JP2015108097A - Active energy ray-polymerizable resin composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new active energy ray-polymerizable resin composition having excellent heat resistance and the like, and a laminate for an optical element which achieves easy and firm adhesion or a tight contact regardless of types of various optical films, has excellent polymerization curability at a low exposure dose, contains substantially no organic solvent, and has high durability and excellent flexibility by using an active energy ray-polymerizable adhesive and/or an active energy ray-polymerizable coating agent using the above active energy ray-polymerizable resin composition in lamination of various optical films.SOLUTION: The active energy ray-polymerizable adhesive and/or the active energy ray-polymerizable coating agent essentially comprise a boron-based softening agent (A) and an α,β-ethylenically unsaturated double bond group-containing compound (B).

Description

  The present invention relates to a novel active energy ray polymerizable resin composition and a laminate using the resin composition, and more particularly, to a laminate suitable for use in an optical element.

The active energy ray-polymerizable resin composition has a high polymerization rate and generally can be used in the absence of a solvent. Therefore, the active energy ray-polymerizable resin composition has excellent workability and has extremely low energy required for polymerization. The active energy ray polymerizable resin composition typically contains a resin component that can be polymerized by active energy rays and a monomer component having an α, β-unsaturated double bond group. Examples of the resin component include oligomers having a low molecular weight and an α, β-unsaturated double bond group at the molecular end, such as polyester resins, polyurethane resins, polyepoxy resins, and polyacrylic resins. It's being used. The monomer component is polymerized together with the resin component by irradiation with active energy rays, but can function as a solvent until the polymerization is completed. Therefore, the active energy ray polymerizable resin does not require a separate solvent, and thus has an advantage that the solvent does not volatilize when the coating film is formed.

  From the above viewpoints, the use of the active energy ray-polymerizable resin composition can reduce environmental pollution in order to improve recent environmental pollution problems. Therefore, active energy ray polymerizable resin compositions are used in various fields including building materials, packaging materials, printing materials, display device materials such as displays, and electric and electronic component materials such as optical devices. The field of use is expanding.

  For example, in the various fields described above, the resin composition can be used for adhesive applications. However, the resin composition does not necessarily have good adhesion to a substrate (surface to be coated), and various methods for improving adhesion to various substrates have been reported. For example, Patent Document 1 discloses a method of fundamentally changing the molecular skeleton of the oligomer in the resin composition by using a specific saturated copolyester. Patent Document 2 discloses a method of blending a metal salt of a terminally modified phosphate ester of an α, β-unsaturated double bond group as an adhesion improver in an active energy ray polymerizable resin composition. Yes. Furthermore, Patent Document 3 discloses a method of blending a compound having a tricyclodecenyl group and an α, β-unsaturated double bond group in an active energy ray polymerizable resin composition.

  In addition, the reactive oligomers used in the active energy ray-polymerizable resin composition generally have a very high viscosity, so that it is difficult to handle them alone as a binder for paints and adhesives. Therefore, the operability as a binder is usually enhanced by using a reactive diluent having an α, β-unsaturated double bond group and a low viscosity. As the reactive diluent, many compounds such as monomers having an α, β-unsaturated double bond group are known (Patent Documents 4 to 6). Among these, acrylic esters are generally used because they generally exhibit excellent polymerizability with respect to active energy rays. However, on the other hand, since the odor and skin irritation are strong, it is desired to improve the environment at the time of use such as a coating operation with respect to a paint or an adhesive containing acrylic esters.

  On the other hand, in recent years, the development and generalization of information communication devices including displays has been remarkable, and in the field of display devices, further improvements in the performance and productivity of materials such as coating agents, adhesives, and sealing agents are required. . And various embodiment which uses the said active energy ray polymeric resin composition as a material of a display apparatus is proposed.

  In display devices, various films are usually used depending on the application, such as an antireflection film for preventing reflection from an external light source, and a protective film (protection film) for preventing scratches on the surface of the display device. ing. For example, a polarizing plate or a retardation film is laminated as a liquid crystal cell member constituting a liquid crystal display (LCD).

  Further, the flat panel display (FPD) is not only used as a display device, but also provided with a touch panel function on the surface thereof, and may be used as an input device. Also in the touch panel, films such as a protective film, an antireflection film, and an ITO vapor deposition resin film are used.

  The film is typically applied to a display device in the form of a laminate as an optical element member. For example, the above-described film is applied to a display device in a form in which a coating layer made of a coating agent is provided on the surface layer for preventing scratches, preventing fingerprint adhesion, preventing charging, or facilitating adhesion. In another form, the said film is applied to a display apparatus with the form stuck to adherends, such as an optical element, via the adhesive agent. The coating agent or adhesive used in the above-described form is required to have characteristics such as transparency or heat resistance. In response to such demands, in this technical field, a solvent-containing two-component thermosetting adhesive or an active energy ray-polymerizable adhesive mainly containing a polyacrylic resin is used.

  However, while the conventional active energy ray polymerizable resin composition has advantages such as a high polymerization rate, the polymer tends to have difficulty in obtaining sufficient transparency required for optical applications. In addition, when a laminated body for an optical element is produced using the above resin composition, since the dimensional change characteristics of the material of each layer in the laminated body are different, the dimensions change and warp with changes in temperature and humidity. (Also called curl) tends to occur. Furthermore, although it is desirable that the laminate has a high refractive index, it is difficult to adjust the refractive index in the configuration of the resin composition. Even if a resin composition having a high refractive index can be formed, the resin composition tends to have poor adhesion.

  Patent Document 7 is a photocurable resin composition containing a polyurethane poly (meth) acrylate and a photopolymerization initiator of a hydroxyacetophenone oligomer, and this resin composition has a high curing rate and shrinkage upon curing. And has the advantage of excellent dimensional stability. However, the usage form of the disclosed resin composition is limited to the use of the floor covering. Patent Document 7 clarifies that when the resin composition is used as a protective coating agent for flooring, warping of the flooring is reduced. However, when the resin composition is used for a coating film, since the polymerization shrinkage of the resin composition is large, a large warp occurs, and it is difficult to achieve both low curling properties and coating performance such as adhesion. It is. In addition, when a thin coating layer of 2 to 5 μm is produced using the resin composition, when the coating layer is dried by heating and drying at 120 ° C. or higher during the curing step, the resin composition is heated by the heat during drying. The photopolymerization initiator in the product volatilizes, the curing reaction becomes insufficient, and the coatability tends to be inferior.

  Patent Documents 8 and 9 each have a high refractive index obtained by polymerizing an active energy ray polymerizable composition containing a compound containing a sulfur atom and having an α, β-unsaturated double bond. An optical material is disclosed. However, all of the disclosed optical materials have a bending adhesive strength (SA) according to JISK6856 of 0.1 or less, and are poor in adhesiveness.

  Furthermore, in the field of display devices, a backlight system that illuminates a liquid crystal layer from the back surface is widespread. Typically, a backlight unit such as an edge light type or a direct type is provided on the lower surface side of the liquid crystal layer. Equipped. Such an edge light type backlight unit basically includes a linear lamp serving as a light source, a rectangular plate-shaped light guide plate arranged so that an end thereof is along the lamp, and a surface side of the light guide plate. And a prism sheet disposed on the surface side of the sheet. In recent years, light-emitting diodes (LEDs) that excel in color reproducibility and power saving are often used as light sources in place of the cathode-ray tube (COFL), and as a result, the heat resistance and dimensional stability of display devices are increased. There is a growing demand for sex.

  By the way, a flexible display using a resin flexible film substrate has been attracting attention in recent years because it is thin and lightweight, is not easily damaged, and can be formed into a curved surface. However, the flexible display is not a conventional glass substrate, but a resin flexible film substrate is used as a component of the flexible display. Therefore, the transparent substrate has rigidity and heat resistance that can withstand expansion and contraction due to mechanical stress and heat in the process of forming electrodes, etc. I need sex. In addition, since it is often used for portable use, it is subject to a relatively slow and large bending deformation of several Hz or less from the outside. There is a risk of being connected. Since polarizing films and the like used as conventional optical element members are bonded to a glass substrate, the emphasis is particularly on adhesion and heat resistance, and materials with considerably high rigidity have been used. In addition, in order to cope with flexibility, it has been demanded that moderate flexibility and stress relaxation property capable of diffusing outside with strain energy as heat can be maintained.

As described above, in the field of display devices, it is desired to develop an active energy ray polymerizable resin composition that is excellent in various properties required for optical applications in addition to conventional advantages and has flexibility. Yes. More specifically, it is an active energy ray-polymerizable resin composition that can be suitably used as a coating agent or an adhesive that constitutes a laminate for an optical element, substantially containing no organic solvent, and having adhesion and In addition to excellent dimensional stability during curing, and excellent optical properties such as refractive index, total light transmittance, and haze, it has good durability in harsh environments under high humidity and high temperature, There is a need for a resin composition that retains stress relaxation properties and flexibility.

JP-A-56-95902 JP-A-57-180618 JP-A-57-87409 JP-A-6-329731 JP 2001-240609 A JP 2004-099644 A Japanese Patent Laid-Open No. 08-27397 JP-A-4-108816 Japanese Patent Laid-Open No. 5-271383

  In view of the above situation, the present invention is excellent in heat resistance, moist heat resistance, thermal dimensional stability, flexibility, weather resistance, etc., and can be suitably used in optical applications, and is substantially free of organic solvents and handled. It is an object of the present invention to provide a novel active energy ray polymerizable resin composition useful as a coating agent or an adhesive. Further, the present invention is a laminate having a resin layer formed by using the resin composition on at least one main surface of various transparent films, particularly various optical films, regardless of the type of the various optical films. The present invention provides a laminate, particularly an optical element laminate, in which the resin layer can be easily or firmly adhered or coated to the optical film, and is excellent in punching workability and wet heat durability as compared with conventional ones. Objective.

As a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned target can be achieved by the active energy ray polymerizable composition and adhesive shown below, and have completed the present invention.

That is, the present invention provides a boron-based softening agent (A),
The present invention relates to an active energy ray polymerizable resin composition comprising an α, β-ethylenically unsaturated double bond group-containing compound (B) as an essential component.

Furthermore, the present invention relates to the total amount of the active energy ray polymerizable composition,
0.1-50% by weight of softener (A),
50-99.9% by weight of compound (B),
It contains about the said active energy ray polymeric resin composition characterized by containing.

Furthermore, the present invention relates to the above resin composition, wherein the boron softener (A) is a compound obtained by reacting a boron compound (a1) with a hydroxyl group-containing compound (a2).

Furthermore, this invention relates to the said resin composition characterized by the boron-type softening agent (A) having surface active ability.

Furthermore, the present invention relates to the above resin composition, wherein the compound (B) comprises an α, β-ethylenically unsaturated double bond group-containing compound (b1) having a hydroxyl group.

Furthermore, the present invention relates to the above resin composition, wherein the compound (B) contains an α, β-ethylenically unsaturated double bond group-containing compound (b2) having one or more cyclic structures.

Furthermore, the present invention provides a substrate (G),
And a resin layer comprising the resin composition provided on at least one main surface of the substrate (G).

Furthermore, this invention relates to the said laminated body characterized by the said base material (G) being a transparent film (H).

Further, in the present invention, the transparent film (H) is a polyacetyl cellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide. It is at least 1 sort (s) selected from the group which consists of a system film, It is related with the said laminated body characterized by the above-mentioned.

Furthermore, the present invention provides an optical film,
It is related with the laminated body for optical elements which has the resin layer which consists of the said resin composition provided in the at least one main surface of this optical film.

ADVANTAGE OF THE INVENTION According to this invention, the active energy ray polymeric resin composition which can superpose | polymerize by low illumination intensity can be provided. In addition, according to the present invention, by using the resin composition as an adhesive or a coating agent, the optical film can be easily and firmly adhered or adhered, and punching processability, heat resistance, moist heat resistance, and flexibility can be achieved. It is possible to provide a laminate having excellent properties, particularly a laminate for optical elements.

Hereinafter, embodiments of the present invention will be described.
<Active energy ray polymerizable resin composition>
The active energy ray polymerizable resin composition of the present invention comprises a boron-based softening agent (A) and an α, β-ethylenically unsaturated double bond group-containing compound (B) as essential components, It is required to be flexible and flexible.

Here, the “active energy ray” means an energy ray in a broad sense that can provide energy necessary for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. . The active energy ray polymerizable resin composition of the present invention (hereinafter referred to as “resin composition”) undergoes a polymerization reaction upon irradiation with the active energy ray to form a cured product. Although it does not specifically limit, In one Embodiment of this invention, it is preferable that the said active energy ray is light energy containing an ultraviolet-ray.

Hereinafter, the constituent components of the resin composition will be specifically described.
(A) component:
In the resin composition of the present invention, the boron-based softening agent (A) is a compound formed by reacting the boron-based compound (a1) with the hydroxyl-containing compound (a2), and one or more in the molecule Of B atoms. The softening agent (A) may have various functional groups. These reactions can be obtained by general reactions as described in Boronic acids-Preparation and applications in organic synthesis and medicine 2005 Dennis G. Hall.

As the boron-based compound (a1), there are many boron-based compounds (a1) which have one or more B—O—H bonds or can be hydrolyzed in the presence of water to form one or more B—O—H bonds. Any boron-containing compound can be suitably used without limitation. Specific but non-limiting examples of the boron-based compound (a1) include boric acid oxides (for example, B ₂ O ₃ ), orthoboric acid, metaboric acid, perboric acid, hypoboric acid, boronic acid, Boric acid such as borinic acid;
For example, those obtained by reaction of boric acid with alcohol or phenol, such as trimethyl borate, triethyl borate, tri-n-propyl borate, tri-n-butyl borate, triphenyl borate, triborate borate Isopropyl, tri-t-amyl borate, triphenyl borate, trimethoxyboroxine, tri-2-cyclohexylcyclohexyl borate, triethanolamine borate, triisopropylamine borate, mannitol borate, glycerol borate, and Examples thereof include boric acid esters such as triisopropanolamine borate.
Further, the boron-based compound (a1) of the present invention includes boronic acid derivatives. For example, alkyl or alkenyl boronic acids such as methyl boronic acid, ethyl boronic acid, butyl boronic acid, cyclohexyl boronic acid;
Examples thereof include aryl boronic acids such as phenyl boronic acid, naphthalene boronic acid, and anthracene boronic acid, 1,4-benzenediboronic acid, and substituted aryl boronic acids having an arbitrary substituent on these aryl groups.

In addition, other amino-containing borates and tertiary amine salts of boric acid may be useful. Such boron-containing compounds include 2- (β-dimethylaminoisopropoxy) -4,5-dimethyl-1,3,2-dioxaborolane, 2- (β-diethylaminoethoxy) -4,4,6-trimethyl. -1,3,2-dioxaborinane, 2- (β-dimethylaminoethoxy) -4,4,6-trimethyl-1,3,2-dioxaborinane, 2- (β-diisopropylaminoethoxy) -1,3,2 -Dioxabonarine, 2- (β-diisopropylaminoethoxy) -4-methyl-1,3,2-dioxaborinane, 2- (γ-dimethylaminopropoxy) -1,3,6,9-tetrapoxa-2-boracycloundecane And 2- (β-dimethylaminoethoxy) -4,4- (4-hydroxybutyl) -1,3,2-dioxaborinane. But it is not limited to these.

The boron-based compound (a1) may also include a metal salt of boric acid (that is, a metal borate) provided that it can easily dissociate in an aqueous medium to form boric acid. Suitable examples of metal borates include, for example, calcium borate, potassium borate (eg, potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate and potassium octaborate), sodium borate (eg, per Sodium borate, sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium perborate, sodium hexaborate and sodium octaborate). Similarly, ammonium borate may be useful.

As the boron-based compound (a1) used in the present invention, boric acid, boric acid esters and tertiary amine salts of boric acid are preferable in terms of solubility, and boric acid is particularly preferable from the viewpoint of adhesiveness. The amount of the boron-based compound (a1) used in the present invention is 0.1% by weight or more and 50% by weight or less when the total amount of the boron-based softening agent (A) is 100% by weight. Is preferred. If it is less than 0.1% by weight, the content of B atoms decreases and it becomes difficult to form hydrogen bonds, so that the desired adhesive strength cannot be achieved. If it is 50% by weight or more, problems such as precipitation over time or gelation due to excessive increase in viscosity as a liquid may occur. Especially preferably, it is 0.5 to 40 weight%.

In addition, the boron-based softening agent (A) can also include organic oligomers and polymer compounds containing a boron-containing moiety. Suitable examples include reacting a polymer borate ester (eg, an active hydrogen-containing polymer (eg, a hydroxyl group-containing acrylic polymer or polysiloxane polymer)) to form a polymer having borate ester groups. A boron-based compound (a1), which is formed by introducing an α, β-ethylenically unsaturated double bond group by a reaction such as amidation, esterification, acylation or etherification. Can be mentioned.
Suitable polymers for this purpose include any of a variety of active hydrogen-containing polymers including, for example, at least one of an acrylic polymer, a polyester polymer, a polyurethane polymer, and a polyether polymer. Selected from.

Industrially, at least the boron softener (A) of the present invention is preferably obtained by reacting a boron compound (a1) with a hydroxyl group-containing compound (a2). The presence of one or more B—O—H bonds in the structure of the boron compound (a1) is more preferable because the reaction rate with the hydroxyl group-containing compound (a2) is high and the production efficiency is higher.
After the resin composition is cured with active energy rays, if a B—O—R bond (R is a hydrogen atom or a carbon atom) remains in the softener (A), the B atom contained A coating film bonded to the hydroxyl group derived from the hydroxyl group-containing compound (a2) is formed by the hydrogen bonding performance derived from the origin. Moreover, there exists an effect which forms a bond with the surface functional group of the below-mentioned base material (G), and improves adhesiveness.

As the hydroxyl group-containing compound (a2) that forms the boron-based softening agent (A) of the present invention, the compound (b1) described later having a hydroxyl group and an α, β-ethylenically unsaturated double bond group is If it is a compound which does not contain and does not have an α, β-ethylenically unsaturated double bond group and has a hydroxyl group, it can be used without any particular limitation, and the number average molecular weight (Mn): Low molecular weight polyols (a2-1) and relatively high molecular weight polyols (a2-2) having a number average molecular weight (Mn) of 500 to 30,000 can be mentioned, and can be used without any particular limitation.

More specific examples of the relatively low molecular weight polyols (a2-1) include 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2 -Octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetra Decanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol 1 Ikosanoru, oleyl alcohol, geraniol _{{(CH 3) 2 C =} CH (CH 2) 2 C (CH 3) = CHCH 2 OH}, Rinaruoru _{{(CH 3) 2 C =} CH (CH 2) 2 C ( CH3) (OH) CH = CH2 }, myricyl alcohol _{(C 30 H 61 OH),} 2- Puropiru 1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isononyl alcohol, 3,7 dimethyl-3-octanol, 2,4 dimethyl-1-heptanol, 2-heptylundecanol , 1-butanol ethoxylate _{(C 6 H13OC 2 H 4 OH} ), 2- butanol propoxylate _{(C 6 H 13 OCH 2 CH} (OH) C H _3), 1-octanol ethoxylates, 2-octanol propoxylate, butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, hexadecyl phenol, nonadecyl phenol, icosyl (C ₂₀ H _21), octylphenol ethoxylate, nonylphenol Ethoxylate, dodecylphenol ethoxylate, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norbonol, terpineol, water-added rosin alcohol (trade name Abitol, manufactured by Hercules Inc.) Monohydric alcohols such as these, and alkylene oxides were added to these monohydric alcohols. Valence alcohols;

For example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1 , 8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (added mole number of 10 or less), polyoxypropylene glycol (added mole number) 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butyl Ethylpentanediol, 2-e Aliphatic or alicyclic diols such as til-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol;

3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 ′ -(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, addition-type bisphenol obtained by adding alkylene oxide to bisphenol, etc. Aromatic diols;

For example, glycerin, trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, 1,1,1-trimethylol Heptane, 1,1,1-trimethyloloctane, 1,1,1-trimethylol nonane, 1,1,1-trimethyloldecane, 1,1,1-trimethylolundecane, 1,1,1-trimethylol Dodecane, 1,1,1-trimethylol tridecane, 1,1,1-trimethylol tetradecane, 1,1,1-trimethylol pentadecane, 1,1,1-trimethylol hexadecane, 1,1,1-tri Methylol heptadecane, 1,1,1-trimethylol octadecane, 1,1,1-trimethylol nanodecane, 1- Limethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert-tridecane, 1,1,1 -Trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl -Hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylolisoheptadecane, trimethylolbutene, trimethylolheptene, trimethylolpentene, trimethylolhexene, trimethylolhept Ten, trimethylol octene, trimethylol decene, trimethylol dodecene, trimethyl Roll tridecene, trimethylol pentadecene, trimethylol hexadecene, trimetroleheptadecene, trimethylol octadecene, 3-methylpentane-1,3,5-triol, 1,2,6-hexanetrio, pentaerythritol, di Pentaerythritol, tripentaerythritol, diglycerin, triglycerin, polyglycerol, ditrimethylolethane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, inositol, tetrakishydroxymethylphosphonium chloride, sorbitan, sorbitol, mannitol, Examples include trihydric or higher polyhydric alcohols such as sucrose and cellulose, and polyhydric alcohols obtained by adding alkylene oxide to these polyhydric alcohols. Each of them may be used alone or in combination of two or more.

More specific examples of the relatively high molecular weight polyols (a2-2) include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by reacting the above-mentioned relatively low molecular weight diol with a carbonate or phosgene.

Examples of the above-mentioned commercially available high molecular weight polyester polyol include Byron GK640 manufactured by Toyobo Co., Ltd. [number average molecular weight (hereinafter also referred to as “Mn”) = 18,000, glass transition temperature (hereinafter referred to as “Tg”). Described) = 79 ° C., hydroxyl value = 5, acid value <4, linear type], Byron GK880 (Mn = 18,000, Tg = 84 ° C., hydroxyl value = 5, acid value <4, linear type), Byron 300 (Mn = 23,000, Tg = 7 ° C., hydroxyl value = 5, acid value <2, linear type), Byron 500 (Mn = 23,000, Tg = 4 ° C., hydroxyl value = 5, acid value <2) , Linear type), Byron 560 (Mn = 19000, Tg = 7 ° C., hydroxyl value = 8, acid value <2, branched type) and Byron 630 (Mn = 20,000, Tg = 75 ° C., hydroxyl group) Value = 5, Valence = 1, linear type); UE-3600 (Mn = 20,000, Tg = 75 ° C., hydroxyl value = 4, acid value = 1), UE-3690 (Mn = 14,000, Tg =) manufactured by Kuraray Co., Ltd. 91 ° C., hydroxyl value = 8, acid value = 1) [above, manufactured by Unitika Ltd.], P1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), P2010 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), P4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), P5010 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type), P6010 (Mn = 6,000, hydroxyl value = 19, acid value <0.5, linear liquid type), P4050 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear Type), P6010 (Mn = 6,000, hydroxyl value = 19, acid value <0.5, linear liquid type), N4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear) Liquid type), PNOA4014 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), P2011 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear) Liquid type), and P4011 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type); Kyowapol 2000BA (Mn = 2,000, hydroxyl value = Kyowa Hakko Chemical Co., Ltd.) 58, acid value <0.5, linear liquid type), and Kyowapol 5000PA (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type).

In addition, propylene glycol monolaurate, propylene glycol monooleate, glycerol monolaurate, glycerol monostearate, glycerol monooleate, glycerol monolinoleate, glycerol monoricinoleate, glycerol monocaprylate, glycerol dilaurate, glycerol dioleate, Glycerol trioleate, glycerin dilinoleate, glycerin diricinolate, glycerin diacetomonolaurate, glycerin diacetomonolaurate, sorbitan laurate, sorbitan oleate, diglycerin laurate, diglycerin oleate, diglycerin monolaurate, diglycerin mono Olate, tetraglycerin oleate, hexaglycerin laurate, decaglycerin laurate, decaglycerin la Rate, polyoxyethylene glycerol monolaurate, polyoxyethylene glycerol monostearate, polyoxyethylene glycerol monooleate, polyoxyethylene glycerol monolinoleate, polyoxypropylene glycerol monolaurate, polyoxypropylene glycerol monostearate, poly Oxypropylene glyceryl monooleate, polyoxypropylene glyceryl monolinoleate, polyoxyethylene glyceryl dilaurate, polyoxyethylene glyceryl diolate and other esters of glycerin, alkylene oxide and fatty acids, compounds having hydroxyl groups, polycaprolactone diol, poly Obtained by ring-opening polymerization of lactones such as (β-methyl-γ-valerolactone) diol and polyvalerolactonediol That the polyester polyols and the like are also included in the high molecular weight polyester polyol.

  As a commercial product of the high molecular weight polyamide polyol, TPAE617 (Mn = 15,000, Tg = 90 ° C., hydroxyl value = 16, acid value = 1, linear type) manufactured by Fuji Kasei Kogyo Co., Ltd. can be used.

  Commercially available products of the above high molecular weight polycarbonate polyol include, for example, Oxomer N112 (Mn = 1,000, Tg = 60 ° C., hydroxyl value = 112, acid value <0.5, linear type) manufactured by Perstorp; Asahi Kasei Chemicals Corporation PCDL-T5651 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), PCDL-T5652 (Mn = 2,000, hydroxyl value = 56, acid value <0.05) , Linear liquid type), PCDL-T4671 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), and PCDL-T4672 (Mn = 2,000, hydroxyl value = 52, Acid value <0.05, linear liquid type); PMHC-1050 manufactured by Kuraray Co., Ltd. (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid tie) ), PMHC-2050 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), C-1090 (Mn = 1,000, hydroxyl value = 112, acid value <0.5). , Linear liquid type), C-2090 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), C-3090 (Mn = 3,000, hydroxyl value = 37, acid value). <0.5, linear liquid type), C-4090 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), C-5090 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type), C-1065N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), C-2065N (Mn = 2,000) , Hydroxyl value = 56, acid value <0.5, linear liquid type), C-1 15N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type) and C-2015N (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear) Liquid type).

  Examples of commercially available high molecular weight polyurethane polyols include Byron UR1350 (Mn = 30,000, Tg = 3 ° C., hydroxyl value = 46, acid value <1, linear type) manufactured by Toyobo Co., Ltd., Byron UR1400 (Mn = 40,000, Tg = 83 ° C, hydroxyl value = 2, acid value <1, linear type), Byron UR3210 (Mn = 40,000, Tg = -3 ° C, hydroxyl value = 3, acid value <1, linear) Type), Byron UR5537 (Mn = 20,000, Tg = 34 ° C., hydroxyl value = 17, acid value <1, linear type), and Byron UR9500 (Mn = 25,000, Tg = 15 ° C., hydroxyl value = 5, acid value <1, linear type); Takelac E158 (hydroxyl value = 20, acid value <3), Takelac E551T (hydroxyl value = 30, acid) manufactured by Mitsui Chemicals Polyurethanes <3), and, Takelac A2789 (hydroxyl value = 10, acid number <2), and the like.

  In the present invention, the relatively high molecular weight polyols (a2-2) can be used alone or in combination of two or more. Moreover, it can also use together with the said comparatively low molecular weight polyol (a2-1). Among these hydroxyl group-containing compounds (a2), when polyols having an alkylene oxide chain such as a polyethylene oxide chain or a propylene oxide chain are used, the flexibility (flexibility) of a coating film polymerized and cured by active energy rays It is preferable because the stress relaxation property that can diffuse the strain energy by bending as heat is obtained.

  The molecular weight of the hydroxyl group-containing compound (a2) is not particularly limited as long as it can be dissolved in the later-described α, β-ethylenically unsaturated double bond group-containing compound (B), but the number average molecular weight (Mn) is 300. Polyols in the range of ~ 30,000 are preferred. When such a hydroxyl group-containing compound (a2) is used, a coating film excellent in flexibility and stress relaxation properties can be obtained. More preferably 500 to 20,000, most preferably 1,000 to 10,000 are used. When the number average molecular weight (Mn) of the hydroxyl group-containing compound (a2) is smaller than 300, the generated softening agent (A) becomes excessively hard and it becomes difficult to express flexibility (flexibility). In addition, if a plastic composition containing a too hard softener (A) is used to laminate plastic films or a glass plate and a plastic film, the adhesive strength is weakened, and such a laminate is prolonged under high temperature and high humidity. It will be easier to peel off when the period is over. On the other hand, when the Mn of the hydroxyl group-containing compound (a2) exceeds 50,000, the solubility and compatibility of the softener (A) in the later-described α, β-ethylenically unsaturated double bond group-containing compound (B) will be described. Is lowered, and the viscosity of the resin composition is increased, which makes it difficult to handle during coating.

  The glass transition temperature (Tg) of the hydroxyl group-containing compound (a2) is also not particularly limited, but is preferably -70 to 80 ° C, more preferably -50 to 20 ° C. If the glass transition temperature is less than -70 ° C, the adhesiveness and cohesive force of the resin composition may be insufficient, and cohesive failure may occur after lamination, resulting in peeling. On the other hand, when the temperature exceeds 80 ° C., the coating film becomes too hard and may not exhibit adhesiveness or may affect the coating processability. The glass transition temperature of the hydroxyl group-containing compound (a2) can be adjusted by appropriately selecting the kind of the polyol as the raw material. Moreover, it can also adjust to a suitable glass transition temperature using the 2 or more types of hydroxyl-containing compound (a2) from which a glass transition temperature differs.

The hydroxyl value of the hydroxyl group-containing compound (a2) is preferably in the range of 5 to 500 mgKOH / g, more preferably in the range of 10 to 300 mgKOH / g. When the hydroxyl value exceeds 500 mgKOH / g, the softening agent (A) becomes too hard and it may be difficult to develop adhesiveness. When the hydroxyl value is less than 5 mg KOH / g, the solubility of the softening agent (A) in the below-mentioned α, β-ethylenically unsaturated double bond group-containing compound (B) is lowered, and the prepared resin composition Since the viscosity of the product increases, handling at the time of coating processing becomes difficult, which hinders workability and the like.

As the hydroxyl group-containing compound (a2) of the present invention, a polyol having a balanced structure of hydrophobicity and hydrophilicity, in particular, a nonionic surfactant, is preferable. This is preferable because it has a stress relaxation property capable of diffusing energy as heat. Industrially, diglycerol monolaurate, diglycerol monooleate, polyoxyethylene glycerol monolaurate, polyoxyethylene glycerol monostearate, polyoxyethylene glycerol monooleate, nonylphenol polyethylene glycol adduct (addition mole number 9) Polyethylene glycol (addition mole number 4) / polypropylene glycol (addition mole number 2) polymer and the like are preferably used.
In addition, the measuring method of a number average molecular weight (Mn), a weight average molecular weight (Mw), an acid value (AV), and a hydroxyl value (OHV) is mentioned later.

(B) component:
In one embodiment of the resin composition of the present invention, it is important that the resin composition contains an α, β-ethylenically unsaturated double bond group-containing compound (B) in addition to the essential components described above. . In particular, any compound containing one or more α, β-unsaturated double bond groups can be used without any limitation, but α, β-ethylene containing one or more hydroxyl groups in the structure thereof can be used. It is preferable to contain a polymerizable unsaturated double bond group-containing compound (b1). The compound (b1) is divided into a compound (b1-1) having a hydroxyl group and not having a cyclic structure and a compound (b1-2) having a hydroxyl group and having a cyclic structure, both of which have a hydroxyl group. By this, a big effect is shown in the adhesive improvement with the below-mentioned base material (G), and the solubility of a softening agent (A).
Furthermore, an α, β-ethylenically unsaturated double bond group-containing compound which does not have a hydroxyl group in the molecule and has one or more cyclic structures from the viewpoint of improving durability such as heat resistance or heat and humidity resistance It is preferable to contain (b2). Moreover, (alpha), (beta) -ethylenically unsaturated double bond group containing compound (b3) other than (b1) and (b2) can also be contained.

By adding the compound (B) to the resin composition, it is easy to increase the efficiency and sensitivity of the copolymerization reaction between the compound (A) and the compound (B). Further, the viscosity of the resin composition can be easily reduced, and the workability during coating can be easily improved. Although it does not specifically limit, The following is mentioned as a compound which can be used as a component (B).
In the present application, when “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” are expressed, Unless otherwise stated, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or methacryloyloxy”, and “allyl and / or methallyl”, respectively. ".

  Among the compounds (b1), the compound (b1-1) having a hydroxyl group and not having a cyclic structure is not particularly limited as long as it has a hydroxyl group in the structure but does not have a cyclic structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxy (meth) acrylate Butyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate Octyl, cyclohexanedimethanol mono (meth) acrylic acid ester, (meth) acrylic acid 10-hydro Sidedecyl, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional glycerol (meth) acrylate, or (meth) acrylate glycidyl laurate, (meth) acryl Acid-containing glycidyl oleate, fatty acid ester (meth) acrylate such as glycidyl stearate (meth) acrylate, or the above hydroxyl group-containing α, β such as 2- (acryloyloxy) ethyl 6-hydroxyhexanoate -(Meth) acrylic acid ester having a hydroxyl group at the terminal by the ring-opening addition of ε-caprolactone lactone to the ethylenically unsaturated double bond group-containing compound, or the hydroxyl group-containing α, β-ethylenically unsaturated double bond Ethylene oxide, propylene for group-containing compounds Emissions oxide, alkylene oxide addition was repeated adding an alkylene oxide such as butylene oxide (meth) aliphatic hydroxyl group-containing acrylic acid ester (meth) acrylate;

  For example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, triethylene glycol Hydroxyl-containing aliphatic vinyl ethers such as methylolpropane monovinyl ether, pentaerythritol monovinyl ether, or alkylene oxide-added vinyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added;

  For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

  For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;

  For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. Of (meth) acrylamides;

Examples thereof include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.
As the compound (B), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε-caprolactone An α, β-ethylenically unsaturated double bond group-containing compound having 2 to 18 carbon atoms, such as 1 to 2 mol added (meth) acrylic acid 2-hydroxyethyl, is particularly preferable.

Among the compounds (b1), the compound (b1-2) having a hydroxyl group and having a cyclic structure can be used without particular limitation as long as it has both of the cyclic structures. Since the compound (b1-2) has one or more ring structures in the molecule, it is preferable from the viewpoint of water resistance in addition to durability such as heat resistance and moist heat resistance even if it has a hydroxyl group. .
The compound (b1-2) is not particularly limited as long as it has both a hydroxyl group and a cyclic structure in its structure. For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, ( 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy- (meth) acrylate 3-phenoxyoctadecyl, (meth) acrylic acid monohydroxyethyl phthalate, (meth ) Having a cyclic structure other than a hydroxyl group and a hetero ring such as acrylic acid 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate;

For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone [2-hydroxy-4- {2-acryloyloxy} ethoxybenzophenone and 2-hydroxy-4- {2-methacryloyloxy} ethoxybenzophenone Are also expressed as “2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone”. The same applies below. ], 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- Hydroxyl-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-ben Hydroxyl group-containing benzotriazole-based triazole (meth) acrylic acid esters;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Hydroxyl-containing triazines such as triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (meta ) Acrylic acid esters and the like, and these may be used alone or in combination of two or more.

As the compound (b1-2), in view of compatibility with the softening agent (A) and durability such as heat resistance and water resistance, 1,2-cyclohexanedimethanol acrylate, 1,3-cyclohexanediacrylate Particularly preferred are methanol, 1,4-cyclohexanedimethanol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like.

  The α, β-ethylenically unsaturated double bond group-containing compound (b2) having no hydroxyl group in the molecule and having one or more cyclic structures has a ring structure containing no heteroatoms in the molecule. α, β-ethylenically unsaturated double bond group-containing compound (b2-1) and α, β-ethylenically unsaturated double bond group-containing compound (b2-2) having a ring structure containing a hetero atom in the molecule (B2-1) is preferable from the viewpoint of heat-resistant yellowing.

The compound (b2-1) is not particularly limited as long as it has a ring structure other than a heterocyclic ring in its structure. For example, cyclohexyl (meth) acrylate, 1-methyl-1- (meth) acrylate Cyclopentyl, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, 1-ethyl (meth) acrylate 1-cyclohexyl, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, iso-bornyl (meth) acrylate, (meth) Phenyl acrylate, 2-methoxyethyl (meth) acrylate, 2-oxo-1, (meth) acrylate, -Phenylethyl, 2-oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, (meth ) 1-anthryl acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (Meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid 2-ethyladamantyl-2-yl, (meth) acrylic acid 2 -N-propyladamantyl-2-yl, 2-isopropyladamantyl-2-yl (meth) acrylate, 1- (adamantan-1-yl) -1-methylethyl (meth) acrylate, 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-(meth) acrylic acid Yl) -1-methylpropyl, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1. 0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl, (meth) acrylic acid dihydro -Α-Turpinyl, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3 3.1] Oct-2-yl 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) acrylic (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2-propenylphenyl, (Meth) acrylic acid cyclic esters such as (meth) acrylic acid cyclohexyl glycidyl ether and (meth) acrylic acid phenylglycidyl ether;

  For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings, and acid anhydrides thereof Kind;

  For example, (meth) acrylic acid cyclic esters containing a sulfonyl group, such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

  For example, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- ( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acryloyloxyethyl phosphate;

  For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxy) di (meth) acrylate Propyl) benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) Tetraethylene oxide adduct of lopan, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide of di (meth) acrylic acid-4,4′-sulfonyldiphenol Adduct, Tetraethylene oxide adduct of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, Tetra of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane Ethylene oxide adduct, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meta ) Tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) propane-dicap Bifunctional (meth) acrylic acid cyclic esters such as lolactonate, tetraethylene oxide adduct of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinyl Cyclic compounds containing alkenyl groups such as benzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexyl vinyl ether, cyclohexylmaleimide, vinylcyclohexene monooxirane ;

  For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyl) Aromatic vinyl compounds having an acyl group such as oxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene;

  For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoylpropionate (meth) allyl, benzoylbutyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Aromatic (meth) allyl having an acyl group such as hexanoic acid (meth) allyl Ethylenically unsaturated cyclic monomers containing carbonyl groups of compounds, and the like;

  For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

For example, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2- Cyclic vinyl ethers such as naphthyl vinyl ether;

  For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl ether-based monomers having a long-chain alkyl groups such as E methylpropenylmethyl docosyl ether;

  For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate , Octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenyl Decyl benzoate, 4-isopropenylbenzoic acid dodecyl, 4-isopropenylbenzoic acid tetradecyl, 4-isopropenylbenzoic acid hexadecyl, 4-isopropenylbenzoic acid octadecyl, 4-isopropenylbenzoic acid eicosyl, 4-isopropenylbenzoic acid Docosil How long vinylbenzoic acid ester having a chain alkyl group or isopropenyl benzoic acid ester monomers;

  For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether N-butyltetra (propylene oxide) vinyl phenyl ether, n Pentaxytetra (propylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene Oxide) vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl Benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl Ether, ethyl poly (propylene oxide) vinyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether Vinyl phenyl ether monomers having a long-chain polyalkylene oxide moiety such as methyl poly (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Type monomers;

For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl Ether, methyl poly (propylene oxide) Isopropenyl-based monomers having a polyalkylene oxide moiety, such as propenyl benzyl ether;

  For example, mono-long-chain alkyl ester cyclic monomers of dicarboxylic acid such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate monomers having a moiety;

  For example, alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid, 2-propenyloxybenzenesulfonic acid, 2-methyl-2-propenyloxybenzenesulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, triethyl styrene sulfonate Styrenesulfonic acid such as ammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, etc .;
2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Examples include acid metal salts and ammonium salts.

  In addition, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like have an α, β-unsaturated double bond group, compound (b2-1) included. These may use only 1 type or may use multiple types together.

  As the compound (b2-1), from the viewpoint of durability such as heat resistance and water resistance of the coating film, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, Particularly preferred are dicyclopentanyl acrylate, dicyclopentanyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyl diacrylate, and 2-ethyladamantyl-2-yl acrylate.

  The compound (b2-2) is not particularly limited as long as it has a heterocyclic structure in its structure. For example, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, Heterocyclic (meth) acrylic acid esters containing a nitrogen atom such as 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

  For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2 -Vinyl-2-imidazoline, 4,5-dihydro-2-vinyl-1H-imidazole, 2-vinyl-1H-imidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl-1H-pyrazole 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1-vinylindazole 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, Nilcarbazole, 1,1′-divinyl-2,2′-bi (1H-imidazole), N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, Vinyl group-containing compounds having a nitrogen atom-containing heterocycle such as 1-vinyl-2 (1H) -pyridinethione;

  For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- ( (Meth) allyl-3-ethyl-1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 2-vinyl Piperazine, 4-vinylpiperazine, 1-benzyl-2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinylpyridine, -Vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3- Vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl-1,3,5-dimethyl-2,4-diamine, 3 -Vinyl group-containing compounds having a nitrogen atom-containing six-membered ring such as vinyl-1,2,4,5-tetrazine;

  For example, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinyliso Xaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meta ) Nitrogen atoms such as allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline Containing heteropolycyclic vinyl group-containing compounds;

  For example, 1-methyl-4,5-divinyl-1H-imidazole, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6-divinylpyridine and the like containing nitrogen atoms Compounds having a ring structure and two or more vinyl groups;

For example, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5-isopropylpyrimidine, 2- (Meth) allylpyridine-containing compounds having a nitrogen atom-containing heterocyclic structure, such as (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-3- (meth) allylpyridine;

  For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylindazole, 3-phenyl-4- (meth) allylisoquinoline, 9- (meth) allyl (Meth) allyl group-containing compounds having a heteropolycyclic structure containing a nitrogen atom, such as -9H-carbazole;

  For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification (Meth) acrylic acid esters having;

  For example, 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2 -Heterocyclic acrylamides such as (ylmethoxymethyl) (meth) acrylamide;

  For example, maleimide derivatives having both nitrogen and oxygen atoms such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, 2-vinyl oxazole, 2-phenyl-4-vinyl oxazole, 2-phenyl-5-vinyl oxazole, 5-ethoxy-2-vinyl oxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole Ethenyl group-containing compounds;

  For example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( (Meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxoteto Hydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-Dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, and the like. ;

  For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

  For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Examples thereof include vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom such as thiazole, and these may be used alone or in combination of two or more.

  As the compound (b2-2), from the viewpoint of durability such as heat resistance and water resistance, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl methacrylate, 4-acryloylmorpholine, 1-vinyl Particularly preferred are imidazole, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, di (meth) acrylic acid ethoxylated isocyanuric acid, and tri (meth) acrylic acid ethoxylated isocyanuric acid.

  The compound (b3) other than (b1) or (b2) is not particularly limited as long as it has an α, β-ethylenically unsaturated double bond group in its structure. ) Monomethylaminoethyl acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid-mono or di-alkylamino esters such as diethylaminoethyl, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate;

  For example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylic acid sec- Butyl, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acryl iso-nonyl, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Of (meth) acrylic acid alkyl esters;

  For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth ) Acrylic acid dimer, maleic acid; fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, Angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (Meth) acryloyloxyethyl succine , Mono (meth) acrylic acid ω-carboxy polycaprolactone ester, etc., repeating polylactone-based (meth) acrylic acid ester, ethylene oxide, propylene oxide and other alkylene oxides having a carboxyl group at the terminal by ring-opening addition of a lactone ring Carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acids such as esters of adducted alkylene oxide-added succinic acid having a carboxyl group at the terminal and (meth) acrylic acid And acid anhydrides thereof;

  For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

  For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

  For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

  For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

  For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, (meth) acrylic acid phosphooxyethylene oxide (ethylene oxide addition moles: 4-10), (meth) acrylic acid phosphooxypropylene oxide (propylene oxide addition moles: 4-10) and other phosphonic acid group-containing (meth) acrylic acid esters;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

  For example, metal salts and ammonium of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

  For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Gio Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7- Heptanediol, 1,8-octanediol di (meth) acrylic acid, 1,2-octanediol di (meth) acrylic acid, 1,9-nonanediol di (meth) acrylic acid, 1, di (meth) acrylic acid 1, 2-decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) a 1,16-hexadecanediol silylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1 di (meth) acrylate , 5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, di (meth) 2,2-diethyl-1,3-propanediol acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, di (meth) 2-ethyl-1,3-hexanediol acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl di (meth) acrylate , 8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di (meth) 2-methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1, di (meth) acrylate 3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-di (meth) acrylate Hexanediol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, di (meth) acrylate ) Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate;

  For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

  For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;

  For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

  For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;

  For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexanedecyl vinyl ether , Octa Sil vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxy Butyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, diethylene glycol butyl vinyl ether, etc. The aliphatic Vinyl ether compounds;

  For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol Divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1,4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether ( HDVE), trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether (TMPEOTVE), epentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. Vinyl ethers of

  For example, fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

  For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

  For example, monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide Mono- or di-alkylaminoalkyl (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

  For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- N-alkoxy group-containing (meth) acrylamides such as 2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

  For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;

  For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconnitrile, 2-propenenitrile, 2-cyanoethyl (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

  For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;

  For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

  For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

  For example, vinyl halides such as vinyl chloride, vinylidene chloride and allyl chloride;

  For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

As the other α, β-ethylenically unsaturated double bond group-containing compound (b3), a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and the resin composition of the present invention is subjected to active energy ray polymerization. When used as a reactive adhesive or an active energy ray polymerizable coating agent, it is preferable that bifunctional or higher (meth) acrylic acid esters are included from the viewpoint of the active energy ray polymerization rate.

  In the α, β-ethylenically unsaturated double bond group-containing compound (B) of the present invention, compatibility with the softening agent (A), polymerization curability by active energy ray irradiation, and a base material (G) described later The superiority of the compound (B) in terms of adhesion and durability such as heat resistance, moist heat resistance and water resistance is (b1-2)> (b1-1) ≧ (b2-1)> (b2- Although 2)> (b3), a good resin composition can be obtained by blending in a timely manner so that both the hydroxyl group and the cyclic structure are contained.

Preferred proportions of the components constituting the α, β-ethylenically unsaturated double bond group-containing compound (B) of the present invention include 1 part by weight to 45 parts by weight of the compound (b1) and 1 part by weight of the compound (b2). 45 parts by weight and 10 parts by weight to 98 parts by weight of the compound (b3).
When the amount of the compound (b1) is less than 1 part by weight, the compatibility with the softening agent (A) is lowered or the adhesion with the base material (G) described later is lowered. When the amount of the compound (b1) is more than 45 parts by weight, the water resistance is inferior, which is not preferable. When the compound (b2) is less than 1 part by weight, the heat resistance and moist heat resistance of the coating film are lowered. When the amount of the compound (b2) is more than 45 parts by weight, the flexibility of the coating film is lost and the coating becomes brittle.

  The boron-based softening agent (A) of the present invention preferably has a surface activity. By having the surface activity ability, it becomes possible to delocalize the polar part and the nonpolar part uniformly in the coating film, and because of hydrogen bonding accompanying the contained B atom, under high humidity and high temperature, Durability in a harsher environment is improved. In addition, it is easy to release the energy generated by a relatively slow and large bending deformation as heat to the outside of the coating film, so that it is possible to suppress the occurrence of cracks at the interface between the laminates, adhesion failure, etc. . As such a boron-based softening agent (A), industrially, diglycerin borate monostearate (“Emalbon S-60” manufactured by Toho Chemical Co., Ltd.), diglycerin borate monooleate (“Emalbon S-manufactured by Toho Chemical Co., Ltd.”). 80 ”), polyoxyethylene glycerol borate monolaurate (“ Emalbon T-40 ”manufactured by Toho Chemical Co., Ltd.), polyoxyethylene glycerol borate monooleate (“ Emalbon T-80 ”manufactured by Toho Chemical Co., Ltd.) is preferably used. .

The resin composition of the present invention comprises a compound (A) with respect to the boron-based softening agent (A) and the α, β-ethylenically unsaturated double bond group-containing compound (B) being 100% by weight. ) 0.1 to 50% by weight and compound (B) 50 to 99.9% by weight, preferably 1 to 30% by weight of compound (A) and 70 to 99% by weight of compound (B) More preferably, it is contained in a ratio of%.
When the softening agent (A) is 0.1% by weight or more, sufficient flexibility (flexibility) and cohesive force can be easily obtained, and an effect of improving heat resistance and moist heat resistance can be expected. On the other hand, when the compound (A) is 50% by weight or less, when the resin composition is used as a coating agent or an adhesive, the stretchability and flexibility of the coating film can be sufficiently secured. G) is preferable because adhesion and adhesion to G) are improved.

Ingredient (E):
The resin composition of the present invention can be cured by a polymerization reaction that proceeds by irradiation with various activation energy rays. However, the resin composition may contain an active energy ray polymerization initiator (E) as necessary, in addition to the essential components (A) and (B). By using the active energy ray polymerization initiator (E), the polymerization reaction can be promoted. In one embodiment of the present invention, the activation energy is preferably ultraviolet light, and when the polymerization reaction proceeds by irradiation with ultraviolet light, the resin composition preferably includes an active energy ray polymerization initiator (E). .

In the present invention, as the component (E), a compound arbitrarily selected from known compounds as an active energy ray polymerization initiator can be used.
Specific examples include the following. 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like.
Moreover, as a commercial item, the following is mentioned, for example. Irgacure 184,907,651,1700,1800,819,369, 261 (BASF), DAROCUR-TPO (BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Darocur-1173 (Merck), Ezacure KIP150, and TZT (Nihon Shibel Hegner), Kayacure BMS, Kayacure DMBI (Nippon Kayaku) and the like.
Moreover, the photoinitiator which has at least 1 (meth) acryloyl group in a molecule | numerator can also be used.
Further, as the α, β-ethylenically unsaturated double bond group-containing compound (b2-2) having a heterocyclic structure, glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) Heterocycle-containing (meth) acrylic acid esters having a 3-membered or 4-membered oxygen atom such as (3-methyl-3-oxetanyl) methyl acrylate and (meth) acrylic acid-3,4-epoxycyclohexylmethyl When a cationically polymerizable compound (D) described later is used, it is preferable to contain a known photoacid generator as the active energy ray polymerization initiator as necessary. Examples of the photoacid generator include sulfonium salts such as UVACURE 1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by Sun Apro), IRGACURE 250 (manufactured by Ciba Specialty Chemicals), and WPI-113 (Wako Pure Chemical). ), And Rp-2074 (made by Rhodia Japan). Examples include iodonium salts and the like, and by using in combination, the polymerization cross-linking proceeds and the adhesive layer is excellent in durability against heat and humidity. It is preferable to form.
Moreover, the active energy ray polymerization initiator which has at least 1 (meth) acryloyl group in a molecule | numerator can also be used.
In the present invention, as the component (E), the above-mentioned compounds can be used alone or in combination of two or more. In the present invention, as the component (E), the above-mentioned compounds can be used alone or in combination of two or more.

From the viewpoint of reactivity, the blending ratio of the component (E) is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, with the total amount of the resin composition being 100 parts by weight. It is a range.

  The resin composition of the present invention does not substantially contain an organic solvent. The resin composition preferably contains no organic solvent, but the active energy ray polymerization initiator (E) is often poorly soluble in the polymerizable component. Therefore, a small amount of an organic solvent may be included to dissolve the active energy ray polymerization initiator (E). The content of the organic solvent in the resin composition is preferably within 5% by weight.

  Furthermore, in order to improve the performance of the active energy ray polymerization initiator (E), an active energy ray sensitizer may be used in combination. Representative examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles or other nitrogen-containing compounds. Of these, anthracene or benzophenone, thioxanthone or perylene, phenothiazine, and rose bengal are preferably used.

Component (C):
In one embodiment of the resin composition of the present invention, the resin composition may contain an oligomer (C) in addition to the essential components. By using the oligomer (C), when the resin composition is used as a coating agent or an adhesive, adhesion and adhesion to the substrate can be further improved. Moreover, it becomes easy to improve the heat resistance or heat-and-moisture resistance of the resin layer.

  The oligomer (C) is a compound obtained by adding an α, β-unsaturated double bond group to a polymer of monomers and / or various compounds having at least an α, β-unsaturated double bond group. , One or more α, β-unsaturated double bond groups in the molecule. The oligomer may have various functional groups in addition to the α, β-unsaturated double bond group. In one embodiment of the present invention, the oligomer (C) is selected from the group consisting of a polyester oligomer (c1), a polyurethane oligomer (c2), a polyepoxy oligomer (c3), and a polyacrylic oligomer (c4). Including at least one kind, these can be used without any particular limitation.

(C1) Polyester oligomer As the polyester oligomer (c1), the terminal of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol on the main chain skeleton or a hydroxyl group in the polyester chain and (meth) acrylic acid, maleic A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as an acid, or a carboxyl group in the terminal or polyester chain of the polyester ( It is a compound obtained by esterification with the aforementioned compound (b1) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. In addition, a polyester oligomer obtained from an acid anhydride, glycidyl (meth) acrylate, and the above-mentioned hydroxyl group-containing compound (a2) having at least one hydroxyl group can also be used as the polyester oligomer (c1).

  Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, and each can be used without any particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedioic acid. Examples thereof include acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride Phosphate, also anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like can be used. .

  More specifically, as the alicyclic polybasic acid, for example, as the alicyclic dicarboxylic acid, for example, dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid , Cyclopropane-1β, 2α-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -Cyclopentane-1β, 2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1, 3-dicarboxylic acid, (1S, 2S) -1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid , Saturated alicyclic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid, 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid Acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene- 1,3-dicarboxylic acid, 2,5-hexadiene-1α, 4α-dicar Unsaturated double bond in such phosphate rings include one or two unsaturated alicyclic dicarboxylic acid having, like these alicyclic dicarboxylic acids and anhydrides thereof can be used.

  Further, derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), derivatives of tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride, 3- Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) Hydrogenated phthalic anhydride derivatives can also be used as alicyclic dicarboxylic acid anhydrides.

  More specifically, examples of the aromatic polybasic acid include, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (−)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracenedical Acids, 1,2-phenanthrene dicarboxylic acids, 4,5-phenanthrene dicarboxylic acids, aromatic dicarboxylic acids such as 3,9-perylene dicarboxylic acid, and aromatic dicarboxylic acids such as phthalic anhydride and 4-methylphthalic anhydride An anhydride is mentioned, These aromatic dicarboxylic acid and its anhydride etc. can be utilized.

  Furthermore, chlorendic anhydride, het anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as the polybasic acid.

  Moreover, as a compound which has at least 1 hydroxyl group, the above-mentioned hydroxyl-containing compound (a2) is mentioned, and it can use without a restriction | limiting in particular, respectively.

(C2) Polyurethane-based oligomer The polyurethane-based oligomer (c2) is a compound obtained by reacting at least one compound having an isocyanate group and the compound (b1), or a compound having at least one isocyanate group and the above-mentioned compound. A compound obtained by reacting the compound (b1) with a urethane prepolymer having a terminal isocyanate group obtained by reacting the hydroxyl group-containing compound (a2) with a compound containing at least one isocyanate group and a hydroxyl group-containing compound ( a urethane prepolymer of a terminal isocyanate group obtained by reacting with a2), a urethane prepolymer of a terminal isocyanate group obtained by further reacting a compound having at least one amino group, and the compound (b1) Obtained by reacting Thing is. Moreover, what contains the urea bond group obtained by making an isocyanate group and an amino group react is also contained in a polyurethane-type oligomer (d2).

  Examples of the compound having at least one isocyanate group include monofunctional polyisocyanates and polyfunctional isocyanates, and aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, etc., respectively. Can be mentioned. More specifically, as monofunctional polyisocyanate, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl Isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methyl Benzyl isocyanate, (S)-(−)-α-methylbenzyl isocyan Nate, (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- And toluenesulfonyl isocyanate.

  Among polyfunctional isocyanates, the aromatic polyisocyanate is more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( Alias: 4,4'-MDI), 2,4-tolylene diisocyanate (alias: 2,4-TDI), 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-tri Examples include isocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, and the like.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

  Moreover, as a part of (c2) component, the above-mentioned 2-methylpentane-2,4-diol adduct of polyisocyanate, trimer having an isocyanurate ring, and the like can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

  More specifically, as amines having an amino group, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2 , 4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethyl Propylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di 2-hydroxypropyl ethylene) diamine, aliphatic such as piperazine polyamine;

Alicyclic polyamines such as isophorone diamine and dicyclohexylmethane-4,4′-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis- ( sec-butyl) aromatic diamines such as diphenylmethane;
Silylamines having a monofunctional silylamino group such as trimethylsilyldimethylamine;
Silylamines having a bifunctional silylamino group such as 1,1,3,3-tetramethyldisilazane can be used.

(C3) Polyepoxy oligomer The polyepoxy oligomer (c3) is a compound having a glycidyl group and one or more hydroxyl groups or carboxyl groups in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. A compound obtained by a reaction with an α, β-unsaturated double bond group-containing compound having a compound, substantially having no glycidyl group and having an α, β-unsaturated double bond group-containing compound It is. Representative examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. As the bisphenol type polyepoxy oligomer, α, β-unsaturation having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols and epichlorohydrin and (meth) acrylic acid It is obtained by reacting with a double bond group-containing compound.

  The epoxidized oil polyepoxy oligomer has at least one hydroxyl group or carboxyl group in the molecule such as epoxidized oil such as soybean oil and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. Those obtained by reaction with an α, β-unsaturated double bond group-containing compound can be used. As the novolak type polyepoxy oligomer, α, β-unsaturation having novolak type epoxy resin and one or more hydroxyl groups or carboxyl groups in the molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. What is obtained by reaction with a double bond group containing compound can be used. Examples of the alicyclic polyepoxy oligomer include α, β- having one or more hydroxyl groups or carboxyl groups in the molecule such as alicyclic epoxy resin and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid and the like. What was synthesize | combined by reaction with an unsaturated double bond group containing compound can be used.

(C4) Polyacrylic oligomer In the present invention, an acrylic oligomer (c4) can also be used as the oligomer (C). Specific examples of usable compounds include modified polyethers having α, β-unsaturated double bond groups, amine-modified α, β-unsaturated double bond group-containing compounds, alkyd resins, and spiroacetal resins. Selected from the group consisting of a modified α, β-unsaturated double bond group-containing compound obtained by adding an α, β-unsaturated double bond group to various compounds such as polybutadiene resin, polythiol polyene resin and polyhydric alcohol. Oligomers or prepolymers of one or more compounds can be used.

In addition to the aggregation density, the weight average molecular weight of the oligomer (C) (below) from the viewpoint of obtaining excellent properties in terms of compatibility with other components that form a coating film by polymerization, and durability such as heat resistance and moist heat resistance. , Mw.) Is preferably in the range of 300 to 50,000 in terms of compatibility of the polymer coating film, good durability (heat resistance, moist heat resistance) and agglomeration density, and 400 to 30,000. It is preferable that it is the range of these. By using an oligomer having Mw of 50,000 or less, it is possible to easily provide a resin composition having excellent fluidity and compatibility with the components (A) and (B). Along with this, it is possible to easily suppress problems such as a decrease in coating properties of the resin composition, a decrease in coating film durability such as adhesion, and a whitening of the coating film. On the other hand, by using an oligomer having an Mw of 300 or more, when the base material (G) and another base material (G) are attached using the resin composition as an adhesive, Cohesive failure is less likely to occur.
In addition, the measuring method of a number average molecular weight (Mn), a weight average molecular weight (Mw), an acid value (AV), and a hydroxyl value (OHV) is mentioned later.

  Although it does not specifically limit, In preferable one Embodiment of this invention, it is preferable that the said oligomer (C) contains a polyurethane-type oligomer (c2) at least. When using the said resin composition for uses, such as an adhesive agent, there exists a tendency for the elasticity and softness | flexibility of a contact bonding layer to change depending on the coupling group in the said oligomer (C). When the bonding group is an ester or ether group, it is easy to obtain excellent flexibility. However, it tends to have low elasticity and low hydrolysis resistance. On the other hand, when the component (c2) is used, it is easy to balance elasticity and flexibility based on the urethane bond. Moreover, since the said component (c2) also has favorable hydrolysis resistance, it can improve water resistance and heat-and-moisture resistance easily. Furthermore, generally, when a corona treatment or the like is performed on a film-like substrate, a carbonyl group is interposed on the surface of the film-like substrate. For such a carbonyl group, the urethane bond is easy to form a counter electrode bond (acid-base interaction) at a basic site caused by a nitrogen atom, and therefore has good adhesion and adhesion to a film-like substrate. It can be improved easily. On the other hand, when the linking group is an ester or ether, the interaction with the carbonyl group on the film-like substrate occurs between the oxygen atom and a relatively weak bond compared to the case where the linking group is urethane. Become. Actually, in the resin composition prepared at the same blending ratio, when the component (c2) is used as the oligomer (C) and when other components are used, the former is different in various characteristics. Tends to give superior results. However, even when an oligomer component other than the component (c2) is used in the present invention, desired characteristics can be easily obtained by appropriately blending other constituent components.

  In one embodiment of the resin composition of the present invention, the total amount of components (A) and (B) is preferably 100 parts by weight, and the amount of oligomer (C) is preferably 1 to 250 parts by weight. More preferably, it is the range of 1-100 weight part. By setting the oligomer (C) to 1 part by weight or more, deficiency in cohesive force can be improved, and characteristics such as heat resistance and moist heat resistance can be easily improved. On the other hand, by setting the oligomer (C) to 250 parts by weight or less, when the resin composition is used as a coating agent or an adhesive, it becomes easy to obtain excellent adhesion or adhesion to the substrate.

Component (D):
In one embodiment of the resin composition of the present invention, the resin composition may contain a cationically polymerizable compound (D) in addition to the essential components. By using the cationic polymerizable compound (D), when the resin composition is used as a coating agent or an adhesive, different types of polymerization curing by active energy ray irradiation is possible, so that the cured coating film forms a phase separation structure. In addition, since it is easy to control elasticity, stress relaxation property, and creep characteristics, it is possible to further improve the adhesion or adhesion to the substrate. Moreover, it becomes easy to improve the heat resistance or heat-and-moisture resistance of the resin layer.

The cationically polymerizable compound (D) contains at least one functional group that is cationically polymerized by an acid catalyst, and these can be used without any particular limitation.
The cationic polymerizable compound (D) is preferably a cyclic hetero compound or a vinyl ether exemplified in the above-mentioned compound (B) from the viewpoint of reactivity by active energy rays. Among the cyclic hetero compounds, a 3-membered cyclic ether group is preferred. An oxirane compound (d1) having one or more of them is particularly preferably used.
Examples of the three-membered cyclic ether group include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloromethyl) oxirane. , Aliphatic cyclic ether groups such as (bromomethyl) oxirane and oxiranyl acetonitrile;
For example, 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, ethylenebis (3,4-oxirane Cyclohexanecarboxylate), bis (3,4-oxiranecyclohexylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis ( 3,4-oxiranecyclohexyl methyl ether), 2,3,4,15-dioxirane-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] heny Sun (also a compound which can be named 3,4-oxiranecyclohexanespiro-2 ′, 6′-dioxanespiro-3 ″, 5 ″ -dioxanespiro-3 ′ ″, 4 ′ ″-oxiranecyclohexane), 4- (3,4-oxiranecyclohexyl) -2,6-dioxa-8,9-oxiranespiro [5.5] undecane, 4-vinylcyclohexene dioxide, bis-2,3-oxiranecyclopentyl ether, and dicyclo Examples thereof include a three-membered cyclic ether group bonded to an alicyclic ring such as pentadiene dioxide. In these three-membered cyclic ether group-containing compounds, a group in which one or a plurality of hydrogen atoms are removed is combined with another chemical structure, which can be an oxirane compound (d1).
The oxirane compounds exemplified here may be used alone or in combination with a plurality of oxirane compounds.

The oxirane equivalent of the oxirane compound (d1) is usually 30 to 3000 g / eq, preferably 50 to 1500 g / eq. When the oxirane equivalent is 30 g / eq or more, the flexibility of the coating film after polymerization and curing is excellent, and the adhesion to the substrate (G) is improved. On the other hand, it is preferable that it is 3000 g / eq or less because of excellent compatibility with other components.

  The oxirane compound (d1) is more preferably an oxirane compound (d1-1) having an aromatic ring substituent in order to improve heat resistance and moist heat resistance.

  More specifically, examples of the aromatic ring substituent include phenyl, phenylene, tolyl, tolreno, benzyl, benzylidene, benzylidine, xylyl, xylylene, phthalylidene, isophthalylidene, terephthalylidene, phenethylidene, phenethylidine, styryl, styrylidene, as-pseudocumyl. , V-pseudocumyl, s-pseudocumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, cinnamylidene, cinnamilidine, duryl, jurylene, thymyl, carbacrylyl, cuminyl, cuminylidene, neophyll, xenyl, benzhydryl, benzhydrylidene, trityl, etc. The representative substituents include benzene, toluene, xylene, styrene, hemimeritene, pseudocumene, mesitylene, cumene, Ningu, isodurene, durene, cymene, an aromatic ring can be mentioned one or more forms of group obtained by removing a hydrogen atom in the benzene derivatives such as Meriten can bind to other chemical structures.

  In addition, for example, cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene;

  For example, [4n + 2] annulene having a carbon number other than benzene and having 3 or more carbon atoms constituting the ring;

  For example, aromatic polycyclic compounds such as biphenyl and triphenylmethane;

For example, pentalene, indene, indane, ninhydrin, naphthalene, tetralin, decalin, sapotalene, cadalene, eudarene, naphthol, menadiol, gossypol, naphthoquinone, lauson, juglone, menadione, plumbagin, futhiocol, echinochrome A, alkanenin, shikonin, acetonaphthone Carbon condensed bicyclic compounds such as acid, naphthoyl, naphthalic acid, naphthalate, acetomenaphton, naphthionic acid, naphthionate, naphthionyl, dansyl, crocenic acid, flavianic acid, chromotropic acid, neocuperone, azulene, camazulene, guaiazulene, heptalene, octalene, purprogaline ;

For example, as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene, perinaphthene, phenanthrene, phenanthryl, phenanthryllium, phenanthryllidene, Phenanthrylene, phenanthrol, molhole, phenanthrone, phenanthraquinone, pimantrene, reten, anthracene, anthryl, anthryllium, anthrylidene, anthrylene, anthrol, anthranol, anthrobin, anthraline, ditranol, anthroyl, anthrone, bianthrone, anthraquinone , Anthraquinonyl, anthraquinonylene, alizarin, quinizarin, anthralphine, chrysazine, anthragalo Carbon-fused tricyclic compounds such as rupurpurpurin, flavopurpurin, anthrapurpurin, quinalizarin, tectoquinone, chrysophanol, chrysophanoic acid, emodin, lane, kermesic acid, carminic acid, dianthrimide, anthrimide, chrysanmic acid, colchicine ;

  For example, trindene, trindane, fluoranthene, acephenanthrylene, acephenanthrene, acanthrylene, aceanthrene, triphenylene, pyrene, chrysene, tetraphen, tetracene, naphthacene, rubrene, tetracycline, chlortetracycline, oxytetracycline, pleiadene, benzo Carbon-fused tetracyclic compounds such as anthrone;

  For example, carbon condensed pentacyclic compounds such as picene, perylene, pentaphen, pentacene, tetraphenylene, coranthrylene, coranthrene;

For example, corannulene, fluorene, anthanthrene, zetrene, hexahelicene, hexaphen, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyranthrene, octaphene, octacene, terylene, naphthacenonaphthacene, nonaphene, nonacene, violanthrene, violanthrene, isolan One hydrogen atom in a cyclic compound such as a condensed carbon compound having 6 or more rings such as violanthrene, isoviolanthrone, obalene, decaphen, decacene, decacyclene, pentasenopentacene, quaterrylene, hexasenohexacene, etc. Or the aromatic ring which can couple | bond the group of the form removed two or more with another chemical structure is mentioned.

  As the oxirane compound (d1-1) having an aromatic ring, glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, and 1,3-phenylenebis (methylene) bis (7-oxabicyclo [4. 1.0] heptane-3-carboxylate), 1,4-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), 1,3-{(7- Oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene and 1,4-{(7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene are particularly preferred compounds. .

  An oxirane compound (d1-2) having no aromatic ring can also be used in the resin composition of the present application. The combination of the oxirane compound (d1-1) having an aromatic ring and the oxirane compound (d1-2) having no aromatic ring makes it possible to adjust the amount of the aromatic ring contained in the resin composition. You can select and use.

  Among the cyclic hetero compounds, the cyclic hetero compounds other than the oxirane compounds include a 4-membered ether oxetanyl group-containing compound (d2), a 5-membered or higher cyclic ether compound (d3), two or more oxygens or oxygen other than oxygen. There is a compound (d4) having a hetero group.

  Examples of the oxetanyl group-containing compound (d2) include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di (1-ethyl-3- Oxetanyl) methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) Methyl} oxetane and the like. The oxetanyl group-containing compound (d2) may be used alone or in combination of two or more.

  Examples of the cyclic ether compound (d3) having 5 or more members include 2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H)- Frangion, 2,4-dioxotetrahydrofuran-3-carboxylate, 1,5-di (tetrahydrofuran-2-yl) pentan-3-yl propanoate, 4- (2,5-dioxotetrahydrofuran-3-yl) ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, methoxytetrahydropyran, 2- (propadienyloxy) tetrahydro-2H-pyran, 2- (tetrahydrofurfuryloxy) tetrahydropyran N- (2,6-Dioxotetrahydro-2H-pyran-3-yl) phthal Luimide, 3- [3-hydroxypropyl] oxy] oxepane, (2R, 3R) -2-methyl-3- (benzyloxymethyl) oxepane-3-ol, 5-chloro-2- (2-phenylethyl) oxepane Etc. may be used alone or in combination of two or more.

Examples of the compound (d4) having two or more oxygen or hetero groups other than oxygen include a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, and a fluorine-containing cyclic compound. The cyclic ester compound is preferably a lactone. More preferably, the cyclic formal compound is a compound selected from dioxolanes, dioxanes and trioxanes.
Industrially, propiolactone, butyrolactone, valerolactone, caprolactone, 1,3-dioxolane, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane, ethylene carbonate , Propylene carbonate, glycerin carbonate and the like are preferably used in terms of reactivity.

  Among the cationically polymerizable compounds (D), vinyl ethers can be selected and used from the above-mentioned compound (B) in a timely manner.

Examples of the cationically polymerizable compound (D) include (d1), (d2), (d3), (d4) and vinyl ethers, and are not particularly limited, but a saturated heterocyclic 3-membered cyclic oxirane compound ( d1) is preferred. The oxirane compound (d1) has a large steric distortion and tends to cause a nucleophilic ring-opening reaction. Therefore, interaction with the below-mentioned base material (G) is large, and it is industrially preferable. These may be used alone or in combination of two or more depending on the purpose of use.
As described above, by using the cationic polymerizable compound (D) in combination with the resin composition of the present invention, it is easy to suppress the curing shrinkage of the coating film that is polymerized and cured by irradiating active energy rays, so that the curing shrinkage is large. It becomes possible to improve the appearance defect of the laminated body resulting from this.

  In one Embodiment of the resin composition of this invention, it is preferable that the total amount of component (A) and (B) is 100 weight part, and a cationically polymerizable compound (D) is the compounding quantity of 1-350 weight part. More preferably, it is the range of 1-150 weight part. By setting the cationic polymerizable compound (D) to 1 part by weight or more, deficiency of cohesive force can be improved, and improvement of characteristics such as heat resistance and moist heat resistance is facilitated. On the other hand, by setting the cationic polymerizable compound (D) to 350 parts by weight or less, when the resin composition is used as a coating agent or an adhesive, it is easy to obtain excellent adhesion or adhesion to the substrate. Become.

Other components (F):
If the resin composition of this invention is a range which does not impair the effect by this invention, it is also possible to mix | blend various additives suitably. For example, organic or inorganic fillers from the viewpoints of polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. Can be blended. Such fillers may be composed of materials such as polymers, ceramics, metals, metal oxides, metal salts, and dyes and pigments. Moreover, about the shape, it is not specifically limited, For example, a particulate form, fibrous form, etc. may be sufficient. When blending the above polymer materials, silane coupling agents, flexibility imparting agents, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy imparting agents, dispersion stability It is also possible to dissolve, semi-dissolve, or micro-disperse in the resin composition as a polymer blend or polymer alloy, not as independent fillers, such as agents, fluidity imparting agents, and antifoaming agents.

  The resin composition of the present invention can be prepared by uniformly mixing the above-described components according to a method well known in the art. The resin composition can be applied to various uses in any form of liquid, paste, and film. In one Embodiment of this invention, Preferably, the said resin composition is used for the use of a coating agent or an adhesive agent.

  It is preferable that the viscosity of the resin composition of the present invention is appropriately adjusted according to the usage form. The resin composition of the present invention preferably contains substantially no organic solvent, but a solvent may be used as needed to adjust the viscosity. For example, organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents, or water can be used as the solvent. . By using such a solvent, the viscosity of the resin composition can be easily adjusted. Moreover, a viscosity can also be reduced by heating a resin composition, without using a solvent.

  In one embodiment of the present invention, a resin layer typically having a film thickness of 0.1 to 6 μm is formed using a resin composition. Therefore, from the viewpoint of coating film formation, the viscosity of the resin composition is at least in the range of 1-1,500 mPa · s, preferably in the range of 10-1,300 mPa · s, and more preferably in the range of 20-1,000 mPa · s. It is desirable that When the viscosity is 1,500 mPa · s or less, a thin film having a thickness of 0.1 to 6 μm can be easily formed on the substrate by coating, and optical characteristics such as transmittance can be easily improved. On the other hand, when the viscosity is 1 mPa · s or more, it is easy to control the thickness of the resin layer formed from the resin composition.

  Moreover, in another embodiment, the resin layer which has a film thickness of 6-300 micrometers is formed using a resin composition. In this case, the viscosity of the resin composition is at least in the range of 1,500 to 100,000 mPa · s, and preferably in the range of 3,000 to 50,000 mPa · s. Adjustment of the viscosity and coating of the resin composition according to the above embodiment can be easily performed by adding a solvent to the resin composition as necessary.

  The resin composition of the present invention is preferably used for a coating agent or an adhesive. Typically, the resin composition is applied to one side or both sides of a substrate by an appropriate method according to a conventional method, and then polymerized and cured to form a resin layer. Therefore, one embodiment of the present invention relates to a laminate having a base material (G) described later and a resin layer made of a resin composition provided on at least one main surface of the base material (G). . In this embodiment, the film thickness of the resin layer is set according to the use of the laminate.

  For example, when using the said resin composition for the use of the laminated bodies for optical elements, such as the below-mentioned hard coat film or a polarizing film, the said resin composition is thin-film coated. The thickness of the resin layer formed by coating is preferably from 0.1 to 6 μm, and more preferably from 0.1 to 3 μm. By setting the thickness of the resin layer to 0.1 μm or more, it is easy to obtain sufficient adhesion or adhesive force when the resin composition is used as a coating agent or an adhesive. On the other hand, when the thickness of the resin layer exceeds 6 μm, there is often no change in properties such as adhesion or adhesive strength.

  Moreover, when using the said resin composition for the uses of laminated bodies for optical elements, such as the below-mentioned decorating film (meaning the filling sheet for touchscreens), the said resin composition is thick-coated. The thickness of the resin layer formed by coating is preferably 6 to 300 μm, and more preferably 20 μm to 250 μm. By making the thickness of the resin layer 6 μm or more, it is easy to obtain sufficient stress relaxation and creep characteristics in addition to the filling function of the touch panel when the resin composition is used as a coating agent or an adhesive. is there. On the other hand, by setting the thickness of the resin composition layer to 300 μm or less, it is easy to suppress a decrease in coating properties such as streaking.

  There is no restriction | limiting in particular in the coating method of the said resin composition. For example, various well-known methods such as Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater, comma coater, curtain coater, knife coater, reverse coater, spin coater, etc. Can be applied. Moreover, it can select without particular restriction | limiting also about forms, such as thin film coating or thick film coating.

  The resin composition of the present invention can be applied onto a substrate by a known and usual method, and then has an α, β-unsaturated bonding group by irradiating the formed coating layer with active energy rays. The polymerization reaction of the compound proceeds to form a cured product. In one embodiment of the present invention, it is preferable that the active energy ray is mainly composed of light energy in the wavelength range of 150 to 550 nm including ultraviolet rays. Suitable light sources for providing such light energy include, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, LED lamps, xenon lamps, and metal halide lamps. Is mentioned. In addition, in another embodiment of the present invention, a laser beam, an X-ray, an electron beam, or the like can be used as an active energy ray for exposure.

The irradiation intensity of the active energy ray is preferably 0.1 to 500 mW / cm ² . When the light irradiation intensity is less than 0.1 mW / cm ² , it takes a long time for curing, and when it exceeds 500 mW / cm ² , the substrate may be deteriorated in various substrates due to heat radiated from the lamp. This is not preferable. The integrated dose expressed as the product of the irradiation intensity and the irradiation time is preferably 0.1 to 5,000 mJ / cm ² . When the total irradiation amount is less than 0.1 mJ / cm ^2, requiring a long time for polymerization and curing, since the larger 5,000 mJ / cm ^2, the irradiation time is very long, poor productivity, which is not preferable. A typical active energy ray polymerizable resin composition generally requires an integrated dose of 1,000 mJ / cm ² or more. However, the above resin composition according to the present invention is favorably polymerized even at a low integrated dose of less than 1,000 mJ / cm ² .

  In the laminate of the present invention, the resin layer on the substrate is formed by polymerization and curing of the resin composition by irradiation with active energy rays, and has a glass transition temperature of approximately −80 ° C. to 150 ° C. ( Hereinafter referred to as Tg). From the viewpoint of punching workability and bendability of the laminate, the Tg of the resin layer is more preferably in the range of −40 to 120 ° C., and further preferably in the range of 0 to 120 ° C.

  In view of the above, in one embodiment of the present invention, the resin composition has a boron softening agent (A) and α, so that the Tg of the resin layer (polymerized cured product of the resin composition) is within the above range. The β-ethylenically unsaturated double bond group-containing compound (B) is an essential component, and, if necessary, an oligomer (C), a cationic polymerizable compound (D), a polymerization initiator (E), and others It is preferable that an additional component such as the additive (F) is appropriately selected and configured. In such an embodiment, it is preferable to use a compound having a (meth) acryloyl group as the α, β-unsaturated double bond group of the components (B) and (C), and a compound having an acryloyl group. More preferably, is used.

  In one embodiment of the present invention, the resin composition is used as an active energy ray polymerizable coating agent (hereinafter referred to as a coating agent), and the resin composition forms a coating layer covering one side or both sides of the substrate. In such an embodiment, the base material may be a wood, a metal plate, a plastic plate, a film-like base material, a glass plate, a processed paper product, or the like, and these can be used without particular limitation.

  On the other hand, in another embodiment of the present invention, the resin composition is used as an active energy ray polymerizable adhesive (hereinafter referred to as an adhesive), and the resin composition bonds two or more substrates (G). An adhesive layer is formed. In such an embodiment, the base material (G) needs to be made of a material that easily transmits active energy rays in order to advance the polymerization reaction by irradiation with active energy rays. As the substrate (G), it is particularly preferable to use a transparent film (H) or a transparent glass plate. However, if a transparent film or a transparent glass plate is used as one substrate, the other substrate is difficult to transmit active energy rays, such as wood, metal plates, plastic plates, paper processed products, etc. The base material which consists of can also be used. In this case, the resin composition can be polymerized and cured by irradiating active energy rays from the transparent film (H) or the transparent glass plate side.

  In the laminated body of this invention, it is preferable to use a film-form base material as a base material (G). Specific examples of the film-like substrate include cellophane, various plastic films, and paper. Of these, the use of various transparent plastic films is preferred. Moreover, as a film-like base material, as long as the film is transparent, it may have a single layer structure, or may have a multilayer structure formed by laminating a plurality of base materials. Even if it has a film, it can be used conveniently. When constituting the laminate of the present invention, it is preferable to form a resin layer comprising the resin composition of the present invention on at least one surface of a transparent film.

  Hereinafter, more specific embodiments of the laminate of the present invention will be described by taking as an example the case where a transparent film (H) is used as a substrate. That is, the following description relates to a laminate having a resin layer, such as a coat layer or an adhesive layer, formed of the resin composition of the present invention on at least one main surface of a transparent film.

  A laminate constituted by using the resin composition of the present invention as a coating agent is typically a sheet-like film having a structure of transparent film / coat layer or coat layer / transparent film / coat layer. . Such a laminate can be obtained by applying a resin composition to at least one main surface of the transparent film (H), polymerizing and curing the resin composition, and forming a coat layer.

  On the other hand, a laminate constituted by using the resin composition of the present invention as an adhesive is typically transparent film / adhesive layer / transparent film, or transparent film / adhesive layer / transparent film / adhesive layer / transparent film. The sheet-like multilayer film obtained by laminating a plurality of transparent films. In another embodiment, the laminate is a sheet-like multilayer film such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film, and other optical members such as glass or optical molded bodies. It may have a fixed configuration. The laminate can be obtained by curing the adhesive layer by polymerizing and curing the approximate resin composition from one side or both sides of the film with active energy rays.

  When the resin composition is used as a coating agent or an adhesive, the polymerization and curing of the resin composition is carried out by applying active energy rays to the coating layer at the time of coating the resin composition, at the time of laminating or after laminating the film-like substrate. It is implemented by irradiating. Although it does not specifically limit, it is preferable that the said irradiation is implemented after lamination | stacking, such as a film-form base material.

  Generally, the thickness of the coating layer is set to 5 μm to 20 μm, and the elastic modulus of the coating polymerized and cured by irradiating active energy rays is 100 MPa to 2 GPa at room temperature (25 ° C.). It is preferable that it is 40 Mpa or more at a temperature of 70C. If it is less than 100 MPa, it is weak against bending and peeling or cracking occurs. The reason why the upper limit is set to 2 GPa is that, from the viewpoint of flexibility, there is currently no product exceeding 2 GPa and it is not necessary.

  As above-mentioned, when a transparent film (H) is used as a base material (G), the said laminated body can be used suitably for an optical use. From the viewpoint of obtaining good optical properties, the transparent film (H) used in the laminate is, for example, heat excellent in optical properties such as transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropic properties. It is preferable that it is various transparent films (H) comprised from a plastic resin. Such various transparent films (H) are also referred to as various plastic films or plastic sheets. Specific examples include, for example, polyvinyl alcohol films, polytriacetyl cellulose films, polyolefin films such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymers, polyester films such as polyethylene terephthalate and polybutylene terephthalate, Examples include polycarbonate films, polynorbornene films, polyarylate films, polyacrylic films, polyphenylene sulfide films, polystyrene films, polyvinyl films, polyamide films, polyimide films, and polyoxirane films.

  In the laminate of the present invention, when a multilayer film is formed by laminating a plurality of transparent films (H), the transparent films (H) to be used may be the same or different. For example, a polyacrylic film may be laminated on a polycycloolefin film via an adhesive layer.

  The thickness of the transparent film (H) can be appropriately determined, but is generally 1 to 500 μm and preferably 1 to 300 μm from the viewpoints of workability such as strength or handleability and thin layer properties. 5 to 200 μm is more preferable. In the optical application, the thickness of the transparent film (H) is particularly preferably in the range of 5 to 150 μm.

  In one embodiment of the optical element laminate according to the present invention, it is preferable to use the optical film (I) mainly used in optical applications as the transparent film (H). Here, the optical film (I) is a film obtained by subjecting the transparent film (H) itself to a special treatment and has optical functions such as light transmission light diffusion, light collection, refraction, scattering, and HAZE. Intended for things. Such optical film (I) can be used alone or in combination of several kinds. In one Embodiment of this invention, the laminated body for optical elements can be comprised by forming the resin layer which consists of the said resin composition in at least one main surface of the said optical film (I).

  Specific examples of the optical element laminate include, for example, a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness enhancement film, Examples include a prism film (also referred to as a prism sheet), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like. You may stick the said laminated body for optical elements to glass plates, such as a liquid crystal display device, a PDP module, a touch panel module, and an organic EL module, using the resin composition of this invention as an adhesive agent. As another form, the resin composition of the present invention may be used as an adhesive, and the optical element laminate may be adhered to the various optical films (I).

  Hereinafter, a polarizing film is mentioned as an example of the laminated body for optical elements, and the embodiment of the laminated body will be described more specifically. The polarizing film is also called a polarizing plate, and is an optical film (I) having a multilayer structure in which a polarizer is sandwiched between two film-like substrates. In the polarizing film, when the transparent films (H) are provided on both sides of the polarizer, the transparent film (H) made of the same polymer material on the front and back sides or the transparent film made of a different polymer material or the like may be used. Good. The polarizing film has a structure in which, for example, both surfaces of a polyvinyl alcohol-based polarizer are sandwiched between two polytriacetylcellulose-based protective films (hereinafter referred to as “TAC films”) that are polyacetylcellulose-based films. As another example, the polarizing film has one or both sides of a polyvinyl alcohol polarizer sandwiched between films such as polycycloolefin film, polyacrylic film, polycarbonate film, and polyester film that are polynorbornene films. It has a structure.

Although it does not specifically limit, For example, the said polarizing plate (polarizing film) can be manufactured as follows.
(I) The resin composition of the present invention is applied as an adhesive to one main surface of the first transparent film (first protective film) to form a first polymerizable adhesive layer. Moreover, the resin composition of this invention is apply | coated to one main surface of a 2nd transparent film (2nd protective film) as an adhesive agent, and a 2nd polymeric contact bonding layer is formed. Next, the first polymerizable adhesive layer and the second polymerizable adhesive layer are simultaneously and / or sequentially overlapped on both main surfaces of the polyvinyl alcohol polarizer. Next, the obtained laminate is irradiated with active energy rays to polymerize and cure the first and second adhesive layers.

  (II) The resin composition of the present invention is applied as an adhesive to one main surface of the polyvinyl alcohol-based polarizer to form a first polymerizable adhesive layer, and the surface of the first polymerizable adhesive layer Is covered with a first transparent film (first protective film). Next, the other main surface of the polyvinyl alcohol-based polarizer is coated with the resin composition of the present invention as an adhesive to form a second polymerizable adhesive layer, and the surface of the second polymerizable adhesive layer is Cover with a second protective film. Next, the obtained laminate is irradiated with active energy rays to polymerize and cure the first and second polymerizable adhesive layers.

  (III) The end portion of the first transparent film (first protective film) overlaid with one main surface of the polyvinyl alcohol polarizer, and the second protective film overlaid on the other surface of the polyvinyl alcohol polarizer. The resin composition of the present invention is dropped as an adhesive on each end, and the laminate is passed between rolls to spread the adhesive between the layers. Next, the active energy ray is irradiated to the laminate to polymerize and cure the active energy ray-polymerizable adhesive.

  The polarizing film has been described as an example as an embodiment of the optical element laminate. However, the laminate is characterized by using the resin composition of the present invention as a coating agent or adhesive for various substrates. Therefore, it is not limited to the polarizing film, and it should be easily understood that a laminated body that can be suitably used for optical applications can be configured in other embodiments using other various substrates.

Hereinafter, the present invention will be described with reference to specific examples. However, the present invention is not limited to the following examples. Further, “parts” and “%” described in the following Examples and Comparative Examples represent “parts by weight” and “% by weight”, respectively.

<Adjustment of resin composition>
[Composition Examples 1-40]
An α, β-unsaturated double bond group-containing compound (A) having a carbonyl group in the molecule and no carbonyl group in the molecule in a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less Table 1 shows the α, β-unsaturated double bond group-containing compound (B), amine compound (C), oligomer (D), active energy ray polymerization initiator (E), and other additives (F). After mixing at a ratio and sufficiently stirring and sufficiently defoaming, the resin compositions shown in the formulation examples were obtained.

  About the active energy ray polymeric resin composition of the compounding example shown in Table 1, the solution external appearance and viscosity were calculated | required according to the following method, and the result was shown in Table 2. Moreover, the measuring method of molecular weight, an acid value, a hydroxyl value, and a glass transition temperature was also shown below.

The details of the active energy ray polymerizable resin composition described in Table 1 are as follows. In Table 1, the symbol “-” means no formulation.
・ Ingredient (A)
T-40: Polyoxyethylene glycerol borate monolaurate (“Emalbon T-40” manufactured by Toho Chemical Co., Ltd.), T-80: Polyoxyethylene glycerol borate monooleate (“Emalbon T-80” manufactured by Toho Chemical Co., Ltd.)
・ Ingredient (b1-1)
4HBA: 4-hydroxybutyl acrylate, 2HEA: 2-hydroxyethyl acrylate, component (b1-2)
CHDMA: 1,4-cyclohexanedimethanol acrylic acid, HPPA: 2-hydroxy-3-phenoxypropyl acrylate, component (b2-1)
IBXA: isobornyl acrylate, DCPA: dicyclopentanyl acrylate, ADCP: dicyclopentanyl diacrylate-component (b2-2)
ACMO: 4-acryloylmorpholine, GMA: glycidyl mesylate / component (b3)
NPGDA: neopentyl glycol diacrylate, BA: butyl acrylate, component (c1)
885: Polyester acrylate “Ebecryl 885” manufactured by Daicel Cytec Co., Ltd.
・ Ingredient (c2)
3000B: Polyurethane oligomer (urethane acrylate) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. “Purple light UV3000B”
・ Ingredient (c3)
600: manufactured by Daicel Cytec Co., Ltd. Polyepoxy oligomer (epoxy acrylate) “Ebecryl 600”
・ Ingredient (d1-1)
CEP01: 1,3-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), JER828: Bisphenol A type oxirane resin (manufactured by Mitsubishi Chemical Corporation)
・ Ingredient (d1-2)
2021P: 3,4-oxiranecyclohexylmethyl-3,4-oxiranecyclohexanecarboxylate (manufactured by Daicel Chemical Industries)
・ Ingredient (d2)
DOME: Di (1-ethyl-3-oxetanyl) methyl ether component (d3)
GC: Glycerin carbonate, component (E)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, DAROCUR TPO), CPI-110P: p-phenylthiophenyldiphenylsulfonium PF ₆ salt / component (F)
DEX-S: Nippon Kayaku Co., Ltd. thioxanthone sensitizer, A-174: Tanac Co., Ltd. silane coupling agent In this invention, it is not limited to the above-mentioned component, Active energy ray polymerizability excellent in various characteristics A resin composition can be provided.

  About the active energy ray polymeric resin composition of the compounding example shown in Table 1, the solution external appearance and viscosity were calculated | required according to the following method, and the result was shown in Table 2. Moreover, the measuring method of molecular weight, an acid value, a hydroxyl value, and a glass transition temperature was also shown below.

"appearance"
The appearance of the resin composition obtained in each formulation example was observed and visually evaluated.

"viscosity"
About 1.2 ml of the resin composition obtained in each blending example was measured with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) under an atmosphere of 23 ° C., and a rotation speed of 0.5 to The solution viscosity (mPa · s) was measured at 100 rpm for 1 minute.

《Molecular weight》
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography) “Shodex GPC System-21”. GPC is a liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and the number average molecular weight (Mn) and weight average molecular weight (Mn) are determined in terms of polystyrene. It was.

<< Hydroxyl value (OHV) >>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

《Acid value (AV)》
About 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<< Glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
About 10 mg of a sample is put in an aluminum pan, weighed and set in a differential scanning calorimeter, and heated for 5 minutes at a temperature of 100 ° C. using the same type of aluminum pan without a sample as a reference. Rapid cooling was performed to 120 ° C. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained during the temperature elevation.

<Example of production of laminate A>
[Examples 1-42] [Comparative Examples 1-4]
Using the resin compositions shown in Tables 1 and 2 as active energy ray polymerizable adhesives, the following laminates were prepared.
As a protective film (1) which is a transparent film (H), a polynorbornene-based film containing no UV absorber manufactured by Nippon Zeon Co., Ltd .: trade name “ZF-14” (thickness: 100 μm) is used. Made of Mitsubishi Rayon Co., Ltd. Polyacrylic film containing no UV absorber: The product name “HDB-002” (thickness 50 μm) is used, and the surface is corona-treated with a discharge amount of 300 W · min / m ² , respectively. Within 1 hour after the treatment, the adhesive shown in the formulation example was applied using a wire bar coater so as to have a film thickness of 4 μm, an adhesive layer was formed, and the above polyvinyl alcohol polarizer between the adhesive layer Then, a laminate comprising protective film (1) / adhesive layer / PVA polarizer / adhesive layer / protective film (2) was obtained.
Four sides of this laminate were fixed with cellophane tape so that the protective film (1) was in contact with the tin plate, and was fixed to the tin plate.
A polarizing plate was produced by irradiating ultraviolet rays having a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm ² from the protective film (2) side with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation).

  About the obtained laminated body (polarizing plate), peel strength, gel fraction, punching workability, shrinkage rate, heat resistance, moist heat resistance and flexibility were determined according to the following methods, and the results are also shown in Table 3.

<Peel strength>
The adhesive strength was measured in accordance with JIS K6 854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained polarizing plate was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. The sample was affixed on a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) using a laminator to obtain a laminate for measurement of the polarizing plate and the metal plate. The polarizing plate of the laminate for measurement is provided with a peeling flicker between the protective film and the polarizer in advance, and the laminate for measurement is 300 mm / min under the conditions of 23 ° C. and 50% relative humidity. It peeled at the speed | rate of and was set as peeling force. Under the present circumstances, the peeling force of both a polyvinyl alcohol-type polarizer and a protective film (1) and a polyvinyl alcohol-type polarizer and a protective film (2) was measured. This peeling force was evaluated as an adhesive force in four stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: Unpeelable or polarizing plate breakage O: Peeling force is 2.0 (N / 25 mm) or more to less than 5.0 (N / 25 mm).
(Triangle | delta): Peeling force is 1.0 (N / 25mm) or more-less than 2.0 (N / 25mm).
X: Peeling force is less than 1.0 (N / 25 mm).

<Gel fraction>
A non-corona-treated polynorbornene-based film (trade name “Zeonor ZF-14: 100 μm”) with an active energy ray-polymerizable adhesive and a wire bar coater to a film thickness of 20 to 25 μm. After coating Zeonor ZF-14 that has not been subjected to corona treatment on the adhesive layer to obtain a laminate composed of three layers, an active energy ray irradiation device (Toshiba Corporation) was applied. The adhesive layer was polymerized and cured by irradiating active energy rays with a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm ^{2 with} a high-pressure mercury lamp manufactured by peeling off the three-layer laminate ZEONOR ZF-14. Got.
After the weight of the adhesive layer was measured (weight 1) was sandwiched between metal meshes so that the adhesive layers did not overlap each other, and refluxed in methyl ethyl ketone (MEK) for 3 hours. The film was further dried at 80 ° C. for 30 minutes, and the weight of the adhesive layer was measured (weight 2). The gel fraction was calculated from the following formula and evaluated in three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
Gel fraction (%) = {1− (weight 1−weight 2) / weight 1)} × 100
(Evaluation criteria)
○: Gel fraction is 90% or more Δ: Gel fraction is 80% to less than 90% ×: Gel fraction is less than 80%

<Punching workability>
The produced polarizing plate was punched out from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The peripheral peeling distance of the punched polarizing plate was measured with a ruler and evaluated according to the following four levels. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: 0 mm
○: 1mm or less △: 1-3mm
×: 3 mm or more

"Shrinkage factor"
The polarizing plate pieces are left in a constant temperature and humidity chamber of 60 ° C.-dry and 60 ° C.-90 RH%, the amount of shrinkage in the stretching direction after 60 hours is measured, and the ratio of the amount of shrinkage to the original length (100 mm) Was determined as the shrinkage rate and evaluated in the following three stages.
Note that “dry” is a test condition when only the temperature is controlled and humidity is not controlled in an oven with a humidity adjusting function. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: Shrinkage rate is 0.2% or less Δ: Shrinkage rate is greater than 0.2% and 0.4% or less ×: Shrinkage rate exceeds 0.4%

"Heat-resistant"
The polarizing plate obtained in each Example and Comparative Example was cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the conditions of 80 ° C.-dry and 100 ° C. dry. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: No peeling at all even under the condition of 100 ° C.-dry.
○: No peeling at all at 80 ° C.-dry condition.
(Triangle | delta): There exists peeling less than 1 mm on 80 degreeC-dry conditions.
X: 1 mm or more peeled off at 80 ° C.-dry condition.

《Moisture and heat resistance》
The polarizing plates obtained in each Example and Comparative Example were cut into a size of 50 mm × 40 mm and exposed for 1000 hours under conditions of 60 ° C.-90% RH and 85 ° C.-85% RH. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
A: No peeling at all at 85 ° C. to 85% RH.
○: No peeling at all at 60 ° C.-90% RH.
(Triangle | delta): There exists peeling of less than 1 mm on the conditions of 60 degreeC-90% RH.
X: There is peeling of 1 mm or more under the condition of 60 ° C.-90% RH.

《Flexibility (measurement of folding resistance)》
The polarizing plate obtained in each example and comparative example is cut into a size of 50 mm × 40 mm, and a bending test is performed according to JIS P8115 using an MIT tester (manufactured by Toyo Seiki). Was evaluated as flexibility evaluation.
In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: No cracking or peeling of the adhesive layer even at 300 times or more.
(Triangle | delta): There are some cracks and peeling in the adhesive layer after 200 to 300 times.
X: There are cracks and peeling in the adhesive layer in less than 200 times.

The symbols shown in Table 3 are as follows.
ZF-14: a polynorbornene-based film manufactured by Nippon Zeon Co., Ltd., HBD-002: an acrylic film manufactured by Mitsubishi Rayon Co., Ltd.

<Example of production of laminate B>
[Examples 101 to 151] [Comparative Examples 11 to 14]
Using the resin compositions shown in Table 1 and Table 2 as active energy ray polymerizable coating agents, the following laminates were prepared.
As an optical film, an ultraviolet absorber-containing polytriacetylcellulose-based film manufactured by Fuji Film Co., Ltd .: trade name “Fujitack: 80 μm” was used. Using a wire bar coater, the surface of the optical film is subjected to corona treatment with a discharge amount of 300 W · min / m ² , and the resin composition shown in the formulation example is used as an active energy ray polymerizable coating agent within 1 hour after the surface treatment. Coating was carried out to a film thickness of 4 μm to form a coating agent layer.
The four sides of this laminate were fixed to the tinplate with cellophane tape so that the optical film was in contact with the tinplate.
After replacing the inside of the UV irradiation device (Toshiba High Pressure Mercury Lamp) with dry nitrogen, the coating agent layer is irradiated with ultraviolet rays having a maximum illuminance of 300 mW / cm ^{2 at} a wavelength of 365 nm and an integrated light amount of 300 mJ / cm ² from the coating agent layer side. The laminated body which has was produced.

  About the obtained laminated body, adhesive force, heat resistance, and a softness | flexibility were calculated | required in accordance with the following method, and the result was similarly shown in Table 4.

"Adhesion"
According to JIS K5400, a cross-cut peel test was performed. The number of cells peeled in 100 cells was evaluated in four stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
◎: 0 square ○: 1-10 square △: 11-30 square ×: 31 squares or more

"Heat-resistant"
The laminates obtained in each Example and Comparative Example were cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of 80 ° C.-dry. After the exposure, the presence or absence of peeling at the end of the laminate was visually evaluated in the following three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: No peeling △: 1 mm or less peeling ×: 1 mm or more peeling

《Flexibility (measurement of folding resistance)》
The polarizing plate obtained in each example and comparative example is cut into a size of 50 mm × 40 mm, and a bending test is performed according to JIS P8115 using an MIT tester (manufactured by Toyo Seiki). Was evaluated as flexibility evaluation.
In the case of “△” evaluation or higher, there is no problem in actual use.
(Evaluation criteria)
○: No cracking or peeling of the adhesive layer even at 300 times or more.
(Triangle | delta): There are some cracks and peeling in the adhesive layer after 200 to 300 times.
X: There are cracks and peeling in the adhesive layer in less than 200 times.

  In the present invention, as representative examples of the optical film, exemplary compounds are specifically shown in Table 5 below, but are not limited thereto. In addition, as a notation of an example film, Fujitac: TAC film (80 μm) containing an ultraviolet absorber manufactured by Fuji Film Co., Ltd. ZF-14: Polynorbornene film (100 μm) containing no UV absorber manufactured by Nippon Zeon Co., Ltd., HBD- 002: manufactured by Mitsubishi Rayon Co., Ltd. Polyacrylic film containing no UV absorber (50 μm), R-140: manufactured by Kaneka Co., Ltd. polycarbonate film containing no UV absorber (43 μm), Emplet S: manufactured by Unitika Co., Ltd. Polyester film (50 μm) contained, TUX-HZ: manufactured by Tosero Co., Ltd. A polyethylene film (50 μm) containing an ultraviolet absorber is shown.

When the resin composition of the present invention is used as an adhesive, there is no particular problem in Examples 6 to 42 as shown in Table 3. Moreover, in Examples 1-5, although levels, such as adhesiveness, heat resistance, heat-and-moisture resistance, and a softness | flexibility, are low, it can be used. On the other hand, in Comparative Examples 1-2, it turns out that a softness | flexibility is especially bad, and in Comparative Examples 3-4, in addition to a softness | flexibility, adhesive force, wet heat resistance, and a shrinkage | contraction rate are inferior.
Further, when the resin composition of the present invention is used as a coating agent, the tendency is the same as in Table 3. As shown in Table 4, in Examples 106 to 146, both adhesion and heat resistance are excellent, and particularly a problem. No. Moreover, although Examples 101-105 have a low level of adhesiveness and heat resistance, they can be used. On the other hand, in Comparative Examples 11-19, it turns out that it is especially inferior to a softness | flexibility or heat resistance.

Claims (10)

Boron softener (A),
An active energy ray polymerizable resin composition comprising an α, β-ethylenically unsaturated double bond group-containing compound (B) as an essential component. In the total amount of the active energy ray polymerizable composition,
0.1-50% by weight of softener (A),
50-99.9% by weight of compound (B),
The active energy ray polymerizable resin composition according to claim 1, which is contained.   3. The resin composition according to claim 1, wherein the boron softener (A) is a compound obtained by reacting a boron compound (a1) with a hydroxyl group-containing compound (a2). The resin composition according to any one of claims 1 to 3, wherein the boron-based softening agent (A) has a surface activity. The resin composition according to any one of claims 1 to 4, wherein the compound (B) comprises an α, β-ethylenically unsaturated double bond group-containing compound (b1) having a hydroxyl group. The resin composition according to any one of claims 1 to 5, wherein the compound (B) comprises an α, β-ethylenically unsaturated double bond group-containing compound (b2) having one or more cyclic structures. . A substrate (G);
A laminate having a resin layer made of the resin composition according to any one of claims 1 to 6 provided on at least one main surface of the substrate (G).   The laminate according to claim 7, wherein the substrate (G) is a transparent film (H).   The transparent film (H) is selected from the group consisting of a polyacetylcellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide film. The laminate according to claim 8, wherein the laminate is at least one selected. An optical film;
The laminated body for optical elements which has a resin layer which consists of a resin composition in any one of Claims 1-6 provided in the at least one main surface of this optical film.