JP6471493B2 - Active energy ray polymerizable resin composition and laminate - Google Patents

Description

  The present invention relates to an active energy ray polymerizable resin composition and a laminate using the resin composition. In particular, the present invention relates to a resin composition and a laminate that are suitable for use in optical elements.

In addition to various characteristics such as fast polymerization rate, good workability due to the absence of solvent, energy saving of extremely low energy requirements, active energy ray polymerization technology has recently reduced environmental pollution due to environmental pollution problems. Therefore, the field of use is expanding in the fields of building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical devices, displays, and the like.

These contain a resin that can be polymerized with active energy rays and a monomer having an α, β-ethylenically unsaturated double bond group, and the monomer also functions as a solvent. There is an advantage that the solvent does not volatilize sometimes. And as this resin having active energy ray polymerizability, α, β-ethylenically unsaturated double bond group at the molecular terminal of low molecular weight polyester resin, polyurethane resin, polyepoxy resin, polyacrylic resin, etc. And oligomers having an α, β-ethylenically unsaturated double bond group are used. (Patent Document 1)

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

  In display devices, various films are usually used depending on the application, such as an antireflection film for preventing reflection from an external light source, and a protective film (protection film) for preventing scratches on the surface of the display device. ing. For example, a polarizing plate or a retardation film is laminated as a liquid crystal cell member constituting a liquid crystal display (LCD). Such a film is attached to an adherend via an adhesive and is used in a display device as a laminate for an optical element, and an active energy ray polymerizable composition is used as an adhesive as one form. .

  However, while the conventional active energy ray polymerizable resin composition has advantages such as a high polymerization rate, the polymer tends to have difficulty in obtaining sufficient transparency required for optical applications. In addition, when a laminated body for an optical element is produced using the above resin composition, since the dimensional change characteristics of the material of each layer in the laminated body are different, the dimensions change and warp with changes in temperature and humidity. (Also called curl) tends to occur. Patent Document 2 discloses an ultraviolet curable composition using polyester acrylate and a conjugated diene polymer and having low transparency and small volume shrinkage. However, the composition using the polyester acrylate cannot satisfy the adhesion and heat and humidity resistance of the coat layer.

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

Recently, as the needs for thinning of these display devices and miniaturization of images have increased, the resin for optical films such as prism sheets, Fresnel lenses and lenticular lenses having the fine optical structure used for these displays has been developed. High refractive index resins have been developed and are becoming thinner. However, the reduction in thickness makes the film strength weak and makes it difficult to increase the size. In order to solve this problem, a method of reinforcing the optical film with a transparent film imparting rigidity has been proposed. As an adhesive for bonding these films in the method, a resin composition comprising a thermoplastic resin and a polyisocyanate, a thermoplastic resin and an acrylate compound, and a polyisocyanate and a polyester is disclosed (for example, In this case, a method of using an active energy ray-polymerizable resin composition such as ultraviolet rays in order to increase the curing rate is being studied. However, when these active energy ray polymerizable resin compositions are used as an adhesive, there are cases where sufficient adhesive force and adhesion cannot be obtained due to moisture absorption or distortion due to temperature change.

As described above, in the field of display devices, development of an active energy ray-polymerizable resin composition that is excellent in various properties required for optical applications in addition to conventional advantages is desired. More specifically, it is an active energy ray-polymerizable resin composition that can be suitably used as a coating agent or an adhesive that constitutes a laminate for an optical element, substantially containing no organic solvent, and having adhesion and In addition to excellent transparency, there is a need for a resin composition that has good durability under harsher environments under high humidity and high temperatures.

JP 2013-140365 A JP 2003-192745 A JP-A-10-158349

  In view of the above situation, an object of the present invention is to provide an active energy ray-polymerizable resin composition that is excellent in adhesion, workability, heat-and-moisture resistance, and can be suitably used as a coating agent or an adhesive in the optical field. To do. In addition, the present invention is excellent in adhesion between the base material and the resin layer comprising the above resin composition, punching workability and heat-and-moisture resistance, and has a problem of yellowing in use, particularly a transparent body such as a prism sheet or an optical film. It aims at providing the laminated body which uses a film as a base material.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the following active energy ray-polymerizable resin composition can achieve the above target, and have completed the present invention.

That is, the present invention provides an active energy comprising a polyester oligomer (A) having one or more α, β-unsaturated double bond groups and an organic base (b1) or a metal salt (b2) of an organic acid. It is a linear polymerizable resin composition, Comprising: A polyester-type oligomer (A) is an active energy ray polymeric resin composition whose weight average molecular weight is 1000-60000.
Moreover, this invention is the said active energy ray polymeric resin composition whose polyester-type oligomer (A) is the weight average molecular weights 6001-60000.
Moreover, this invention is said active energy ray polymeric resin composition whose organic base (b1) is the organic base (b1-2) which has an (alpha), (beta) -ethylenically unsaturated double bond group.
Moreover, this invention is said active energy ray polymeric resin composition whose content rate of organic base (b1) or metal salt (b2) of organic acid is 0.01-10 mass%.
Further, the present invention further provides the active energy ray-polymerizable resin composition (provided that the compound (X) comprises a compound (X) having a hydroxyl group and an α, β-ethylenically unsaturated double bond group). Polyester oligomer (A) and an organic base (b1-2) having an α, β-ethylenically unsaturated double bond group).
Moreover, this invention is said active energy ray polymeric resin composition formed by containing 0.01-10 mass% of water further.
Moreover, this invention is a laminated body which has a base material (G) and the resin layer which consists of the said active energy ray polymeric resin composition provided in the at least one surface of this base material (G).
Moreover, this invention is the said laminated body whose base material (G) is a transparent film (H).
In the present invention, the transparent film (H) is a polyacetylcellulose film, a polynorbornene film, a polypropylene film, a polyacrylic film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide film. It is the said laminated body which is at least 1 sort (s) selected from the group which consists of.

According to the present invention, it is possible to provide an active energy ray-polymerizable resin composition and a laminate excellent in transparency (yellowing resistance), adhesion, workability, wet heat resistance, and the like. As a result, a coating agent, an adhesive, and a laminate that can be suitably used in the optical field can be provided.

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 (hereinafter sometimes simply referred to as “resin composition”) includes a polyester-based oligomer (A) having at least one α, β-unsaturated double bond group and , An active energy ray-polymerizable resin composition comprising an organic base (b1) or a metal salt (b2) of an organic acid, wherein the polyester oligomer (A) has a weight average molecular weight of 1000 to 60000. It is an energy beam polymerizable resin composition.

Here, the “active energy ray” means an energy ray in a broad sense that can provide energy necessary for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. . The active energy ray-polymerizable resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) undergoes a polymerization reaction upon irradiation with the active energy ray to form a cured product. Although it does not specifically limit, In one Embodiment of this invention, it is preferable that the said active energy ray is a light ray containing an ultraviolet-ray.
In addition, in this specification, when expressed as “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or methacryloyloxy”, and “allyl and / or Or "methallyl".

Hereinafter, the constituent components of the resin composition will be specifically described.
<Polyester oligomer (A)>
First, a polyester-based oligomer (A) having one or more α, β-unsaturated double bond groups (hereinafter sometimes simply referred to as “oligomer (A)”) will be described. Although there is no restriction | limiting in the structure and manufacturing method of a polyester-type oligomer (A), A polyester-type oligomer (A) has a carboxyl group or a hydroxyl group as a terminal functional group obtained by polycondensation of a polybasic acid and a polyhydric alcohol. Polyester, carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, epoxy group-containing α, β-ethylenically unsaturated diester It can be obtained by reacting a heavy bond group-containing compound and / or an isocyanate group-containing α, β-ethylenically unsaturated double bond group-containing compound. Further, it is obtained by reacting a urethane prepolymer of a terminal isocyanate group obtained by reacting a polyester with a compound having two or more isocyanate groups and a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound. A thing is also contained in a polyester-type oligomer (A).

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

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

Also, derivatives of hexahydrophthalic anhydride ((3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), tetrahydrophthalic anhydride derivatives (1,2,3,6-tetrahydrophthalic anhydride, 3 -Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) The hydrogenated phthalic anhydride derivative can also be used as an alicyclic dicarboxylic acid anhydride.

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

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

Polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500, but can be used without any particular limitation.

More specific examples of relatively low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (Addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, Aliphatic or cycloaliphatic diols such as octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol;

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

Examples of the raw material bisphenol of addition-type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.

  In addition, a polyol containing three or more hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol may be used.

  Among the above polyhydric alcohols, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3 To branched alkanes such as' -dimethylol heptane, 2-butyl-2-ethyl-1,3-propanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, trimethylolpropane, pentaerythritol Those having two or more hydroxyl groups introduced are preferred in terms of the adhesion and heat resistance of the oligomer.

First, the polyester-based oligomer (A) is obtained by polycondensing a polybasic acid and a polyhydric alcohol by a known method. At this time, the molecular weight and the terminal functional group are adjusted by the balance between the amount of carboxyl groups contained in the polybasic acid and the amount of hydroxyl groups of the polyhydric alcohol.

When “the amount of carboxyl groups contained in the polybasic acid> the amount of hydroxyl groups contained in the polyhydric alcohol”, the terminal functional group is a carboxyl group, and the hydroxyl-containing α, β-ethylenically unsaturated double bond group-containing compound The target polyester-based ligomer (A) can be obtained by condensation reaction of the hydroxyl group of the compound or by addition reaction of the epoxy group of the epoxy group-containing α, β-ethylenically unsaturated double bond group-containing compound. .

Examples of the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (Meth) ethyl acrylate-α- (hydroxymethyl) Monofunctional (meth) acrylic acid glycerol, or (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate, etc. Or a (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, or the hydroxyl group-containing α, Hydroxyl group-containing aliphatic (meth) such as alkylene oxide-added (meth) acrylic acid ester obtained by repeatedly adding alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to β-ethylenically unsaturated double bond group-containing compound Acrylic acid Ethers, and the like.

Further, when “the amount of carboxyl groups contained in the polybasic acid <the amount of hydroxyl groups contained in the polyhydric alcohol”, the terminal functional group is a hydroxyl group, and the carboxyl group-containing α, β-ethylenically unsaturated double bond group Condensation reaction of the carboxyl group of the containing compound, or addition reaction of the isocyanato group of the isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound, or a compound having two or more isocyanate groups The desired polyester oligomer (A) can be obtained by reacting a urethane prepolymer having a terminal isocyanate group obtained by reacting with a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound. .

Examples of the epoxy group-containing α, β-ethylenically unsaturated double bond group-containing compound include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,2-glycidoxyethyl (meth) acrylate, and 3,4- Examples thereof include epoxycyclohexyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 4,5-epoxypentyl (meth) acrylate.

Examples of the isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound include vinyl isocyanate, allyl isocyanate, isocyanate (meth) acryloyl, isocyanatoalkyl (meth) acrylate and the like.

Examples of the compound having two or more isocyanate groups include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

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

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

  As the aromatic aliphatic polyisocyanate, 2,4-diisocyanate-1-methyl-benzene (alias: 2,4-TDI), 2,6-diisocyanate-1-methyl-benzene (alias: 2,6-TDI), 1,3-phenylene bismethylene diisocyanate (alias: m-XDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2′-diphenylmethane diisocyanate (alias: 2,2- MDI), 4,4'-diphenylmethane diisocyanate (alias: 4,4-MDI), 1,3-naphthalenediyl diisocyanate (alias: 1,3-NDI), 1,5-naphthalenediyl diisocyanate (alias: 1,5) -NDI) and the like.

As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI), 1,4-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate, etc. Can be mentioned.

  In addition, as a polyhydric alcohol, it is more preferable from points, such as adhesiveness and heat resistance, to use the polyhydric alcohol by which two or more hydroxyl groups were introduce | transduced into the branched alkane. Among the above exemplary compounds, for example, neopentyl glycol, 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, butylethylpentanediol, 2-ethyl-1,3-hexanediol, trimethylolpropane, pentaerythritol and the like can be mentioned.

The weight average molecular weight (hereinafter sometimes referred to as Mw) of the oligomer (A) is in the range of 1000 to 60,000, and preferably in the range of 6001 to 60,000. By using an oligomer having an Mw of 60,000 or less, it is possible to easily provide a composition having excellent fluidity and compatibility with other components. In addition, it is possible to suppress problems such as a decrease in polymerization curability of the composition, a decrease in durability such as curing shrinkage of the cured product, and whitening of the cured product. On the other hand, when an oligomer having an Mw of 1000 or more is used, when the resin composition is used as an adhesive, cohesive failure within the adhesive layer or the coat layer is less likely to occur. When an oligomer having an Mw of 6001 or more is used, cohesive failure inside the adhesive layer or the coat layer is further less likely to occur.
In addition, the measuring method of a number average molecular weight (Mn), a weight average molecular weight (Mw), an acid value (AV), and a hydroxyl value (OHV) is mentioned later.

In one Embodiment of the resin composition of this invention, it is preferable that an oligomer (A) is 1-60 mass% content in a composition. More preferably, it is the range of 1-40 mass parts. By setting the oligomer (A) to 1 part by mass or more, a lack of cohesive force can be improved, and characteristics such as heat resistance and heat-and-moisture resistance can be easily improved. On the other hand, when the oligomer (A) is 60 parts by mass or less, curing shrinkage can be suppressed when the resin composition is used as an adhesive or a coating agent.

<Organic base (b1) or metal salt of organic acid (b2)>
The organic base (b1) or the metal salt (b2) of the organic acid will be described. The organic base (b1) used in the present invention is a compound having the properties of a Bronsted base. Examples of the organic base (b1) include organic bases (b1-1) having no active energy ray polymerizable functional group and organic bases (b1-2) having an active energy ray polymerizable functional group. The organic acid salt (b2) of an inorganic base includes an organic acid salt (b2-1) of an inorganic base formed from an organic acid having no active energy ray polymerizable functional group and an inorganic base, and active energy ray polymerization. Organic acid salt (b2-2) of an inorganic base formed from an organic acid having a functional functional group and an inorganic base.

Examples of the organic base (b1-1) having no active energy ray polymerizable functional group include the following.
For example, aminomethane, aminoethane, 1-aminopropane, 1-aminobutane, 1-aminopentane, isoamylamine, 1-aminohexane, 1-aminoheptane, 1-aminooctyl, 1-aminononane, 1-aminodecane, 1-amino Dodecane (laurylamine), 1-aminotridecane, 1-aminohexadecane, 1-aminotetradecane (myristylamine), 1-aminopentadecane, cetylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, Allylamine, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 3-a No-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryl Oxypropylamine, 3-myristyloxypropylamine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, 2-aminobenzophenone, 4-amino Nzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol Primary amines such as

For example, N, N-dimethylamine, N, N-diethylamine, N-methyl-N-ethylamine, N-methyl-N-isopropylamine, N-methyl-N-hexylamine, N, N-diisopropylamine, N, N-dipropylamine, N, N-dibutylamine, N, N-disec-butylamine, N-ethyl-N- (1,2-dimethyl) propylamine, piperidine, 2-pipecholine, 3-pipecholine, 4- Pipecoline, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, diamylamine, N-methylaniline, N-ethylaniline, N, N-di Benzylamine, N, N-diphenylamine, N, N-dicocoalkylamino N, N-dicured beef tallow alkylamine, N, N-distearylamine, morpholine, 2-aminopropane, 2-aminobutane, 2-aminopentane, 3-aminopentane, 2-aminoheptane, 2-amino-2 -Secondary amines such as methylpropane;

For example, N, N, N-trimethylamine, N, N, N-triethylamine, N-ethyl-N, N-dimethylamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-trioctylamine, N, N-diethyl-N-isopropylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethyl-N-coconutamine, N, N-dimethyl -N-octylamine, N, N-dimethyl-N-decylamine, N, N-dimethyl-N-laurylamine, N, N-dimethyl-N-myristylamine, N, N-dimethyl-N-palmitylamine, N, N-dimethyl-N-stearylamine, N, N-dimethyl-N-behenylamine, N, N-dilauryl-N-methylamine, N, N-dimethylethanol N, N-dimethylisopropanolamine, N-methyldiethanolamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-butylpiperidine, N-methylhexamethyleneimine, N- Ethylhexamethyleneimine, N-methylmorpholine, N-butylmorpholine, N, N′-dimethylpiperazine, N, N′-diethylpiperazine, 1-methyl-1,4,5,6-tetrahydropyrimidine, 1,2- Dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 4-dimethyl Aminopyridine, 1,2-dimethylimidazoline, 1,2,4-trimethylimidazoline, 1, , 5-trimethylimidazoline, 1,4-dimethyl-2-ethylimidazoline, 1-methyl-2-ethylimidazoline, 1-methyl-2-heptyluimidazoline, 1-methyl-2- (4′-heptyl) imidazoline, 1 -Tertiary amines such as methyl-2-dodecylimidazoline, dimethyloxazoline;

Ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1 , 4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], diethylenetriamine, triamino Propane, 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, dimer diamine, dicyclohexylmethane-4,4'-diamine, diethylene glycol bis (3-aminopropyl) Ether, poly Oxyalkylene glycol diamine (the number of added moles of alkylene glycol is an arbitrary integer of 2 to 50), phenylenediamine, xylylenediamine, dicyclohexylmethane-4,4'-diamine, 2,4-tolylenediamine, 2,6 -Tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis- (sec-butyl) diphenylmethane, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, Diamines having two monosubstituted amino groups such as diaminobenzoic acid and diaminobenzenesulfonic acid;

For example, diamines having two disubstituted amino groups such as N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-di-tert-butylethylenediamine, piperazine;

For example, diamines having two disubstituted amino groups such as N, N, N ′, N′-tetramethylethylenediamine and N, N, N ′, N′-tetraethylethylenediamine;

For example, N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or Methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1, 3-propanediamine or isopropylaminopropylamine], and N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or laurylaminopropylamine], triethyltetramine, diethylenetriamine, 2- Droxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2- Polyamines having mono- and di-substituted amino groups such as hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine;

For example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, hexadecanediohydrazide, eicosanedioic acid dihydrazide, maleic acid dihydrazide acid, maleic acid dihydrazide acid, Hydrazides such as dihydrazide, phthalic acid dihydrazide, carbonic acid dihydrazide, carbodihydrazide, thiocarbodihydrazide, oxalyl dihydrazide, polyacrylic acid hydrazide;

Pyridine, picolines, quinoline, 2,2′-bipyridyl, imidazole, 1-methylimidazole, 1-ethylimidazole, 1-ethyl-2-methylimidazole, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole Nitrogen-containing aromatic heterocyclic compounds such as 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole, 1,4-dimethyl-2-ethylimidazole;

Examples of the organic base (b1-2) having an α, β-ethylenically unsaturated double bond group include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, and (meth) acrylic acid. Monomethylaminopropyl, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate and the like ( Alkylamino substituted alkyl esters of meth) acrylic acid, monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, dimethyl Amines having (meth) acryloyl groups, such as alkylamino-substituted alkyl derivatives of (meth) acrylamides such as tilaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, etc. Kind;

For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole [2- (2′-hydroxy-5′-acryloyloxyethylphenyl) -2H-benzotriazole and 2 Combined with-(2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, "2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole" Is written. The same applies below. ], 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl- 5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H -Benzotriazole, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]- S-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxy) Phenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- { 2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4 -Diethoxy Phenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4 -{2- (meth) acryloyloxyethoxy})]-S-triazine, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, 4- (pyrimidin-2-yl) piperazine-1 -Cyclic amines having a (meth) acryloyl group such as yl (meth) acrylate, pentamethylpiperidinyl methacrylate (PMPMA);

For example, vinylamine, methylvinylamine, ethylvinylamine, propylvinylamine, butylvinylamine, 2-vinylpiperazine, 4-vinylpiperazine, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-benzyl- 2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 6-vinyl-1,3,5-dimethyl-2,4-diamine, N- (meth) allylquinoline Amines having a vinyl group such as -4-amine;

2-vinylimidazole, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2-vinyl Pyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquinoline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine 2,6-divinylpyridine, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 1-vinyl-1H-pyrazole, 1-vinyl -3,5-dimethyl-1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl -1H-benzimidazole, 1-vinylindazole, 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1-vinylcarbazole, 1,1'-divinyl-2,2 ' -Bi (1H-imidazole), 1-vinylpyridine-2 (1H) -one, 1-vinyl-2 (1H) -pyridinethione 2-vinyl-4,6-diamino-1,3,5-triazine, 3-vinyl-1,2,4,5-tetrazine, 1-vinyl-1H-benzimidazole, 1-vinyl-5,6- Dimethyl-1H-benzimidazole, 1-vinylindazole, 1-vinylquinoline, 1-vinylisoquinoline, 1-vinylquinoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meth) allyl-4-methyl-1H-indazole, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2 A nitrogen-containing aromatic heterocyclic compound having a vinyl group such as dihydroisoquinoline, 1-methyl-4,5-divinyl-1H-imidazole;

For example, allylamine, diallylamine, 1- (meth) allyl-1H-imidazole [1-allyl-1H-imidazole and 1-methallyl-1H-imidazole are collectively described as “1- (meth) allyl-1H-imidazole” To do. The same applies below. ], 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazole-3-ium, 1- (meth) allyl-3-ethyl-1H-imidazole -3-ium, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5-bromo-1--1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 5- ( 1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5-isopropylpyrimidine, 1- (meth) allyl-5,5-diethylpyrimidine, 2- (meth) allylpyridine, 4- (Meth) allylpyridine, 3,6-dihydro-3- (meth) allylpyridine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6 Dichloro-1,3-5-triazin-2-amine, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 1- (meth) allyl-1H-benzimidazole, 2- (Meth) allylindazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meth) allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di ( (Meth) allyl quinoline, 3-phenyl-4- (meth) allylisoquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline, (meth) allyl such as 9- (meth) allyl-9H-carbazole Amines having a group;

  Examples of the metal salt (b2) of an organic acid include a salt formed from a metal and an organic acid. Examples of the metal include Li, Na, K, Be, Mg, Ca, Sr, Ba, Ti, Zr, Cu, Ag, Zn, Cd, Al, Ga, In, and Sn.

As the organic acid, as an organic acid having no active energy ray polymerizable functional group, for example, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, etc. Dibasic acids such as oxalic acid, succinic acid, fumaric acid, adipic acid, maleic acid, oxaloacetic acid, glutaric acid; lactic acid, glycolic acid, tartaric acid, malic acid, citric acid, ascorbic acid, gluconic acid, Hydroxycarboxylic acids such as glyceric acid; acidic amino acids such as 2-oxoglutamic acid and aspartic acid; keto acids such as pyruvic acid, acetoacetic acid, and levulinic acid; aromatic carboxylic acids such as benzoic acid and salicylic acid; polys such as ethylenediaminetetraacetic acid Carboxylic acids; other isocitrate, malonic acid, glutaric acid, cururonic acid, kojic acid, phytic acid Aconitic acid, can be mentioned glycerophosphate and the like.

Examples of the organic acid having an active energy ray polymerizable functional group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 3-carboxypropyl (meth) acrylate. , (Meth) acrylic acid 4-carboxybutyl, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid , Citraconic acid, mesaconic acid, itaconic acid, tiglic acid, angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4 -Acrylamide butanoic acid, 6-acrylamide hexane , 2- (meth) acryloyloxyethyl succinate, mono (meth) acrylic acid ω-carboxypolycaprolactone ester, etc., polylactone-based (meth) acrylic acid ester having a carboxyl group at the terminal by ring-opening addition of a lactone ring A carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acid or acid anhydride thereof;

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

  The mechanism for improving the adhesion and durability in the active energy ray polymerizable resin composition of the present invention is unknown, but the polyester oligomer (A) and an appropriate amount of organic base (b1) or metal salt of organic acid ( By including b2), it is considered that a hydrogen bond is formed with the polyester-based oligomer and the cohesive strength of the coating film is improved, which leads to an improvement in adhesion and durability. Moreover, it is thought that there exists an effect which improves adhesiveness by forming a hydrogen bond with a base material by including a moderate amount of organic base (b1) or metal salt (b2) of an organic acid. An organic base is more preferable from the viewpoint of the stability of the coating solution. The base preferably has an α, β-ethylenically unsaturated double bond group from the viewpoint of the gel fraction of the coating film. Moreover, as the usage-amount of the organic base (b1) or the metal salt (b2) of an organic acid, 0.01-10 mass% is preferable with respect to the composition total amount.

Next, compound (X) having a hydroxyl group and an α, β-ethylenically unsaturated double bond group (hereinafter sometimes referred to as compound (X)) will be described. The active energy ray polymerizable resin composition of the present invention preferably contains a compound (X) having a hydroxyl group and an α, β-ethylenically unsaturated double bond group.

Compound (X) is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2-hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylic acid 4-hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, (meth) acrylate 10-hydroxydecyl, (meth) acryl Acid 12-hydroxylauryl, ethyl (meth) acrylate-α Fatty acid esters such as (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate (Meth) acrylic acid ester, or (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, Hydroxyl group-containing α-, β-ethylenically unsaturated double bond group-containing compounds such as alkylene oxide-added (meth) acrylic acid esters obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. fat (Meth) acrylic acid esters;

For example, repeated addition of hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, or alkylene oxide such as ethylene oxide or propylene oxide Hydroxyl group-containing aliphatic vinyl ethers such as alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal end;

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

For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;
For example, N-hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as “N-hydroxyethyl (meth) acrylamide”. The same applies below. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

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

Furthermore, the composition of the present invention contains an α, β-ethylenically unsaturated double bond group-containing compound (C) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures. May be. Since it has a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures, the bulkiness is increased, and there is an effect of suppressing curing shrinkage.

About α, β-ethylenically unsaturated double bond group-containing compound (C) (hereinafter sometimes referred to as compound (C)) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures explain. The compound (C) is a compound having two or more cycloalkane skeletons and / or cycloalkene skeletons and one or more α, β-ethylenically unsaturated double bonds. As the compound (C), a cycloalkene skeleton having two or more ring structures and / or a compound (c1) in which the ring structure is separated from the ring structure by an alkyl group, an ether group, an ester group, and the like, and Examples of the compound include a norbornane, norbornene skeleton (c2), and a compound having a cyclocyclic bridged structure such as a compound (c3) having an adamantane structure. Compound (c2) or compound (c3) is preferred to compound (c1).

As an α, β-ethylenically unsaturated double bond group-containing compound (c1) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures, the ring structure and the ring structure being separated from each other Examples include hydrogenated biphenol A diacrylate and 3,3-dicyclopropyl acrylate.
The α, β-ethylenically unsaturated double bond group-containing compound (c2) having norbornene and / or norbornane skeleton may have at least one norbornene and / or norbornane skeleton and ethylenically unsaturated double bond. For example, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol (meth) Examples include acrylate and isobornyl (meth) acrylate.

Among the above compounds (c2), the compound (c2 ′) having 3 or more cyclic skeletons is particularly preferable because it suppresses curing shrinkage by increasing the bulk and improves the adhesive force. ') Includes dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, and the like.

The α, β-ethylenically unsaturated double bond group-containing compound (c3) having an adamantane skeleton is a radically polymerizable compound having three or more cyclic skeletons similar to the above compound (c2 ′). Adhesion is improved. Specific examples of the compound (c3) include 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and 2-propyl. -2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyldiol di (meth) acrylate, 1,3,5-adamantyl (meth) acrylate, 3- Hydroxy-1,5-adamantyl di (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate and the like can be mentioned, but α, β-ethylenically unsaturated double bonds are excellent in terms of adhesion. 1 3-hydroxy-1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2 -Adamantyl acrylate is preferred.

The active energy ray polymerizable resin composition of the present invention comprises an oligomer (A), an organic base (b1) or a metal salt of an organic acid (b2), a hydroxyl group and an α, β-ethylenically unsaturated double bond group. Compound (X) having two or more ring structures and / or α, β-ethylenically unsaturated double bond group-containing compound (C) having a cycloalkene skeleton and / or other α, The β-ethylenically unsaturated double bond group-containing compound (D) (hereinafter sometimes referred to as compound (D)) can be used as necessary.

Examples of the other α, β-ethylenically unsaturated double bond group-containing compound (D) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, (meth) 2-propyl acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate , (Meth) acrylic acid iso-amyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid iso-octyl, (meth) acrylic Acid n-nonyl, (meth) acrylic iso-nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, octa (meth) acrylate (Meth) acrylic acid alkyl esters such as decyl, lauryl (meth) acrylate, stearyl (meth) acrylate;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, 2-oxo- (meth) acrylate 1,2-diphenylethyl, (meth) acrylic acid (ethoxylated o-phenylphenol), ( T) 1-naphthyl acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, (meth) acrylic acid 9-anthryl, (meth) acrylic acid 9-anthrylmethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) One cycloalkane skeleton or cycloalkene skeleton such as acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, etc. Have an aromatic ring (Meth) acrylic acid esters having;

For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, It further contains unsaturated groups such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, vinyl (meth) acrylate, and the like. Meth) acrylic acid esters;
For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic Acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran-4- Yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2-dimethyl-5 -Oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydro Lan-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, etc. Heterocycle-containing (meth) acrylic acid esters having an oxygen atom;

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

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

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

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

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

For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate, (meth) acrylic acid Phosphonic acid group-containing (meth) acrylic acid esters such as acid phosphooxyethylene oxide (ethylene oxide addition moles: 4 to 10) and (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition moles: 4 to 10) Kind;

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

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

For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di (Meth) acrylic acid dipropylene glycol, di (meth) acrylic acid tripropylene glycol, di (meth) acrylic acid polypropylene glycol, di (meth) acrylic acid 1,2-butanediol, di (meth) acrylic acid 1,2 -Pentanediol, di (meth) acrylic acid 2,2-dimethylpropyldiol, di (meth) acrylic acid hydroxypivalyl hydroxypivalate, di (meth) acrylic acid hydroxypivalyl hydroxypivalate dicaprolactonate, di ( Meta) acrylic acid 1 4-butanediol, di (meth) acrylic acid 1,5-heptanediol, di (meth) acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7-heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) 1,2-octanediol acrylic acid, 1,9-nonanediol di (meth) acrylic acid, 1,2-decanediol di (meth) acrylic acid, 1,10-decanediol di (meth) acrylic acid, di (Meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1,2-dodecanediol, di (Meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16-hexadecanediol, di (meth) acrylic acid 1,2-hexadecanediol, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1, di (meth) acrylate, 3-propanediol, di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 2,2-diethyl-1,3-propanediol, di (meth) acrylic acid 2 , 2,4-trimethyl-1,3-pentanediol, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-di (meth) acrylate Xanthdiol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2 di (meth) acrylate -Ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, Di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 2,2-diethyl-1,3-propanediol, di (meth) acrylic acid 2,2,4- Trimethyl-1,3-pentanediol, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-di (meth) acrylic acid Methyl-2,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di Bifunctional (meth) acrylic acid esters such as (meth) acrylic acid 1,1,1-trishydroxymethylethane;

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

For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;
For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;
For example, ethyl vinyl ether, 1-propyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, n-hexyl, 2-ethylhexyl vinyl ether, n -Aliphatic vinyl ethers such as octyl vinyl ether, iso-octyl vinyl ether, n-nonyl vinyl ether, iso-nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;

For example, fluorine-containing ethenyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;
For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;
For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

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

For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- 2-methoxyethyl (meth) acrylamide, N- (oxetane-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) (Meth) acrylamides containing N-alkoxy groups such as (meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

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

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate, (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;
For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

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

For example, vinyl esters such as vinyl chloride, vinylidene chloride and allyl chloride;
For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

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

As said other (alpha), (beta) -ethylenically unsaturated double bond group containing compound (D), the compound which has a (meth) acryloyl group from a reactive viewpoint is preferable, and also as an active energy ray polymeric resin composition, From the viewpoint of the polymerization rate, it is preferable to contain bifunctional or higher (meth) acrylic acid esters.
Further, as other α, β-ethylenically unsaturated double bond group-containing compound (D), glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3- A heterocycle-containing (meth) acrylic acid ester having a 3-membered or 4-membered ring oxygen atom, such as methyl-3-oxetanyl) methyl, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, and the like. If necessary, known photoacid generators such as sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 (Japanese) Iodonium salts such as Ryo-2074 (manufactured by Rhodia Japan) By using together those exemplified, it is preferable because crosslinking proceeds and an adhesive layer having excellent durability against heat and humidity is formed.

  As a preferred ratio of the components constituting the resin composition of the present invention, when the total amount of the resin composition is 100% by mass, the oligomer (A) is 1 to 50% by mass, the organic base (b1) or the metal of the organic acid 0.01 to 50% by mass of salt (b2), 0 to 70% by mass of compound (X), 0 to 70% by mass of compound (C), containing other α, β-ethylenically unsaturated double bond groups It is preferable that a compound (D) is 0-50 mass% and water is 0.01-10 mass%. More preferably, the oligomer (A) is 5 to 40% by mass, the organic base (b1) or the metal salt (b2) of the organic acid is 0.01 to 10% by mass, the compound (X) is 10 to 50% by mass, and the compound (C) is 10 to 50% by mass, the other α, β-ethylenically unsaturated double bond group-containing compound (D) is 10 to 50% by mass, and water is 0.01 to 10% by mass.

Next, the active energy ray polymerization initiator (E) will be described. The active energy ray polymerization initiator (E) can be arbitrarily selected from known ones, and specific examples thereof include, for example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, Benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one etc. It is. Commercially available products include, for example, Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF), Darocur- 1173 (manufactured by Merck), Ezacure KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.) and the like.

An active energy ray polymerization initiator having at least one (meth) acryloyl group in the molecule can also be used. These active energy ray polymerization initiators (E) can be used alone or as a mixture of two or more.

The blending ratio of the active energy ray polymerization initiator (E) is 0.01 to 20% of the active energy ray polymerization initiator (E) with respect to 100 parts by mass of the resin composition of the present invention in terms of reactivity. It is preferable to contain a mass part.

The active energy ray-polymerizable resin composition of the present invention has an active energy ray polymerization initiator (E) in which the active energy ray-polymerization initiator (E) becomes insoluble in the active energy ray-polymerizable resin composition or has a high viscosity. A small amount of an organic solvent may be contained to dissolve the linear polymerization initiator (E). The content of the organic solvent in the active energy ray polymerizable resin composition is within 5% by mass. The organic solvent that can be used is not particularly limited, but specifically, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbons An organic solvent such as a system solvent can be further added to adjust the viscosity of the active energy ray polymerizable resin composition, or the active energy ray polymerizable resin composition can be heated to lower the viscosity.

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

In the active energy ray polymerizable resin composition of the present invention, additives other than the above-described components can be appropriately blended as long as the effects of the present invention are not impaired. For example, blending organic or inorganic fillers from the viewpoints of polymerization cure shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. it can. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like can be used, and the shape is not particularly limited, such as particles and fibers. In addition, when blending the above polymers, flexibility imparting agents, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy imparting agents, dispersion stabilizers, fluidity imparting agents, dissipators. It is also possible to dissolve, semi-dissolve or micro-disperse in the active energy ray-polymerizable resin composition as a polymer blend or a polymer alloy, not as a filler, such as a foaming agent.

The active energy ray-polymerizable resin composition of the present invention can be used in any form of liquid, paste, and film, but is preferably liquid from the viewpoint of ease of use.
The active energy ray polymerizable resin composition in the present invention has a viscosity of 1 to 1500 mPa · s when the film thickness of the active energy ray polymerizable resin composition layer is 0.1 to 6 μm depending on the intended use. Is important, preferably 10 to 1300 mPa · s, and more preferably 20 to 1000 mPa · s. When the viscosity is higher than 1500 mPa · s, when the base material (F) is coated, a thin film coating of 0.1 to 6 μm cannot be performed, and optical characteristics such as transmittance are deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it becomes difficult to control the film thickness of the active energy ray polymerizable resin composition layer.

Moreover, when the film thickness of the active energy ray polymerizable resin composition layer is 6 to 300 μm depending on the intended use, it is important that the viscosity is 1500 to 100,000 mPa · s, preferably 3,000 to More preferably, it is 50,000 mPa · s.

Next, the properties of the active energy ray polymerizable resin composition will be described.
The active energy ray polymerizable resin composition of the present invention can be used in any form of liquid, paste, and film, but is preferably liquid from the viewpoint of ease of use.
In addition, although it is preferable that the active energy ray polymeric resin composition in this invention does not contain an organic solvent substantially, it can also contain an organic solvent. For example, by further adding an organic solvent such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbon solvents, water, The viscosity of the resin composition can be adjusted, or the viscosity can be lowered by heating the resin composition.

  In the active energy ray polymerizable resin composition in the present invention, it is important that the viscosity at 25 ° C. is 1 to 2000 mPa · s, preferably 10 to 1500 mPa · s, and 20 to 1000 mPa · s. More preferred. When the viscosity is higher than 2000 mPa · s, when the resin cured product is used, the molding process cannot be performed and the hardness deteriorates. On the other hand, if the viscosity is lower than 1 mPa · s, it becomes difficult to control the dimensional stability of the cured resin resin.

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

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

Next, the coating process of the active energy ray polymerizable resin composition will be described.
The resin composition of the present invention is preferably used for a coating agent or an adhesive. Typically, the resin composition is applied to one side or both sides of a substrate by an appropriate method according to a conventional method, and then polymerized and cured to form a resin layer. Therefore, one Embodiment of this invention is related with the laminated body which has the below-mentioned base material (G) and the resin layer which consists of a resin composition provided in the at least one surface of this base material (G). In this embodiment, the film thickness of the resin layer is set according to the use of the laminate.

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

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

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

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

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

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

Here, the laminated body characterized by laminating | stacking on the single side | surface or both surfaces of a base material (G) using an active energy ray polymeric resin composition is demonstrated generally.
The polymerization reaction by the active energy ray of the active energy ray polymerizable resin composition of the present invention is positioned on at least one surface of the transparent film that is a film-like substrate and the transparent film among the above-described substrates (G). The active energy ray polymerizable resin composition layer is preferably used for forming a laminate.
In the present invention, a laminate of transparent films can be obtained as follows.

The resin composition of the present invention is applied to one side of a transparent film that is a film-like substrate, another transparent film is laminated on the surface of the resin composition layer, and the resin composition is further applied to one side or both sides of the laminate. A laminate can be obtained by coating and further laminating on another transparent film, glass, or transparent molded body.

The active energy ray polymerization reaction of the resin composition of the present invention used as a coating agent proceeds by irradiating an active energy ray at the time of coating the resin composition on one side or both sides. It is preferable to proceed the polymerization reaction. Under the present circumstances, the said base material (G) may be a timber, a metal plate, a plastic plate, a film-like base material, a glass plate, a paper processed product, etc., and these can be especially used without a restriction | limiting.

  The active energy ray polymerization reaction of the resin composition of the present invention used as an adhesive proceeds when the resin composition is applied or laminated, and further after irradiation with active energy rays. It is preferable to advance the polymerization reaction by irradiating active energy rays later. At this time, the base material (G) needs to be made of a material that easily transmits the active energy rays in order to advance the polymerization reaction by irradiation with the active energy rays. As the substrate (G), it is particularly preferable to use a transparent film (H) or a transparent glass plate. However, if a transparent film or a transparent glass plate is used as one substrate, the other substrate is difficult to transmit active energy rays, such as wood, metal plates, plastic plates, paper processed products, etc. The base material which consists of can also be used. In this case, the resin composition can be polymerized and cured by irradiating active energy rays from the transparent film (H) or the transparent glass plate side.

  The transparent film of this invention can be used for optical films, such as information communication apparatuses, such as a display and a touch panel.

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

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

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

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

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

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

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

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

  In one embodiment of the optical element laminate according to the present invention, it is preferable to use the optical film (I) mainly used in optical applications as the transparent film (H). Here, the optical film (I) is a film obtained by subjecting the transparent film (H) itself to a special treatment, such as optical functions (light transmission, light diffusion, light collection, refraction, scattering, and HAZE). A film having an optical function is called an optical film. In order to impart these optical functions, these functional materials are not only kneaded into a film or laminated by sputtering, but also an adhesive containing a functional material or a coating agent is used. In general, the contained film is laminated with an adhesive or the like to give an optical function. In addition, the optical film (I) is used alone or by laminating several kinds of optical films in multiple layers with a coating agent or an adhesive.

  Specific examples of the optical film include, for example, a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness enhancement film, a prism film ( A prism sheet), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like. The laminated optical film using the resin composition of the present invention as an adhesive is a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, and an organic EL module, and a transparent film such as the above various plastic films. Furthermore, it is preferable that the resin composition of the present invention is further laminated and pasted as an adhesive and used as a laminate for optical elements.

Lamination of each optical film (reflection sheet, light guide plate, prism sheet, diffusion sheet, brightness enhancement film, 3D film, etc.) in the backlight unit using the active energy ray polymerizable resin composition as an adhesive, especially the lamination of the prism sheet. More specifically, can be obtained as follows. Hereinafter, as an example of the laminated body for an optical element, a laminate of prism sheets is given, and the embodiment of the laminated body will be described more specifically.
A prism sheet is a sheet that is used on a display and is installed on the upper surface of the light guide plate of the backlight of a liquid crystal panel to improve the brightness in the front direction. It is an optical film (I) called a lens sheet.
The above-mentioned prism sheet generally has a structure in which a prism portion (lens portion) of an acrylic resin is finely laminated on a base film of a polyester resin, and illuminance distribution, luminance distribution, and emission angle characteristics. In consideration of the above, two prism sheets are stacked (substantially orthogonal) so that the optical axes are different from each other in order to improve the front luminance. At this time, the front luminance changes depending on the prism pitch, prism depth, prism material, and optical axis angle, and is used by being laminated and fixed with an adhesive or the like. Laminated and used as a laminated body for optical elements.

  Although not particularly limited, for example, the prism sheet can be laminated as follows. Apply the active energy ray-polymerizable resin composition as an adhesive to the back side of the prism sheet (the side where the convex lens surface is not laminated) or any sheet-like optical film, and then apply the other to the formed adhesive layer. After overlapping the lens surface which is the convex part of the prism sheet, the active energy ray is irradiated from the back side of one sheet or the optical film side, and the adhesive layer that has been cured with the active energy ray is placed between both sheet-like members. Form and stack. This method irradiates active energy rays with an adhesive layer formed by using an active energy ray polymerizable resin composition as an adhesive between two optical films, so that the adhesive is polymerized and cured. Has the advantage of being less susceptible to oxygen inhibition. However, on the other hand, since the active energy rays are irradiated to the adhesive layer through the optical film, the optical film on the side irradiated with the active energy rays is easy to transmit without attenuating the active energy rays as much as possible. Is preferably used.

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

  Hereinafter, specific embodiments of the present invention will be described with reference to examples. However, the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively. Prior to the description of the examples, methods for measuring weight average molecular weight (Mw), acid value (AV), and hydroxyl value (OHV) will be described.

  The weight average molecular weight uses gel permeation chromatography “HLC-8220GPC” manufactured by Tosoh Corporation, and separation columns: “TSK-GEL SUPER H5000”, “TSK-GEL SUPER H4000”, “TSK-GEL” manufactured by Tosoh Corporation. The “SUPER H3000” and “TSK-GEL SUPER H2000” were connected in series, and tetrahydrofuran at a temperature of 40 ° C. was used as the mobile phase, and the polystyrene-equivalent weight average molecular weight was measured at a flow rate of 0.6 ml / min.

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

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

<Synthesis Example 1 of Polyester Oligomer (Oligomer 3)>
In a 5-neck separable flask equipped with a stirrer, a distillation tube, a gas introduction tube, and a thermometer, 503 parts of adipic acid, 497 parts of 2-butyl-2-ethyl-1,3-propanediol, and 0.04 of zinc oxide Then, esterification was performed while distilling off the produced condensed water at 210 ° C. while passing dry air under normal pressure, and polyester dicarboxylic acid having an acid value of 43 mgKOH / g was obtained. Subsequently, 15.5 parts of 4-hydroxybutyl acrylate glycidyl ether, 0.5 part of tetrabutylammonium borate and 0.1 part of hydroquinone monomethyl ether are added to 100 parts of the obtained polyester dicarboxylic acid, and the acid value is 1 mgKOH / The addition reaction was carried out at 100 ° C. until it became g or less, and polyester acrylate oligomer 3 was obtained. The weight average molecular weight of the oligomer 3 was 9800.

<Synthesis Example 2 of Polyester Oligomer (Oligomer 4)>
A five-neck separable flask equipped with a stirrer, distillation tube, gas introduction tube, and thermometer was charged with 497 parts of adipic acid, 503 parts of 3-methyl-1,5-pentanediol, and 0.04 part of zinc oxide. The esterification was carried out while distilling off the produced condensed water at 210 ° C. while passing nitrogen gas under pressure. When the acid value of the produced polyester polyol became 15 mgKOH / g or less, a vacuum pump was connected to the flask to reduce the pressure, and the reaction was completed to obtain a polyester polyol having a hydroxyl value of 13 mgKOH / g. Next, 10 parts of isophorone diisocyanate and 0.05 part of dibutyltin dilaurate are added to 100 parts of the obtained polyester polyol and reacted at 120 ° C. for 2 hours. Thereafter, 4-hydroxybutyl acrylate, hydroquinone monomethyl ether 0.1 Part was added and reacted at 70 ° C. for 5 hours to obtain polyester acrylate oligomer 5. The weight average molecular weight was 15900.

<Synthesis Example 3 of Polyester Oligomer (Oligomer 5)>
In a 5-neck separable flask equipped with a stirrer, a distillation tube, a gas introduction tube, and a thermometer, 78 parts of terephthalic acid, 252 parts of isophthalic acid, 338 parts of azelaic acid, 146 parts of neopentyl glycol, 186 parts of ethylene glycol, zinc oxide 0.04 part was charged, and esterification was performed while distilling off the produced condensed water at 210 ° C. while passing nitrogen gas under normal pressure. When the acid value of the produced polyester polyol became 0.3 mgKOH / g or less, a vacuum pump was connected to the flask to reduce the pressure, and the reaction was completed to obtain a polyester polyol having a hydroxyl value of 11 mgKOH / g. Next, 3.6 parts of acrylic acid and 0.1 part of hydroquinone monomethyl ether were added to 100 parts of the obtained polyester polyol, and esterification was performed at 180 ° C. to obtain a polyester acrylate oligomer 4. The weight average molecular weight was 38000.

<Synthesis Example 4 of Polyester Oligomer (Oligomer 6)>
A five-necked separable flask equipped with a stirrer, distillation tube, gas introduction tube, and thermometer was charged with 497 parts of adipic acid, 503 parts of 1,6-hexanediol, and 0.04 part of zinc oxide, and nitrogen gas under normal pressure The esterification was carried out while distilling off the condensed water produced at 210 ° C. When the acid value of the produced polyester polyol became 0.3 mgKOH / g or less, a vacuum pump was connected to the flask to reduce the pressure, and the reaction was completed to obtain a polyester polyol having a hydroxyl value of 28 mgKOH / g. Next, 3.6 parts of acrylic acid and 0.1 part of hydroquinone monomethyl ether were added to 100 parts of the obtained polyester polyol, and esterification was performed at 180 ° C. to obtain polyester acrylate oligomer 6. The weight average molecular weight of the oligomer 6 was 7300.

[Examples 1 to 22, Comparative Examples 1 to 6]
In an atmosphere with an oxygen concentration of 10% or less, each material was charged in a shielded glass bottle with a sealed capacity of 300 ml at the ratio (parts by mass) shown in Table 1, stirred with a disper, and an active energy ray polymerizable resin composition Each thing was obtained. Using this active energy ray polymerizable resin composition, a laminate was prepared and evaluated according to the following methods.

In Table 1, numerical values represent parts by mass, and abbreviations are as follows.
<Polyester oligomer (A) having one or more α, β-unsaturated double bond groups>
Oligomer 1: EBECRYL 810: Polyester acrylate manufactured by Daicel Ornex Co., Ltd. Mw = 1000
Oligomer 2: EBECRYL 885: Polyester acrylate manufactured by Daicel Ornex Co., Ltd. Mw = 6000
Oligomer 3: Polyester oligomer obtained in Synthesis Example 1 Mw = 9800
Oligomer 4: Polyester oligomer obtained in Synthesis Example 2 Mw = 38000
Oligomer 5: Polyester oligomer obtained in Synthesis Example 3 Mw = 15900
Oligomer 6: Polyester oligomer obtained in Synthesis Example 4 Mw = 7300
<Organic base (b1)>
DMAEA: N, N-dimethylaminoethyl acrylate DEEAA: N, N-diethylaminoethyl acrylate DMAPAA: N, N-dimethylaminopropyl acrylate PMPMA: Pentamethylpiperidinyl methacrylate VIM: 1-vinylimidazole VRP: 4-vinylpyridine < Compound (X)>
4HBA: 4-hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate CHDMMA: 1,4-cyclohexanedimethanol monomethacrylate <Compound (C)>
DCPA: dicyclopentanyl acrylate IBXA: isobornyl acrylate DCPDMDA: tricyclodecane dimethanol diacrylate <compound (D)>
THFA: Tetrahydrofurfuryl acrylate PEA: Phenoxyethyl acrylate PET3A: Pentaerythritol triacrylate IINA: Isocyanuric acid EO-modified triacrylate (Toagosei Co., Ltd .: Aronix M-315)
NPDA: neopentyl glycol diacrylate GMA: glycidyl methacrylate <active energy ray polymerization initiator (E)>
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide <acid generator>
CPI-110P: a triarylsulfonium salt type photoacid generator manufactured by San Apro

<Example of production of laminate A>
[Reference Examples 1 to 16], [Example 17], [Reference Examples 18 to 19], [Example 20 ], [Reference Example 21 ], [ Example 22], [Comparative Examples 1 to 6]
A laminate A was prepared using the active energy ray polymerizable resin composition shown in Table 1. Two prism sheets (prism sheet made by Nippon Special Optical Resin Co., Ltd .: trade name “LPV90-1.0”, material: poly (methyl methacrylate), thickness: 2 mm), which is a polyacrylic transparent film, are prepared as a base material. did. The corona treatment was performed on the back surface (the surface having no prism) of the first prism sheet with a discharge amount of 300 W · min / m 2, and then the compositions shown in the examples and comparative examples described in Table 1 were used. Using a wire bar coater, coating was performed such that the film thickness after coating was 1 μm to form a resin layer. Next, the front surface (prism surface) of the second prism sheet is laminated so that the optical axis of the first prism sheet and the optical axis of the second prism sheet are orthogonal to each other, and the first prism sheet / resin layer / A laminate composed of the second prism sheet was obtained. Next, the four sides of the laminate were fixed to the tinplate using cellophane tape so that the front surface of the first prism sheet was in contact with the tinplate. A laminate of prism sheets fixed by irradiating ultraviolet rays with a maximum illuminance of 300 mW / cm 2 and an integrated light amount of 300 mJ / cm 2 from the back side of the second prism sheet with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). A was produced.
Incidentally, Embodiment Table Example 1-16, Example 18 to 19, 21 deemed to be replaced with, reference example 1 to 16, Reference Examples 18 to 19, which is the meaning of 21.

With respect to the obtained laminate A (fixed prism sheet laminate), peel strength, gel fraction, punching workability, and heat-and-moisture resistance were determined according to the following methods, and the results are also shown in Table 1.

<Peel strength>
Peel strength was measured according to JIS K6854-4 Adhesive-Peel Adhesive Strength Test Method-Part 4: Floating Roller Method. That is, the obtained laminate A (fixed prism sheet laminate) was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. Using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.), the sample was attached on a metal plate using a laminator to obtain a laminate for measuring the fixed prism sheet laminate A and the metal plate. . The measurement laminate is cut in advance between the two prism sheets, and the measurement laminate is peeled off at a speed of 300 mm / min at 23 ° C. and a relative humidity of 50%. The peel strength was determined. The peel strength was evaluated according to the following four levels. .
(Evaluation criteria)
A: Peeling force is 5.0 (N / 25 mm) or more, peeling is impossible or prism sheet is broken. (Very good)
○: Peeling force is 1.0 (N / 25 mm) or more and less than 5.0 (N / 25 mm). (Good)
(Triangle | delta): The peeling force is 0.5 (N / 25mm) or more and less than 1.0 (N / 25mm). (Available)
X: Peeling force is less than 0.5 (N / 25 mm). (Bad)

<Gel fraction>
After coating a polynorbornene-based film (manufactured by Nippon Zeon Co., Ltd., trade name “Zeonor film (registered trademark) ZF-14, thickness: 100 μm”) with an active energy ray polymerizable resin composition using a wire bar coater. The film was coated so that the film thickness was 25 μm, and a resin layer was formed. Further, after a polynorbornene-based film is laminated on the resin layer to obtain a laminate composed of three layers, a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm are obtained with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). ² active energy rays were irradiated to polymerize and cure the resin layer. Thereafter, the polynorbornene-based film was peeled off to obtain a resin layer. After measuring the mass of the resin layer (referred to as “mass 1”), the resin layer was sandwiched between metal meshes (SUS316, 150 mesh) and refluxed in methyl ethyl ketone (MEK) for 3 hours. Further, it was dried at 80 ° C. for 30 minutes, and the mass of the resin layer (referred to as “mass 2”) was measured. The gel fraction was calculated from the following formula and evaluated in three stages.
Gel fraction (%) = {1- (mass 1-mass 2) / mass 1}} × 100
(Evaluation criteria)
○: Gel fraction is 90% or more (good)
Δ: Gel fraction 80% to less than 90% (can be used)
X: Gel fraction is less than 80% (defect)

<Punching workability>
Using a super straight cutter (100 mm × 100 mm) manufactured by Dumbbell, the fixed prism sheet laminate A produced in the above example was punched from the back side of the second prism sheet. About the laminated body A punched out, the distance between the prism sheet and the resin layer produced by punching was measured with a ruler, and the average value of the distance was evaluated in the following three stages.
(Evaluation criteria)
○: 0 mm, no floating, no peeling (good)
Δ: 0 to 0.5 mm (can be used)
×: Over 0.5 mm (defect)

《Moisture and heat resistance》
The fixed prism sheet laminate was cut into a size of 50 mm × 40 mm and exposed to an environment of 60 ° C.-90% RH and 85 ° C.-85% RH for 1000 hours. About the laminated body after exposure, the distance of the prism sheet and resin layer which arose by exposure was measured with the ruler, and the average value of the distance was evaluated in the following four steps.
(Evaluation criteria)
A: No peeling under conditions of 85 ° C.-85% RH. (Very good)
○: No peeling under conditions of 60 ° C. and 90% RH. (Good)
(Triangle | delta): There exists peeling of less than 0.5 mm on the conditions of 60 degreeC-90% RH. (Available)
X: There exists peeling of 0.5 mm or more on condition of 60 degreeC-90% RH. (Bad)

<Example of production of laminate B>
[Reference Examples 1 to 16], [Example 17], [Reference Examples 18 to 19], [Example 20 ], [Reference Example 21 ], [ Examples 22 to 22], [Comparative Examples 1 to 6]
Using the active energy ray polymerizable resin composition shown in Table 1, the following laminate B was prepared.
As the transparent film, a polyacetylcellulose-based film (manufactured by Fuji Film Co., Ltd., trade name “Fujitack: 80 μm”, UV absorber-containing polytriacetylcellulose-based film) was used. After the surface of the transparent film was subjected to corona treatment with a discharge amount of 300 W · min / m 2, the wire bar coater was prepared using the compositions shown in the examples and comparative examples described in Table 1 as active energy ray polymerizable coating agents. Using this, coating was performed so that the film thickness after coating was 2 μm, and a resin layer was formed. The four sides of the laminate B were fixed to the tinplate with cellophane tape so that the transparent film was in contact with the tinplate. After replacing the inside of the UV irradiation apparatus (high pressure mercury lamp manufactured by Toshiba Corporation) with dry nitrogen, a laminate B was prepared by irradiating ultraviolet rays with a wavelength of 365 nm with a maximum illuminance of 300 mW / cm 2 and an integrated light amount of 300 mJ / cm 2 from the resin layer side. Incidentally, embodiment Table example 1-16, example 18 to 19, 21 deemed to be replaced with, reference example 1 to 16, reference examples 18 to 19, which is the meaning of 21.

About the obtained laminated body, adhesive force, wet heat resistance, and heat yellowing were calculated | required in accordance with the following method, and the result was similarly shown in Table 1.

"Adhesion"
According to JIS K5600-5-6: 1999, a cross-cut peel test was performed. The number of cells peeled in 100 cells was evaluated in four stages.
(Evaluation criteria)
A: 0 square (very good)
○: 1-10 mass (good)
△: 11-30 squares (usable)
X: 31 squares or more (defect)

《Moisture and heat resistance》
The wet heat resistance of the laminate B was evaluated based on the same method and evaluation criteria as the wet heat resistance of the laminate A.

《Heat-resistant yellowing》
The laminate B obtained in each example and comparative example was cut into a size of 50 mm × 40 mm, and the resin layer surface of the cut laminate B was measured with a spectrophotometer in accordance with JIS Z8722. : YI) was measured, and the yellowness (YI _a ) was calculated based on the value in accordance with JIS K7373: 2006. Next, as a heat test, the sample was exposed for 1000 hours at 80 ° C., and then the yellowness after the heat test was measured in the same manner as described above to calculate the yellowness (YI _b ). The difference in yellowness before and after the heat resistance test was defined as the degree of yellowing (ΔYI), and was evaluated in the following three stages. The yellowness before the heat test was (YI _a ) <0.5.
(Evaluation criteria)
Yellowness (ΔYI) = Yellowness after heat test (YI _b ) − (Initial yellowness (YI _a ))
○: Yellowing degree (ΔYI) is 1.0 or less (good)
Δ: Yellowing degree (ΔYI) is 1.0 to 2.0 (usable)
X: Yellowing degree (ΔYI) is 2.0 or more (defect)

It is clear that the laminates (Examples 1 to 22) using the active energy ray polymerizable resin composition of the present invention are superior to the laminates of Comparative Examples 1 to 6 in peel strength, punching workability, and moisture and heat resistance. It became. In addition, it became clear that there was no problem in use in anti-yellowing.

Claims (5)

Polyester oligomer (A) having at least one α, β-unsaturated double bond group and a weight average molecular weight of 6001 to 60000, and an organic base having an α, β-ethylenically unsaturated double bond group Or (b1-2) and 0.01 to 10% by mass of water,
Or
Polyester oligomer (A) having at least one α, β-unsaturated double bond group and a weight average molecular weight of 6001 to 60000, and an organic base having an α, β-ethylenically unsaturated double bond group (B1-2), isobornyl acrylate, and isocyanuric acid EO-modified triacrylate ,
Furthermore, it contains a compound (X) having a hydroxyl group and an α, β-ethylenically unsaturated double bond group,
Active energy ray polymerizable resin composition.
(However, the compound (X) excludes the polyester oligomer (A) and the organic base (b1-2) having an α, β-ethylenically unsaturated double bond group.) The active energy ray polymerizable resin composition according to claim 1, wherein the content of the organic base (b1-2) is 0.01 to 10% by mass. It has a base material (G) and the resin layer which consists of an active energy ray polymeric resin composition of Claim 1 or 2 provided in the at least one surface of this base material (G), It is characterized by the above-mentioned. Laminated body. The laminate according to claim 3 , wherein the substrate (G) is a transparent film (H). The transparent film (H) is selected from the group consisting of a polyacetylcellulose film, a polynorbornene film, a polypropylene film, a polyacryl film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, and a polyimide film. The laminate according to claim 4 , wherein the laminate is at least one kind.