JP2013043952A - Photopolymerizable composition, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel photopolymerizable composition having excellent heat resistance, moisture resistance, thermal dimensional stability, weatherability, and the like, a low viscosity photocurable adhesive using the photopolymerizable composition for attaching various kinds of optical films enabling easy and firm adhesion regardless of the kind of various optical films with excellent curability in a low exposure amount substantially not including an organic solvent, and a polarizing plate using the same with excellent punching processability and wet heat durability compared with the conventional polarizing plates.SOLUTION: The photopolymerizable composition includes (A) a three-membered ring-like oxirane compound as the main component, and (B) a four or more-membered ring-like compound having two or more oxygen atoms. It does not include substantially an organic solvent. Its viscosity at 23°C is 1-1,500 mPa s. Also provided are a photocurable adhesive composition prepared by adding a photopolymerization initiator thereto, and a laminate using the same, and a polarizing plate.

Description

  The present invention relates to a novel photopolymerizable oxirane composition, a photocurable adhesive using the composition, and an optical film laminate.

  Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL display, light emitting diode display, etc. It has come to be used as a display device in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also used in vehicles such as car navigation displays.

For such display devices, various films 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 are usually used. For example, in a liquid crystal cell member constituting an LCD, a polarizing plate and a retardation film are laminated.
Further, the FPD is not only used as a display device, but may be used as an input device by providing a touch panel function on the surface thereof. 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) that are excellent in color reproducibility and power saving have been used as light sources from the cathode ray tube (COFL), and thus demands for more heat resistance and dimensional stability are increasing. .
Such a film is attached to an adherend via an adhesive and used in a display device. Since an adhesive used for a display device is required to have excellent transparency and heat resistance, a solvent-containing two-component curable adhesive mainly containing an acrylic resin is generally used.

By the way, among the various films described above, the polarizing film is attached with a water-based adhesive by sandwiching both surfaces of a polyvinyl alcohol (PVA) polarizer with a protective film of triacetyl cellulose (TAC) or cycloolefin (COP). A combined three-layer structure is common.
For this reason, in a polarizing film, since the dimensional change characteristic of the material which comprises each layer differs, it is easy to produce the warp by the dimensional change accompanying the change of temperature or humidity.

    Since the TAC-based film has high moisture permeability, it can be adhered using a water-based adhesive and drying the water in a state where it is directly stacked on the PVA-based polarizer without volatilizing water.

  As a protective film, a polyester film, a polyvinyl chloride film, a polycarbonate film, an acrylic film, an amorphous polyolefin film, which is inexpensive and has excellent optical properties such as transparency, instead of a TAC film. A film, a cycloolefin type film, etc. are proposed (patent documents 1, 2, and 3). Since these protective films are more hydrophobic than TAC-based films and have low moisture permeability, it is necessary to sufficiently dry the water before being stacked on the PVA-based polarizer. There were problems such as insufficient adhesive strength and poor appearance.

  Therefore, it has been proposed to use an ultraviolet curable adhesive in place of the aqueous adhesive in order to bond the polyvinyl alcohol polarizer and the hydrophobic protective film.

  By the way, the polarizing plate for liquid crystal display devices is stuck on a liquid crystal cell through an adhesive layer. At this time, if a bonding mistake such as mixing of foreign matter is found, the polarizing plate is peeled off and the liquid crystal cell is reused. If the adhesive strength between the PVA polarizer and the protective film is not sufficient, the PVA polarizer and the protective film are peeled off when the polarizing plate is peeled off, and the protective film remains in the liquid crystal cell, making it impossible to reuse the liquid crystal cell. . Therefore, the adhesive force between the PVA polarizer and the protective film is required to be higher than the adhesive strength of the pressure-sensitive adhesive for bonding the polarizing plate and the liquid crystal cell, and the PVA polarizer and the protective film cannot be peeled off. More preferably.

  Further, since the liquid crystal display device is used in various environments such as high temperature and high humidity, the polarizing plate is also required to have extremely severe wet heat resistance. When the adhesive strength between the PVA polarizer and the protective film is not sufficient, peeling between the PVA polarizer and the protective film occurs due to dimensional changes of the PVA polarizer when exposed to high temperature and high humidity for a long time (wet heat exposure). Will occur.

JP-A-2004-245925 (Patent Document 4) discloses an adhesive mainly composed of a hydrogenated (also referred to as hydrogenated) bisphenol-type oxirane resin as an oxirane-based resin that does not contain an aromatic ring. An adhesion method using cationic polymerization by irradiation with energy rays has been proposed.
However, the adhesive described in Patent Document 4 has a very high viscosity and is difficult to coat.
Furthermore, when the main component is a hydrogenated bisphenol type oxirane compound like the adhesive described in Patent Document 4, when a protective film such as a polyester film, a polyvinyl chloride film, a polycarbonate film, or an acrylic film is used, There was a problem that these protective films did not adhere at all.

By the way, the thickness of the adhesive layer that bonds the PVA polarizer and the protective film is required to be as thin as possible in order to increase the light transmittance and to reduce the cost. Specifically, the adhesive layer is required to be smooth with a thickness of 0.1 to 6 μm.
In order to industrially provide such a thin adhesive layer, it is preferable to use a micro gravure coater when applying the optical adhesive. The small-diameter gravure coater can form a thin film by using a finer intaglio. However, when the viscosity of the adhesive is high, an adhesive layer having a thickness of 0.1 to 6 μm cannot be formed even if an intaglio as fine as possible (for example, 500 lines / inch) is used.
Therefore, in order to form an adhesive layer having a thickness of 0.1 to 6 μm, it is necessary to set the viscosity of the adhesive to 1 to 1500 mPa · s.

Japanese Patent Application Laid-Open No. 2008-63397 (Patent Document 5) discloses a relatively low-viscosity adhesive mainly composed of an aliphatic oxirane compound, and an adhesion method based on cationic polymerization by heating or irradiation with active energy rays. Has been proposed.
When the adhesive described in Patent Document 5 is used, the PVA polarizer and the TAC film, and the PVA polarizer and the cycloolefin film can be bonded with sufficient strength without being exposed to wet heat.
However, when the adhesive described in Patent Document 5 is used, when it is exposed to wet heat, peeling occurs between the PVA polarizer and one of the protective films, or between the PVA polarizer and the two protective films.
Furthermore, when an aliphatic oxirane compound is a main component like the adhesive described in Patent Document 5, when a protective film such as a polyester film, a polyvinyl chloride film, a polycarbonate film, or an acrylic film is used, these There was a problem that the protective film did not adhere at all.

JP 2008-257199 A (Patent Document 6) discloses a polyfunctional oxirane resin having one or more alicyclic epoxy groups in the molecule and a three-membered cyclic ether bonded to the alicyclic ring in the molecule. An adhesive containing a polyfunctional oxirane resin having no group is disclosed.
In general, an alicyclic epoxy resin has good photocurability but has a high viscosity of 200 mPa · s or more. On the other hand, polyfunctional oxirane resins that do not have a three-membered cyclic ether group bonded to an alicyclic ring are low in photocurability but have a low viscosity of 100 mPa · s or less. Therefore, if the adhesive viscosity is lowered for thin film coating, the content of polyfunctional oxirane resin having no three-membered cyclic ether group bonded to the alicyclic ring must be increased. However, as a result, curability is lowered, and peeling occurs between the PVA polarizer and the protective film when exposed to poor adhesion or exposed to wet heat.
On the other hand, if the curability is to be maintained, the resin having a three-membered cyclic ether group bonded to the alicyclic ring must be increased, resulting in an increase in the viscosity of the adhesive, and as a result, thin film coating cannot be performed.

 Furthermore, when the alicyclic epoxy resin is increased, there is a problem that when a protective film such as a polyester film, a polyvinyl chloride film, a polycarbonate film, or an acrylic film is used, it does not adhere to these protective films at all. there were.

In order to reduce the viscosity of the adhesive, there is a method of diluting with an organic solvent. However, if an organic solvent is used, it is necessary to make the coating equipment explosion-proof or install a special solvent recovery device.
Therefore, a photocurable adhesive for forming a polarizing plate is required to have a low viscosity in a state that does not substantially contain an organic solvent.

JP 2001-324616 A JP 2009-300768 A JP 2007-140092 A JP 2004-245925 A JP 2008-63397 A JP 2008-257199 A

  The present invention is a novel photopolymerizable composition having excellent heat resistance, moisture resistance, thermal dimensional stability, weather resistance, etc., and uses an almost photopolymerizable composition in laminating various optical films. By using the photo-curing adhesive, photo-curing adhesion that can be easily and firmly bonded regardless of the type of various optical films, is substantially free of organic solvents, has low viscosity, and is excellent in thin film coatability. It is an object of the present invention to provide a polarizing plate excellent in punching workability and wet heat durability as compared with a conventional polarizing plate using an agent.

As a result of intensive studies to solve the above problems, the present inventors have found that the above-described target can be achieved by the photopolymerizable composition shown below, and further, the present invention has been completed by the photocurable adhesive composition. It was.
That is, the present invention is a substantially organic solvent containing a three-membered cyclic oxirane compound (A) as a main component and further containing a four-membered or higher cyclic compound (B) having two or more oxygen atoms. It is related with the photopolymerizable composition characterized by the measurement viscosity in 23 degreeC being 1-1500 mPa * s.

In addition, the present invention provides 0.5 to 4-membered cyclic compound (B) having two or more oxygen atoms with respect to 100 parts by weight of the three-membered cyclic oxirane compound (A) as the main component. The photopolymerizable composition is characterized by containing 60 parts by weight.

In the present invention, the cyclic compound (B) having four or more members having two or more oxygen atoms has a cyclic structure of at least one of a lactone ring, a carbonate ring, a dioxolane ring and a dioxane ring. It is related with the said photopolymerizable composition characterized by the above-mentioned.

The present invention also relates to the photopolymerizable composition, wherein the three-membered cyclic oxirane compound (A) comprises a compound (a-1) having an aromatic ring.

The present invention also relates to the photopolymerizable composition, wherein the three-membered cyclic oxirane compound (A) contains a compound (a-2) having two or more three-membered cyclic oxirane rings.

The present invention also relates to a photopolymerizable composition comprising a photopolymerization initiator in the photopolymerizable composition.

In the present invention, the photopolymerization initiator is a salt represented by A + B− that generates an acidic active species by light irradiation, and the cation A + is composed of an aromatic iodonium ion and an aromatic sulfonium ion. The photopolymerizable composition selected from the above.

Moreover, this invention relates to the laminated body formed by adhere | attaching an optical film using the said photopolymerizable composition.

Moreover, this invention relates to the polarizing plate formed by adhere | attaching a protective film on the single side | surface or both surfaces of a polyvinyl-alcohol-type polarizer using the said photopolymerizable composition.

  The present invention also relates to the above polarizing plate, wherein at least one of the protective films of the polarizing plate is an acetyl cellulose film, a norbornene film, an acrylic film, or a polycarbonate film.

  According to the present invention, a photopolymerizable composition that can be polymerized at low illuminance, and a photocurable adhesive composition using the same, an optical film can be easily and firmly bonded, and punching workability, heat resistance, and It became possible to obtain a laminate having good resistance to moisture and heat, and a particularly excellent polarizing plate could be provided.

The photopolymerizable composition of the present invention is characterized by having a three-membered cyclic oxirane compound (A) and a four-membered or higher cyclic compound (B) having two or more oxygen atoms as essential components.
In the photopolymerizable composition of the present invention, the three-membered cyclic oxirane compound (A) is a compound having at least one three-membered cyclic ether group in the molecule as a reactive functional group, and is not particularly limited. Can be used.
Examples of the three-membered cyclic ether group in the molecule include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloro Aliphatic cyclic ether groups such as methyl) oxirane, (bromomethyl) oxirane, and oxiranylacetonitrile;
For example, 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, ethylenebis (3,4-oxirane Cyclohexanecarboxylate), bis (3,4-oxiranecyclohexylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis ( 3,4-oxiranecyclohexyl methyl ether), 2,3,4,15-dioxirane-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] heny Cosane (also a compound that can be named 3,4-oxiranecyclospiro-2 ′, 6′-dioxanespiro-3 ″, 5 ″ -dioxanespiro-3 ′ ″, 4 ′ ″-oxiranecyclohexane), 4- (3,4-oxiranecyclohexyl) -2,6-dioxa-8,9-oxiranespiro [5.5] undecane, 4-vinylcyclohexene dioxide, bis-2,3-oxiranecyclopentyl ether, and dicyclo Examples include three-membered cyclic ether groups bonded to alicyclic rings such as pentadiene dioxide, and other groups in which one or more hydrogen atoms are removed from these three-membered cyclic ether group-containing compounds. A compound bonded to the chemical structure can be a three-membered cyclic oxirane compound (A).

  The oxirane compounds exemplified here may be used alone or in combination with a plurality of oxirane compounds.

  The oxirane equivalent of such a three-membered cyclic oxirane compound (A) is usually 30 to 3000 g / eq, and preferably 50 to 1500 g / eq. When the oxirane equivalent is less than 30 g / eq, the flexibility of the cured optical film may be lowered or the adhesive strength may be lowered. On the other hand, if it exceeds 3000 g / eq, the compatibility with other components may decrease, which is not preferable.

  The three-membered cyclic oxirane compound (A) of the present invention contains an oxirane compound (a-1) having an aromatic ring in addition to the three-membered cyclic ether group in order to improve heat resistance and moist heat resistance. Is preferred. Preferable aromatic ring substituents are more specifically, for example, phenyl, phenylene, tolyl, tolreno, benzyl, benzylidene, benzylidine, xylyl, xylylene, phthalylidene, isophthalylidene, terephthalylidene, phenethylidene, phenethylidine, styryl, styrylidene, as- Pseudocumyl, v-pseudocumyl, s-pseudocumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, cinnamilidene, cinnamiridin, duryl, jurylene, thymyl, carvacryl, cuminyl, cuminylidene, neophyll, xenyl, benzhydryl, benzhydrylden, etc. Substituents represented by benzene, toluene, xylene, styrene, hemimeritene, pseudocumene, mesitylene, Emissions, planing, isodurene, durene, cymene, an aromatic ring can be mentioned one or more forms of group obtained by removing a hydrogen atom in the benzene derivatives such as Meriten can bind to other chemical structures.

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

  Examples thereof include [4n + 2] annulene having a carbon number other than benzene and having 3 or more carbon atoms constituting the ring.

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

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

  For example, as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene, perinaphthene, phenanthrene, phenanthryl, phenanthryllium, phenanthryllidene, Phenanthrylene, phenanthrol, molhole, phenanthrone, phenanthraquinone, pimantrene, reten, anthracene, anthryl, anthryllium, anthrylidene, anthrylene, anthrol, anthranol, anthrorobin, anthralin, dithranol, anthroyl, anthrone, bianthrone, anthraquinone , Anthraquinonyl, anthraquinonylene, alizarin, quinizarin, anthralphine, chrysazine, anthragalo Le, purpurin, flavonol pull pudding, Anne tiger pull pudding, quinalizarin, Tekutokinon, chrysophanol, chrysolite fan acid, emodin, rain, Kermes acid, carmine acid, Jiantorimido, Antorimido, Kurisanmin acid, carbon fused tricyclic ring system, such as colchicine;

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

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

For example, corannulene, fluorene, anthanthrene, zetrene, hexahelicene, hexaphen, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyranthrene, octaphene, octacene, terylene, naphthathenonaphthacene, nonaphene, nonacene, violanthrene, violanthrene, iso A carbon condensed ring system having 6 or more rings such as violanthrene, isoviolanthrone, obalene, decaphene, decacene, decacyclene, pentasenopentacene, quaterrylene, hexasenohexacene;
An aromatic ring in which a group in which one or a plurality of hydrogen atoms in a cyclic compound are removed can be bonded to another chemical structure.

  The three-membered cyclic oxirane compound (A) of the present invention preferably contains a compound (a-2) having two or more three-membered cyclic oxirane rings. By containing a plurality of three-membered oxirane rings, the crosslinkability of the adhesive composition to be described later is improved, and it becomes possible to maintain effective adhesive force, heat resistance, and moist heat resistance.

Here, (a-1) and (a-2) are the same compound, that is, a compound (a-12) having an aromatic ring and having two or more three-membered oxirane rings. Can be used without any problem. The content of these in the three-membered cyclic oxirane compound (A) is 50% by weight of any one of (a-1), (a-2) and (a-12) in 100% by weight of (A). Containing above is preferable from the viewpoints of polymerizability and wet heat resistance, and it is particularly preferable to contain 60% by weight or more.
Further, (a-3) which does not belong to any of (a-1), (a-2) and (a-12) can be used without any problem. These may use only 1 type or may use multiple types together.

  Further, the photopolymerizable composition of the present invention preferably has a cyclic compound (B) having four or more members having two or more oxygen atoms, and (B) is a lactone ring, a carbonate ring, a dioxolane ring, a dioxane. From the viewpoint of photopolymerization, it is preferable to have at least one of the rings.

  The lactone ring-containing cyclic compound (b-1) in the present invention is an oxyacid condensate in which a hydroxyl group of a hydroxycarboxylic acid and a carboxylic acid are dehydrated and condensed in a molecule or between molecules to form a ring structure. Preferably, it may be a dimer or a multimer higher than a trimer. As the hydroxycarboxylic acid, aliphatic, alicyclic, aromatic and heterocyclic compounds can be used.

  Examples of the aliphatic hydroxycarboxylic acid include hydroxyethanoic acid, 2-hydroxypropanoic acid, hydroxypropenoic acid, α-oxybutanoic acid, α-hydroxyisobutanoic acid, hydroxypentanoic acid, α-hydroxyhexanoic acid, and δ-hydroxyhexanoic acid. 2,3-dihydroxypropanoic acid, 2-oxopropanoic acid, hydroxybutanedioic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, hydroxyoctanoic acid, hydroxydodecanoic acid, hydroxy (9Z, 12Z) -octadeca -9,12-dienoic acid, α-hydroxytriacontanoic acid, α-hydroxytetratriacontanoic acid, α-hydroxyhexatriacontanoic acid, α-hydroxyoctatriacontanoic acid, α-hydroxytetraacontanoic acid, hydroxy- 2,2-dimension Rupropanoic acid, hydroxypropanoic acid, 6-hydroxypentanoic acid, α-hydroxyheptanoic acid, 10-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 3-hydroxytetradecanoic acid, 16 -Hydroxyhexadecanoic acid, 15-hydroxypentadecanoic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaicosanoic acid, α -Hydroxytriacontanoic acid, β-hydroxymitetradecanoic acid, 1,3-bis (hydroxymethyl) propanoic acid and the like.

  Examples of the alicyclic, aromatic and heterocyclic hydroxycarboxylic acids include 2-hydroxybenzoic acid, 3,5-di-tert-butyl-2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 3,4- Dihydroxybenzoic acid, 4-hydroxy-3-phenylbenzoic acid, 4-hydroxy-3-methoxybenzoic acid, 4-hydroxy-3,5-dimethoxybenzoic acid, 4'-hydroxy-4-carboxybiphenyl, 6-hydroxy- Examples include 2-naphthalene carboxylic acid, 3-hydroxy-2-naphthalene carboxylic acid, and 5-hydroxy-1-naphthalene carboxylic acid.

  These hydroxycarboxylic acids may be organic compounds having a carboxylic acid and a hydroxyl group in one molecule, and are not limited to the above examples.

  Among the above oxyacid condensates, lactones are preferable from the viewpoint of reactivity. Specifically, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, δ-caprolactone, γ-heptanolactone, γ-octa Nolactone, δ-octanolactone, ε-octanolactone, δ-nonalactone, ε-caprolactone glycolide, pivalolactone, 7-heptanolide, 8-octonolide, 11-undecanolide, 12-dodecanolide, 15-pentadecanolide, 10-oxahexalide Decanolide, 2-nonene-4-olide, 16-hexadodecanolide, 7-decene-4-olide, 9-decene-5-olide, 2-decene-5-olide, 7-decene-5-olide 6-decene-4-olide, 8-decene-5-olide, 8-undecen-5 Lido, 4-methyl-cis-7-decen-4-olide, 2-butene-4-olide, 2-methyl-4-butanolide, 3-methyl-4-octanolide, 3-methyl-4-nonanolide, 4- Methyl-4-decanolide, cyclopentadecalide, 2,4-decadiene-5-olide, 4-methyl-5-hexene-4-olide, pentano-4-lactone, 4-ethenyl-γ-valerolactone, glucurono Lactone, Jasmolactone, Assoy lactone, Mentone lactone, Mint lactone, Masoa lactone, Wine lactone, Panto lactone, Homoserin lactone, Mevalono lactone, Glucono delta lactone, Bergapten, Umbrolito, Sclareolide, α-angelica lactone, β-angelica lactone, 7-decene-1,4-lactone, 9- Decene-5-olide, 2,3-dimethyl-2,4-nonadiene-4-olide, dihydroxyactinidiolide, 5-hydroxy-8-undenesenoic acid-δ-lactone, 2-hydroxy-3,3 -Dimethyl-4-butanolide, 1,4-dioxacycloheptadecane-5,17-dione, α-acetyl-γ-butyrolactone α-methyl-β-propiolactone, β-methyl-α-propiolactone, α, α-dimethyl-β-propiolactone, D-glucono-1,5-lactone, 4-hydroxy-4-methyltetrahydropyran-2-one, phenanthrene-1,10: 9,8-dicarbolactone, 3α-hydroxy-5α-cholano-24,17-lactone and the like.

  In the present invention, as a cyclic dimer of hydroxycarboxylic acid that can be used as the lactone ring-containing cyclic compound (b-1), 3,6-dimethyl-1,4-dioxane-2,5-dione by lactic acid is used. 1,4-dioxane-2,5-dione and the like with glycolic acid.

  Among the lactones, the number of carbon atoms constituting the ester ring is 4 to 18 in terms of the side chain length formed by ring opening and the ring-opening copolymerizability with the three-membered cyclic oxirane compound (A). The range is preferable, and specifically, propiolactone, butyrolactone, valerolactone, and caprolactone are particularly preferable.

As the carbonate ring-containing cyclic compound (b-2) in the present invention, a method of depolymerizing a polymer obtained by reaction of glycol and dialkyl carbonate (see JP-A-2-56356), or a corresponding alkylene oxide and It can be synthesized by the reaction of carbon dioxide. The cyclic carbonate has a 5-membered ring, 6-membered ring or 7-membered ring structure, and specific examples thereof include, for example, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, allyl ethylene carbonate, fluoroethylene carbonate, glycerin carbonate. 5-membered ring carbonates such as allyl succinic anhydride;
For example, 6-membered ring carbonates such as 1,3-propylene carbonate and neopentyl glycol carbonate (which may be named 5,5-dimethyl-1,3-dioxan-2-one);
For example, although 7-membered ring carbonates, such as 1, 4- butanediol carbonate, are mentioned, 5-membered ring carbonates, such as ethylene carbonate, propylene carbonate, and glycerol carbonate, are preferably used at the point of reactivity.

  The dioxolane ring-containing cyclic compound (b-3) in the present invention is obtained by acetalizing carbonyl of ethylene glycol, and more specifically, for example, 1,2-dioxolane, 1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane-4-methanol, (R)-(−)-2,2-dimethyl-1,3-dioxolane-4- Methanol, (+)-4,5-bis [hydroxy (diphenyl) methyl] -2,2-dimethyl-1,3-dioxolane, (4S) -α, α, α ′, α-tetraphenyl-2,2 -Dimethyl-1,3-dioxolane-4α, 5β-dimethanol, 4α, 5β-bis (hydroxydiphenylmethyl) -2,2-dimethyl-1,3-dioxolane, (4S, 5S) -2, 2-dimethyl-α, α, α ′, α′-tetraphenyl-1,3-dioxolane-4,5-dimethanol, 2,2-dimethyl-1,3-dioxolane-4α, 5β-diylbis (diphenylmethanol ), (4S) -2,2-dimethyl-4α, 5β-bis (α-hydroxybenzhydryl) -1,3-dioxolane, α, α, α ′, α′-tetraphenyl-2,2-dimethyl -1,3-dioxolane-4α, 5β-dimethanol, 2,2-dimethyl-α, α, α ′, α′-tetraphenyl-1,3-dioxolane-4α, 5β-dimethanol, (4S, 5S ) -2,2-dimethyl-1,3-dioxolane-4,5-bis (diphenylmethanol) α, α ′-(2,2-dimethyl-1,3-dioxolane-4,5-diyl) bis (α- Phenylbenzyl alcohol), (4S, 5S) -2 2-dimethyl-α, α, α ′, α′-tetraphenyl-1,3-dioxolane-4,5-bis (methanol), 2,2-dimethyl-1,3-dioxolane-4α, 5β-bis ( Diphenylmethanol), (4S) -2,2-dimethyl-4α, 5β-bis (α-hydroxy-α-phenylbenzyl) -1,3-dioxolane, (4S, 5S) -α, α, α ′, α '-Tetraphenyl-2,2-dimethyl-1,3-dioxolane-4α, 5β-dimethanol, [(4S, 5S) -2,2-dimethyl-4,5-dihydro-1,3-dioxole]- 4,5-diylbis (diphenylmethanol), α, α ′-[(4S, 5S) -2,2-dimethyl-1,3-dioxolane-4,5-diyl] bis (α-phenylbenzyl alcohol), α , Α, α ′, α′-tetraphenyl-2,2-dimethyl- 1,3-dioxolane-4,5-dimethanol, α, α, α ′, α′-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4α, 5β-bismethanol, α, α′- (2,2-dimethyl-1,3-dioxolane-4,5-diyl) bis (diphenylmethanol), (4S, 5S) -α, α, α ′, α′-tetraphenyl-2,2-dimethyl- 1,3-dioxolane-4,5-dimethanol, (+)-trans-α ′, α ′-(2,2-dimethyl-1,3-dioxolane-4,5-diyl) bis (diphenylmethanol), 1,1,4,4-tetraphenyl-2-O, 3-O-isopropylidene-D-threitol, [(4S, 5S) -2,2-dimethyl-1,3-dioxolane-4,5- Diyl] bis (diphenylmethanol), (4S) -2,2-dimethyl-4α, 5β- (Hydroxydiphenylmethyl) -1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane-4,5-bis (α ', α'-diphenylmethanol), (4S) -2,2-dimethyl -Α, α, α ', α'-tetraphenyl-1,3-dioxolane-4α, 5β-dimethanol, (4S, 5S) -2,2-dimethyl-4α, 5β-bis (α-hydroxy-α -Phenylbenzyl) -1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane-4α, 5β-bis (α, α'-diphenylmethanol), α, α '-(2,2-dimethyl- 1,3-dioxolane-4α, 5β-diyl) bis (diphenylmethanol) dioxane, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, (2-methyl-2-ethyl- 1,3-dioxolane- -Yl) methyl methacrylate, [cyclohexanespiro-2- (1,3-dioxolan-4-yl)] methyl acrylate, [cyclohexanespiro-2- (1,3-dioxolan-4-yl)] methyl methacrylate, (2 -Methyl-2-oxo-1,3-dioxolan-4-yl) methyl acrylate, (2-methyl-2-oxo-1,3-dioxolan-4-yl) methyl methacrylate and the like.

  Among the dioxolane ring-containing cyclic compounds (b-3), 1,3-dioxolane and (2-methyl-2-ethyl) are preferred from the viewpoint of ring-opening copolymerizability with the three-membered cyclic oxirane compound (A). -1,3-Dioxolan-4-yl) methyl methacrylate is particularly preferred.

  As the dioxane ring-containing cyclic compound (b-4) in the present invention, a method of reacting (poly) ethylene glycol in the presence of a mineral acid such as sulfuric acid or an aromatic sulfonic acid catalyst, sulfuric acid, boron trifluoride, etc. It can synthesize | combine by the method of cyclodimerizing ethylene oxide using the acid catalyst of. More specifically, for example, 1,2-dioxane, 4-acetyl-6-hexyl-3-methyl-1,2-dioxane-3-ol, 4-acetyl-3,4-dimethyl-6,6- Diphenyl-1,2-dioxane-3-ol, 4-acetyl-6-phenyl-3-methyl-1,2-dioxane-3-ol, 6,6-diphenyl-4- (phenylaminocarbonyl) -3- Methyl-1,2-dioxane-3-ol, 6,6-diphenyl-4-benzoyl-3-methyl-1,2-dioxane-3-ol, (3S) -3β, 6αdimethyl-4α, 5β-bis (4-acetoxy-3-methoxyphenyl) -1,2-dioxane, 6,6-diphenyl-4-acetyl-3-methyl-4-ethyl-1,2-dioxane-3-ol, (3S) -4α -Acetyl-6,6 -Diphenyl-3-methyl-1,2-dioxane-3α-ol, (3S) -3-β, 6α-dimethyl-4α, 5β-bis (4-hydroxy-3-methoxyphenyl) -1,2-dioxane, 4-acetyl-6,6-bis (4-methylphenyl) -3-methyl-1,2-dioxane-3-ol, 4-acetyl-6,6-bis (4-chlorophenyl) -3-methyl-1 , 2-Dioxane-3-ol, 4-acetyl-6,6-bis (4-methoxyphenyl) -3-methyl-1,2-dioxan-3-ol, 4-acetyl-6,6-bis (4 -Fluorophenyl) -3-methyl-1,2-dioxane-3-ol, α, 6-dimethyl-6- [4-methyl-6- (2,6,6-trimethyl-1-cyclohexen-1-yl) ) -3-hexenyl] -1,2-dioxane- -Acetic acid, 4-ethyl-6- (2-ethyl-3-hexenyl) -6-methyl-1,2-dioxane-3-methyl acetate, (3R, αR, 6R) -6- [2-[[( 4aR, 8aS) -1,4,4αβ, 7,8,8αβ-Hexahydro-1,1,3,6-tetramethylnaphthalen] -2-yl] ethyl] -α, 6-dimethyl-1,2-dioxane -3-acetic acid, (R) -2-[(3R, 6R) -6β-methyl-6-[[(2S) -2,3,3α, 4,5,9β-hexahydro-3aα, 4α, 7, 9bα-tetramethylnaphtho [1,2-b] furan] -2α-yl] -1,2-dioxane-3β-yl] methyl propionate, (2S) -2-[(3S, 6S) -6- [ 2-[(1S, 2R, 4aα, 8αβ) -Decahydro-1,2α, 4a-trimethyl-5-methylenenaphthalen-1β-yl] ethyl] -6-methyl 1,2-dioxane-3-yl] propanoic acid, (R) -2-[(3R, 6S) -6β-methyl-6- [2-[[(2R, 4aβ, 8aβ) -decahydro-1,1 -1,2-dioxane derivatives such as -dimethyl-3,6-dimethylenenaphthalene] -2α-yl] ethyl] -1,2-dioxane-3β-yl] propionic acid;

  For example, 1,3-dioxane, 2,4-diphenyl-1,3-dioxane, 5-hydroxy-1,3-dioxane, 2-cyclohexyl-1,3-dioxane, 1,3-dioxane-2-one, 2α, 4α-dimethyl-1,3-dioxane, 5,6-dimethyl-1,3-dioxane, 5,5-diethyl-1,3-dioxane, 4,6-dibutyl-1,3-dioxane, 2- Ethyl-1,3-dioxane, 2-methylene-1,3-dioxane, 4,6-dimethyl-1,3-dioxane, 2,2-diphenoxy-1,3-dioxane, 2,2,4-trimethyl- 1,3-dioxane, 5,5-difluoro-1,3-dioxane, 2α-tert-butyl-4α-methyl-1,3-dioxane, 2-phenyl-4-methyl-1,3-dioxane, 4- Methyl 4-phenyl-1,3-dioxane, 4,6-dimethyl-2-methylene-1,3-dioxane, 4,5,5-trimethyl-1,3-dioxane, 4,6-dineopentyl-1,3- Dioxane, 2-ethyl-5-methyl-1,3-dioxane, 2,5-dimethyl-5-phenyl-1,3-dioxane, 2-pentadecyl-1,3-dioxane, 2-hexyl-1,3- Dioxane, 2-butyl 2,5,5-trimethyl-1,3-dioxane, 5- (1-methylethyl) -1,3-dioxane, 2-phenyl-2-benzoyl-1,3-dioxane, 4- Phenyl-1,3-dioxane-2-one, 2,4,4,6-tetramethyl-1,3-dioxane, 2α, 4α, 5α-trimethyl-1,3-dioxane, 2α-hexyl-1,3 -Dioxane -5β-ol, 5,5-dimethyl-2-vinyl-1,3-dioxane, 4- (1-methylethenyl) -1,3-dioxane, 2-methyl-1,3-dioxane-2- (1- Propanol), 4,5-dimethyl-1,3-dioxane-5-methanol, 4,5-dimethyl-1,3-dioxane-4-methanol, 4,4,5-trimethyl-1,3-dioxane-5 -Ol, 5-ethyl-2- (2-furyl) -4-propyl-1,3-dioxane, 5,5'-spirobi [1,3-dioxane], 4-methyl-1,3-dioxane, 2 , 2-Dimethyl-5-phenyl-1,3-dioxane-4,6-dione, 3,3-dimethyl-1,5-dioxaspiro [5,5] undecan-9-one, 2- (1,3- Dioxane-2-yl) ethyltriphenylphosphoni Mubromide, 2,2-dimethyl-5-methyl-1,3-dioxane-4,6-dione, 4-phenyl-1,3-dioxane, 5,5-dimethyl-1,3-dioxane-2-one, 5-bromo-2,2,5-trimethyl-1,3-dioxane-4,6-dione, 5-propyl-2- [2- (4-trifluoromethylphenyl) ethyl] -1,3-dioxane, 5-propyl-2- [4- (3,4,5-trifluorophenyl) cyclohexyl] -1,3-dioxane, 5-propyl-2- [4- (3,5-difluorophenyl) ethyl] -1 , 3-dioxane, 5-propyl-2- [4- (3-fluoro-4-trifluoromethoxyphenyl) cyclohexyl] -1,3-dioxane, 5-propyl-2- [4- (4-trifluoromethyl) Phenyl) butyl] -1,3-dioxane, 5-propyl-2- [4- (3,5-difluorophenyl) cyclohexyl] -1,3-dioxane, 5-propyl-2- [4- {4- (3-fluoro- 4-chlorophenyl) -3,5-difluorophenyl} cyclohexyl] -1,3-dioxane, 4- (5-pentyl-1,3-dioxan-2-ylcyclohexane) carboxylic acid, 4- [5-pentyl- ( 1,3-dioxane) -2-yl] -cyclohexanecarboxylic acid 3,4,5-trifluorophenyl ester, 1- [2- (1,3-dioxan-2-yl) ethyl] cyclohexyl-3,4, 5-trifluorobenzene, 1- [2- (5-propyl-1,3-dioxan-2-yl) ethyl] cyclohexyl-3,4,5-trifluorobenzene, (Z) -6-(-2- (2-chlorophenyl) -4- (2-hydroxyphenyl) -1,3-dioxan-5-yl) hex-4-enoic acid, (Z) -6-(-2- [4-methoxyphenoxy-o- Phenyl] -4-o-hydroxyphenyl-1,3-dioxane-cis-5-yl) hex-4-enoic acid], (Z) -6- (2-3- [6-chloro-4H-chromene- 4-one 6-chloro-4-oxo-4H-chromen-3-yl] -4- (2-hydroxyphenyl-1,3-dioxane-cis-5-yl) hex-4-enoic acid, (Z) -6-((2R, 4R, 5S) -2- (2-chlorophenyl) -4- (2-hydroxyphenyl) -1,3-dioxan-5-yl) hex-4-enoic acid, (Z)- 6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- 2-methoxyphenyl) -1,3-dioxan-5-yl) hex-4-enoic acid, (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- (2 -Acetoxyphenyl) -1,3-dioxan-5-yl) hex-4-enoic acid, methyl- (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- ( 2-hydroxyphenyl) -1,3-dioxan-5-yl) hex-4-enoate, (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- (2- Hydroxyphenyl) -1,3-dioxan-5-yl) hex-4-enoatemethyl, (Z) -6-((2S, 4S, 5R) -4- (2-acetoxyphenyl) -2- (2) -Chlorophenyl) -1,3-dioxane-5-yl) hex 1,3-dioxane derivatives such as 4-enoic acid;

  For example, 1,4-dioxane, 1,4-dioxane-2,3-dithione, 2,5-dimethyl-1,4-dioxane, 5α, 6α-dimethyl-1,4-dioxane-2-one, 2, 5-divinyl-1,4-dioxane, 2,2′-bi (1,4-dioxane), 2,2,3,3,5,6,6-heptachloro-1,4-dioxane, methylene-1, 4-dioxane, (2R, 3S) -2,3-dichloro-1,4-dioxane, 2-methyl-3-methylene-1,4-dioxane, 2,5-dimethyl-3-methylene-1,4- Dioxane, 2-ethyl-5-methyl-1,4-dioxane, 3,6-diethyl-1,4-dioxane-2,5-dione, 2,6-dimethyl-1,4-dioxane, 2-methyl- 1,4-dioxane-2,3-diol, 2- (2-furanyl) -1, 4-dioxane, 3,6-diisobutyl-1,4-dioxane-2,5-dione, 2,2,3,3,5,6-hexafluoro-5,6-dichloro-1,4-dioxane, 2 , 3-bis (oxiranylmethyl) -1,4-dioxane, 1,4-dioxane-2-yl hydroperoxide, 3,6-dipropyl-1,4-dioxane-2,5-dione, 2,5 , 6-trimethyl-1,4-dioxane-2,3-diol, 2,3,3-trifluoro-2- (trifluoromethyl) -1,4-dioxane, 5,6-dimethyl-1,4- Dioxane-2,3-diol, 2-[(tetrahydro-2H-pyran) -2-ylmethyl]-1,4-dioxane, (1,4-dioxane-2-yl) methyl acetate, 2,2,3 , 3-Tetrafluoro-5,5,6,6-tetrac B-1,4-dioxane, 1,4-dioxane-2,6-dimethanol, 2- (1,4-dioxane-2-yl) -1,4-naphthoquinone, 1,4-dioxane-2,5 -Bismethanol, N, N'-bis (benzyloxy) -1,4-dioxane-2,5-diimine, 3,6-bis [(trimethylsilyl) oxy] -1,4-dioxane-2,5-dione , -2,3,3-trifluoro 5,5,6,6-tetrachloro-2- (trifluoromethyl) -1,4-dioxane, 2,3-epoxy-2,3,5,5,6 -Pentafluoro-6- (trifluoromethyl) -1,4-dioxane, 2,2 '-(3,6-dimethoxy-1,4-dioxane-2,5-diylidene) diacetate dimethyl, bis [morpholine- 4- (dithioformic acid)], 1,4-dioxane-2α, 3β-diyl, , 5-bis (chloromethyl) -1,4-dioxane, 3,3-dichloro-5- (1-methylpropoxy) -1,4-dioxane-2-one, 2,5-dimethyl-1,4- Dioxane, 2- (2-fluoro-2-phenylsulfonylethyl) -1,4-dioxane, 2,3,3,5,6-pentafluoro-2- (trifluoromethyl) -5,6-dichloro-1 , 4-dioxane, (2H8) -1,4-dioxane, trans-2,3-dichloro-1,4-dioxane, 2- [3- (3,3-dimethyl-2-isopropyloxiranyl) -1 -Methylene-2-propynyl] -1,4-dioxane, 2,5-dihydroxy-3,6-dimethyl-3,6-diphosphono-2,5-diphospha (V) -1,4-dioxane-2,5 -Dione, N, N '-[(1,4-dioxane-2,5-diyl) bi (Methylene)] bis [N- (carboxymethyl) glycine], (3S, 5R) -3α-isopropyl-5α-[(2S) -1- [butoxycarbonyl] pyrrolidin-2-yl] -6-[(E ) -Bromomethylene] -1,4-dioxane-2-one, 3,5,5,6-tetrafluoro-3,6-bis (trifluoromethyl) -1,4-dioxane-2-one, 2, 2,3,5,6-pentafluoro-5- (pentafluoroethoxy) -3,6-bis (trifluoromethyl) -1,4-dioxane, (3S, 5S) -3α-isopropyl-5β-[( 2S) -1- [butoxycarbonyl] pyrrolidin-2-yl] -6-[(E) -bromomethylene] -1,4-dioxan-2-one, (3S, 5S) -3α-isopropyl-5β- [ (2S) -1- [butoxycarbonyl] pyrrolidin-2-yl] -6-methylene-1,4- Oxan-2-one, 3,3,6,6-tetramethyl-1,4-dioxane-2,5-dione, [(2S, 3R) -1,4-dioxane-2,3-diyl] bis (Thio) bis (thiophosphonic acid O, O-diethyl), α-[(3,3-dimethyl-2-isopropyloxiranyl) ethynyl] -α-methyl-1,4-dioxane-2-methanol, 2, 3-dichloro-p-dioxane, 3,6-bis (methylmercuric acetate) -1,4-dioxane, 1,4-dioxane-2-one, (3S, 5S) -3α-isopropyl-5α-[( 2S) -1- [N- (4-methoxy-1,4-dioxobutyl) -L-Ala-L-Ala-] pyrrolidin-2-yl] -6-methylene-1,4-dioxane-2-one, 5-methoxy-1,4-dioxacyclohexane, 2,2,3,5,6-pentafluoro -5-[(trifluoroethenyl) oxy] -3,6-bis (trifluoromethyl) -1,4-dioxane, 2,3,5,6-tetramethyl-1,4-dioxane-2,5- Diol, (3S, 5S) -3α-Isopropyl-5β-[(2S) -1- [N- (4-methoxy-1,4-dioxobutyl) -L-Ala-L-Ala-] pyrrolidin-2-yl ] -6-methylene-1,4-dioxan-2-one, 1,1,1,2,4,5,5,5-octafluoro-2,4-bis [[2,3,5,5, 6-pentafluoro-3,6-bis (trifluoromethyl) -1,4-dioxane-2-yl] oxy] -3-pentanone, 1,3-dihydroxyacetone (dimer), 1,4-dioxane-2α , 5β-diol, 1,4-dioxane-2,3-diol, 1,4-dioxane- , 5-dione, [(1,4-dioxane-2,3-diyl) Bisuchio] bis (thiophosphonate O, O-diethyl) 1,4-dioxane derivatives such as and the like.

Among the dioxane ring-containing cyclic compounds (b-4), 1,2-dioxane, 1,3-dioxane, 1, from the viewpoint of ring-opening copolymerization with the three-membered cyclic oxirane compound (A). 4-dioxane and 1,3-dioxane-2-one are particularly preferred.
These cyclic compounds (B) having four or more members having two or more oxygen atoms may be used alone or in combination of two or more.

  In the photopolymerizable composition of the present invention, the cyclic compound (B) having at least four members having two or more oxygen atoms is based on 100 parts by weight of the three-membered cyclic oxirane compound (A) as the main component. It is preferable to contain (B) in the range of 0.5 to 60 parts by weight, and more preferably in the range of 5 to 30 parts by weight. When the amount of the four-membered or higher cyclic compound (B) having two or more oxygen atoms is less than 0.5 parts by weight, the polymerization rate of the three-membered cyclic oxirane compound (A) is improved upon photopolymerization. And the cohesive strength does not increase, and it is difficult to obtain an effective crosslinked coating film. On the other hand, when the amount exceeds 60 parts by weight, when the polymerizable composition is used as a photocurable adhesive, the polarity of the cross-linked coating film becomes too large, resulting in a nonpolar optical film (polyester film, norbornene film). Etc.), it is not preferable.

  In the photopolymerizable composition of the present invention, the three-membered cyclic oxirane compound (A) has a viscosity of 200 mPa · s or more (23 ° C. measured viscosity), and the viscosity of the compound (a-1) having an aromatic ring. Are mostly 5000 mPa · s or more, and many are solid.

The photopolymerizable composition of the present invention comprises a photopolymerizable composition comprising a photopolymerizable component other than the three-membered cyclic oxirane compound (A) and a four-membered or higher cyclic compound (B) having two or more oxygen atoms. It is also possible to include it in the range of 50 wt% or less in 100 wt% of the product.
As a photopolymerizable component other than (A) and (B), an ethylenically unsaturated compound (C) is preferably included. The ethylenically unsaturated compound (C) is a compound having an unsaturated double bond in the molecular structure. As an ethylenically unsaturated compound (C), a thing with a viscosity of 0.5-2000 mPa * s (23 degreeC measurement viscosity) is preferable, and the thing of 1-1000 mPa * s is preferable. By using such an ethylenically unsaturated compound (C), the aromatic ring (a-1), the compound (a-2) having two or more oxirane rings, and both (a-12) are included. While suppressing the increase in viscosity of the resulting photopolymerizable composition and improving thin film coatability, it is possible to maintain the photopolymerizability and maintain the adhesive force and workability of the adhesive described later.

  The ethylenically unsaturated compound (C) has a hydroxyl group-containing ethylenically unsaturated compound (c-1) and / or a cycloalkane skeleton and / or a cycloalkene skeleton in consideration of adhesion to an optical film. It is preferable that it is an ethylenically unsaturated compound (c-2).

  The hydroxyl group-containing ethylenically unsaturated compound (c-1) is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate [2-hydroxyacrylate] Ethyl and 2-hydroxyethyl methacrylate are collectively referred to as “(meth) acrylic acid 2-hydroxyethyl”. The same applies hereinafter. ], 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxy (meth) acrylate Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy (meth) acrylate Decyl, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) acrylate glycerol, or (meth) acrylate glycidyl laurate, (meth) acryl Acid glycidyl oleate, (meth) acte Fatty acid ester (meth) acrylic acid esters such as glycidyl stearate ester, polylactone (meth) acrylic acid esters having a hydroxyl group at the terminal by ring-opening addition of a lactone ring, or alkylene oxides such as ethylene oxide and propylene oxide A hydroxyl group-containing aliphatic (meth) acrylic acid ester such as an alkylene oxide addition system (meth) acrylic acid ester having a hydroxyl group at the terminal repeatedly added, or (meth) acrylic acid 2-hydroxyethyl phosphate;

  For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid cyclohexyl glycidyl ether, (Meth) acrylic acid phenylglycidyl ether, (meth) acrylic acid 2-hydroxy-3-phenoxymethyl, (meth) acrylic acid 2-hydroxy-3-phenoxyethyl, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl , 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxy (meth) acrylate Ethyl phthalate, (me ) 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2- Hydroxyl-containing alicyclic or aromatic (meth) acrylic acid esters such as hydroxypropyl) benzene;

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) Hydroxyl groups such as acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole Containing benzotriazole-based (meth) acrylic acid esters;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl group-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxy Ethoxy}]-S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-hydroxyl group such as S-triazine Containing triazine-based (meth) acrylic acid esters;

  For example, glucose ring system (meth) acrylate esters such as glycosyl methyl (meth) acrylate, glycosyl ethyl (meth) acrylate, glycosyl propyl (meth) acrylate, glycosyl butyl (meth) acrylate;

  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, 1,2-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 2-hydroxy-3-phenoxymethyl monovinyl ether, 2-hydroxy-3-phenoxy Ethyl monovinyl ether, 2-hydroxy-3-phenoxypropyl monovinyl ether, 2-hydroxy-3-phenoxybutyl monovinyl ether, 2-hydroxy-3-phenoxydecyl monovinyl ether, 2-hydroxy-3-phenoxyoctadecyl monovinyl ether, 2- Vinyl ethers having a hydroxyl group-containing alicyclic or aromatic ring such as (4-benzoyl-3-hydroxyphenoxy) ethyl monovinyl ether;

  For example, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 2-methyl-3- Hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4, Hydroxyl group-containing aromatic vinyl compounds such as 6-trihydroxystyrene and 2-hydroxy-6-vinylnaphthalene;

  For example, (meth) allyl alcohol [allyl alcohol and methallyl alcohol are collectively referred to as “(meth) allyl alcohol”. The same applies hereinafter. ], 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 an alkylene oxide such as ethylene oxide or propylene oxide repeatedly added to the terminal Hydroxyl group-containing aliphatic (meth) allyl alcohols or (meth) allylate such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group Kind;

  For example, 1,2-cyclohexanedimethanol mono (meth) allyl ether, 1,3-cyclohexanedimethanol mono (meth) allyl ether, 1,4-cyclohexanedimethanol mono (meth) allyl ether, o- (meth) allyl Phenol, m- (meth) allylphenol, p- (meth) allylphenol, 2-hydroxy-3-phenoxymethyl mono (meth) allyl ether, 2-hydroxy-3-phenoxyethyl mono (meth) allyl ether, 2- Hydroxy-3-phenoxypropyl mono (meth) allyl ether, 2-hydroxy-3-phenoxybutyl mono (meth) allyl ether, 2-hydroxy-3-phenoxydecyl mono (meth) allyl ether, 2-hydroxy-3-phenoxy Octadecyl mono (meth) allyl Ether, 2- (4-benzoyl-3-hydroxyphenoxy) Echirumono (meth) having an alicyclic or aromatic ring of the hydroxyl group-containing and allyl ether (meth) allyl ethers;

  For example, ethylenically unsaturated monomers having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, glycerol di (meth) acrylate, and o-di (meth) allylbisphenol A;

  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 hereinafter. ], 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 alkenyl group such as hydroxystyrene and vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  The ethylenically unsaturated compound (c-2) having a cycloalkane skeleton and / or a cycloalkene skeleton is a polymerizable functional group having a cycloalkane skeleton and / or a cycloalkene skeleton and one or more ethylenically unsaturated double bonds. The cycloalkene skeleton and / or the cycloalkene skeleton having two or more ring structures may be separated from each other by an alkyl group, an ether group, an ester group, or the like, A cyclo-bridged structure such as a norbornene or adamantane structure may be used, but a norbornane, norbornene or adamantane skeleton is preferred because of its excellent heat resistance.

More specific examples of the ethylenically unsaturated compound (c-2) having a cycloalkane skeleton and / or a cycloalkene skeleton include, for example, cyclohexyl (meth) acrylate and 1-methyl-1-cyclopentyl (meth) acrylate. 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1 (meth) acrylate -Cyclohexyl, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, iso-bonyl (meth) acrylate, (meth) acryl Acid phenyl, (meth) acrylic acid 2-phenoxyethyl, (meth) acrylic acid -Oxo-1,2-phenylethyl, 2-oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, (meth) acrylic acid 1 -Naphthylmethyl, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyl (meth) acrylate Adamantyl-2-yl, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, (Meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl, (meth) acrylic acid 1- (adamantane-1- L) -1-ethylethyl, 1- (adamantan-1-yl) -1-methylpropyl (meth) acrylate, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) Acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2. 1.0 ^3,8 ] dec-2-yl, dihydro-α-terpinyl (meth) acrylate, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2- (Meth) acrylic acid cyclic esters such as yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl;

  For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 3-allyladamantan-1-ol, 1-allyladamantane-containing cyclic Compounds.

  Further, for example, hydrogenated bisphenol A having a hydrogenated aromatic ring structure is included in (C-2) if it has an ethylenically unsaturated double bond. These may use only 1 type or may use multiple types together.

  In the photopolymerizable composition of the present invention, as described above, when the ethylenically unsaturated compound (C) is contained, it can be contained in 50% by weight or less in 100% by weight of the photopolymerizable composition. . If (C) exceeds 50% by weight, the unreacted ethylenically unsaturated compound (C) may remain, so the polymerization rate does not improve, the cohesive strength does not improve, and odor may be generated. This is not preferable.

In this invention, it can be set as a photocurable adhesive composition by containing a photoinitiator (D) in the said photopolymerizable composition.
Although said photoinitiator (D) is a salt represented by A + B- which generate | occur | produces an acidic active species by light irradiation, Comprising: Although it does not specifically limit, Generally onium salt is known well. Examples of onium salts include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, and the like. In the present invention, the cation A + is preferably an aromatic iodonium ion and / or an aromatic sulfonium ion.

  Examples of the photopolymerization initiator (D) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by Sun Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 ( Iodonium salts such as Rp-2074 (manufactured by Rhodia Japan Co., Ltd.) and the like may be mentioned, but are not limited thereto.

Moreover, as a photoinitiator (D), it is also possible to have a radical photopolymerization initiator. Examples of such photo radical polymerization initiators include Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (2,4,6-trimethylbenzoyl manufactured by Ciba Specialty Chemicals). -Diphenyl-phosphine oxide), Darocur-1173 (manufactured by Merck & Co., Inc.), Ezacure KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI, (manufactured by Nippon Kayaku Co., Ltd.) and the like.
The blending ratio of the photopolymerization initiator (D) is 0.5 to 20 parts by weight and preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the photopolymerizable composition.

  Furthermore, in order to improve the performance of the photopolymerization initiator (D), a photosensitizer (E) may be used in combination. Examples of the photosensitizer include anthracene series, benzophenone series, thioxanthone series, perylene, phenothiazine, and rose bengal.

The photocurable adhesive composition in the present invention may further contain an antioxidant (F). By containing the antioxidant (F), coloring of the adhesive layer after photocuring with time can be suppressed.
Examples of the antioxidant (F) include phenolic antioxidants such as ADK STAB AO-50 and ADK STAB AO-80 (Asahi Denka Kogyo), IRGANOX-PS-800FD (Ciba Specialty Chemicals), Sulfur-based antioxidants such as TINUBIN 622LD, TINUBIN 144, and TINUBIN 765, but are not limited thereto.
The mixture ratio of antioxidant (F) is 0-5 weight part with respect to 100 weight part of polymeric components, and it is preferable that it is 0.01-3 weight part.

  The photocurable adhesive composition of the present invention contains substantially no organic solvent. Although it is preferable not to contain any organic solvent, the photopolymerization initiator (D) is often poorly soluble in the polymerizable component. Therefore, a small amount of an organic solvent may be contained in order to dissolve the photopolymerization initiator (D). The content of the organic solvent in the photocurable adhesive composition is within 5% by weight.

  The photocurable adhesive composition of the present invention is a polymerizable monomer or oligomer, a silane coupling agent, a polymerization inhibitor, a softening agent, a dye, a pigment, or an antifoaming agent as long as the effects of the present invention are not impaired. Various known additives such as tackifiers, plasticizers, fillers and anti-aging agents can be included within the range that does not impair the effects of the present invention, if necessary.

The photocurable adhesive composition in the present invention preferably contains substantially no organic solvent, and it is important that the measured viscosity at 23 ° C. is 1-1500 mPa · s, preferably 10-1300 mPa · s. It is more preferable that it is 20-1000 mPa * s. When the viscosity is higher than 1500 mPa · s, when the protective film is applied, a thin film of 0.1 to 6 μm cannot be applied, and optical characteristics such as transmittance are deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it is difficult to control the thickness of the adhesive layer.
Since the viscosity of the photocurable adhesive composition is almost determined by the viscosity of the photopolymerizable composition, by controlling the viscosity of the photopolymerizable composition in the range of 1 to 1500 mPa · s, photocurable adhesive The viscosity of the agent composition can also be controlled.

A photocurable adhesive layer can be formed on the optical film by applying the photocurable adhesive composition to the optical film by an appropriate method according to a conventional method.
The thickness of the photocurable adhesive layer is preferably 0.1 to 6 μm, and more preferably 0.1 to 3 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if it exceeds 6 μm, characteristics such as adhesive strength are often not improved further.

  The method for applying the photocurable adhesive composition of the present invention to an optical film or the like is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater, Various coating methods such as a comma coater, knife coater, reverse coater, spin coater and the like can be mentioned, but there is no particular limitation as long as thin film coating is possible.

The photocurable adhesive composition of the present invention is further suitable as a photocurable adhesive composition for optics. That is, it is preferably used for forming a laminate comprising an optical film as a film-like substrate and an adhesive layer located on at least one surface of the optical film.
The laminate of the optical film of the present invention can be obtained as follows.
An optical photocurable adhesive composition is applied to one side of an optical film that is a film-like substrate, and another optical film is laminated on the surface of the photocurable adhesive layer. An optical laminate can be obtained by applying an optical photocurable adhesive composition on both sides and further laminating it on another optical film, glass, or optical molded body.
The photo-curing reaction of the optical photo-curable adhesive composition proceeds when the optical photo-curable adhesive composition is applied or laminated, and further after irradiation with active energy rays. It is preferable to advance the photocuring reaction by irradiating active energy rays after the lamination.

Here, the optical photocurable adhesive composition and the optical laminate are generally described.
The photocurable adhesive composition is used for forming an optical laminate.
The basic laminate structure of the optical laminate is film-like substrate / photocurable adhesive layer / film-like substrate, or film-like substrate / photocurable adhesive layer / film-like substrate / photocurable adhesive layer / It is a sheet-like double-sided photosensitive curable adhesive laminate such as a film-like substrate. Further, film-like substrate / photo-curable adhesive layer / film-like substrate / photo-curable adhesive layer / film-like substrate / photo-curable adhesive layer / film-like substrate, glass, or optical molded body It is used as an optical laminate in which a multilayer optical film is fixed to an optical member.

  Examples of the film-like substrate include cellophane, various plastic films, and film-like substrates such as paper. Moreover, as a film-form base material, the thing of a single layer may be used, and the thing in the multilayer state formed by laminating | stacking a some base material can also be used.

  Various plastic films used as a film-like substrate are also referred to as various plastic sheets. For example, polyolefin-based films such as polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer. Film, Polyester film such as polyethylene terephthalate and polybutylene terephthalate, Polycarbonate film, Polynorbornene film, Polyarylate film, Acrylic film, Polyphenylene sulfide film, Polystyrene film, Vinyl film, Polyamide film, Polyimide And oxirane films.

As the optical laminate in the present invention, among the above-mentioned various plastic films, optical films mainly used for optical applications are preferably used. As an optical film, the above-mentioned plastic film is subjected to a special treatment, and an optical film having optical functions (functions such as light transmission, light diffusion, light collection, refraction, scattering, and HAZE) is an optical film. It is called. These optical films are used alone or several optical films are laminated in layers with an adhesive and used as an optical laminate. For example, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness enhancement film, a prism film (also referred to as a prism sheet), a light guide film (also referred to as a light guide plate), and the like can be given.
A polarizing film is also referred to as a polarizing plate, and is a triacetyl cellulose protective film (hereinafter referred to as “TAC film”) that is two acetyl cellulose films on both sides of a polyvinyl alcohol polarizer, or a polyvinyl alcohol polarizer. It is a multilayered sheet-like optical laminate in which one side or both sides are sandwiched by a cycloolefin film, an acrylic film, a polycarbonate film or the like, which is a norbornene film.

  The laminated body of the optical film using the photocurable adhesive composition of the present invention is optically bonded to a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, or an organic EL module or the above-mentioned various plastic films. It is preferably used as a laminate.

More specifically, the polarizing plate of the present invention can be obtained as follows.
(I) A photocurable adhesive composition is applied to one surface of the first protective film to form a first curable adhesive layer (2 ′),
On one surface of the second protective film, a photocurable adhesive composition is applied to form a second photocurable adhesive layer,
Next, the first photocurable adhesive layer and the second curable adhesive layer are simultaneously and / or sequentially laminated on each surface of the polyvinyl alcohol polarizer, and then irradiated with active energy rays. A method of manufacturing by curing the first curable adhesive layer and the second photocurable adhesive layer.

(II) A first photocurable adhesive formed by applying a photocurable adhesive composition to one surface of a polyvinyl alcohol-based polarizer to form a first photocurable adhesive layer. Cover the surface of the layer with the first protective film, then apply the photo-curable adhesive composition to the other surface of the polyvinyl alcohol-based polarizer to form the second photo-curable adhesive layer The surface of the second photocurable adhesive layer thus formed is covered with a second protective film, irradiated with active energy rays, and the first photocurable adhesive layer and the second photocurable adhesive layer are cured. The method of manufacturing by doing.

(III) Photo-curing property at the end of the first protective film and the end of the second protective film superimposed on the surface where the first protective film of the polyvinyl alcohol-based polarizer is not provided. After dripping the adhesive composition, it is passed between rolls to spread the adhesive between the layers. Next, there is a method of producing by irradiating active energy rays and curing the photocurable adhesive composition, but it is not particularly limited.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.

[Composition Examples 1-27]
In a light-shielded 300 cc mayonnaise bottle substituted with an oxygen concentration of 10% or less, a three-membered cyclic oxirane compound (A), a four-membered or higher cyclic compound (B) having two or more oxygen atoms, and light The polymerization initiator (D) was charged at the ratio shown in Table 1, and sufficiently stirred with an air motor and sufficiently defoamed, and then the photocurable adhesive composition shown in the formulation example was obtained.

  About the photocurable adhesive composition of the formulation example shown in Table 1, solution external appearance and a viscosity were calculated | required according to the following method, and the result was shown in Table 2.

"appearance"
The liquid appearance of the photocurable adhesive composition obtained in each formulation example was visually evaluated.

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

In the present invention, a three-membered oxirane compound (A), a four-membered or higher cyclic compound (B) having two or more oxygen atoms, an ethylenically unsaturated compound (C), a photopolymerization initiator (D), As representative examples of the sensitizer (E) and the antioxidant (F), exemplary compounds are specifically shown in Table 1 below, but are not limited thereto. In addition, EX141 (a-1): Phenoxymethyloxolane (manufactured by Nagase Chemtech), EX212 (a-2): (1,6-hexyleneglycoxymethyl)) dioxirane (Nagasechem) Tech), 2021P (a-2): 3,4-oxiranecyclohexylmethyl-3,4-oxirane cyclohexanecarboxylate (Daicel Chemical Industries), JER828 (a-12): bisphenol A type oxirane resin (Mitsubishi) Chemicals), EX201 (a-12): (resorcinoyloxymethyl) dioxirane (manufactured by Nagase Chemtech), EX121 (a-3): 2-ethylhexinoylmethyloxirane, PL (b-1) : Β-propiolactone, BL (b-1): γ-butyrolactone, EC (b-2): ethylene car Bonate, PC (b-2): propylene carbonate, 13DOL (b-3): 1,3-dioxolane, MEDOL (b-3): (2-methyl-2-ethyl-1,3-dioxolan-4-yl ) Methyl acrylate, 14DOX (b-4): 1,4-dioxane, 13DOXO (b-4): 1,3-dioxane-2-one, 4HBA (c-1): 4-hydroxybutyl acrylate, IBOA ( c-2): Isobonyl acrylate, CP110P (D): p-phenylthiophenyldiphenylsulfonium PF ₆ salt, IRG250: IRGACURE250 (manufactured by Ciba Specialty Chemicals), DET-X (E): 2,4-diethyl Thioxanthone, AO-50 (F): Stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) pro It shows the onato.

[Example 1]
The following laminated body was created using the photocurable adhesive composition obtained in Formulation Example 1.
As the protective film (1), an ultraviolet absorber-containing triacetyl cellulose film manufactured by Fuji Film Co., Ltd .: trade name “Fujitack: 80 μm” is used, and as the protective film (2), an ultraviolet absorber manufactured by Fuji Film Business Supply Co., Ltd. is used. Uncontained triacetyl cellulose film: The product name “TAC50μ” (thickness 50 μm) is used, each surface is subjected to corona treatment with a discharge amount of 300 W · min / m ² , and within 1 hour after the surface treatment, the formulation example The photocurable adhesive composition shown in 1 is applied using a wire bar coater so as to have a film thickness of 4 μm, a photocurable adhesive layer is formed, and the above described photocurable adhesive layer is the above-mentioned The protective film (1) / curable adhesive layer / PVA polarizer / curable adhesive layer / protective film (2) To obtain a laminated body composed.
Four sides of this laminate were fixed with cellophane tape so that the protective film (1) was in contact with the tin plate, and was fixed to the tin plate.
A polarizing plate was produced by irradiating ultraviolet rays having a maximum illuminance of 300 mW / cm ² and an integrated light quantity of 300 mJ / cm ² from the protective film (2) side with a UV irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation).

[Comparative Example 1]
The photocurable adhesive shown in Formulation Example 20 in which a cyclic compound (B) having four or more membered oxygen atoms is not used in place of the photocurable adhesive composition (Formulation Example 1) in Example 1. A polarizing plate was produced in the same manner as in Example 1 except that the composition was changed to the agent composition.

[Comparative Example 2]
Except having changed into the photocurable adhesive composition shown in the compounding example 27 which does not use a three-membered cyclic | annular oxirane compound (A) instead of a photocurable adhesive composition (formulation example 1) in Example 1, A polarizing plate was produced in the same manner as in Example 1.

[Examples 2 to 25]
Instead of the photocurable adhesive composition (Formulation Example 1) in Example 1, a polarizing plate was prepared in the same manner as in Example 1 except that it was changed to Formulation Examples 2 to 19 and 21 to 27 as shown in Table 1. Was made.

[Examples 26 to 28]
The protective film (2) used in Example 3 was replaced with a norbornene film (trade name “Zeonor ZF-14: 100 μm” manufactured by Nippon Zeon Co., Ltd. (Example 26)), an acrylic film (trade name manufactured by Mitsubishi Rayon Co., Ltd.). Except for changing to “HDB-002: 50 μm”) (Example 27) and Kaneka's polycarbonate film (trade name “R-140: 43 μm” (Example 28)), the same as Example 1 A polarizing plate was obtained and evaluated in the same manner.

[Examples 29 to 31]
The protective film (1) used in Example 3 was replaced with a polypropylene film (trade name “OPU-1: 50 μm” manufactured by Tosero Co., Ltd. (Example 29), a polyethylene film manufactured by Tosero Co., Ltd. (trade name “TUX-”). HZ: 50 μm ”) (Example 30), unitary polyester film (trade name“ Embret S: 50 μm ”(Example 31)), except that the respective changes were made in the same manner as in Example 1. Plates were obtained and evaluated similarly.

  For the laminates (polarizing plates) obtained in the examples and comparative examples, the peel strength, gel fraction, punching workability, and heat and humidity resistance were determined according to the following methods, and the results are shown in Table 3.

<Peel strength>
The adhesive strength was measured in accordance with JIS K6 854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained polarizing plate was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. The sample was attached on a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyo Ink Manufacturing Co., Ltd.) using a laminator to obtain a laminate for measuring a polarizing plate and a metal plate. The polarizing plate of the laminate for measurement is provided with a peeling flicker between the protective film and the polarizer in advance, and the laminate for measurement is 300 mm / min under the conditions of 23 ° C. and 50% relative humidity. It peeled at the speed | rate of and was set as peeling force. Under the present circumstances, the peeling force of both a polyvinyl alcohol-type polarizer and a protective film (1) and a polyvinyl alcohol-type polarizer and a protective film (2) was measured. This peeling force was evaluated as an adhesive force in four stages.
A: Unpeelable or polarizing plate breakage O: Peeling force is 2.0 (N / 25 mm) or more to less than 5.0 (N / 25 mm).
(Triangle | delta): Peeling force is 1.0 (N / 25mm) or more-less than 2.0 (N / 25mm).
X: Peeling force is less than 1.0 (N / 25 mm).

<Gel fraction>
The photocurable adhesive composition shown in Formulation Example 1 is applied to a norbornene-based film (trade name “Zeonor ZF-14: 100 μm”) manufactured by Nippon Zeon that has not been subjected to corona treatment, using a wire bar coater. A photocurable adhesive layer was formed by coating to a thickness of ˜25 μm, and ZEONOR ZF-14 that had not been subjected to corona treatment was laminated on the photocurable adhesive layer to form a laminate composed of three layers. After being obtained, the photo-curing adhesive layer was cured by irradiating ultraviolet rays with a maximum illuminance of 300 mW / cm ² and an integrated light quantity of 300 mJ / cm ² with a UV irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). The ZEONOR ZF-14 was peeled off to obtain an adhesive layer.
After the weight of the adhesive layer was measured (weight 1) was sandwiched between metal meshes so that the adhesive layers did not overlap each other, and refluxed in methyl ethyl ketone (MEK) for 3 hours. The film was further dried at 80 ° C. for 30 minutes, and the weight of the adhesive layer was measured (weight 2). The gel fraction was calculated from the following formula and evaluated in three stages.
Gel fraction (%) = {1− (weight 1−weight 2) / weight 1)} × 100
○: Gel fraction is 90% or more Δ: Gel fraction is 80% to less than 90% ×: Gel fraction is less than 80%

<Punching workability>
The produced polarizing plate was punched out from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The peripheral peeling distance of the punched polarizing plate was measured with a ruler and evaluated according to the following four levels.
A: 0 mm
○: 1mm or less △: 1-3mm
×: 3 mm or more

《Moisture and heat resistance》
The polarizing plates obtained in each Example and Comparative Example were cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of 60 ° C.-90% RH. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages.
○: No peeling △: 1 mm or less peeling ×: 1 mm or more peeling

As shown in Table 3, the photocurable adhesive composition of the present invention has a slightly high viscosity in Examples 1 to 10, 13 to 19, and 26 to 31, but there is no particular problem. Of the three-membered cyclic oxirane compound (A), Examples 20 to 22 which do not contain an aromatic ring at all have difficulty in heat-and-moisture resistance because the cured coating film of the photocurable adhesive composition is slightly soft, but this is particularly problematic. There is no. Further, Example 24, which does not contain an aromatic ring and has only one three-membered oxirane ring, has difficulty in gel fraction, punching workability, and wet heat resistance, but there is no particular problem. Thus, it can be seen that in any of the examples, the viscosity is 1500 mPa · s or less, and a polarizing plate excellent in adhesive force, punching workability, and wet heat resistance is formed.
On the other hand, in Comparative Example 1 which does not contain a cyclic compound (B) having two or more oxygen atoms and having four or more members, the viscosity is as high as 1600 mPa · s, and the gel fraction is low and the curability is poor. It turns out that it is inferior to punching workability and wet heat resistance. Moreover, in Comparative Example 2, since it does not have a three-membered cyclic oxirane compound (A), the photocurability becomes insufficient, and it can be seen that the adhesive strength, the gel fraction, the punching workability, and the wet heat resistance are all inferior.

As a result of intensive studies to solve the above problems, the present inventors have found that the above-described target can be achieved by the photopolymerizable composition shown below, and further, the present invention has been completed by the photocurable adhesive composition. It was.
That is, the present invention is a substantially organic solvent containing a three-membered cyclic oxirane compound (A) as a main component and further containing a four-membered or higher cyclic compound (B) having two or more oxygen atoms. It is related with the photopolymerizable composition characterized by the measurement viscosity in 23 degreeC being 1-1500 mPa * s.
However, the cyclic compound (B) having four or more members having two or more oxygen atoms has a cyclic structure of at least one of a propiolactone ring, a carbonate ring, a dioxolane ring, and a dioxane ring. Is a photopolymerizable composition.

Further, in the present invention, a cyclic compound (B) having four or more members having two or more oxygen atoms is a propiolactone ring, carbonate ring, 1,2-dioxolane ring, 1,3-dioxane ring, 1,4 -It has the cyclic structure of at least any 1 type of a dioxane ring and a 1, 3- dioxane-2-one ring .

[ Reference Example 2, Examples 3 to 25]
Instead of the photocurable adhesive composition (Formulation Example 1) in Example 1, a polarizing plate was prepared in the same manner as in Example 1 except that it was changed to Formulation Examples 2 to 19 and 21 to 27 as shown in Table 1. Was made.

As shown in Table 3, the photocurable adhesive composition of the present invention has slightly higher viscosity in Examples 1 , 3 to 10, 13 to 19, and 26 to 31, but there is no particular problem. Of the three-membered cyclic oxirane compound (A), Examples 20 to 22 which do not contain an aromatic ring at all have difficulty in heat-and-moisture resistance because the cured coating film of the photocurable adhesive composition is slightly soft, but this is particularly problematic. There is no. Further, Example 24, which does not contain an aromatic ring and has only one three-membered oxirane ring, has difficulty in gel fraction, punching workability, and wet heat resistance, but there is no particular problem. Thus, it can be seen that in any of the examples, the viscosity is 1500 mPa · s or less, and a polarizing plate excellent in adhesive force, punching workability, and wet heat resistance is formed.
On the other hand, in Comparative Example 1 which does not contain a cyclic compound (B) having two or more oxygen atoms and having four or more members, the viscosity is as high as 1600 mPa · s, and the gel fraction is low and the curability is poor. It turns out that it is inferior to punching workability and wet heat resistance. Moreover, in Comparative Example 2, since it does not have a three-membered cyclic oxirane compound (A), the photocurability becomes insufficient, and it can be seen that the adhesive strength, the gel fraction, the punching workability, and the wet heat resistance are all inferior.

Claims (10)

  The main component is a three-membered cyclic oxirane compound (A), and further contains a four-membered or higher cyclic compound (B) having two or more oxygen atoms. The photopolymerizable composition characterized by having a measured viscosity of 1 to 1500 mPa · s.   It contains 0.5 to 60 parts by weight of a cyclic compound (B) having four or more members having two or more oxygen atoms with respect to 100 parts by weight of the three-membered cyclic oxirane compound (A). The photopolymerizable composition according to claim 1. The cyclic compound (B) having at least four members having two or more oxygen atoms has a cyclic structure of at least one of a lactone ring, a carbonate ring, a dioxolane ring, and a dioxane ring. Or the photopolymerizable composition of 2.   The photopolymerizable composition according to any one of claims 1 to 3, wherein the three-membered cyclic oxirane compound (A) contains a compound (a-1) having an aromatic ring. The photopolymerizable composition according to any one of claims 1 to 4, wherein the three-membered cyclic oxirane compound (A) contains a compound (a-2) having two or more three-membered cyclic oxirane rings. .   6. A photopolymerizable composition comprising the photopolymerizable composition according to claim 1 containing a photopolymerization initiator. The photopolymerization initiator is a salt represented by A ⁺ B ⁻ that generates an acidic active species by light irradiation, and the cation A ⁺ is selected from the group consisting of aromatic iodonium ions and aromatic sulfonium ions. The photopolymerizable composition according to claim 6. The laminated body formed by adhere | attaching an optical film using the photopolymerizable composition in any one of Claims 1-7. A polarizing plate comprising a protective film adhered to one side or both sides of a polyvinyl alcohol polarizer using the photopolymerizable composition according to claim 1. The polarizing plate according to claim 9, wherein at least one of the protective films of the polarizing plate is an acetylcellulose film, a norbornene film, an acrylic film, or a polycarbonate film.