JP6135118B2 - Photopolymerizable oxirane resin composition, photopolymerizable coating agent, photopolymerizable adhesive, and optical film laminate - Google Patents

Description

  The present invention relates to a novel photopolymerizable oxirane-based resin composition, a photopolymerizable coating agent, a photopolymerizable 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 displays (LCD), plasma displays (PDP), rear projection displays (RPJ), EL displays (ELD), and light emitting diode displays However, it has been 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.

In addition, these antireflection films and protective films (protective films) for preventing scratches on the surface of the display device, particularly coating films used for image display devices with flat surfaces such as PDP, LCD, ELD, In addition to optical properties, scratch resistance, pencil hardness, chemical resistance, weather resistance, etc. are required, so usually heat-polymerized resin by heating (also called thermosetting resin) or active energy such as ultraviolet rays It is manufactured as a coating film in which a thin film of about 0.5 to 20 μm is formed on a transparent substrate directly or via a primer layer with a photopolymerizable resin such as a UV-ray-polymerizing type (also called UV-curable type). Yes.

  However, even if the hardness of the coating layer of the conventional coating film is sufficient, when the underlying transparent substrate is deformed due to the thin coating thickness, the coating layer is also changed accordingly. There was a problem that it deformed and the hardness of the entire coating film decreased. On the other hand, if the thickness of the coating layer is simply thicker than the usual 0.5 to 20 μm, the hardness of the resulting coating film is improved, but cracking and peeling of the coating layer are likely to occur, and at the same time polymerization shrinkage (also referred to as curing shrinkage). There is a problem that the curling of the coating film due to the above increases. Further, for the purpose of further improving the hardness of the coating layer, there is a method of increasing the photopolymerization reaction rate (also referred to as a crosslinking rate) of the photopolymerizable resin, but the curl of the coating film is also increased.

  If the curl is large, the productivity in the process of bonding to the display surface of the next process, or the durability after bonding, etc. will be significantly reduced, so when providing a coating layer on a transparent substrate, the thickness of the coating layer, The photopolymerization reaction rate of the photopolymerizable resin must be limited. Therefore, the pencil hardness is often limited to 2H to 3H with the thickness of the coating layer that does not hinder the next process.

  In order to achieve both low curl and high pencil hardness, Patent Document 1 discloses a technique in which a Vickers hardness of a photopolymerizable resin is defined on at least one surface of a transparent film or a sheet substrate and two coating layers are provided. (See Patent Document 1).

  However, this technique describes that curl is increased when only the photopolymerizable composition is used, and fine particles such as silica are contained in the coating layer in order to improve curl. However, the coating layer containing such fine particles has a problem of low contrast when used in various image display devices because the transmittance of the film decreases.

  Moreover, in order to improve the hardness of a coating layer, patent document 2 describes the technique of improving photopolymerizability and improving adhesiveness by using butyrolactone together with oxirane resin (refer patent document 2).

  However, this method is combined with photo-ring-opening polymerization of butyrolactone. However, because of the 5-membered ring having a comparatively low stability structure, photo-ring-opening polymerization is usually insufficient at a light irradiation amount of 1000 mJ or less. It is known that lactones such as bleed to the interface and cause migration. In order to carry out photo-ring-opening polymerization of such lactones, it requires a considerable amount of energy such as whether to apply a considerable amount of light of active energy rays or to use a heat treatment together. There is a problem that it is difficult to cope with high sensitivity corresponding to high-speed coating.

Furthermore, 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.

Of the various films described above, a polarizing film (also referred to as a polarizing plate) is a protective film made of polytriacetylcellulose (TAC) or polycycloolefin (COP) on both sides of a polyvinyl alcohol (PVA) polarizer. A three-layer structure is generally sandwiched between and bonded with a water-based adhesive.
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, a polyacrylic film, an amorphous polyolefin, which is inexpensive and has excellent optical properties such as transparency, instead of a TAC film. Films and polycycloolefin films have been proposed (Patent Documents 3, 4, and 5). 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 a photopolymerizable 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 film (polarizing plate) for liquid crystal display devices is affixed on a liquid crystal cell through an adhesive layer. At this time, if there is a bonding mistake such as mixing of foreign matter, the polarizing film 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 adhesive for bonding the polarizing film and the liquid crystal cell, and further, 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). Occurs.

Japanese Patent Application Laid-Open No. 2004-245925 (Patent Document 6) discloses an adhesive mainly composed of a hydrogenated (also referred to as hydrogenated) bisphenol-type oxirane resin as an oxirane-based resin not containing an aromatic ring. An adhesion method by photopolymerization by irradiation with energy rays has been proposed.
However, the adhesive described in Patent Document 6 has a very high viscosity and is difficult to coat.
Furthermore, when a hydrogenated bisphenol-type oxirane compound is used as a main component as in the adhesive described in Patent Document 6, when a protective film such as a polyester film, a polyvinyl chloride film, a polycarbonate film, or a polyacrylic 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 7) discloses a relatively low-viscosity adhesive mainly composed of an aliphatic oxirane compound, and an adhesion method by photopolymerization by heating or irradiation with active energy rays. Has been proposed.
When the adhesive described in Patent Document 7 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 7 is used, peeling occurs between the PVA polarizer and one of the protective films or between the PVA polarizer and both protective films when exposed to wet heat.
Furthermore, when an aliphatic oxirane compound is a main component like the adhesive described in Patent Document 7, when a protective film such as a polyester film, a polyvinyl chloride film, a polycarbonate film, or a polyacrylic film is used, these There was a problem that the protective film did not adhere at all.

JP 2008-257199 A (Patent Document 8) 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 photopolymerizability 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 photopolymerizability 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, the photopolymerizability is lowered, and peeling occurs between the PVA polarizer and the protective film when exposed to poor adhesion or wet heat.
On the other hand, if the photopolymerizability 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, if the number of alicyclic epoxy resins is increased, when protective films such as polyester film, polyvinyl chloride film, polycarbonate film, and polyacrylic film are used, there is a problem that these protective films do not adhere at all. was there.

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 photopolymerizable adhesive for forming a polarizing film is required to have a low viscosity in a state that does not substantially contain an organic solvent.

JP 2000-127281 A Japanese Patent Publication No. 03-041234 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 provides a photopolymerizable oxirane-based resin composition having excellent photopolymerizability even at low illuminance and having excellent heat resistance, moisture resistance, thermal dimensional stability, weather resistance and the like when cured. This is the issue. In addition, in the bonding of various optical films, regardless of the type of various optical films, a photopolymerizable coating agent that can be easily and firmly bonded, substantially does not contain an organic solvent, has low viscosity and excellent thin film coatability, Alternatively, it is an object to provide a photopolymerizable adhesive. Furthermore, it aims at providing the polarizing plate which was excellent in the punching workability and wet heat durability compared with the conventional polarizing plate using it.

As a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned goal can be achieved by the photopolymerizable oxirane-based resin composition shown below, and further a photopolymerizable adhesive composition using the same. Thus, the present invention has been completed.

That is, the present invention is a photopolymerizable oxirane-based resin composition containing the oxirane compound (A) as a main component and further containing no more than a four-membered cyclic compound (B) having two or more oxygen atoms. A polymerizable oxirane system in which 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 carbonate ring, a dioxolane ring, and a dioxane ring. The present invention relates to a resin composition.

Furthermore, the present invention contains 0.5 to 60 parts by weight of a cyclic compound (B) having four or more membered rings having two or more oxygen atoms with respect to 100 parts by weight of the oxirane compound (A) as the main component. The present invention relates to the above-mentioned photopolymerizable oxirane resin composition.

Furthermore, the present invention provides a fluorine-containing cyclic compound (B ′) in which at least one or more 4-membered cyclic compound (B) having two or more oxygen atoms is substituted with a substituent having an F atom. The above-mentioned photopolymerizable oxirane-based resin composition, which contains

Furthermore, this invention relates to said photopolymerizable oxirane resin composition characterized by the oxirane compound (A) containing the compound (a-1) which has an aromatic ring.

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

Furthermore, this invention relates to the photopolymerizable coating agent characterized by containing a photoinitiator in the photopolymerizable oxirane resin composition in any one of said.

Furthermore, this invention relates to the photopolymerizable adhesive composition characterized by including a photoinitiator in the photopolymerizable oxirane resin composition in any one of said.

Furthermore, the present invention is a group wherein 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 above-mentioned photopolymerizable contact coating agent selected from the above.

Furthermore, the present invention is a group wherein 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 above-mentioned photopolymerizable adhesive selected from the above.

Furthermore, the present invention provides a layer comprising the above-mentioned photopolymerizable oxirane-based resin composition and / or photopolymerizable coating agent and / or the photopolymerizable adhesive according to the eighth invention on a base material (G ) On one side or both sides of the laminate.

Furthermore, this invention relates to said laminated body characterized by the base material (G) being a transparent film (H).

Furthermore, this invention relates to said laminated body characterized by the transparent film (H) being an optical film (I).

Furthermore, the present invention is characterized in that the optical film (I) is a polyacetyl cellulose film, a polynorbornene film, a polyacryl film, a polycarbonate film, a polyester film, a polyimide film or a polyvinyl alcohol film. It is related with said laminated body.

Furthermore, this invention relates to the polarizing plate characterized by adhere | attaching said laminated body on the single side | surface or both surfaces of a polyvinyl alcohol-type polarizer.

  According to the present invention, a photopolymerizable oxirane-based resin composition that can be polymerized at low illuminance, and a photopolymerizable coating agent or photopolymerizable adhesive composition using the photopolymerizable oxirane-based resin composition can be easily and firmly bonded. In addition, it is possible to obtain a laminate having good punchability, heat resistance, and heat-and-moisture resistance, and a particularly excellent polarizing plate can be provided.

  The photopolymerizable oxirane-based resin composition of the present invention is characterized in that an oxirane compound (A) and a cyclic compound (B) having at least four members having two or more oxygen atoms are essential components.

First, the oxirane compound (A) will be described.
In the photopolymerizable oxirane resin composition of the present invention, the 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 used without any particular limitation. it can.
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 an 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 an oxirane compound (A) is usually 30 to 3000 g / eq, 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 oxirane compound (A) of the present invention preferably contains an oxirane compound (a-1) having an aromatic ring in addition to a three-membered cyclic ether group in order to improve heat resistance and moist heat resistance. 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, 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, 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, trindene, 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 oxirane compound (A) of the present invention 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 associated with the photopolymerization of the adhesive described later is improved, and it is 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. These contents in the oxirane compound (A) are such that any one of (a-1), (a-2) and (a-12) contains 50% by weight or more in 100% by weight of (A). However, it is preferable in terms of polymerizability and heat and humidity 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.

Next, the cyclic compound (B) having four or more members having two or more oxygen atoms will be described.
Further, the photopolymerizable oxirane-based resin 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 carbonate ring, a dioxolane ring, a dioxane. From the viewpoint of photopolymerization, it is preferable to have at least one of the rings.

As the carbonate ring-containing cyclic compound (b-1) 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 structure of a 5-membered ring, a 6-membered ring or a 7-membered ring or more, 1,5-dioxolanes for the 5-membered ring, 1,3-dioxanes for the 6-membered ring, and 1 for the 7-membered ring. , 3-Dioxepanes, but is independently classified as cyclic carbonates because the carbon at the 2-position is a carbonyl carbon.
Specific examples thereof include, for example, ethylene carbonate (also referred to as 1,3-dioxolan-2-one), propylene carbonate, butylene carbonate, 4-pentyl-1,3-dioxolan-2-one, 4-butyl-1, 3-dioxolane-2-one, 4-propyl-1,3-dioxolane-2-one, 4- (isopropoxymethyl) -1,3-dioxolane-2-one, 4-hexyl-1,3-dioxolane- 2-one, 4-hexyl-5-methylene-1,3-dioxolane-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4,5,5-tetramethyl-1 , 3-dioxolane-2-one, 4-octyl-1,3-dioxolane-2-one, 4-nonyl-5-vinyl-1,3-dioxolan-2-one, 4-decyl -1,3-dioxolan-2-one, 4,5-bismethylene-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4,4,5,5 -Tetraethyl-1,3-dioxolan-2-one, hexahydro-1,3-benzodioxol-2-one, 4-isopropyl-4-methyl-5-methylene-1,3-dioxolan-2-one, Vinylene carbonate, allyl ethylene carbonate, allyl succinic anhydride, 4-vinyl-1,3-dioxolan-2-one, 4-phenethyl-5-vinyl-1,3-dioxolan-2-one, 4-methylene-1, 3-dioxolan-2-one, 4- (3-butenyl) -1,3-dioxolan-2-one, 4- (5-hydroxy-6,6-dimethyltetrahydro-2H-pi N-2-yl) -1,3-dioxolane-2-one, 4-[(E) -iodomethylene] -5-cyclopropyl-1,3-dioxolan-2-one, 4-cyclohexyl-5-vinyl -1,3-dioxolan-2-one, 4- (allyloxy) -4,5,5-trimethyl-1,3-dioxolan-2-one, 4-[(1E) -1,3-butadienyl] -1 , 3-Dioxolane-2-one, 4-Ethyl-4-methyl-5-methylene-1,3-dioxolane-2-one, 4- (2-Methyl-2-propenylidene) -5,5-dimethyl-1 , 3-Dioxolane-2-one, 4- [4- (methoxycarbonyloxy) butyl] -1,3-dioxolane-2-one, 4-vinyl-5,5-diethyl-1,3-dioxolane-2- ON, 4-phenyl-5- Vinyl-1,3-dioxolan-2-one, 4,5,5-trimethyl-4- (1-propynyl) -1,3-dioxolan-2-one, 4-vinyl-5,5-bis (2- (Cyclohexylethyl) -1,3-dioxolane-2-one, 4,5,5-trimethyl-4- (3-methyl-3-buten-1-ynyl) -1,3-dioxolan-2-one, 4- (Vinyloxymethyl) -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(E) -3-buten-1-ylidene] -1,3-dioxolan-2-one, 4- [(E) -3-butene-1-ylidene] -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -1-phenyl-3-buten-1-ylidene]- 1,3-dioxolan-2-one, methacrylic acid (2-oxo-1 3-Dioxolan-4-yl) methyl, 4-methyl-5-[(E) -3-buten-1-ylidene] -1,3-dioxolan-2-one, 4-methyl-5-[(Z) -3-butene-1-ylidene] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(Z) -2-butyn-1-ylidene] -1,3-dioxolane-2- ON, 4,4-dimethyl-5-[(E) -ethylidene] -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -3-buten-1-ylidene]- 1,3-dioxolane-2-one, 4- (1-hexynyl) -4-methyl-1,3-dioxolan-2-one, 4- (1-propenyloxymethyl) -1,3-dioxolane-2- ON, 4-[(1E) -1-methyl-3-butenylidene] -1,3-di Xolan-2-one, 4-[(1Z) -1-phenyl-3-butenylidene] -1,3-dioxolan-2-one, 4,4-dipentyl-5-[(1E) -1,3-butadienyl ] -1,3-dioxolane-2-one, 4-phenyl-5-methylene-1,3-dioxolane-2-one, 4-methyl-5-methylene-1,3-dioxolan-2-one, 4- Methyl-4-vinyl-5-methylene-1,3-dioxolane-2-one, 4-propargyl-5-methylene-1,3-dioxolan-2-one, 4-[(E) -bromomethylene] -1 , 3-Dioxolan-2-one, [(E) -2-oxo-5,5-dimethyl-1,3-dioxolane-4-ylidene] ethyl acetate, 4-[(E) -2- (tert-butoxy) Carbonyloxy) ethylidene] -1,3-dioxolan-2-one, 4-ethyl-5-methylene-1,3-dioxolan-2-one, 4- (hydroxymethyl) -1,3-dioxolan-2-one, 4- [ (E) -2- (tert-Butoxycarbonyloxy) ethylidene] -5-methyl-1,3-dioxolan-2-one, 4,5-divinyl-1,3-dioxolan-2-one, 4- (1 -Naphthyl) -5-vinyl-1,3-dioxolane-2-one, 4,4-bis (2-cyclohexylethyl) -5-[(1E) -1,3-butadienyl] -1,3-dioxolane- 2-one, (4S) -4-phenyl-4-methyl-5- (1,3-butadienyl) -1,3-dioxolan-2-one, 4- (2-propyne-1-ylidene) -5 5-Dimethyl-1,3-dioxola -2-one, 4,4-dimethyl-5-methylene-1,3-dioxolane-2-one, 5-butyl-5-methyl-4-methylene-1,3-dioxolan-2-one, glycerin carbonate, 4- (Butoxymethyl) -1,3-dioxolane-2-one, 4- (allyloxymethyl) -1,3-dioxolane-2-one, 4- (hydroxymethyl) -1,3-dioxolane-2- ON, 4- (methoxymethyl) -1,3-dioxolane-2-one, 4- (4-ethenylbenzyloxymethyl) -1,3-dioxolane-2-one, 4-ethyl-4-methyl-5 -(3-Phenylpropylidene) -1,3-dioxolane-2-one, 4-ethyl-4-methyl-5-benzylidene-1,3-dioxolan-2-one, 4- (hexylthiomethyl) 1,3-dioxolan-2-one, 4,4-dimethyl-5-[(E) -2-phenylethylidene] -1,3-dioxolan-2-one, 4- (p-tolyl) -1,3 -Dioxolan-2-one, 4-methyl-5-phenyl-1,3-dioxolane-2-one, 4-benzyl-1,3-dioxolan-2-one, 4- (benzyloxymethyl) -1,3 -Dioxolane-2-one, 4-phenyl-1,3-dioxolane-2-one, 4-phenyl-4-methyl-5-methylene-1,3-dioxolan-2-one, 4-phenyl-1,3 -Dioxolane-2-one, 4-methyl-4-phenyl-1,3-dioxolane-2-one, 4-phenoxy-1,3-dioxolan-2-one, 4-butoxy-4,5-dimethyl-5 -Phenyl-1,3-di Oxolane-2-one, (4S) -4β- (phenylethynyl) -4-phenethyl-5-[(Z) -benzylidene] -1,3-dioxolan-2-one, 4- [4- (phenoxycarbonyloxy) ) Butyl] -1,3-dioxolan-2-one, 4- [4- (glycidylcarbamoyloxy) butyl] -1,3-dioxolan-2-one, 4-oxiranyl-1,3-dioxolan-2-one 4- [4- (2-Oxo-1,3-dioxolan-4-ylmethylcarbamoyloxy) butyl] -1,3-dioxolan-2-one, 4- (2-oxo-1,3-dioxolane- 4-ylmethylcarbamoyloxymethyl) -1,3-dioxolan-2-one, 4,4'-bi [1,3-dioxolan-2-one], 4,4'-tetramethylenebis 1,3-dioxolan-2-one), 4,4 '-(ethylenebisthiobistetramethylene) bis (1,3-dioxolan-2-one), 4,4'-[1,6-hexanediylbis (Oxymethylene)] bis (1,3-dioxolan-2-one), 4,4 '-[hexamethylenebis (thioethylene)] bis (1,3-dioxolan-2-one), 4,4'-[ Isobutylidenebis (4,1-phenylene) bisoxybismethylene] bis (1,3-dioxolan-2-one), 4,4 '-[isopropylidenebis [(4,1-phenylene) oxymethylene]] Bis (1,3-dioxolan-2-one), 4,4-dimethyl-5-[(Z) -benzylidene] -1,3-dioxolan-2-one, 4- [2- (benzyloxy) ethyl] -1,3-di Oxolane-2-one, 4- [2- (trityloxy) ethyl] -1,3-dioxolan-2-one, 4,5-diphenyl-1,3-dioxolan-2-one, 4,4-dimethyl- 5- [1- (1-naphthyl) ethenyl] -1,3-dioxolane-2-one, 4,4-dimethyl-5- [1- (2-naphthyl) ethenyl] -1,3-dioxolane-2- ON, 4,4-Dimethyl-5- [1- (4-methylphenyl) ethenyl] -1,3-dioxolan-2-one, 4,4-Dimethyl-5- [1- (4-methoxyphenyl) ethenyl ] -1,3-dioxolan-2-one, 4,4-dimethyl-5- [1- (4-hydroxyphenyl) ethenyl] -1,3-dioxolan-2-one, 4,4-dimethyl-5- (1-methylene-2-phenyl-2-propyl Penyl) -1,3-dioxolan-2-one, 4,4-dimethyl-5-[(E) -1-methylene-3-phenyl-2-propenyl] -1,3-dioxolan-2-one, 4, , 4-Dimethyl-5- (1-phenylethenyl) -1,3-dioxolan-2-one, 4-methyl-5- (1-phenylethenyl) -1,3-dioxolan-2-one, 4, , 4-Dimethyl-5-[(E) -3-phenyl-1-propenyl] -1,3-dioxolane-2-one, 4- (1-phenylethenyl) -1,3-dioxolan-2-one 4,4-dimethyl-5- (1-phenyl-1-propenyl) -1,3-dioxolan-2-one, 4,4-dimethyl-5- (1,2-diphenylethenyl) -1,3 -Dioxolan-2-one, 4,4-dimethyl-5- (2 Methyl-1-phenyl-1-propenyl) -1,3-dioxolan-2-one, 4,4,5-trimethyl-5- (1-phenylethenyl) -1,3-dioxolan-2-one, 4, -(Benzyloxymethyl) -1,3-dioxolan-2-one, 4,4-diphenyl-1,3-dioxolan-2-one, 4,4 '-[(1,3-phenylene) bis (oxymethylene )] Bis (1,3-dioxolan-2-one, 4,4-dimethyl-5-[(Z) -1-naphthylmethylene] -1,3-dioxolan-2-one, 4,4-dimethyl-5 -[(Z) -4-methoxybenzylidene] -1,3-dioxolane-2-one, 4,4-dimethyl-5-[(Z) -4-hydroxybenzylidene] -1,3-dioxolane-2-one 4- (Phenylethynyl) -4-Methyl-1,3-dioxolan-2-one, 4- (phenylethynyl) -4,5-dimethyl-1,3-dioxolan-2-one, 4- [1- (4-methoxyphenoxy) vinyl ] -5,5-diethyl-1,3-dioxolan-2-one, 4- [1- (4-methoxyphenoxy) ethenyl] -5,5-dimethyl-1,3-dioxolan-2-one, 4- [3- (Benzyloxy) propyl] -5-methyl-1,3-dioxolan-2-one, 7- [2- (2-oxo-1,3-dioxolan-4-yl) ethoxy] -2H-1 -Benzopyran-2-one, 7- [2- (2-oxo-4-methyl-1,3-dioxolan-4-yl) ethoxy] -2H-1-benzopyran-2-one, 5- (benzyloxy) -1,3-Dioxolane-2- 4- (Isobutoxymethyl) -1,3-dioxolane-2-one, 4- (4-nonylbenzyloxymethyl) -1,3-dioxolane-2-one, 4- (4-chlorophenylthiomethyl) -1,3-dioxolane-2-one, 4- [3- (chloromethyl) phenyl] -1,3-dioxolane-2-one, 4- [4- (chloromethyl) phenyl] -1,3-dioxolane -2-one, 4,4-dipropyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolan-2-one, 4,4-dipentyl-5- [1- (4-methoxy Phenoxy) ethenyl] -1,3-dioxolan-2-one, 4,4-diisopropyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolan-2-one, 4,4-diphe Tyl-5- [1- (4-methoxyphenoxy) ethenyl] -1,3-dioxolan-2-one, 4,4-bis (2-cyclohexylethyl) -5- [1- (4-methoxyphenoxy) ethenyl ] -1,3-dioxolane-2-one, 4- [1- (phenylthio) cyclohexyl] -1,3-dioxolane-2-one, 4- (3-methoxy-4-ethoxyphenyl) -5- (hydroxy Methyl) -1,3-dioxolane-2-one, 4- (phenoxycarbonyloxymethyl) -1,3-dioxolane-2-one, 4-benzylidene-5,5-dimethyl-1,3-dioxolane-2- ON, 4-[(2-naphthyl) methylene] -5,5-dimethyl-1,3-dioxolan-2-one, 4- (4-chlorobenzylidene) -5,5-dimethyl-1, 3-Dioxolane-2-one, 5-methyl-5-phenyl-4- (3-phenylpropylidene) -1,3-dioxolan-2-one, 5,5-dimethyl-4- (3-phenylpropylidene)- 1,3-dioxolan-2-one, 4- [4- (chlorocarbonyloxy) butyl] -1,3-dioxolan-2-one, 4-chloro-1,3-dioxolan-2-one, 4-chloro -4,5-dimethyl-1,3-dioxolan-2-one, 4- (chlorocarbonyloxymethyl) -1,3-dioxolan-2-one, 4- (p-chlorophenoxymethyl) -1,3- Dioxolane-2-one, 4- (chloromethyl) -1,3-dioxolane-2-one, 4,5-dichloro-1,3-dioxolan-2-one, (4S, 5R) -4,5-diphenyl - , 3-dioxolan-2-one, 4α, 5α-dimethyl-1,3-dioxolan-2-one, (4R, 5R) -4,5-dimethyl-1,3-dioxolan-2-one, (4S, 5S) -4,5-dimethyl-1,3-dioxolane-2-one, (4S) -4β-methyl-1,3-dioxolan-2-one, (R) -4-methyl-1,3-dioxolane -2-one, (S) -5-ethyl-1,3-dioxolane-2-one, 4-[(triphenylsilyl) methyl] -5,5-dimethyl-1,3-dioxolan-2-one, 4- [9- (3-Thienyl) nonyl] -1,3-dioxolan-2-one, 4- (methylaminomethyl) -1,3-dioxolan-2-one, 4- (4-chlorophenylthio)- 1,3-Dioxolan-2-one, 4- (Fe Ruthio) -1,3-dioxolane-2-one, 4- (4-methoxyphenylthio) -1,3-dioxolane-2-one, 4- (4-bromophenylthio) -1,3-dioxolane-2 -One 4- (phenylthiomethyl) -1,3-dioxolane-2-one, 4,4 '-[sulfonylbis (p-phenyleneoxymethylene)] bis (1,3-dioxolan-2-one), 4 -(4-Methylphenylthio) -1,3-dioxolane-2-one, 4,4,5,5-tetramethyl-2- (phenylsulfonyloxyimino) -1,3-dioxolane, 2- (4- Nitrophenoxy) -4-methyl-2-phospha (V) -1,3-dioxolan-2-one, 4- (glycidyloxymethyl) -1,3-dioxolan-2-one, glycidylcarbamic acid (2-Oxo-1,3-dioxolan-4-yl) methyl, 4- (norborna-5-en-2-yl) -1,3-dioxolan-2-one, 4- [2- (2-naphthyl) ) Ethyl] -5-methoxy-1,3-dioxolan-2-one, 4- [2- (1-naphthyl) ethyl] -5-methoxy-1,3-dioxolan-2-one, 4,4-dimethyl -5- (3-thienylmethylene) -1,3-dioxolane-2-one, 4- [2- [dimethyl (trimethylsilyloxy) silyl] ethyl] -1,3-dioxolan-2-one, 4- [2 -[(Methyl) bis (trimethylsilyloxy) silyl] ethyl] -1,3-dioxolane-2-one, 4- [2- (trimethylsilyl) ethyl] -1,3-dioxolan-2-one, 4- [4 -(Glycidylcar Moyloxy) butyl] -1,3-dioxolan-2-one, 4- [4- (2-oxo-1,3-dioxolan-4-ylmethylcarbamoyloxy) butyl] -1,3-dioxolan-2-one 4- [4- (Glycidylcarbamoyloxy) butyl] -1,3-dioxolan-2-one, 4- (2-oxo-1,3-dioxolan-4-ylmethylcarbamoyloxymethyl) -1,3- 5-membered ring carbonates such as dioxolan-2-one;

For example, trimethylene carbonate (also called 1,3-dioxan-2-one), 4-methyl-1,3-dioxan-2-one, 2,2-dimethoxypropane-1,3-diyl carbonate, 5-methyl- 1,3-dioxane-2-one, 5,5-dimethyl-1,3-dioxane-2-one (also called neopentyl glycol carbonate), 5-methyl-5-propyl-1,3-dioxane-2- ON, 5-hydroxymethyl-5-methyl-1,3-dioxane-2-one, 4-phenyl-1,3-dioxan-2-one, 5- (hydroxymethyl) -5-ethyl-1,3- Dioxane-2-one, 4-methylene-1,3-dioxane-2-one, 5,5-dimethyl-4-ethenyl-1,3-dioxane-2-one, 5-cyano-5-methyl-1, 3- Oxan-2-one, 4,4-dimethyl-1,3-dioxane-2-one, 5-butyl-1,3-dioxane-2-one, 5,5-diethyl-1,3-dioxane-2- ON, 5-ethyl-5-phenyl-1,3-dioxane-2-one, 2-oxo-5-ethyl-1,3-dioxane-5-ylmethyl methacrylate, 5-methyl-5-phenyl-1, 3-Dioxane-2-one, 4-styryl-5,5-dimethyl-1,3-dioxane-2-one, 4-styryl-1,3-dioxane-2-one, 4- (1-heptenyl)- 1,3-dioxane-2-one, 4-ethenyl-6-phenyl-1,3-dioxane-2-one, 4-isopropenyl-6-phenyl-1,3-dioxane-2-one, 4-allyl -6-Phenyl-1,3-dioxy -2-one, 4-ethenyl-6-tert-butyl-1,3-dioxane-2-one, 4-styryl-5,5-dimethyl-6-isopropyl-1,3-dioxane-2-one, 5- [2- (2-Amino-9H-purin-9-yl) ethyl] -1,3-dioxane-2-one, 4- (1-phenylethenyl) -1,3-dioxane-2-one 5,5-diphenyl-1,3-dioxane-2-one, 5-methyl-4- (1-phenylethenyl) -1,3-dioxane-2-one, 4,4-dimethyl-6- ( 1-Phenylethenyl) -1,3-dioxane-2-one, 5-methylene-1,3-dioxane-2-one, 4-[(E) -styryl] -1,3-dioxane-2-one 5-octyl-1,3-dioxane-2-one, 5-dodecyl- 1,3-Dioxane-2-one, Benzyl 2-oxo-5-methyl-1,3-dioxane-5-carboxylate, 4,6-dimethyl-1,3-dioxane-2-one, 4-methoxybenzoate 2-oxo-5-methyl-1,3-dioxan-5-ylmethyl acid, 2-oxo-5-methyl-1,3-dioxan-5-ylmethyl benzoate, 4-oxobenzoic acid 2-nitrobenzoate Methyl-1,3-dioxane-5-ylmethyl, 4,4,6-trimethyl-1,3-dioxane-2-one, 5-ethyl-5- (methoxycarbonyloxymethyl) -1,3-dioxane-2 -One, 5-ethyl-5- (ethoxycarbonyloxymethyl) -1,3-dioxane-2-one, 5- (4-butoxyphenyl) -1,3-dioxane-2-one, 5- [4- (pen Ruoxy) phenyl] -1,3-dioxane-2-one, 5- (4-propoxyphenyl) -1,3-dioxane-2-one, 5- [4- (hexyloxy) phenyl] -1,3- Dioxane-2-one, 5-allyl-1,3-dioxane-2-one, 5- (benzyloxycarbonyl) -1,3-dioxane-2-one, 5-methyl-4- (benzoyloxymethyl)- 1,3-dioxane-2-one, 5-methyl-4- (4-nitrobenzoyloxymethyl) -1,3-dioxan-2-one, 5-methyl-4- (4-methoxybenzoyloxymethyl)- 1,3-dioxane-2-one, 5- (4-methylene-5-hexen-1-ylidene) -1,3-dioxane-2-one, 5-ethyl-5- (4-vinylbenzyloxymethyl) 1,3-dioxane-2-one, 5-ethyl-5- (4-vinylbenzyloxymethyl) -1,3-dioxane-2-one, 5- (benzyloxy) -1,3-dioxane-2- ON, 5-hydroxy-1,3-dioxane-2-one, 4-methylene-5,5-dimethyl-1,3-dioxane-2-one, 5-ethyl-5- (2-hydroxyethyl) -1 , 3-Dioxane-2-one, 4- [1- (phenylthio) cyclohexyl] -1,3-dioxane-2-one, 4- [4- (octyloxy) phenylazo] -6-hexyl-1,3- Dioxane-2-one, 4- (4-methoxyphenylazo) -6-hexyl-1,3-dioxane-2-one, 4- [4- (octyloxy) phenylazo] -6-decyl-1,3- Dioxane-2- ON, 2-oxo-5-methyl-1,3-dioxane-5-carboxylate allyl, 4- [1- (phenylthio) cyclohexyl] -5,5-dimethyl-1,3-dioxane-2-one, 4 -Allyl-6-methyl-1,3-dioxane-2-one, 5-ethyl-5- (benzyloxymethyl) -1,3-dioxane-2-one, 5- [2- (benzyloxy) ethoxy] -1,3-dioxane-2-one, 5- (allyloxy) -1,3-dioxane-2-one, 5- [3- (2-hydroxyethylthio) propoxy] -1,3-dioxane-2- ON, 5- (benzyloxycarbonylamino) -1,3-dioxane-2-one, 5- [6- [4- (4-pentylcyclohexyl) phenoxy] hexyloxy] -1,3-dioxane-2-o 4- (Iodomethyl) -6- [2- (4-methoxybenzyloxy) ethyl] -1,3-dioxan-2-one, (5S) -4-vinyl-5β- (2,2-dimethoxyethyl) -1,3-dioxane-2-one, 5-allyl-5-propargyl-1,3-dioxan-2-one, 4-vinyl-5- (1-methyl-5-imidazolylmethyl) -1,3- Dioxane-2-one, 5-benzylidene-1,3-dioxane-2-one, 5- (glycidyloxymethyl) -5-ethyl-1,3-dioxane-2-one, 5- (allyloxymethyl)- 5-ethyl-1,3-dioxane-2-one, 5,5-bis (azidomethyl) -1,3-dioxane-2-one, 5-methyl-5-[[2- (vinylsulfonyl) ethyl] thiomethyl ] -1,3-Di Oxan-2-one, 5- (allyloxymethyl) -5-ethyl-1,3-dioxane-2-one, 5,5 '-(oxybismethylene) bis (5-ethyl-1,3-dioxane- 2-one), 5,5 '-(4,7-dithiadecane-1,10-diyl) bis (1,3-dioxane-2-one), 5,5'-(ethylenebisthiobistetramethylene) bis (1,3-Dioxane-2-one), 5-methyl-5- (2-oxo-1,3-dioxolan-4-ylmethyl) -1,3-dioxane-2-one, 5-ethyl-5- (2-Oxo-1,3-dioxolan-4-ylmethyl) -1,3-dioxan-2-one, 5-[(2-oxo-1,3-dioxolan-4-yl) methyl] -5-propyl -1,3-dioxane-2-one, 5- (2-o Seo-1,3-dioxolan-4-ylmethoxy) -5-ethyl-1,3-dioxan-2-one 6-membered ring carbonates such as;

For example, tetramethylene carbonate (also referred to as 1,3-dioxepan-2-one), 5-methyl-1,3-dioxepan-2-one, 4-methyl-1,3-dioxepan-2-one, 5,5 -Dimethyl-1,3-dioxepan-2-one, 5-phenyl-1,3-dioxepan-2-one, 4-phenyl-1,3-dioxepan-2-one, 4- [1- (phenylthio) cyclohexyl ] 7-membered ring carbonates such as 1,3-dioxepan-2-one, 5,5 '-(ethylenebisthiobistrimethylene) bis (1,3-dioxepan-2-one) 5-membered ring carbonates such as propylene carbonate and glycerin carbonate are preferably used in terms of reactivity.

The dioxolane ring-containing cyclic compound (b-2) in the present invention is obtained by acetalizing a carbonyl group. 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-dimethano 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-dioxy Lan, 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-dioxolane) -4-yl) methyl acrylate, (2-methyl-2-oxo-1,3-dioxolan-4-yl) methyl methacrylate, 2,2′-bi (1,3-dioxolane), 2-phenyl-2 , 2′-bi (1,3-dioxolane) and the like.

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

Examples of the dioxane ring-containing cyclic compound (b-3) 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) -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 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-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] -ON 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) hexa 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, -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-tetrachrome 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, 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, 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) bis ( Tylene)] 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-di Xan-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-dioxane-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, Examples include 1,4-dioxane derivatives such as 5-dione and [(1,4-dioxane-2,3-diyl) bisthio] bis (thiophosphonic acid O, O-diethyl).

Among the dioxane ring-containing cyclic compounds (b-3), 1,2-dioxane, 1,3-dioxane and 1,4-dioxane are preferable from the viewpoint of ring-opening copolymerization with the oxirane compound (A). 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.

Next, the fluorine-containing cyclic compound (B ′) substituted with at least one or more substituents having F atoms will be described.
In the cyclic compound (B) having four or more membered rings having two or more oxygen atoms of the present invention, F is further included in the cyclic structure of the cyclic compound (B) for further improvement of heat resistance and moist heat resistance. It is preferable to include a fluorine-containing cyclic compound (B ′) substituted with at least one or more substituents having atoms.
More preferable examples of the F atom-containing substituent include F-, CF3-, CF2H-, CFH2-, CF3CF2-, CHF2CF2-, CH3CF2-, CF3CH2-, CF3CF2CH2-, CF3CF2CF2-, CH (CF3 ) 2-, CHF2CF2CH2-, CHF2CF2CH2-, CF3CH2CH2-, CF3CF2CF2CF2-, CHF2CF2CF2CH2-, CF3CHFCF2CH2-, CHF2CF (CF3) CH2-, CF3CF2CH2CH2-, CHF2CF2CF2CF2CH2-, CF3CF2CF2CF2- Or it is a fluorine-containing alkyl group having 3 or less carbon atoms in that it is possible to maintain effective adhesive force, heat resistance and moist heat resistance. Preferred.
Moreover, it is preferable in any position on the structure of the cyclic compound (B), and the effect can be sufficiently exhibited.

  In the photopolymerizable oxirane resin composition of the present invention, the fluorine-containing cyclic compound (B ′) substituted with at least one substituent having an F atom may be a fluorine-containing carbonate (b-1 ′). From the viewpoint of heat resistance and heat-and-moisture resistance, it is preferable to have at least one of fluorine-containing dioxolanes (b-2 ′).

More specifically, examples of the fluorine-containing carbonates (b-1 ′) include fluoroethylene carbonate, trifluoromethyl ethylene carbonate, 4- (trifluoromethyl) -5- (phenylthio) -1,3-dioxolane. -2-one, 4- [4- (trifluoromethyl) benzylidene] -5,5-dimethyl-1,3-dioxolane-2-one, 4-fluoro-4-methyl-1,3-dioxolane-2- ON, 4-fluoro-5-methyl-1,3-dioxolane-2-one, 4-trifluoromethyl-4-methyl-1,3-dioxolane-2-one, 4- (trifluoromethyl) -1, 3-dioxolan-2-one, 4- (2,2,3,3,4,4,5,5,5-nonafluoropentyl) -1,3-dioxolan-2-one, 4,5- Difluoro-1,3-dioxolane-2-one, 4-fluoro-4-ethyl-1,3-dioxolan-2-one, 4,4-difluoro-1,3-dioxolan-2-one, 4- (α , Α-Difluorobenzyl) -1,3-dioxolan-2-one, 4-[(tetrahydrofuran-3-yl) difluoromethyl] -1,3-dioxolan-2-one, 4-fluoro-4-[(4 -Methoxyphenyl) thio] -1,3-dioxolane-2-one, 4-fluoro-4- (4-bromophenylthio) -1,3-dioxolan-2-one, 4- (phenylthiofluoromethyl)- 1,3-dioxolan-2-one, 4- (phenylthiodifluoromethyl) -1,3-dioxolan-2-one, 4- [difluoro (phenylsulfonyl) methyl] -1,3- Dioxolane-2-one, 4- [difluoro (phenylsulfinyl) methyl] -1,3-dioxolane-2-one, 4-fluoro-4- (4-methylphenylthio) -1,3-dioxolan-2-one 4-[[4- (Fluoromethyl) phenyl] thio] -1,3-dioxolane-2-one, 4-fluoro-4- (phenylthio) -1,3-dioxolan-2-one, 4-fluoro- 5-membered fluorine-containing carbonates such as 4- (4-chlorophenylthio) -1,3-dioxolan-2-one;

For example, 4-fluoro-1,3-dioxane-2-one, 4-fluoro-4-methyl-1,3-dioxane-2-one, 4-fluoro-5-methyl-1,3-dioxane-2- ON, 4,5-difluoro-1,3-dioxane-2-one, 4-trifluoromethyl-1,3-dioxane-2-one, 4,5-di (trifluoromethyl) -1,3-dioxane 6-membered fluorine-containing carbonates such as -2-one;

For example, 4-fluoro-1,3-dioxepan-2-one, 5-fluoro-1,3-dioxepan-2-one, 4-fluoro-4-methyl-1,3-dioxepan-2-one, 4- 7-membered ring-containing fluorinated carbonates such as trifluoromethyl-1,3-dioxepan-2-one are exemplified, but fluoroethylene carbonate, trifluoromethylethylene carbonate, 4,4-difluoro-1,3-dioxolane-2 A 5-membered ring-containing fluorinated carbonate of -one, 4,5-difluoro-1,3-dioxolan-2-one is preferably used in terms of reactivity.

More specific examples of the fluorine-containing dioxolanes (b-2 ′) include 2-fluoro-1,3-dioxolane, 4-fluoro-1,3-dioxolane, 2- (fluoromethylene) -1, 3-dioxolane, 2- (trifluoromethyl) -1,3-dioxolane, 2-difluoromethyl-1,3-dioxolane, 2-oxo-4α-fluoromethyl-1,3-dioxolane, 2,2-dimethyl- 4- (fluoromethyl) -1,3-dioxolane, cis-4-fluoromethyl-2-methyl-1,3-dioxolane, 2- (3-chloropropyl) -2- (p-fluorophenyl) -1, Fluorine-containing 1,3-dioxanes such as 3-dioxolane and the like, but fluorine-containing 1,3 of 2-fluoro-1,3-dioxolane and 4-fluoro-1,3-dioxolane Dioxanes are preferred in view of reactivity.
The fluorine-containing cyclic compound (B ′) substituted with at least one or more substituents having these F atoms may be used alone or in combination of two or more.

  In the photopolymerizable oxirane-based resin composition of the present invention, the cyclic compound (B) having a 4-membered ring or more having two or more oxygen atoms is based on 100 parts by weight of the oxirane compound (A) as a main component. B) is preferably contained 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 oxirane compound (A) is not improved when photopolymerization is performed. Since the force does not increase, it is not preferable because it is difficult to obtain an effective crosslinked coating film by photopolymerization. On the other hand, when the amount exceeds 60 parts by weight, when the photopolymerizable oxirane resin composition is used as a photopolymerizable adhesive, the polarity of the crosslinked coating film by photopolymerization becomes too large, and a nonpolar optical film ( Polyester film, norbornene film, etc.) is not preferable because it causes a decrease in adhesive strength.

In the present invention, the fluorine-containing cyclic compound (B ′) substituted with at least one or more substituents having an F atom is 100% by weight of a cyclic compound (B) having four or more members having two or more oxygen atoms, It is preferable to contain (B ') in the range of 10 to 100% by weight, and more preferably in the range of 50 to 100% by weight. By using at least one fluorine-containing cyclic compound (B ′) substituted with a substituent having an F atom within this range, it is possible to add heat resistance and heat and humidity resistance under even more severe conditions. Therefore, it is more preferable.

In the photopolymerizable oxirane-based resin composition of the present invention, the viscosity of the oxirane compound (A) is more than 200 mPa · s (viscosity at 23 ° C., the same shall apply hereinafter) and has an aromatic ring (a-1). The viscosities are often 5000 mPa · s or more, and many are solid.

Next, the ethylenically unsaturated compound (C) will be described.
The photopolymerizable oxirane-based resin composition in the present invention comprises a photopolymerizable oxirane-based photopolymerizable component other than the oxirane compound (A) and a cyclic compound (B) having four or more members having two or more oxygen atoms. It is also possible to include it in the range of 50% by weight or less in 100% by weight of the resin composition.
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. The ethylenically unsaturated compound (C) preferably has a viscosity of 0.5 to 2000 mPa · s, more preferably 1 to 1000 mPa · s. 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 oxirane-based resin composition and improving the thin film coatability, it is possible to maintain the photopolymerizability and maintain the adhesive strength and workability of the adhesive described later. it can.

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

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 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.

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 [4.2.1.03,7] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1] .03,8] dec-2-yl, dihydro-α-terpinyl (meth) acrylate, 6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl (meth) acrylate, (Meth) acrylic acid cyclic esters such as (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 oxirane resin composition of the present invention, as described above, when the ethylenically unsaturated compound (C) is contained, 50 wt% or less in 100 wt% of the photopolymerizable oxirane resin composition. Can be contained. When (C) exceeds 50% by weight, an unreacted ethylenically unsaturated compound (C) may remain. Therefore, the photopolymerization reaction rate does not improve, the cohesive force does not improve, and odor generation occurs. This is not preferable because there is a possibility.

Next, the photopolymerization initiator (D) will be described.
In this invention, it can be set as a photopolymerizable coating agent or a photopolymerizable adhesive agent by containing a photoinitiator (D) in the said photopolymerizable oxirane resin 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 Siebel 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, preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of the photopolymerizable oxirane resin 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.

Next, the antioxidant (F) will be described.
The photopolymerizable coating agent and photopolymerizable adhesive in the present invention may further contain an antioxidant (F). By containing the antioxidant (F), the coloration of the coating agent layer and the adhesive layer after photopolymerization 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 Co., Ltd.), and IRGANOX-PS-800FD (Ciba Specialty Chemicals). And the like, and hindered amine light stabilizers 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.

Next, a photopolymerizable coating agent or a photopolymerizable adhesive will be described.
The photopolymerizable coating agent or photopolymerizable adhesive of the present invention does not substantially contain an 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 photopolymerizable adhesive is within 5% by weight.

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

The photopolymerizable coating agent or the photopolymerizable adhesive in the present invention preferably contains substantially no organic solvent, and it is important that the viscosity is 1-1500 mPa · s, preferably 10-1300 mPa · s. s, and more preferably 20 to 1000 mPa · s. When the viscosity is higher than 1500 mPa · s, a thin film having a thickness of 0.1 to 6 μm cannot be applied when a polarizing film is formed, and optical properties such as transmittance are deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it becomes difficult to control the film thickness of the coating agent or the adhesive layer.
Since the viscosity of the photopolymerizable coating agent or the photopolymerizable adhesive is almost determined by the viscosity of the photopolymerizable oxirane resin composition, the viscosity of the photopolymerizable oxirane resin composition is 1 to 1500 mPa · s. By controlling in the range, the viscosity of the photopolymerizable coating agent or photopolymerizable adhesive can also be controlled.

According to a conventional method, a photopolymerizable coating agent or a photopolymerizable adhesive may be applied to the optical film by an appropriate method to form a photopolymerizable coating agent layer or an adhesive layer on the optical film.
The thickness of the photopolymerizable coating agent layer and the adhesive 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 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 photopolymerizable coating agent or the photopolymerizable adhesive 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 coater. Various coating methods such as a gravure coater, a lip coater, a comma coater, a curtain coater, a knife coater, a reverse coater, and a spin coater can be mentioned, but there is no particular limitation as long as thin film coating is possible.

The photopolymerizable coating agent or the photopolymerizable adhesive of the present invention is further suitable as an optical photopolymerizable coating agent or an optical photopolymerizable adhesive.
That is, as the base material (G), when the photopolymerizable oxirane resin composition is used as a coating agent on one or both sides of the base material (G), cloth, wood, metal plate, plastic plate, film It can be used without particular limitation, such as a shaped substrate, a glass plate, and a processed paper product. On the other hand, when the photopolymerizable oxirane-based resin composition is used as an adhesive for bonding two or more base materials (G), active energy rays are used for polymerization by irradiation with active energy rays such as ultraviolet rays. It is necessary to use a base material that easily permeates, and it is particularly preferable to use a transparent film (H) or a transparent glass plate. Even when using a base material that does not easily transmit active energy rays on one side, such as wood, metal plates, plastic plates, paper products, etc., the other side uses a transparent film (H) or a transparent glass plate. It can be used if it is irradiated from (H) or the transparent glass plate side and a photopolymerization reaction (photocuring) is performed.

As the substrate (G), it is preferable to use a film-like substrate. Examples of the film-like substrate include cellophane, various plastic films, and film-like substrates such as paper. Use is preferred. Moreover, as a film-form base material, as long as it is transparent, a single-layer thing may be used, and the thing in the multilayer state formed by laminating | stacking a several base material can also be used.

Here, the laminated body formed by laminating | stacking on the single side | surface of a base material (G) or both surfaces using a photopolymerizable coating agent or a photopolymerizable adhesive agent is demonstrated generally.
When using the photopolymerization reaction by the active energy ray of the photopolymerizable oxirane resin composition, that is, among the above-mentioned base materials (G), the transparent film (H) which is a film-like base material and the transparent film (H And a photopolymerizable oxirane resin composition layer located on at least one surface of the laminate.

The laminate of the transparent film (H) can be obtained as follows.
When the photopolymerizable oxirane resin composition is used as a photopolymerizable coating agent, a laminate can be obtained by applying the coating agent to one side of the transparent film (H) which is a film-like substrate. . At this time, the coat layer is also used as a primer layer for easy adhesion.
In addition, when the photopolymerizable oxirane resin composition is used as a photopolymerizable adhesive, the photopolymerizable adhesive is applied to one side of the transparent film (H) which is a film-like substrate, and another transparent film Laminating (H) on the surface of the adhesive layer, or further applying an adhesive on one or both sides of this laminate, and further laminating it on another transparent film (H), glass, or transparent molded body. Thus, a laminate can be obtained.
The photopolymerization reaction by the active energy rays of the photopolymerizable coating agent or polymerizable adhesive proceeds when the coating agent or adhesive is applied or laminated, or by irradiating the active energy rays after lamination. However, it is preferable to advance the photopolymerization reaction by irradiating active energy rays after lamination.

The transparent film (H) can be used for the optical film (I) of information communication equipment such as a display and a touch panel.

Here, a general description of the optical element laminate will be given.
A photopolymerizable coating agent or a photopolymerizable adhesive composition is used to form a laminate for an optical element.
When the photopolymerizable oxirane resin composition is used as a photopolymerizable coating agent, the basic laminate structure of the optical element laminate is transparent film / coat layer or coat layer / transparent film / coat layer. A sheet-like optical coat laminate.
In addition, when used as an adhesive, it is a transparent film / adhesive layer / transparent film or a sheet-like double-sided photopolymerizable adhesive laminate such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film. is there. Furthermore, as a laminated body for an optical element in which a multilayer optical film such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film, glass, or optical molded article is fixed to an optical member. used.

  As the various transparent films (H) used as the optical film (I), for example, thermoplastic resins having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like are used. The various transparent films (H) are also referred to as various plastic sheets, such as polyvinyl alcohol films, triacetyl cellulose films, polyolefin films such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer, polyethylene terephthalate, Polyester film such as polybutylene terephthalate, polycarbonate film, polynorbornene film, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl film, polyamide film, polyimide film, poly Examples include oxirane films.

  The transparent film (H) may have the same composition or different when used in multiple layers. For example, a polycycloolefin film may be used on one side, and a polyacrylic film may be used on the other side.

The thickness of the transparent film (H) can be appropriately determined, but is generally about 1 to 500 μm from the viewpoints of workability such as strength and handleability, and thin layer properties. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable. The transparent film (H) is particularly suitable when the thickness is 5 to 150 μm.
In addition, when providing a transparent film (H) on both sides of a polarizer of a polarizing film (also referred to as a polarizing plate) which is an optical film, the transparent film (H) made of the same resin material may be used on the front and back sides, and different resins A transparent film (H) made of a material or the like may be used.

As the optical laminate in the present invention, among the various transparent films (H), the optical film (I) mainly used for optical applications is preferably used. As the optical film (I), the transparent film (H) is subjected to a special treatment and has optical functions (light transmission, light diffusion, light collection, refraction, scattering, HAZE and other functions). What it has is called an optical film. These optical films are used alone or as a laminated body for an optical element by laminating several kinds of optical films in multiple layers with a coating agent or an adhesive. For example, hard coat film, antistatic coat film, antiglare coat film, polarizing film, retardation film, elliptically polarizing film, antireflection film, light diffusion film, brightness enhancement film, prism film (also called prism sheet), light guide Examples thereof include a film (also referred to as a light guide plate).
A polarizing film is also called a polarizing plate, and a polytriacetylcellulose-based protective film (hereinafter referred to as “TAC film”), which is a polyacetylcellulose-based film on both sides of a polyvinyl alcohol-based polarizer, or a polyvinyl alcohol-based polarized light. It is a sheet-like optical laminate having a multilayer structure in which one side or both sides of a child are sandwiched between polycycloolefin films, polyacrylic films, polycarbonate films, polyester films, etc., which are polynorbornene films.

  The laminated body of optical films using the photopolymerizable adhesive composition of the present invention can be used for glass plates such as liquid crystal display devices, PDP modules, touch panel modules, organic EL modules, and transparent films (H) of the various plastic films described above. It is preferable to stick and use as a laminated body for optical elements.

More specifically, the polarizing plate of the present invention can be obtained as follows.
(I) A photopolymerizable adhesive is applied to one surface of the first protective film to form a first photopolymerizable adhesive layer (2 ′), and one surface of the second protective film And applying a photopolymerizable adhesive to form a second photopolymerizable adhesive layer,
Next, the first photopolymerizable adhesive layer and the second photopolymerizable adhesive layer are simultaneously and / or sequentially stacked on each surface of the polyvinyl alcohol polarizer, and then irradiated with active energy rays. A method for producing a photopolymerization reaction of a first photopolymerizable adhesive layer and a second photopolymerizable adhesive layer.

(II) A photopolymerizable adhesive is applied to one surface of the polyvinyl alcohol polarizer to form a first photopolymerizable adhesive layer, and the formed first photopolymerizable adhesive layer The surface was covered with a first protective film, and then a photopolymerizable adhesive was applied to the other surface of the polyvinyl alcohol-based polarizer to form a second photopolymerizable adhesive layer. By covering the surface of the photopolymerizable adhesive layer with a second protective film, irradiating active energy rays, and photopolymerizing the first photopolymerizable adhesive layer and the second photopolymerizable adhesive layer How to manufacture.

(III) The 2nd protective film which piled up the edge part which accumulated the protective film and polyvinyl alcohol type polarizer which are the 1st transparent films (H), and the surface without the 1st protective film of polyvinyl alcohol type polarizer After putting a photopolymerizable adhesive on the end of the film, it is passed between rolls to spread the adhesive between the layers. Next, there is a method of manufacturing by irradiating active energy rays and curing the photopolymerizable adhesive, 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. In the present specification, Examples 1 to 31 and 41 to 71 are reference examples.

[Composition Examples 1-36]
In a light-shielded 300 cc mayonnaise bottle substituted with an oxygen concentration of 10% or less, an oxirane compound (A), a cyclic compound (B) having four or more rings having two or more oxygen atoms, and a substituent having F atoms The fluorine-containing cyclic compound (B ′) and the photopolymerization initiator (D) substituted with at least one or more were charged in the ratios shown in Table 1, sufficiently stirred with an air motor, and sufficiently defoamed. Then, the photopolymerizable coating agent or photopolymerization adhesive shown in the formulation example was obtained.

  The solution appearance and viscosity of the photopolymerizable coating agent or photopolymerizable adhesive of the formulation examples shown in Table 1 were determined according to the following methods, and the results are shown in Table 2.

"appearance"
The liquid appearance of the photopolymerizable coating agent or photopolymerizable adhesive obtained in each formulation example was visually evaluated.

"viscosity"
About 1.2 ml of the photopolymerizable coating agent or photopolymerizable adhesive obtained in each formulation example was measured with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) in an atmosphere of 23 ° C. A sample was measured under the conditions of a rotation speed of 0.5 to 100 rpm and a rotation for 1 minute to obtain a solution viscosity (mPa · s).

In the present invention, among the oxirane compound (A), the cyclic compound (B) having four or more rings having two or more oxygen atoms, and the cyclic compound (B) having four or more rings having two or more oxygen atoms, Fluorine-containing cyclic compound (B ′), ethylenically unsaturated compound (C), photopolymerization initiator (D), sensitizer (E), and antioxidant substituted with at least one or more substituents having F atoms As representative examples of the agent (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) Chemical Co., Ltd.), EX201 (a-12): (resorcinoyloxymethyl) dioxirane (manufactured by Nagase Chemtech), EX121 (a-3): 2-ethylhexinoylmethyloxirane, EC (b-1) : Ethylene carbonate, PC (b-1): Propylene carbonate, BC (b-1): Butyl Carbonate, GC (b-1): glycerin carbonate, 13DOL (b-2): 1,3-dioxolane, MEDOL (b-2): (2-methyl-2-ethyl-1,3-dioxolan-4-yl ) Methyl acrylate, 14DOX (b-3): 1,4-dioxane, 13DOXO (b-3): 1,3-dioxane-2-one, FEC (b-1 ′): fluoroethylene carbonate, FPC (b— 1 ′): fluoropropylene carbonate, BL (others): γ-butyrolactone, VL (others): δ-valerolactone, FDOL (b-2 ′): 2-fluoro-1,3-dioxolane, 4HBA (c-1) ): 4-hydroxybutyl acrylate, IBOA (c-2): isobonyl acrylate, CP110P (D): p-phenylthiophenyldiphenyls Ruphonium PF6 salt, IRG250: IRGACURE250 (manufactured by Ciba Specialty Chemicals), DET-X (E): 2,4-diethylthioxanthone, AO-50 (F): stearyl-β- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate.

[Example 1]
Using the photopolymerizable coating agent or photopolymerizable adhesive obtained in Formulation Example 1, the following laminate was prepared.
As the protective film (1), an ultraviolet absorber-containing polytriacetylcellulose-based 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. -Free polytriacetylcellulose-based film: Using the product name “TAC 50 μ” (thickness 50 μm), each surface is corona treated with a discharge amount of 300 W · min / m 2 and blended within 1 hour after the surface treatment. The photopolymerizable adhesive shown in Example 1 was coated using a wire bar coater so as to have a film thickness of 4 μm, a photopolymerizable adhesive layer was formed, and the above-mentioned photopolymerizable adhesive layer was interposed between Sandwiching a polyvinyl alcohol polarizer, protective film (1) / polymerizable adhesive layer / PVA polarizer / polymerizable adhesive layer / protective film (2) It was obtained Ranaru laminate.
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 apparatus (high pressure mercury lamp manufactured by Toshiba Corporation).

[Comparative Example 1]
Instead of the photopolymerizable adhesive (Formulation Example 1) in Example 1, the photopolymerizable adhesive shown in Formulation Example 20 does not use a cyclic compound (B) having four or more membered rings having two or more oxygen atoms. A polarizing plate was produced in the same manner as in Example 1 except for the change.

[Comparative Examples 2 and 3]
Γ-Butyrolactone (Formulation 35—Comparative Example 3), wherein the cyclic compound (B) having two or more oxygen atoms is a lactone ring having neither a carbonate ring, a dioxolane ring nor a dioxane ring. A polarizing plate was produced in the same manner as in Example 1, except that δ-valerolactone (Formulation Example 36—Comparative Example 3) was changed.
[Comparative Example 4]
Polarized light in the same manner as in Example 1 except that the photopolymerizable adhesive shown in Formulation Example 27 without using the oxirane compound (A) was used instead of the photopolymerizable adhesive (Formulation Example 1) in Example 1. A plate was made.

[Examples 2 to 25]
A polarizing plate was prepared in the same manner as in Example 1 except that the photopolymerizable adhesive (Formulation Example 1) was changed to Formulation Examples 2 to 19 and 21 to 27 as shown in Table 1 instead of the photopolymerizable adhesive in Example 1. did.

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

[Examples 29 to 31]
The protective film (1) used in Example 3 was applied to a polypropylene film (trade name “OPU-1: 50 μm”) manufactured by Tosero (Example 29), and a polyethylene film (trade name “TUX” manufactured by Tosero). -HZ: 50 [mu] m ") (Example 30), and a unitary polyester film (trade name" Embret S: 50 [mu] m ") (Example 31). A polarizing plate was obtained and evaluated in the same manner.

[Examples 32-38]
Instead of the photopolymerizable adhesive used in Example 1 (Formulation Example 1), a polarizing plate was produced in the same manner as in Example 1 except that the composition was changed to Formulation Examples 28 to 38 as shown in Table 1. Evaluation was performed in the same manner.

  For the laminates (polarizing plates) obtained in Examples 1 to 38 and Comparative Examples 1 to 4, peel strength, gel fraction, punching workability, and wet heat resistance were determined according to the following methods, and the results are shown in Table 3. It was.

<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>
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 polymerizable adhesive shown in Formulation Example 1 with a film thickness of 20 to 25 μm using a wire bar coater. Then, a polymerizable adhesive layer was formed, and ZEONOR ZF-14 not subjected to corona treatment was laminated on the polymerizable adhesive layer to obtain a laminate composed of three layers, and then UV. The polymerizable adhesive layer was cured by irradiating ultraviolet rays with a maximum illuminance of 300 mW / cm 2 and an integrated light amount of 300 mJ / cm 2 with an irradiation device (a high-pressure mercury lamp manufactured by Toshiba Corp.) The three-layer laminate ZEONOR ZF-14 was peeled off An adhesive layer was obtained.
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

"Heat-resistant"
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 conditions of 80 ° C.-dry and 100 ° C. dry. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages.
A: No peeling at all at 100 ° C. dry.
○: No peeling at all at 80 ° C.-dry condition.
(Triangle | delta): There exists peeling less than 1 mm on 80 degreeC-dry conditions.
X: 1 mm or more peeled off at 80 ° C.-dry condition.

《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 conditions of 60 ° C.-90% RH and 85 ° C.-85% RH. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages.
A: No peeling at all at 85 ° C. to 85% RH.
○: No peeling at all at 60 ° C.-90% RH.
(Triangle | delta): There exists peeling of less than 1 mm on the conditions of 60 degreeC-90% RH.
X: There is peeling of 1 mm or more under the condition of 60 ° C.-90% RH.

[Example 41]
Using the photopolymerizable coating agent or photopolymerizable adhesive obtained in Formulation Example 1, the following laminate was prepared.
As the optical film (I), an ultraviolet absorber-containing polytriacetylcellulose-based 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 photopolymerizable coating agent shown in Formulation Example 1 is made to have a film thickness of 4 μm using a wire bar coater. To form an easily adhesive photopolymerizable coating layer.
The four sides of this laminate were fixed to the tinplate with cellophane tape so that the optical film (I) 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 side of the easy adhesive coating agent layer. A laminate having a polymerizable coating agent layer was produced.

[Comparative Example 5]
Instead of the photopolymerizable coating agent (Formulation Example 1) in Example 41, the photopolymerizable coating agent shown in Formulation Example 20 in which a cyclic compound (B) having two or more oxygen atoms is not used is used. Except having changed, the laminated body which has an easily-adhesive photopolymerizable coating agent layer was produced like Example 41. FIG.

[Comparative Examples 6 and 7]
Γ-Butyrolactone (Formulation 35—Comparative Example 6), wherein the cyclic compound (B) having two or more oxygen atoms is a lactone ring having no carbonate ring, dioxolane ring or dioxane ring. A laminate having an easy-adhesive photopolymerizable coating agent layer was prepared in the same manner as in Example 41, except that δ-valerolactone was changed to Formulation Example 36-Comparative Example 7.

[Comparative Example 8]
In Example 41, the photopolymerizable coating agent (Formulation Example 1) was used instead of the photopolymerizable coating agent shown in Formulation Example 27 without using the oxirane compound (A). A laminate having an adhesive photopolymerizable coating agent layer was prepared.

[Examples 42 to 65]
In the same manner as in Example 41 except that the photopolymerizable coating agent (Formulation Example 1) was changed to Formulation Examples 2 to 19 and 21 to 27 as shown in Table 1, instead of the photopolymerizable coating agent (Embodiment Example 1) A laminate having a polymerizable coating agent layer was produced.

[Examples 66 to 71]
The optical film (I) used in Example 43 was changed to a polynorbornene-based film (trade name “Zeonor ZF-14: 100 μm”) manufactured by ZEON Corporation (Example 66), and a polyacrylic film manufactured by Mitsubishi Rayon Co., Ltd. (Product name “HDB-002: 50 μm”) (Example 67), Polycarbonate film manufactured by Kaneka (trade name “R-140: 43 μm”) (Example 68), Polypropylene film manufactured by Tosero (Product name “OPU-1: 50 μm”) (Example 69), Polyethylene film manufactured by Tosero (trade name “TUX-HZ: 50 μm”) (Example 70), Polyester film manufactured by Unitika (Product name “Embret S: 50 μm”) (Example 71) A laminate having a bonding agent layer was obtained and evaluated in the same manner.

[Examples 72 to 78]
Instead of the photopolymerizable coating agent used in Example 1 (Formulation Example 1), it was changed to Formulation Examples 28 to 38 as shown in Table 1 in the same manner as in Example 41, and was easily adhesive photopolymerizable. A laminate having a coating agent layer was prepared and evaluated in the same manner.

  About the laminated body (laminated body which has an easily-adhesive photopolymerizable coating agent layer) obtained in Examples 41-78 and Comparative Examples 5-8, according to the following method, it is a gel fraction about adhesive force and heat resistance. Was determined according to the method described above, and the results are shown in Table 4.

"Adhesion"
The laminates obtained in Examples 41 to 78 and Comparative Examples 5 to 8 were subjected to a cross-cut peel test in accordance with JIS K5400. The number of cells peeled in 100 cells was evaluated in four stages.
◎: 0 cell ○: 1-10 cell Δ: 11-30 cell ×: 31 cell or more

"Heat-resistant"
The laminates obtained in Examples 41 to 78 and Comparative Examples 5 to 8 were cut into a size of 50 mm × 40 mm and exposed for 1000 hours under conditions of 80 ° C. and dry. After the exposure, the presence or absence of peeling at the end of the laminate was visually evaluated in the following three stages.
A: No peeling at all B: Peeling of less than 1 mm, but no problem in practical use.
Δ: Peeling of 1 mm or more and less than 2 mm ×: Peeling of 2 mm or more

As shown in Table 3, the photopolymerizable adhesive 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. Among the oxirane compounds (A), Examples 20 to 22 which do not contain any aromatic ring have difficulty in moisture and heat resistance because the cured coating film by photopolymerization of the photopolymerizable adhesive is slightly soft, but there is no particular problem. 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. In Examples 28 to 34, part or all of the cyclic compound (B) is replaced with the fluorine-containing cyclic compound (B ′), and thus the heat resistance and heat and humidity resistance are significantly improved.
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 strength, punching workability, heat resistance, and heat and humidity resistance is formed.
On the other hand, in Comparative Example 1 that does not contain a four-membered or higher cyclic compound (B) having two or more oxygen atoms and Comparative Examples 2 and 3 that have other cyclic compounds, the viscosity is as high as 1600 mPa · s. Further, it can be seen that the gel fraction is low and the curability by photopolymerization is poor, so that the punching processability, heat resistance, and moist heat resistance are poor. Moreover, in Comparative Example 4, since it does not have the oxirane compound (A), the curability by photopolymerization becomes insufficient, and it can be seen that the adhesive strength, the gel fraction, the punching workability, the heat resistance, and the heat resistance to moisture are all inferior. .

On the other hand, as shown in Table 4, the photopolymerizable coating agent of the present invention has a slightly high viscosity in Examples 41 to 50, 53 to 59, and 66 to 71, and when used as a photopolymerizable adhesive. Similarly, there is no particular problem. Among the oxirane compounds (A), Examples 60 to 62, which do not contain any aromatic ring, have difficulty in moisture and heat resistance because the cured coating film by photopolymerization of the photopolymerizable coating agent is slightly soft, but the photopolymerizable adhesive As in the case of using as, there is no particular problem. Further, Example 64 which does not contain an aromatic ring and has only one three-membered oxirane ring has difficulty in adhesion, gel fraction, and heat resistance, but is used as a photopolymerizable adhesive. As with the case, there is no problem. In Examples 68 to 74, a part or all of the cyclic compound (B) is replaced with the fluorine-containing cyclic compound (B ′), and thus the heat resistance and heat and humidity resistance are remarkably improved.
Thus, it can be seen that in any of the Examples, a laminate having a photopolymerizable coating agent layer excellent in adhesion and heat resistance is formed.
In contrast, Comparative Example 5 that does not contain a cyclic compound (B) having four or more members having two or more oxygen atoms and Comparative Examples 6 and 7 that have other cyclic compounds have a low gel fraction, light It can be seen that the adhesiveness, the gel fraction, and the heat resistance are inferior because of poor curability due to polymerization. Moreover, in Comparative Example 8, since it does not have an oxirane compound (A), the curability by photopolymerization becomes insufficient, and it can be seen that the adhesiveness, the gel fraction, and the heat resistance are all inferior.

Claims (13)

A photopolymerizable oxirane-based resin composition containing, as a main component, an oxirane compound (A), and further containing a cyclic compound (B) having four or more members having two or more oxygen atoms and substantially free of an organic solvent. Because
The fluorine-containing cyclic compound (B) having a cyclic structure of at least one of a carbonate ring, a dioxolane ring, and a dioxane ring, wherein the cyclic compound (B) is substituted with at least one substituent having an F atom. A photopolymerizable oxirane-based resin composition characterized by having ') .   The oxirane compound (A) contains 0.5 to 60 parts by weight of a four-membered or higher cyclic compound (B) having two or more oxygen atoms with respect to 100 parts by weight of the oxirane compound (A). A photopolymerizable oxirane-based resin composition. The photopolymerizable oxirane resin composition according to claim 1 or 2 , wherein the oxirane compound (A) comprises a compound (a-1) having an aromatic ring. The photopolymerizable oxirane resin composition according to any one of claims 1 to 3, wherein the oxirane compound (A) contains a compound (a-2) having two or more three-membered cyclic oxirane rings. The photopolymerizable coating agent characterized in that it contains a photopolymerization initiator to claim 1-4 photopolymerizable oxirane-based resin composition according to any one. The photopolymerizable adhesive which contains a photoinitiator in the photopolymerizable oxirane resin composition in any one of Claims 1-4 . Photopolymerization initiator, a salt represented by A + B- to generate acidic active species by light irradiation, + the cation A is claim is selected from the group consisting of aromatic iodonium ions and an aromatic sulfonium ions 5 The photopolymerizable coating agent as described. Photopolymerization initiator, a salt represented by A + B- to generate acidic active species by light irradiation, claim the cation A + is selected from the group consisting of aromatic iodonium ions and an aromatic sulfonium ion 6 The photopolymerizable adhesive as described. The photopolymerizable oxirane resin composition according to any one of claims 1 to 4 , and / or the photopolymerizable coating agent according to claim 5 , and / or the photopolymerizable adhesive according to claim 6. A laminate comprising a layer laminated on one side or both sides of the substrate (G). The laminate according to claim 9, wherein the substrate (G) is a transparent film (H). The laminate according to claim 10, wherein the transparent film (H) is an optical film (I). The optical film (I) is poly acetylcellulose-based film, a polynorbornene-based film, polyacrylic film, polycarbonate film, polyester film, according to claim 11, characterized in that a polyimide film or polyvinyl alcohol film Laminated body. A polarizing plate comprising the laminate according to any one of claims 10 to 12 adhered to one or both sides of a polyvinyl alcohol polarizer.