JP5320614B2 - Photopolymerizable composition and optical film laminate - Google Patents

Description

  The present invention relates to a novel photopolymerizable composition, and a photocurable easy-adhesive coating agent, a photocurable adhesive, and an optical film laminate using the photopolymerizable oxirane-based resin composition.

  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 used by applying a coating agent to a film such as a cellulose-based film or a norbornene-based film, or is attached to an adherend via an adhesive and used for 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. If the adhesive force between the PVA polarizer and the protective film is not sufficient, peeling between the PVA polarizer and the protective film 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 by irradiation of 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.

Japanese Unexamined Patent Application Publication No. 2008-63397 (Patent Document 5) discloses a relatively low-viscosity adhesive mainly composed of an aliphatic oxirane compound, and proposes an adhesion method by heating or irradiation with active energy rays. ing.
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.
However, when the adhesive described in Document 6 is used, if the alicyclic epoxy resin is increased, the 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 the film did not adhere at all.

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.

Recently, in order to increase the production rate, it is required to cure at a low exposure amount. Documents 4 to 6 require an integrated light quantity of 1000 mJ / cm ² or more, and production efficiency is poor.

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 curability at a low exposure amount, and further having excellent heat resistance, moisture resistance, thermal dimensional stability, weather resistance and the like. Regardless of the type of optical film, it can be applied to various optical films by using a photocurable easy-adhesive coating agent and photocurable adhesive that use an almost photopolymerizable composition. An object of the present invention is to provide a coating agent, a photocurable adhesive, and a laminate using the same, which have good adhesion to a film and substantially do not contain an organic solvent.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned target can be achieved by the photopolymerizable composition shown below, and further, a photocurable easily-adhesive coating agent composition, a photocurable adhesive property. The present invention was completed by the composition.

That is, the present invention is a photopolymerizable composition containing 0.5 to 10 parts by weight of a photopolymerization initiator (B) with respect to 100 parts by weight of a three-membered cyclic oxirane compound (A), The present invention relates to a photopolymerizable composition characterized by containing 0.05 to 3 parts by weight of water in 100 parts by weight of the polymerizable composition and further substantially free of an organic solvent.
The present invention also relates to the photopolymerizable composition, wherein the three-membered cyclic oxirane compound (A) contains an oxirane compound (a1) having an alicyclic structure.
The present invention also relates to the photopolymerizable composition, wherein the oxirane compound (a1) having an alicyclic structure is a compound (a1-1) further having an aromatic ring.

In the present invention, the photopolymerizable composition further contains 0.5 to 60 parts by weight of a 4-membered or higher cyclic compound (C) having two or more oxygen atoms with respect to 100 parts by weight of the oxirane compound (A). It contains the said photopolymerizable composition characterized by containing.
In the present invention, the cyclic compound (C) having four or more members having two or more oxygen atoms is at least one of the cyclic ester compound (c1), the cyclic formal compound (c2), and the cyclic carbonate compound (c3). It is related with the said photopolymerizable composition characterized by being a compound which has 1 type of cyclic structure.
The present invention also relates to a photopolymerizable composition, wherein the cyclic ester compound (c1) is a lactone.
The present invention also relates to the photopolymerizable composition, wherein the cyclic formal compound (c2) is at least one of dioxolanes, dioxanes, and trioxanes.

In the present invention, the photopolymerizable composition further comprises 5 to 1000 parts by weight of the ethylenically unsaturated compound (D) based on 100 parts by weight of the oxirane compound (A). The present invention relates to a sex composition.
Moreover, this invention relates to the said photopolymerizable composition characterized by the ethylenically unsaturated compound (D) containing the ethylenically unsaturated compound (d1) which has a hydroxyl group.
The present invention also relates to the photopolymerizable composition, wherein the ethylenically unsaturated compound (d1) having a hydroxyl group is an ethylenically unsaturated compound (d1-1) having 2 to 18 carbon atoms.

Furthermore, this invention relates to the easily bonding coating agent which uses the said photopolymerizable composition.
Furthermore, this invention relates to the photopolymerizable adhesive agent which uses the said photopolymerizable composition.
Furthermore, the present invention provides a laminate characterized by being laminated on the optical film (E) using any one of the above-mentioned photopolymerizable composition, and / or an easily adhesive coating agent, and / or a photopolymerizable adhesive. About.
Furthermore, the present invention relates to the laminate, wherein the optical film (E) is an acetyl cellulose film or a norbornene film, an acrylic film, a polycarbonate film, a polyethylene terephthalate film, or a polyvinyl alcohol film.
In addition, the present invention provides an optical film (E) on one side or both sides of a polyvinyl alcohol polarizer using any of the photopolymerizable composition and / or the easy-adhesive coating agent and / or the photopolymerizable adhesive. It is related with the laminated body characterized by bonding.

  According to the present invention, a photopolymerizable composition that can be polymerized at a low exposure amount, and a photocurable adhesive coating agent and a photocurable adhesive composition that use the photopolymerizable composition, have good adhesion to various optical films. Therefore, it is possible to obtain a laminate having good heat resistance and wet heat resistance, and a particularly excellent polarizing plate can be provided.

The present invention is characterized in that the three-membered cyclic oxirane compound (A), the photopolymerization initiator (B), and an appropriate amount of water are 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 include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloromethyl) oxirane. , Aliphatic cyclic ether groups such as (bromomethyl) oxirane and oxiranyl acetonitrile;
For example, 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-
Oxirane-6-methylcyclohexanecarboxylate, ethylenebis (3,4-oxiranecyclohexanecarboxylate), bis (3,4-oxiranecyclohexylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, Diethylene glycol bis (3,4-oxirane cyclohexyl methyl ether), ethylene glycol bis (3,4-oxirane cyclohexyl methyl ether),
2,3,14,15-dioxirane-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] henicosane (also 3,4-oxirane cyclohexane spiro-2 ' , 6′-dioxanespiro-3 ″, 5 ″ -dioxanespiro-3 ′ ″, 4 ′ ″-compound that can also be named oxiranecyclohexane), 4- (3,4-oxiranecyclohexyl) -2,6 3-membered bonded to an alicyclic ring such as dioxa-8,9-oxirane spiro [5.5] undecane, 4-vinylcyclohexenedioxide, bis-2,3-oxiranecyclopentyl ether, and dicyclopentadiene dioxide Cyclic cyclic ether groups, and groups in which one or a plurality of hydrogen atoms are removed from these three-membered cyclic ether group-containing compounds are other chemical groups. A compound bonded to the 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 preferably contains an oxirane compound (a1) having an alicyclic structure in order to improve photopolymerizability. The oxirane compound (a1) having an alicyclic structure is a compound having a cyclic structure having three or more members other than a three-membered cyclic ether group, and examples of the alicyclic structure include cyclopropane, cyclopentane, and cyclohexane. , Cyclic alkane compounds such as cycloheptane and cyclooctane, cyclic alkene compounds such as cyclopentene, cyclopentadiene, cyclohexene and cyclohexadiene, and cyclic compounds having a crosslinking structure such as norbornane, norbornene, adamantane, dicyclopentane and dicyclopentene. It is done.

The oxirane compound (a1) having an alicyclic structure of the present invention contains an oxirane compound (a1-1) having an aromatic ring in addition to a three-membered cyclic ether group in order to improve heat resistance and moist heat resistance. It is preferable. More preferable examples of the aromatic ring substituent include phenyl, phenylene, tolyl, tolreno, benzyl, benzylidene, benzylidine, xylyl, xylylene, phthalylidene, isophthalylidene, terephthalylidene, phenethylidene, phenethylidine, styryl, styrylidene, as- Pseudocumyl, v-pseudocumyl, s-pseudocumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, 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, purprogaline

For example, as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene, perinaphthene, phenanthrene, phenanthryl, phenanthryllium, phenanthryllidene, Phenanthrylene, phenanthrol, molhole, phenanthrone, phenanthraquinone, pimantrene, reten, anthracene, anthryl, anthryllium, anthrylidene, anthrylene, anthrol, anthranol, anthrobin, anthraline, ditranol, anthroyl, anthrone, bianthrone, anthraquinone , Anthraquinonyl, anthraquinonylene, alizarin, quinizarin, anthralphine, chrysazine, anthragalo 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.

  Moreover, it is preferable that the three-membered cyclic oxirane compound (A) of the present invention contains a cyclic compound (C) having four or more members having two or more oxygen atoms. 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, the oxirane compound (a1) having the alicyclic structure and the compound (a1-1) having an aromatic ring are the same compound, that is, a three-membered oxirane ring having an alicyclic structure and an aromatic ring. Even if it is a compound (a2) which has this, it can be used without a problem. These contents in the three-membered cyclic oxirane compound (A) are as follows: (A1), (a1-
The total of 1) and (a2) is preferably 50% by weight or more from the viewpoint of polymerizability and moist heat resistance, and particularly preferably 60% by weight or more.
Moreover, the three-membered cyclic oxirane compound (a3) which does not belong to any of (a1), (a1-1) and (a2) can be used without any problem. These may use only 1 type or may use multiple types together.

In this invention, it can be set as a photocurable adhesive composition by containing a photoinitiator (B) in the said photopolymerizable oxirane resin composition.
Although said photoinitiator (B) is a salt represented by A + B- which generate | occur | produces an acidic active seed | 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 (B) 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 (B), it is also possible to have a radical photopolymerization initiator. Examples of such radical photopolymerization initiator include Irgacure 184,907,651,1700,1800,819,369,261, LUCIRIN TPO (manufactured by BASF) 2,4,6-trimethylbenzoyl-diphenyl-phos. Finoxide), Darocur-1173 (manufactured by Merck), Ezacure KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI, (manufactured by Nippon Kayaku Co., Ltd.) and the like.
The blending ratio of the photopolymerization initiator (B) is 0.5 to 10 parts by weight and preferably 1 to 7 parts by weight with respect to 100 parts by weight of the three-membered cyclic oxirane compound (A).
If the blending ratio of the photopolymerization initiator (B) is less than 0.5 parts by weight, sufficient curability cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the heat resistance and the like deteriorate due to the photopolymerization initiator remaining after curing.

  Furthermore, in order to improve the performance of the photopolymerization initiator (B), 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 photopolymerizable composition of the present invention contains 0.05 to 3 parts by weight of water as an essential component. In general, in the photopolymerization reaction of a three-membered cyclic oxirane compound, it is known that moisture deteriorates curability, but by including it in the range of 0.05 to 3 parts by weight, the curability is improved. I found it.
If the water content is less than 0.05 parts by weight, the curability is not improved, and if it is more than 3 parts by weight, the curability deteriorates.

Moreover, in the photopolymerizable composition of the present invention, it is preferable to have a cyclic compound (C) having four or more membered rings having two or more oxygen atoms, wherein (C) is a cyclic ester compound (c1) or a cyclic formal compound. It is preferable from a photopolymerizable point to have at least any one of (c2) and the cyclic carbonate compound (c3).
Furthermore, the cyclic ester compound (c1) is a lactone (c1-1), and the cyclic formal compound (c2) is a dioxolane (c2-1), a dioxane (c2-2), or a trioxane (c2-3). Is more preferable.

  The lactone ring-containing cyclic compound (c1-1) 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, the cyclic dimer of hydroxycarboxylic acid that can be used as the lactone ring-containing cyclic compound (c1-1) is 3,6-dimethyl-1,4-dioxane-2,5-dione by lactic acid. 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.

The dioxolane ring-containing cyclic compound (c2-1) in the present invention is obtained by acetalizing a carbonyl group 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-dimethyl1, 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-bis (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-dioxolan-4-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 above dioxolane ring-containing cyclic compounds (c2-1), 1,3-dioxolane, (2-methyl-2-ethyl) is 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.

Examples of the dioxane ring-containing cyclic compound (c2-2) in the present invention include 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) -3β, 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-dioxane-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-3-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] propionate methyl, (2S) -2-[(3S, 6S) -6- [2-[(1S, 2R, 4aα, 8αβ) -decahydro-1,
2α, 4a-trimethyl-5-methylenenaphthalen-1β-yl] ethyl] -6-methyl-1,2-dioxan-3-yl] propanoic acid, (R) -2-[(3R, 6S) -6β- Methyl-6- [2-[[(2R, 4aβ, 8aβ) -decahydro-1,1-dimethyl-3,6-dimethylenenaphthalene] -2α-yl] ethyl] -1,2-dioxane-3β-yl ] 1,2-dioxane derivatives such as 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-dioxan-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-dioxan-2-yl) ethyltriphenylphosphonium bromide, 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-trifluoromethylphenyl) 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-Dioxane-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-tri Fluorobenzene, 1- [2- (5-propyl-1,3-dioxane-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 -Chromen-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-dioxane-5-yl) hex-4-enoic acid, (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl)- 4- (2-acetoxyphenyl) -1,3-dioxane-5-yl) hex-4-enoic acid, methyl- (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4- (2-hydroxyphenyl) -1,3-dioxane-5-yl) hex-4-enoate, (Z) -6-((2S, 4S, 5R) -2- (2-chlorophenyl) -4 -(2-hydroxyphenyl) -1,3-dioxane-5-yl) hex-4-enoatemethyl, (Z) -6-((2S, 4S, 5R) -4- (2-acetoxyphenyl)- 2- (2-Chlorophenyl) -1,3-dioxane-5-yl 1,3-dioxane derivatives such as hex-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-dioxan-2-yl) methyl acetate, 2,2,3,3-tetrafluoro-5,5,6, 6-tetrachloro-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, bis [morpholine-4- (dithioformic acid)] 1,4-dioxane-2α, 3β-diyl, 2,5-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, tr
ans-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) bis (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-dioxane-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-2,5-dione, [(1,4-dioxane-2,3-diyl) bisthio] bis (thiophosphonic acid O, O-diethyl) 1 etc.
, 4-dioxane derivatives and the like.

Among the dioxane ring-containing cyclic compounds (c2-2), 1,2-dioxane, 1,3-dioxane, 1, from the viewpoint of ring-opening copolymerizability with the three-membered cyclic oxirane compound (A). 4-dioxane and 1,3-dioxane-2-one are particularly preferred.
These cyclic compounds having four or more members having two or more oxygen atoms (C) may be used alone or in combination of two or more.

The trioxane ring-containing cyclic compound (c2-3) in the present invention can be synthesized by condensing formaldehyde with an acid catalyst.
Specifically, 1,3,5-trioxane, paraaldehyde, cyanide, 2,4,6-tris (chloromethyl) -1,3,5-trioxane, 2,4,6-triisopropyl-1,3 5-trioxane, 2,4,6-trivinyl-1,3,5-trioxane, 2,4,6-tripropyl-1,3,5-trioxane, 2- (1,1-dimethylethyl) -1, 3,5-trioxane, 2,4,6-triethyl-1,3,5-trioxane, 2,4,6-tributyl-1,3,5-trioxane, 2,4-diethyl-6-methyl-1, 3,5-trioxane, 2-ethyl-4,6-dimethyl-1,3,5-trioxane, 2,4,6-tris (dichloromethyl) -1,3,5-trioxane, 2,4,6- Tris (2-chloroethyl) -1,3 - trioxane, 1,3,5-trioxane-2,4,
6-tripropionitrile, 2,4,6-tribenzyl-1,3,5-trioxane, 2,4,6-triisobutyl-1,3,5-trioxane, 11β- (methoxymethoxy) spiro [androsta- 1,4-diene-17,2 '-[1,3,5] trioxane] -3-one, 11β- (methoxymethoxy) spiro [androsta-1,4-diene-17,2'-[1, 3,5] trioxane] -3-thione, 1,7,9-trimethyl-3,5,12-trioxatetracyclo [5.3.1.12,6.04,9] dodecane, 2,4, 6-tris (1-chloroethyl) -1,3,5-trioxane, 2,4,6-triphenethyl-1,3,5-trioxane, 2,4,6-tricyclohexyl-1,3,5-trioxane 2-Cyclohexyl Ru-4,6-dimethyl-1,3,5-trioxane, 2-cyclohexyl-4,6-dibenzyl-1,3,5-trioxane, 2,2,4,4,6,6-hexamethyl-1, 3,5-trioxane, 4,4 ', 4 "-(1,3,5-trioxane-2,4,6-triyl) tributyric acid, tris (p-toluenesulfonic acid) 1,3,5-trioxane -2,4,6-triyltrisethylene, 1,3,5,7-tetramethyl-6- [3- (1,3,5,7-tetramethyl-2,4,9-trioxa-6- Phosphaadamantan-6-yl) propyl] -2,4,8-trioxa-6-phosphaadamantane, 2,4,6-triacetyl-1,3,5-trioxane, 1,3,5-trioxane- 2-one, 2,2,4,4,6,6-hexachloro-1,3,5-trioxane, 2,2-dichloro-1,3,5-trioxane Xane, 1,3,5-trioxane-2,4-dione, 1,3,5-trioxane-2,4,6-trione, 2- (triethylsilyl) -1,3,5-trioxane, 2- ( Trimethylsilyl) -1,3,5-trioxane, 2,4,6-trihexyl-1,3,5-trioxane, 2,4,6-trioctyl-1,3,5-trioxane, 1,3,5-trioxane -2,4,6-tris (methyl propanoate), 2,2 ', 2 "-(1,3,5-trioxane-2,4,6-triyl) trisacetonitrile, 2,4,6-tri Cyclopentyl-1,3,5-trioxane, 2,4,6-tris (2,6-dimethylheptyl) -1,3,5-trioxane, 2,4,6-tris (9-decenyl) -1,3 , 5-trioxane, 2,4, -Tris (4-pentenyl) -1,3,5-trioxane, 2,4,6-tris [3- (benzyloxy) propyl] -1,3,5-trioxane, 2,4,6-tris [4 -Benzoyloxybutyl] -1,3,5-trioxane, 2,4,6-tris (3-methoxycarbonylpropyl) -1,3,5-trioxane, 2,4,6-tris [4- (methoxycarbonyl ) Butyl] -1,3,5-trioxane, 2,4,6-tris [5- (methoxycarbonyl) pentyl] -1,3,5-trioxane, 2,4,6-tris [2- (benzoyloxy) Carbonyl) ethyl] -1,3,5-trioxane, 2,4,6-tris (5-bromopentyl) -1,3,5-trioxane, 2,4,6-tris (3-methyl-5-bromo Pentyl) -1,3,5-trioxane, 2,4,6-tris (5-azidopentyl) -1,3,5-trioxane, 2,4,6-tris [2- (acetoxymethyl) -3-acetoxypropyl ] -1,3,5-trioxane, 2,2 ′, 2 ″-(1,3,5-trioxane-2,4,6-triyl) trisethanol, 5,5 ′, 5 ″-(1 , 3,5-trioxane-2,4,6-triyl) trispentanoic acid, 3,3 ′, 3 ″-(1,3,5-trioxane-2,4,6-triyl) trispropionic acid, 2 , 4,6-Tris (5-aminopentyl) -1,3,5-trioxane, 2,2 ', 2 "-[(1,3,5-trioxane-2,4,6-triyl) trismethylene ] Tris (1,3-propanediol), (2H6) -1,3,5 Trioxane, 2,4,6-tri -tert- butyl-1,3,5-trioxane, 2,4,
6-trinonyl-1,3,5-trioxane, 2,4,6-triheptyl-1,3,5-trioxane, triethyl 1,3,5-trioxane-2,4,6-tricarboxylate, 2,4,6 6-tris (1-phenylethyl) -1,3,5-trioxane, 2,4,6-tris (2,6-dimethyl-5-hepten-1-yl) -1,3,5-trioxane, 2 4,6,8,9,10-hexaoxaadamantane and the like.

Among the trioxane ring-containing cyclic compounds (c2-3), 1,3,5-trioxane is particularly preferable from the viewpoint of ring-opening copolymerizability with the three-membered cyclic oxirane compound (A).

As the cyclic compound (c3) containing a carbonate ring 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 carbon dioxide It can be synthesized by the reaction of 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.

  In the photopolymerizable oxirane-based resin composition of the present invention, the four-membered or higher cyclic compound (C) having two or more oxygen atoms is added to 100 parts by weight of the three-membered cyclic oxirane compound (A) as a main component. On the other hand, it is preferable to contain (C) 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 cyclic compound (C) having two or more oxygen atoms is not 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, if it exceeds 60 parts by weight, when the polymerizable oxirane resin composition is used as a photocurable adhesive, the polarity of the crosslinked coating film becomes too large, and a nonpolar optical film (polyester film, Such as norbornene-based film), which is not preferable.

The photopolymerizable composition of the present invention includes the three-membered cyclic oxirane compound (A) and the photopolymerization initiator (B), and a four-membered or higher cyclic compound (C) having two or more oxygen atoms, It is preferable to include an ethylenically unsaturated compound (D) having an unsaturated double bond in the molecular structure.
By containing an ethylenically unsaturated compound (D), the viscosity of a photopolymerizable composition can be lowered | hung or the adhesive force with a base material can be improved.

Examples of the ethylenically unsaturated compound (D) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl. (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl Ethylenically unsaturated compounds such as (meth) acrylate, stearyl (meth) acrylate, and “isostearyl acrylate” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

For example, ethylenically unsaturated compounds having a cycloalkane skeleton and / or a cycloalkene skeleton (cyclohexyl) (meth) acrylate, 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-cyclohexyl (meth) acrylate, 1-isopropyl-1 (meth) acrylate -Cyclohexyl, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, iso-bonyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, (Meth) acrylic acid 2-oxo-1,2-phenylethyl (Meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid 1-naphthyl, (meth) acrylic acid 2-naphthyl, (meth) acrylic acid 1-naphthylmethyl, (meth) acrylic acid 1 -Anthryl, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (meth) acryl Acid 2-ethyladamantyl-2-yl, (meth) acrylic acid 2-n-propyladamantyl-2-yl, (meth) acrylic acid 2-isopropyladamantyl-2-yl, (meth) acrylic acid 1- (adamantane- 1-yl) -1-methylethyl, (meth) acrylic acid 1- (adamantan-1-yl) -1-ethylethyl, (meth) 1- (adamantan-1-yl) -1-methylpropyl crylate, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) acrylate-5-oxo-4-oxa -Tricyclo [4.2.1.03,7] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.03,8] dec-2-yl , (Meth) acrylic acid dihydro-α-terpinyl, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo- (Meth) acrylic acid cyclic esters such as 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 Ethylenically unsaturated compounds.

For example, aromatic ring-containing ethylenically unsaturated compounds such as styrene, α-methylstyrene, vinyltoluene, and benzyl (meth) acrylate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- ( Ethylenically unsaturated compounds having alkoxysilyl groups such as meth) acryloyloxypropyltrimethoxysilane and γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate Perfluoroalkyl (meth) acrylates such as; ethylenically unsaturated compounds having fluorinated alkyl groups such as fluoroolefins; ethylenically unsaturated compounds having a photopolymerizable functional group such as maleimide groups; N-vinylpyrrole Vinyl compounds such as don, ethylene, butadiene, chloroprene, vinyl propionate and vinyl acetate; carboxyl group-containing ethylenically unsaturated compounds such as (meth) acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate; Acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N
, N-dimethylaminopropyl (meth) acrylamide, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, dimethylaminoethyl (meth) acrylate, nitrogen-containing ethylenic compounds such as adducts of glycidyl (meth) acrylate and amines Unsaturated compounds; ethylenically unsaturated compounds having two or more ethylenically unsaturated groups in one molecule such as allyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate; glycidyl (meta ) Acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (
(Meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate,
Epoxy group-containing ethylenically unsaturated compounds such as allyl glycidyl ether; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is an alkoxy group; 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate , Allylsulfonic acid, 4-styrenesulfonic acid and ethylenically unsaturated compounds having a sulfonic acid group such as sodium salt and ammonium salt thereof; 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxy Propyl acid phosphate, 2-methacryloyloxypropyl acid phosphate,
Examples thereof include ethylenically unsaturated compounds having a phosphoric acid group such as acid phosphooxypolyoxyethylene glycol mono (meth) acrylate and acid phosphooxypolyoxypropylene glycol mono (meth) acrylate.
These may use only 1 type or may use multiple types together.

  The ethylenically unsaturated compound (D) is preferably a hydroxyl group-containing ethylenically unsaturated compound (d1) in view of adhesion to the optical film.

  The hydroxyl group-containing ethylenically unsaturated compound (d1) is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate [2-hydroxyethyl acrylate and Together with 2-hydroxyethyl methacrylate, it is expressed as “(2-methyoxyacrylate) 2-hydroxyethyl”. The same applies below. ], 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) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2 ′
Hydroxyl group-containing benzotriazole-based (meth) acrylic esters such as -hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole;

For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- (Meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′
-Hydroxyl-containing benzophenone-based (meth) acrylic acid esters such as-(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 below. ], 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 below. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

  Examples thereof include monomers having a hydroxyl group and an 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.

As the ethylenically unsaturated compound (d1) containing a hydroxyl group, from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Particularly preferred are 4-hydroxybutyl (meth) acrylate and 1,3-cyclohexanedimethanol (meth) acrylate.

  When the ethylenically unsaturated compound (D) is contained in the photopolymerizable composition of the present invention, it is used at a ratio of 5 to 1000 parts by weight with respect to 100 parts by weight of the three-membered cyclic oxirane compound (A). Can do. When the amount of the ethylenically unsaturated compound (D) is less than 5 parts by weight, the viscosity of the photopolymerizable composition cannot be sufficiently reduced, and when it is more than 1000 parts by weight, the three-membered cyclic oxirane compound (A) due to moisture Hinders the improvement of the polymerizability.

  The ethylenically unsaturated compound (D) preferably has a viscosity at 23 ° C. of 0.5 to 2000 mPa · s, and preferably 1 to 1000 mPa · s. By using such an ethylenically unsaturated compound (D), the adhesion to the substrate is improved, the viscosity of the photopolymerizable composition is lowered, and the photopolymerizability is maintained while improving the thin film coatability. In addition, the adhesive strength and workability of the adhesive described later can be maintained.

The photocurable adhesive composition in the present invention may further contain an antioxidant. By containing the antioxidant, coloring of the adhesive layer after photocuring with time can be suppressed.
Examples of antioxidants include phenolic antioxidants such as ADK STAB AO-50 and ADK STAB AO-80 (Asahi Denka Kogyo), and sulfur such as IRGANOX-PS-800FD (Ciba Specialty Chemicals). Examples of the antioxidant include hindered amine light stabilizers such as TINUBIN 622LD, TINUBIN 144, and TINUBIN 765, but are not limited thereto.
The mixture ratio of antioxidant 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 composition of the present invention does not substantially contain an organic solvent. Although it is preferable not to contain any organic solvent, the photopolymerization initiator (B) 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 (B). The content of the organic solvent in the photocurable composition is within 5% by weight.

The viscosity at 23 ° C. of the photocurable composition in the present invention is preferably 1 to 1500 mPa · s.
More preferably, it is 10-1300 mPa * s, and it is especially 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 composition is almost determined by the viscosity of the photopolymerizable oxirane resin composition, by managing the viscosity of the photopolymerizable oxirane resin composition in the range of 1 to 1500 mPa · s, The viscosity of the photocurable adhesive composition can also be controlled.

  The photocurable 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, an antifoaming agent, a tackifier, as long as the effects of the present invention are not impaired. Various known additives such as fire, plasticizer, filler and anti-aging agent can be included as needed within the range not impairing the effects of the present invention.

A photocurable composition can be formed on the optical film by applying the photocurable composition to the optical film by an appropriate method according to a conventional method.
The thickness of the photocurable composition layer is preferably a thin film coating of 0.1 to 6 μm, and more preferably 0.1 μm to 3 μm. If the thickness is less than 0.1 μm, sufficient adhesion to the substrate may not be obtained. If the thickness exceeds 6 μm, the properties such as adhesion do not often improve further.

  The method for applying the photocurable 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, comma. Various coating methods such as a 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 composition of the present invention is cured by irradiation with active energy rays, but the light source used is not particularly limited, and has a light emission distribution at a wavelength of 500 nm or less, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure. Mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, issuing diodes, and the like can be used.
The light irradiation intensity is preferably 10 to 500 mW / cm 2. When the light irradiation intensity is less than 10 mW / cm 2, a long time is required for curing, and when it exceeds 500 mW / cm 2, the substrate may be deteriorated due to heat radiated from the lamp. The integrated light amount expressed as the product of irradiation intensity and irradiation time is preferably 50 to 5000 mJ / cm 2. If the integrated light quantity is less than 50 mJ / cm 2, a long time is required for curing, and if it is greater than 5000 mJ / cm 2, the irradiation time becomes very long and the productivity is inferior.

The photocurable adhesive composition of the present invention is further suitable as a photocurable easily adhesive coating agent or 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 a photocurable composition 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.
<< Laminated body of easy-adhesive coating agent and optical film >>
A photocurable easy-adhesive coating agent is applied to one or both sides of an optical film that is a film-like substrate, and then photocured. Under the present circumstances, irradiation of an active energy ray may be performed from the easily-adhesive coating agent side, and may be performed from the film side. Furthermore, in order to prevent photocuring inhibition by oxygen or the like, it is preferable to fill the surface of the easy-adhesive coating agent with dry nitrogen or the like during irradiation with active energy rays.
<< Laminated body of adhesive and optical film >>
The optical photocurable adhesive composition is applied to one or both sides of an optical film that is a film-like substrate, and another optical film is laminated on the surface of the photocurable adhesive layer. Alternatively, an optical laminate can be obtained by coating the photocurable adhesive composition for optics on both sides and 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 easy-adhesive coating agent, the optical photocurable adhesive composition, and the optical laminate are generally described.
The optical photocurable easy-adhesive coating agent and the photocurable adhesive composition are used to form an optical laminate.
The basic laminate structure of the optical laminate is a film-like substrate / light-curable easy-adhesive coating agent layer, a film-like substrate / photo-curable adhesive layer / film-like substrate, or a film-like substrate / photo-curing property. It is a sheet-like double-sided photosensitive curable adhesive laminate such as adhesive layer / film-like substrate / photocurable adhesive layer / 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 photocurable adhesive composition is applied to one surface of a polyvinyl alcohol polarizer to form a first photocurable adhesive layer, and the first photocurable adhesive formed. 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, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

[Formulation Example 1]
Into a light-shielded 300 cc mayonnaise bottle substituted with an oxygen concentration of 10% or less, a three-membered cyclic oxirane compound (A) and a photopolymerization initiator (B) are charged in the ratios shown in Table 1, and sufficient with an air motor. The mixture was stirred and sufficiently defoamed, and the photocurable composition shown in the formulation example was obtained.

  The water content and viscosity of the obtained photocurable composition were determined according to the following method, and the results are shown in Table 1.

<Moisture measurement>
It measured according to JIS K 0113-2005 by the Karl Fischer titration method.

"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.

[Composition Examples 2-8]
After obtaining a composition in the same manner as in Formulation Example 1, purified water was added so that the water content shown in Table 1 was obtained, and the mixture was sufficiently stirred with an air motor to obtain a photocurable composition.

[Composition Examples 9-34]
Similar to Formulation Example 2 except that a 4-membered or higher cyclic compound (C) and / or ethylenically unsaturated compound (D) having two or more oxygen atoms in the ratio shown in Table 1 and a photosensitizer are added. The water content was adjusted to obtain a photopolymerizable composition.

[Example 1]
Using the photocurable composition obtained in Formulation Example 2, the following laminate was prepared.
As the optical film, an ultraviolet absorber-containing triacetyl cellulose film manufactured by Fuji Film Co., Ltd .: trade name “Fujitack: 80 μm” was used. The optical film 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 photocurable composition shown in Formulation Example 1 is made to have a film thickness of 4 μm using a wire bar coater. Coating was carried out to form a photocurable easily adhesive coating agent layer.
The four sides of this laminate were fixed to the tinplate with cellophane tape so that the optical film was in contact with the tinplate.
After replacing the inside of the UV irradiation device (Toshiba High Pressure Mercury Lamp) with dry nitrogen, irradiate UV light with a maximum illuminance of 200 mW / cm 2 with a wavelength of 365 nm and an integrated light quantity of 200 mJ / cm 2 from the easy adhesive coating layer side. A laminate having an agent layer was produced.

[Examples 2-34, Comparative Examples 1-5]
A laminated body was produced in the same manner as in Example 1 except that instead of the photocurable composition (Formulation Example 2) in Example 1, the composition example shown in Table 2 was changed to an optical film.

  The laminates obtained in Examples 1 to 34 and Comparative Examples 1 to 5 were determined for adhesion, gel fraction, and heat resistance according to the following methods, and the results are shown in Table 3.

"Adhesion"
A cross-cut peel test was performed according to JIS K5400. The number of cells peeled in 100 cells was evaluated in four stages.
◎: 0 square ○: 1-10 square △: 11-30 square ×: 31 squares or more

<Gel fraction>
A norbornene-based film (trade name “Zeonor ZF-14: 100 μm” manufactured by Nippon Zeon Co., Ltd., which has not been subjected to corona treatment, is coated with the photocurable composition shown in Table 1 with a film thickness of 20 to 25 μm using a wire bar coater. After coating a zeonoa ZF-14 that has not been subjected to corona treatment on the photocurable composition layer, a three-layer laminate was obtained. The photocurable composition layer was cured by irradiating UV light with a maximum illuminance of 200 mW / cm 2 with a wavelength of 365 nm and an integrated light quantity of 200 mJ / cm 2 with a UV irradiation apparatus (high pressure mercury lamp manufactured by Toshiba Corporation). ZF-14 was peeled off to obtain a photocurable composition layer.
After the weight of the photocurable composition 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%

"Heat-resistant"
The laminates obtained in each Example and Comparative Example were cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of 80 ° C.-dry. After the exposure, the presence or absence of peeling at the end of the laminate was visually evaluated in the following three stages.
○: No peeling at all Δ: Peeling less than 1 mm × Peeling over 1 mm

[Example 35]
Using the photocurable composition obtained in Formulation Example 2, the following polarizing plate was prepared.
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: Trade name “TAC50μ” (thickness 50 μm) is used, each surface is corona-treated with a discharge amount of 300 W · min / m2, and within 1 hour after the surface treatment, Formulation Example 2 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-mentioned photocurable adhesive layer is interposed between the photocurable adhesive layer and the photocurable adhesive layer. With a polyvinyl alcohol polarizer in between, protective film (1) / curable adhesive layer / PVA polarizer / curable adhesive layer / protective film (2) To obtain a laminated body composed.
The four sides of the laminate were fixed to the tinplate with cellophane tape so that the protective film (1) was in contact with the tinplate.
A polarizing plate was produced by irradiating ultraviolet rays with a maximum illuminance of 200 mW / cm 2 having a wavelength of 365 nm and an integrated light quantity of 200 mJ / cm 2 from the protective film (2) side with a UV irradiation apparatus (high pressure mercury lamp manufactured by Toshiba Corporation).

[Examples 36 to 69, Comparative Examples 6 to 10]
A polarizing plate was produced in the same manner as in Example 35 except that instead of the photocurable composition (Formulation Example 2) in Example, the composition example and optical film shown in Table 3 were changed.

  For the polarizing plates obtained in Examples 35 to 69 and Comparative Examples 6 to 10, the peel strength, punching workability, and heat resistance were determined, 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: Peeling force is 5.0 (N / 25 mm) or more or polarizing plate breakage B: 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).

<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 peel distance at the end 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

When the photocurable composition of the present invention is used as an easy-adhesive coating agent, as shown in Table 2, in Examples 1 to 6 and 27 to 29, an optical film laminate excellent in adhesion, gel fraction, and heat resistance Form.
On the other hand, Comparative Examples 1 and 4 having a small amount of water and Comparative Example 2 having a large amount of water have a low gel fraction because the curability is poor at a low irradiation amount such as a maximum illuminance of 200 mW / cm 2 and an integrated light amount of 200 mJ / cm 2. Poor adhesion and heat resistance.

Similarly, Examples 7 to 21, 22 to 26 including the cyclic compound (C) having four or more rings having two or more oxygen atoms and the ethylenically unsaturated compound (D) are excellent optical film laminates. Form.
On the other hand, Comparative Example 3 having a small amount of water is inferior in adhesiveness, gel fraction, and heat resistance because of poor curability at a low dose. Comparative Example 5 not containing the three-membered cyclic oxirane compound (A) has a high gel fraction but is inferior in adhesion and heat resistance.
Moreover, although Examples 30-34 are evaluation results in various optical films, excellent optical film laminates from a hydrophobic norbornene-based film to a hydrophilic acetylcellulose-based film are formed.

Table 3 shows the evaluation results for the polarizing plate. Although it is the tendency similar to the evaluation result of Table 2, in the case of a polarizing plate, the photocurable adhesive between the protective film 1 and the polyvinyl alcohol-type polarizer is the protective film 2, the photocurable adhesive, and the polyvinyl alcohol-type polarized light. Due to absorption of active energy rays by the child, the dose becomes even weaker, and the adhesive strength is more significantly different.
Although Examples 35-69 form the outstanding polarizing plate, Comparative Examples 6, 8, and 9 with a small amount of moisture and Comparative Example 7 with a large amount of moisture have poor curability and particularly have an extremely strong adhesive force on the protective film 1 side. Inferior. Since Comparative Example 10 containing no three-membered cyclic oxirane compound (A) has poor adhesion, it is inferior in punching workability and heat resistance.

Claims (13)

A photopolymerizable composition containing a three-membered cyclic oxirane compound (A), a photopolymerization initiator (B), an ethylenically unsaturated compound (D), and water, comprising the following (1) to ( 3) A photopolymerizable composition, which is characterized in that
(1) 0.5-100 weight part of photoinitiators (B) and 5-1000 weight part of ethylenically unsaturated compound (D) are contained with respect to 100 weight part of oxirane compound (A) .
(2) It contains 0.05 to 3 parts by weight of water with respect to 100 parts by weight of the whole photopolymerizable composition .
(3) The three-membered cyclic oxirane compound (A) contains the oxirane compound (a1) having an alicyclic structure.   The photopolymerizable composition according to claim 1, wherein the ethylenically unsaturated compound (D) contains an ethylenically unsaturated compound (d1) having a hydroxyl group.   The photopolymerizable composition according to claim 2, wherein the ethylenically unsaturated compound (d1) having a hydroxyl group is an ethylenically unsaturated compound (d1-1) having 2 to 18 carbon atoms. The photopolymerizable composition according to any one of claims 1 to 3, wherein the oxirane compound (a1) having an alicyclic structure is a compound (a1-1) further having an aromatic ring. The photopolymerizable composition further contains 0.5 to 60 parts by weight of the cyclic compound (C) having four or more members having two or more oxygen atoms with respect to 100 parts by weight of the oxirane compound (A). The photopolymerizable composition according to any one of claims 1 to 4, wherein One or more cyclic structures in which the cyclic compound (C) having at least four members having two or more oxygen atoms is selected from the cyclic ester compound (c1), the cyclic formal compound (c2), and the cyclic carbonate compound (c3) The photopolymerizable composition according to claim 5 , which is a compound having The photopolymerizable composition according to claim 6 , wherein the cyclic ester compound (c1) is a lactone. The photopolymerizable composition according to claim 6 or 7 , wherein the cyclic formal compound (c2) is one or more compounds selected from dioxolanes, dioxanes and trioxanes. Made with claim 1-8 photopolymerizable composition according to any one, easy-adhesion coating. Made with claim 1-8 photopolymerizable composition according to any one of the photopolymerizable adhesive. Claims 1-8 or according photopolymerizable composition and / or easy-adhesion coating agent according to claim 9, wherein and / or claim 10, wherein the photopolymerizable adhesive was laminated to the optical film (E) A laminate characterized by comprising: The laminate according to claim 11, wherein the optical film (E) is an acetyl cellulose film, a norbornene film, an acrylic film, a carbonate film, a polyethylene terephthalate film, or a polyvinyl alcohol film. A photopolymerizable composition according to any one of claims 1 to 8 and / or an easily adhesive coating agent according to claim 9 and / or a photopolymerizable adhesive according to claim 10 , wherein a polyvinyl alcohol polarizer is used. A laminate comprising an optical film (E) bonded to one side or both sides.