmed that the content was out of the range of 0 to 5.0 KOH mg / g, no particular retreatment was carried out to obtain the comparative polymerizable resin composition of the present invention.

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, 3 parts by weight of D-1173 as a photopolymerization initiator was added. , Uniformly mixed to prepare an active energy ray-curable resin composition. Then, using these resin compositions, an active energy ray-cured film was prepared and its characteristics were evaluated by the following method.

Using a tabletop coating machine (Coater TC-1, manufactured by Mitsui Denki Seiki Co., Ltd.), an aluminum substrate (Al, A5052) is coated with ultraviolet rays and then irradiated with ultraviolet rays (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm ² , integrated light amount: 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 of moisture resistance heat yellowing resistance and light yellowing resistance was carried out as follows, and the transparency and yellowing resistance after the test were evaluated in the same manner. Further, using an amyl substrate and a copper foil as metal materials, the corrosion resistance was evaluated by the following method, and the results are shown in Table 2.

(7) Transparency (transmittance)
Using the obtained cured film after the initial or yellowing resistance acceleration test, the film was allowed to stand still for 24 hours in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%. After that, the transmittance of the cured film was measured with a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the transparency was evaluated in four stages as follows.
⊚: Transmittance is 90% or more ○: Transmittance is 85% or more and less than 90% Δ: Transmittance is 50% or more and less than 85% ×: Transmittance is less than 50% (8) Moisture-resistant thermal yellowing The initial cured film was allowed to stand still for 24 hours in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%. After that, the transmission spectrum of the cured film was measured with a transmission color measurement dedicated machine (TZ-6000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) and used as the initial b value. Using the cured film, the mixture was allowed to stand in a constant temperature and humidity chamber set at 85 ° C. and a relative humidity of 85% for 500 hours to perform an accelerated test of moisture resistance and thermal yellowing. Similarly, the cured film after the test was allowed to stand still for 24 hours in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%, and the transmitted color was measured to obtain the b value after moist heat. Further, the difference between the b value after moist heat and the initial b value was set to the change value Δb (Δb = b value after moist heat − initial b value). Moisture-resistant thermal yellowing was evaluated in four stages as follows.
⊚: The initial b value and the b value after moist heat are both 0.2 or less, and Δb is 0.1 or less. ◯: The initial b value and the b value after moist heat both exceed 0.2. , Both are 0.5 or less, and Δb is 0.2 or less Δ: The initial b value and the b value after moist heat are any one or both are more than 0.5, but both are 1.0 or less. And, Δb is 0.3 or less ×: Initial b value, b value after moist heat exceeds 1.0, or Δb exceeds 0.3 (9) Light yellowing resistance In the same manner as the evaluation of moisture resistance and thermal yellowing, an accelerated test of light yellowing was performed, 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 condition of 500 W / m2. Similar to the moisture-resistant thermal yellowing, the evaluation was performed in 4 stages.
(10) Corrosion resistance A test piece (for evaluation of Al corrosion resistance) in which an active energy ray-cured film is prepared by the above method and the obtained cured film is still attached to an aluminum substrate, and the cured film is slowly removed from the aluminum substrate. Using a test piece (for evaluation of Cu corrosion resistance) that was peeled off and attached to a copper foil (thickness 80 μm), it was allowed to stand in a constant temperature and humidity chamber set at a temperature of 60 ° C. and a relative humidity of 95% for 168 hours. Then, the cured film is peeled off from the aluminum substrate or the copper foil, the surfaces of the aluminum substrate and the copper foil are visually observed, the corrosion resistance of the cured film is evaluated, and the results are shown in Table 2.
◎: No corrosion ○: 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 and mixed uniformly at room temperature, and the total base value and total acid value were measured. As shown in Table 3, it was confirmed that the total base value of the mixture was 1.80 KOH mg / g, the total acid value was 2.0 KOH mg / g, and the difference between the total base value and the total acid value was -0.2 KOH mg / g. The thermopolymerizable resin composition of the present invention was obtained without any particular retreatment.
200 g of ethyl acetate and 100 g of the thermopolymerizable resin composition were added to a reactor equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen introduction tube, and nitrogen gas was introduced while stirring to remove air from the device. After substituting 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 having a solid content of 30%. The solution viscosity was measured at 25 ° C. using a cone plate type viscometer (RE550 type manufactured by Toki Sangyo Co., Ltd.) according to JIS K5600-2-3, and was 3500 mPa · s.
Further, 30 parts were taken out from the polymer solution, 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 the mixture was allowed to stand overnight. The THF solution of the polymer was filtered through a 0.45 μm membrane filter, and gel permeation chromatography (GPC) measurement was performed using a filtrate (Prominence GPC system manufactured by Shimadzu Corporation, Shodex KF-806L column, eluent THF). The weight average molecular weight (Mw) of the polymer was calculated to be 1.16 million by the polystyrene conversion value.

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 the heat-polymerizable resin composition in the same manner as in Example B-1 except that the composition was changed to the polymerizable composition shown in Table 3. Was prepared, and the total base value and total acid value were measured. Further, thermal polymerization was carried out in the same manner, the solid content of the obtained polymer solution was adjusted to 30%, and the viscosity of the solution was measured. Further, as in Example B-1, each polymer was obtained by completely removing the volatile components in the solution, and the weight average molecular weight was measured. The results of various evaluations are shown in Table 3. Examples B-1 to B-6 are reference examples.

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 90 ° C. Was dried for 2 minutes to form a pressure-sensitive adhesive layer. Then, it was left in an environment of a temperature of 23 ° C. and a relative humidity of 50% for one day to obtain a test adhesive sheet (type a).

Examples C-3 and 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 solution of hexamethylene diisocyanate (HDI) in 50% ethyl acetate was added. After adding and uniformly mixing, the mixture was similarly applied to a PET film having a thickness of 25 μm after drying, and dried at 90 ° C. for 2 minutes to form an adhesive layer. Then, it was aged in a constant temperature bath at 40 ° C. for 3 days and left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type b). Examples C-1 to C- 9 are reference examples.

Examples C-5 and 6 and Comparative Example C-13
100 g of the 30% solid content polymer solution obtained in Examples B-2 and B-6 and 70 g of the 30% solid content polymer solution obtained in Comparative Example B-9 were weighed and polyfunctional. 5 g of a 50% ethyl acetate solution of DPHA and 1 g of a photopolymerization initiator I-184 were added as monomers, mixed uniformly, and then similarly applied to a PET film having a thickness of 25 μm after drying, and 2 at 90 ° C. Allowed to dry for minutes to form a pressure-sensitive adhesive layer. After that, it is irradiated with ultraviolet rays (device: ECS-4011GX, an inverter type conveyor device manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm ² , integrated light ^{intensity: 1000 mJ / cm 2} ) and cured. The mixture was allowed to stand in an environment having a temperature of 23 ° C. and a relative humidity of 50% for one day to obtain a test adhesive sheet (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, it is coated on a heavy peeling separator (silicone coated PET film), and a tabletop roll type laminator machine (made by Royal Sovereign) so as not to bite air bubbles with a light peeling separator (silicone coated PET film). Using RSL-382S), the adhesive layer is bonded so that the thickness is 25 μm, and irradiated with ultraviolet rays (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, The ultraviolet illuminance: 700 mW / cm ² , the integrated light amount ^{: 1000 mJ / cm 2} ) was used to prepare a transparent adhesive sheet for optics (type d).

Example C-10 and Comparative Example C-14
Weigh 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 in the predetermined amounts shown in Table 4. After mixing uniformly, an adhesive sheet was prepared in the same manner as in type c, and cured by ultraviolet rays. Then, it was aged in a constant temperature bath at 40 ° C. for 3 days and left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type e).

The characteristics of the produced adhesive sheet were evaluated by the following method, and the results are shown in Table 4.
(11) Transparency The prepared adhesive sheet was allowed to stand still for 24 hours in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%. After that, the transmittance was measured with a haze meter in the same manner as described above, and the transparency was evaluated.
(12) Under the conditions of an adhesive temperature of 23 ° C. and a relative humidity of 50%, the adherend is transferred to a PET film or glass substrate having a thickness of 100 μm and reciprocated twice using a pressure-bonding roller weighing 2 kg. It was pressure-applied and left in the same atmosphere for 30 minutes. Then, using a tensile tester (device name: Tencilon RTA-100 manufactured by ORIENTEC), 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min.
⊚: 30 (N / 25 mm) or more ○: 15 (N / 25 mm) or more, less than 30 (N / 25 mm) Δ: 8 (N / 25 mm) or more, less than 15 (N / 25 mm) ×: 8 (N / 25 mm) ) Less than (13) Stain-resistant adhesive sheet is attached to the adherend in the same manner as in the above-mentioned measurement of adhesive strength, left at 80 ° C. for 24 hours, and then the surface of the adherend is contaminated after the adhesive sheet is peeled off. Observed visually.
⊚: No contamination ○: Very slightly contaminated.
Δ: Slightly contaminated.
X: There is adhesive (adhesive) residue.
(14) The light yellowing resistance evaluation of the light yellowing resistant adhesive sheet was carried out 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, weighed together with other components in a predetermined amount shown in Table 5, mixed uniformly, and an ultraviolet curable sealant. Was prepared. Then, using the obtained encapsulant, a cured product of the encapsulant resin by ultraviolet curing was prepared and its physical properties were evaluated by the following method.

UV curable sealant Method for manufacturing resin cured product A silicon spacer (length 30 mm x width 15 mm x thickness 3 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm), and inside the spacer. A copper foil (length 5 mm × width 50 m × thickness 80 μm) was put in, and the ultraviolet curable sealant prepared above was injected. After sufficient deaeration, irradiate with ultraviolet rays (device: Inverter type conveyor device ECS-4011GX made by Eye Graphics, metal halide lamp: M04-L41 made by Eye Graphics, ultraviolet illuminance: 700 mW / cm2, integrated light intensity: 1000 mJ / cm2) Then, a cured resin resin was prepared. The characteristics of the obtained cured product were evaluated by the following method, and the results are shown in Table 5.

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

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

Equation 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% Δ: Occurrence rate is 0.3% or more and less than 1.0% ×: Occurrence rate is 1 0.0% or more (19) Heat cycle resistance The obtained cured product was left at −40 ° C. for 30 minutes and then left at 100 ° C. for 30 minutes 100 times as one cycle, and the state of the cured product was visually observed.
⊚: No change is seen 〇: Slight bubbles are seen, but no cracks are seen. It is transparent.
Δ: Some bubbles or cracks were observed, and it was slightly cloudy.
X: Bubbles or cracks are generated on the entire surface, and the state is translucent.
(20) Corrosion resistance After the moisture-heat yellowing test, the surface of the copper foil was visually observed, the corrosion resistance of the cured film was evaluated in the same manner as described above, and the results are shown in Table 5.

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

Fabrication of Polarizing Plate by UV Irradiation Using a desktop roll-type laminator machine (RSL-382S manufactured by Royal Sovereign), a polarizing film is sandwiched between two transparent films, and an example or the case is used between the transparent film and the polarizing film. The adhesive of the comparative example was bonded so as to have a thickness of 10 μm. Irradiate ultraviolet rays from the upper surface of the bonded transparent film (device: Inverter type conveyor device ECS-4011GX made by Eye Graphics, metal halide lamp: M04-L41 made by Eye Graphics, ultraviolet illuminance: 700 mW / cm2, integrated light amount: 1000 mJ / cm2 ), And a polarizing plate having transparent films on both sides of the polarizing film was prepared. As the transparent film, an acrylic protective film (Sanduren 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.
⊚: Fine streaks and unevenness of unevenness cannot be confirmed on the surface of the polarizing plate ○: Fine streaks can be partially confirmed on the surface of the polarizing plate Δ: Fine streaks and unevenness of unevenness can be confirmed on the surface of the polarizing plate ×: Clear streaks and unevenness can be confirmed on the surface of the polarizing plate. (22) Under the conditions of peeling strength temperature of 23 ° C. and relative humidity of 50%, the polarizing plate (test piece) cut into 20 mm × 150 mm was subjected to a tensile tester (Shimadzu). It was attached to a test plate attached to an Autograph AGXS-X 500N manufactured by Mfg. Co., Ltd. using a double-sided adhesive tape. Peel off the transparent protective film and the piece of polarizing film from which the double-sided adhesive tape is not attached in advance by about 20 to 30 mm, chuck them on the upper gripper, and peel off at 90 ° strength (N /) at a peeling speed of 300 mm / min. 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) Δ: 1.0 (N / 20 mm) or more, 1.5 (N / Less than 20 mm) ×: Less than 1.0 (N / 20 mm) (23) Water resistance The obtained polarizing plate is cut into 20 × 80 mm, immersed in warm water at 60 ° C. for 48 hours, and then the polarizer and protective film, position. The presence or absence of peeling at the interface between the retardation film and the optical compensation film was confirmed. The judgment was made according to the following criteria.
⊚: No peeling at the interface between the polarizer and the protective film (less than 1 mm)
◯: There is peeling at a part of the interface between the polarizer and the protective film (1 mm or more and less than 3 mm).
Δ: There is peeling at a part of the interface between the polarizer and the protective film (3 mm or more and less than 5 mm).
X: There is peeling at the interface between the polarizer and the protective film (5 mm or more)
(24) Durability The obtained polarizing plate is cut into 150 mm × 150 mm, placed in a thermal shock device (TSA-101LA manufactured by ESPEC), and heat shocked at -40 ° C to 80 ° C 100 times for 30 minutes each. The results were evaluated according to the following criteria.
⊚: No cracks ◯: Short cracks of 5 mm or less are generated only at the end Δ: Cracks are generated in a short linear shape at a place other than the end. However, the line does not separate the polarizing plate into two or more parts. ×: There is a crack in a place other than the end part, and the line separates the polarizing plate into two or more parts ( 25) Heat-resistant yellowing The obtained polarizing plate is cut into 30 mm × 30 mm, the a value and b value of the transmitted hue are measured, and the wavelength is 380 with an ultraviolet visible spectrophotometer UV-2450 manufactured by Shimadzu Corporation. The parallel transmission hue a value and the orthogonal transmission hue b value of about 780 nm were measured, and the ab value of the transmission hue (ab = (a2 + b2) 1/2) was calculated. After that, the polarizing plate was placed in a constant temperature bath at 90 ° C. for 48 hours. The heat-resistant yellowing test was carried out. The ab value after the test was calculated in the same manner, and the value of Δab (Δab = ab value after the test-ab value before the test) was used as an index of yellowing. When it is 0, it does not turn yellow, and the larger Δab, the larger the yellowing.
⊚: 0 <= Δab <= 2
◯: 2 <Δab <= 6
Δ: 6 <Δab <= 10
X: 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 obtained printed matter was evaluated. The clear ink composition does not contain a pigment and a pigment dispersant, and the black ink composition contains pigment pigment black 7 (abbreviated as PMB-7) and pigment dispersant azisper PB821 (abbreviated as PB821) in a predetermined amount shown in Table 7. It is the one that was mixed in.

(26) Viscosity The viscosity of the obtained ink composition was measured using a cone plate type viscometer (device name: RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.) according to JIS K5600-2-3. Based on inkjet printing, the viscosity of the ink composition at 20 ° C. is preferably 2 to 50 mPa · s (Δ evaluation), preferably 3 to 30 mPa · s (○ evaluation), and more preferably 5 to 20 mPa · s. It is preferably s (⊚ evaluation). If it is less than 2 mPa · s (× evaluation), printing bleeding after ejection and a decrease in ejection followability due to printing misalignment are observed, and if it exceeds 50 mPa · s (× evaluation), a decrease in ejection stability due to clogging of the ejection nozzle is observed. Therefore, it is not preferable.
(27) Compatibility The ink composition prepared by the above method was visually confirmed to be compatible.
⊚: No insoluble matter in the ink composition 〇: Slightly insoluble matter is found in the ink composition Δ: Insoluble matter is found in the entire ink composition ×: Precipitate is found in the ink composition

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

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

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

(30) Discharge stability The printed state of the obtained printed matter was visually evaluated.
⊚: Good printing without nozzle removal.
〇: There is a slight nozzle omission.
Δ: Nozzle is missing in a wide range.
X: There is non-discharge.
(31) Sharpness The image sharpness 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: Some ink bleeding was observed.
X: Ink bleeding was significantly observed.
(32) Heat-resistant yellowing The obtained clear ink composition was applied to a substrate substrate (# 125-E20) with a bar coater so as to have a film thickness of 10 μm, and cured with a metal halide lamp in the same manner as described above. The hue of the obtained coating film was measured by Spcetorolino (manufactured by Gretag Macbeth) and left in a constant temperature bath maintained at 60 ° C. for 1 week. Then, 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
〇: 0.2 <ΔE <= 0.5
Δ: 0.5 <ΔE <= 1.0
X: 1.0 <ΔE

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

A 75 μm-thick heavy-release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is adhered to a horizontally installed glass plate, and a spacer with a thickness of 1 mm and an inside of 20 mm × 40 mm is installed and activated inside the spacer. After filling the energy ray-curable resin composition, a light peeling PET film (made by Toyobo Co., Ltd., polyester film E7002) with a thickness of 50 μm is further laminated and irradiated with ultraviolet rays (device: made by Eye Graphics, inverter type). Conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance 300 mW / cm2, integrated light amount 900 mJ / cm2) to obtain a cured product of the composition. After that, the cured product was allowed to stand still for 24 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and the peeled PET films on both sides were removed. Shrinkage rate, surface strength, etc. were measured.

(33) Tensile test According to JIS K-7113, a tensile test was performed on the curing test piece obtained using a precision universal testing machine (manufactured by Shimadzu Corporation, AG-X 500N), and tensile strength, tensile elongation and tensile elasticity were performed. The rate was measured. Each of the obtained measured values was evaluated based on the following criteria.
Tensile strength ⊚: Maximum point stress is 40 MPa or more 〇: Maximum point stress is 30-40 MPa
Δ: Maximum point stress is 15 to 30 MPa
X: Maximum point stress is 15 MPa or less Tensile elongation ◎: Breaking point elongation is 100% or more 〇: Breaking point elongation is 80 to 100%
Δ: Breaking point elongation is 50% to 80%
X: Fracture point elongation is 50% or less Tension elastic modulus ⊚: 1500 MPa or more 〇: 1000 to 1500 MPa
Δ: 500 to 1000 MPa
X: 500 MPa or less (34) Bending test Using the obtained hardening test piece, it was processed into a bar shape conforming to JIS K-7171 to obtain a test piece for the bending test. A bending test of a hardening test piece was performed using a precision universal testing machine (AG-X 500N manufactured by Shimadzu Corporation) according to JIS K-7171, and the bending strength and flexural modulus of the test piece were measured. Each of the obtained measured values was evaluated based on the following criteria.
Bending strength ⊚: Maximum bending stress is 80 MPa or more 〇: Maximum bending stress is 50 to 80 MPa
Δ: Maximum bending stress is 30 to 50 MPa
X: Maximum bending stress is 30 MPa or less Bending elastic modulus ⊚: 1500 MPa or more 〇: 1000 to 1500 MPa
Δ: 500 to 1000 MPa
X: 500 MPa or less (35) Surface hardness Using the above curing test piece, the surface hardness was measured by the durometer method of "Ascar D type hardness tester (manufactured by Polymer Meter Co., Ltd.)" in accordance with JIS K6253, and the following criteria were used. Evaluation was made based on.
⊚: Exceeds D80 〇: Exceeds D60 ~ D80
Δ: Over D40 ~ D60
X: D40 or less (36) Thermal deformation temperature Using the above curing test piece, the thermal deformation temperature was measured in accordance with JIS K7207, and evaluation was performed based on the following criteria.
⊚: Exceeds 50 ° C 〇: Exceeds 40 ° C to 50 ° C
Δ: Over 25 ° C to 40 ° C
X: 25 ° C. or lower (37) Light yellowing resistance Evaluation of the light yellowing resistance was carried out in the same manner as described above using the obtained curing test piece.

Using the above clear ink composition, using an ultra-high-speed stereolithography system (manufactured by Nabtesco, SOLIFORM500B) with a semiconductor laser (manufactured by Spectraphysics, semiconductor-pumped solid-state laser BL6 type, wavelength 355 nm), liquid surface irradiation amount 100 mJ / Under the condition of cm2, three-dimensional modeling was performed at a slice pitch of 0.10 mm for a time of 2 minutes per layer to prepare a rectangular three-dimensional model.

(38) Curing Shrinkage Resistance The curing shrinkage rate is calculated from the specific gravity (d0) of the ink composition before photocuring and the specific gravity (d1) of the modeled product obtained after curing from the following formula, and the curing shrinkage resistance is used as a reference below. Evaluated based on.
Curing shrinkage rate (%) = {(d1-d0) / d1} × 100
⊚: less than 2% 〇: 2% to less than 5% Δ: 5% to less than 10% ×: 10% or more

Examples H-1 to 6 and Comparative Examples H-7 to 10
Using the polymerizable composition obtained in Example A and the polymer obtained in Example B, the four types (b, c, d, e) of the anti-fog coating composition described in Example C are shown in the table. It was prepared with the composition shown in 9, and applied to glass, aluminum, PET and a PC substrate so that the film thickness after drying was 1 μm. Then, depending on each type, it was cured by thermosetting, active energy ray curing, or a combination thereof, and the performance of the obtained anti-fog film was evaluated by the following method, and the results are shown in Table 10.

(39) Transparency The transparency and hue of the evaluation test piece coated with the anti-fog paint were visually observed and evaluated in four stages.
⊚: Excellent (colorless, transparent and glossy)
◯: Good (colorless and transparent, but slightly inferior in glossiness)
Δ: Slightly bad (slightly cloudy and poorly glossy)
×: Bad (almost opaque, cloudy)
(40) The surface of the coating film of the tack resistance evaluation test piece was directly touched with a finger, and the stickiness was evaluated on a 4-point scale.
◎: Excellent (no stickiness at all)
◯: Good (There is some stickiness, but fingers do not stick to the surface of the coating film.)
Δ: Slightly bad (sticky, fingers stick to the surface of the coating film)
×: Bad (severe stickiness, fingers stick to the surface of the coating film)
(41) Adhesion In accordance with JIS K5400, a grid is made with a cutter knife, cellophane tape is attached, and then the cellophane tape is peeled off at an angle of 90 degrees, and the degree of peeling of the coating film from the substrate is in 4 steps. evaluated.
⊚: Excellent (no peeling at all)
◯: Good (slightly peeled, but less than 10%)
Δ: Slightly bad (10% or more and less than 50% peeled off)
X: Bad (50% or more peeled off)
(42) Anti-fog property The anti-fog property was evaluated by the exhaled anti-fog method using an evaluation test piece coated with an anti-fog paint. In a constant temperature and humidity chamber at 23 ° C. and a relative humidity of 50%, exhaled air was sprayed on a glass plate with an antifog film from a distance of 15 cm for 1 second, and the cloudy state was visually observed and evaluated on a 4-point scale.
◎: Excellent (does not fog at all)
○: Good (slightly cloudy for a moment, but cloudy soon clears)
△: Slightly bad (slightly cloudy)
×: Bad (clearly cloudy)
(43) A mixed solution of antifouling oil / carbon pigment = 1/1 was adhered as a pollutant on the coating film of the evaluation test piece in a streak-like manner, and after 3 hours, running water was poured from above for 1 minute to clean the mixed solution. The performance was visually confirmed and evaluated on a 4-point scale.
⊚: Excellent (no dirt remains on the surface of the test piece, and no trace of dirt flow is observed.)
◯: Good (No dirt remains on the surface of the test piece, but there are slight traces of dirt flowing.)
Δ: Slightly bad (slight dirt remains on the surface of the test piece)
×: Bad (a considerable amount of dirt remains on the surface of the test piece)
(44) The test piece for water resistance evaluation was immersed in warm water at 40 ° C. for 240 hours, dried at room temperature, and the appearance of the coating film was visually observed. Compared with the appearance before the test, it was evaluated on a 4-point scale.
⊚: Excellent (no change)
◯: Good (the surface of the coating film is slightly rough)
Δ: 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 constant temperature and humidity chamber at 60 ° C. and a relative humidity of 90% for 5 minutes, and then dried at 90 ° C. for 5 minutes. This was set as one cycle, and after 5 cycles, the anti-fog property was evaluated by the exhaled anti-fog method in the same manner as described above.
(46) Moisture-resistant heat-yellowing The evaluation of moisture-resistant heat-yellowing was carried out in the same manner as described above using the obtained test piece with an anti-fog film.
(47) Corrosion resistance After the moisture-heat yellowing test, the surface of the aluminum substrate was visually observed to evaluate the corrosion resistance of the cured film in the same manner as 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 performed by the following method. A coat layer having a thickness of 3 μm was formed on the film and cured by irradiating with an ultraviolet LED lamp (UV-LED), and the UV-LED curability and the physical properties of the obtained hard coat were evaluated. The evaluation results are shown in Table 11.

Method for Producing Active Energy Ray Coating Film Using the obtained hard coating composition, apply it to the PET film anchor coat surface with a thickness of 100 μm with a bar coater (RDS 1) so that the thickness of the dry coating film becomes 3 μm. A coating film was prepared in. When a solvent was contained, the obtained coating film was dried at 80 ° C. for 2 minutes in an explosion-proof dryer. UV-LED irradiator (HOYA CANDEO OPTRONICS Co., Ltd. EXECURE-H-1VC2, sport type) in which the distance between the coating film and the lamp is adjusted so that the ultraviolet energy of the obtained coating film is 2.7 mJ / cm2 per second. ) To prepare a UV-LED cured film. The UV-LED curability was evaluated by the following method, and the adhesion, pencil strength and scratch resistance of the cured film were evaluated by the following method, and the results are shown in Table 11.

(48) Using the curable and 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 light amount was calculated. Complete curing is a state in which no trace is left when the surface of the cured film is traced with silicone rubber.
(49) Adhesion Using the obtained test piece with a coating film, the adhesion was evaluated in the same manner as described above.
(50) Using steel wool having scratch resistance # 0000, the surface of the obtained coating film was rubbed 10 times back and forth while applying a load of ^{200 g / cm 2, and the presence or absence of scratches was visually evaluated.}
⊚: Almost no peeling of the film or occurrence of scratches is observed.
◯: A slight scratch is observed on a part of the film.
Δ: Streaky scratches are observed on the entire surface of the membrane.
X: The film peels off.
(51) Pencil hardness Using the obtained test piece with a coating film, evaluation was performed based on the JIS K 5400 8.4 hand-drawing method (1990 version).
(52) Light Yellow Degeneration Using the same hard coating composition as described above, a coating film was prepared on a PC substrate instead of a PET film. Using the obtained PC substrate with a coating film as a test piece, a light yellowing resistance evaluation was carried out in the same manner as described above.

As shown in the evaluation results of each of the above-mentioned Examples and Comparative Examples, the polymerizable resin composition containing N-substituted (meth) acrylamide of the present invention has a total base value of 12.0 KOHmg / g or less and a total acid. Heat by controlling the valence to 8.0 KOHmg / g or less and the difference between the total base value and the total acid value (total base value-total acid value) within the range of -1.0 to 5.0 KOHmg / g. It was confirmed that yellowing did not occur with respect to light or light, and that it was suitably used in various fields such as adhesives, adhesives, encapsulants, inks, antifogging agents, and hard coating agents. Further, N-substituted (meth) acrylamide has good compatibility with various organic solvents, general-purpose monomers, and oligomers, and an optimum polymerizable resin composition can be easily prepared according to each application. -The energy ray curability of substituted (meth) acrylamide is extremely high, both thin and thick films can be easily cured, and the resulting cured product has low shrinkage, high transparency, excellent corrosion resistance, heat resistance and strength. , Elongation, etc., and can be widely used for electronic materials, optical components, semiconductors, solar cells, etc.

As described above, the polymerizable resin composition of the present invention has a special purification process or an addition of concern as long as the total base value, total acid value and their differences are within the range limited to the present invention. Industrial grade N-substituted (meth) acrylamide produced by a general production method without blending agents is preferably used. Further, it is possible to provide a polymerizable resin composition thereof, or a resin composition using a polymer composed of the same, which does not substantially cause yellowing or coloring and does not cause metal corrosion. In addition, by eliminating the concern about yellowing, a large amount of N-substituted (meth) acrylamide can be blended in the resin composition, resulting in adhesion to a substrate, weather resistance, heat resistance, and scratch resistance (scratch resistance). Coating film hardness), chemical resistance, etc. can be improved.

Claims (4)

An active energy ray-curable pressure-sensitive adhesive composition containing 1 to 90% by weight of N-substituted (meth) acrylamide represented by the general formula [1].
The adhesive composition may contain a basic component and acidic component,
Total base number of the adhesive composition, the total base number derived from the basic component of the adhesive composition 0.4KOHmg / g or more and less 12.0KOHmg / g,
Total acid number of the adhesive composition, 0.5KOHmg / g or more as the sum of acid value derived from the acid component of the adhesive composition, or less 8.0KOHmg / g, and,
Total base number and the difference between the total acid number of the adhesive composition (total base number - total acid number) is Ri -1.0~5.0KOHmg / g der,
PSA compositions, urethane-based multifunctional monomer 2 to 35 wt% and non-urethane-based multifunctional monomer with an active energy ray-curable pressure-sensitive adhesive composition characterized that you further contain 3-40% by weight.

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are the same or different, and may be substituted with a hydrogen atom, a hydroxyl group, an amine group, an alkoxy group, or a carbonyl group. It exhibits a linear or branched alkyl group of 6, an aliphatic or aromatic ring having 3 to 6 carbon atoms, and R ₂ and R ₃ together with a nitrogen atom carrying them further oxygen. contain an atom or a nitrogen atom may form a 5- to 7-membered ring may be saturated or unsaturated., except if R ₂ and R ₃ are simultaneously hydrogen atom.) The N-substituted (meth) acrylamide is (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth). ) The active energy ray-curable pressure-sensitive adhesive composition according to claim 1, wherein the active energy ray-curable pressure-sensitive adhesive composition is one or more selected from acrylamide, N-methyl-N- hydroxyethyl (meth) acrylamide, and diacetone acrylamide. The active energy ray-curable pressure-sensitive adhesive composition according to claim 1 or 2 , wherein the total base value of the pressure-sensitive adhesive composition is the total base value derived from the basic components in the pressure-sensitive adhesive composition. It is 0.4 KOH mg / g or more and 3.0 KOH mg / g or less, and the total acid value is 0.5 KOH mg / g or more and 2.0 KOH mg / g or less as the total acid value derived from the acidic component in the pressure-sensitive adhesive composition. An optical active energy ray-curable pressure-sensitive adhesive composition, wherein the difference between the total base value and the total acid value of the pressure-sensitive adhesive composition is −0.2 to 1.0 KOH mg / g. The active energy ray-curable pressure-sensitive adhesive composition according to claim 1 or 2 , wherein the total base value of the pressure-sensitive adhesive composition is the total base value derived from the basic components in the pressure-sensitive adhesive composition. It is 0.4 KOH mg / g or more and 4.0 KOH mg / g or less, and the total acid value is 0.5 KOH mg / g or more and 2.0 KOH mg / g or less as the total acid value derived from the acidic component in the pressure-sensitive adhesive composition. The active energy ray-curable pressure-sensitive adhesive composition for a metal substrate, wherein the difference between the total base value and the total acid value of the pressure-sensitive adhesive composition is −0.8 to 2.0 KOH mg / g. thing.