Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/16—Cyclic ethers having four or more ring atoms
  • C08G65/18—Oxetanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording

Definitions

• This technology relates to a composition, a laminated film, a member, an adhesion method, and a sealing method. More specifically, it relates to a composition containing an absorption wavelength maintaining agent, a laminated film, and a member, as well as an adhesion method and a sealing method using the composition.
• Patent Document 1 discloses a technology in which a positive photoresist composition containing a novolac resin and a quinone diazide photosensitizer further contains a reduction inhibitor to suppress the decomposition of the quinone diazide photosensitizer, which is an irreversible reaction, and thereby achieve storage stability.
• the main purpose of this technology is to provide a technique for preventing the absorption wavelength of a composition for producing a photocurable resin from being fixed before exposure.
• the present technology provides a composition containing a sensitizing dye whose light absorption wavelength is reversibly changed, a polymerizable monomer, and an absorption wavelength maintaining agent.
• the composition according to the present technology may further include a polymerization initiator.
• the polymerization initiator is preferably one or more onium compounds, and more preferably one or more of the onium compounds is a salt of a triarylborate compound.
• the absorption wavelength maintaining agent may be an oxidation-reduction inhibitor.
• the composition according to the present technology may contain 1 mol or more of the absorption wavelength maintaining agent per 1 mol of the sensitizing dye.
• the polymerizable monomer may be a cationic polymerizable monomer
• the absorption wavelength maintaining agent may be a reduction inhibitor.
• the reduction inhibitor is preferably at least one selected from nitro compounds, peroxides, or halogen-based compounds, and more preferably at least one selected from nitrobenzenesulfonates, metanitrobenzenesulfonates, nitronaphthalenesulfonates, vanadates, nitrites, chlorates, perchlorates, and percarbonates.
• the cationic polymerizable monomer may be one or more cyclic ether compounds.
• the sensitizing dye may be at least one compound selected from a thiazine compound, an azine compound, and a cyanine compound.
• the composition according to the present technology may further contain a binder resin and a radical polymerizable organic monomer.
• the present technology provides a laminate film including one or more layers including the composition.
• the laminate film of the present technology includes a substrate layer, a resin layer, and a release layer in this order, and the resin layer may include the composition of the present technology.
• the present technology provides a member having a resin layer on at least a portion of the surface, the resin layer being formed by exposing the composition to light.
• the member according to the present technology has a resin layer on at least a portion of the surface, and the resin layer may contain a sensitizing dye or a derivative of the sensitizing dye whose light absorption wavelength is reversibly changed, a polymer of a polymerizable monomer, and an absorption wavelength maintaining agent.
• the present technology provides a method for bonding objects using the composition as an adhesive.
• the composition may be mixed with a polymerization initiator and used as the adhesive.
• the present technology provides a sealing method using the above-mentioned composition as a sealant.
• 1 is data showing the change over time in the transmittance spectrum of a composition according to the present technology. 1 is data showing the effect of the amount of an absorption wavelength maintaining agent added on the storage stability of a composition according to the present technology.
• 1 is an example of a laminated film according to the present technology. 1 is a modified example of a laminated film according to the present technology. 1 is an example of a component according to the present technology.
• 1A to 1C are diagrams showing an example of peeling a resin layer from a member according to the present technology. 1 shows a peeling step in a method for producing a member according to the present technology using a laminate film according to the present technology.
• 1 shows a lamination step in a method for producing a member according to the present technology using a laminate film according to the present technology.
• 1 shows an interference exposure step in a method for manufacturing a member according to the present technology using a laminate film according to the present technology. This is a UV exposure process in a method for manufacturing a component related to this technology using a laminated film related to this technology.
• 1 is a heating step in a method for producing a member according to the present technology using a laminate film according to the present technology.
• 1 is a schematic diagram showing an example of recording interference fringes by exposing a member according to the present technology; This is a reaction equation showing the reversible change of methylene blue.
• 1 is a graph showing a change in the waveform of a transmittance spectrum before and after a high-temperature, high-humidity test of a composition containing an epoxide and a sensitizing dye. This is the reaction formula between methylene blue and epoxide. 13 is data showing the change over time in the waveform of the absorption spectrum when no absorption wavelength maintaining agent is included. 1 is a graph showing a linear function used to calculate absorbance retention during storage.
• composition contains a sensitizing dye whose light absorption wavelength is reversibly changed, a polymerizable monomer, and an absorption wavelength maintaining agent.
• sensitizing dye contained in the composition according to the present technology reversibly changes the light absorption wavelength through a reversible reaction.
• a "reversible reaction” refers to a chemical reaction in which the equilibrium is not extremely biased toward the product system, and in which the reverse reaction can also occur.
• Light absorption wavelength refers to the wavelength at the maximum value of the absorption spectrum waveform, with the horizontal axis representing wavelength and the vertical axis representing absorbance.
• a “sensitizing dye” is a substance that can cause "photosensitization”; specifically, it is a substance that absorbs the energy of light of a specific wavelength and transfers that energy to a reactant, such as a polymerization initiator or a radically polymerizable organic monomer, thereby causing a photochemical reaction, such as a polymerization reaction, of the reactant.
• a reactant such as a polymerization initiator or a radically polymerizable organic monomer
• photochemical reaction refers to a chemical reaction that occurs when a substance absorbs light.
• the sensitizing dye contained in the composition according to the present technology is in equilibrium in a state in which the light absorption wavelength changes reversibly.
• the sensitizing dye contained in the composition according to the present technology is not particularly limited as long as it is a compound as described above, and includes, for example, at least one selected from the group consisting of thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, thiazine dyes such as methylene blue, azine dyes, phenazine dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes, cyclopentanone dyes, and cyclohexanone dyes.
• Cyanine and merocyanine dyes include, for example, at least one selected from the group consisting of 3,3'-dicarboxyethyl-2,2'-thiocyanine bromide, 1-carboxymethyl-1'-carboxyethyl-2,2'-quinocyanine bromide, 1,3'-diethyl-2,2'-quinothiacyanine iodide, and 3-ethyl-5-[(3-ethyl-2(3H)-benzothiazolylidene)ethylidene]-2-thioxo-4-oxazolidine.
• Coumarin and ketocoumarin dyes include, for example, at least one selected from the group consisting of 3-(2'-benzimidazole)-7-diethylaminocoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), 3,3'-carbonylbiscoumarin, 3,3'-carbonylbis(5,7-dimethoxycoumarin), and 3,3'-carbonylbis(7-acetoxycoumarin).
• the sensitizing dye contained in the composition according to the present technology may contain at least one ionic sensitizing dye.
• the composition according to the present technology contains an ionic sensitizing dye, the effect of improving the light absorption efficiency of the composition by the polyhydric alcohol becomes particularly remarkable.
• the sensitizing dye contained in the composition according to the present technology may include either a dye that absorbs in the visible light region, or a UV sensitizing dye (such as anthracene compounds) that is added for the purpose of improving the light efficiency during UV irradiation, or both.
• a dye that absorbs in the visible light region or a UV sensitizing dye (such as anthracene compounds) that is added for the purpose of improving the light efficiency during UV irradiation, or both.
• the composition according to the present technology may contain only one type of sensitizing dye, or multiple types of sensitizing dyes may be used to accommodate multiple wavelengths.
• the sensitizing dye may contain at least two types of sensitizing dyes that have absorption in the visible light region. In this case, these at least two types of sensitizing dyes may contain at least one ionic sensitizing dye.
• the sensitizing dye that has absorption in the visible light region may have a maximum value of the absorption spectrum in the visible light region.
• the visible light region refers to the wavelength range of 360 nm or more and 830 nm or less.
• the content of the sensitizing dye contained in the composition according to the present technology is not particularly limited, but photosensitization can be suitably achieved by including, for example, 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more, relative to 100% by mass of the composition.
• the upper limit of the amount of sensitizing dye contained in the composition according to the present technology is not particularly limited, but can be suitably adjusted to, for example, 10% by mass or less, more preferably 1% by mass or less, relative to 100% by mass of the composition.
• Figure 13 is a reaction formula showing the equilibrium state of methylene blue as a sensitizing dye contained in the composition according to the present technology.
• Thiazine compounds such as methylene blue can increase the phase separation of the composition according to the present technology after a photochemical reaction and improve the refractive index modulation degree ⁇ n, so the composition according to the present technology can be suitably used, for example, when used in applications such as holograms used in holographic reproduction.
• holography refers to the generation of three-dimensional images
• hologram refers to a medium that records interference fringes related to the information of the three-dimensional image.
• the "polymerizable monomer” contained in the composition according to the present technology is a monomer that is a low molecular weight compound, and refers to a compound that can generate a polymer by repeated bonding of the monomer.
• polymerization is promoted mainly by ultraviolet (UV: Ultra Violet) irradiation, heating, or the like, and the composition can be cured.
• the polymerizable monomer contained in the composition according to the present technology is not particularly limited as long as it is a monomer that can achieve the above-mentioned functions, and may be a cationic polymerizable monomer or an anionic polymerizable monomer.
• the above polymerizable monomers may be effective in producing a high refractive index modulation amount ( ⁇ n).
• the polymerizable monomers may also be effective in adjusting the adhesion, flexibility, hardness, and other physical properties of the photosensitive composition.
• the polymerizable monomers may include at least one selected from the group consisting of ester-based plasticizers and ether-based plasticizers.
• the polymerizable monomer contained in the composition according to the present technology may be nonionic. If the polymerizable monomer is nonionic, the light absorption efficiency of the composition containing an ionic sensitizing dye decreases, but if the composition contains a polyhydric alcohol, the light absorption efficiency of the composition can be improved.
• Ionic sensitizing dyes have poor dispersibility in nonionic polymerizable monomers, so when a composition contains a nonionic polymerizable monomer, the dispersibility of the ionic sensitizing dye in the composition deteriorates.
• a polyhydric alcohol By adding a polyhydric alcohol to a composition containing a nonionic polymerizable monomer, the dispersibility of the ionic sensitizing dye in the composition is improved, and the light absorption rate of the composition is improved.
• the use of one or more cyclic ether compounds can improve the high temperature and high humidity resistance of the composition according to the present technology. Therefore, even when the composition according to the present technology is used for holograms or the like under high temperature and high humidity conditions, such as outdoors in summer, it can suppress changes in the diffraction wavelength.
• Cyclic ether compounds suitable as polymerizable monomers contained in the composition of the present technology include, for example, compounds such as epoxides (oxiranes), oxetanes, tetrahydrofurans, and tetrahydropyrans. These compounds may be used alone or in combination.
• the above epoxide compounds include, for example, glycidyl ethers.
• the glycidyl ether includes at least one selected from the group consisting of, for example, allyl glycidyl ether, phenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
• the above oxetane compound includes, for example, at least one selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylene bisoxetane, 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl)methoxy]methyl ⁇ oxetane, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and 2-ethylhexyl vinyl ether.
• the transparency of the composition according to the present technology can be improved after exposure to UV light.
• the epoxide as a cyclic ether compound is a compound having one or more epoxy groups in the molecule, and the number of epoxy groups in the molecule is not particularly limited.
• a compound having one epoxy group, a compound having two epoxy groups, a compound having three or more epoxy groups, etc. can be suitably used, and as described above, depending on the usage situation of the composition according to the present technology, one type of compound may be used alone, or multiple compounds may be used in combination. It can also be used in combination with other cyclic ether compounds.
• the content of the polymerizable monomer contained in the composition is not particularly limited, but by containing, for example, 1% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more relative to 100% by mass of the composition, polymerization can be efficiently promoted by ultraviolet irradiation, heating, etc., and the composition according to the present technology can be effectively cured.
• the upper limit of the content of the polymerizable monomer contained in the composition is not particularly limited, but can be suitably adjusted to, for example, 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less, relative to 100% by mass of the composition.
• the content of the polymerizable monomer contained in the composition is not particularly limited, as in the case of hologram applications, but the content ratio can be adjusted depending on the composition of other components.
• Figure 14 is a graph showing the change in the spectral waveform, with the horizontal axis representing wavelength and the vertical axis representing transmittance, before and after a high-temperature, high-humidity test when the epoxide 6-hexanediol diglycidyl ether is used as the polymerizable monomer contained in a holographic diffraction grating made using a composition according to the present technology.
• the inclusion of the epoxide suppresses the change in the waveform, resulting in high resistance to high temperatures and high humidity.
• the high temperature and high humidity test was carried out on a holographic diffraction grating containing methylene blue as a sensitizing dye and 6-hexanediol diglycidyl ether as a polymerizable monomer, at 60°C and 80% humidity for 100 hours.
• the composition according to the present technology may further contain a polymerization initiator.
• the "polymerization initiator” refers to a substance necessary for easily generating radicals or ions to initiate a chain polymerization reaction.
• the polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable monomer or a radically polymerizable organic monomer.
• the polymerization initiator that may be contained in the composition according to the present technology can be appropriately selected according to the characteristics of the polymerizable monomer or radically polymerizable organic monomer contained in the composition according to the present technology.
• the photopolymerization initiator may include a radical polymerization initiator (radical generator), a cationic polymerization initiator (acid generator), or one that has both functions.
• the photopolymerization initiator may also include an anionic polymerization initiator (base generator).
• a cationic polymerizable monomer when used as the polymerizable monomer, from the viewpoint of obtaining a high refractive index modulation amount ( ⁇ n) and diffraction efficiency, it is preferable to include at least one of an organic boron salt-based initiator such as an organic boron compound or a derivative thereof, and an onium salt-based initiator such as an onium compound or a derivative thereof, and it is more preferable to include both an organic boron salt-based initiator and an onium salt-based initiator.
• an anionic polymerizable monomer when used as the polymerizable monomer, a radical initiator or a derivative thereof can be preferably used. These polymerization initiators may be used alone as one type of compound, or multiple compounds may be used in combination.
• an onium compound is a compound containing an onium ion, also called an onium salt.
• an onium compound is used as a polymerization initiator in the composition according to the present technology
• one or more of the onium compounds may be a salt of an organic boron compound such as a triarylborate compound.
• it can be suitably used as a polymerization initiator for a cyclic ether compound such as an epoxide, and by using these in combination, the high temperature and high humidity resistance of the composition according to the present technology can be improved.
• Onium salt initiators such as onium compounds or derivatives thereof include, for example, tris(4-(4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate (manufactured by BASF Japan Ltd., product name: Irgacure 290), diphenyl(4-(phenylsulfanyl)phenyl)sulfonium trifluoride tris(pentafluoroethane-1-ido)phosphate (manufactured by San-Apro Ltd., product code: CPI-210S), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) ) borate (manufactured by Tokyo Chemical Industry Co., Ltd., product code: I0591), (2-methylphenyl) (2,4,6-trimethylphenyl) iodonium trifluoromethane
• the organic boron salt initiator such as an organic boron compound or a derivative thereof, includes at least one selected from the group consisting of triaryl borate compounds such as tetrabutylammonium butyltriphenyl borate (manufactured by Showa Denko K.K., product name: P3B) and tetrabutylammonium butyltrinaphthyl borate (manufactured by Showa Denko K.K., product name: N3B).
• triaryl borate compounds such as tetrabutylammonium butyltriphenyl borate (manufactured by Showa Denko K.K., product name: P3B) and tetrabutylammonium butyltrinaphthyl borate (manufactured by Showa Denko K.K., product name: N3B).
• the triarylborate compound is not particularly limited, but for example, triarylsulfonium salts can be suitably used.
• the polymerization initiator may be contained in the composition beforehand, or the polymerization initiator may be added at the time of use.
• a suitable form of use can be suitably adopted depending on the intended use of the composition according to the present technology.
• An example of a form in which the polymerization initiator is added at the time of use is when a composition containing components other than the polymerization initiator and a composition containing the polymerization initiator are mixed at the time of use, but the use is not limited to this form.
• the content of the polymerization initiator that may be contained in the composition according to the present technology is not particularly limited, but by containing, for example, 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, relative to 100% by mass of the composition, the polymerization reaction of the polymerizable monomer or the radically polymerizable organic monomer can be suitably initiated.
• the upper limit of the content of the polymerization initiator that may be contained in the composition according to the present technology is not particularly limited, but can be adjusted, for example, to a range of 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, relative to 100% by mass of the composition.
• the "absorption wavelength maintaining agent" contained in the composition according to the present technology maintains the light absorption wavelength of the composition according to the present technology, and in particular is a material that suppresses the fixation of the light absorption wavelength due to the equilibrium state of a sensitizing dye being biased toward either oxidation or reduction when the sensitizing dye, whose absorption wavelength changes reversibly, is exposed to light energy.
• the composition according to the present technology contains an absorption wavelength maintaining agent, which can prevent the absorption wavelength of the light of the sensitizing dye from being fixed. This can prevent the absorption wavelength of the composition from being fixed before exposure to light to produce a photocurable resin using the composition according to the present technology. This improves the shelf life of the composition, making it possible to achieve long-term storage compared to conventional products.
• the absorption wavelength maintainer contained in the composition according to the present technology is not particularly limited as long as it is a material having the above-mentioned functions, but examples thereof include an oxidation-reduction inhibitor that prevents the oxidation-reduction of the sensitizing dye.
• the oxidation-reduction inhibitor that can be suitably used as an absorption wavelength maintaining agent contained in the composition according to the present technology can be appropriately selected and used depending on the situation in which the sensitizing dye is exposed to light energy and tends to be either oxidized or reduced when the composition contains either a cationic polymerizable monomer or an anionic polymerizable monomer.
• the sensitizing dye may be biased toward a reduced state when the composition is exposed to light energy, and therefore a reduction inhibitor can be suitably used as an absorption wavelength maintaining agent.
• composition according to this technology contains 1 mol or more of an absorption wavelength maintaining agent per 1 mol of sensitizing dye, which can effectively prevent the absorption wavelength of the sensitizing dye from being fixed.
• the fixation of the absorption wavelength of the sensitizing dye can be effectively suppressed, but there is no particular limit to this content, and depending on the combination of the sensitizing dye and the absorption wavelength maintaining agent, a content of 0.1 mol or more, 0.5 mol or more, etc. can be appropriately selected.
• the polymerizable monomer contained in the composition according to the present technology is a cationic polymerizable monomer and a reduction inhibitor is used as the absorption wavelength maintaining agent
• a reduction inhibitor is used as the absorption wavelength maintaining agent
• at least one compound selected from nitro compounds, peroxides such as percarbonates, halogen compounds, vanadates, and nitrites can be suitably used as the reduction inhibitor, with nitro compounds being particularly preferred. These compounds may be used alone or in combination.
• the nitro compound that can be used as a reduction inhibitor in the composition according to the present technology is not particularly limited as long as it is a compound having a nitro group, but for example, nitrobenzenesulfonate salts such as nitrobenzenesulfonate and metanitrobenzenesulfonate salts, and nitronaphthalenesulfonate salts can be suitably used, and among these, nitrobenzenesulfonate salts are preferred, with metanitrobenzenesulfonate salts being particularly preferred.
• the peroxide that can be used as the reduction inhibitor is not particularly limited as long as it is a compound having a peroxide structure, but for example, percarbonate can be suitably used.
• halogen-based compounds that can be used as reduction inhibitors are not particularly limited as long as they have a halogen element in the molecule, but for example, chlorates and perchlorates can be suitably used.
• any element such as a metal that forms a salt of the above compound can be used depending on the characteristics of the molecular structure that constitutes the acid.
• a salt with an element such as an alkali metal such as sodium or potassium, or an alkaline earth metal such as magnesium or calcium, among which an alkali metal is preferred, and sodium is particularly preferred.
• Figure 15 shows a reaction formula showing that in a composition in which the sensitizing dye is methylene blue and the polymerizable monomer is the cationic polymerizable monomer 6-hexanediol diglycidyl ether, the methylene blue is irreversibly reduced by reaction with 6-hexanediol diglycidyl ether, thereby fixing the light absorption wavelength.
• the sensitizing dye is methylene blue
• the polymerizable monomer is the cationic polymerizable monomer 6-hexanediol diglycidyl ether
• the composition according to the present technology contains a reducing agent such as sodium m-nitrobenzenesulfonate as an absorption wavelength maintaining agent, which suppresses the reaction between methylene blue and 6-hexanediol diglycidyl ether and advantageously prevents the absorption wavelength of the composition from being fixed before exposure.
• a reducing agent such as sodium m-nitrobenzenesulfonate as an absorption wavelength maintaining agent, which suppresses the reaction between methylene blue and 6-hexanediol diglycidyl ether and advantageously prevents the absorption wavelength of the composition from being fixed before exposure.
• Figure 16 shows data showing the change over time in the waveform of the absorption spectrum for a composition in which the sensitizing dye is methylene blue and the polymerizable monomer is the cationic polymerizable monomer 6-hexanediol diglycidyl ether, but which does not contain an absorption wavelength maintaining agent. It can be seen that the absorbance in the vicinity of 660 nm decreases over time.
• the composition according to the present technology may further contain a radically polymerizable organic monomer.
• the "radically polymerizable organic monomer” contained in the composition according to the present technology is a monomer that is a low molecular weight compound, and is a compound that can undergo a polymerization reaction as a photochemical reaction by the light energy transmitted from the sensitizing dye to generate a polymer.
• the composition according to this technology contains a radically polymerizable organic monomer
• a photochemical reaction proceeds due to the light energy transmitted from the sensitizing dye, and a polymer of the radically polymerizable organic monomer is synthesized.
• the polymerization reaction does not proceed.
• the composition according to the present technology contains a radically polymerizable organic monomer, the composition can record interference fringes. Therefore, the composition can be suitably used as a hologram for reproducing holography.
• the radical polymerizable organic monomer that may be contained in the composition according to the present technology is not particularly limited as long as it is a compound that can undergo a polymerization reaction as a photochemical reaction by the light energy transmitted from the sensitizing dye to generate a polymer.
• it includes a polymerizable compound capable of radical polymerization, a polymerizable compound capable of cationic polymerization, or both.
• the radical polymerizable organic monomer may include a polymerizable compound capable of anion polymerization.
• the radical polymerizable organic monomer may include a polymerizable monomer, a polymerizable oligomer, or a mixture thereof.
• the radical polymerizable organic monomer may include a monofunctional compound, a polyfunctional compound, or a mixture thereof.
• the radical polymerizable organic monomer may include one type of polymerizable compound, or two or more types of polymerizable compounds.
• X1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom.
• a is 0, when X1 is a nitrogen atom or a phosphorus atom, a is 1, and when X1 is a carbon atom or a silicon atom, a is 2.
• Y1 and Y2 are each a benzene ring or a naphthalene ring. Y1 and Y2 may be benzene rings at the same time, or may be excluded from being benzene rings at the same time.
• R 1 to R 3 is hydrogen or a substituent represented by *-Z 1 (R 4 ) d (* represents a bonding position).
• R 4 d represents a bonding position
• Z 1 represents a single bond, a divalent or higher saturated hydrocarbon group, or a divalent or higher unsaturated hydrocarbon group, and the saturated or unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond.
• Z 1 is a single bond
• d is 1
• Z 1 is a saturated or unsaturated hydrocarbon group
• d is an integer of 1 or more.
• R4 represents hydrogen or a polymerizable substituent. When a plurality of R4s are present, the plurality of R4s may be the same or different, but all R4s in the general formula (1) are not hydrogen at the same time.
• X1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom, or a silicon atom. It is also believed that the effects of the present disclosure can be expected for Group 14 elements, Group 15 elements, and Group 16 elements (excluding transition metals) other than those mentioned above.
• oxygen atom, nitrogen atom, and carbon atom which are typical elements of organic compounds, are preferred from the viewpoint of ease of compound synthesis, and the respective atomic refractions are oxygen atom: 1.6 to 2.2, nitrogen atom: 3.5 to 4.4, and carbon atom: 1.7 to 2.4 (Kogaku, Vol. 44, No. 8, 2015, pp. 298-303).
• X 1 in general formula (1) is preferably a nitrogen atom having a high value of atomic refraction.
• the radical polymerizable organic monomer polymerizable compound can have the following structure:
• Y1 and Y2 are each a benzene ring or a naphthalene ring.
• Y1 and Y2 may be benzene rings at the same time, or may be excluded from being benzene rings at the same time.
• b or c corresponding to Y1 and/or Y2 which are the benzene rings is 4.
• Y1 and/or Y2 are naphthalene rings
• b and/or c corresponding to Y1 and/or Y2 which are the naphthalene rings is 6.
• R 1 , R 2 , R 3 , R 11 and R 12 are each a hydrogen atom or a substituent represented by *-Z 1 (R 4 ) d (* represents a bonding position).
• R 1 , R 2 , R 3 , R 11 and R 12 in the general formulae (2-1) to ( 2-5 ) are not all hydrogen atoms at the same time.
• Z 1 represents a single bond, a divalent or higher saturated hydrocarbon group, or a divalent or higher unsaturated hydrocarbon group, and the saturated or unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond.
• R 4 represents hydrogen or a polymerizable substituent.
• the plurality of R 4s may be the same or different, but all of the R 4s in the general formulae (2-1) to (2-5) are not hydrogen at the same time.
• Y1 and Y2 are each a benzene ring or a naphthalene ring. Y1 and Y2 may be benzene rings at the same time, or may be excluded from being benzene rings at the same time.
• the molecular refraction of phenyl (C 6 H 5 ) and naphthyl (C 10 H 7 ) is 25.5 for phenyl (C 6 H 5 ) and 43.3 for naphthyl (C 10 H 7 ) (Optics, Vol. 44, No. 8, 2015, pp. 298-303).
• Y 1 and Y 2 are each a naphthalene ring having a high molecular refraction value.
• the radical polymerizable organic monomer can have the following structure:
• X 1 is an oxygen atom, a nitrogen atom, a phosphorus atom, a carbon atom or a silicon atom.
• a is 0, when X 1 is a nitrogen atom or a phosphorus atom, a is 1, and when X 1 is a carbon atom or a silicon atom, a is 2.
• R 1 , R 21 to R 26 , and R 31 to R 36 are each a hydrogen atom or a substituent represented by *-Z 1 (R 4 ) d (* represents a bonding position).
• R 1 , R 21 to R 26 , and R 31 to R 36 may be the same or different from each other. When a plurality of R 1s are present, the plurality of R 1s may be the same or different from each other. However, R 1 , R 21 to R 26 , and R 31 to R 36 in the general formulae (0-1), (3-1) to (3-3), and (4-1) to (4-6) are not all hydrogen atoms at the same time.
• Z 1 represents a single bond, a divalent or higher saturated hydrocarbon group, or a divalent or higher unsaturated hydrocarbon group, and the saturated or unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond.
• R 4 represents hydrogen or a polymerizable substituent.
• the plurality of R 4s may be the same or different, but all of the R 4s in the general formulae (0-1), (3-1) to (3-3) and (4-1) to (4-6) are not hydrogen at the same time.
• Z1 represents a single bond, a divalent or higher saturated hydrocarbon group, or a divalent or higher unsaturated hydrocarbon group.
• the saturated or unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond.
• Z1 is a saturated hydrocarbon group having a valence of 2 or more
• the saturated hydrocarbon group may be a linear, branched or cyclic substituted or unsubstituted hydrocarbon group.
• the longer the number of simple carbon chains in an organic compound the easier it is to obtain solubility, but on the other hand, the longer the number of simple carbon chains, the lower the refractive index.
• the number of simple carbon chains in the saturated hydrocarbon group is preferably 1 to 15, and more preferably 1 to 10.
• the unsaturated hydrocarbon group may be a linear, branched or cyclic substituted or unsubstituted hydrocarbon group or an aromatic group.
• the unsaturated hydrocarbon group preferably has a simple carbon chain number of 1 to 15, more preferably 1 to 10.
• the aromatic group is preferably a substituted or unsubstituted divalent or higher aromatic group represented by the following chemical formulas (5-1) to (5-8).
• the aromatic group preferably has a structure in which four or more benzene rings are not arranged in a straight line, and the linear shape is preferably a benzene ring, a naphthalene ring or an anthracene ring.
• the polymerizable substituent represented by R 4 may be one having a polymerizable unsaturated group or one having a reactive substituent.
• examples of those having a polymerizable unsaturated group include vinyl groups, acrylic groups, methacrylic groups, acrylamide groups, methacrylamide groups, cyanoacrylate groups, cyanomethacrylate groups, vinyl ether groups, cyanide vinyl groups, nitrated vinyl groups, conjugated polyene groups, halogenated vinyl groups, vinyl ketone groups, and styryl groups.
• Examples of those having a reactive substituent include epoxy groups, oxetane groups, hydroxyl groups, amino groups, carboxyl groups, acid anhydride groups, acid halide groups, and isocyanate groups.
• X1 is a nitrogen atom
• Y1 and Y2 are each a naphthalene ring. That is, the above compound is preferably a compound represented by the following general formula (1-1).
• R 1 , R 21 to R 26 , and R 31 to R 36 are hydrogen or a substituent represented by *-Z 1 (R 4 ) d (* represents a bonding position).
• R 1 , R 21 to R 26 , and R 31 to R 36 may be the same or different from each other. However, R 1 , R 21 to R 26 , and R 31 to R 36 are not all hydrogen at the same time.
• Z 1 represents a single bond, a divalent or higher saturated hydrocarbon group, or a divalent or higher unsaturated hydrocarbon group, and the saturated or unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond.
• R 4 represents hydrogen or a polymerizable substituent. When a plurality of R 4s are present, the plurality of R 4s may be the same or different, but all of R 4s in the general formula (1-1) are not hydrogen at the same time.
• R 1 is a substituent represented by *-Z 1 (R 4 ) d (* represents a bonding position), and R 21 to R 26 and R 31 to R 36 are hydrogen.
• X1 is a carbon atom and Y1 and Y2 are each a naphthalene ring. That is, the above compound is preferably a compound represented by the following general formula (1-2).
• R 11 , R 12 , R 21 to R 26 , and R 31 to R 36 are hydrogen or a substituent represented by *-Z 1 (R 4 ) d (* represents a bonding position).
• R 11 , R 12 , R 21 to R 26 , and R 31 to R 36 may be the same or different from each other. However, R 11 , R 12 , R 21 to R 26 , and R 31 to R 36 in general formula (1-2) are not all hydrogen at the same time.
• Z 1 represents a single bond, a divalent or higher saturated hydrocarbon group, or a divalent or higher unsaturated hydrocarbon group, and the saturated or unsaturated hydrocarbon group may contain an ether bond and/or a thioether bond.
• R 4 represents hydrogen or a polymerizable substituent. When a plurality of R 4s are present, the plurality of R 4s may be the same or different, but all of R 4s in the general formula (1-2) are not hydrogen at the same time.
• R 11 and/or R 12 is a substituent represented by *-Z 1 (R 4 ) d (* represents a bonding position), and R 21 to R 26 and R 31 to R 36 are hydrogen.
• the radical polymerizable organic monomer that may be contained in the composition according to the present technology may contain a polymerizable compound other than the compound represented by general formula (1) in place of the compound represented by general formula (1) or in addition to the compound represented by general formula (1).
• the polymerizable compound other than the compound represented by general formula (1) may include an aliphatic polymerizable compound.
• the refractive index modulation degree ⁇ n can be improved by using a monomer that can achieve a high refractive index through polymerization.
• the content of the radical polymerizable organic monomer that may be contained in the composition according to the present technology is not particularly limited, but by containing, for example, 1% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more, relative to 100% by mass of the composition, a polymerization reaction occurs as a photochemical reaction due to the light energy transmitted from the sensitizing dye, and a polymer can be suitably produced.
• the upper limit of the content of the radical polymerizable organic monomer that may be contained in the composition according to the present technology is not particularly limited, but can be suitably adjusted to, for example, 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 60% by mass or less, relative to 100% by mass of the composition.
• the composition according to the present technology may further contain a binder resin.
• the "binder resin” contained in the composition according to the present technology is a polymer compound that can suitably disperse the components contained in the composition according to the present technology within the composition. In addition, it can be effective in improving the film strength and improving the heat resistance and mechanical strength.
• the composition according to the present technology contains a binder resin, which makes it possible to maintain the concentration gradient that occurs as the polymerization reaction of the radically polymerizable organic monomer progresses, and therefore interference fringes can be suitably recorded by a method such as irradiating the composition according to the present technology with interference light. This allows three-dimensional image information, etc. to be suitably recorded, making it suitable for use in applications such as holograms.
• composition according to the present technology contains a binder resin, the viscosity of the composition can be ensured, so that a laminated film having a layer containing the composition according to the present technology can be suitably manufactured by a method such as extrusion molding or coating.
• the binder resin that may be contained in the composition of the present technology is not particularly limited, so long as it is a polymeric compound with a low Tg (glass transition point) that can suitably disperse the components contained in the composition within the composition.
• the binder resin may include at least one selected from the group consisting of vinyl acetate resins such as polyvinyl acetate or hydrolysates thereof, acrylic resins such as poly(meth)acrylic acid esters or partial hydrolysates thereof, polyvinyl alcohol or partial acetalization products thereof, triacetyl cellulose, polyisoprene, polybutadiene, polychloroprene, silicone rubber, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, polyarylate, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinylcarbazole or derivatives thereof, poly-N-vinylpyrrolidone or derivatives thereof, polyarylate, copolymers of styrene and maleic anhydride or half esters thereof, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, acrylamide, acrylonitrile, ethylene, propylene,
• the binder resin may contain an oligomer-type curable resin.
• it may contain an epoxy compound produced by a condensation reaction between a phenolic compound and epichlorohydrin.
• the phenolic compound includes at least one selected from the group consisting of bisphenol A, bisphenol S, novolac, o-cresol novolac, and p-alkylphenol novolac.
• the polymeric compounds that can be used as the binder resins described above can have a Tg range that can be adjusted to suit the components of the composition of the present technology so that the components can be suitably dispersed.
• the content of the binder resin that may be contained in the composition according to the present technology is not particularly limited, but by containing, for example, 1% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, relative to 100% by mass of the composition, the components contained in the composition can be suitably dispersed within the composition.
• the upper limit of the amount of binder resin that can be contained in the composition according to this technology is not particularly limited, and can be adjusted to any range depending on the components of the composition.
• the composition according to the present technology may further contain a polyhydric alcohol.
• the polyhydric alcohol functions as a color stabilizer that stabilizes the color development of the sensitizing dye.
• the polyhydric alcohol preferably contains a polyhydric alcohol that is in a liquid state at room temperature and normal pressure. By containing a polyhydric alcohol that is in a liquid state at room temperature and normal pressure, the dispersibility of the sensitizing dye in the composition can be improved. In addition, the inhibition of mass transfer during hologram recording can be suppressed.
• room temperature and normal pressure refers to 25° C. and 1 atm.
• the lower limit of the valence of the polyhydric alcohol (the number of hydroxyl groups in the polyhydric alcohol molecule) is divalent or more. If the valence of the polyhydric alcohol is divalent or more, the volatility of the polyhydric alcohol is low, so that when a photosensitive layer is formed from the photosensitive composition, the polyhydric alcohol can remain in the photosensitive layer.
• the upper limit of the valence of the polyhydric alcohol (the number of hydroxyl groups in the polyhydric alcohol molecule) is not particularly limited, and may be, for example, 6 or less, 7 or less, or 8 or less.
• the lower limit of the total carbon number of the polyhydric alcohol is not particularly limited, and may be, for example, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more.
• the upper limit of the total carbon number of the polyhydric alcohol is not particularly limited, and may be, for example, 18 or less, 16 or less, 14 or less, 12 or less, or 10 or less.
• Dihydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, It contains at least one selected from the group consisting of hexanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-
• the trihydric alcohol includes, for example, at least one selected from the group consisting of glycerin, trimethylolpropane, trimethylolethane, triethylolethane, etc.
• the tetrahydric alcohol includes, for example, at least one selected from the group consisting of diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, D-threitol, etc.
• the pentahydric alcohol includes, for example, at least one selected from the group consisting of L-arabinitol, ribitol, xylitol, and L-rhamnitol.
• the hexahydric alcohol includes, for example, at least one selected from the group consisting of D-glucitol, D-mannitol, and galactitol.
• the heptahydric alcohol includes, for example, at least one selected from the group consisting of pentaglycerin and heptitol.
• the octahydric alcohol includes, for example, at least one selected from the group consisting of sucrose, trehalose, maltose, gentiobiose, lactose, and melibiose.
• the composition according to the present technology may further contain inorganic fine particles.
• the inorganic fine particles include, for example, metal oxide fine particles.
• the metal oxide fine particles include at least one selected from the group consisting of titanium oxide (TiO x ) fine particles and zirconium oxide (ZrO x ) fine particles.
• the photosensitive composition may contain one type of inorganic fine particles, or may contain two or more types of inorganic fine particles. Specifically, for example, the photosensitive composition may contain both titanium oxide fine particles and zirconium oxide fine particles.
• the composition according to the present technology may further contain a chain transfer agent.
• the chain transfer agent extracts a radical from the growing end of the polymerization reaction, stops the growth, and becomes a new polymerization reaction initiating species, which can be added to the radical polymerizable monomer to start the growth of a new polymer.
• the frequency of chain transfer in radical polymerization increases, thereby increasing the reaction rate of the radical polymerizable monomer and improving the sensitivity to light.
• the reaction rate of the radical polymerizable monomer increases, and the reaction contributing components increase, making it possible to adjust the polymerization degree of the radical polymerizable monomer.
• the chain transfer agent includes, for example, at least one selected from the group consisting of ⁇ -methylstyrene dimer, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, tert-butyl alcohol, n-butanol, isobutanol, isopropylbenzene, ethylbenzene, chloroform, methyl ethyl ketone, propylene, vinyl chloride, etc.
• the composition according to the present technology may further contain a polymerization inhibitor.
• the polymerization inhibitor may be effective in suppressing unnecessary polymerization of the polymerizable compound due to light, heat, etc.
• the polymerization inhibitor includes at least one selected from the group consisting of, for example, quinone compounds (e.g., hydroquinone), hindered phenol compounds, benzotriazole compounds, and thiazine compounds (e.g., phenothiazine).
• the composition according to the present technology may further contain a UV sensitizing dye.
• the UV sensitizing dye is effective for absorbing UV light and improving the curing speed and cured product properties of the composition, and can promote the polymerization reaction of polymerizable monomers and radical polymerizable organic monomers remaining as monomers in the composition during UV exposure, which will be described later.
• the UV sensitizing dye includes, for example, anthracene-based compounds.
• the composition according to the present technology may contain a solvent.
• the solvent may be effective for adjusting the viscosity and improving the film-forming property, etc.
• the solvent may include at least one selected from the group consisting of, for example, acetone, xylene, toluene, methyl ethyl ketone, tetrahydrofuran, benzene, methylene chloride, dichloromethane, chloroform, methanol, ethanol, etc.
• composition according to the present technology may contain other components in addition to the above-mentioned components as necessary, as long as the desired physical properties are not significantly impaired. These may be contained alone or in any combination and ratio of two or more.
• the laminate film according to the present technology includes one or more layers containing the composition according to the present technology.
• the composition according to the present technology By using the composition according to the present technology as a layer of the laminate film, for example, it can be used efficiently when needed.
• film refers to a molded body shaped into a membrane of any thickness, and also includes so-called sheets.
• the laminate film according to the present technology may include a substrate layer, a resin layer, and a release layer in this order, and the resin layer may contain the composition according to the present technology.
• the "substrate layer" of the laminate film in this embodiment is a layer that can ensure the strength of the entire laminate film depending on the intended use of the laminate film, and a laminate film having functions according to the intended use can be manufactured by laminating layers having various functions, such as a resin layer containing the composition according to the present technology, on one or both sides of the substrate layer.
• the substrate layer can also function as a protective layer to protect the layers having various functions.
• the material forming the substrate layer is not particularly limited as long as it is a material that can ensure the strength of the entire laminated film depending on the use of the laminated film.
• a material that has high light transmittance and low oxygen permeability it is preferable to use a material that has high light transmittance and low oxygen permeability.
• a material with low oxygen permeability is assumed to have an oxygen permeability measured in an environment of 23°C and 0% RH of more than 0.1 cm3 ( m2 day atm) -1 and 10000 cm3 ( m2 day atm) -1 or less.
• the substrate layer may be a layer made of a single compound, or a layer made of a composition containing multiple compounds.
• the two or more compounds may be mixed, the two or more compounds may be copolymerized, or the two or more compounds may be laminated to form a laminate film.
• the cycloolefin resin includes, for example, at least one selected from the group consisting of norbornene polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Of these, it is preferable to include a norbornene polymer.
• the norbornene polymer includes, for example, at least one selected from the group consisting of ring-opening polymers of norbornene monomers and norbornene copolymers obtained by copolymerizing a norbornene monomer with an ⁇ -olefin such as ethylene.
• the polycarbonate resin includes, for example, at least one selected from the group consisting of aliphatic polycarbonate resins and aromatic polycarbonate resins.
• the polyester resin includes, for example, polyethylene terephthalate resins.
• the cellulose resin includes, for example, acetyl cellulose resins.
• the acetyl cellulose resin includes, for example, at least one selected from the group consisting of triacetyl cellulose (TAC) and diacetyl cellulose.
• TAC triacetyl cellulose
• the thickness of the substrate layer can be selected appropriately according to the intended use of the laminate film, but from the viewpoint of the transparency and rigidity of the holographic recording medium 10, it is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and even more preferably 3 ⁇ m or more. There is no particular upper limit to the thickness of the substrate layer, but it can be suitably adjusted, for example, within the range of 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 70 ⁇ m or less.
• the base layer may have a coating layer, if necessary.
• the coating layer may be provided on both the first surface and the second surface of the base layer, or on either surface.
• the coating layer may contain, for example, an ultraviolet curing resin.
• the coating layer may contain additives, such as fine particles, if necessary.
• the "release layer" of the laminate film according to the present technology is a layer provided on the surface of the laminate film opposite to the surface of the substrate layer of the resin layer containing the composition according to the present technology, and is peeled off and separated from the portion of the laminate film containing the resin layer when the resin layer is attached to the surface of a member.
• the release layer can also function as a protective layer that protects layers having various functions, such as the resin layer, of the laminate film before peeling.
• the material forming the release layer is not particularly limited as long as it can be peeled off from a predetermined interface in the laminated film when the resin layer is attached to the surface of a member, but from the viewpoint of protecting the resin layer containing the composition for recording interference fringes, it is preferable to use a material with an oxygen permeability that satisfies the above-mentioned conditions.
• a material with an oxygen permeability that satisfies the above-mentioned conditions. Examples of such materials that can be suitably used include cycloolefin resins, polycarbonate resins, polyester resins, etc.
• the release layer may be a layer made of a single compound, or a layer made of a composition containing multiple compounds.
• the thickness of the release layer can be selected appropriately according to the intended use of the laminated film.
• the "resin layer” included in the laminate film according to the present technology is a layer containing the composition according to the present technology.
• the thickness of the resin layer can be selected appropriately according to the intended use of the laminated film, but from the viewpoint of diffraction efficiency and sensitivity to light, it is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more. There is no particular upper limit to the thickness of the resin layer, but it can be suitably adjusted, for example, to a range of 100 ⁇ m or less, and more preferably 30 ⁇ m or less.
• the resin layer can be formed, for example, by applying the prepared composition according to the present technology onto a substrate layer and then drying it.
• the application method include a spin coater, gravure coater, slot die, comma coater, or bar coater.
• the laminate film according to the present technology may further include an adhesive layer.
• the "adhesive layer” refers to a layer that exists between any two layers (at the interface, etc.) included in the laminate film and bonds the two layers together.
• the position of the adhesive layer is not limited, and by providing it between any two layers, the adhesive strength of the two layers can be strengthened.
• the exposed adhesive layer can be used to suitably attach the film to the surface of any member.
• the material that forms the adhesive layer can be selected to suit the characteristics of the materials that make up the two layers whose adhesive strength is to be strengthened and the characteristics of the materials that make up the surfaces of the components to be bonded, and can be selected to suitably bond the materials.
• the adhesive layer may be a layer made of a single compound, or a layer made of a composition containing multiple compounds.
• the thickness of the adhesive layer can be selected appropriately to suit the characteristics of the materials that make up the two layers whose adhesive strength is to be strengthened.
• the laminate film according to the present technology may include layers other than the above-mentioned layers, if necessary, so long as the layers do not significantly impair the desired physical properties.
• FIG. 3 shows an example of a laminated film according to the present technology.
• the laminated film 10 includes a resin layer 12 provided on one side of a substrate layer 11, and a release layer 13 provided on the side of the resin layer 12 opposite to the side in contact with the substrate layer 11.
• the release layer 13 peels off and separates from the portion of the laminated film 10 that includes the resin layer 12 at the interface between the resin layer 12 and the release layer 13.
• FIG. 4 shows a modified example of the laminated film according to the present technology, in which an adhesive layer 14 is provided at the interface between the resin layer 12 and the peel layer 13 of the laminated film shown in FIG. 3.
• the release layer 13 is peeled off and separated from the portion of the laminated film 10 that includes the resin layer 12 at the interface between the adhesive layer 14 and the release layer 13. This allows the exposed adhesive layer 14 to suitably bond the laminated film 10 that includes the resin layer 14 to the surface of any member.
• FIG. 5 is a cross-sectional view showing an example of the configuration of an optical member 20 according to the third embodiment.
• the optical member 20, which is a holographic recording medium is a volume holographic recording medium and includes a member body 21 and a resin layer 12.
• the member body 21 is for supporting the resin layer 12.
• the member body 21 also functions as a protective layer for protecting the resin layer 12.
• the member body 21 is transparent to visible light.
• the member body 21 may be a film or a substrate having rigidity. Examples of materials for forming the substrate having rigidity include, but are not limited to, materials such as glass.
• the member body 21 is formed, for example, from a composition containing a compound such as a polymeric material.
• the polymeric material contains, for example, at least one selected from the group consisting of cycloolefin-based resins, polycarbonate-based resins, polyester-based resins, and cellulose-based resins.
• the member body 21 contains two or more types of resins, the two or more types of resins may be mixed, the two or more types of resins may be copolymerized, or the two or more types of resins may be laminated to form a laminated film.
• the cycloolefin resin includes, for example, at least one selected from the group consisting of norbornene polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Of these, it is preferable to include a norbornene polymer.
• the norbornene polymer includes, for example, at least one selected from the group consisting of ring-opening polymers of norbornene monomers and norbornene copolymers obtained by copolymerizing a norbornene monomer with an ⁇ -olefin such as ethylene.
• the polycarbonate resin includes, for example, at least one selected from the group consisting of aliphatic polycarbonate resins and aromatic polycarbonate resins.
• the polyester resin includes, for example, polyethylene terephthalate resins.
• the cellulose resin includes, for example, acetyl cellulose resins.
• the acetyl cellulose resin includes, for example, at least one selected from the group consisting of triacetyl cellulose (TAC) and diacetyl cellulose.
• TAC triacetyl cellulose
• the thickness of the member body 21 may be set as appropriate by a person skilled in the art, but from the viewpoint of the transparency and rigidity of the optical member 20, it is preferably 0.1 ⁇ m or more and 200 ⁇ m or less, more preferably 1 ⁇ m or more and 150 ⁇ m or less, and even more preferably 3 ⁇ m or more and 70 ⁇ m or less.
• the member body 21 may have a coating layer as necessary.
• the coating layer may be provided on both the first surface and the second surface of the member body 21, or on either surface.
• the coating layer includes, for example, an ultraviolet curing resin.
• the coating layer may include additives such as fine particles as necessary.
• the resin layer 12 contains the composition according to the first embodiment.
• the thickness of the resin layer 12 may be set as appropriate by those skilled in the art, but from the standpoint of diffraction efficiency and sensitivity to light, it is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, and more preferably 1 ⁇ m or more and 30 ⁇ m or less.
• the prepared composition is applied onto the member body 21 and then dried to form the resin layer 12.
• a spin coater, a gravure coater, a comma coater, a bar coater, or the like can be used as the application method. In this manner, the desired optical member 20 can be obtained.
• the optical member 20 may further include a release layer 13, similar to the laminated film shown in FIG. 3.
• the release layer 13 is provided on one of both sides of the resin layer 12, the other side opposite the member body 21.
• the release layer 13 may be a film or a substrate having rigidity, but from the viewpoint of increasing the oxygen permeability of the member body 21, it is preferable that the release layer 13 be a film.
• FIG. 6 is a diagram showing an example of peeling the resin layer from the member body 12 in the member shown in FIG. 5. In this form, peeling progresses at the interface between the resin layer 12 and the member body 21.
• the resin layer 12 which is the hologram, can be peeled off from the member body 21 and used in the form of a film. Furthermore, the film can then be cut into any shape for use.
• a flat component can be used as the main body of the component according to this technology to create a hologram or the like by exposure to record interference fringes, and then the resin layer can be peeled off from the main body and transferred to a curved component.
• the optical member 20 according to the third embodiment can be manufactured, for example, by the following method.
• FIG. 7 shows the peeling process in the method for manufacturing a member according to the present technology using a laminated film according to the present technology.
• the peeling layer 13 is separated by peeling at the interface between the resin layer 12 of the laminated film 10 and the peeling layer 13.
• Figure 8 shows the lamination process in the method for manufacturing a component according to the present technology using the laminated film according to the present technology.
• the laminated film 10 from which the aforementioned peeling layer 13 has been separated is laminated to the surface of the component body 21.
• an adhesive auxiliary tool such as a roller or laminating device, it is possible to prevent bubbles or wrinkles caused by air, etc., from occurring on the adhesive surface between the component body 21 and the resin layer 12.
• the adhesive aid used in this case is not particularly limited, but any laminating device such as a hand roller (HAL-TEC (HAL320) manufactured by Sankyo Co., Ltd.) can be suitably used.
• HAL-TEC HAL320 manufactured by Sankyo Co., Ltd.
• the optical member of the hologram optical element according to the fourth embodiment is a volume hologram optical element, and is obtained by exposing the optical member 20.
• the hologram optical element includes an exposed resin layer 12, i.e., a hologram layer.
• the polymerizable compound contained in the exposed resin layer 12 is polymerized.
• the exposed resin layer 12 may include, for example, a polymer and/or oligomer containing a structural unit derived from the compound represented by the above-mentioned general formula (1), and a polymerization initiator that has undergone a structural change by generating active species upon irradiation with external energy.
• the member according to this technology has a resin layer on at least a portion of the surface, and the resin layer contains a sensitizing dye or a derivative of the sensitizing dye whose light absorption wavelength changes reversibly, a polymer of a polymerizable monomer, and an absorption wavelength maintaining agent.
• Figure 9 shows the interference exposure process in a method for manufacturing a component related to this technology using a laminated film related to this technology.
• [Hologram recording optical system] 12 is a schematic diagram showing an example of the configuration of a hologram recording optical system used for exposing the optical member 20.
• the hologram recording optical system includes a semiconductor-excited solid-state laser 31A, a semiconductor-excited solid-state laser 31B, a semiconductor-excited solid-state laser 31C, electronic shutters 32A, 32B, and 32C, half-wave plates 33A, 33B, and 33C, objective lenses 34A, 34B, and 34C, beam expanders 35A, 35B, and 35C, a mirror 36, a dichroic mirror 37, a dichroic mirror 38, an iris diaphragm 39, a beam splitter 40, a mirror 41, and a mirror 42.
• the semiconductor-pumped solid-state laser 31A emits red laser light with a peak wavelength of 660 nm.
• the red laser light emitted from the semiconductor-pumped solid-state laser 31A passes through the electronic shutter 32A, the half-wave plate 33A, the objective lens 34A, and the beam expander 35A and is incident on the mirror 36.
• the red laser light reflected by the mirror 36 passes through the dichroic mirror 37, the dichroic mirror 38, and the iris diaphragm 39 and is incident on the beam splitter 40.
• the semiconductor-pumped solid-state laser 31B emits green laser light with a peak wavelength of 532 nm.
• the green laser light emitted from the semiconductor-pumped solid-state laser 31B passes through the electronic shutter 32B, the half-wave plate 33B, the objective lens 34B, and the beam expander 35B and enters the dichroic mirror 37.
• the dichroic mirror 37 reflects the green laser light but transmits the red laser light.
• the green laser light reflected by the dichroic mirror 37 enters the beam splitter 40 via the dichroic mirror 38 and the iris diaphragm 39.
• the semiconductor-pumped solid-state laser 31C emits blue laser light with a peak wavelength of 460 nm.
• the blue laser light emitted from the semiconductor-pumped solid-state laser 31C passes through the electronic shutter 32C, the half-wave plate 33C, the objective lens 34C, and the beam expander 35C and enters the dichroic mirror 38.
• the dichroic mirror 38 reflects the blue laser light but transmits the red and green laser lights.
• the blue laser light reflected by the dichroic mirror 38 enters the beam splitter 40 via the iris diaphragm 39.
• Each color laser light that enters the beam splitter 40 is separated into a first light beam 44 and a second light beam 45.
• the separated first light beam 44 and second light beam 45 are reflected by mirrors 41 and 42, respectively, and irradiated onto the optical element 20.
• the member 20 is irradiated with interference light.
• the energy of the light absorbed by the sensitizing dye is transferred to reactants such as polymerization initiators and radically polymerizable organic monomers depending on the amount of light irradiation, and the polymerization reaction of the radically polymerizable organic monomers proceeds.
• reactants such as polymerization initiators and radically polymerizable organic monomers depending on the amount of light irradiation
• the polymerization reaction of the radically polymerizable organic monomers proceeds.
• the polymerization reaction does not proceed, so a concentration gradient of the polymer of the radically polymerizable organic monomer occurs, and a phase separation structure is formed inside the resin layer 12.
• phase separation structure increases the refractive index difference between the separated phases in the resin layer 12, improving the refractive index modulation degree ⁇ n.
• the conditions for the two-beam exposure when irradiating the interference light may be appropriately set by a person skilled in the art depending on the use and purpose of the holographic optical element.
• the light intensity of one beam on the holographic recording medium can be set to 0.1 mW/cm2 or more and 100 mW/cm2 or less, and the exposure conditions for 1 second or more and 1000 seconds or less can be appropriately adjusted.
• interference exposure can be performed so that the angle between the two beams is 0.1 degrees or more and 179.9 degrees or less.
• Figure 10 shows the UV exposure process in the method for manufacturing a component according to the present technology using a laminated film according to the present technology.
• UV light is irradiated onto the entire member 20 that has been subjected to the interference exposure.
• the UV irradiation excites the polymerization initiator, and the polymerization reaction of the polymerizable monomer proceeds.
• the phase separation structure formed inside the resin layer 12 is fixed, and the interference fringes generated by the interference light can be suitably recorded.
• Figure 11 shows the heating process in a method for manufacturing a component according to the present technology using a laminated film according to the present technology.
• the entire member 20 that has been subjected to the UV exposure is heated to promote the polymerization reaction of the unreacted radical polymerizable organic monomers and polymerizable monomers, which diffuses the radical polymerizable organic monomers and polymerizable monomers inside the resin layer 12.
• further phase separation proceeds due to the polymerization reaction centered on the existing phase separation structure, which further increases the refractive index difference between the phases and improves the refractive index modulation degree ⁇ n.
• a hologram using the member according to the present technology obtained by the above-mentioned method or the like can be suitably used as an optical device, an optical component, etc.
• the optical device and the optical component include image display devices such as eyewear, holographic screens, transparent displays, head-mounted displays, and head-up displays, imaging devices, imaging elements, color filters, diffractive lenses, light guide plates, spectroscopic elements, hologram sheets, information recording media such as optical disks and magneto-optical disks, optical pickup devices, polarizing microscopes, and sensors.
• Optical devices and optical components using holograms made using the components according to the present technology can achieve excellent diffraction characteristics and transparency. As a result, optical devices and optical components with high optical characteristics and optical stability can be realized. Furthermore, when the present disclosure is used in a display, a display with high see-through properties can be obtained.
• This embodiment provides a method for forming a hologram diffraction grating, which selectively reacts the resin layer 12 with electromagnetic rays whose amplitude is spatially modulated, and can preferably record interference fringes, in an optical member 20 including a sensitizing dye, a polymerizable monomer, an absorption wavelength maintaining agent, a radical polymerizable organic monomer including a compound represented by the above-mentioned general formula (1), a binder resin, and a polymerization initiator.
• the method for forming the hologram diffraction grating is the interference exposure described in the above-mentioned fourth embodiment.
• the description of the method for forming the hologram diffraction grating is omitted. According to the method for forming the hologram diffraction grating, the effects as described in the above-mentioned fourth embodiment are achieved.
• the "electromagnetic rays” are waves that propagate changes in electric and magnetic fields, and include radio waves, infrared rays, visible light, ultraviolet rays, X-rays, and the like.
• composition according to the present technology can also be suitably used as an adhesive or sealant.
• composition of this technology can cause a polymerization reaction of the polymerizable monomer through photosensitization by the sensitizing dye contained therein, so the composition can be cured using long-wavelength light depending on the combination of the sensitizing dye and polymerizable monomer used.
• the sensitizing dye reacts with the polymerizable monomer in a reaction as shown in FIG. 15, fixing the absorption wavelength of the sensitizing dye and erasing the color of the reacted portion.
• the composition according to the present technology is used as an adhesive or sealant, the appropriateness of the application position and the presence or absence of overflow can be visually confirmed, while the application position can be made less noticeable by erasing the color after curing.
• the composition according to the present technology contains an absorption wavelength maintaining agent, the equilibrium state of the sensitizing dye can be prevented from shifting to either oxidation or reduction until light is irradiated, preventing the light absorption wavelength from being fixed, thereby improving the shelf life of the composition.
• a polymerization initiator may be mixed into the composition at the time of use.
• the shelf life of the composition can be further improved.
• the object to be sealed is not particularly limited, but examples include LEDs (Light Emitting Diodes).
• Methods for analyzing the absorption wavelength maintaining agent contained in the optical member 20 or the hologram optical element and substances derived therefrom include, for example, the following analysis method 1, but are not limited to these methods.
• the analysis conditions are as follows. Equipment: GC (Agilent Technologies 7890A) / MS (Agilent Technologies 5975Cinert) Column: DB-5MS 0.25 mm ID x 30 m (film thickness 0.25 ⁇ m) Oven temperature: 40°C (5 min) - 20°C/min - 320°C (10 min) Inlet temperature: 280°C Carrier gas: He (constant flow rate mode, 1.0 ml/min) Injection method: splitless Interface temperature: 280°C Ionization chamber temperature: 250°C EM voltage: 2500 eV Measurement mass range: m / z 29-800 Injection volume: 1 ⁇ L
• the solvent used was a mixture of methyl ethyl ketone (manufactured by Kanto Chemical Co., Ltd.) and ethanol (manufactured by Kanto Chemical Co., Ltd.) in a weight ratio of 80:20.
• the above prepared composition was applied to a 50 ⁇ m thick cycloolefin resin substrate layer using a bar coater to a dry film thickness of 5 ⁇ m.
• the holographic recording medium (component) prepared above was stored in a double black bag in a light-shielded state for the period shown in Table 1.
• the absorbance spectrum before and after storage was measured and evaluated using the method described below. Since there was a risk of contamination if the sample was taken out of the black bag once, the sample after storage was evaluated using a different sample prepared under the same conditions on the same day, rather than the sample used for measurement immediately after preparation.
• the transmittance spectrum was calculated by measuring the transmittance in the range of 400 nm to 700 nm using a spot light source manufactured by Hamamatsu Photonics K.K. as the light source and a compact fiber optic spectrometer (USB-4000) manufactured by Ocean Insight Inc. as the spectrometer. The absorbance at a wavelength of 660 nm was calculated using the calculated transmittance spectrum. The results are shown in Table 1.
• Figure 1 shows data showing the change over time in the transmittance spectrum of the composition of Example 1.
• a holographic recording medium component having a resin layer composed of the aforementioned composition
• the transmittance spectra were measured by the aforementioned method for a sample immediately after production, a sample after 70 hours, and a sample after 336 hours.
• the inclusion of an absorption wavelength maintaining agent reduces the change in the waveform of the transmittance spectrum over time, preventing the equilibrium state of the sensitizing dye from shifting to either oxidation or reduction, thereby improving the shelf life of the composition.
• Figure 2 shows data showing the effect of the amount of absorption wavelength maintaining agent added on the storage stability of the composition according to this technology.
• Sodium m-nitrobenzenesulfonate, a reduction inhibitor was used as the absorption wavelength maintaining agent, and the content was set to 0 mass%, 0.2 mass%, 0.5 mass%, and 2.5 mass%, and the other components were adjusted to the composition of Example 1 to prepare compositions.
• holographic recording media (components) with resin layers made of each composition were produced by the method described above, and the change over time in the ratio of the absorbance of the sensitizing dye (methylene blue) at a wavelength of 660 nm to the absorbance of the UV sensitizing dye (9,10 dibutoxyanthracene) at a wavelength of 365 nm is shown in the graph in Figure 2.
• the sensitizing dye methylene blue
• the UV sensitizing dye (9,10 dibutoxyanthracene) at a wavelength of 365 nm is shown in the graph in Figure 2.
• Each of the holographic recording media (components) of the examples and comparative examples was simultaneously exposed to two beams of light using three types of semiconductor lasers with wavelengths in the visible light region of 460 nm, 532 nm, and 660 nm, respectively, to diffuse and harden the contained radical polymerizable organic monomers in the composition. After that, the entire surface was irradiated with UV (ultraviolet rays) to harden the unhardened radical polymerizable organic monomers and polymerizable monomers, and the refractive index distribution was fixed in the holographic recording media (components).
• UV ultraviolet
• the remaining radical polymerizable organic monomers and polymerizable monomers were further diffused and hardened in the composition by applying heat treatment at 40°C to 280°C for at least 1 minute.
• the conditions for the dual-beam exposure were a total light intensity of 35 W/ cm2 for all types of laser light, exposure time of 30 seconds, and an angle between the dual beams of light of 16 degrees.
• compositions according to the presented examples and comparative examples can also be used as a curing agent for a sealant or the like.
• composition according to the Examples and Comparative Examples was evaluated by the method described below before the storage evaluation (on the day the composition was made) and after one month of storage in a dark place. Before the storage evaluation, it was confirmed that each composition was able to harden, and that the resin layer composed of the composition was visually transparent. On the other hand, after one month of storage in a dark place, only the composition according to the Examples was able to harden and become visually transparent.
• each of the above compositions was applied to the inside of a glass sample tube. At this time, it was confirmed for each composition whether the applied portion of the composition could be visually confirmed.
• Each sample tube was coated with the composition and sealed under a nitrogen atmosphere.
• the sample tube was then irradiated with light of a wavelength of 660 nm, and the sample tube was then tilted to check whether the composition would flow in response to the tilt. If the composition flowed, it was determined to be photocurable.
• composition of the example was cured to a deep portion when irradiated with light of a long wavelength such as 660 nm. This means that the composition of this technology can be used to cure to a deep portion that cannot be reached by light of a short wavelength such as UV, through photosensitization.
• the present technology can have the following configurations.
• a composition comprising a sensitizing dye whose light absorption wavelength is reversibly changed, a polymerizable monomer, and an absorption wavelength maintaining agent.
• the composition according to (1) further comprising a polymerization initiator.
• the composition according to any one of (1) to (3) comprising 1 mol or more of the absorption wavelength maintaining agent per 1 mol of the sensitizing dye.
• composition according to (5), wherein the reduction inhibitor is at least one selected from the group consisting of nitro compounds, peroxides, and halogen-based compounds.
• the reduction inhibitor is at least one selected from the group consisting of nitrobenzenesulfonate, metanitrobenzenesulfonate, nitronaphthalenesulfonate, vanadate, nitrite, chlorate, perchlorate, and percarbonate.
• a laminated film comprising at least one layer containing the composition according to any one of (1) to (12).
• the resin layer is a laminated film containing the composition according to any one of (1) to (12).
• a method for adhering objects comprising using the composition according to any one of (1) to (12) as an adhesive.
• a method for adhering objects comprising using as an adhesive a composition obtained by mixing a polymerization initiator with the composition according to any one of (1) to (12).
• a sealing method comprising using the composition according to any one of (1) to (12) as a sealant.
• Adhesive layer 10 Laminated film 11 Substrate layer 12 Photosensitive layer 13 Release layer 14 Adhesive layer 20 Member (optical member) 21 Member body 22 Adhesion assistant tool (roller) 31A, 31B, 31C Semiconductor pumped solid-state lasers 32A, 32B, 32C Electronic shutters 33A, 33B, 33C 1/2 wavelength plates 34A, 34B, 34C Objective lenses 35A, 35B, 35C Beam expander 36 Mirror 37 Dichroic mirror 38 Dichroic mirror 39 Iris diaphragm 40 Beam splitter 41 Mirror 42 Mirror 44 First light beam 45 Second light beam

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  • 2024-03-18 JP JP2025510530A patent/JPWO2024203523A1/ja active Pending
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