JP2017137395A - Active energy ray-polymerizable adhesive for optical use and optical laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray adhesive for optical use, which has excellent adhesive force in a wide temperature range from a high temperature to a low temperature.SOLUTION: A active energy ray-polymerizable adhesive for optical use is provided, which comprises: a (meth)acrylate monomer (A) having a molecular weight of less than 500 and a heterocycle; a (meth)acrylate monomer (B) having a molecular weight of less than 500 and a hydroxyl group (excluding the (meth)acrylate monomer (A) having a heterocycle); and a (meth)acrylate monomer (C) having a molecular weight of less than 500 and a ring except for a heterocycle (excluding the (meth)acrylate monomer (A) having a molecular weight of less than 500 and a heterocycle and the (meth)acrylate monomer (B) having a hydroxyl group). The above heterocycle includes least two heteroatoms, as atoms constituting the ring, selected from the group consisting of sulfur, oxygen and nitrogen.SELECTED DRAWING: None

Description

  The present invention relates to an optical active energy ray-polymerizable adhesive and an optical laminate.

  For optical applications such as display devices such as displays, active energy ray polymerizable adhesives have a high polymerization rate and can generally be used in the absence of a solvent, so they are excellent in workability and have a very low energy required for polymerization. Because of its excellent characteristics, it is widely used. Active energy ray polymerizable adhesives are generally known as radical polymerizable active energy ray polymerizable adhesives and cationic polymerizable active energy ray polymerizable adhesives.

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

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

  In addition, a backlight system in which a liquid crystal layer is illuminated from the backside is widely used in display devices, and an edge light type, a direct type backlight unit or the like is provided on the lower surface side of the liquid crystal layer. Such an edge light type backlight unit basically includes a linear lamp 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 light diffusion sheet. Recently, light-emitting diodes (LEDs) with excellent color reproducibility and power saving have been used as light sources instead of cooling cathode tubes (CCFLs), and demands for heat resistance and dimensional stability have increased. It is coming.

  By the way, display devices are used in various environments as their applications expand. For example, an in-vehicle liquid crystal display device such as a car navigation system is exposed to a severe high-temperature atmosphere in the summer, and thus requires an adhesive force at a high temperature. Furthermore, in cold regions in winter, adhesion at low temperatures is required.

  As an adhesive used for the display device, an adhesive containing a carboxyl group-containing vinyl polymer and a vinyl monomer (Patent Document 1) is disclosed.

  Patent Document 2 discloses an active energy ray adhesive containing an alicyclic epoxy resin, a polyol having a number average molecular weight of 400 or more, and an active energy ray-sensitive catalyst.

Japanese Patent Application Laid-Open No. 2015-110663 JP 2007-224235 A

  However, the conventional display device using the active energy ray adhesive has insufficient adhesive force in a wide temperature range from high temperature to low temperature such as in-vehicle use, and particularly, the adhesive force at low temperature is insufficient.

  The problem to be solved by the present invention is to provide an optical active energy ray adhesive having excellent adhesive force in a wide temperature range from high temperature to low temperature.

In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, completed the present invention.
That is, the present invention relates to a (meth) acrylate monomer (A) having a heterocyclic ring having a molecular weight of less than 500 (excluding acryloylmorpholine), a (meth) acrylate monomer having a hydroxyl group having a molecular weight of less than 500 (B) (provided that (Excluding (meth) acrylate monomer (A) having a heterocyclic ring) and (meth) acrylate monomer (C) having a ring other than a heterocyclic ring having a molecular weight of less than 500 (however, having a heterocyclic ring having a molecular weight of less than 500 ( The heterocyclic ring is selected from the group consisting of sulfur, oxygen and nitrogen as atoms constituting the ring. 2) (excluding (meth) acrylate monomer (A) and (meth) acrylate monomer (B) having a hydroxyl group) The present invention relates to an optically active energy ray polymerizable adhesive containing one or more heteroatoms.

The present invention further includes a polyurethane oligomer (D1) having a (meth) acryloyl group, a polyester oligomer (D2) having a (meth) acryloyl group, and an epoxy oligomer (D3) having a (meth) acryloyl group. The above-mentioned optical active energy ray-polymerizable adhesive comprising at least one oligomer selected from the group consisting of:
About.

Moreover, this invention WHEREIN: (meth) acrylate monomer (A) 5-70 mass% which has a heterocyclic ring in the optical active energy ray polymeric adhesive, (meth) acrylate monomer (B) 20-80 which has a hydroxyl group. The above-mentioned active energy ray polymerizable adhesive for optical use comprising 5 to 50% by mass of (meth) acrylate monomer (C) having a mass structure other than heterocyclic ring.
About.

  Moreover, this invention relates to the laminated body for optics provided with the 1st base material, the resin layer which is a hardened | cured material of the said optical active energy ray polymeric adhesive, and a 2nd base material.

  According to the present invention, an optical active energy ray-polymerizable adhesive having excellent adhesive force in a wide temperature range from high temperature to low temperature can be provided.

Hereinafter, embodiments of the present invention will be described.
<Active energy ray-polymerizable adhesive for optics>
The optically active energy ray-polymerizable adhesive of the present invention (hereinafter sometimes simply referred to as “adhesive”) is a (meth) acrylate monomer (A) having a heterocyclic ring having a molecular weight of less than 500 (provided that acryloyl is used). (Except morpholine), (meth) acrylate monomer (B) having a hydroxyl group with a molecular weight of less than 500 (except for (meth) acrylate monomer (A) having a heterocyclic ring) and a ring other than a heterocyclic ring with a molecular weight of less than 500 (Meth) acrylate monomer (C) having a molecular weight (except for (meth) acrylate monomer (A) having a heterocyclic ring having a molecular weight of less than 500 and (meth) acrylate (B) having a hydroxyl group) Represents two or more hete atoms selected from the group consisting of sulfur, oxygen and nitrogen as atoms constituting the ring. Characterized in that it comprises an atom.

  Here, the term “active energy rays” refers to energy rays in a broad sense that can provide energy necessary for activation to cause a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams (EB), and radiation. means. In the active energy ray-polymerizable adhesive of the present invention, the polymerization reaction proceeds by irradiation with the active energy ray to form a cured product such as a resin layer.

  In addition, in the present specification, when “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” are expressed. 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".

<(Meth) acrylate monomer (A) having a heterocyclic ring with a molecular weight of less than 500>
The (meth) acrylate monomer (A) (hereinafter also referred to as compound (A)) having a heterocyclic ring having a molecular weight of less than 500 is a group consisting of sulfur, oxygen, and nitrogen as atoms (ring member atoms) constituting the ring. The compound which has a (meth) acryloyl group and the heterocyclic ring containing 2 or more heteroatoms selected from more.
By including the compound (A) in the adhesive, a hydrogen bond is formed between the hetero atom of the heterocyclic ring and a functional group such as a hydroxyl group on the surface of the base material, and the adhesive strength at room temperature and low temperature is improved. Furthermore, the cohesive force at high temperature is improved by the annular structure, and the adhesive force at high temperature is improved.

As the heterocyclic ring containing two or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen as ring member atoms, a heterocyclic ring having two or more sulfur atoms such as a dithiolane ring and a dithiol ring, a carbonate ring, Heterocycle having two or more oxygen atoms such as dioxolane ring, dioxane ring, etc., heterocycle having two or more nitrogen atoms such as isocyanuric ring, imidazole ring, pyrazole ring, pyrazine ring, pyrimidine ring, piperazine ring, oxazole ring , Isoxazole rings, oxazine rings, oxadiazole rings, oxadiazine rings, heterocycles having oxygen and nitrogen atoms, thiazole rings, benzothiazole rings, isothiazole rings, thiazine rings, thiadiazole rings, thiadiazine rings, dithiazine rings, etc. And a heterocyclic ring having a sulfur atom and a nitrogen atom.
Among these heterocycles, a heterocycle having two or more oxygen atoms as ring member atoms is preferred in that it is excellent in a wide temperature range from high temperature to low temperature, and a heterocycle having two oxygen atoms as ring member atoms. Is preferred. Moreover, a monocyclic heterocycle is preferable to a fused heterocycle, and an aliphatic heterocycle is preferable to an aromatic heterocycle. More specifically, a dioxolane ring and a dioxane ring are particularly preferable.

  Although the reason is unknown, it is not preferable to include acryloylmorpholine in the optical active energy ray-polymerizable adhesive because the viscosity of the adhesive is lowered when stored for a long time.

  The number of (meth) acryloyl groups in the compound (A) is preferably 1 to 6 in terms of improving adhesive force in a wide temperature range from high temperature to low temperature, and particularly preferably one.

  Specific examples of the compound (A) include (2-methyl-2-ethyl-1,3dioxolan-4-yl) methyl (meth) acrylate, 5-ethyl-1,3-dioxane-5 (meth) acrylate. -Ylmethyl, (meth) acrylic acid (2-oxo-1,3-dioxolan-4-yl) methyl, 1,3-dioxan-2-one-5-yl (meth) acrylate, 1- (meth) acryloyl- 4-methylpiperazine, (meth) acrylic acid 11- [1 ′, 3 ′, 3′-trimethylspiro [3H-naphtho [2,1-b] [1,4] oxazine-3,2 ′ (3′H )-[1H] indole] -5′-yloxy] undecyl, 2,5-bis ((meth) acryloyloxyethylthiomethyl) -1,4-dithiane, etc., and 2-methyl-2-ethyl- 1,3 dioxolane 4-yl) methyl (meth) acrylate and 5-ethyl-1,3-dioxan-5-ylmethyl (meth) acrylate are preferred in that they are excellent in a wide temperature range from high temperature to low temperature.

<(Meth) acrylate monomer (B) having a hydroxyl group with a molecular weight smaller than 500>
The (meth) acrylate (B) having a hydroxyl group with a molecular weight smaller than 500 (hereinafter also referred to as compound (B)) is not particularly limited as long as it is a (meth) acrylate having a hydroxyl group.
By including the compound (B) in the adhesive, a hydrogen bond is formed with the hydroxyl group or the like of the base material, and the adhesive strength at room temperature and low temperature is improved.

Examples of the compound (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- ( Monofunctional (meth) acrylic acid glycerol such as hydroxymethyl);
Fatty acid ester-based (meth) acrylic acid ester such as (meth) acrylic acid glycidyl lauric acid ester;

Cyclic rings such as cyclohexanedimethanol mono (meth) acrylate, cyclohexanediethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-a (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, etc. (Meth) acrylic acid ester;
(Meth) acrylic acid ester having a hydroxyl group attached to the molecular end by ring-opening addition of ε-caprolactone to the (meth) acrylate having a hydroxyl group;
Alkylene oxide addition (meth) acrylate ester etc. which added alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide repeatedly, to the (meth) acrylate which has the said hydroxyl group; Aliphatic (meth) acrylate ester etc. are mentioned It is done.

  The compound (B) is excellent in adhesive strength at low temperatures, and is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic. 4-hydroxybutyl acid is preferable, and 4-hydroxybutyl (meth) acrylate is particularly preferable.

<(Meth) acrylate monomer (C) having a ring structure other than a heterocyclic ring having a weight average molecular weight of less than 500>
A (meth) acrylate monomer (C) having a ring structure other than a heterocyclic ring having a molecular weight of less than 500 (hereinafter also referred to as a compound (C)) is a hydrocarbon ring other than a heterocyclic ring (an aromatic hydrocarbon ring or an aliphatic group). A (meth) acrylate compound containing a hydrocarbon ring). The compound (C) is preferably a (meth) acrylate compound containing no hydrocarbon ring and containing a hydrocarbon ring (aromatic hydrocarbon ring or aliphatic hydrocarbon ring). By including the compound (C), it is possible to obtain an optical active energy ray-polymerizable adhesive having excellent adhesive strength at high temperatures.

Examples of the compound (C) include benzyl (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, bisphenol A di (meth) acrylate, alkylene oxide modified bisphenol A di (meth) acrylate, and bisphenol. It has an aromatic hydrocarbon ring such as F di (meth) acrylate, alkylene oxide modified bisphenol F di (meth) acrylate, 2- (meth) acryloyloxyethyl phthalic acid, neopentyl glycol-acrylic acid-benzoic acid ester (meta ) Acrylate compounds;
(Meth) acrylate compounds having one or more aliphatic hydrocarbon rings such as di (meth) acrylate of hydrogenated bisphenol A, 2- (meth) acryloyloxyethylhexahydrophthalic acid, cyclohexyl methacrylate;
3,3-dicyclopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, Tricyclodecane dimethanol di (meth) acrylate, isobornyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meta ) Acrylate, 2-propyl-2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyldiol di (meth) acrylate, 1,3,5-adamantyl ( (Meta) Acrylate, 3-hydroxy-1,5 having Adamanchiruji (meth) aliphatic hydrocarbon condensed rings such as acrylates (meth) acrylate compounds, and the like.

  As the compound (C), a (meth) acrylate compound having a condensed aliphatic hydrocarbon ring is preferable from the viewpoint of excellent adhesive strength at high temperatures. Specifically, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and isobornyl (meth) acrylate are preferable. Tricyclodecane dimethanol di (meth) acrylate and isobornyl (meth) acrylate are particularly preferable.

  The content ratio of the compounds (A), (B), and (C) in the optical active energy ray polymerizable adhesive is 5 to 70% by mass of the compound (A), 20 to 80% by mass of the compound (B), and the compound ( C) It is preferably 5 to 50% by mass, more preferably 10 to 70% by mass of compound (A), 30 to 70% by mass of compound (B), and 5 to 40% by mass of compound (C). Moreover, it is preferable that the total amount of compound (A), (B), (C) is 70 mass% or more in the active energy ray polymerizable adhesive for optics.

The optically active energy ray-polymerizable adhesive of the present invention further comprises a polyurethane oligomer (D1) having a (meth) acryloyl group (hereinafter also referred to as compound (D1)) and a polyester oligomer having a (meth) acryloyl group. It contains at least one oligomer selected from the group consisting of (D2) (hereinafter also referred to as compound (D2)) and an epoxy oligomer (D3) having a (meth) acryloyl group (hereinafter also referred to as compound (D3)). In view of improving the adhesive strength at room temperature.
The weight average molecular weights of the compounds (D1), (D2), and (D3) are preferably 500 to 100,000. In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) using polystyrene having a known weight average molecular weight as a standard substance.

<Polyurethane oligomer (D1) having (meth) acryloyl group>
The polyurethane-based oligomer (D1) (compound (D1)) having a (meth) acryloyl group is a compound having a urethane bond and a (meth) acryloyl group in the molecule. For example, it can be obtained by reacting a compound having an isocyanate group at the terminal obtained by reacting a compound having one or more isocyanate groups and a compound having a hydroxyl group with a (meth) acryloyl group having a hydroxyl group.

  Examples of the compound having at least one isocyanate group include aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 1,4-phenylene bismethylene diisocyanate, and 3-isocyanate methyl- And aliphatic isocyanates such as 3,5,5-trimethylcyclohexyl isocyanate and hexamethylene diisocyanate.

  Specific examples of the compound (D1) include aromatic polyurethane oligomers such as EBECRYL210, EBECRYL220 (manufactured by Daicel Ornex), CN9782, CN9783 (manufactured by SARTOMER), purple light 3000B, purple light 3700B (and above, Japan). Synthetic Chemical Industry Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402 and EBECRYL8701 (above, manufactured by Daicel Ornex) and the like.

<Polyester oligomer (D2) having (meth) acryloyl group>
The polyester-based oligomer (D2) (compound (D2)) having a (meth) acryloyl group is a compound having an ester bond and a (meth) acryloyl group in the molecule. For example, the main chain skeleton has one or more carboxyl groups in a molecule such as a terminal of a polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol or a hydroxyl group in the polyester chain and (meth) acrylic acid ) It can be obtained by esterification reaction with acrylate.

  Examples of the polybasic acid include aliphatic polyacids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride, and maleic anhydride. Examples include alicyclic systems such as basic acids, dimer acids, and cyclohexanedicarboxylic acids, and aromatic systems such as isophthalic acid, terephthalic acid, and biphenyldicarboxylic acid.

  Examples of the polyhydric alcohol include relatively low molecular weight polyols having a number average molecular weight (Mn) of 50 to 500 and relatively high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000.

  Specific examples of the compound (D2) include aromatic polyester oligomers such as CN296, CN2203, CN2259, CN2261 (above, manufactured by SARTOMER), and aliphatic polyesters such as CN294, CN2270, CN2271 (above, made by SARTOMER). System oligomers.

<Epoxy oligomer having (meth) acryloyl group (D3)>
An epoxy oligomer (D3) (compound (D3)) having a (meth) acryloyl group is a partial structure obtained by reacting an epoxy group of an epoxy compound with a compound having a carboxyl group and / or a hydroxyl group, and (meth) It is a compound having an acryloyl group.

  Examples of the epoxy compound include aromatic epoxy compounds such as bisphenol-type epoxy, aliphatic epoxy compounds such as diglycidyl ether of diol having 2 to 20 carbon atoms, and alicyclic epoxy compounds.

  Specific examples of the compound (D3) include CN104, CN110 (above, manufactured by SARTOMER), EBECRYL600, EBECRYL3701 (above, made by Daicel Ornex), CN111, CN113 (above, made by SARTOMER) ), Aliphatic epoxy type oligomers such as EBECRYL860 (manufactured by Daicel Ornex).

  The total content of the compounds (D1), (D2) and (D3) is 1 to 30% by mass in the contents of the compounds (D1), (D2) and (D3) in the optical active energy ray polymerizable adhesive. It is preferable that it is 3 to 20% by mass.

  The optical active energy ray-polymerizable adhesive for optical use of the present invention includes compounds (A), (B), (C), (D1), (D2), and other (meth) acrylate compounds (E) other than (D3). (Hereinafter also referred to as compound (E)) and cationically polymerizable compound (F) (hereinafter also referred to as compound (F)) may be included.

  By including the compound (E), the viscosity of the optical active energy ray polymerizable adhesive can be lowered to improve the coating property, and the durability such as wet heat resistance can be further improved.

Examples of the compound (E) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, and (meth). (Meth) acrylic acid alkyl esters such as stearyl acrylate;
(Meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 3,7-dimethyloct-6-en-1-yl, acrylic acid 2- (2-vinyloxyethoxy) (Meth) acrylic acid esters containing ethyl and other unsaturated groups such as vinyl (meth) acrylate;

(Meth) acrylic acid perfluoroalkyl esters such as (meth) acrylic acid perfluoromethyl, (meth) acrylic acid 2-perfluoroethylethyl, and (meth) acrylic acid 2-perfluorohexadecylethyl;
(Meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) hexyl, (meth) acrylic acid 2- (propoxycarbonyloxy) ethyl, and (meth) acrylic acid 2- (octyloxy) Aliphatic (meth) acrylic acid ester having one carbonyl group such as carbonyloxy) butyl;
(Meth) acrylic acid 2-oxobutanoylethyl, (meth) acrylic acid 3-oxobutanoylpropyl, (meth) acrylic acid 2,3-di (oxobutanoyl) butyl, (meth) acrylic acid 2,3- Aliphatic (meth) acrylic acid esters having two carbonyl groups such as di (oxobutanoyl) hexyl;

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, Alkoxy group-containing (meth) acrylic acid ester such as 3-butoxyethyl (meth) acrylate and 4-butoxyethyl (meth) acrylate;
Alkylene oxide-containing (meth) acrylic acid derivatives such as alkylene oxide adducts of (meth) acrylic acid;

Di (meth) acrylic acid ethylene glycol, di (meth) acrylic acid triethylene glycol, di (meth) acrylic acid tetraethylene glycol, di (meth) acrylic acid 2,2-dimethylpropyldiol, hydroxy di (meth) acrylic acid Pivalyl hydroxypivalate, 2,5-hexanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate , And bifunctional (meth) acrylic acid esters such as 2,5-dimethyl-2,5-hexanediol di (meth) acrylate;
Tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid trimethylol hexane, tri (meth) acrylic acid trimethylol octane, and tri (meth) acrylic acid 1,1,1-trishydroxy Trifunctional (meth) acrylic acid esters such as methylethane;

Tetra (meth) acrylate pentaerythritol, tetra (meth) acrylate 2,2-bis (hydroxymethyl) 1,3-propanediol, and hepta (meth) acrylate di 2,2-bis (hydroxymethyl) 1, Polyfunctional (meth) acrylic acid esters such as 3-propanediol polyalkylene oxide;
(Meth) acrylate compounds having a cationically polymerizable functional group such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate;
And (meth) acrylate compounds having a heterocycle containing one hetero atom such as tetrahydrofurfuryl (meth) acrylate.

<Cationically polymerizable compound (F)>
As the compound (F), a compound having an epoxy group which is a 3-membered ring ether, a compound having an oxetanyl group which is a 4-membered ring ether, a vinyl ether compound, a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, and a fluorine-containing compound A cyclic compound or the like is preferable. Among the above compounds, any of the compounds having a ring does not have a (meth) acryloyl group, and therefore is different from the compounds (A), (B) and (C).
By containing the compound (F), the curing shrinkage of the adhesive is reduced, and the adhesive force at room temperature is improved.

  As the compound having an epoxy group (epoxy compound), an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, or the like is preferable.

  Examples of the aromatic epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl ether of bisphenol A propylene oxide adduct, and phenol novolac. Epoxy, cresol novolac epoxy, biphenyl type epoxy, resorcin diglycidyl ether, phenyl glycidyl ether, phenol ethylene oxide glycidyl ether, t-butylphenyl glycidyl ether and the like can be mentioned.

  As the aliphatic epoxy compound, an aliphatic monoalcohol, an aliphatic polyalcohol, and a glycidyl ether of an alkylene oxide adduct thereof are preferable. Examples of the aliphatic epoxy compound include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, One or two for aliphatic polyhydric alcohols such as triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, polypropylene glycol, and glycerin Polyglycidyl ether of polyether polyol obtained by adding more than one kind of alkylene oxide (ethylene oxide or polypropylene oxide) And the like.

  Examples of the alicyclic epoxy compound include 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2 -(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6) -Methylcyclohexylmethyl) adipate and the like.

  The epoxy equivalent of the epoxy compound is usually preferably about 30 to 3000 g / eq, more preferably 50 to 1500 g / eq. When the epoxy equivalent is 30 g / eq or more, the flexibility of the cured sheet is excellent, and the adhesive force is further improved. Moreover, when it becomes 3000 g / eq or less, it is excellent in sclerosis | hardenability and adhesive force improves.

  Examples of the compound having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and di (1-ethyl-3-oxetanyl). Methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol-novolak oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) Methyl} oxetane.

Examples of the vinyl ether compound include 5 to 20 carbon atoms such as n-amyl vinyl ether, i-amyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether, and oleyl vinyl ether. Vinyl ethers of alkyl alcohols and alkenyl alcohols;
Monoalcohol vinyl ethers having aliphatic or aromatic rings such as cyclohexyl vinyl ether, 2-methylcyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, benzyl vinyl ether;
Glycerol monovinyl ether, 1,4-butanediol monovinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, neopentyl glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol Tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane monovinyl ether, 1,4-dihydroxy Monovinyl ethers and polyvinyl ethers of polyhydric alcohols such as methylcyclohexane divinyl ether;
Polyalkylene glycol monodivinyl ether and divinyl ether such as triethylene glycol divinyl ether, diethylene glycol monobutyl monovinyl ether;
Other vinyl ethers such as glycidyl vinyl ether and ethylene glycol vinyl ether methacrylate are listed.

  Examples of cyclic ester compounds include lactones. Examples of the cyclic carbonate compound include ethylene carbonate and propylene carbonate. Examples of the cyclic formal compound include dioxolane, dioxane, trioxane and the like. Compound (F) can be used alone or in combination of two or more.

  The compound (F) is preferably a compound having an epoxy group or a compound having an oxetanyl group. Among compounds having an epoxy group and compounds having an oxetanyl group, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, bisphenol A di Glycidyl ether, bisphenol F diglycidyl ether, and 1,6-hexanediol diglycidyl ether are preferred because of their particularly excellent reactivity.

<Active energy ray polymerization initiator (G)>
The optical active energy ray-polymerizable adhesive may contain an active energy ray polymerization initiator (G) (hereinafter also referred to as compound (G)). Examples of the compound (G) include an active energy ray radical polymerization initiator (g1), an active energy ray cationic polymerization initiator (g2), and an active energy ray anionic polymerization initiator (g3).
A known active energy ray radical polymerization initiator can be used as the active energy ray radical polymerization initiator (g1). For example, Irgacure-184, 907, 651, 1700, 1800, 819, 369, 261, DAROCUR-TPO (manufactured by BASF), Darocur-1173 (manufactured by Merck), Ezacure-KIP150, Examples thereof include TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI, and the like (manufactured by Nippon Kayaku Co., Ltd.).

  As the active energy ray cationic polymerization initiator (g2), a known active energy ray cationic polymerization initiator can be used. Examples of commercially available products include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by BASF), WPI-113 (manufactured by Wako Pure Chemical Industries), Rp Examples include iodonium salts such as -2074 (manufactured by Rhodia Japan).

  As the active energy ray anionic polymerization initiator (g3), a known active energy ray anionic polymerization initiator can be used. Commercially available products include, for example, WPBG-165, WPBG-018, WPBG-172, WPBG-140, WPBG-166, WPBG-027, WPBG-082, WPBG-167, WPBG-168, WPBG-266 (above, Wako Pure Chemical Industries, Ltd.).

  The compound (G) is preferably blended in an amount of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, in 100% by mass of the optical active energy ray polymerizable adhesive.

  The optically active energy ray-polymerizable adhesive of the present invention may further comprise a photosensitizer, an amine catalyst, a phosphorus catalyst, a filler, an antistatic agent, an anti-aging agent, an antioxidant, and a tackifier, if necessary. , An antiblocking agent, an antifoaming agent, a plasticizer, a silane coupling agent, a titanium coupling agent, and the like.

  The optical active energy ray polymerizable adhesive of the present invention preferably contains substantially no organic solvent, and preferably contains no organic solvent. However, since the compound (G) is often poorly soluble in the polymerizable component, a small amount of an organic solvent may be included in order to dissolve the compound (G). The content of the organic solvent in the adhesive is preferably 5% by mass or less.

  The optical active energy ray polymerizable adhesive of the present invention preferably has a viscosity at 25 ° C. of 1 to 2000 mPa · s from the viewpoint of controlling the smoothness of the coating film and the dimensional stability of the cured resin. 10 to 1500 mPa · s, more preferably 20 to 1000 mPa · s.

  When the optical active energy ray polymerizable adhesive is used as an adhesive layer of an optical laminate (hereinafter sometimes simply referred to as “laminate”), the thickness of the adhesive layer is 0.1 to 6 μm. Is preferable, and 0.1 to 3 μm is more preferable. When the thickness of the adhesive layer is within the above range, the adhesive force is further improved.

  A known coating apparatus can be used to apply the adhesive to the substrate. For example, wire bar, applicator, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater, comma coater, Examples thereof include a curtain coater, a knife coater, a river coater, and a spin coater.

  The active energy ray used for curing the adhesive is preferably light including ultraviolet rays, and the wavelength in that case is preferably 150 to 550 nm. Examples of the active energy ray light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, an LED lamp, a xenon lamp, and a metal halide lamp. .

The irradiation intensity of the active energy ray is preferably 10 to 500 mW / cm ² . Integrated irradiation dose, expressed as the product of the irradiation intensity and the irradiation time is preferably ^{10~5000mJ / cm 2, 30~4000mJ / cm} 2 is more preferable.

  The optical laminate of the present invention comprises a resin layer, an adhesive layer, and a substrate formed from an optical active energy ray polymerizable adhesive.

  The polymerization reaction of the adhesive proceeds when the adhesive is applied or laminated, and further by irradiating active energy rays after laminating. It is preferable to proceed the polymerization reaction. In that case, in order to advance the polymerization reaction by irradiation with active energy rays, at least one of the first base material and the second base material is preferably composed of a material that easily transmits active energy rays, Specifically, a transparent film, a plastic lens, a transparent glass plate and the like are preferable. For example, if a transparent film or a transparent glass plate is used as the first substrate, a substrate that is difficult to transmit active energy rays as the second substrate, such as a wood, a metal plate, a plastic plate, a paper processed product, etc. May be used.

  In the laminate of the present invention, it is preferable to use a film-like substrate as the substrate. Examples of the film-like substrate include cellophane, various plastic films, paper and the like. Of these, the use of various transparent plastic films is preferred. The film-like substrate may be a single layer or a multilayer structure in which a plurality of substrates are laminated as long as the film is transparent.

  Hereinafter, more specific embodiments of the optical laminate of the present invention will be described by taking as an example the case where a transparent film is used as a substrate.

  The laminate of the present invention is, for example, a sheet-like sheet obtained by laminating a plurality of transparent films such as transparent film / adhesive layer / transparent film or transparent film / adhesive layer / transparent film / adhesive layer / transparent film. It is a multilayer film. Moreover, the structure which adhere | attached the sheet-like multilayer film on other optical members, such as glass or an optical sheet, is also preferable. The laminate can be obtained by curing the adhesive layer by irradiating the active energy ray-polymerizable adhesive for optics with an active energy ray from one or both sides of the film and curing it.

Examples of the transparent film include polyolefin film such as polyvinyl alcohol film, polytriacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer; polyester film such as polyethylene terephthalate and polybutylene terephthalate. Polycarbonate film, polynorbornene film, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl film, polyamide film, polyimide film, and polyoxirane film. .
When a transparent film is used for the substrate, the laminate of the present invention can be suitably used for optical applications.

  The thickness of the transparent film can be determined as appropriate, but in general, from the viewpoint of film strength, workability, thin layer properties, etc., 1 to 500 μm is preferable, 1 to 300 μm is more preferable, and 5 to 200 μm is preferable. Further preferred. Moreover, when using for an optical use, 5-150 micrometers is preferable for the thickness of a transparent film.

  As an example of the embodiment of the optical laminate of the present invention, the optical element laminate preferably uses an optical film mainly used for optical applications as a transparent film.

  Examples of the optical film include 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 (prism sheet (prism sheet). -Also referred to as a sheet), a decorative film (including a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like.

  Using the optically active energy ray polymerizable adhesive of the present invention, a laminate of a liquid crystal display device, a PDP module, a touch panel module, an organic EL module or the like can be formed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. “Part” is “mass%”, and “%” represents “mass%”.

<Weight average molecular weight>
The weight average molecular weight was measured using GPC (Gel Permeation Chromatography) “Shodex GPC System-21” manufactured by Showa Denko KK as a measuring device, two shodex GPC LF-604 manufactured by Showa Denko KK as a column, and tetrahydrofuran ( THF), flow rate 0.6 ml / min, column temperature 40 ° C. The weight average molecular weight was determined by a calibration curve prepared using polystyrene having a known monodispersed molecular weight as a standard substance.

[Example 1]
<Production example of active energy ray polymerizable adhesive>
(2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (trade name MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd., molecular weight 208) as a compound (A) in a light-shielded glass bottle with a capacity of 300 mL. ) 40 parts, 40 parts of 4-hydroxybutyl acrylate as compound (B), 18 parts of dicyclopentenyl acrylate (trade name FANCLILL 511AS, molecular weight 204, manufactured by Hitachi Chemical Co., Ltd.) as compound (C), Irgacure 184 (manufactured by BASF) 2 parts of radical polymerization initiator) was added, and the mixture was sufficiently stirred and defoamed to obtain an active energy ray polymerizable adhesive. The viscosity (initial viscosity) measured under the following conditions immediately after the production of the adhesive was 8 mPa · s.

《Viscosity with time》
The obtained active energy ray polymerizable adhesive was stored at 40 ° C. for one month, and then the viscosity with time was measured under the following conditions. It should be noted that the adhesive that can be used has a viscosity change rate calculated by Formula 1 within ± 20%.
<Formula 1>
Viscosity change rate (%) = ((aging viscosity−initial viscosity) / initial viscosity) × 100

<Viscosity measurement conditions>
Using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.), 1.2 mL of an active energy ray-polymerizable adhesive was used as a measurement sample, and the conditions were 23 ° C., rotation speed 0.5-100 rpm, and rotation for 1 minute. The viscosity was measured at

<Production example of laminate>
As a transparent film, an ultraviolet absorber-containing polytriacetylcellulose-based film manufactured by Fuji Film Co., Ltd .: trade name “Fujitack: 80 μm” (thickness 80 μm), and a polynorbornene-based film containing no UV absorber manufactured by Nippon Zeon (Thickness 100 μm) was used. The surface of one side of the two transparent films was subjected to corona treatment with a discharge amount of 300 W · min / m ² . Then, within 1 hour, the active energy ray-polymerizable adhesive is formed on the corona-treated surface of the ultraviolet absorber-containing polytriacetylcellulose-based film using a wire bar coater to a thickness of 4 μm. So that it was coated. Further, a polynorbornene-based film not containing an ultraviolet absorber was stacked, and the four sides were fixed to the tinplate with a cellophane tape so that the ultraviolet absorber-containing polytriacetylcellulose-based film was in contact with the tinplate.

Irradiate ultraviolet rays with a maximum illuminance of 500 mW / cm ² and an integrated light quantity of 1000 mJ / cm ² from the polynorbornene film side that does not contain UV absorbers manufactured by Nippon Zeon Co., Ltd. A laminate was created.

  About the obtained laminated body, room temperature adhesive force, high temperature adhesive force, and low temperature adhesive force were calculated | required in accordance with the following method, and the result was shown in Table 1.

《Room temperature adhesion》
The adhesive strength was measured in accordance with Japanese Industrial Standard (JIS) K6854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method. That is, the obtained laminate was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to the polynorbornene-based film surface containing no UV absorber as a sample, and fixed on a metal plate using a laminator. The measurement laminate was previously provided with a peeling peel between the transparent films, and this measurement laminate was subjected to a speed of 300 mm / min, 90 ° under conditions of 23 ° C. and 50% relative humidity. The UV absorber-containing polytriacetylcellulose-based film was peeled off at an angle of, and the adhesive strength was measured. This adhesive strength was evaluated in four stages. If it is evaluated as ○, ○, or Δ, it is practically satisfactory.
A: Unpeelable or substrate destruction (very good)
○: Peeling force is 2.0 (N / 25 mm) or more (good)
Δ: Peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) (can be used)
X: Peeling force is less than 1.0 (N / 25 mm) (unusable)

<High temperature adhesive strength>
In the evaluation method of the room temperature adhesive force, the adhesive force was measured in the same manner as the room temperature adhesive force except that the temperature was changed from 23 ° C. to 60 ° C. This adhesive strength was evaluated in four stages. If it is evaluated as ○, ○, or Δ, it is practically satisfactory.
A: Peeling force is 1.5 (N / 25 mm) or more (very good)
○: Peeling force is 1.0 (N / 25 mm) or more and less than 1.5 (N / 25 mm) (good)
Δ: Peeling force is 0.5 (N / 25 mm) or more and less than 1.0 (N / 25 mm) (can be used)
X: Peeling force is less than 0.5 (N / 25mm) (unusable)

<Low-temperature adhesive strength>
In the evaluation method of the room temperature adhesive force, the adhesive force was measured in the same manner as the room temperature adhesive force except that the temperature was changed from 23 ° C. to 0 ° C. This adhesive strength was evaluated in four stages. If it is evaluated as ○, ○, or Δ, it is practically satisfactory.
A: Unpeelable or substrate destruction (very good)
○: Peeling force is 1.0 (N / 25 mm) or more (good)
Δ: Peeling force is 0.5 (N / 25 mm) or more and less than 1.0 (N / 25 mm) (can be used)
X: Peeling force is less than 0.5 (N / 25mm) (unusable)

[Examples 2 to 26, Comparative Examples 1 to 5]
Except that the materials and compositions shown in Tables 1 and 2 were changed, the active energy ray-polymerizable adhesive and the laminate were produced in the same manner as in Example 1, and the viscosity, viscosity with time, viscosity change rate, room temperature adhesive force, High temperature adhesion and low temperature adhesion were evaluated. The evaluation results are shown in Tables 1 and 2.

The materials used in the examples and their abbreviations are shown below.
<Compound (A)>
MEDOL-10: (2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name MEDOL-10
Biscoat 200: 5-ethyl-1,3-dioxane-5-ylmethyl acrylate, manufactured by Osaka Organic Chemical Industry, trade name Biscoat # 200

<Compound (C)>
FA511AS: Dicyclopentenyl acrylate, manufactured by Hitachi Chemical Co., Ltd. Product name FANCLIL FA511AS
IBXA: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name IBXA
A-DCP: Tricyclodecane dimethanol diacrylate Shin-Nakamura Chemical Co., Ltd. Trade name NK Ester A-DCP
BPE-80N: ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Product name NK ester BPE-80N

<Compound (D1)>
UV3000B: Urethane acrylate oligomer, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Purple light UV3000B
EBECRYL210: Urethane acrylate oligomer, manufactured by Daicel Ornex Co., Ltd., trade name EBECRYL210
<Compound (D2)>
EBECRYL525: Polyester acrylate oligomer (containing 40% by mass of tripropylene glycol diacrylate), manufactured by Daicel Ornex Co., Ltd., trade name EBECRYL525
EBECRYL884: Polyester acrylate oligomer, manufactured by Daicel Ornex, Inc., trade name EBECRYL884
<Compound (D3)>
KAYARAD R-9485: Epoxy acrylate oligomer, manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD R-9485
BAEM-100: Mepoxymethacrylate oligomer, manufactured by KSM Co., Ltd., trade name BAEM-100

<Compound (E)>
THFA: Tetrahydrofurfuryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name Biscote # 150
<Compound (F)>
2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexyl carboxylate, manufactured by Daicel Corporation, trade name Celoxide 2021P
EX212L: 1,6-hexanediol diglycidyl ether (low chlorine grade), manufactured by Nagase Chemitex Corporation, trade name Denacol EX212L
<Compound (G)>
Irgacure 184: 1-hydroxy-cyclohexyl luphenyl ketone, manufactured by BASF, trade name Irgacure 184
CPI-100P: Active energy ray cationic polymerization initiator, manufactured by Sun Apro, trade name CPI-110P

  The active energy ray polymerizable adhesive of the present invention is excellent in storage stability, and the laminates (Examples 1 to 26) using the active energy ray polymerizable adhesive of the present invention are the laminates of Comparative Examples 1 to 5. It became clear that it was excellent in room temperature adhesive force, high temperature adhesive force, and low temperature adhesive force.

Claims (4)

(Meth) acrylate monomer (A) having a heterocyclic ring having a molecular weight of less than 500 (excluding acryloylmorpholine),
(Meth) acrylate monomer (B) having a hydroxyl group with a molecular weight smaller than 500 (excluding (meth) acrylate monomer (A) having a heterocyclic ring) and a ring other than a heterocyclic ring with a molecular weight smaller than 500 (meth) Acrylate monomer (C) (excluding (meth) acrylate monomer (A) having a heterocyclic ring having a molecular weight of less than 500 and (meth) acrylate monomer (B) having a hydroxyl group),
The optical active energy ray-polymerizable adhesive, wherein the heterocycle includes two or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen as atoms constituting the ring.   Further, an oligomer selected from the group consisting of a polyurethane oligomer (D1) having a (meth) acryloyl group, a polyester oligomer (D2) having a (meth) acryloyl group, and an epoxy oligomer (D3) having a (meth) acryloyl group The active energy ray-polymerizable adhesive for optical use according to claim 1, comprising at least one of the above.   In optically active energy ray-polymerizable adhesive, (meth) acrylate monomer (A) having a heterocyclic ring of 5 to 70% by mass, (meth) acrylate monomer having a hydroxyl group (B) of 20 to 80% by mass, other than heterocyclic ring The optical active energy ray polymerizable adhesive according to claim 1 or 2, comprising 5 to 50% by mass of a (meth) acrylate monomer (C) having a ring structure of:   The optical laminated body provided with the 1st base material, the resin layer which is a hardened | cured material of the optical active energy ray polymeric adhesive of any one of Claims 1-3, and the 2nd base material. .