TWI570142B - Active energy ray-polymerizable resin composition and laminate using the same - Google Patents

Description

Active energy ray polymerizable resin composition, and laminate using the same

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

The active energy ray-polymerizable resin composition has a high polymerization rate and can be generally used without a solvent, so that it has excellent workability and extremely low energy required for polymerization. The active energy ray-polymerizable resin composition typically includes a resin component polymerized by an active energy ray and a monomer component having an α,β-unsaturated double bond group. The resin component is an oligomer having a low molecular weight and having an α,β-unsaturated double bond at the molecular terminal, such as a polyester resin, a polyurethane resin, a polyepoxy resin, or a polyacrylic resin. . The monomer component and the resin component can be polymerized by irradiation with an active energy ray, but the function of the solvent is also obtained until the polymerization is completed. Therefore, the above active energy ray-polymerizable resin has an advantage that no solvent is volatilized at the time of formation of a coating film, since it does not require another solvent.

From the above viewpoint, the above active energy ray polymerizable resin composition The use of materials is suitable for improving environmental pollution problems in recent years, and can achieve a low reduction in environmental pollution. Therefore, the active energy ray-polymerizable resin composition is used in various fields including display device materials, packaging materials, printing materials, and display device materials such as displays and optical components such as optical components, and the fields of use thereof. There is a tendency to expand.

For example, in the above various fields, the above resin composition can be used in the use of an adhesive. However, the adhesion of the above-mentioned resin composition to the substrate (coated surface) is not necessarily good, and there are various reports for improving the adhesion to various substrates. For example, in Patent Document 1, a method of fundamentally changing the molecular skeleton of the above oligomer in the above resin composition by using a specific saturated copolyester is disclosed. In the case of the photocurable resin composition, a method of blending a metal salt of a terminal modified phosphate of an α,β-unsaturated double bond group as a tackifier is disclosed. Further, Patent Document 3 discloses a method of formulating a compound having a tricyclodecenyl group and an α,β-unsaturated double bond group in a photocurable resin composition.

Further, since the reactive oligomers used in the active energy ray-polymerizable resin composition are generally highly viscous, it is difficult to operate as a binder for a coating material and an adhesive. Therefore, in general, the operability when used as a binder is improved by using a reactive diluent having an α,β-unsaturated double bond group and having a low viscosity. The above-mentioned reactive diluent is known as a compound having a monomer having an α,β-unsaturated double bond group (Patent Documents 4 to 6). Among them, acrylates, generally, exhibit excellent polymerizability to active energy rays, and thus are widely used. On the other hand, since the odor and skin irritation are strong, it is desirable to improve the environment for use such as a coating operation for an acrylate-containing paint or an adhesive.

On the other hand, in recent years, the development and generalization of information communication apparatuses including displays have been remarkable, and in the field of display devices, higher performance and productivity have been demanded for materials such as coating agents, adhesives, and sealing materials. Meanwhile, the material of the display device has various proposals for using various embodiments of the above active energy ray-polymerizable resin composition.

In the display device, generally, an antireflection film for preventing reflection from an external light source, a protective film for preventing damage to the surface of the display device, and the like are used, and various films are used depending on the application. For example, a polarizing plate and a retardation film are laminated as a member for a liquid crystal cell constituting a liquid crystal display (LCD).

At the same time, the flat panel display (FPD) is not only used as a display device, but also has a function of adding a touch panel on its surface as a use of an input device. In the touch panel, a film such as a protective film, an antireflection film, and an ITO vapor-coated resin film is used.

Among the above-mentioned films, the representative of the film is used as a member for an optical element in a form of a laminate in a display device. For example, the film is used in a display device in a form in which a coating layer composed of a coating agent is provided on the surface layer in order to prevent damage, prevent fingerprints, antistatic, or facilitate adhesion. In other aspects, the film is used in a display device by being attached to an adhesive such as an optical element via an adhesive. However, the coating agent or the adhesive used in the above form first requires properties such as transparency or heat resistance. In view of such a demand, in the technical field, a two-component type thermosetting adhesive containing a polyacrylic resin as a main component and containing a solvent, or an active energy ray-polymerizable adhesive is generally used.

However, the prior active energy ray-polymerizable resin composition has advantages such as a high polymerization rate, but on the other hand, it is difficult to obtain the polymer in the light. The propensity for adequate transparency required for use. At the same time, when the above-mentioned resin composition is used to produce a laminate for an optical element, dimensional changes and characteristics of each layer of the material in the laminate are different, and dimensional changes and warpage may occur due to changes in temperature and humidity (also referred to as The tendency to curl). Further, the laminated body preferably has a high refractive index, but the composition of the resin composition is difficult to adjust the refractive index. Further, even if a resin composition having a high refractive index can be formed, the resin composition tends to lack adhesiveness.

Patent Document 7 discloses a photocurable resin composition comprising a polyaminoester poly(meth)acrylate and a photopolymerization initiator of a hydroxyethene benzene oligomer, which has a hardening speed and hardening. The advantage of less shrinkage and excellent dimensional stability. However, the disclosed form of use of the resin composition is limited to the use of the floor material film. According to Patent Document 7, when the resin composition is used as a protective coating agent for a flooring material, the warpage of the flooring material is reduced. However, when the resin composition is used as a coating film, the resin composition has a large shrinkage during polymerization, which causes large warpage, and it is difficult to achieve both low curling property and adhesion property. Meanwhile, when a coating layer of a film of 2 to 5 μm is formed from the above resin composition, when it is heated and dried at 120 ° C or higher in the curing step to dry the coating layer, light in the above resin composition is caused by heat during drying. When the polymerization initiator is volatilized, the hardening reaction is incomplete, and thus the coating property tends to be deteriorated.

Meanwhile, in Patent Documents 8 and 9, each discloses that an active energy ray-polymerizable composition containing a compound containing a sulfur atom and having an α,β-unsaturated double bond is polymerized to obtain a high refractive index optical material. However, the optical material disclosed has a bending strength (SA) of 0.1 or less in accordance with JIS K 6856, and lacks adhesion.

Further, in the field of display devices, a backlight method in which a liquid crystal layer is illuminated by a back surface is generally used, and a representative thereof is mounted on the lower side of the liquid crystal layer. Backlight units such as edge lighting and direct type. The side light type backlight unit basically includes a linear light-emitting body serving as a light source, a square plate-shaped light guide plate disposed along an edge portion of the light-emitting body, a light-diffusing sheet provided on a surface side of the light guide plate, and a sheet disposed on the sheet A sheet of enamel on the surface side. Recently, in terms of its light source, in place of a cold cathode fluorescent lamp (COFL), there are many cases in which a light-emitting diode (LED) excellent in color reproducibility and power saving is used, and the heat resistance of the display device is accompanied by this situation. And the requirements for dimensional stability are also improved.

As described above, in the field of display devices, it is also desired to develop an active energy ray-polymerizable resin composition which is superior in various characteristics required for optical applications, which is not only the prior advantages. More specifically, it is an active energy ray-polymerizable resin composition suitable for use as a coating agent or an adhesive constituting a laminate for an optical element, and is substantially free of an organic solvent, and has a dimensional stability and a dimensional stability at the time of hardening. It is also excellent in terms of properties, and a resin composition excellent in refractive index, total light transmittance, and optical characteristics of haze.

[Previous Technical Literature] Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 56-95902

Patent Document 2: Japanese Laid-Open Patent Publication No. SHO 57-180618

Patent Document 3: Japanese Laid-Open Patent Publication No. SHO 57-87409

Patent Document 4: Japanese Laid-Open Patent Publication No. Hei 6-329731

Patent Document 5: Japanese Laid-Open Patent Publication No. 2001-240609

Patent Document 6: Japanese Patent Laid-Open Publication No. 2004-099644

Patent Document 7: Japanese Patent Publication No. 08-27397

Patent Document 8: Japanese Patent Laid-Open No. 4-108816

Patent Document 9: Japanese Patent Laid-Open No. Hei 5-271383

In view of the above, the object of the present invention is to provide heat resistance, moist heat resistance, dimensional stability of heat, weather resistance, and the like, and it is suitable for use as an optical application, and substantially does not contain an organic solvent, and has excellent workability and usefulness. A novel active energy ray polymerizable resin composition used as a coating agent or an adhesive. Meanwhile, an object of the present invention is to provide a laminate having a resin layer composed of the above resin composition on at least one main surface of various transparent films, particularly various optical films, regardless of the type of various optical films. In the optical film, the resin layer can be easily and firmly adhered or coated, and the laminate is more excellent in punching processability and wet heat durability than the above, especially for the optical element. body.

According to a first aspect of the invention, there is provided an active energy ray-polymerizable resin composition comprising: an oligomer having at least one or more α,β-unsaturated double bond groups in a molecule (A) A compound monomer (B) having an α,β-unsaturated double bond group having one or more carboxyl groups in the molecule, and a cyclic imine compound (C1) or a carbodiimide compound (C2).

The resin composition preferably contains 1 to 99.8 parts by weight of the above oligomer (A), 0.1 to 49.5 parts by weight of the above-mentioned α,β-unsaturated double bond-containing compound monomer (B), and 0.1 to 49.5 parts by weight of the above cyclic imine compound (C1) or carbodiimide compound (C2).

In the above resin composition, the oligomer (A) is preferably selected from the group consisting of The polyester oligomer (a-1), the polyurethane oligomer (a-2), the polyepoxy oligomer (a-3), and the polyacrylic oligomer (a-4) are formed. At least one or more oligomers in the group.

In the above resin composition, the weight average molecular weight of the above oligomer (A) is preferably from 300 to 30,000.

In the above resin composition, the acid value of the above-mentioned α,β-unsaturated double bond group-containing compound monomer (B) is preferably from 100 to 1,000 mg KOH/g.

In the above resin composition, the cyclic imine compound (C1) is preferably a compound having an imine ring having one or more three-membered ring structures in the molecule.

In the above resin composition, the carbodiimide compound (C2) is preferably a compound having one or more carbodiimide linkage groups in the molecule.

The resin composition preferably contains a monomer (D) further containing a compound having an α,β-unsaturated double bond group having no carboxyl group in the molecule.

The resin composition further contains an active energy ray polymerization initiator (E), and the amount of the active energy ray polymerization initiator (E) is from 0.01 to 100 parts by weight based on the total amount of the resin composition. A range of 20 parts by weight is preferred.

The above resin composition preferably contains a decane compound (F).

The resin composition is preferably used for an active energy ray-polymerizable coating agent or an active energy ray-polymerizable adhesive.

According to a second aspect of the invention, there is provided a laminate comprising a resin layer comprising a substrate and a resin composition provided on at least one main surface of the substrate, wherein the resin composition is the invention The resin composition of the first aspect.

In the above laminated body, the substrate is preferably a transparent film. Meanwhile, the transparent film is preferably selected from the group consisting of a polyethylene-based cellulose film, a polynorbornene film, At least one of a group consisting of a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide film.

According to a third aspect of the invention, there is provided a laminated body for an optical element comprising an optical film and a resin layer provided on at least one main surface of the optical film, wherein the resin composition is the first invention A resin composition of the form.

According to the present invention, an active energy ray-polymerizable resin composition polymerizable under low illuminance can be provided. Meanwhile, according to the present invention, it is also possible to provide a simple and strong adhesion or adhesion to an optical film by using the above-described resin composition as an adhesive or a coating agent, and punching workability, heat resistance, and heat and humidity resistance. Excellent laminate, especially for laminated layers for excellent optical components.

The Japanese Patent Application No. 2012-155822, filed on December 27, 2012, and Japanese Patent Application No. 2012-285822, filed on February 18, 2013, filed on July 11, 2012 The subject matter of the Japanese Patent Application No. 2013-080718, filed on Apr. 8, 2013, is hereby incorporated by reference.

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 is characterized by comprising an oligomer (A) having at least one or more α,β-unsaturated double bond groups in the molecule, and having one or more carboxyl groups in the molecule. Compound monomer (B) containing α,β-unsaturated double bond, and ring Amine compound (C1) or carbodiimide compound (C2).

Among them, the "active energy line" is a broad energy line containing ultraviolet rays, visible light, infrared rays, electron beams, and radiation which can provide energy necessary for activation of a chemical reaction. The active energy ray-polymerizable resin composition of the present invention (hereinafter referred to as "resin composition") is irradiated with the active energy ray to cause a polymerization reaction to proceed to form a cured product. Although it is not particularly limited, in one embodiment of the present invention, the active energy ray is preferably light energy containing ultraviolet rays.

Hereinafter, the constituent components of the resin composition will be specifically described.

(A) Ingredients:

In the resin composition of the present invention, the above oligomer (A) is a polymer of a monomer having at least an α,β-unsaturated double bond group and/or various compounds, and is added to an α,β-unsaturated double. The compound obtained by the bond group has one or more α,β-unsaturated double bond groups in the molecule. The above oligomer may contain various functional groups in addition to the α,β-unsaturated double bond group. In one embodiment of the present invention, the oligomer (A) is selected from the group consisting of a polyester-based oligomer (a-1), a polyurethane-based oligomer (a-2), and a polyepoxy oligomer. At least one or more of the group formed by (a-3) and the polyacryl-based oligomer (a-4) are not particularly limited as long as they can be used.

(a-1) Polyester oligomer

The polyester-based oligomer (a-1) is not particularly limited as long as it has one or more ester bonds in the main chain skeleton. For example, it may be a hydroxyl group obtained by polycondensation of a polybasic acid and a polyhydric alcohol, or a hydroxyl group in a polyester chain, and a component (B) described later, such as (meth)acrylic acid and maleic acid, that is, A compound obtained by esterification of a compound containing an α,β-unsaturated double bond group having one or more carboxyl groups in its molecule. In addition, for example, it may be: a hydroxyl group at the end of the polyester or in the polyester chain, and 2-hydroxyl (meth)acrylate A compound obtained by esterification of a compound containing an α,β-unsaturated double bond group having one or more hydroxyl groups in a molecule, such as a ethyl ester and a 2-hydroxypropyl (meth)acrylate. Other examples thereof include a polyester-based oligomer obtained from a glycidyl (meth)acrylate and a compound having at least one hydroxyl group.

The polybasic acid may, for example, be an aliphatic, an alicyclic or an aromatic system, but the use of the various types is not particularly limited. Examples of the aliphatic polybasic acid include more specifically oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, suberic acid, maleic acid, and chlorinated cisplatin. Alkenoic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, etc., such aliphatic two can be used. Carboxylic acid and its anhydride. Meanwhile, derivatives of the above acid anhydrides can also be used.

For example, specific examples of the above derivatives include the compounds listed below.

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, and Phenyl succinic anhydride and the like.

Derivatives of glutaric anhydride: glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethylglutaric anhydride, 2,4-diethylglutaric anhydride, butyl glutaric anhydride, and hexyl Glutaric anhydride and the like.

Derivatives of maleic anhydride: 2-methyl maleic anhydride, 2,3-dimethyl maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl-butylene Diacid anhydride, octyl maleic anhydride, mercapto maleic anhydride, dodecyl maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride, and 2,3-diphenyl maleic anhydride or the like.

For the alicyclic polybasic acid, for example, the following alicyclic ring is used. Group dicarboxylic acids and their derivatives.

Saturated alicyclic dicarboxylic acid: dibasic 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, transcyclopentane-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, 1,3-cyclohexanedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, 1,1-cycloheptane dicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornane dicarboxylic acid, hexahydroterephthalic acid, hexahydrogen Isophthalic acid, hexahydrophthalic acid, and tetrahydrophthalic acid.

An unsaturated alicyclic dicarboxylic acid having 1 or 2 unsaturated double bonds in the ring: 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1 -cyclopentene-1,2-dicarboxylic 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, and 2,5-hexadiene-1α, 4α-dicarboxylic acid, etc. .

Meanwhile, as the alicyclic dicarboxylic acid anhydride, a hydrogenated phthalic anhydride derivative can be used. Specific examples thereof include the following: derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, and 4-methyl-hexahydrophthalic anhydride). a derivative 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, and methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.).

As an example of the aromatic polybasic acid, more specifically, for example, the following aromatic dicarboxylic acid or its anhydride can be used.

Aromatic dicarboxylic acids: phthalic acid, isophthalic acid, terephthalic acid, toluene Dicarboxylic acid, 2,5-dimethylterephthalic acid, 2,2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,6- Naphthalene dicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenyl dihydroindole dicarboxylic acid, 1,2-decanedicarboxylic acid, 1,3-anthracene Carboxylic acid, 4,5-nonanedicarboxylic acid, (-)-1,3-indole dicarboxylic acid, 1,4-nonanedicarboxylic acid, 1,5-anthracene dicarboxylic acid, 1,8-decanedicarboxylic acid Acid, 2,3-decanedicarboxylic acid, 1,2-phenanthrene dicarboxylic acid, 4,5-phenanthrene dicarboxylic acid, and 3,9-nonanedicarboxylic acid.

Aromatic dicarboxylic anhydride: phthalic anhydride, 4-methylphthalic anhydride, and the like.

Meanwhile, as the acid anhydride to be used as the polybasic acid, the following compounds may be mentioned: chlorendic anhydride, HET anhydride (1, 4, 5, 6, 7, 7-hexachloro-5-norbornene-2) , 3-dicarboxylic anhydride), biphenyldicarboxylic anhydride, amicic anhydride, endamethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endo Methylene-1,2,3,6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene Dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, and octahydro-1,3-di- oxy-4,5-isobenzofuran dicarboxylic anhydride.

Meanwhile, as the above polyol, a lower molecular weight polyol having a number average molecular weight (Mn) of about 50 to 500 and a higher molecular weight polyol having a number average molecular weight (Mn) of about 500 to 50,000 may be mentioned. However, there is no particular limitation on the use of various classes.

Examples of lower molecular weight polyols, more specifically, for example, the following.

Aliphatic or alicyclic diols: ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butanediol, 3-methyl-1,5-pentanediol, 2, 4-Diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane, 2-butyl-2-ethyl -1,3-propanediol, polyethylene oxide diol (additional molar number is 10 or less), poly Propylene oxide diol (addition molar number is 10 or less), propane diol, 1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6 -hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexane Alkanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, and dimer diol.

Aromatic diols: 1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene , 4,4'-methylene diphenol, 4,4'-(2-indenyl)diphenol, 4,4'-dihydroxydiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidene phenol, and addition of bisphenol to bisphenol addition alkylene oxide.

Further, examples of the raw material bisphenol to be added to the bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.

Examples of the higher molecular weight polyols, more specifically, high molecular weight polyester polyols, high molecular weight polyamine polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyesters. The high molecular weight polycarbonate polyol can be obtained by reacting the above lower molecular weight diol with a carbonate or phosgene.

The above high molecular weight polyester polyols are also commercially available.

For example, the product manufactured by Toyobo Co., Ltd. is as follows: Vylon GK640 (the number average molecular weight (hereinafter also referred to as "Mn") = 18,000, and the glass transition temperature (hereinafter also referred to as "Tg") = 79 ° C, Hydroxyl value = 5, acid value < 4, linear type); Vylon GK880 (Mn = 18,000, Tg = 84 ° C, hydroxyl value = 5, acid value < 4, linear type); Vylon 300 (Mn = 23,000, Tg = 7 ° C, hydroxyl value = 5, acid value < 2, linear type); Vylon 500 (Mn = 23,000, Tg = 4 ° C, hydroxyl value = 5, acid value < 2, linear type); Vylon 560 (Mn) = 19,000, Tg = 7 ° C, hydroxyl value = 8, acid value < 2, branched type; and Vylon 630 (Mn = 20,000, Tg = 75 ° C, hydroxyl value = 5, acid value = 1, linear type).

The products manufactured by Unitika are as follows: UE-3600 (Mn = 20,000, Tg = 75 ° C, hydroxyl value = 4, acid value = 1); UE-3690 (Mn = 14,000, Tg = 91 ° C, hydroxyl value = 8, acid value = 1).

The products manufactured by Kuraray are as follows: P1010 (Mn = 1,000, hydroxyl value = 12, acid value < 0.5, linear liquid type); P2010 (Mn = 2,000, hydroxyl value = 56, acid value < 0.5, line 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 liquid 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); PNOA 4014 (Mn = 4,000, Hydroxyl value = 28, acid value < 0.5, linear liquid form); P2011 (Mn = 2,000, hydroxyl value = 56, acid value < 0.5, linear liquid form); and P4011 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type).

The products manufactured by Concord Fermentation Chemicals Co., Ltd. are as follows: Kyowa Paul 2000BA (Mn = 2,000, hydroxyl value = 58, acid value < 0.5, linear liquid type); and Kyowa Paul 5000PA (Mn = 5,000, hydroxyl value = 22) , acid value <0.5, linear liquid type) and the like.

For example, TPAE 617 (Mn = 15,000, Tg = 90 ° C, hydroxyl value = 16, acid value = 1, linear type) manufactured by Fuji Chemical Industry Co., Ltd., and the like can be exemplified as the product of the above-mentioned high molecular weight polyamine polyalcohol.

The commercial product of the above-mentioned high molecular weight polycarbonate polyol may, for example, be Oxymer N112 (Mn = 1,000, Tg = 60 ° C, hydroxyl value = 12, acid value < 0.5, linear type) manufactured by PERSTORP.

The products manufactured by Asahi Kasei Chemical Co., Ltd. are as follows: PCDL-T5651 (Mn=1,000, hydroxyl value=110, acid value <0.05, linear liquid type); CDL-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).

The products manufactured by Kuraray are as follows: PMHC-1050 (Mn = 1,000, hydroxyl value = 12, acid value < 0.5, linear liquid type); PMHC-2050 (Mn = 2,000, hydroxyl value = 56, acid value) <0.5, linear liquid type); C-1090 (Mn = 1,000, hydroxyl value = 12, 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 = 12, acid value <0.5, linear liquid type); C-2065N (Mn=2,000, hydroxyl value=56, acid value <0.5, linear liquid type); C-1015N (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) and the like.

The above high molecular weight polyurethane polyester can also be obtained commercially.

For example, the products manufactured by Toyobo Co., Ltd. are as follows: Vylon UR1350 (Mn=30,000, Tg=3°C, hydroxyl value=46, acid value <1, linear type); Vylon UR1400 (Mn=40,000, Tg =83 ° C, hydroxyl value = 2, acid value < 1, linear type); Vylon UR3210 (Mn = 40,000, Tg = -3 ° C, hydroxyl value = 3, acid value < 1, linear type); Vylon UR5537 ( Mn=20,000, Tg=34°C, hydroxyl value=17, acid value<1, linear type); and Vylon UR9500 (Mn=25,000, Tg=15°C, hydroxyl value=5, acid value<1, linear type) ).

The products manufactured by Mitsui Chemical Polyurethane Co., Ltd. are as follows: TAKELAC E158 (hydroxyl value = 20, acid value < 3); TAKELAC E551T (hydroxyl value = 30, acid value < 3); and TAKELAC A2789 (hydroxyl value = 10, acid value < 2).

Others, polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly(β-methyl-γ-valerolactone) diol, and polyvalerolactone diol, etc. It is used as the above-mentioned high molecular weight polyalcohol.

(a-2) Polyurethane oligomer

The above-mentioned polyurethane-based oligomer (a-2) can be obtained by reacting a compound having at least one or more isocyanate groups with a compound containing an α,β-unsaturated double bond group having one or more hydroxyl groups in the molecule to be described later. compound of. Further, an amine ester precursor polymer having an isocyanate group at a terminal obtained by reacting at least one isocyanate group-containing compound with the above polyol, and α,β-unsaturated having one or more hydroxyl groups in a molecule to be described later may be mentioned. A compound obtained by reacting a double bond-based compound. In another example, a reaction product obtained by reacting a compound having at least one isocyanate group with a polyhydric alcohol, and then reacting with a compound having at least one amino group to obtain an amine ester precursor having an isocyanate group having a chain-extended terminal. A polymer obtained by reacting a polymer with a compound containing an α,β-unsaturated double bond group having one or more hydroxyl groups in a molecule to be described later. The polyol is a polyester polyol of a higher molecular weight polyol, and is also contained in the polyurethane oligomer (a-2). Meanwhile, the urea-containing bond group obtained by reacting an isocyanate group with an amine group is also contained in the polyurethane-based oligomer (a-2).

The compound having at least one isocyanate group may be a monofunctional polyisocyanate or a polyfunctional isocyanate. Specific examples of the compound include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

Specific examples of the monofunctional polyisocyanate may be exemplified as follows: isocyanic acid Methyl ester, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, isocyanide Cyclohexyl acrylate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, isocyanic acid-2 ,4-dichlorophenyl ester, isocyanate-3-chloro-4-methylphenyl ester, trichloroacetate isocyanate, sulfonate isocyanate, isocyanate-(R)-( +)-α-methylbenzyl ester, isocyanate-(S)-(-)-α-methylbenzyl ester, isocyanate-(R)-(-)-1-(1-naphthyl) Ethyl ester, isocyanate-(R)-(+)-1-phenylethyl ester, isocyanate-(S)-(-)-1-phenylethyl ester, and p-toluenesulfonate isocyanate Ester and the like.

Among the polyfunctional isocyanates, the aromatic polyisocyanate may specifically be exemplified by the following: 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4, 4'-diphenylmethane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, 4,4'-toluidine diisocyanate, toluene-2,4,6- Triisocyanate, benzene-1,3,5-triisocyanate, dimethoxyaniline diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and the like.

Specific examples of the aliphatic polyisocyanate include trimethylmethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HDI), pentamethylene diisocyanate, and 1,2-extension. Propyl diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Specific examples of the araliphatic polyisocyanate include 1,3-dimethylbenzene-ω, ω'-diisocyanate, 1,4-dimethylbenzene-ω, ω'-diisocyanate, and 1, 4-diethylbenzene-ω,ω'-diisocyanate, 1,4-tetramethyl-terephthalic diisocyanate, and 1,3-tetramethyl-terephthalic diisocyanate.

Specific examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (alias: IPDI), 1,3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-Asia Methyl bis(cyclohexyl isocyanate), and 1,4-bis(isocyanatemethyl)cyclohexane.

Further, as a part of the component (a-2), a 2-methylpentane-2,4-diol adduct of the above polyisocyanate and a terpolymer having a trimer isocyanate ring may be used in combination. At the same time, polyphenylmethane polyisocyanate (alias: PAPI), naphthyl diisocyanate, and polyisocyanate modifications such as these can also be used. Further, as the polyisocyanate modified substance, a carbodiimide group, a uretdione group, a uretonimine group, a reaction with water, a biuret group, a trimeric isocyanate may also be used. An arbitrary group of the base or a modified substance having two or more such bases. As the reactant of the polyol and the diisocyanate, a compound having at least 2 isocyanate groups can be used.

Meanwhile, specific examples of the amine having an amine group can be exemplified as follows. Monoamine: triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, hexahydropyridine, N-methylhexahydropyridine, cyclohexylamine, n-butylamine, dimethyl Oxazoline, imidazole, N-methylimidazole, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethylisopropanolamine, and N-methyldiethanolamine.

Examples of the aliphatic polyamines include, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and tri-ethylidene Amine, diethyltriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethyl Ethylene diamine, hexamethylene diamine-2-hydroxyethyl ethylene ethylamine, N-(2-hydroxyethyl) propyl diamine, (2-hydroxyethyl propyl) diamine, (di-2-hydroxyethyl-extended ethyl)diamine, (di-2-hydroxyethyl-propyl)diamine, (2-hydroxypropyl-extended ethyl)diamine, (di-2-hydroxypropyl-extended ethyl) Diamine, and piperazine Wait.

The alicyclic polyamine: isophorone diamine, and dicyclohexylmethane-4, 4'-diamine, and the like.

Aromatic diamines: phenyldiamine, benzodimethyldiamine, 2,4-methylphenylene diamine, 2,6-methylphenylene diamine, diethyltoluenediamine, 3, 3'-Bicyclo-4,4'-diaminodiphenylmethane, 4,4'-bis(t-butyl)diphenylmethane, and the like.

Examples of the mercaptoamine having a monofunctional mercaptoamine group include, for example, mercaptoamine trimethyldecyldimethylamine, trimethyldecyldiethylamine, and dimethylamino group III. Methyl decane, allylamino trimethyl decane, N-methyl-N-trimethyl decyl acetamide, anilinotrimethyl decane, 1-trimethyldecylpyrrole, 1-trimethyl Base pyrrolidone, 1-trimethyldecyl imidazole, 1-trimethyldecyl-1,2,4-triazole, and the like.

Examples of the mercaptoamines having a 2-functional mercaptoamine group include 1,1,3,3-tetramethyldiazane, hexamethyldioxane, and 1,3-diethylene. Base-1,1,3,3-tetramethyldiazepine, and N,N'-bis(trimethyldecyl)-N-phenylurea.

Examples of the mercaptoamine having a trifunctional or higher cyclodecylamine group include 1,1,3,3,5,5-hexamethylcyclotriazane, and 1,1,3,3,5. , 5,7,7-octamethylcyclotetraazane, and the like.

Other compounds which can be used as the above amines can be exemplified below.

Aliphatic amines: 2,5-dimethyl-2,5-hexamethylenediamine, and menthene diamine, 1,4-bis(2-amino-2-methylpropane) Base Polypropylene glycol with an amine group bonded to a propyl branched chain at both ends of the molecule: "Jeffamine D230" and "Jeffamine D400" manufactured by San Techno Chemical Co., Ltd., which is a propyl skeleton diamine, and a propyl group "Jeffamine T403" manufactured by San Techno Chemical Co., Ltd., which is a skeleton triamine, etc., such as ethyl diamine, propyl diamine, butyl bisamine, diethylidene triamine, triethylidene tetraamine, and tetra Ethylpentamine, pentaethylhexamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,2-diaminopropane, iminodipropylamine, methylimido Dipropylamine, 2,5-dimethyl-2,5-hexamethylenediamine; polypropylene glycol with an amine group bonded to a propyl branched chain at both ends of the molecule: San of a propyl skeleton diamine Products such as "Jeffamine D230" and "Jeffamine D400" manufactured by Techno Chemical Co., Ltd., and "Jeffamine T403" manufactured by San Techno Chemical Co., Ltd., which is a propyl group-triamine, and a methylene group bonded to amine nitrogen. Diamine of polyether skeleton: H ₂ N(CH ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ [Ethylene glycol skeleton manufactured by San Techno Chemical Co., Ltd. Amine "Jeffamine EDR148", etc., and 1,5-diamino-2-methylpentane ("MPMD" manufactured by Du Pont Japan Co., Ltd.), etc.; cyclic amines: N-aminoethylpiperine 1,4-bis(2-amino-2-methylpropyl)per Ethamamine-containing amines: m-xylylenediamine ("MXDA" manufactured by Du Pont Japan Co., Ltd.), etc.; amine-containing amines: polyamide amine (Sanwa Chemical Co., Ltd.) Manufactured "X2000"), etc., menthane diamine, isophorone diamine, 1,3-diaminomethylcyclohexane ("1,3 BAC" manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1-cyclohexyl Amino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine; polyamine: dimethyleneamine of a norbornane skeleton (manufactured by Mitsui Chemicals, Inc.) NBDA"), a dimer diamine in which a carboxyl group of a dimer acid is converted into an amine group, a dendrimer having a primary or secondary amine group at the end; and an alicyclic amine: a propoxyamine at both ends Polyoxyalkylene dialkyl glycol diamine and the like.

(a-3) Polyepoxy oligomer

The polyepoxy oligomer (a-3) is a compound having a glycidyl group, a component (B) described later with (meth)acrylic acid or maleic acid, and the like, that is, a molecular inclusion 1 A compound obtained by reacting a compound (B) containing an α,β-unsaturated double bond group having at least a carboxyl group. Representative examples thereof include a bisphenol type, an epoxidized oil type, a phenol novolak type, and an alicyclic type. The bisphenol type polyepoxy oligomer can be reacted with a bisphenol type diglycidyl ether obtained by reacting a bisphenol with epichlorohydrin, and a component (B) described later, such as (meth)acrylic acid. The resulting compound of Mn 400 to 2,000.

As the epoxidized oil-type polyepoxy oligomer, a compound obtained by reacting an oil such as epoxidized soybean oil with a component (B) described later such as (meth)acrylic acid or maleic acid can be used. As the phenol resin type polyepoxy oligomer, a phenol resin type epoxy resin and a compound obtained by reacting the component (B) described later with (meth)acrylic acid can be used. As the alicyclic polyepoxy oligomer, an alicyclic epoxy resin and a compound synthesized by reacting a component (B) described later with (meth)acrylic acid can be used. In addition, in order to adjust the crosslink density at the time of active energy ray polymerization, it is also necessary to use a plurality of α,β-unsaturated double bond groups in the molecule, and other polyfunctional α,β-unsaturated doubles. A bond-based compound.

(a-4) Polyacrylic oligomer

In the present invention, as the oligomer (A), a polyacrylic oligomer (a-4) can be used. Specific examples of the compound which can be used, for example, a compound selected from the group consisting of a modified polyether having an α,β-unsaturated double bond group, an amine-modified α,β-unsaturated double bond group, and an alcohol can be used. Alkyd resin, acetal resin, polybutadiene resin, polythiol olefin Various compounds such as a resin and a polyhydric alcohol are added to an α,β-unsaturated double bond group to modify a compound containing an α,β-unsaturated double bond group, and one or more compounds of the group formed, oligomers or Precursor polymer.

The above oligomer (A) is not only in agglomerated density, but also in terms of compatibility with other components which form a coating film by polymerization, and durability against heat resistance and moist heat resistance, from the viewpoint of obtaining excellent characteristics. The weight average molecular weight (hereinafter, referred to as Mw) is preferably in the range of 300 to 50,000, more preferably in the range of 400 to 30,000. By using an oligomer having an Mw of 50,000 or less, it is possible to easily provide a resin composition which is excellent in fluidity and which is excellent in miscibility with other components (B) and (C1) or (C2) which will be described later. At the same time, it is possible to easily suppress the deterioration of the coating property of the resin composition, the deterioration of the durability of the coating film such as adhesion, and the problem of whitening of the coating film. On the other hand, when an oligomer having Mw of 300 or more is used, when a resin composition is used as an adhesive and the film substrate and the adherend are attached, aggregation failure is less likely to occur in the adhesive layer.

In a preferred embodiment of the present invention, the oligomer (A) is preferably at least (a-2) a polyurethane-based oligomer. When the resin composition is used as an adhesive or the like, the elasticity and flexibility of the adhesive layer tend to change depending on the bonding group in the oligomer (A). When the above-mentioned bonding group is an ester or an ether group, excellent flexibility is easily obtained. However, there is also a tendency to have low elasticity and low hydrolysis resistance. On the other hand, when the above component (a-2) is used, it is easy to balance the elasticity and the flexibility depending on the bonding of the amine ester. At the same time, the component (a-2) can easily improve water resistance and moist heat resistance because of good hydrolysis resistance. Further, in general, when the film is subjected to corona treatment or the like, the surface of the film is interposed with a carbonyl group. For such a carbonyl group, the above amine ester bond, which is derived from the basic portion of the nitrogen atom It is easy to form a relative bond (acid-base interaction), so that adhesion to the film and adhesion can be easily improved. On the other hand, in the case where the bonding group is an ester or an ether, the interaction with the carbonyl group on the above film occurs between the oxygen atom and the weaker one when compared with the case where the bonding group is an amine ester. Bonding. In the case of the resin composition prepared by the same blending ratio, when the component (a-2) is used as the oligomer (A), compared with the case of using other components, the former may be used in various characteristics. The tendency to get better results. However, in the case of using the oligomer other than the above component (a-2), the present invention can easily obtain desired characteristics by appropriately blending other constituent components.

(B) Ingredients:

Next, a compound monomer (B) containing an α,β-unsaturated double bond group having one or more carboxyl groups in the molecule (hereinafter referred to as a compound monomer (B) or a component (B)) will be described. In the present invention, the component (B) is a monomer having at least one carboxyl group in the molecule and containing at least one compound of an α,β-unsaturated double bond group. That is, it is a polymer which does not contain the polymerizable monomer of the above oligomer (A), and is different. The carboxyl group in the above compound monomer (B) exhibits an interaction with an acid-base reaction or a ring-opening addition reaction with a reactive group in the cyclic imine compound (C1) or the carbodiimide compound (C2) to be described later. As a result, since the above-mentioned interaction forms a polyfunctional α,β-unsaturated double bond group compound having a plurality of α,β-unsaturated double bond groups, the crosslinking density of the polymer cured film is greatly improved. .

The compound monomer (B) is not particularly limited as long as it is a compound having one or more carboxyl groups and one or more α,β-unsaturated double bond groups in the structure, and can be used. There is no particular limitation, but specific examples thereof include the following compounds.

Carboxylic acid-containing carboxylic acids containing α,β-unsaturated double bond groups and anhydrides thereof Class: (Meth)acrylic acid [The combination of acrylic acid and methacrylic acid means "(meth)acrylic acid". The same as the following], 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate Ester, (meth)acrylic acid dimer, maleic acid, fumaric acid, monomethyl maleic acid, monomethyl fumaric acid, aconitic acid, hexadienoic acid, cinnamic acid, α - chlorohexadienoic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, glycyrrhizic acid, leucovoric acid, isovaleric acid, crotonic acid, isocrotonic acid, mucobromic acid, sticky Chloric acid, hexadienoic acid, muconic acid, aconitic acid, penicillic acid, geranic acid, citronellic acid, 4-acrylamide, butyric acid, 6-acrylamide, succinic acid, succinic acid -2-(Methyl) propylene methoxyethyl ester; a polylactone system in which a lactone ring such as mono(meth)acrylic acid-ω-carboxypolycaprolactone ester is ring-opened and a carboxyl group at the terminal is substituted (A) Acrylate; an alkylene oxide addition succinic acid having a carboxyl group at the terminal of repeated addition of an alkylene oxide such as ethylene oxide or propylene oxide; and an ester of (meth)acrylic acid.

Examples of the α,β-unsaturated double bond group-containing carboxylic acid having an alicyclic ring and an aromatic ring and an acid anhydride thereof, and the like, may be exemplified by hexahydrophthalic acid-2-(methyl) propylene oxime Ethyl ethyl ester, 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl) propylene methoxy propyl phthalate, phthalic acid-2-(methyl ) propylene methoxy butyl ester, phthalic acid-2-(methyl) propylene decyl hexyl phthalate, phthalic acid-2-(methyl) propylene methoxy octyl phthalate, phthalic acid-2 -(Methyl) propylene oxime oxime ester, 2-vinyl benzoic acid, 3-vinyl benzoic acid, 4-vinyl benzoic acid, 4-isopropenyl benzene carboxylic acid, cinnamic acid, 7-amino group - 3-vinyl-3-vinyl-3-cephem-4-carboxylic acid or the like.

The above compounds may be used singly or in combination of plural kinds. In one embodiment of the present invention, the compound monomer (B) is used (meth) Acrylic acid and a (meth) acrylate having a carboxyl group in the molecule are preferred.

The above-mentioned compound monomer (B) which can be used in the present invention has an acid value in the range of 100 to 1,000 mg KOH/g from the viewpoint of obtaining a desired crosslinking density from the polymerized cured coating film (hereinafter, referred to as AV) is better. The AV is preferably in the range of 150 to 800 mg KOH/g. When the AV of the compound monomer (B) is 1,000 mg KOH/g or less, it is easy to suppress the deterioration of the heat resistance and the water resistance of the polymer cured film. Meanwhile, when AV is 100 mg KOH/g or more, it is easy to obtain better crosslinking due to the interaction of the above compound monomer (B) with a cyclic imine compound (C1) or a carbodiimide compound (C2) described later. density. In the case where the resin composition is used as a coating agent, it is easy to obtain durability such as excellent heat resistance and moist heat resistance in the coating layer composed of the resin composition. Further, when a resin composition is used as an adhesive and the film substrate is attached to an adherend such as various substrates, aggregation failure of the adhesive layer is less likely to occur.

The cyclic imine compound (C1) and the carbodiimide compound (C2) used in the present invention are each a reactive nitrogen-containing compound which can interact with the carboxyl group of the above-mentioned compound monomer (B). The compound containing a reactive nitrogen is a compound which reacts with a carboxyl group by acid-base reaction of a carboxyl group and a nitrogen atom to form a salt. The above addition reaction is promoted by irradiation with an active energy ray. The cyclic imine compound (C1) and the carbodiimide compound (C2) are specifically as follows.

(C1) ingredients:

In the present invention, the cyclic imine compound (C1) is a compound having one or more cyclic imine groups as a reactive group, and the cyclic imine group may be bonded to other bonding groups such as a carbonyl group and a thiocarbonyl group. . Specific examples thereof include a 3-membered ring of ethyleneimine (also known as aziridine) and a 4-membered ring of azetidine (also referred to as a Azetidine, 5-membered pyrrolidine (also known as tetrahydropyrrole), 6-membered hexahydropyridine (also known as azinane), and 7-membered hexamethylene A saturated heterocyclic ring such as an imine (also known as azepan). In addition, other examples may also be exemplified by a 3-membered ring of 1H-hydrazine propane, 2H-hydrazine propane, a 4-membered ring azee, and a 5-membered ring pyrrole (also known as azole); A compound having one or more unsaturated heterocyclic rings as a reactive group, such as a 6-membered ring pyridine or a 7-membered ring azatropilidene (also known as azepine). It is not particularly limited, but an ethyleneimine having a 3-membered ring of a saturated heterocyclic ring is preferred. Ethyleneimine is susceptible to nucleophilic ring-opening reactions because of its weak basicity but large steric strain. Therefore, the interaction with the compound (B) is large and industrially preferable.

Specific examples of the 3-membered ethyleneimine which can be used as the cyclic imine compound (C1) can be exemplified below.

The monofunctional aliphatic ethyleneimines may, for example, be ethyleneimine, 1-methylpropanepropane, 1-ethylpropanepropane, 1-propylpropanepropane, 1-butylpropanepropane, 1-third Butyl oxime, 1-hexyl hydrazine, 1-octyl hydrazine, 1-mercaptopropane, 1-octadecyl hydrazine, propylene imine (also known as 2-methyl hydrazine), (S)-2-methyloximepropane, 2-ethyloximepropane, 2-propylpropanepropane, 2-butylpropanepropane, 2-hexylpropanepropane, 2-octylpropanepropane, 2-mercaptopropene Propane, 2-octadecylalkyl hydrazine, 1-hexyl-2-methyl hydrazine propane, 2,2-dimethyl hydrazine propane, 2,3-dimethyl hydrazine propane, 1-(2-ethyl Butyl) oxime propane, 2-heptyl-3-methyloxime propane, (2R)-1-hexyl-1α-methyloxime propane, 1,2α,3β-trimethylpropane propane, 2,2,3 , 3-tetramethylguanidinium, 2α-tert-butyl-3β-methyloxime propane, 2α-isopropyl-1,3β-dimethylhydrazine, 2α-methyl-3β-(1-A Base ethyl) oxime propane, 2α-(t-butyl)-1,3β-dimethylhydrazine, (1S,2S)-1,2-diisopropyldipropane, 1,2α-diiso Propyl-3β-methylpropanepropane, (1R, 2R)-1,2-diisopropyldihydropropane, 2β-(t-butyl)-1-ethyl-3α-methyloximepropane, 1-isopropyl-2α,3α-di Methyl hydrazine, 1-ethyl-2-methylene hydrazine, 1-ethyl-2α-methyl-3β-(1-methylethyl) hydrazine, 1β-tert-butyl-2β, 3β-dimethylhydrazine, 2α-t-butyl-1-hexyl-3β-methyloxime propane, 1-ethyl-2α-methyl-3β-(1-methylethyl)propane propane, and 1-butyl-2?-methyl-3?-(1-methylethyl)anthracene or the like.

The monofunctional aromatic ethyleneimines may, for example, be 1-phenylhydrazine, (R)-2-phenylhydrazine, (S)-2-phenylhydrazine, 2-(phenylmethyl)吖propane, 2-(phenylethyl) hydrazine, 2-methyl-2-phenyl hydrazine, 1-ethyl-2-phenyl hydrazine, 1-(phenylmethyl) hydrazine, (2β,3α)-1,2-dimethyl-3-phenylhydrazine, 2-t-butyl-2-phenylpropanepropane, 1-benzyl-2-methylpropanepropane, 1- Benzyl-2-ethylindenyl-2-methylpropanepropane, 2-benzyl-3-phenylindole propane, (2R)-1-benzyl-2α-methylpropanepropane, (2R, 3R)-1-benzyl-2-phenyl-3-benzhydrylpropane, 1-benzyl-2-butyrid-3-methylpropanepropane, 2β-phenyl-1, 3β-dimethylhydrazine, 2α-methyl-3β-phenylhydrazine, (2S)-2β-phenyl-3β-benzylhydrazine, (2R)-1-benzyl-2β, 3α - dimethylhydrazine, 1-(2,4,6-trinitrophenyl)anthracene, 1-cyclohexyl-2β-phenyl-3β-(p-methoxybenzhydryl)propane propane, 1-cyclohexyl-2α-phenyl-3α-(p-methylbenzoguanidino)propane, 1-cyclooctyl-2β-phenyl-3β-(p-methoxybenzylidene)propane, 1-cyclooctyl-2α-phenyl-3α- (p-Methylbenzylidene) hydrazine, 1-(2-naphthylmethyl)propane, 1-(1,2,3,4-tetrahydronaphthalen-2-yl)propane, and 1- (p-nitrobenzylidene) hydrazine and the like.

The monofunctional alicyclic ethyleneimines may, for example, be 1-cyclohexyl hydrazine, 2-cyclohexyl hydrazine propane, 1-(1-adamantyl) fluorene propane, and 1-(1-norbornane). ) 吖 propane and the like.

Hydroxy-containing monofunctional ethyleneimines, which may be mentioned, for example, 1-(2-hydroxyethyl)ethenimine, 2-(indol-1-yl)-2-propanol, 3-(2-methyl Indole propan-1-yl-1,2-propanediol, 1-(heptadecylammoniummethylmercapto)hydrazine, 1-(dodecylammoniummethylmercapto)ethyleneimine, α -(吖propan-1-yl)phenylethanol, α-(indol-1-ylmethyl)benzyl alcohol, α-vinyl-1-hydrazine propanol, and α-(2,2,3, 3,4,4,5,5,6,6,7,7,8,8,9,9-heptadecafluoroindenyl)-1-indol propane ethanol.

The monofunctional carboxyl group-containing ethyleneimine or a metal salt thereof may, for example, be 1-indole propane-propane acid, 1-indole propane butyric acid, 1-indol propane hexane acid or 2-indol propanecarboxylic acid, or Sodium 2-indole propanecarboxylate, and the like.

The alkoxy-containing monofunctional ethyleneimine may, for example, be 1-(methoxymethyl)hydrazine, 2-(methoxymethyl)hydrazine, 1-(methoxyethyl)fluorene. Propane, 2-(methoxyethyl)hydrazine, (2R)-2α-methyl-1-(4-methoxybenzyl)propane, 1-(4-methoxybenzyl) -2-methylhydrazine propane, and (S)-hydrazine propane-2α-carboxaldehyde diethyl acetal.

The monofunctional ethyleneimine containing an ester group may, for example, be methyl propane-2-carboxylate, isopropyl 1-hydrazinepropanecarboxylate, butyl 1-hydrazinepropanecarboxylate or 1-butyl-2. -methylmethylpropane-2-carboxylate, methyl 1-(triphenylmethyl)-2-hydrazinepropane, ethyl 3-phenylhydrazine-2-carboxylate, 1-phenyl Mercaptopropane-2-carboxylic acid isopropyl ester, 1-benzyl-2-methylindole propane-2-carboxylic acid methyl ester, 1-phenyl-2-methylindole propane-2-carboxylic acid A Ester, dimethyl 1-[(methoxycarbonyl)methoxy]propanepropane-2,2-dicarboxylate, ethyl 1-hydrazinepropane propionate, propyl 1-pyranpropane propionate, 1-oxime Benzyl propane propionate, 2-methoxyethyl 1-propanepropionate, 2-propyl propanone propionate, isopropyl 1-propanepropane propionate, 1-indole propane propionic acid Cyclopropylmethyl ester, 1-butane propane propionic acid second butyl ester, 1-hydrazine propane propionic acid cycloheptyl ester, 1-hydrazine propane propionic acid cyclohexyl ester, 1-hydrazine propane propionic acid-2-methylcyclohexane Ester, 1-oxime propane Cyclopentyl propionate, phenyl 1-propanepropane propionate, neopentyl 1-propanepropane propionate, cinnamyl 1-propanepropane propionate, phenylethyl 1-propanepropane propionate, and 1-propane propane Acid-2-nitrobutyl ester and the like.

The monofunctional ethyleneimine containing a mercapto group may, for example, be 1-ethylhydrazinium propane, 2-ethenylhydrazine propane, 1-butyl-2-ethenyl-2-methyloxime propane, 1 -Phenyl-2-ethenyl-2-methyloximepropane, 1-[(1-naphthalenyloxy)ethenyl]propane, 1-hexylhydrazine, 1-mercaptopropane, 1-Lauryl-based propane, 1-oleyl-based propane, 1-stearyl hydrazine propane, 1-myristyl hydrazine, phenyl (indol-1-yl) ketone, 1-(2 -Methyl-1-oxopropyl)propane propane, 1-(1-oxobutyl)propane propane, phenyl(indole propan-1-yl)one, and phenyl(p-propane-1- Ketone and the like.

The amine group-containing monofunctional ethylene imines may, for example, be oxime propan-1-amine, oxime propan-2-amine, 1-(2-aminoethyl) fluorene propane, (2S)-2-[( S)-1-hydroxyethyl]pyridin-1-amine, (2S)-N-ethyl-2α-ethinyl-3β-(4-methoxyphenyl)pyran-1-amine, 2 -(吖propan-1-yl)-4,6-dimethoxy-1,3,5-three , 6-(吖propan-1-yl)-1,3,5-three -2,4-diamine, and 4,6-di(indol-1-yl)-N-(2,2-dimethyl-1,3-di Alkan-5-yl)-1,3,5-three -2-amine and the like.

The monofunctional ethyleneimine containing an aminocarbonyl group may, for example, be N-(p-methylphenyl)-1-hydrazine propanecarboxamide, and N-(4-nitrophenyl)-1-propanepropane Carboxyamine and the like.

The monofunctional ethyleneimine containing a carboxy guanamine group may, for example, be N-cyclohexyl-1-hydrazine propane carbamide, N-methyl-1-hydrazine propane carbamide, N,2-dimethyl -1-吖 propane carboxamide, N-benzyl-1-hydrazine propionamine, N-phenyl hydrazine-1-carboxyguanamine, N-(4-methoxyphenyl)-1- Propane carboxamide, 1-phenyl-2-methyloxime-2-carboxyguanamine, 1-benzyl-2-methylpropane-2-carboxyguanamine, 1-butyl-2- Methyl oxime-2-carboxyguanamine, 1-(2-aminoethyl) oxime, N-(2-methoxyphenyl)-1-propane carboxy guanamine, N-(1-naphthyl)-1-indolyl carboxy decylamine, N,N-dimethyl-1-hydrazine propanylcarboxamide, N,N-diethyl-1-hydrazine propanylamine, and N-(2-methoxyphenyl)-1-propanepropane carboxamide and the like.

A monofunctional ethyleneimine containing a carbonitrile group, which may be exemplified by 2-anthranilonitrile, 3-(p-propan-1-yl)propionitrile, and 1-phenyl-2-methylpropanepropane. -2-Carboxylenonitrile, 1-benzyl-2-methylhydrazine propane-2-carbonitrile, 1-butyl-2-methyloxime-2-carbonylonitrile, 1-[(2H3)methyl] Propane-2-carbonitrile, 1-benzylidenepropane-2-carboxonitrile, 1-tert-butoxycarbonylpropane-2-carboxonitrile, and 1-[(p-nitrophenoxy) Ethyl hydrazine] hydrazine and the like.

The cyano group-containing monofunctional ethyleneimine can be exemplified by 1-cyano-2,2-dimethylhydrazine, 1-(t-butyl)-2-cyano-3,3-dipropene. Propylene, 1-(t-butyl)-2-cyano-3,3-diethylpropane, 1-(t-butyl)-2-cyano-3-methyl-3-propanyl Base propane, and 1-(t-butyl)-2-cyano-3,3-dimethylhydrazine propane.

The monofunctional ethyleneimine containing a sulfonyl group may, for example, be 1-phenylsulfonylhydrazine, 1-[(8-methoxy-5-quinolinyl)sulfonyl]propane propane, 4 -methylphenyl(2-butylindole-1-yl)anthracene, 1-toluenesulfonyl-2,3-diphenylpyridinium, 1-(p-tolylsulfonyl)-2-benzene Propylene, and 1-toluenesulfonyl-2-phenyl-2-tert-butylpropanepropane, and the like.

The monofunctional ethyleneimine containing a halogen group may, for example, be 1-chloropropane propane, 2-chloropropane propane, (1S, 2S)-1-chloro-2-methylpropanepropane, 1-(m-chlorobenzene) Mercapto)propane, α-trichloromethyl-1-hydrazine propane methanol, 1-[(4-chlorophenoxy)ethenyl]propane propane, N-(3-chlorophenyl)-1- Propane carboxamide, 1-[(2-chlorophenoxy)ethenyl]propane, N-(4-chlorophenyl)-1-propanecarboxycarboxamide, N-(3,4-di Chlorophenyl)-1-indol propane carboxamide, N-(3,4-dichlorophenyl)-1-indole propanamine, 2-tert-butyl-2-(fluoromethyl)propane propane 1-吖propanepropionic acid-2,2,3,3,4,4,4-heptafluorobutyl ester, 1-indole propane-propionic acid-2,2,2- Trifluoroethyl ester, and 1-toluenesulfonyl-2-t-butyl-2-(fluoromethyl)propanepropane.

The monofunctional ethyleneimine containing a mercapto group may, for example, be 1-(4-methylphenyl)-2-trimethoxyindolizane or 1-(phenyl)-2-(trimethylhydrazine). Base) hydrazine, 1-(phenyl)-2-(trimethylmethyl) hydrazine, and 1-(phenyl)-2-(trimethylhydrazinyl) hydrazine.

The monofunctional ethyleneimine containing an α,β-unsaturated group may, for example, be 2-methyl(meth)acrylic acid-2-(indol-1-yl)ethyl ester or 1-vinylpropanepropane. Β-vinyl-1-hydrazine propane ethanol, β-vinyl-1-hydrazine propane ethanol acetaldehyde, [αS, (-)]-2-methylene-α-vinyl-1-hydrazine propane ethanol, [ αR,(+)]-2-methylene-α-vinyl-1-hydrazinethanol, N-allyl-1-indole propanamine, and 1-allyl-3β-isopropyl -2?-methylpropanepropane and the like.

The bifunctional ethyleneimines may, for example, be 1,1'-bipropane propane, 1,4-bis(indol-1-yl)butane, 1,2-ethanediol bis(propionic acid-1) -吖propane ester), 3,6-bis(1-mercaptopropyl)-1,4-benzoquinone, 1,1'-p-xylylenedihydropropane, N,N'-stretched vinyl double (1-indol propanecarboxamide), 1,1'-tetramethylenebis(carbonyl) biguanide, 1,1'-(octamethylenedicarbonyl) biguanide, 1,1'-( Tetramethylidene disulfonyl) dipyridane, 1,1'-(pentamethylenebissulfonyl) dipyridane, 1,1'-(octamethylenebissulfonyl) biguanide 1,1'-(1,5-Extenothinylbissulphonyl)biguanide, 1,1'-(meta-phenylbissulfonyl)diguanidin, 1,4-butanediol -1,4-bis(1-indol propane propionate), N,N'-diphenylmethane-4,4'-bis(1-indol propane carboxylate), N,N'-toluene-2 , 4-bis(1-indol propane carboxylate), bis-m-xylylene-1-(2-methylpropanepropane), tri-1-indolylphosphine oxide, N,N'-hexa Methyl-1,6-bis(1-indol propane carboxylate), diphenyl (methane-bis-4,4-N,N'-diethylethyl), diphenylmethane-4,4 - double-N, N'-extended ethyl urea, 1,6-hexamethylene double-N, N'-extension Ethyl urea), bis[1-(2-ethyl) propyl propyl] benzene-1,3-carboxyguanamine, and the like.

The trifunctional ethyleneimines may, for example, be tris(p-propan-2-yl)phosphine oxide, 2,2-bishydroxymethylbutanol tris[3-(1-mercaptopropyl)propionate], 2 , 2-bishydroxymethylbutanol tris[3-(2-methyl-1-indolyl)propionate], tris-2,4,6-(1-indolyl)-1,3, 5-three , 2-methylpentane-2,4-diol tris[3-(1-mercaptopropyl)propionate], 2-methylpentane-2,4-diol tris[3-(1-吖 propyl) butyrate], 2-methylpentane-2,4-diol tris[3-(1-(2-methyl) propyl)propionate], 2-methylpentane -2,4-diol tris[3-(1-mercaptopropyl)-2-methylpropionate], and 2,4,6-(trisethylidene)-Syn-III Wait.

A tetrafunctional ethyleneimine such as 2,4,4,6-tetrakis(indol-1-yl)-2,6-[oxybis(exoethyloxyethyloxy)]- 2,4,6-triphosphorus (V)-1,3,5-three And 2,2-bis(hydroxymethyl)-1,3-propanediol tetra[3-(1-mercaptopropyl)propionate].

Further, an amine ester oxime derivative obtained by reacting 1-oxime propanol with a compound having one or more isocyanate groups in the molecule, and an ester oxime propane obtained by reacting 1-anthane propanol with an acid anhydride or an acid halide may also be used. A derivative or the like, a chemically modified compound by a generally known reaction. These derivatives may be used singly or in combination of two or more kinds.

In one embodiment of the resin composition of the present invention, when the total amount of the components (A), (B) and (C1) is 100 parts by weight, the oligomer (A) is used in an amount of from 1 to 99.8 parts by weight in the molecule. The compound (B) containing an α,β-unsaturated double bond group having one or more carboxyl groups is preferably 0.1 to 49.5 parts by weight, and the cyclic imine compound (C1) is preferably 0.1 to 49.5 parts by weight. More preferably, it is (A) in the range of 10 to 80 parts by weight, (B) in the range of 10 to 45 parts by weight, and (C1) in the range of 10 to 45 parts by weight. When the amount of the oligomer (A) is 1 part by weight or more, and when (B) and/or (C1) is 0.1 part by weight or more, the insufficient cohesive force can be improved, and the properties of heat resistance and moist heat resistance can be easily improved. On the other hand, in the oligomer (A) When it is 99.8 parts by weight or less and (B) and/or (C1) is 49.5 parts by weight or less, when a resin composition is used as a coating agent or an adhesive, it is easy to obtain excellent adhesion to a substrate or adhesion. .

Further, in an embodiment of the resin composition of the present invention, when the total weight of the component (B) and the component (C1) is 100% by weight, the ratio of the above (C1) is preferably in the range of 20 to 80% by weight. The ratio of 30 to 70% by weight is more preferable. When the ratio of the above (C1) is 80% by weight or less, the viscosity of the resin composition is suppressed from increasing, and excellent coatability is easily obtained. On the other hand, when the ratio of the above (C1) is 20% by weight or more, when the resin composition is used as a coating agent or an adhesive, it is easy to obtain excellent adhesion to the substrate or adhesion.

(C2) ingredients:

In the present invention, the carbodiimide compound (C2) has a carbodiimide linkage group as a reactive group, that is, a compound having one or more -N=C=N- in the molecule. Among them, a compound having 1 to 4 carbodiimide linkage groups in the molecule is preferred. Further, the carbodiimide linkage group may be bonded to other bond groups including an amine group, a nitro group, a thiol group, a carbonyl group, a decylamino group, and an ester group. An example of the method for producing the carbodiimide compound (C2) in the present invention is a compound having at least one or more isocyanate groups in an organic solvent or a catalyst at a temperature of from 100 to 200 ° C. A method of performing a decarbonation reaction. The reaction takes a long time at a temperature of 100 ° C or lower, and on the other hand, a side reaction is likely to occur at 200 ° C or higher. This reaction is preferably carried out under a nitrogen atmosphere.

In the above production method, the carbodiimide compound (C2) may be any one of a monofunctional polyisocyanate and a polyfunctional isocyanate, which is a compound containing at least one or more isocyanate groups as a raw material. Specifically, it may be in the previous component (a-2) Various compounds exemplified in the above.

Examples of the catalyst used in the reaction for forming the carbodiimide bonding group include a cyclophosphene and a phosphine oxide. More specifically, 1-ethyl-3-methyl-3-oxocyclophosphene, 1-phenyl-3-methyl-3-oxocyclophosphene, and 1-phenyl-3- can be used. Methyl-3-oxocyclophosphene or the like.

The organic solvent used in the reaction for forming the carbodiimide-bonding group must have a high boiling point and do not have a compound having at least one or more isocyanate groups with the raw material, and the produced carbodiimide compound ( C2) Active hydrogen reacted. Examples of the organic solvent which can be used in the present invention are exemplified below.

Examples of the aromatic hydrocarbons include toluene, xylene, and diethylbenzene.

Glycol ether esters: diethylene glycol diacetate, dipropylene glycol dibutyrate, hexanediol diacetate, glycol diacetate, methyl glycol acetate, ethyl glycol B An acid ester, a butyl glycol acetate, an ethyl-di-diol acetate, and a butyl-di-diol acetate.

Ketones: ethyl butyl ketone, ethyl benzene benzene, acetophenone benzene, diisobutyl ketone, and cyclohexanone.

Aliphatic esters: aluminum acetate, propyl propionate, ethyl butyrate, and the like.

The formation of the carbodiimide bond group can be confirmed by the disappearance of the isocyanate group absorption peak at 2260 cm ^-1 and the formation of the carbodiimide bond group absorption peak.

The carbodiimide compound (C2), in addition to the above-mentioned basic method, may be in accordance with, for example, U.S. Patent No. 2,941,956, Japanese Patent Publication No. Sho 47-33279, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. The method disclosed is manufactured. At the same time, it can also be produced according to the method described in J. Org. Chem., 28, 2069 (1963), Chem., Review 81, 619 (1981). In addition, according to the recent Japanese Patent Laid-Open No. 5-179854, and Japanese Patent Laid-Open No. Hei 6-56950 It is produced by a method which is carried out without a solvent, in the manner disclosed. In this specification, reference is also made to this and is incorporated as part of this specification.

Further, in general, in the case of a carbodiimide compound, it is also known to have one or more isocyanate groups in the molecule in addition to the carbodiimide linkage group (that is, -N=C=N-). Compound. However, in the present invention, when the oligomer (A) or the compound monomer (B) in the resin composition contains a functional group containing an active hydrogen such as a hydroxyl group or an amine group, the isocyanate group in the above compound and the above The functional group reaction significantly causes an increase in viscosity. Therefore, when such a resin composition is used as a coating agent or an adhesive agent, coating becomes difficult. At the same time, even if it can be applied, it is likely to cause a problem that the coated surface is rough and scratches are generated, so that the adhesion and the adhesion are liable to be lowered, which is not preferable. Therefore, the carbodiimide compound (C2) used in the present invention preferably contains no isocyanate groups in the molecule.

The specific example of the carbodiimide compound (C2) which can be used in the present invention is exemplified below.

Aliphatic carbodiimides, such as: N, N'-diisopropylcarbodiimide, N, N'-dibutylcarbodiimide, N, N'-di-t-butyl Carbodiimide, 1-ethyl-3-t-butylcarbodiimide, and the like.

Examples of the cyclic carbodiimides such as alicyclic or aromatic rings include 1,3-diphenylcarbodiimide, N,N'-di-p-tolylmethyl carbodiimide, and N,N'. - bis(2-methylphenyl)carbodiimide, N,N'-bis(2-methylphenyl)carbodiimide, N,N'-bis(3-methylphenyl)carbonate Imine, 1-butyl-3-phenylcarbodiimide, bis(2,3-dipropylphenyl)carbodiimide, N-ethyl-N'-phenylcarbodiimide, double (3,4-dipropylphenyl)carbodiimide, N-phenyl-N'-vinylcarbodiimide, bis(3,5-dipropylphenyl)carbodiimide, double ( 2,5-dipropylphenyl)carbodiimide, bis(2,6-dipropylphenyl)carbodiimide, double (two Propyl phenyl) carbodiimide, bis(dipropylphenyl)carbodiimide, bis(2,6-diisopropylphenyl)carbodiimide, N-benzyl-N'- (1-naphthyl)carbodiimide, N-phenyl-N'-isopropylcarbodiimide, N,N'-bis(4-methoxyphenyl)carbodiimide, N-( 2,6-Diisopropyl-4-phenoxyphenyl)-N-t-butylcarbodiimide, 1,3-bis(p-tolyl)carbodiimide, N-benzyl- N'-(t-butyl)carbodiimide, N-phenyl-N'-vinylcarbodiimide, N-phenyl-N'-(1-phenylvinyl)carbodiimide, N,N'-dicyclohexylcarbodiimide, N-(5,5-dimethyl-3-oxo-1-cyclohexenyl)-N'-(1-naphthyl)carbodiimide Amine, N-(5,5-dimethyl-3-oxo-1-cyclohexenyl)-N'-phenylcarbodiimide, N-(5,5-dimethyl-3- Sideoxy-1-cyclohexenyl)-N'-toluenesulfonylcarbodiimide, and N-(5,5-dimethyl-3-o-oxy-1-cyclohexenyl)- N'-butylcarbodiimide and the like.

A carbodiimide having an amine group or a nitro group, which may be, for example, N-(4-carboxy-4-aminobutyl)carbodiimide or 1-(3-dimethylaminopropyl)- 3-ethylcarbodiimide, N-propyl-N'-(4-dimethylaminobutyl)carbodiimide, 3-[(ethylcarbamido)amino]-N, N-Dimethyl-1-propanamine, N-phenyl-N'-(1,3,5-cycloheptatrien-1-yl)carbodiimide, N-cyclohexyl-N'-(2 -(N-morpholinyl)ethyl)carbodiimide, N-cyclohexyl-N'-[2-(2-methyl(N-morpholinyl))ethyl]carbodiimide, 4- [2-[(cyclohexylcarbinimino)amino]ethyl]-4-methylmorpholinium, carbodiimide-m-p-toluenesulfon-1-cyclohexyl-3-(2-( N-morpholinyl)ethyl)ester, 3-[(ethylcarbamido)amino]-N,N,N-trimethyl-1-propane aluminum iodide, 1-ethyl-3- (3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-(3-dimethyl Aminopropyl)-3-ethylcarbodiimide hydrochloride, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, and 1,3- Bis(4-nitrophenyl)carbodiimide and the like.

Chlorine-containing carbodiimides, such as: N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide chloride, N,N'-bis(3-chloro -2-methylphenyl)carbodiimide An amine, and N-(5,5-dimethyl-3-o-oxy-1-cyclohexenyl)-N'-(3-chlorophenyl)carbodiimide.

The carbodiimide containing a mercapto group may, for example, be bis(trimethyldecyl)carbodiimide or 1-(triisopropyldecyl)-3-(triisopropyldecyl)carbon Imine, 1-(triisopropyldecyl)-3-[bis(diisopropylamino)phosphino]carbodiimide, and 1-(triisopropyldecyl)-3-[double (Diisopropylamino) thiophosphino] carbodiimide and the like.

Further, the carbodiimide compound (C2) can also be obtained from a commercial product. For example, monocarbodiimide starting from diphenylmethane diisocyanate (MDI) may, for example, be Lupranate XTB-3003 (manufactured by BASF Corporation) and Stabaxol P (manufactured by Sumitomo Byeramine Co., Ltd.). In addition, as the polycarbodiimide which is made of tetramethyl benzene dimethyl diisocyanate, Carbodilite V-03, V-09, and HMV-8CA (made by Nisshinbo Co., Ltd.), etc. are mentioned. These products are compounds having 1 to 4 carbodiimide linkage groups in the molecule. These carbodiimide compounds (C2) may be used singly or in combination of two or more kinds. From the industrial point of view, in particular, it is preferred to use N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

In one embodiment of the resin composition of the present invention, when the total amount of the components (A), (B) and (C2) is 100 parts by weight, the oligomer (A) is 1 to 99.8 parts by weight, and is intramolecular. The α,β-unsaturated double bond group-containing compound (B) having one or more carboxyl groups is preferably 0.1 to 49.5 parts by weight, and the carbodiimide compound (C2) is preferably 0.1 to 49.5 parts by weight. More preferably, it is (A) in the range of 10 to 80 parts by weight, (B) in the range of 10 to 45 parts by weight, and (C2) in the range of 10 to 45 parts by weight. When the amount of the oligomer (A) is 1 part by weight or more, and when (B) and/or (C2) is 0.1 part by weight or more, the insufficient cohesive force can be improved, and the properties of heat resistance and moist heat resistance can be easily improved. On the other hand, when the oligomer (A) is 99.8 parts by weight or less, and (B) and/or (C2) is 49.5 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 to the substrate or adhesion.

Further, in an embodiment of the resin composition of the present invention, when the total weight of the component (B) and the component (C2) is 100% by weight, the ratio of the above (C2) is preferably in the range of 20 to 80% by weight. The ratio of 30 to 70% by weight is more preferable. When the ratio of the above (C2) is 80% by weight or less, the viscosity of the resin composition is suppressed from increasing, and excellent coatability is easily obtained. On the other hand, when the ratio of the above (C2) is 20% by weight or more, when the resin composition is used as a coating agent or an adhesive, it is easy to obtain excellent adhesion to the substrate or adhesion.

In general, the reactive nitrogen-containing compound of the above (C1) or (C2) is known to interact with a functional group having an active hydrogen such as an amine group or a hydroxyl group in addition to a carboxyl group. However, the resin composition of the present invention is preferentially generated from the viewpoint of the stability of the resin composition and the adhesion or adhesion to the substrate when the resin composition is used as a coating agent or an adhesive. The nitrogen atom of the imido group or the carbodiimide bond group and the interaction with the hydroxyl group are preferred. From this point of view, the component (A) and the component (B) are preferably those which do not contain an active hydrogen-containing functional group such as a hydroxyl group or an amine group. Therefore, the component (B) is an end obtained by ring-opening addition of a lactone ring using, for example, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, or ω-carboxy polycaprolactone monoacrylate. A compound such as a polylactone-based (meth) acrylate having a carboxyl group (manufactured by Toagosei Co., Ltd., acid-containing acrylate "M-5300") is preferred.

On the other hand, in one embodiment of the present invention, the component (C1) or (C2) is further reactive with no isocyanate group other than a cyclic imine group or a carbodiimide group in the molecule. A compound having a nitrogen functional group is preferred. When the above component (C1) or (C2) is an isocyanate group-containing compound, the carboxyl group acts as a target to each other. It is more preferentially contributed to the promotion of reaction with water and OH groups, and thus is liable to cause an increase in viscosity or blistering due to a decarbonation reaction. Therefore, in the use of an adhesive or the like, there is a tendency to cause a decrease in function.

As described above, the resin composition of the present invention is characterized in that it contains the components (A), (B) and (C1) or (C2) in terms of essential components, in particular, the component (B) and the component (C1) or The interaction of C2) with a change in the compound having a polyfunctional α,β-unsaturated double bond group. According to the resin composition of the present invention, as the crosslinking density is increased, the cohesive force can be improved, and durability such as heat resistance and moist heat resistance can be expected to increase. Therefore, in the present invention, it is not intended to directly seek the improvement of the above characteristics by using components other than the above components. However, the resin composition of the present invention may contain additional components in consideration of the desired properties depending on the form in which it is used. Hereinafter, an example of the components that can be added will be described.

(D) Ingredients:

In one embodiment of the resin composition of the present invention, the resin composition may further contain a compound monomer (α) containing an α,β-unsaturated double bond group having no carboxyl group in addition to the above-mentioned essential components. . Among them, the above component (D) is used as a reactive diluent. Among the various compounds generally known as reactive diluents in the art, a compound monomer having no carboxyl group in the molecule can be arbitrarily selected and used. That is, the component (D) is a reactive compound monomer which does not contain the oligomer (A) and the carboxyl group-containing compound monomer (B). When the component (D) is added to the resin composition, it is easy to achieve efficiency and high sensitivity of the copolymerization reaction of the oligomer (A) and the component (B). At the same time, the above resin composition can be easily made low in viscosity, and workability at the time of coating can be easily improved. The compound which can be used as the component (D) is not particularly limited, and the following compounds can be mentioned.

Hydroxy-containing aliphatic (meth) acrylates: more specifically, exemplified by: 2-hydroxyethyl (meth) acrylate [2-hydroxyethyl acrylate and -2- hydroxy methacrylate The ester combination is indicated as "2-hydroxyethyl (meth)acrylate". The same applies hereinafter, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxyl (meth)acrylate Butyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate , 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl-α-(hydroxyl)(meth)acrylate Ester, monofunctional (meth) acrylate, (meth)acrylic acid epoxy laurate, (meth)acrylic acid propyl oleate, and (meth)acrylic acid epoxy propyl Fatty acid ester (meth) acrylate such as stearate; polyhydroxylactone (meth) acrylate having a hydroxyl group at the terminal via ring-opening addition of a lactone ring; and ethylene oxide and propylene oxide An alkylene oxide addition-type (meth) acrylate having a hydroxyl group at the end of repeated addition of an alkylene oxide; and 2-hydroxyethyl (meth)acrylate or the like.

The hydroxyl group-containing alicyclic ring or the aromatic (meth) acrylate may, for example, be a 1,2-cyclohexanedimethanol ester of (meth)acrylic acid or a 1,3-cyclohexyl (meth)acrylate. Alkanediethanol ester, (meth)acrylic acid-1,4-cyclohexanedimethanol ester, (meth)acrylic acid cyclohexyl epoxypropyl ether, (meth)acrylic acid phenylepoxypropyl ether, (A) 2-hydroxy-3-phenoxymethyl acrylate, 2-hydroxy-3-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate Ester, 2-hydroxy-3-phenoxybutyl (meth)acrylate, 2-hydroxy-3-phenoxy oxime (meth)acrylate, 2-hydroxy-3-(methyl)acrylate Phenoxy octadecyl ester, monohydroxyethyl methacrylate (meth) acrylate, 2-(4-benzylidene-3-hydroxyphenoxy)ethyl (meth)acrylate Benzene-di(meth)acrylic acid-1,4-bis(2-hydroxypropyl) ester, and benzene-di(meth)acrylic acid-1,3-bis(2-hydroxypropyl) ester.

The hydroxy-containing benzotriazole-based (meth) acrylate may, for example, be 2-(2,-hydroxy-5'-(meth)acrylomethoxyethylphenyl)-2H-benzo Triazole [2-(2'-hydroxy-5'-propenyloxyethylphenyl)-2H-benzotriazole and 2-(2'-hydroxy-5'-methylpropenyloxyethyl) The phenyl)-2H-benzotriazole is combined and expressed as "2-(2'-hydroxy-5'-(meth)acryloxyethylphenyl)-2H-benzotriazole". The same as the following], 2-(2'-hydroxy-5'-(meth)acryloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-(2'-hydroxy-5' -(Meth)acryloxypropylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-(methyl)propenyloxypropylphenyl)-5-chloro -2H-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloxyethylphenyl)-2H-benzotriazole, and 2 -(2'-Hydroxy-3'-t-butyl-5'-(meth)acryloxyethylphenyl)-5-chloro-2H-benzotriazole or the like.

The benzophenone-based (meth) acrylate having a hydroxyl group may, for example, be 2-hydroxy-4-{2-(methyl)propenyloxy}ethoxybenzophenone or 2-hydroxyl -4-{2-(Methyl)propenyloxy}butoxybenzophenone, 2,2'-dihydroxy-4-{2-(methyl)propenyloxy}ethoxydiphenyl Methyl ketone, and 2-hydroxy-4-{2-(methyl) propylene methoxyl} ethoxy-4'-(2-hydroxyethoxy) benzophenone and the like.

Hydroxy-containing three The (meth) acrylates may, for example, be 2,4-diphenyl-6-[2-hydroxy-4-{2-(methyl)acryloxyethoxyethoxy}]-S- three , 2,4-bis(2-methylphenyl)-6-[2-hydroxy-4-{2-(methyl)propenyloxyethoxy}]-S-three 2,4-bis(2-methoxyphenyl)-6-[2-hydroxy-4-{2-(methyl)acryloxyethoxyethoxy}]-S-three , 2,4-bis(2-ethylphenyl)-6-[2-hydroxy-4-{2-(methyl)propenyloxyethoxy}]-S-three 2,4-bis(2-ethoxyphenyl)-6-[2-hydroxy-4-{2-(methyl)acryloxyethoxyethoxy}]-S-three 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-{2-(methyl)propenyloxyethoxy}]-S-three 2,4-bis(2,4-diethoxyphenyl)-6-[2-hydroxy-4-{2-(methyl)propenyloxyethoxy}]-S-three And 2,4-bis(2,4-diethylphenyl)-6-[2-hydroxy-4-{2-(methyl)propenyloxyethoxy}]-S-three Wait.

Examples of the α,β-unsaturated compound having a plurality of hydroxy groups include propane diol, butane diol, heptane diol, octane diol, glyceryl di(meth) acrylate, and o-di (Methyl)allyl bisphenol A or the like.

The hydroxyl group-containing (meth) acrylamide may, for example, be N-hydroxyethyl(meth)acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide combined It is expressed as "N-hydroxyethyl (meth) acrylamide". The same as the following], N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, and N-hydroxy octyl (A Base) acrylamide and the like.

The (meth)acrylic acid alkyl esters may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, 1-propyl (meth)acrylate or (meth)acrylic acid-2- Propyl ester, n-butyl (meth)acrylate, second butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, Isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (A) N-decyl acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, (methyl) Lauryl acrylate, stearyl (meth) acrylate, and the like.

The (meth)acrylic acid cyclic esters may, for example, be cyclohexyl (meth)acrylate, 1-methyl-1-cyclopentyl (meth)acrylate or 1-ethyl (meth)acrylate. -1-cyclopentyl ester, 1-isopropyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)acrylate, (meth)acrylic acid-1- Ethyl-1-cyclohexyl ester, (meth)acrylic acid-1-isopropyl-1- Cyclohexyl ester, 1-ethyl-1-cyclooctyl (meth)acrylate, benzyl (meth)acrylate, isodecyl (meth)acrylate, phenyl (meth)acrylate, (methyl) )-2-phenoxyethyl acrylate, 2-methoxy-1,2-phenylethyl (meth)acrylate, 2-oxo-1,2-diphenyl (meth)acrylate Ethyl ethyl ester, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate, 1-onion ester of (meth)acrylate, (Methyl)acrylate-2-onion ester, (meth)acrylic acid-9- onion ester, (meth)acrylic acid-9-onion methyl ester, (meth)acrylic acid-2-methyladamantyl-2 - ester, 2-ethyladamantyl-2-(meth)acrylate, 2-n-propyladamantyl-2-(meth)acrylate,-2-isopropyl (meth)acrylate Fund, cycloalkyl-2-ester, (meth)acrylic acid-1-(adamantan-1-yl)-1-methylethyl ester, (meth)acrylic acid-1-(adamantan-1-yl)- 1-ethylethyl ester, (meth)acrylic acid-1-(adamantan-1-yl)-1-methylpropyl ester, (meth)acrylic acid-1-(adamantan-1-yl)-1- Ethyl propyl ester, (meth)acrylic acid-5-o-oxy-4-oxatricyclo[4.2.1.03,7]non-2-ester, (meth)acrylic acid-5-side oxygen 4-oxatricyclo[5.2.1.03,8]non-2-ester, dihydro-α-terpinyl (meth)acrylate, (meth)acrylic acid- 6-Sideoxy-7-oxa-bicyclo[3.2.1]oct-2-ester, and (meth)acrylic acid-7-oxooxy-8-oxa-bicyclo[3.3.1]oct-2 - esters, etc.

The aliphatic (meth) acrylate having one carbonyl group may, for example, be (meth)acrylic acid (methoxycarbonyl)methyl ester or (meth)acrylic acid (methoxycarbonyl)ethyl ester, ( (Methoxycarbonyl) propyl (meth) acrylate, (methoxy) butyl (meth) acrylate, (methoxycarbonyl) decyl (meth) acrylate, (meth) acrylate (ethoxy) Carbonyl)methyl ester, (meth)acrylic acid (ethoxycarbonyl)ethyl ester, (meth)acrylic acid (ethoxycarbonyl)propyl ester, (meth)acrylic acid (ethoxycarbonyl)butyl ester, (methyl) Acrylic acid (ethoxycarbonyl) hexyl acrylate, (meth) octyl (meth) acrylate, 2-(ethoxycarbonyloxy) ethyl (meth) acrylate, (meth) acrylate - 2-(ethoxycarbonyloxy)propyl ester, (meth)acrylic acid -2-(ethoxycarbonyloxy)butyl butyl, 2-(ethoxycarbonyloxy)hexyl (meth)acrylate, 2-(ethoxycarbonyloxy) octyl (meth)acrylate Ester, 2-(propoxycarbonyloxy)ethyl (meth)acrylate, 2-(butoxycarbonyloxy)ethyl (meth)acrylate, 2-(butyl)(meth)acrylate Oxycarbonyloxy)butyl butyl ester, 2-(octyloxycarbonyloxy)ethyl (meth)acrylate, and 2-(octyloxycarbonyloxy)butyl (meth)acrylate.

The aliphatic (meth) acrylate having two carbonyl groups may, for example, be 2-methyloxybutyl decyl ethyl (meth) acrylate or 2-butoxy butyl propyl methacrylate (meth) acrylate. , (meth)acrylic acid 2-oxobutylbutanyl butyl acrylate, (meth)acrylic acid 2-oxobutylbutanyl hexyl ester, (meth)acrylic acid 2-oxobutylbutenyl octyl ester, (methyl) 2-oxobutyl decyl decyl acrylate, 2-methoxybutylidene dodecyl (meth) acrylate, 3-methoxybutyl decyl ethyl (meth) acrylate, (meth) acrylate - 3-sided butyl butyl propyl acrylate, 3-methyloxybutyl butyl (meth) acrylate, 3-methoxybutyl hexyl hexyl (meth) acrylate, 3-oxooxy (meth) acrylate Butyl octyl octyl ester, 3-methyloxybutyl decyl methacrylate (meth) acrylate, 3-oxobutoxy decyl decyl (meth) acrylate, 4-cyanooxyl (meth) acrylate Butyric acid ethyl ester, (meth)acrylic acid-4-cyanoxyloxybutyl propyl propyl ester, (meth)acrylic acid-4-cyanoxyloxybutyl butyl ketone, (meth)acrylic acid 4-cyano side oxygen Butyl decyl hexyl ester, (meth) acrylate 4-cyano oxybutyl hydrazine Octyl ester, (meth)acrylic acid-2,3-di(p-oxybutyl)propyl ester, (meth)acrylic acid-2,3-di(p-oxybutyl) butyl ester, (meth)acrylic acid-2 , 3-di(oxetoxybutylidene)hexyl ester, and (meth)acrylic acid-2,3-di(p-oxybutyl)-octyl ester.

The (meth)acrylic acid cyclic ester having a carbonyl group may, for example, be (meth)acrylic acid-9-methoxycarbonyl-5-sideoxy-4-oxatricyclo[4.2.1.03,7]壬2-ester, (meth)acrylic acid-10-methoxycarbonyl-5-o-oxy-4-oxatricyclo[5.2.1.03,8]non-2-ester, (meth)acrylic acid-4 -methoxycarbonyl-6-o-oxy-7-oxabicyclo[3.2.1]oct-2- Ester, and 4-methoxycarbonyl-7-oxo-8-oxabicyclo[3.3.1]oct-2-ester (meth)acrylate, and the like.

The (meth) acrylamide having a carbonyl group may, for example, be N-(2-o-oxybutylbutenylethyl)(meth)acrylamide or N-(2-o-oxybutylidenepropyl) ( Methyl) acrylamide, N-(2-oxetoxybutyl butyl butyl) (meth) acrylamide, N-(2- oxobutylbutylidene) (meth) decylamine, N-(2 - oxobutylbutenyl octyl) (meth) acrylamide, and diacetone (meth) acrylamide.

Further, the (meth) acrylate containing an unsaturated group may, for example, be (meth)acrylic acid (meth)acrylic acid ester, (meth)acrylic acid-1-butene ester, or (meth)acrylic acid- 2-butenyl ester, 3-butenyl (meth)acrylate, -1,3-methyl-3-butenyl (meth)acrylate, 2-chloro-2-propene (meth)acrylate Ester, 3-chloro-2-propenyl (meth)acrylate, o--2-propenylphenyl (meth)acrylate, 2-(2-propenyloxy)ethyl (meth)acrylate, 2-Methyl acrylate (meth) acrylate, 3,7-dimethyloct-6-en-1-yl (meth)acrylate, rhodyl (meth) Acrylate), cinnamyl (meth)acrylate, and vinyl (meth)acrylate.

Examples of the perfluoroalkyl (meth)acrylates include perfluoromethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoropropyl (meth)acrylate, and (methyl). Perfluorobutyl acrylate, perfluorooctyl (meth)acrylate, trifluoromethyl methyl (meth)acrylate, 2-trifluoromethyl ethyl (meth)acrylate, and (meth)acrylic acid Fluoromethyl methyl ester, 2-perfluoroethyl ethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth)acrylate, tris(meth)acrylate Fluoromethyl methyl ester, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth)acrylate, 2-perfluorohexyl ethyl (meth)acrylate, (meth)acrylic acid-2 - perfluorodecyl ethyl ester, and (meth)acrylic acid-2-perfluorohexadecyl ethyl ester.

The amino group-containing (meth) acrylate may, for example, be (meth)acrylic acid-N-methylaminoethyl ester or (meth)acrylic acid-N-tributylaminoethyl ester (A). Acrylic acid-N,N-dimethylaminoethyl ester, (meth)acrylic acid-N,N-diethylaminoethyl ester, (meth)acrylic acid-N,N-diethylaminol Ester, pentamethylhexahydropyridyl (meth)acrylate, tetramethylhexahydropyridyl (meth) acrylate, and 2,4-diamino-6,2-methacryloxyethyl -s-three Wait.

The (meth) acrylate containing a hetero ring containing an oxygen atom may, for example, be a glycidyl (meth)acrylate or a (meth)acrylic acid (3,4-epoxycyclohexyl)methyl ester ( (3-methyl-3-epoxypropenyl)methyl methacrylate, tetrahydrofuran methyl (meth) acrylate, 2-oxotetrahydropyran-4-yl (meth) acrylate, ( Methyl)acrylic acid 4-methyl-2-oxotetrahydropyran-4-yl, (meth)acrylic acid-4-ethyl-2-oxotetrahydropyran-4-yl, ( Methyl)acrylic acid-4-propyl-2-oxooxytetrahydropyran-4-ester, (meth)acrylic acid-5-sided oxytetrahydrofuran-3-ester, (meth)acrylic acid-2,2 - dimethyl-5-oxo-tetrahydrofuran-3-ester, (meth)acrylic acid-4,4-dimethyl-5-oxo-tetrahydrofuran-3-ester, (meth)acrylic acid-2-side Oxytetrahydrofuran-3-ester, (meth)acrylic acid-4,4-dimethyl-2-oxo-tetrahydrofuran-3-ester, (meth)acrylic acid-5,5-dimethyl-2- side Oxytetrahydrofuran-3-ester, 2-methyloxytetrahydrofuran-3-(meth)acrylate, 5-(oxy)tetrahydrofuran-2-ylmethyl (meth)acrylate, (meth)acrylic acid- 3,3-dimethyl-5-oxo-tetrahydrofuran-2-ylmethyl ester And (meth) acrylate, 4,4-dimethyl-5-oxo-tetrahydrofuran-2-yl ester and the like.

The (meth) acrylate group containing an alkoxy fluorenyl group may, for example, be 3-(meth)acryloxypropylmethyldimethoxydecane or 3-(meth)acryloxyloxy group. Propyltrimethoxydecane, 3-(meth)acryloxypropyltripropoxydecane, 3-(meth)acryloxypropyltributoxydecane, 3-(methyl)propene Methoxypropylmethyl dimethyl Oxydecane, 3-(methyl)propenyloxypropylmethyldiethoxydecane, 3-(methyl)propenyloxypropylethyldimethoxydecane, 3-(methyl) Propylene methoxypropyl butyl dimethoxy decane, 3-(methyl) propylene methoxy propyl ethyl di propoxy decane, 3-(methyl) propylene methoxy propyl methyl di Oxydecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, and 3-(methyl)propenyloxyl Propyltripropoxydecane, and the like.

The sulfonyl group-containing (meth)acrylic acid alkyl esters may, for example, be sulfonic acid methyl (meth)acrylate, 2-sulfonic acid ethyl (meth)acrylate, or (meth)acrylic acid. 2-sulfonate propyl ester, (meth)acrylic acid-3-sulfonate propyl ester, (meth)acrylic acid-2-sulfobutyl butyl ester, (meth)acrylic acid-4-sulfobutyl butyl ester , (meth)acrylic acid-2-sulfonic acid butyl ester, (meth)acrylic acid-6-sulfonic acid hexyl ester, (meth)acrylic acid octyl octyl ester, (meth)acrylic acid sulfonyl decyl ester And (meth)acrylic acid sulfonate lauryl ester, and (meth)acrylic acid sulfoyl stearyl ester.

Examples of the sulfonyl group-containing (meth)acrylic acid cyclic esters include, for example, (meth)acrylic acid sulfophenoxyethyl ester, (meth)acrylic acid sulfocyclohexyl ester, and (meth) Acrylic acid phenyl methacrylate and the like.

The phosphonic acid group-containing (meth) acrylate may, for example, be (meth)acrylic acid diphosphoryloxyethyl ester, (meth)acrylic acid diphosphoryl propyl acrylate, (methyl) Acidic dioxyphosphoryl acrylate, 3-chloro-2-acid dioxyphosphoryl (meth)acrylate, 3-chloro-2-acid dioxyphosphoryl (meth)acrylate Ester, 3-chloro-2-acid dioxyphosphoryl (meth)acrylate, phenyl-2-(methyl)propenyloxyethyl phosphate, acid oxyphosphoric acid (meth)acrylate Ethylene oxide (ethylene oxide addition molar number 4 to 10), and (meth)acrylic acid acidic dioxyphosphoryloxypropylene oxide (propylene oxide addition molar number 4 to 10).

The alkoxy group-containing (meth) acrylate may, for example, be 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or (methyl). 2-propoxyethyl acrylate, 3-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 3-butoxyethyl (meth)acrylate Ester, and 4-butoxyethyl (meth)acrylate.

The alkylene oxide-containing (meth)acrylic acid derivative may, for example, be an alkylene oxide adduct of (meth)acrylic acid.

Examples of the bifunctional (meth) acrylates include epoxyethyl bis(meth)acrylate, triepoxyethyl bis(meth)acrylate, and tetraethoxyethyl bis(meth)acrylate. Poly(ethylene) acrylate (meth) acrylate, glycidyl bis (meth) acrylate, diglycidyl di(meth) acrylate, triglycidyl di(meth) acrylate, di(a) Polyacrylic acid acrylate, butyl butyl (meth) acrylate, pentyl methacrylate, 2,2-dimethyl propyl (meth) acrylate, Methyl) hydroxytrimethylethyl hydroxy hydroxytrimethyl acetate (commonly known as MANDA), dicaprolactone hydroxytrimethyl ethinyl hydroxytrimethyl acetate di(meth) acrylate, two 1,6-hexanediol (meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate,-1,7-heptanediol di(meth)acrylate,-1,8-octanediol di(meth)acrylate , 1,2-octanediol di(meth)acrylate, 1,9-decanediol di(meth)acrylate, di-(meth)acrylic acid-1,2- Alkylene glycol ester, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, di(meth)acrylic acid-1,12- Dodecanediol ester, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, di(methyl) ) 1,2-tetradecanediol acrylate, 1,16-hexadecacyclopropane di(meth)acrylate, 1,2-hexadecane di(meth)acrylate alcohol Ester, 2-methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, di(methyl) ) 2-methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, di(a) 2,2-diethyl-1,3-propanediol acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, II Methyl) dimethyl octyl acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2 di(meth)acrylate , 5-hexanediol ester, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,di(meth)acrylate, 3-propanediol ester, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, two (meth)acrylic acid-1,5-hexanediol ester, di(meth)acrylic acid-2,5-hexanediol ester, di(meth)acrylic acid-1,7-heptanediol ester, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9-decanediol di(meth)acrylate Di(meth)acrylic acid-1,2-decane Alcohol ester, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-tityl di(meth)acrylate Carbacycloester, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, di(meth)acrylic acid -1,2-tetradecanediol ester, 1,16-hexadecacyclopropane di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate , 2-methyl-2,4-pentane bis(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, di(meth)acrylic acid- 2-methyl-2-propyl-1,3-propanediol ester, 2,4-diethyl-2,4-pentanediol di(meth)acrylate, di(meth)acrylic acid -2,2-diethyl-1,3-propanediol ester, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, di(methyl) Dimethylol octyl acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate,-2,5-dimethyl-2,5-di(meth)acrylate Hexanediol ester, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate,-2,4-di(meth)acrylate Ethyl-1,5-pentanediol ester, 1,2-adamantyl glycol di(meth)acrylate, 1,3-adamantyl glycol di(meth)acrylate, di(a) Acrylic acid-1,4-adamantyl glycol ester, tricyclodecyl dihydroxymethyl (meth)acrylate, 1,1,1-trihydroxymethyl ethane di(meth)acrylate, Tricyclodecane dihydroxymethyl (meth)acrylate, dicaprolactone tricyclodecane dihydroxymethyl (meth)acrylate, di(meth)acrylic acid-2,2-bis(hydroxyphenyl) a tetraethylene oxide adduct of propane ester, a tetraethylene oxide adduct of-2,2-bis(hydroxyphenyl)methane di(meth)acrylate, di(meth)acrylic acid-4 Tetraethylene oxide adduct of 4'-sulfonyl diphenolate, tetraethylene oxide adduct of di(meth)acrylic acid-hydrogenated-2,2-bis(hydroxyphenyl)propane ester Tetraethylene oxide adduct of di(meth)acrylic acid-hydrogenated-2,2-bis(hydroxyphenyl)methane ester, di(meth)acrylic acid-hydrogenated-2,2-bis(hydroxyphenyl) Propane ester, di(2-methyl)propionic acid-hydrogenated-2,2-bis(hydroxyphenyl)methane, di(meth)acrylic acid-2,2-bis(hydroxyphenyl)propane ester Ethylene oxide adduct - two a lactone compound and a tetraethylene oxide adduct-dicaprolactone compound of 2,2-bis(hydroxyphenyl)methane di(meth)acrylate.

The trifunctional (meth) acrylates may, for example, be tris(meth)acrylic acid-1,2,3-propane triol ester or tris(meth)acrylic acid-2-methylpentane-2,4. -diol ester, tricaprolactone tris(meth)acrylic acid-2-methylpentane-2,4-diol ester, tris(meth)acrylic acid-2,2-dimethylpropane-1,3 -diol ester, trimethylolhexane tris(meth)acrylate, trimethylol octyl tris(meth)acrylate,-2,2-bis(hydroxymethyl)tris(meth)acrylate -1,3-propanediol ester,-1,1,1-trihydroxymethylethane tris(meth)acrylate, 1,1,1-trihydroxymethylpropane tris(meth)acrylate , tris(meth)acrylic acid ethoxylated trimeric isocyanic acid, ε-caprolactone modified tris-(2-propenyloxyethyl) trimer isocyanate, and neopentyl glycol tri(meth)acrylate Wait.

Polyfunctional (meth) acrylates, such as tetrakis (meth) propylene Acid neopentyl glycol ester, ethoxylated pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, four (meth)acrylic acid-2,2-bis(hydroxymethyl)-1,3-propanediol ester, tetrahexylide tetrakis(meth)acrylate-2,2-bis(hydroxymethyl)-1, 3-propanediol ester, di-1,2,3-propane triol tetra(meth)acrylate, di-2-methylpentane tetra(methyl)pentane-2,4-diol ester, four Caprolactone di-2-methylpentane-2,4-diol ester of tetrakis(meth)acrylate, di-2,2-dimethylpentane-1,3-diol tetra(meth)acrylate Ester, di-trimethylolbutane tetra(meth)acrylate, di-trimethylolhexane tetra(meth)acrylate, di-trimethylol octyl tetra(meth)acrylate, Di-2,2-bis(hydroxymethyl)-1,3-propanediol tetra(meth)acrylate, di-2,2-bis(hydroxymethyl)-1,3 hexa(meth)acrylate -propanediol ester, tris-2,2-bis(hydroxymethyl)-1,3-propanediol hexa(meth)acrylate, tris-2,2-bis(hydroxyl-7) 1,3-propanediol ester, tris-2,2-bis(hydroxymethyl)-1,3-propane octyl (meth)acrylate Glycol esters, and polyethylene oxide hepta (meth) acrylate, 2,2-bis (hydroxymethyl) -1,3-propanediol ester.

The alkoxy group-containing ethylenically unsaturated monomer may, for example, be (meth)allylchlorodecane, (meth)allyltrimethoxydecane or (meth)allyl III. Ethoxy decane, (meth)allylaminotrimethyl decane, diethoxyethyl vinyl decane, trichlorovinyl decane, trimethoxy vinyl decane, triethoxy vinyl decane, Tripropoxyvinyl decane, and vinyl tris(2-methoxyethoxy) decane, and the like.

The aromatic vinyl monomer may, for example, be styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene or 2-methoxyl. Styrene, 3-methoxystyrene, 4-methoxystyrene, 4-tert-butoxystyrene, 4-tert-butoxy-α-methylstyrene, 4-(2-B 2-propoxy)styrene, 4-(2- Ethyl-2-propoxy)-α-methylstyrene, 4-(1-ethoxyethoxy)styrene, 4-(1-ethoxyethoxy)-α-methylbenzene Ethylene, 1-butylstyrene, and 1-chloro-4-isopropenylbenzene.

The aliphatic or aromatic (meth) acrylamide may, for example, be (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) propylene. Indoleamine, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) propylene oxime Amine, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-fluorenyl (meth) acrylamide , N-docosylalkyl (meth) acrylamide, N-nonadecylamyl (meth) acrylamide, N-docosaalkyl (meth) acrylamide, N- Methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N-(4-aminomethyl phenyl) (meth) acrylamide, β-(2 -furyl)(meth)acrylamide, 2,3-bis(2-furyl)propenamide, N-(9H-indol-2-yl)(meth)acrylamide, 2,3, 3-trichloro(meth)acrylamide, N-[(R)-1-phenylethyl](meth)acrylamide, N-[(S)-1-phenylethyl](A Acrylamide, N-(5,5-dimethylhexyl)(meth)acrylamide, (Z)-N-methyl-3-(phenyl)(meth)acrylamide, Z)-3-(phenyl) (A) Acrylamide, N,N-diethyl-3-phenyl(meth)acrylamide, N-[2-(1H-imidazol-5-yl)ethyl](methyl) decylamine, (Z)-N,N-dimethyl-3-(phenyl)(meth)acrylamide, crotonamide, maleimide, fumaride, mesaconamine, lemon Concanamide, Iccomidine, 3-Phenyl-2-propenylamine, 2-methylprop-2-endecylamine, N,N-dimethyl(meth)acrylamide, N,N -Diethyl(meth)acrylamide, N-[3-(N',N'-dimethylamino)propyl]-(methyl)propenylamine, N-(dibutylamino group Methyl)(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-vinylmethaneamine, and N-vinylacetamide.

The (meth) acrylamide containing N-alkoxy group can be exemplified by N-A Oxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxy butyl ( Methyl) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxyoctyl (meth) acrylamide, N-methoxyindolyl (meth) acrylamide , N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) propylene oxime Amine, N-ethoxyethyl (meth) acrylamide, N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-B Oxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-isopropoxyethyl (Meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxy butyl (meth) acrylamide, N-isopropoxy hexyl (methyl Acrylamide, N-isopropoxyoctyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide , N-butoxypropyl (meth) acrylamide, N-butoxy Butyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide, N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (methyl Acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) acrylamide, N-isobutoxybutyl (meth) propylene Indoleamine, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N-(pentyloxymethyl) (meth) acrylamide , N-1-methyl-2-methoxyethyl (meth) acrylamide, N-(propylene oxide-2-ylmethoxymethyl) (meth) acrylamide, N-( Propylene oxide-3-ylmethoxymethyl)(meth)acrylamide, N,N-bis(methoxymethyl)(meth)acrylamide, and N,N-di(ethoxylate) Methyl) (meth) acrylamide and the like.

The sulfonic acid-containing (meth) acrylamide may, for example, be (meth) propylene decyl sulfonic acid, tert-butyl-(meth) acryl decyl sulfonic acid, and (meth) acrylonitrile. Amine-2-methyl-1-propanesulfonic acid and the like.

The (meth) acrylamide containing a cyclic guanamine group may, for example, be 4-propenylmorphomorpholine, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactone. Amines, etc.

The nitrile group-containing ethylenically unsaturated monomer may, for example, be (meth)acrylonitrile, α-chloroacrylonitrile, crotononitrile, maleiconitrile, fumaronitrile, meconazole, and lemon. Conne nitrile, Ikonic dinitrile, and 2-cyanoethyl (meth)acrylate.

The heterocyclic vinyl monomer having a nitrogen atom may, for example, be 2-vinylpyridine, 4-vinylpyridine or 2-vinylpiperidone. , N-vinylimidazole, 4-vinylpiperidone And 2,4-diamino-6-vinyl-s-three Wait.

The maleimide derivative may, for example, be maleimide, methyl maleimide, ethyl maleimide or propyl-butene. Yttrium imine, butyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl-p-butene Yttrium imine, and cyclohexyl maleimide.

Examples of the vinyl ester of a carboxylic acid include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octylate, vinyl laurate, vinyl versatate, and top three. Vinyl acetate, vinyl palmitate, vinyl stearate, and the like.

Meanwhile, the component (D) may be a monomer monomer obtained by reacting the above plural compounds. For example, it may be a compound monomer which is copolymerizable and which contains an α,β-unsaturated group obtained by reacting the above-mentioned epoxy group-containing vinyl ester with a fatty acid. In another example, the halogenated alkylstyrene may be at least one selected from the group consisting of long-chain alcohols, poly(ethylene oxide), and poly(ethylene oxide) monoalkyl ethers. A compound obtained by a reaction of an alcoholic hydroxyl group, a compound which can be copolymerized and which contains an α,β-unsaturated group, and the like. In addition, other examples may also have a weight average molecular weight (Mw) of 200 to 2,000,000. A high molecular weight α,β-unsaturated group-containing compound monomer having a polymer moiety and an ethylenically unsaturated double bond, a so-called macromonomer. In the present invention, the component (D) is not particularly limited. Only one type of the above monomer may be used, or a plurality of types may be used in combination.

Ingredient (E):

The resin composition of the present invention can be polymerized by irradiation with various active energy rays to be hardened. However, the above resin composition may contain, in addition to the essential components of the components (A), (B), and (C1) or (C2), an active energy ray polymerization initiator (E). The polymerization reaction can be promoted by using the active energy ray polymerization initiator (E). In one embodiment of the present invention, the active energy ray is preferably ultraviolet ray, and when the polymerization reaction is carried out by ultraviolet ray irradiation, the resin composition contains the active energy ray polymerization initiator (E).

In the present invention, as the component (E), any compound which is generally known as an active energy ray polymerization initiator can be used.

Specific examples thereof can be exemplified by 2,2-dimethoxy-2-phenylethyl benzene, acetophenone, benzophenone, xanthone, anthrone, benzaldehyde, hydrazine.醌, 3-methylethyl benzene, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl Ketalketone, 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-(N-morpholinyl)propan-1-one.

In addition, examples of the product include Irgacure 184, 907, 651, 1700, 1800, 819, 369, and 261 (manufactured by BASF Japan); DAROCUR-TPO (manufactured by BASF Japan, 2, 4, 6- Trimethyl benzhydryl-diphenyl-phosphine oxide; Darocur-1173 (manufactured by Merck); Esacure KIP150, and TZT (Siber) Hegner Japan company); KAYACURE BMS, and KAYACURE DMBI (manufactured by Nippon Kayaku Co., Ltd.).

Meanwhile, a photopolymerization initiator having at least one (meth)acryl fluorenyl group in the molecule can also be used.

In the present invention, the above-mentioned component (E) may be used singly or in combination of two or more.

The ratio of the above component (E) is preferably from 0.01 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the total of the resin composition from the viewpoint of reactivity. good.

The resin composition of the present invention contains substantially no organic solvent. The resin composition is preferably completely free of an organic solvent, but the active energy ray polymerization initiator (E) is often poorly soluble in the polymerizable component. Therefore, in order to dissolve the active energy ray polymerization initiator (E), a small amount of an organic solvent may be contained. The content of the organic solvent in the resin composition is preferably 5% by weight or less.

Further, in order to improve the performance of the above 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, and nitriles or other nitrogen-containing compounds. Among them, use: lanthanide or benzophenone, thioxanthone or guanidine, thiophene And compounds such as Bengal Rose Bengal are preferred.

Ingredient (F):

In an embodiment of the resin composition of the present invention, the resin composition may further contain a decane compound in addition to the above-mentioned essential components. By using a decane compound, when a resin composition is used as a coating agent or an adhesive, the adhesion to the substrate or the adhesion can be further improved. Moreover, it is easy to improve the heat resistance or the moist heat resistance of the resin layer.

As the decane compound (F), a generally known decane compound can be used, and it is not particularly limited as long as it is added to the substrate to be described later. For example, an alkyl alkoxy decane, an aryl alkoxy decane, a vinyl alkoxy decane, an amine alkoxy decane, an epoxy alkoxy decane, a halogen alkoxy group An alkoxy decane having an alkoxy group such as a decane, a (meth) acrylonitrile-based alkoxy decane, a thiol-based alkoxy decane, a cationic alkoxy decane, or an isocyanate-based alkoxy decane; / or a reactive organic decane or the like in which a hydrogen atom is directly bonded to a ruthenium atom.

More specifically, the following examples are also possible.

The alkyl alkoxy decane may, for example, be tetramethoxy decane, tetraethoxy decane, tetraisopropoxy decane, methyl trimethoxy decane, methyl triethoxy decane or methyl tri Isopropoxydecane, methyltriethoxydecane, methyltris(methoxyethoxy)decane, methyltris(methoxypropoxy)decane, ethyltrimethoxydecane, ethyl Triethoxy decane, ethyl triisopropoxy decane, propyl trimethoxy decane, propyl triethoxy decane, propyl triisopropoxy decane, butyl trimethoxy decane, butyl triethyl Oxydecane, hexyltrimethoxydecane, hexyltriethoxydecane, cyclohexyltrimethoxydecane, cyclohexyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, Dimethyldiisopropoxydecane, dimethyldiethoxydecane, dimethylbis(methoxyethoxy)decane, dimethylbis(methoxypropoxy)decane, diethyl Dimethoxy decane, diethyl diethoxy decane, diethyl diisopropoxy decane, diethyl diethyl decyl decane, methyl ethyl dimethoxy decane Methyl ethyl diethoxy decane, methyl ethyl diisopropoxy decane, methyl ethyl diethoxy decane, methyl propyl dimethoxy decane, methyl propyl diethoxy Decane, methyl propyl diisopropoxy decane, and methyl propyl diethoxy decane.

Examples of the aryl alkoxydecanes include phenyltrimethoxydecane, phenyltriethoxydecane, phenyltriisopropoxydecane, phenyltriethoxydecane, and tolyltrimethoxy. Base decane, and tolyl triethoxy decane.

Examples of the vinyl alkoxy decanes include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, vinyl triethoxy decane, and vinyl tri Methoxyethoxy)decane, vinyl tris(methoxypropoxy)decane, allyltrimethoxydecane, allyltriethoxydecane,divinyldimethoxydecane,diethylene Diethoxy decane, divinyl diisopropoxy decane, divinyl dimethyl decyl decane, methyl vinyl dimethoxy decane, and methyl vinyl diethoxy decane.

Amino alkoxy decanes, which may be mentioned, for example, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxylate Decane, N-(2-aminomethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-amine Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, and N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxydecane salt Acid salt, etc.

Examples of the epoxy alkoxydecanes include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and γ-glycidoxy Propyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, Γ-glycidoxypropylmethyldiethoxydecane, and β-(3,4-epoxycyclohexyl)ethylmethyldiethoxydecane.

Examples of the halogen alkoxydecanes include chloromethyltrimethoxydecane, chloromethyltriethoxydecane, γ-chloropropyltriethoxydecane, and 3-chloropropylmethyl. Diethoxy decane and the like.

(Methyl) acrylonitrile-based alkoxy decane, which may, for example, be 3-methylpropenyloxypropyltrimethoxydecane or γ-methylpropenyloxypropylmethyldimethoxydecane. , 3-propenyloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, γ-methylpropenyloxypropylmethyldiethoxydecane, And γ-acryloxypropylmethyldimethoxydecane.

The thiol-based alkoxy decanes may, for example, be 3-hydrothiopropyltrimethoxydecane, 3-hydrothiopropyltriethoxydecane, and γ-thiopropylpropylmethyldi Ethoxy decane and the like.

The alkoxy decane represented by the isocyanate-based alkoxy decane may, for example, be γ-isocyanate propyl triethoxy decane.

Others may also be exemplified by methyl decane, ethyl decane, dimethyl decane, diethyl decane, diethyl methyl decane, butyl dimethyl decane, di-tert-butyl methyl decane, Triethyl decane, trihexyl decane, butyl dimethyl decane, cyclohexyl dimethyl decane, tripropyl decane, triisopropyl decane, triisobutyl decane, phenyl decane, methyl phenyl decane, Dimethylphenyl decane, methyl phenyl vinyl decane, dimethyl benzyl decane, diphenyl decane, methyl dimethoxy decane, dimethoxy methyl decane, methyl diethoxy Decane, dimethyl ethoxy decane, diethoxy decane, trimethoxy decane, triethoxy decane, 1,1,2-trimethyldioxane, 1,1,2,2-tetraphenyl Dioxane, 1,1,3,3-tetramethyldiazepine, tris(trimethyldecyloxy)decane, tetramethyldiazepine, dimethyldecyldimethylamine, bis ( Dimethylamino)methyl decane, tris(dimethylamino) decane, three (two Methyl decyl)amine, N,N-dimethylaminomethylethoxy decane, diethyl methoxymethyl decane, thiol dimethyl decane, cyclopropane decane, tris(trimethyl hydrazine Base) decane, 1,1,3,3-tetramethyldiazepine, and oily or waxy organodecane containing a mercapto group.

The above decane compound (F) may be a commercially available compound. Further, an oligomer-based decane compound obtained by subjecting a mixture of two or more kinds of decane compounds to oligomerization by hydrolysis and condensation can be used as the above component (F). The above component (F) may be used singly or in combination of two or more.

In the resin composition of the present invention, the compounding ratio of the above decane compound (F) is preferably in the range of 0.01 to 10 parts by weight, and in the range of 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the resin composition. Better. When the compounding ratio is 0.01 parts by weight or more, the effect of improving heat resistance or moist heat resistance is easily obtained. On the other hand, when the blending ratio is within 10 parts by weight, the foaming force is insufficient, and foaming of the polymer coating film can be suppressed in the durability test such as heat resistance or moist heat resistance. At the same time, when a resin composition is used as a coating agent or an adhesive, it is easy to obtain excellent adhesion to a substrate or adhesion.

Other ingredients:

The resin composition of the present invention may further contain various additives without departing from the effects of the present invention. In one embodiment of the present invention, the resin composition may further contain an antioxidant in addition to the above components. By using an antioxidant, coloring of the polymerized coating layer after polymerization by the active energy ray can be suppressed.

Specific examples of the antioxidant which can be obtained as a commercial product are not particularly limited, and the following are exemplified below.

Examples of the phenolic antioxidant include ADK STAB AO-50 and ADK STAB AO-80 (manufactured by Asahi Kasei Kogyo Co., Ltd.).

A sulfur-based antioxidant: IRGANOX-PS-800FD (manufactured by BASF Corporation) or the like.

Hindered amine light stabilizers: TINUBIN 622LD, TINUBIN 144, and TINUBIN 765 (all manufactured by BASF Corporation).

The compounding ratio of the antioxidant is preferably in the range of 0.01 to 20 parts by weight, more preferably in the range of 0.01 to 10 parts by weight, based on 100 parts by weight of the total amount of the resin composition. When the compounding ratio is 0.01 parts by weight or more, it is consumed at an early stage due to the active energy ray, and thus it is possible to suppress a problem that the polymerization rate of the resin composition is lowered. On the other hand, when the compounding ratio exceeds 20 parts by weight, the polymerization rate is increased, but the molecular weight of the polymer coating film is liable to lower. Therefore, when the resin composition is used as a coating agent or an adhesive agent when the compounding ratio is 20 parts by weight or less, the aggregation strength of the polymerized crosslinked coating film is reduced, and the deterioration in durability can be suppressed.

In the present invention, additives other than the antioxidant may be appropriately formulated in the resin composition in accordance with the form of use thereof without departing from the effects of the present invention. For example, from the viewpoints of reduction in polymerization hardening shrinkage ratio, reduction in thermal expansion coefficient, improvement in dimensional stability, improvement in elastic modulus, adjustment in viscosity, improvement in thermal conductivity, improvement in strength, improvement in toughness, and improvement in coloring, etc. In other words, organic or inorganic fillers can be formulated. Such fillers may be composed of materials such as polymers, ceramics, metals, metal oxides, metal salts, and dyed pigments. Meanwhile, the shape thereof is not particularly limited, and examples thereof include a particulate form and a fibrous form. In addition, when the polymer material is blended, a softness imparting agent, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a shake imparting agent, a dispersion stabilizer, a fluidity imparting agent, and Foaming agent, etc., can not be used as a separate filler, but as a poly The mixture or polymer blend is dissolved, semi-dissolved or finely dispersed in the resin composition.

The resin composition of the present invention can be prepared by uniformly mixing the above components in accordance with a method generally known in the art. The resin composition can be used in various forms in a liquid form, a slurry form, or a film form. In one embodiment of the present invention, the resin composition is preferably used as a coating agent or an adhesive.

The resin composition of the present invention preferably has a viscosity which is appropriately adjusted in accordance with the form of use thereof. The resin composition of the present invention is preferably substantially free of an organic solvent, but a solvent may be used in order to adjust the viscosity as needed. For example, the solvent can be used: methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene And other organic solvents such as hydrocarbon solvents or water. The viscosity of the resin composition can be easily adjusted by using such a solvent. Further, the viscosity can be lowered by heating the resin composition without using a solvent.

In one embodiment of the present invention, a resin layer typified by 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 1 to 1500 mPa. The range of s is good, at 10 to 1300 mPa. The range of s is better, and it is between 20 and 1000 mPa. The range of s is even better. The above viscosity is 1500mPa. When s or less, a film of 0.1 to 6 μm can be easily formed on the substrate by coating, and optical characteristics such as light transmittance can be easily improved. On the other hand, the viscosity is 1mPa. When s or more, it is easy to control the film thickness of the resin layer formed by the resin composition.

Meanwhile, in another embodiment, a resin composition is used to form a tool. A resin layer having a film thickness of 6 to 300 μm. In this case, the viscosity of the resin composition is at least 1500 to 100,000 mPa. The range of s is good, at 3,000 to 50,000 mPa. The range of s is better. In actual operation, the viscosity of the resin composition is almost determined by the viscosity of the oligomer (A). Therefore, by managing the viscosity of the oligomer (A), it is from 1 to 100,000 mPa. In the range of s, it is easy to manage the viscosity of the resin composition. In the above embodiment, the adjustment of the viscosity and the application of the resin composition can be easily carried out by adding a solvent to the resin composition as needed.

The resin composition of the present invention is preferably used in the use of a coating agent or an adhesive. The representative of the resin composition is applied to one side or both sides of the substrate by an appropriate method according to the usual method, and then hardened to form a resin layer. Therefore, an embodiment of the present invention relates to a laminate having a substrate and a resin layer containing a resin composition provided on at least one main surface of the substrate. In the present embodiment, the film thickness of the resin layer is set depending on the use of the laminate.

For example, when the resin composition is used as a laminate for an optical element such as a hard coat film or a polarizing film to be described later, the resin composition is subjected to film coating. The thickness of the above resin layer formed by coating is preferably 0.1 to 6 μm, more preferably 0.1 μm to 3 μm. When the thickness of the resin layer is 0.1 μm or more, when a resin composition is used as a coating agent or an adhesive, it is easy to obtain sufficient adhesion or adhesion. On the other hand, when the thickness of the resin layer exceeds 6 μm, in many cases, no change in characteristics such as adhesion or adhesion is observed.

In addition, when the resin composition is used in the use of a laminate for an optical element such as a decorative film (referred to as a filler sheet for a touch panel) to be described later, the resin composition is subjected to a thick film coating. The thickness of the above-mentioned resin layer formed by coating is preferably 6 to 300 μm, more preferably 20 μm to 250 μm. By When the thickness of the resin layer is 6 μm or more, when the resin composition is used as a coating agent or an adhesive, it is easy to obtain sufficient stress relaxation in addition to the filling function of the touch panel. On the other hand, when the thickness of the resin composition layer is 300 μm or less, it is easy to suppress a decrease in coatability such as occurrence of a coating.

The coating method of the above resin composition is not particularly limited. For example, a mayer bar, an applicator, a brush, a sprayer, a roll, a gravure coater, a die coater, a micro gravure coater, a lip coater, a horn coater (comma coater) Various methods generally known, such as a curtain coater, a knife coater, a reverse coater, and a spin coater, are suitable for use. At the same time, the form of film coating or thick film coating may be determined depending on the application, and there is no particular limitation on the selection.

The resin composition of the present invention can be applied to a substrate by a conventionally known conventional method, and secondly, a compound containing an α,β-unsaturated double bond group is further irradiated by irradiating the formed coating layer with an active energy ray. Polymerization to form a hardened material. In an embodiment of the present invention, the active energy ray is preferably 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, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light lamp, and a microwave excited mercury. Lamps, LED lights, xenon lights, and metal halide lamps. In addition, in another embodiment of the present invention, the active energy ray may be a laser beam or an electron beam or the like as an active energy ray for exposure.

The irradiation intensity of the active energy ray is preferably 10 to 500 mW/cm ² . When the light irradiation intensity is less than 10 mW/cm ² , it is necessary to irradiate for a long time at the time of hardening. When it exceeds 500 mW/cm ² , the heat of the lamp may cause deterioration of the substrate in various substrates, which is not preferable. . The cumulative irradiation amount indicated by the product of the irradiation intensity and the irradiation time is preferably 50 to 5,000 mJ/cm ² . When the cumulative irradiation amount is less than 50 mJ/cm ² , the polymerization hardening takes a long time, and when it exceeds 5,000 mJ/cm ² , the irradiation time is extremely long, and the productivity is deteriorated, so that it is also unfavorable. A representative active energy ray-polymerizable resin composition generally requires a total irradiation amount of 1000 mJ/cm ² or more. However, in the resin composition of the present invention, the polymerization is favorably carried out even at a low total irradiation amount of less than 1000 mJ/cm ² .

In the laminate of the present invention, the resin layer on the substrate is formed by polymerizing and curing the resin composition by irradiation with an active energy ray, and has a glass transition temperature of approximately -80 ° C to 100 ° C (hereinafter referred to as Tg). From the viewpoint of punching workability of the above laminated body, the Tg of the resin layer is preferably in the range of -60 ° C to 40 ° C, more preferably in the range of -60 ° C to 0 ° C.

In view of the above, in the resin composition, the resin composition (the polymer cured product of the resin composition) has a Tg within the above range, and (A) an oligomer or (B) A compound containing an α,β-unsaturated double bond group having one or more carboxyl groups in the molecule, a (C1) cyclic imine compound or a (C2) carbodiimide compound is an essential component, and a component is appropriately selected as necessary ( D) It is preferable to constitute an additional component such as a compound containing an α,β-unsaturated double bond group, a (E) polymerization initiator, and a (F) decane compound which does not contain a carboxyl group in the molecule. In such an embodiment, the α,β-unsaturated double bond groups of the components (B) and (D) are preferably a compound having a (meth)acryl fluorenyl group, and a compound having an acryl fluorenyl group is used. Better.

In one embodiment of the present invention, a resin composition is used as an active energy ray-polymerizable coating agent (hereinafter referred to as a coating agent), and a coating layer in which a resin composition is coated on one surface or both surfaces of a substrate is formed. In this embodiment, the substrate may be: Wood, metal plate, plastic plate, film-form substrate, glass plate, paper processed product, and the like are not particularly limited.

On the other hand, in another embodiment of the present invention, a resin composition is used as an active energy ray-polymerizable adhesive (hereinafter referred to as an adhesive), and an adhesive layer in which two or more substrates are bonded together with a resin composition is formed. . In this embodiment, in order to carry out a polymerization reaction by irradiation with an active energy ray, the substrate must be made of a material that is easily penetrated by an active energy ray. The above substrate is preferably a transparent film or a transparent glass plate. However, if one of the substrates uses a transparent film or a transparent glass plate, the other substrate may use a substrate that is not easily penetrated by the active energy ray, for example, a material such as wood, metal plate, plastic plate, or paper processed product. Substrate. In this case, the polymer composition can be polymerized and cured by irradiating the active energy ray from the side of the transparent film or the transparent glass plate.

In the laminate of the present invention, it is preferred to use a film-form substrate in terms of a substrate. Specific examples of the film-form substrate include cellophane, various plastic films, and paper. Among them, it is preferable to use various transparent plastic films. Meanwhile, the film-form substrate may have a single-layer structure as long as the film is transparent, or may have a multilayer structure in which a plurality of substrate layers are laminated, and a film having any structure may be suitably used. In forming the laminate of the present invention, it is preferred to form a resin layer containing the resin composition of the present invention on at least one side of the transparent film.

Hereinafter, a more specific embodiment of the laminated body of the present invention will be described by taking a case where a transparent film is used as a substrate. That is, the following description relates to a laminate having a resin layer called a coating layer or an adhesive layer composed of the resin composition of the present invention on at least one main surface of the transparent film.

a laminate composed of the resin composition of the present invention as a coating agent The representative body is a sheet-like film having a structure of a transparent film/coating layer or a coating layer/transparent film/coating layer. Such a laminate can be obtained by coating a resin composition on at least one main surface of a transparent film, and then polymerizing and curing the resin layer to form a coating layer.

On the other hand, a laminate comprising the resin composition of the present invention as an adhesive agent has a transparent film/adhesion layer/transparent film, or a transparent film/adhesion layer/transparent film/adhesion layer/transparent. A film, a sheet-like multilayer film obtained by laminating a plurality of transparent films. In addition, in other forms, the laminate may also have a thin film-like multilayer film of a transparent film/adhesion layer/transparent film/adhesion layer/transparent film/adhesion layer/transparent film, and other opticals fixed to the glass or the optical molded body. The composition of the components. The laminate can be obtained by irradiating an active energy ray from one side or both sides of the film to cure the adhesive layer.

When the resin composition is used as a coating agent or an adhesive, the polymerization curing of the resin composition can be carried out by applying an active energy ray to the coating layer at the time of coating the resin composition, at the time of laminating the film, or after laminating. It is not particularly limited, but the above irradiation is preferably carried out after lamination of a film or the like.

As described above, when a transparent film is used as the substrate, the laminate can be suitably used for optical applications. From the viewpoint of obtaining good optical properties, the transparent film used in the above laminated body is, for example, a thermoplastic resin excellent in optical properties such as transparency, mechanical strength, thermal stability, moisture resistance, and isotropic properties. A variety of transparent films are preferred. Such various transparent films are also known as various plastic films or plastic sheets. Specific examples thereof include a polyvinyl alcohol film, a polytrimethylene cellulose film, a polyolefin film such as polypropylene, polyethylene, a polycycloolefin, and an ethylene-vinyl acetate copolymer, and polyphenylene terephthalate. Ethylene formate and polyparaphenylene A polyester film such as butadiene diester, a polycarbonate film, a polydecene film, a polyarylate film, a polyacryl film, a polyparaphenylene sulfide film, a polystyrene film, and a poly A vinyl film, a polyamide film, a polyimide film, a polyethylene oxide film, or the like.

In the laminate of the present invention, when a plurality of transparent films are laminated to form a multilayer film, the transparent film to be used may be of the same composition or different types. For example, a polyacrylic film can be laminated on the polycycloolefin-based film via an adhesive layer.

The thickness of the transparent film can be appropriately determined, but it is preferably 1 to 500 μm, more preferably 1 to 300 μm, and even more preferably 5 to 200 μm from the viewpoints of workability such as strength and workability, and thin layer properties. . In optical applications, the thickness of the transparent film is particularly preferably in the range of 5 to 150 μm.

In one embodiment of the laminate for an optical element of the present invention, it is preferable that the transparent film is an optical film which is mainly used for optical applications. Among them, the optical film is a special processor to which the transparent film itself is applied, and has an optical function such as light diffusion, condensing, refraction, scattering, and HAZE. Such optical films can be used singly or in combination of several kinds. In one embodiment of the present invention, a resin layer containing the resin composition is formed on at least one main surface of the optical film to form a laminate for an optical element.

Specific examples of the laminated body for an optical element include a hard coat film, an antistatic coating film, an antiglare coating film, a polarizing film, a retardation film, a circular polarizing film, an antireflection film, a light diffusing film, and lifting. A brightness film, a ruthenium film (also referred to as a ruthenium film), a decorative film (referred to as a filler for a touch panel), and a light guide film (also referred to as a light guide plate). The above-mentioned optical element laminated body can be further attached to a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, or an organic EL module, using the resin composition of the present invention as an adhesive. In addition, in other forms, the hair can be used. The resin composition of the above is used as an adhesive, and the above-mentioned optical element laminate is attached to the above various optical films.

In the following, when the polarizing film is exemplified as an example of the laminated body for an optical element, the embodiment of the laminated body will be more specifically described. A polarizing film, also called a polarizing plate, is an optical film having a multilayer structure in which a polarizer is sandwiched between two films. In the above polarizing film, when a transparent film is provided on both surfaces of the polarizer, a transparent film containing the same polymer material may be used as the surface of the polarizing film, or a transparent film containing a different polymer material or the like may be used. The polarizing film has, for example, a polytrimethylene cellulose-based protective film (hereinafter also referred to as "TAC film") in which two sides of a polyvinyl alcohol-based polarizer are used as two polyethylene-based cellulose-based films. Clamped structure. In another example, the polarizing film is a polycycloolefin film, a polyacryl film, a polycarbonate film, and a polycycloolefin film having a single or double side of a polyvinyl alcohol-based polarizer. A structure in which a film such as a polyester film is sandwiched.

There is no particular limitation. For example, the above polarizing plate (polarizing film) can be produced as follows.

(I) A resin composition of the present invention as an adhesive is applied onto the main surface on one side of the first transparent film (first protective film) to form a first polymerizable adhesive layer. Moreover, the resin composition of the present invention is applied as an adhesive on the main surface on one side of the second transparent film (second protective film) to form a second polymerizable adhesive layer. Next, the first polymerizable adhesive layer and the second polymerizable adhesive layer are laminated on the both main surfaces of the polyvinyl alcohol-based polarizer simultaneously and/or sequentially. Next, the obtained layered body is irradiated with an active energy ray to cure and cure the first and second subsequent layers.

(II) applying a resin composition of the present invention as an adhesive to the main surface on one side of the polyvinyl alcohol-based polarizer to form a first polymerizable adhesive layer, The surface of the polymerizable adhesive layer is coated with a first transparent film (first protective film). Next, the resin composition of the present invention is applied as an adhesive on the main surface of the other side of the polyvinyl alcohol-based polarizer to form a second polymerizable adhesive layer, and the surface of the second polymerizable adhesive layer is 2 protective film coating. Thereafter, the obtained laminate is irradiated with an active energy ray to thermally cure the first and second polymerizable adhesive layers.

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

The above is an embodiment of the laminated body for an optical element, and an example of a polarizing film will be described. However, in the above laminated body, the resin composition of the present invention is used as a coating agent or an adhesive for various substrates. Therefore, it should be easily understood that it is not limited to the polarizing film, and other layers of other various substrates may be used, and a laminate suitable for optical use may be formed.

Example

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In addition, the "parts" and "%" contained in the following examples and comparative examples each indicate "parts by weight" and "% by weight", 1-1. Modulation of resin composition

(mixing examples 101 to 127)

In the 300 ml mayonnaise bottle which is replaced by an oxygen concentration of 10% or less and light-shielded, it is added in the ratio shown in Table 1 at least one or more α, β- A saturated double bond-based oligomer (A), a compound monomer (B) containing an α,β-unsaturated double bond group having one or more carboxyl groups in the molecule, a cyclic imine compound (C1), and no intramolecular inclusion A compound monomer (D) having an α,β-unsaturated double bond group of a carboxyl group, an active energy ray polymerization initiator (E), and a decane compound (F). Then, the mixture was thoroughly stirred and sufficiently defoamed using a stirrer ("T.K. HOMO DISPER" manufactured by Seiko Kogyo Co., Ltd.) to obtain a resin composition of each of the formulations shown in Table 1.

The details of each component described in Table 1 are as follows. In Table 1, the symbol "-" is unallocated.

‧Ingredients (A)

Violet UV 3000B: manufactured by Japan Synthetic Chemical Industry Co., Ltd., a polyurethane oligomer (amine ester acrylate), Mw = 18,000.

Ebecryl 8402: manufactured by DAICEL-CYTEC, an aliphatic urethane acrylate, Mw = 1000.

Art Resin UN-6301: An amine ester acrylate oligomer manufactured by Gensal Industries, Mw = 30,000.

Ebecryl 885: Made by DAICEL-CYTEC, polyester acrylate, Mw = 6000.

Ebecryl 853: manufactured by DAICEL-CYTEC, polyester acrylate, Mw = 470.

‧Ingredients (B)

AA: Acrylic, AV=780

M-5300: Made by East Asian Synthetic Company, containing acid acrylate, AV=200

‧Ingredients (C1)

HBAP: 2,2-bishydroxymethylbutanol tri [propionic acid-3-(1-indolyl) ester]

HBMAP: 2,2-bishydroxymethylbutanol tri [propionic acid-3-(2-methyl-1-indolyl) ester]

HDU: 1,6-hexamethylenebis-N,N'-ethylene urea

‧Ingredients (D)

4HBA: 4-hydroxybutyl acrylate

HEA: 2-hydroxyethyl acrylate

IBXA: isodecyl acrylate

ACMO: N-propylene decylmorpholine

‧Ingredients (E)

TPO: 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide (manufactured by BASF Corporation, DAROCUR TPO)

‧Ingredients (F)

KBM-5103: manufactured by Shin-Etsu Chemical Co., Ltd., decane compound

The present invention is not limited to the above components, and can constitute a resin composition excellent in various properties.

The weight average molecular weight (Mw) of the component (A) used in the resin composition of each formulation shown in Table 1 and the acid value (AV) of the component (B) are determined according to the following methods. value.

<Molecular weight>

The weight average molecular weight (Mw) was measured by GPC (gel permeation chromatography) "Shodex GPC System-21" manufactured by Showa Denko Co., Ltd. GPC is a liquid chromatographic method in which a substance dissolved in a solvent is separated and quantified according to the difference in molecular size. Tetrahydrofuran was used as a solvent. The value of the weight average molecular weight Mw described is a value converted to polystyrene. Further, the number average molecular weight (Mn) can also be determined in the same manner.

Acid value (AV)

In the plugged conical flask, the compound monomer (B) used as a raw material was accurately weighed to about 1 g, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixture was added and dissolved. To the solution, a phenolphthalein test solution was added as an indicator and held for 30 seconds. Thereafter, the solution was titrated with a 0.1 N alcoholic potassium hydroxide solution until the solution was reddish. then, The acid value (mg KOH/g) was determined as a value of the dry state of the resin according to the following formula.

Acid value (mg KOH/g) = {(5.611 × a × F) / S} / (nonvolatile concentration / 100)

Among them, S: the amount of the test article (g)

a: consumption of 0.1N alcoholic potassium hydroxide solution (ml)

F: the price of 0.1N alcoholic potassium hydroxide solution

Further, when the oligomer (A) to be used contains a hydroxyl group, the hydroxyl value can be determined by the method described below.

<OH value>

The test article was accurately weighed in an amount of about 1 g in a plug-in conical flask, and 100 ml of a toluene/ethanol (capacity ratio: toluene/ethanol = 2/1) mixture was added and dissolved. Further, 5 ml of an acetamidine reagent (25 g of acetic anhydride dissolved in pyridine to obtain a solution having a capacity of 100 ml) was added, and the mixture was stirred for about 1 hour. Further, a phenolphthalein test solution was added as an indicator and held for 30 seconds. Thereafter, the solution was titrated with a 0.1 N alcoholic potassium hydroxide solution until the solution was reddish.

The hydroxyl value was determined according to the following formula. The hydroxyl value is a value of a dry state of the resin (unit: mg KOH/g).

Hydroxyl value (mg KOH/g) = [{(b-a) × F × 28.25} / S] / (nonvolatile concentration / 100) + D

Among them, S: the amount of the test article (g)

a: consumption of 0.1N alcoholic potassium hydroxide solution (ml)

b: consumption of 0.1N alcoholic potassium hydroxide solution in blank test (ml)

F: the price of 0.1N alcoholic potassium hydroxide solution

D: acid value (mg KOH / g)

The resin composition of each of the formulation examples shown in Table 1 was determined according to the following method for the solution appearance, viscosity, and glass transition temperature (Tg). The results are shown in Table 2.

<Exterior>

The liquid appearance of the resin compositions of the respective formulation examples shown in Table 1 was visually evaluated.

<viscosity>

About 1.2 ml of the resin composition of each formulation was used as a test piece for measurement. The viscosity of the solution was determined by using an E-type viscometer (TV-22 model manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 0.5 to 100 rpm and a rotation of 1 minute in an environment of 23 ° C to determine the viscosity of the solution (mPa.s). ).

<Glass state transition temperature (Tg)>

Connect the automatic controller DSC (differential scanning calorimeter, "RDC220" manufactured by Seiko Instruments Inc.) to "SSC 5200 Disc Station" (manufactured by Seiko Instruments Inc.) for measurement.

The resin composition of each of the formulation examples shown in Table 1 was applied onto a release-treated polyester film, and then irradiated with an active energy ray to be polymerized and cured. About 10 mg of the obtained hardened material was taken out and placed in an aluminum pan as a test piece, and the device was placed on a differential scanning calorimeter after weighing. On the other hand, another type of aluminum pan that was not placed in the test article was taken as a reference. The aluminum pans of both sides were heated at a temperature of 100 ° C for 5 minutes, and then rapidly cooled to -120 ° C with liquid nitrogen. 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 rise.

1-2. Manufacturing of laminated bodies (Examples A1 to A22 and Comparative Examples A1 to A7)

The resin composition of each of the previously prepared preparations was used as an adhesive, and was produced as follows, and had a protective film (1)/adhesion layer/PVA-based polarizer/sublayer/protective film (2). The layered structure of the structure.

In the laminated body, a polytrimethylene cellulose film containing an ultraviolet absorber manufactured by Fujifilm Co., Ltd. was used as the protective film (1): trade name "FUJITAC: 80 μm". At the same time, a polytrimethylene cellulose film containing no ultraviolet absorber manufactured by Fujifilm Commodity Logistics Co., Ltd. was used as the protective film (2): trade name "TAC 50 μ" (thickness: 50 μm). The protective films (1) and (2) are both transparent films.

First, for each film surface, at 300W. The discharge amount of min/m ² was subjected to corona treatment. The resin composition of each of the blending examples was applied to the surface of each film by using a wire bar coater to form an adhesive layer having a film thickness of 4 μm within 1 hour after the surface treatment. Next, the surface-treated protective films (1) and (2) are attached so as to sandwich the polyvinyl alcohol-based polarizer. After this operation, a laminate including a protective film (1)/adhesion layer/PVA-based polarizer/sublayer/protective film (2) was obtained.

Next, the protective film (1) was attached to the tinplate sheet, and the square of the laminate was fixed with a siroprofen tape and fixed to a tinplate. Then, using an active energy ray irradiation apparatus (manufactured by Toshiba Corporation, a high-pressure mercury lamp), ultraviolet rays were irradiated from the side of the protective film (2) under the conditions of a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ^{2 to} cause polymerization of the subsequent layer. hardening. The laminate obtained in this manner has the function of a polarizing plate.

The thus obtained laminate (polarizing plate) was obtained by the following methods: peel strength, gel fraction, punching workability, shrinkage ratio, heat resistance, and moist heat resistance. The results are shown in Table 3.

<stripping strength>

Then, the force was measured in accordance with JIS K6 854-4 Adhesive-Peel Strength Test Method - Part 4: Moving Roll Method. That is, the obtained polarizing plate is made into a cutter. It was cut into a size of 25 mm × 150 mm and used as a test piece for measurement. On both surfaces of the test piece for measurement, a metal plate was attached via an adhesive tape (DF8712S manufactured by TOYOCHEM Co., Ltd.) to obtain a laminated body for measurement comprising a polarizing plate and a metal plate. In the laminated body (polarizing plate) for measurement, a peeling portion is provided between the protective film and the polarizer in advance. The laminated body for measurement was peeled off from the peeling portion at a rate of 300 mm/min under conditions of 23 ° C and a relative humidity of 50%, and the peeling force was measured. Here, the measurement of the peeling force is performed between the polyvinyl alcohol-based polarizer and the protective film (1), and between the polyvinyl alcohol-based polarizer and the protective film (2). The peeling force was used as the adhesion force and evaluated according to the following evaluation criteria. When the evaluation is "C" or more, there is no particular problem in actual use.

(assessment basis)

A: not peelable, or polarized plate damage

B: The peeling force was 2.0 (N/25 mm) or more, and it was less than 5.0 (N/25 mm).

C: The peeling force was 1.0 (N/25 mm) or more and less than 2.0 (N/25 mm).

D: The peeling force was less than 1.0 (N/25 mm).

<gel fraction>

In a polynormene-based film (trade name "ZEONOR ZF-14: 100 μm") manufactured by ZEON Co., Ltd., which is not subjected to corona treatment, a wire bar coater is used, and each of them is described as an adhesive. The resin composition was applied to form a polymerizable adhesive layer having a film thickness of 20 to 25 μm. At the same time, a ZEONOR ZF-14 which was not subjected to corona treatment was laminated on the above polymerizable adhesive layer to obtain a laminate having a three-layer structure of a transparent film/polymerizable adhesive layer/transparent film. Thereafter, an active energy ray irradiation apparatus (manufactured by Toshiba Co., Ltd., high pressure mercury lamp) was used, and the active energy ray was irradiated under the conditions of a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ^{2 to} cure and cure the polymerizable adhesive layer. Next, the transparent film (ZEONOR ZF-14) was peeled off from the laminated body of the obtained three-layer structure, and the adhesive layer was obtained. The weight (weight 1) of the adhesive layer was measured, and then the adhesive layer was sandwiched between a metal mesh and a metal mesh to maintain the adhesive layer without lamination, and refluxed in methyl ethyl ketone (MEK). 3 hours. Thereafter, after drying at a temperature of 80 ° C for 30 minutes, the weight (weight 2) of the adhesive layer was measured. Then, the following formula was used to determine the gel fraction.

Gel fraction (%) = {1 - (weight 1 - weight 2) / weight 1} × 100

After that, it will be evaluated according to the following evaluation criteria. When the evaluation is "B" or higher, it is the actual use, no problem level.

(assessment basis)

A: The gel fraction is over 90%.

B: gel fraction of 80% or more to less than 90%

C: gel fraction is less than 80%

<punching processability>

The polarizing plate produced in each of the examples and the comparative examples was punched from the side of the protective film (1) using a 100 mm × 100 mm knife manufactured by Dumbbell Co., Ltd. For the punched polarizing plate, the peeling distance of the periphery was measured with a gauge and evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: 0mm

B: 1mm or less

C: 1 to 3 mm

D: 3mm or more

<Shrinkage>

The polarizing plate piece was placed in a constant temperature and humidity machine at 60 ° C-dry and 60 ° C - 90% RH, and the amount of shrinkage in the extending direction after 60 hours was measured, and the amount of shrinkage relative to the original length (100 mm) was determined. The ratio is taken as the shrinkage rate and is evaluated according to the following evaluation criteria. When the evaluation is "B" or higher, it is the actual use, no problem level. In addition, the "dry" is a test condition in which only the temperature and the humidity are not controlled in the heating box having the humidity adjustment function.

(assessment basis)

A: The shrinkage rate is 0.2% or less

B: Shrinkage ratio is larger than 0.2%, and 0.4% or less

C: The shrinkage rate exceeds 0.4%.

<heat resistance>

Each of the polarizing plates obtained in Examples A1 to A22 and Comparative Examples A1 to A7 was cut into a size of 50 mm × 40 mm, and each exposed to 1000 ° C under conditions of 80 ° C - dry and 100 ° C - dry. The presence or absence of peeling of the end portion of the polarizing plate after exposure was visually confirmed, and evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: No peeling at 100 ° C-dry.

B: No peeling at all under the conditions of 80 ° C-dry.

C: There was a peel of less than 1 mm under the conditions of 80 ° C-dry.

D: Peeling of 1 mm or more under the conditions of 80 ° C-dry.

<Heat and heat resistance>

Each of the polarizing plates obtained in Examples A1 to A22 and Comparative Examples A1 to A7 was cut into a size of 50 mm × 40 mm, at 60 ° C - 90% RH, and Exposure was carried out for 1000 hours under conditions of 85 ° C to 85% RH. The presence or absence of peeling of the end portion of the polarizing plate after exposure was visually confirmed, and evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: No peeling at all under the conditions of 85 ° C to 85% RH.

B: No peeling at all under the conditions of 60 ° C - 90% RH.

C: There is a peel of less than 1 mm under the conditions of 60 ° C - 90% RH.

D: There is a peel of 1 mm or more under the conditions of 60 ° C - 90% RH.

The details of the optical film described in Table 3 are as follows.

ZF-14: Polythene-based film manufactured by ZEON Corporation of Japan, having a film thickness of 100 μm.

HBD-002: Polyacrylic film made by Mitsubishi Corporation, with a film thickness of 50 μm.

(Examples B1 to B25 and Comparative Examples B1 to B7)

As the active energy ray-polymerizable coating agent, the resin composition of each of the formulation examples shown in Tables 1 and 2 was used, and a laminate having a structure of an optical film/coating agent layer was produced by the following procedure. In the laminated body, a polytrimethylene cellulose film containing an ultraviolet absorber manufactured by Fujifilm Co., Ltd. was used as the optical film: trade name "FUJITAC: 80 μm". First, the surface of the optical film is 300W. The discharge amount of min/m ² was subjected to corona treatment. The resin composition of each formulation was applied to the surface of the film by using a wire bar coater within 1 hour after the surface treatment, to form a polymerizable coating agent layer having a film thickness of 4 μm.

Next, the above-mentioned laminated body was fixed to the tinplate by the Siprofen tape by attaching the optical film to the tinplate. Then, after replacing the inside of the UV irradiation apparatus (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp) with dry nitrogen gas, the ultraviolet ray was irradiated from the above polymerization at a wavelength of 365 nm and a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² . The coating agent layer side was irradiated, and it polymerized and hardened, and the laminated body which has a coating agent layer was obtained. The laminate obtained in this manner was subjected to the following methods to determine the adhesion and heat resistance. The results are shown in Table 4.

<tightness>

The square peel test was carried out in accordance with JIS K5400. The number of squares stripped from 100 squares was evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: 0 square

B: 1 to 10 squares

C: 11 to 30 squares

D: 31 squares or more

<heat resistance>

The laminate obtained in Examples B1 to B25 and Comparative Examples B1 to B7 was cut into a size of 50 mm × 40 mm, and exposed to light at 80 ° C-dry for 1000 hours. The laminate after the exposure was visually judged whether or not the end portion was peeled off, and evaluated according to the following evaluation criteria. When the evaluation is "B" or higher, it is the actual use, no problem level.

(assessment basis)

A: No peeling at all.

B: There is a peel of less than 1 mm.

C: There is a peel of 1 mm or more.

The details of the optical film described in Table 4 are as follows.

FUJITAC: A TAC film (80 μm) containing a UV absorber manufactured by Fujifilm.

ZF-14: Polyurethane-based film (100 μm) made of UV-absorbing absorbent manufactured by ZEON Corporation of Japan.

HBD-002: Polyacrylic film (50 μm) without UV absorber manufactured by Mitsubishi Ray.

R-140: A polycarbonate film (43 μm) containing no ultraviolet absorber manufactured by Kaneka Co., Ltd.

Emblet S: A polyester film (50 μm) containing a UV absorber manufactured by Unitika.

TUX-HZ: a polyethylene film (50 μm) containing a UV absorber manufactured by Tohcello.

In the present invention, the optical film is not limited thereto, and various optical films can be used to form a laminate having various characteristics.

In the above case, when the resin composition of the present invention is used as the active energy ray-polymerizable adhesive, as shown in Table 3, in the case of Examples A1 to A22, although there is a somewhat high viscosity, there is no particular problem. It is a laminate that is excellent in various characteristics. On the other hand, in the comparative examples A1 to A7, it was found that the adhesion reduction, the punching workability, and the shrinkage ratio were not particularly good. Further, when the resin composition of the present invention is used as an active energy ray-polymerizable coating agent, the same results as those shown in Table 3 are also observed. That is, as shown in Table 4, in the aspects B1 to B25, the adhesion and the heat resistance were excellent, and the laminate could be formed without any particular problem. On the other hand, it is understood that in Comparative Examples B1 to B7, there is a lack of adhesion and heat resistance, and particularly one of them is particularly inferior.

2-1. Modulation of resin composition (Preparation examples 201 to 230)

In the 300 ml mayonnaise bottle which was replaced with an oxygen concentration of 10% or less and which was shielded from light, each was added in the ratio shown in Table 5: an oligomer having at least one α,β-unsaturated double bond group in the molecule (A) a compound (B) containing an α,β-unsaturated double bond group and a carbodiimide compound (C2) having one or more carboxyl groups in the molecule, and an α,β-unsaturated double bond containing no carboxyl group in the molecule The compound (D), the active energy ray polymerization initiator (E) and the decane compound (F). Next, a stirrer ("T.K. HOMO DISPER" manufactured by Special Machine Chemical Industries, Ltd.) was used, and sufficient stirring and sufficient defoaming were carried out to obtain resin compositions of the respective examples shown in Table 5.

The details of each component described in Table 5 are as follows. In Table 5, the symbol "-" means unallocated.

‧Ingredients (A)

Violet UV 3000B: manufactured by Japan Synthetic Chemical Industry Co., Ltd., a polyurethane oligomer (amine ester acrylate).

Ebecryl 8402: manufactured by DAICEL-CYTEC, an aliphatic urethane acrylate, Mw = 1000.

Art Resin UN-6301: An amine ester acrylate oligomer manufactured by Gensal Industries, Mw = 30,000.

Ebecryl 885: Made by DAICEL-CYTEC, polyester acrylate, Mw = 6000.

Ebecryl 853: manufactured by DAICEL-CYTEC, polyester acrylate, Mw = 470.

‧Ingredients (B)

AA: Acrylic, AV = 780.

M-5300: Made by East Asian Synthetic Company, containing acid acrylate, AV=200

‧Ingredients (C2)

DCC: N,N'-dicyclohexylcarbodiimide.

DIC: N,N'-diisopropylcarbodiimide.

DPC: 1,3-diphenylcarbodiimide.

‧Ingredients (D)

4HBA: 4-hydroxybutyl acrylate.

HEA: 2-hydroxyethyl acrylate.

IBXA: isodecyl acrylate.

ACMO: N-propylene decylmorpholine

‧Ingredients (E)

TPO: 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (manufactured by BASF Corporation, DAROCUR TPO).

‧Ingredients (F)

KBM-5103: decane coupling agent (3-propenyloxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd.

A-174: decane coupling agent (γ-methacryloxypropyltrimethoxydecane) manufactured by TANAC.

Sensitizer: DETX-S (manufactured by Nippon Kayaku Co., Ltd., thioxanthone sensitizer (2,4-diethylthiaxanthone)).

Antioxidant: AO-50, manufactured by ADEKA.

The present invention is not limited to the above components, and can constitute a resin composition excellent in various properties.

The weight average molecular weight (Mw) of the above component (A) and the acid value (AV) of the component (B) used in the resin composition of each formulation shown in Table 5 are the same as those described previously. The method is decided. Meanwhile, the resin composition: the appearance of the solution (hereinafter sometimes referred to simply as the appearance), the viscosity, and the glass transition temperature (Tg) are also determined in the same manner as the method described above. The results are shown in Table 6.

2-2. Manufacture of laminates (Examples C1 to C28, and Comparative Examples C1 to C4)

The resin composition of each of the previously prepared preparation examples was used as an adhesive, and was produced as follows to form a laminate having a structure of a protective film (1)/adhesion layer/PVA-based polarizer/sublayer/protective film (2).

In the laminated body, a polynorbornene film containing no ultraviolet absorber manufactured by Zeon Corporation of Japan is used as the protective film (1): trade name "ZF-14: 100 μm". At the same time, a polyacrylic film containing no ultraviolet absorber manufactured by Mitsubishi Rayon Co., Ltd. was used as the protective film (2): trade name "HBD-002" (thickness: 50 μm). That is, the protective films (1) and (2) are both transparent films.

First, for each film surface, at 300W. The discharge amount of min/m ² was subjected to corona treatment. The resin composition of each formulation was applied to the surface of each film by a wire bar coater within 1 hour after the surface treatment, and a polymerizable adhesive layer having a film thickness of 4 μm was formed. Next, the surface-treated protective film was attached in such a manner as to sandwich a polyvinyl alcohol-based polarizer. After this operation, a laminate including a protective film (1)/adhesion layer/PVA-based polarizer/sublayer/protective film (2) was obtained.

Next, in order to connect the protective film (1) to the tinplate, the square of the laminated body was fixed with a siroprofen tape and fixed to a tinplate. Then, an active energy ray irradiation apparatus (manufactured by Toshiba Co., Ltd., high pressure mercury lamp) was used, and ultraviolet rays were irradiated from the side of the protective film (2) under the conditions of a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ² to form an adhesive layer. Polymerization hardening. The laminate obtained in this manner functions as a polarizing plate.

With respect to the thus obtained laminate (polarizing plate), peel strength, gel fraction, punching workability, shrinkage ratio, heat resistance, and moist heat resistance were evaluated in accordance with the following methods. The results are shown in Table 7.

<stripping strength>

Then, the force was measured in accordance with JIS K6 854-4 Adhesive-Peel Strength Test Method - Part 4: Moving Roll Method. In other words, the obtained polarizing plate was cut into a size of 25 mm × 150 mm with a blade as a test piece for measurement. On the both sides of the test piece for measurement, a metal plate was attached by a laminator using a viscous tape (DF 8712S manufactured by TOYOCHEM Co., Ltd.) to obtain a laminated body for measurement comprising a polarizing plate and a metal plate. In the laminated body (polarizing plate) for measurement, a peeling portion is provided in advance between the protective film and the polarizer. The laminated body for measurement was peeled off from the peeling portion at a rate of 300 mm/min under conditions of 23 ° C and a relative humidity of 50%, and the peeling force was measured. Here, the measurement of the peeling force is performed between the polyvinyl alcohol-based polarizer and the protective film (1), and between the polyvinyl alcohol-based polarizer and the protective film (2). The peeling force was used as the adhesion force and evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: not peelable, or polarized plate damage

B: The peeling force was 2.0 (N/25 mm) or more, and it was less than 5.0 (N/25 mm).

C: The peeling force was 1.0 (N/25 mm) or more and less than 2.0 (N/25 mm).

D: The peeling force was less than 1.0 (N/25 mm).

<gel fraction>

A resin of each formulation as an adhesive was applied to a polynorbornene film (trade name "ZEONOR ZF-14: 100 μm") manufactured by ZEON Co., Ltd., which was not subjected to corona treatment, using a wire bar coater. The composition was formed into a polymerizable adhesive layer having a film thickness of 20 to 25 μm. At the same time, on the above polymerizable adhesive layer, a ZEONOR ZF-14 which is not subjected to corona treatment is laminated to obtain a laminate having a three-layer structure of a transparent film/adhesion layer/transparent film, and thereafter, an active energy ray irradiation device is used. (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp), the active energy ray was irradiated under conditions of a maximum illuminance of 300 mW/cm ² and an integrated light amount of 300 mJ/cm ^{2 to} cure and cure the polymerizable adhesive layer. Next, the transparent film (ZEONOR ZF-14) was peeled off from the laminated body of the obtained three-layer structure, and the adhesive layer was obtained. The weight (weight 1) of the adhesive layer was measured. Next, the adhesive layer was sandwiched between the metal mesh and the metal mesh, and the adhesive layer was left unlaminated, and refluxed in methyl ethyl ketone (MEK) for 3 hours. Thereafter, after drying at a temperature of 80 ° C for 30 minutes, the weight (weight 2) of the adhesive layer was measured. Then, the equivalent value was used, and the gel fraction was determined.

Gel fraction (%) = {1 - (weight 1 - weight 2) / weight 1} × 100

After that, it is evaluated according to the following evaluation criteria.

(assessment basis)

A: The gel fraction is over 90%.

B: gel fraction of 80% or more to less than 90%

C: gel fraction is less than 80%

Further, the gel fraction indicates a dissolution residual of the resin with respect to the solvent, and is related to the crosslinking density in the polymerization hardening, and is a simple method for determining the crosslinking density. If the gel fraction is low, it means a solvent. It has high solubility and low crosslink density. On the other hand, when the gel fraction is high, it means that the solubility in a solvent is low and the crosslinking density is high. In the above evaluation criteria, when the evaluation is "C" or more, there is no problem in the actual use.

<punching processability>

The polarizing plates produced in the respective examples and the comparative examples were punched from the side of the protective film (1) using a 100 mm × 100 mm knife manufactured by Dumbbell Co., Ltd. The polarizing plate of the punched hole was measured, and the peeling distance of the periphery was measured with a gauge, and evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: 0mm

B: 1mm or less

C: 1 to 3 mm

D: 3mm or more

<Shrinkage>

The above-mentioned polarizing plate pieces were placed in a constant temperature and humidity machine at 60 ° C-dry and 60 ° C - 90% RH, and the amount of shrinkage in the extending direction after 60 hours was measured to determine the shrinkage relative to the original length (100 mm). The ratio of the amount is taken as the shrinkage rate. At the same time, it is evaluated according to the following evaluation criteria. In addition, the "dry" is a test condition in which only the temperature and the humidity are not controlled in the heating box having the humidity adjustment function. When the evaluation is "B" or higher, it is the actual use, no problem level.

(assessment basis)

A: The shrinkage rate is 0.2% or less

B: Shrinkage ratio is larger than 0.2%, and 0.4% or less

C: The shrinkage rate exceeds 0.4%.

<heat resistance>

Each of the polarizing plates obtained in each of Examples C1 to C28 and Comparative Examples C1 to C4 was cut into a size of 50 mm × 40 mm, and each exposed for 1000 hours under conditions of 80 ° C-dry and 100 ° C-dry. The presence or absence of peeling of the end portion of the polarizing plate after the exposure was visually judged. At the same time, it is evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: No peeling at 100 ° C-dry.

B: No peeling at all under the conditions of 80 ° C-dry.

C: There was a peel of less than 1 mm under the conditions of 80 ° C-dry.

D: Peeling of 1 mm or more under the conditions of 80 ° C-dry.

<Heat and heat resistance>

Each of the polarizing plates obtained in each of Examples C1 to C28 and Comparative Examples C1 to C4 was cut into a size of 50 mm × 40 mm, and exposed under the conditions of 60 ° C - 90% RH and 85 ° C - 85% RH. 1000 hours. The presence or absence of peeling of the end portion of the polarizing plate after the exposure was visually judged. At the same time, it is evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: No peeling at all under the conditions of 85 ° C to 85% RH.

B: No peeling at all under the conditions of 60 ° C - 90% RH.

C: There is a peel of less than 1 mm under the conditions of 60 ° C - 90% RH.

D: There is a peel of 1 mm or more under the conditions of 60 ° C - 90% RH.

The details of the optical film described in Table 7 are as follows.

ZF-14: Polythene-based film manufactured by ZEON Corporation of Japan.

HBD-002: Polyacrylic film made by Mitsubishi Corporation.

(Examples D1 to D31 and Comparative Examples D1 to D4)

Using the resin composition shown in Tables 5 and 6 as an active energy ray-polymerizable coating agent, a laminate having an optical film/coating agent layer structure was produced as follows. In the laminate, a polytrimethylene cellulose film containing an ultraviolet absorber manufactured by Fujifilm Co., Ltd. was used as an optical film: trade name "FUJITAC: 80 μm". First, the surface of the optical film is 300W. The discharge amount of min/m ² was subjected to corona treatment. The resin composition of each formulation was applied to the surface of the film by using a wire bar coater within 1 hour after the surface treatment, to form a polymerizable coating agent layer having a film thickness of 4 μm.

Next, the above-mentioned laminated body was fixed to the tinplate by the Siprofen tape by attaching the optical film to the tinplate. Then, the UV irradiation device (manufactured by Toshiba Co., Ltd., high-pressure mercury lamp) was replaced with dry nitrogen gas, and ultraviolet rays were coated from the above polymerized polymer under the conditions of a wavelength of 365 nm, a maximum illuminance of 300 mW/cm ² , and an integrated light amount of 300 mJ/cm ² . The agent layer side was irradiated, and it polymerized and hardened, and the laminated body which has a coating agent layer was obtained. The laminate obtained in this manner was subjected to the following methods to determine the adhesion and heat resistance. The results are shown in Table 8.

<tightness>

The square peel test was carried out in accordance with JIS K5400. The number of squares stripped in 100 squares was evaluated according to the following evaluation criteria. When the evaluation is "C" or higher, it is the actual use, no problem level.

(assessment basis)

A: 0 square

B: 1 to 10 squares

C: 11 to 30 squares

D: 31 squares or more

<heat resistance>

The laminate obtained in Examples D1 to D31 and Comparative Examples D1 to D4 was cut into a size of 50 mm × 40 mm, and exposed to light at 80 ° C - dry for 1000 hours. The presence or absence of peeling of the end portion of the laminate after the exposure was visually judged. At the same time, it is evaluated according to the following evaluation criteria. When the evaluation is "B" or higher, it is the actual use, no problem level.

(assessment basis)

A: No peeling at all.

B: There is no peeling up to 1 mm.

C: There is a peel of 1 mm or more.

The details of the optical film described in Table 8 are as follows.

FUJITAC: A TAC film (80 μm) made of Fujifilm Co., Ltd. containing a UV absorber.

ZF-14: Polydecene-based film (100 μm) manufactured by ZEON Corporation of Japan and containing no ultraviolet absorber.

HBD-002: Polyacrylic film (50 μm) made of Mitsubishi Rays Co., Ltd. without UV absorber.

R-140: A polycarbonate film (43 μm) manufactured by Kaneka Co., Ltd., which does not contain a UV absorber.

Emblet S: A polyester film (50 μm) made of Unitika, containing a UV absorber.

TUX-HZ: A polyethylene film (50 μm) made of a UV absorber manufactured by Tohcello.

In the present invention, the optical film is not limited thereto, and various optical films can be used to form a laminate having various characteristics.

As described above, when the resin composition of the present invention is used as the active energy ray-polymerizable adhesive, as shown in Table 7, in Examples C1 to C28, although there are some high viscosities, there is no particular problem. A laminate having excellent properties in various characteristics can be formed. On the other hand, in Comparative Examples C1 to C4, it was found that the adhesion strength, the punching workability, and the shrinkage ratio were not particularly good. Further, when the resin composition of the present invention is used as the active energy ray-polymerizable coating agent, the same results as those shown in Table 7 are also observed. That is, as shown in Table 8, in the examples D1 to D31, the adhesion and the heat resistance were excellent, and the laminate could be formed without any particular problem. On the other hand, it is understood that in Comparative Examples D1 to D4, there is a lack of adhesion and heat resistance. Don't be particularly bad on either side.

Claims (14)

A resin composition comprising an active energy ray-polymerizable resin composition comprising: an oligomer (A) having at least one or more α,β-unsaturated double bond groups in a molecule, and having one or more carboxyl groups in the molecule a compound monomer (B) containing an α,β-unsaturated double bond group, and a cyclic imine compound (C1) or a carbodiimide compound (C2), wherein the oligomer (A) is selected Formed from polyester-based oligomer (a-1), polyurethane-based oligomer (a-2), polyepoxy oligomer (a-3), and polyacrylic oligomer (a-4) At least one type of oligomer of the group, the compound monomer (B) containing an α,β-unsaturated double bond group contains (meth)acrylic acid, and a carboxyl group-containing (meth)acrylate At least one of them. The resin composition according to claim 1, which comprises: 1 to 99.8 parts by weight of the aforementioned oligomer (A), 0.1 to 49.5 parts by weight of the aforementioned compound containing an α,β-unsaturated double bond group. Monomer (B), and 0.1 to 49.5 parts by weight of the aforementioned cyclic imine compound (C1) or carbodiimide compound (C2). The resin composition according to claim 1 or 2, wherein the oligomer (A) has a weight average molecular weight of 300 to 30,000. The resin composition according to the first or second aspect of the invention, wherein the compound having an α,β-unsaturated double bond group (B) has an acid value of from 100 to 1,000 mg KOH/g. The resin composition according to the first or second aspect of the invention, wherein the cyclic imine compound (C1) is a compound having one or more imine rings having a three-membered ring structure in the molecule. The resin composition according to the first or second aspect of the invention, wherein the carbodiimide compound (C2) is a compound having one or more carbodiimide linkage groups in the molecule. The resin composition according to claim 1 or 2, further comprising a compound monomer (D) containing an α,β-unsaturated double bond group having no carboxyl group in the molecule. The resin composition according to claim 1 or 2, further comprising: an active energy ray polymerization initiator (E), and the amount of the active energy ray polymerization initiator (E), relative to the resin The total amount of the composition is 100 parts by weight in the range of 0.01 to 20 parts by weight. The resin composition according to claim 1 or 2, further comprising a decane compound (F). The resin composition according to claim 1 or 2, which is an active energy ray-polymerizable coating agent or an active energy ray-polymerizable adhesive. A laminate comprising a substrate and a resin layer comprising the resin composition according to any one of claims 1 to 10, which is provided on at least one main surface of the substrate. The laminate according to claim 11, wherein the substrate is a transparent film. The laminate according to the invention of claim 12, wherein the transparent film is selected from the group consisting of a polyethylene fluorene-based cellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, and a polycarbonate. At least one selected from the group consisting of a film, a polyester film, a polyvinyl alcohol film, and a polyimide film. A laminated body for an optical element, comprising: an optical film; and one of the first to tenth aspects of the patent application scope, which is provided on at least one main surface of the optical film A resin layer composed of a resin composition.