WO2011034138A1 - 硬化成型体の製造方法及び硬化成型体 - Google Patents
硬化成型体の製造方法及び硬化成型体 Download PDFInfo
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- WO2011034138A1 WO2011034138A1 PCT/JP2010/066066 JP2010066066W WO2011034138A1 WO 2011034138 A1 WO2011034138 A1 WO 2011034138A1 JP 2010066066 W JP2010066066 W JP 2010066066W WO 2011034138 A1 WO2011034138 A1 WO 2011034138A1
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- 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
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- 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
- C08G59/68—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 catalysts used
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- 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
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/105—Onium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Definitions
- the present invention relates to a method for producing a cured molded body and a cured molded body. More specifically, for example, a method for producing a cured molded body applied to various uses such as optical members, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials, and a cured molded body obtained by the manufacturing method. About.
- the cured molded body is a cured product obtained by curing the resin composition, and is applied to various uses such as optical members, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials, etc.
- curable resin compositions For example, a resin composition containing an inorganic substance can not only reduce the coefficient of thermal expansion, but also control the appearance of the resin composition and its cured product by matching the refractive index of the inorganic substance and the resin. Since transparency can also be expressed, it is particularly useful as a material for obtaining a cured molded body for use in electric / electronic parts and optical members.
- thermoplastic resins such as polycarbonate (PC) and polycycloolefin
- PC polycarbonate
- LEDs display elements
- a cured product using a thermoplastic resin does not have sufficient performance, and scratches and wear occur due to dust and cleaning liquid. Therefore, a hard coat film or a cover glass (inorganic glass) may be provided on the upper layer. It is necessary and very expensive.
- the optical member used for a sensor having physical contact, such as a touch panel also needs strength.
- an organic resin for example, an organic resin, an alcohol having 8 to 36 carbon atoms, a carboxylic acid, a carboxylic acid ester, and A transparent organic resin composition containing at least one compound selected from the group consisting of carboxylates is disclosed (see Patent Document 1, etc.).
- a resin composition in which an epoxy group-containing compound is essential as an organic resin component and an organosiloxane compound is essential as an inorganic component.
- Patent Document 2 when a polysiloxane compound having a functional group is used, the viscosity increases with time even at room temperature, and the epoxy compound has a high curing reactivity. Although gelation occurs, it is described that if an organosiloxane compound having a low-reactivity organic group as a functional group is used, it is possible to achieve suppression of thickening and gelation while improving heat resistance and mechanical properties. Yes.
- JP 2008-088249 A (second page, etc.) JP 2008-133442 A (2nd, 4th to 5th pages, etc.) JP 2009-155442 A (second page, etc.)
- the present invention has been made in view of the above situation, and can easily produce a cured cured product that is excellent in heat resistance, wear resistance, and releasability, has a small shrinkage rate, and has no coloration.
- An object of the present invention is to provide a method for producing a cured molded body that can be used, and a cured molded body that is useful for various uses such as an optical member.
- the present inventors have made various studies on the curable resin composition that is a raw material of the cured molded body.
- curable organic compounds such as epoxy groups and oxetane rings can be easily molded (molded), and various kinds of optical members and the like can be obtained.
- It is useful as a material (organic resin component) in applications, and when a condensable inorganic compound is used, it can give or improve optical properties and mechanical properties, and can obtain a cured molded article excellent in releasability. Focused on.
- the curable organic compound and the condensable inorganic compound are cured in the presence of a curing agent, the curable organic compound may not be sufficiently cured depending on the curing conditions, or the curing reactivity of the curable organic compound is high and the condensable inorganic compound. Due to the high shrinkage rate of the compound, it may not be possible to obtain a cured molded product that exhibits sufficient physical properties and excellent surface appearance due to sudden thickening, gelation, or foaming during curing. In addition, it has been found that the properties of each of these components cannot be fully exhibited in a cured product by merely curing a resin composition containing a curable organic compound and a condensable inorganic compound by a normal method. In particular, it has been found that these phenomena become remarkable when the content ratio of the condensable inorganic compound is large.
- the present inventors divided the curing process into two stages, the first process of the first stage is a thermosetting process at a specific temperature and / or a curing process by irradiation with active energy rays, and the second process is heated at a high temperature.
- the curing reaction of the curable organic compound proceeds rapidly in the first step, but the curing reaction of the condensable inorganic compound is difficult to proceed, and the curable organic compound is almost cured. It was newly found that the curing reaction of the condensable inorganic compound proceeds mainly in the second step.
- the cured molded body obtained by such a production method has a specific composition that cannot be obtained by the conventional production method, and therefore, it becomes excellent in various physical properties particularly required for optical members,
- various physical properties such as hardness, heat resistance, abrasion resistance, transparency, low shrinkage, light resistance, releasability can be remarkably exhibited, and the present invention has been achieved. .
- the present invention is a method for producing a cured molded body from a curable resin composition containing a condensable inorganic compound, a curable organic compound, and a curing agent, and the production method comprises the step of producing the curable resin composition.
- a first step comprising a step of thermosetting at 80 to 200 ° C. and / or a step of curing by irradiation with active energy rays, and a step of thermosetting the cured product obtained in the first step at over 200 ° C. and below 500 ° C.
- It is a manufacturing method of the hardening molded object characterized by including 2 processes.
- the present invention is also a method for producing a cured molded article from a polysiloxane compound having a condensable group, a compound having a ring-opening polymerizable group, and a curable resin composition containing a curing agent, the production method Comprises a first step comprising a step of thermally curing the curable resin composition at 80 to 200 ° C. and / or a step of curing by irradiation with active energy rays, and the cured product obtained in the first step exceeds 200 ° C. And a second method of thermosetting at 500 ° C. or lower and a method for producing a cured molded body.
- the present invention further includes a cured molded body containing a metalloxane component and an organic resin component, wherein the metal element constituting the metalloxane component is 10% by mass or more based on 100% by mass of the total amount of the cured molded body, Among the metal elements constituting the metalloxane component, the number of bonds with the hydrocarbon group is n-1 or n-2 (n is the valence of the metal element and represents an integer of 2 or more). The content is 50 atomic% or less with respect to 100 atomic% of the total amount of metal elements constituting the metalloxane component, and among the metal elements constituting the metalloxane component, YM (M represents a metal element. Y represents a metal element.
- the content of the metal element having a bond represented by a hydrogen atom, a halogen atom, a hydroxyl group, and an RO group is a metalloxane compound.
- the content of the particulate component is 50% by mass or less with respect to 100% by mass of the total amount of the metalloxane component. It is also a cured molded body characterized by being. The present invention is described in detail below.
- the first step is a step of thermally curing a curable resin composition (also simply referred to as “resin composition”) at 80 to 200 ° C., and the curable resin composition is irradiated with active energy rays.
- a curable resin composition also simply referred to as “resin composition”
- the curable resin composition is irradiated with active energy rays.
- a second step of thermosetting at 500 ° C. or lower.
- molding (molding) process may be further included.
- the curing temperature is 80 to 200 ° C. If it is less than 80 degreeC, since curable resin composition cannot fully be hardened and an organic resin matrix with a small shrinkage rate cannot be created, there exists a possibility that hardening shrinkage may become large in the following second-stage thermosetting process.
- the temperature exceeds 200 ° C., the curing reaction due to the condensation reaction of the condensable inorganic compound becomes conspicuous, so the curing shrinkage due to the condensable inorganic compound increases, and foaming occurs due to vaporization of water or alcohol by-produced by the condensation reaction.
- the curing reaction cannot be performed, and there is a possibility that a cured molded body having high strength and surface hardness and high appearance cannot be obtained.
- the mold release property is not sufficient, and there is a possibility that a cured molded article excellent in dimensional accuracy and mold transferability cannot be obtained.
- it is 100 degreeC or more, Preferably it is 160 degreeC or less.
- the cationic curing catalyst is used as a curing agent, that is, when curing is performed by a cationic curing reaction, the curing reaction can be sufficiently performed even if the curing time is short. Is preferable because the reaction of the condensable inorganic compound hardly occurs in the first step. Moreover, it is suitable also in the point which can improve manufacturing efficiency. Furthermore, the cationic curing catalyst is an organic resin component that is excellent in heat resistance in that it does not produce alcohol or ester due to the curing reaction.
- the curing time is preferably within 10 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer.
- the curing time is preferably 15 minutes to 48 hours for sufficient curing. More preferably, it is 30 minutes to 36 hours.
- the thermosetting step can also be performed in air and / or under an inert gas atmosphere such as nitrogen under reduced pressure or under pressure.
- the curing temperature may be changed stepwise within the range of the curing temperature of 80 to 200 ° C.
- the curable resin composition is held in the mold at a predetermined temperature and time, and then removed from the mold and left in the atmosphere of an inert gas such as air and / or nitrogen. It is also possible to perform heat treatment. Moreover, you may combine hardening by active energy ray irradiation.
- active energy ray irradiation when making it harden
- active species such as a radical and a cation
- ionizing radiation such as ultraviolet rays, visible rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays, microwaves, high frequencies, infrared rays, laser beams, etc. are suitable, taking into consideration the absorption wavelength of the compound that generates radically active species. And may be selected as appropriate.
- ultraviolet rays or visible rays having a wavelength of 180 to 500 nm are preferable because they can be easily handled.
- a mode in which the curing step by the irradiation of active energy rays is a photocuring step of curing by irradiating ultraviolet rays or visible rays having a wavelength of 180 to 500 nm is also a preferred embodiment of the present invention.
- light having wavelengths of 254 nm, 308 nm, 313 nm, and 365 nm is particularly effective for curing.
- the curing step by irradiation with active energy rays can be performed in air and / or in an inert gas, under any atmosphere under reduced pressure or under pressure.
- Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, Short arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, sunlight and the like are suitable.
- the irradiation time of the said active energy ray irradiation ie, the hardening time in the hardening process by an active energy ray, according to the kind, irradiation amount, etc. of an active energy ray.
- the irradiation time of ultraviolet rays or visible rays having a wavelength of 180 to 500 nm is preferably 0.1 microseconds to 30 minutes, and more preferably 0.1 milliseconds to 1 minute.
- the first step includes at least one of a step of thermally curing the curable resin composition at 80 to 200 ° C. and a step of curing by irradiation with active energy rays. It is preferable to perform at least the step of thermosetting the functional resin composition at 80 to 200 ° C. Thereby, the target shape can be obtained more easily in the first step, the shape can be maintained more easily in the second step, and the molded body by gas that can be generated by condensation of the condensable inorganic compound in the second step. The foaming inside can be prevented more sufficiently.
- the first step is also preferably a curing step using a mold made of metal, ceramic, glass, resin or the like (referred to as “mold”).
- the curing process using a mold may be a curing process normally performed by a mold molding method such as an injection molding method, a compression molding method, a casting molding method, or a sandwich molding method. If it is a hardening process using such a mold, it is excellent in various physical properties such as wear resistance, low shrinkage, dimensional accuracy and mold transferability, and easily produces a transparent cured molded body without coloring. It is possible to more fully exhibit the operational effect of the present invention.
- the form in which the first step is a curing step using a mold is one of the preferred forms of the present invention.
- the first step is a curing step using a mold
- the mold including the demolding process that is, the cured product obtained in the first process is taken out from the mold, and the taken cured product is used for the next second process, whereby the expensive mold is effectively rotated (recycled). ) And the life of the mold can be extended, so that a cured molded body can be obtained at low cost.
- a mode in which the manufacturing method further includes a demolding step between the first step and the second step is also a preferred mode of the present invention.
- the curable resin composition is a one-component composition containing a curing agent and other components as required, and the one-component composition is filled in a mold that matches the shape of the desired cured molded body.
- a method of curing by injection (coating, coating, etc.) and then removing the cured product from the mold is preferably used.
- the cured product obtained in the first step (preferably, the cured product taken out from the mold by the demolding step) is used in the second step, but in the cured product in the second step.
- the pencil hardness of the cured product obtained in the first step is 9B or more. More preferably, it is 6B or more, More preferably, it is 2B or more, Most preferably, it is F or more.
- the pencil hardness can be measured using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho) in accordance with JIS-K5600-5-4 (established in 1999) with a load of 1000 g.
- the cured product obtained in the first step (preferably, the cured product taken out from the mold by the demolding step) is heat-cured at a temperature exceeding 200 ° C. and not more than 500 ° C. Become.
- the thermosetting temperature in the second step is 200 ° C. or lower, the condensable inorganic compound does not sufficiently cure, so it has a high level of surface hardness required for outdoor use, that is, excellent wear resistance. There is a possibility that a cured molded body cannot be obtained.
- it exceeds 500 degreeC there exists a possibility that the coloring and hardness by decomposition
- it is 250 degreeC or more, More preferably, it is 300 degreeC or more, Especially preferably, it is 330 degreeC or more, Most preferably, it is 350 degreeC or more. Moreover, Preferably, it is 400 degrees C or less.
- the curing time in the second step is not particularly limited as long as the curing rate of the resulting cured molded body is sufficient, but considering the production efficiency, for example, it is preferably 30 minutes to 30 hours. is there. More preferably, it is 1 to 10 hours.
- the second step can also be performed in any atmosphere of air and / or an inert gas atmosphere such as nitrogen.
- the second step may be performed in an atmosphere having a low oxygen concentration from the viewpoint of effectively performing a curing reaction of the condensable inorganic compound and further improving transparency and surface hardness (abrasion resistance).
- the curing temperature may be changed stepwise within a temperature range exceeding 200 ° C. and not more than 500 ° C.
- the curable resin composition used in the method for producing the cured molded body will be described.
- the said curable resin composition contains a condensable inorganic compound, a curable organic compound, and a hardening
- the condensable inorganic compound means an inorganic compound having a condensable group.
- a condensable group refers to a functional group that condenses with heat.
- Such a condensable inorganic compound is a compound (polymetalloxane compound) having a condensable group and having a metalloxane bond (MOM bond, M represents a metal element). Is preferred. That is, it is one of the preferred embodiments of the present invention that the condensable inorganic compound of the present invention is a polymetalloxane compound having a condensable group.
- condensable group examples include, for example, a M—O—R group (R represents a hydrocarbon group), a M—OH group, and a M—X group (X represents a halogen atom).
- R represents a hydrocarbon group
- M—OH group a M—OH group
- M—X group a M—X group
- MH groups are preferred.
- an M—O—R group or an M—OH group is particularly preferable from the viewpoint of curing reactivity.
- the compound having a metalloxane bond is not particularly limited, but the metal element represented by M is Si, Mg, Al, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr. Including one or more of Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, Ta, W, Ir, Tl, Pb, Bi, and Ra Is preferred. More preferably, M includes one or more of Si, Al, Ti, Zn, Zr, Sn, Ba, and Ra, and more preferably Si, Ti, Zn, Zr, and It is to include one or more of Sn. It is particularly preferable to include one or two of Si and Sn.
- the compound in which M is Si that is, a polysiloxane compound is included.
- the condensable inorganic compound of the present invention contains a polysiloxane compound having a condensable group.
- metalloid elements include metalloid elements such as Si, Ge, and Sb.
- the content of the siloxane bond is preferably 30% by mass or more with respect to 100% by mass of the total amount of all metalloxane bonds. More preferably, it is 50 mass% or more, More preferably, it is 80 mass% or more.
- the compound having a metalloxane bond has a high hydrolysis rate, and the possibility of gelation or insolubilization increases, making synthesis difficult. Moreover, the viscosity of the resin composition becomes high and molding becomes difficult.
- the condensable inorganic compound includes a polysiloxane compound having a condensable group
- the condensable group is an Si—O—R group (R represents a hydrocarbon group), Si—.
- R represents a hydrocarbon group
- Si— is also a preferred form of the present invention. It is.
- R represents a hydrocarbon group.
- R is preferably an alkyl group, an aryl group, or an aralkyl group, and the M—O—R group may have two or more of them as a whole.
- R is preferably a hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is more preferably 1 to 8, and further preferably 1 to 3.
- Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and 2-ethyl.
- Chain alkyl groups such as xyl group, n-octyl group, lauryl group, stearyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclohexyl group, bicyclohexyl group; one of hydrogen atoms of chain alkyl group A group in which part or all are substituted with a cycloalkyl group; a group in which some or all of the hydrogen atoms of a cycloalkyl group are substituted with a chain alkyl group, and the like.
- aryl group examples include a phenyl group, a naphthyl group, an anthranyl group, etc., and a group in which some or all of these hydrogen atoms are substituted with an alkyl group (for example, a methylphenyl group (toluyl group), Dimethylphenyl group (xylylene group), diethylphenyl group, etc.).
- alkyl group for example, a methylphenyl group (toluyl group), Dimethylphenyl group (xylylene group), diethylphenyl group, etc.
- aralkyl group examples include a benzyl group and the like, and a group in which some or all of these hydrogen atoms are substituted with an alkyl group (for example, a methylbenzyl group).
- an alkyl group that is, a form in which the RO group is an alkoxy group
- an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group is particularly preferable. is there.
- a methyl group or an ethyl group is more preferable, and an ethyl group is most preferable because the reaction can be easily controlled.
- R may have a substituent. Further, it may be a chain (linear or branched) structure or a cyclic structure. Further, the halogen atom represented by X is not particularly limited, but a fluorine atom is particularly preferable.
- a chain structure (straight-chain form, branched form), a ladder-like structure, a cyclic structure, a cage
- a chain shape, a ladder shape, and a cage shape are preferable from the viewpoint of high solubility in a resin component such as a curable organic compound.
- a chain shape and a ladder shape are more preferable. Particularly preferred is a ladder shape.
- the release property, controllability of optical properties can be added with a small amount compared to the case of using other structures.
- the characteristic can be further improved. That is, (1) the cured molded body can be easily released from the molding die after curing (excellent release properties), (2) transparency, Abbe number and refractive index of the curable resin composition Can be strictly controlled (excellent controllability), (3) transparency, Abbe number and refractive index of the cured molded product can be strictly controlled (excellent controllability), (4) Addition effects such as excellent mechanical properties (high modulus of elasticity and high breaking strength) of the cured molded body can be exhibited.
- the polymetalloxane compound may be liquid at normal temperature or may be solid.
- a weight average molecular weight of the said polymetalloxane compound 300 or more are preferable and it is preferable that it is 100,000 or less. If it is less than 300, the storage stability of the resin composition containing the polymetalloxane compound may not be sufficient, and the releasability, controllability of optical properties, and mechanical properties may not be further improved. There is. When it exceeds 100,000, there is a possibility that the compatibility with a resin component such as a curable organic compound cannot be made more satisfactory. More preferably, it is 500 or more, More preferably, it is 1000 or more, More preferably, it is 50,000 or less, More preferably, it is 10,000 or less. In addition, the weight average molecular weight in this specification was measured by the method shown below.
- R 1 xYyMOz (1) (M represents a metal element.
- R 1 represents an alkyl group, an aryl group, an aralkyl group, a group having an oxirane ring, a group having an acryl and / or methacryl group, a group having an S (sulfur) atom, or F (F) represents a functional group having an atom
- Y represents a condensed group or a condensed atom, and is bonded to M to form the above condensable group.
- n is the valence of the metal element M (When M contains two or more kinds of metal elements, the compound represented by the average value of the valence of each element) is particularly preferred. More preferably, the ranges of x, y, and z are 0 ⁇ x ⁇ n ⁇ 2, 0 ⁇ y ⁇ n ⁇ 2, and (n ⁇ 2) / 2 ⁇ z ⁇ n / 2.
- the polysiloxane compound is particularly preferably a structural unit having a silicon atom bonded to three silicon atoms by a siloxane bond (Si—O—Si bond), that is, silyl A compound mainly containing a sesquioxane unit and containing a condensable group in the molecule (this compound is referred to as “silsesquioxane having a condensable group”, simply “silsesquioxane”, or “polysyl Also referred to as “sesquioxane”).
- Such a polysiloxane compound is, for example, the following average composition formula (2): R 1 xYySiOz (2)
- R 1 is an alkyl group, an aryl group, an aralkyl group, a group having an oxirane ring, a group having an acryl and / or methacryl group, a group having an S (sulfur) atom, or a functional group having an F (fluorine) atom.
- Y represents a condensed group or a condensed atom, and is bonded to Si to form the above condensable group
- x, y, and z are bonds of R 1 , Y, and O to Si, respectively.
- a compound represented by an average value of ratios and satisfying 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 2, 1 ⁇ z ⁇ 2, 0 ⁇ (x + y) ⁇ 2, and x + y + 2z 4) is particularly preferable. .
- the curable resin composition can be made into a one-component resin composition (one-component curable resin composition) that is more excellent in handling properties, and more efficient in combination with the operational effects of the production method of the present invention. Therefore, it is possible to obtain a cured molded body having excellent physical properties easily and conveniently.
- R 1 represents an alkyl group, an aryl group, an aralkyl group, a group having an oxirane ring, a group having an acryl and / or methacryl group, a group having an S (sulfur) atom, or F
- R 1 is preferably an alkyl group, an aryl group or an aralkyl group.
- an alkyl group is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, 2 -Chain alkyl groups such as ethylhexyl group, n-octyl group, lauryl group, stearyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclohexyl group, bicyclohexyl group; hydrogen of chain alkyl group A group in which part or all of the atoms are substituted with a cycloalkyl group; a group in which some or all of the hydrogen atoms of the cycloalkyl group are substituted with chain alkyl groups, and the like.
- alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, n-propyl group, and isopropyl group are preferable from the viewpoint of further increasing the surface hardness. More preferably, it is a methyl group. Further, from the viewpoint of increasing the refractive index, an aralkyl group is preferable, and a phenyl group is particularly preferable.
- R 1 may have a substituent, but is particularly preferably a group having no substituent.
- the “alkyl group” includes not only a linear or branched alkyl group but also a cyclic alkyl group (cycloalkyl group).
- the polysiloxane compound may be replaced with one having a group that forms a bond with an organic resin component (such as a curable organic compound) instead of R 1 .
- an organic resin component such as a curable organic compound
- a curable organic compound may be used instead of R 1 .
- Y represents a condensed group or a condensed atom, and is bonded to Si to form the condensable group. Therefore, Y is preferably at least one selected from the group consisting of an OR group (R represents a hydrocarbon group), a hydroxyl group, a halogen atom (X), and a hydrogen atom. Suitable forms of R and X are as described above.
- the above y represents the average value of the bonding ratio of Y to Si, and is a number exceeding 0 and less than 2, but if y is 2 or more, there is a possibility that bubbles are generated in the molded body due to the condensation of Y. .
- it is less than 1, more preferably less than 0.5, particularly preferably less than 0.3.
- the hardness improvement effect by the condensation of silsesquioxane in the second step will be small, and the compatibility with the epoxy resin will be small. More preferred is a value greater than 0.01, even more preferred is a value greater than 0.05, and particularly preferred is a value greater than 0.08.
- the z may be a number greater than 1 and less than 2. Preferably it is greater than 1.2 and less than 1.8, more preferably greater than 1.35 and less than 1.65.
- the x + y may be a number greater than 0 and less than 2. Preferably it is more than 0.4 and less than 1.6, more preferably more than 0.7 and less than 1.3.
- the x is preferably set as appropriate so that y and x + y satisfy the above-described preferable ranges.
- the content of the condensable inorganic compound is preferably 5 to 95% by mass with respect to 100% by mass of the total amount of the condensable inorganic compound and the curable organic compound.
- the higher the content of the condensable inorganic compound the higher the heat resistance, that is, the more difficult it is to color, and the higher the hardness, which is preferable.
- the content of the condensable inorganic compound exceeds 95% by mass, Insufficient organic resin matrix (cured product) cannot be formed in the process, and the mold transferability is not sufficient. Therefore, the obtained cured molded body should be particularly useful for applications such as optical members. You may not be able to.
- the content of the condensable inorganic compound is 10% by mass or more, more preferably 30% by mass or more, particularly preferably 50% by mass with respect to 100% by mass of the total amount of the condensable inorganic compound and the curable organic compound. % Or more, most preferably 60% by mass or more. Moreover, it is preferably 90% by mass or less, more preferably 80% by mass or less.
- the content of the metal element constituting the metalloxane component in the cured molded body is 5% by mass or more in terms of the metal element content in 100% by mass of the finally obtained molded body.
- the condensable inorganic compound contains a polysiloxane compound
- the amount of the siloxane bond in the cured molded body is 5 mass in terms of the Si content in 100% by mass of the finally obtained molded body. % Or more is preferable. More preferably, it is 10 mass% or more, More preferably, it is 15 mass% or more, Most preferably, it is 20 mass% or more.
- the condensable inorganic compound may also contain other metals and inorganic elements as components from the viewpoint of controlling optical properties.
- the metal element include alkaline earth metal elements such as Be, Mg, Ca, Sr, Ba, and Ra; lanthanoid metal elements such as La and Ce; actinoid metal elements such as Ac; IIIa such as Sc and Y Group metal elements; Group IVa metal elements such as Ti, Zr and Hf; Group Va metal elements such as V, Nb and Ta; Group VIa metal elements such as Cr, Mo and W; Group VIIa metals such as Mn, Tc and Re Element; Group VIII metal element such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt; Group Ib metal element such as Cu, Ag, Au; Group IIb metal element such as Zn, Cd, Hg; Group IIIb metal elements such as Al, Ga, In, and Tl; Group IVb metal elements such as Ge, Sn, and Pb; Group
- compositions can be appropriately selected depending on the electrical characteristics, optical characteristics, magnetic characteristics and the like of the composition.
- Ti, Zr, In, Zn, La, Al, Sn, etc. are preferable when it is desired to obtain a resin composition having a high refractive index among optical properties.
- the curable organic compound means an organic compound having a curable functional group.
- the curable functional group refers to a functional group that undergoes a curing reaction by heat or light (a group that causes a curing reaction of the resin composition).
- Examples of the curable functional group include ring-opening polymerizable groups such as epoxy groups, oxetane rings, and ethylene sulfide groups, radical curable groups such as acryl groups, methacryl groups, and vinyl groups, and / or addition curable groups. Can be mentioned.
- the curable organic compound examples include a compound having a ring-opening polymerizable group (epoxy group, oxetane group, ethylene sulfide group, etc.) that is cured by cationic curing, and a compound having an acrylic group and / or a methacryl group that is cured by radical curing.
- a vinyl group that is cured by an addition reaction such as hydrosilylation or enethiol reaction is preferable.
- a compound having a ring-opening polymerizable group that is cured by cationic curing is more preferable in that the shrinkage rate at the time of primary curing is low, and thus it becomes easy to impart a shape with a mold or the like.
- the compound having a ring-opening polymerizable group may be a compound having one or more ring-opening polymerizable groups in one molecule, but a compound having two or more ring-opening polymerizable groups in total, that is, a polyfunctional compound is used. It is preferable to make it essential.
- the form in which the compound having the ring-opening polymerizable group as described above requires the polyfunctional compound is one of the preferred forms of the present invention. More preferably, the polyfunctional compound is 50% by mass or more with respect to 100% by mass of the total amount of the compounds having a ring-opening polymerizable group, more preferably 80% by mass or more, and particularly preferably 100% by mass. As a compound having a ring-opening polymerizable group, only a polyfunctional compound is used.
- the compound having a ring-opening polymerizable group is preferably a compound having an epoxy group and / or an oxetane ring.
- a form in which the compound having the ring-opening polymerizable group is a polyfunctional compound and the ring-opening polymerizable group is an epoxy group and / or an oxetane ring is one of particularly preferable forms of the present invention.
- the epoxy group includes an oxirane ring which is a three-membered ether, and includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group) in addition to an epoxy group in a narrow sense.
- the compound having at least an epoxy group is preferably an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, or a hydrogenated epoxy compound.
- the aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule, for example, a glycidyl compound having an aromatic ring conjugated system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, or an anthracene ring. It is preferable.
- a compound having a bisphenol skeleton and / or a fluorene skeleton is preferable. More preferably, it is a compound having a fluorene skeleton, whereby the refractive index can be remarkably increased and the releasability can be further enhanced.
- Aromatic glycidyl ether compounds are also suitable.
- the Abbe number slightly increases, it is preferably used as appropriate depending on the application.
- aromatic epoxy compound for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a fluorene type epoxy compound, an aromatic epoxy compound having a bromo substituent, and the like are preferable.
- a fluorene epoxy compound is preferred.
- bisphenol A type epoxy compound Japan Epoxy Resin Co., Ltd., 828EL, 1003 or 1007
- bisphenol F type epoxy compound, fluorene type epoxy compound (Osaka Gas Chemical Co., Ltd., ONCOAT EX-1020 or OGSOL EG-) 210)
- a fluorene-based epoxy compound Osaka Gas Chemical Co., Ltd., Oncoat EX-1010 or Ogsol PG
- More preferred are bisphenol A type epoxy compounds and fluorene type epoxy compounds (Ossol EG-210, manufactured by Osaka Gas Chemical Company).
- an aromatic glycidyl ether compound is also suitable.
- the aromatic glycidyl ether compound include an epibis type glycidyl ether type epoxy resin, a high molecular weight epibis type glycidyl ether type epoxy resin, A novolak aralkyl type glycidyl ether type epoxy resin may be mentioned.
- said epibis type glycidyl ether type epoxy resin what is obtained by condensation reaction of bisphenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and epihalohydrin, for example is suitable.
- the high molecular weight epibis type glycidyl ether type epoxy resin can be obtained, for example, by subjecting the epibis type glycidyl ether type epoxy resin to an addition reaction with bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like. Are preferred.
- novolak aralkyl type glycidyl ether type epoxy resin examples include phenols, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like, formaldehyde, acetoaldehyde, propion Polyhydric phenols obtained by condensation reaction of aldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc., and epihalohydrin What is obtained by carrying out a condensation reaction is preferred.
- aromatic epoxy compound further include, for example, an aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, and the like with epihalohydrin, and the bisphenols and tetramethyl.
- aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, and the like with epihalohydrin, and the bisphenols and tetramethyl.
- High molecular weight polymer of aromatic crystalline epoxy resin obtained by addition reaction of biphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc .; obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin It is also possible to use glycidyl ester type epoxy resins and the like.
- the said aliphatic epoxy compound is a compound which has an aliphatic epoxy group, and an aliphatic glycidyl ether type epoxy resin is suitable.
- the aliphatic glycidyl ether type epoxy resin include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG 600), propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol ( PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, pentaerythritol and multimers thereof, mono / polysaccharides such as glucose, fructose, lactose, maltose, and the like, and epihalohydrin Preferred are those obtained, those having a propylene glycol skeleton, an alkylene skeleton, an oxyalkylene
- the alicyclic epoxy compound is a compound having an alicyclic epoxy group, and as the alicyclic epoxy group, for example, an epoxycyclohexane group (epoxycyclohexane skeleton), a cyclic aliphatic hydrocarbon directly or a hydrocarbon. And an epoxy group added through the intermediate. Among these, a compound having an epoxycyclohexane group is preferable. Moreover, the polyfunctional alicyclic epoxy compound which has two or more alicyclic epoxy groups in a molecule
- numerator is suitable at the point which can raise a hardening rate more. A compound having one alicyclic epoxy group in the molecule and an unsaturated double bond group such as a vinyl group is also preferably used.
- Examples of the epoxy compound having an epoxycyclohexane group include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, epsilon-caprolactone modified 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxy. Cyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate and the like are preferable.
- Examples of the alicyclic epoxy compound other than the epoxy compound having an epoxycyclohexane group include 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol. Examples include adducts and alicyclic epoxides such as epoxy resins containing heterocycles such as triglycidyl isocyanurate.
- the hydrogenated epoxy compound is preferably a compound having a glycidyl ether group bonded directly or indirectly to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is preferred.
- a hydrogenated epoxy compound is preferably a complete or partial hydrogenated product of an aromatic epoxy compound, more preferably a hydrogenated product of an aromatic glycidyl ether compound, and still more preferably an aromatic polyfunctional compound. It is a hydrogenated product of a glycidyl ether compound.
- hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, and the like are preferable. More preferred are hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.
- epoxy compound a tertiary amine-containing glycidyl ether type epoxy resin which is obtained by condensation reaction of hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin at room temperature can also be used.
- epoxy compounds alicyclic epoxy compounds and hydrogenated epoxy compounds are particularly suitable. These are hard to be colored of the epoxy compound itself at the time of curing, are less likely to be colored or deteriorated by light, that is, excellent in transparency and low colorability, light resistance, if a resin composition containing these, It is possible to obtain a cured molded body which is not colored and is excellent in light resistance with high productivity. Moreover, since these epoxy compounds are more excellent in releasability and curability when used in combination with a cationic curing catalyst, they are also suitable in that the curing rate can be increased.
- the form in which the compound having the ring-opening polymerizable group includes an alicyclic epoxy compound and / or a hydrogenated epoxy compound is also one of the preferred forms of the present invention. More preferably, the compound having the ring-opening polymerizable group is a form containing a polyfunctional alicyclic epoxy compound and / or a polyfunctional hydrogenated epoxy compound.
- the content of the alicyclic epoxy compound or the hydrogenated epoxy compound is as follows. It is suitable that it is 10 mass% or more with respect to 100 mass% of the total amount of the compound having a ring-opening polymerizable group. As a result, it is possible to further exert the effects of using the above-described alicyclic epoxy compound and / or hydrogenated epoxy compound.
- the compound having the ring-opening polymerizable group includes an alicyclic epoxy compound and / or a hydrogenated epoxy compound, and the total amount of the alicyclic epoxy compound and the hydrogenated epoxy compound is the ring-opening polymerizable property.
- a form that is 10% by mass or more with respect to 100% by mass of the total amount of the compound having a group is also a preferred form of the present invention. More preferably, it is 50 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 90 mass% or more.
- the compound having the ring-opening polymerizable group includes a polyfunctional alicyclic epoxy compound and / or a polyfunctional hydrogenated epoxy compound, and the polyfunctional alicyclic epoxy compound and the polyfunctional hydrogenated epoxy compound.
- the total amount is 10% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, particularly preferably 100% by mass with respect to the total amount of the compound having a ring-opening polymerizable group. Is 90% by mass or more.
- the compound having an oxetane ring is preferably used in combination with an alicyclic epoxy compound and / or a hydrogenated epoxy compound from the viewpoint of curing speed.
- an oxetane compound having an aryl group or an aromatic ring in the molecule From the viewpoint of improving the refractive index while maintaining the curing rate, it is preferable to use an oxetane compound having an aryl group or an aromatic ring in the molecule.
- an oxetane compound having no aryl group or aromatic ring it is preferable to use a polyfunctional oxetane compound, that is, a compound having two or more oxetane rings in one molecule.
- examples of the monofunctional oxetane compound include 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3- Oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether and the like are preferable.
- monofunctional oxetane compounds include, for example, 3-methyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and dicyclopentadiene.
- 3-Ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether and the like are preferable.
- examples of the polyfunctional oxetane compound include di [1-ethyl (3-oxetanyl)] methyl ether and 3,7-bis (3-oxetanyl) -5.
- the polyfunctional oxetane compound includes, for example, a phenol novolak oxetane, a dioxetane compound having a biphenyl skeleton (manufactured by Ube Industries, Ltd., ETERNACOLL (R) OXBP), and a phenyl skeleton.
- a dioxetane compound manufactured by Ube Industries, ETERNACOLL (R) OXTP
- a dioxetane compound having a fluorene skeleton and the like are preferable.
- the content of the compound having a ring-opening polymerizable group is preferably 50% by mass or more with respect to 100% by mass of the total amount of the curable organic compound from the viewpoint of reducing shrinkage. More preferably, it is 80% by mass or more, and most preferably 100% by mass, that is, the curable organic compound consists only of a compound having a ring-opening polymerizable group.
- compounds having one or more of acrylic, methacrylic and vinyl groups include styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene, vinyltoluene, divinylbenzene, diallyl phthalate.
- Aromatic vinyl monomers such as diallylbenzenephosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ⁇ -hydroxyethyl (meth) acrylate , (2-oxo-1,3-dioxolan-4-yl) -methyl (meth) acrylate, (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate
- (Meth) acrylic monomers 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) (meth) acrylate Vinyl (thio) ether compounds having radically polymerizable double bonds such as ethoxyethoxy) ethyl and 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate; use triallyl cyanurate Door is preferable.
- the content of the compound having one or more of acrylic group, methacrylic group and vinyl group is 50% by mass or more with respect to 100% by mass of the total amount of the curable organic compound. It is preferable that More preferably, it is 80% by mass or more, and most preferably 100% by mass, that is, the curable organic compound consists only of a compound having one or more of acrylic group, methacrylic group and vinyl group.
- the curable organic compound is preferably one that does not contain a metal element.
- the curable functional group of the curable organic compound not containing a metal element is 1 mol% or more with respect to 100 mol% of the total amount of the curable functional group. More preferably, it is 10 mol% or more, More preferably, it is 30 mol% or more, More preferably, it is 50 mol% or more. Further, it is particularly preferably 70 mol% or more, and most preferably 90 mol% or more.
- the curable organic compound containing a metal element has too many curable functional groups (particularly, if there are too many curable functional groups bonded to the metal element), the shrinkage rate during primary curing increases, and 2 Cracking of the cured product is likely to occur during the next curing (during the second step).
- the total amount of the curable functional groups is 100 mol%, which is a functional group having an oxirane ring. More preferably, it is 60 mol% or more, More preferably, it is 80 mol% or more. Most preferably, it is 100 mol%, that is, all curable functional groups are functional groups having an oxirane ring.
- thermosetting in addition to the heat latent cationic curing catalyst, a heat latent radical curing catalyst, a commonly used curing agent such as an acid anhydride type, a phenol type or an amine type is used. Can do. Among these, it is preferable to use a heat latent cationic curing catalyst or a heat latent radical curing catalyst. In order to reduce the shrinkage of the cured product, it is particularly preferable to use a heat latent cationic curing catalyst.
- a photoinitiator when hardening by active energy ray irradiation, can be used as a hardening
- curing agents can be used alone or in combination of two or more.
- a cationic curing catalyst such as a thermal latent cationic curing catalyst or a photolatent cationic curing catalyst, and thus, the curing reaction in the first step is suitably advanced in a short time. Since the matrix (cured product) can be formed quickly, the production efficiency can be improved, and the progress of the curing reaction of the condensable inorganic compound in the first step can be sufficiently suppressed. . Furthermore, a cured molded body having excellent heat resistance and high releasability can be obtained, and the curable composition can stably exist as a one-component composition (one-component property) excellent in handling properties.
- curing agent contains a heat latent cationic curing catalyst and / or a photolatent cationic curing catalyst is also one of the suitable forms of this invention.
- the said resin composition for an optical member use it is especially suitable to use a heat
- the thermal latent cationic curing catalyst is also called a thermal acid generator, a thermal latent curing agent, a thermal latent cation generator, or a cationic polymerization initiator.
- the thermal latent cationic curing catalyst is substantially used as a curing agent. It demonstrates a typical function.
- a heat-latent cationic curing catalyst a compound containing a cationic species is excited by heating to cause a thermal decomposition reaction and heat curing proceeds, but a heat-latent cationic curing catalyst is generally used as a curing agent.
- the resin composition does not increase in viscosity over time at normal temperature or cause gelation.
- the curing reaction can be sufficiently promoted to exert an excellent effect, and a one-component resin composition (one-component material) having superior handling properties can be provided. .
- the moisture resistance of the cured molded product obtained from the resulting resin composition is dramatically improved, and the excellent optical properties of the resin composition are maintained even in harsh usage environments.
- it can be suitably used for various applications. Normally, when water having a low refractive index is contained in the resin composition or its cured product, it causes turbidity.However, when a heat-latent cationic curing catalyst is used, excellent moisture resistance can be exhibited, and thus such turbidity is exhibited. It is suppressed and can be suitably used for optical applications such as lenses.
- Examples of the heat latent cationic curing catalyst include the following general formula (4): (R 1 a R 2 b R 3 c R 4 d Z) + m (AXn) -m (4)
- Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements.
- R 1 , R 2 , R 3 and R 4 is the same or different and represents an organic group, a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z.
- Cation (R 1 a R 2 b R 3 c R 4 d Z) + m represents an onium salt
- A represents a metal element or metalloid which is a central atom of a halide complex
- B P, As, Al, At least one selected from the group consisting of Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co.
- X represents a halogen element
- m is a net charge of a halide complex ion.
- N is the number of halogen elements in the halide complex ion Is preferred).
- anion (AXn) -m in the general formula (4) examples include tetrafluoroborate (BF 4 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), hexafluoroantimonate (SbF 6 ⁇ ), hexafluoro Examples include arsenate (AsF 6 ⁇ ) and hexachloroantimonate (SbCl 6 ⁇ ). Furthermore, an anion represented by the general formula AXn (OH) 2 — can also be used.
- anions include perchlorate ion (ClO 4 ⁇ ), trifluoromethyl sulfite ion (CF 3 SO 3 ⁇ ), fluorosulfonate ion (FSO 3 ⁇ ), toluenesulfonate ion, trinitrobenzenesulfone.
- An acid ion etc. are mentioned.
- heat-latent cationic curing catalyst examples include, for example, diazonium salt types such as AMERICURE series (American Can), ULTRASET series (Adeka), and WPAG series (Wako Pure Chemical Industries).
- diazonium salt types such as AMERICURE series (American Can), ULTRASET series (Adeka), and WPAG series (Wako Pure Chemical Industries).
- UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone Poulin (now Rhodia)), WPI series (Wako Pure Chemical Industries) CYRACURE series (Union Carbide), UVI series (General Electric), FC series (3M), CD series (Sartomer), Optomer SP series Optomer CP Sulfonium such as Leeds (manufactured by Adeka), Sun-Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.) Examples include salt type.
- thermal latent radical curing catalyst examples include cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butyl peroxide.
- Organic peroxides such as oxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbox) Nitriles), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), and other azo compounds. These may use only 1 type or may use 2 or more types together.
- the photopolymerization initiator it is preferable to use a photolatent cationic curing catalyst or a photolatent radical curing catalyst as described above.
- the photolatent cationic curing catalyst is also called a photocationic polymerization initiator, and exhibits a substantial function as a curing agent when irradiated with light.
- a photolatent cationic curing catalyst By using a photolatent cationic curing catalyst, a compound containing a cationic species is excited by light, a photodecomposition reaction occurs, and photocuring proceeds.
- photolatent cationic curing catalyst examples include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) Phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [
- SP-150, SP-170 (Asahi Denka); Irgacure 261 (Ciba-Geigy); UVR-6974, UVR-6990 (Union Carbide) CD-1012 (manufactured by Sartomer) is preferred.
- an onium salt it is preferable to use at least 1 sort (s) among a triarylsulfonium salt and a diaryl iodonium salt.
- photolatent radical curing catalyst examples include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 1,1-dichloroacetophenone, etc.
- Acetophenones benzoin, benzoin methyl ether
- Benzoins such as benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether
- benzophenone methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4 , 4′-Tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl Benzophenones such as benzenemethananium bromide and (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-ch
- acetophenones may use only 1 type or may use 2 or more types together.
- benzophenones and acylphosphine oxides are preferably used, and in particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4- Thiomethylphenyl) propan-1-one is preferably used.
- a photosensitizer in addition to the photopolymerization initiator.
- the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2-dimethyl).
- Amines such as amino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, and the like are preferable.
- the amount of the photosensitizer is preferably 0.1 to 20% by mass with respect to 100% by mass of the curable resin composition. If it is less than 0.1% by mass, the photopolymerization may not proceed more efficiently, and if it exceeds 20% by mass, the ultraviolet ray may be prevented from being transmitted to the inside, and the curing may not be sufficient. . More preferably, it is 0.5 to 10% by mass.
- the content of the cationic curing catalyst is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable organic compound as a solid content equivalent amount as an active ingredient amount not containing a solvent or the like. It is. If it is less than 0.01 part by weight, the curing rate cannot be increased sufficiently, and there is a possibility that the effect of the present invention that it can be sufficiently cured in a short time and can be molded cannot be fully exhibited. More preferably, it is 0.1 weight part or more, More preferably, it is 0.2 weight part or more. On the other hand, if the amount exceeds 10 parts by weight, there is a risk of coloring during curing or heating of the molded article.
- heat resistance of 200 ° C. or higher is necessary, and therefore it is preferably 10 parts by weight or less from the viewpoint of colorlessness and transparency. . More preferably, it is 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.
- the content of the radical curing catalyst is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable organic compound as a solid content equivalent amount as an active ingredient amount not containing a solvent or the like. It is. If it is less than 0.01 part by weight, the curing rate cannot be increased sufficiently, and there is a possibility that the effect of the present invention that it can be sufficiently cured in a short time and can be molded cannot be fully exhibited. More preferably, it is 0.1 weight part or more, More preferably, it is 0.2 weight part or more. On the other hand, when the amount exceeds 10 parts by weight, there is a risk of coloring during curing or use of the molded product. More preferably, it is 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.
- a commonly used curing agent such as an acid anhydride, phenol, or amine
- those usually used may be used as these curing agents.
- the acid anhydride-based curing agent tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthal, acid anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, Methyl nadic acid anhydride, het acid anhydride, hymic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydro anhydride Aliphatic carboxylic acid anhydrides such as phthalic acid-maleic anhydride adduct, chlorendic acid, methylendomethylenet
- phenolic curing agent examples include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, 2,2′-methylene-bis (4-methyl-6-tert- Butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), 4,4'-butylene-bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, phenols having a diisopropylidene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene Class of phenolic polybutadiene Novolac resins made from various phenols such as phenol compounds, phenols, cresols, ethylphenols, butylphenols, octylphenols
- acid anhydrides are preferred, more preferably methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydro.
- Phthalic anhydride and hexahydrophthalic anhydride are preferable, and methylhexahydrophthalic anhydride and hexahydrophthalic anhydride are more preferable.
- the content of the curing agent is 25 to 70% by mass with respect to 100% by mass of the curable resin composition. Is preferred. More preferably, it is 35 to 60% by mass.
- the mixing ratio of the curable organic compound and these curing agents is preferably such that the curing agent is mixed at a ratio of 0.5 to 1.6 equivalents with respect to one chemical equivalent of the curable organic compound. More preferably, mixing is performed at a ratio of 0.7 to 1.4 equivalents, and still more preferably 0.9 to 1.2 equivalents.
- a curing accelerator When a commonly used curing agent such as acid anhydride, phenol or amine is used, it is preferable to use a curing accelerator in combination.
- the curing accelerator include organic base acid salts or aromatic compounds having tertiary nitrogen, and organic base acid salts include organic onium salts such as organic phosphonium salts and organic ammonium salts and tertiary nitrogen. Examples thereof include acid salts of organic bases.
- organic phosphonium salts include phosphonium bromides having four phenyl rings such as tetraphenyl phosphonium bromide and triphenyl phosphine / toluene bromide.
- organic ammonium salts include tetraoctyl ammonium bromide, tetra Examples thereof include tetra (C1-C8) alkylammonium bromides such as butylammonium bromide and tetraethylammonium bromide.
- acid salts of organic bases having tertiary nitrogen include alicyclic bases having tertiary nitrogen in the ring. Examples include acid salts and organic acid salts of various imidazoles.
- organic acid salts of alicyclic bases having tertiary nitrogen in the ring include 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, 1,8-diazabicyclo (5,4 , 0) Diaza compounds such as octylate of undecene-7 and salts of phenols, the following polycarboxylic acids, or phosphinic acids.
- organic acid salts of the various imidazoles include salts of imidazoles with organic acids such as polycarboxylic acids.
- imidazoles examples include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl.
- Examples include -2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, and the like.
- Preferable imidazoles include, for example, the same imidazoles as the phenyl group-substituted imidazoles in the aromatic compound having the following tertiary nitrogen.
- polyvalent carboxylic acids examples include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and naphthalenedicarboxylic acid, and aliphatic polyvalent carboxylic acids such as maleic acid and oxalic acid.
- preferred polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, and pyromellitic acid.
- preferable salts of imidazoles with organic acids such as polyvalent carboxylic acids include polyvalent carboxylates of imidazoles having a substituent at the 1-position. More preferred is, for example, trimellitic acid salt of 1-benzyl-2-phenylimidazole.
- Examples of the aromatic compound having tertiary nitrogen include phenyl group-substituted imidazoles and tertiary amino group-substituted phenols.
- Examples of phenyl group-substituted imidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, Examples include 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like.
- tertiary amino group-substituted phenols include phenols having 1 to 3 di (C1-C4) alkylamino (C1-C4) alkyl groups such as 2,4,6-tri (dimethylaminomethyl) -phenol. Is mentioned.
- curing accelerators include, for example, phenol salts of 1,8-diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo (5,4,0) undecene-7 Octylate, 2,4,6-tri (dimethylaminomethyl) -phenol, tetrabutylammonium bromide, tetraethylammonium bromide, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitic acid salt , Tetraphenylphosphonium bromide, and triphenylphosphine-toluene bromide.
- the said hardening accelerator can be used 1 type or in combination of 2 or more types.
- the use amount of the curing accelerator is preferably 0.01 to 5% by mass, and more preferably 0.03 to 3% by mass with respect to 100% by mass of the total amount of the curable resin composition.
- the curable resin composition preferably also includes a flexible component (flexible component), which makes it possible to obtain a resin composition with a sense of unity. Moreover, the hardness of resin improves by including a flexible component.
- the flexible component may be a compound different from the curable organic compound, and at least one of the curable organic compounds may be a flexible component.
- the flexible component is a compound having an oxyalkylene skeleton represented by — [— (CH 2 ) n —O—] m — (n is 2 or more, and m is an integer of 1 or more.
- N is preferably an integer of 2 to 12
- m is an integer of 1 to 1000, more preferably n is an integer of 3 to 6, and m is an integer of 1 to 20.
- An epoxy compound containing an oxybutylene group manufactured by Japan Epoxy Resin, YL-7217, epoxy equivalent 437, liquid epoxy compound (10 ° C. or higher) is preferred.
- suitable flexible components include (2) polymer epoxy compounds (for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resin, YX-8040, epoxy equivalent 1000, solid hydrogenated epoxy compound)); 3) Alicyclic solid epoxy compound (EHPE-3150 manufactured by Daicel Industries, Ltd.); (4) Alicyclic liquid epoxy compound (Delcel Industries, Celoxide 2081); (5) Liquid rubber such as liquid nitrile rubber, polybutadiene, etc. Polymer rubber, fine particle rubber having a particle size of 100 nm or less, and the like are preferable.
- polymer epoxy compounds for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resin, YX-8040, epoxy equivalent 1000, solid hydrogenated epoxy compound)
- Alicyclic solid epoxy compound EHPE-3150 manufactured by Daicel Industries, Ltd.
- Alicyclic liquid epoxy compound (Delcel Industries, Celoxide 2081)
- Liquid rubber such as liquid nitrile rubber, polybutadiene, etc.
- curable functional group refers to a “functional group that cures with heat or light such as an epoxy group (a group that causes the resin composition to undergo a curing reaction)”.
- a compound containing a curable functional group can be suitably used as the flexible component, but the compound is preferably a compound containing an epoxy group, and more preferably oxybutylene.
- a compound having a group (— [— (CH 2 ) 4 —O—] m — (m is the same as above)).
- the content of the flexible component is preferably 40% by mass or less with respect to 100% by mass of the total amount of the curable organic compound and the flexible component. More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less. Moreover, 0.01 mass% or more is preferable, More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more.
- the curable resin composition preferably also contains a release agent.
- a mold release agent an ordinary mold release agent can be preferably used. However, an alcohol having 8 to 36 carbon atoms, a carboxylic acid having 8 to 36 carbon atoms, a carboxylic acid ester having 8 to 36 carbon atoms, and 8 carbon atoms can be used. It is preferable that the compound be at least one compound selected from the group consisting of ⁇ 36 carboxylates. By containing such a mold release agent, the mold can be easily peeled off when cured using a mold, and the appearance is controlled without damaging the surface of the cured product, thereby expressing transparency.
- alcohols more preferred are alcohols, carboxylic acids and carboxylic acid esters, and even more preferred are carboxylic acids (especially higher fatty acids) because the release effect can be sufficiently exhibited without inhibiting the cationic curing reaction. ) And carboxylic acid esters.
- carboxylic acids especially higher fatty acids
- carboxylic acid esters since amines may inhibit a cation curing reaction, when accompanying a cation curing reaction, it is preferable not to use as a mold release agent.
- the above-mentioned compound may have any structure such as linear, branched or cyclic, and is preferably branched.
- the number of carbon atoms of the above compound is preferably an integer of 8 to 36, whereby a cured product exhibiting excellent peelability without impairing functions such as transparency and workability of the resin composition. Become.
- the carbon number is more preferably 8 to 20, and further preferably 10 to 18.
- the alcohol having 8 to 36 carbon atoms is a monohydric or polyhydric alcohol and may be linear or branched. Specifically, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, palmityl alcohol, margaryl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl Alcohol, seryl alcohol, myricyl alcohol, methylpentyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, 3.5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, dipentaerythritol 2-phenylethanol and the like are preferable.
- the alcohol is preferably an aliphatic alcohol, and more preferably octyl alcohol (octanol), lauryl alcohol, 2-ethylhexyl alcohol (2-ethylhexanol), and stearyl alcohol.
- octanol octanol
- lauryl alcohol 2-ethylhexyl alcohol (2-ethylhexanol)
- 2-ethylhexyl alcohol 2-ethylhexanol
- stearyl alcohol stearyl alcohol
- the carboxylic acid having 8 to 36 carbon atoms is a monovalent or polyvalent carboxylic acid, such as 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid.
- Pentadecanoic acid, palmitic acid, 1-heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, 1-hexacosanoic acid, behenic acid and the like are suitable.
- Preferred are octanoic acid, lauric acid, 2-ethylhexanoic acid and stearic acid.
- the carboxylic acid ester having 8 to 36 carbon atoms includes (1) a carboxylic acid ester obtained from the above alcohol and the above carboxylic acid, and (2) methanol, ethanol, propanol, heptanol, hexanol, glycerin, benzyl alcohol, etc.
- carboxylic acid esters of (2) and (3) are preferable, and stearic acid methyl ester, stearic acid ethyl ester, acetic acid octyl ester, and the like are more preferable.
- the carboxylate having 8 to 36 carbon atoms is a carboxylic acid obtained by combining the above carboxylic acid with an amine, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, or Sn. Salts and the like are preferred. Among these, Zn stearate, Mg stearate, Zn 2-ethylhexanoate and the like are preferable.
- stearic acid compounds such as stearic acid and stearic acid esters, and alcohol compounds are more preferable, and stearic acid compounds are more preferable.
- the content of the said mold release agent it is preferable that it is 10 mass% or less with respect to 100 mass% of said curable resin compositions. If it exceeds 10% by mass, the curable resin composition may be difficult to cure. More preferably, the content is 0.01 to 5% by mass, and still more preferably 0.1 to 2% by mass.
- the curable resin composition is not limited to the effects of the present invention, so that inorganic fine particles, a reactive diluent, a saturated compound having no unsaturated bond, Pigments, dyes, antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers and organic fillers, Adhesion improvers such as coupling agents, heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, antisettling agents, thickeners / sagging agents , Anti-color separation agents, emulsifiers, slip / scratch prevention agents, anti-skinning agents, drying agents, antifouling agents, antistatic agents, conductive agents (electrostatic aids), and the like.
- Adhesion improvers such as coupling agents, heat stabilizers, anti
- the curable resin composition preferably has a viscosity of 10,000 Pa ⁇ s or less. Thereby, it becomes more excellent in processing characteristics, and a cured molded body that is further excellent in dimensional accuracy, mold transferability and the like can be obtained. More preferably, it is 1000 Pa.s or less, More preferably, it is 200 Pa.s or less. Moreover, it is preferable that it is 0.01 Pa.s or more. More preferably, it is 0.1 Pa ⁇ s or more, more preferably 1 Pa ⁇ s or more, particularly preferably 5 Pa ⁇ s or more, and most preferably 10 Pa ⁇ s or more. In addition, the said viscosity can be measured with the method mentioned later in an Example.
- the curable resin composition also preferably has a shrinkage rate of 3% or less in primary curing (curing in the first step). More preferably, it is 1% or less.
- the shrinkage ratio in primary curing is in the above range, the transferability of a mold (such as a mold) is improved, and lens molding, shaping on a sheet surface, and the like are facilitated.
- the curing process is divided into two stages, and the reaction of the curable organic compound proceeds mainly in the first stage. At this time, it is possible to impart a shape with a low shrinkage rate in shape transfer using a mold such as a mold.
- the shrinkage rate in the primary curing is the shrinkage rate before and after the first step. Specifically, for example, in the examples described later, the volume shrinkage is obtained from 130 ° C. before and after the curing process at 130 ° C. for 2 minutes. The shrinkage rate is most preferably obtained by actual measurement, but if difficult, it can be estimated by calculation by measuring the linear expansion coefficient and the density from room temperature to 130 ° C., respectively.
- the present invention is also a cured molded body obtained by the above production method. Due to the fact that the cured molded body is obtained by the above-described production method, it has excellent heat resistance and wear resistance, has a small shrinkage rate, and has releasability, low colorability and transparency. It has excellent mechanical properties and optical properties.
- a cured molded body is preferably a mold molded body, but may be in the form of a film, a sheet, a pellet or the like.
- the present invention further includes a cured molded body containing a metalloxane component and an organic resin component, wherein the metal element constituting the metalloxane component is 10% by mass or more based on 100% by mass of the total amount of the cured molded body, Among the metal elements constituting the metalloxane component, the number of bonds with the hydrocarbon group is n-1 or n-2 (n is the valence of the metal element and represents an integer of 2 or more). The content is 50 atomic% or less with respect to 100 atomic% of the total amount of metal elements constituting the metalloxane component, and among the metal elements constituting the metalloxane component, YM (M represents a metal element. Y represents a metal element.
- the content of the metal element having a bond represented by a hydrogen atom, a halogen atom, a hydroxyl group, and an RO group is a metalloxane compound.
- the content of the particulate component is 50% by mass or less with respect to 100% by mass of the total amount of the metalloxane component. It is also a cured molded body characterized by being. With such a configuration, the cured molded body has excellent hardness, heat resistance, and optical characteristics.
- the cured molded body includes a metalloxane component and an organic resin component. As long as these components are essential, other components may be included, and each component may be used alone or in combination of two or more.
- the metalloxane component is a component containing a metalloxane bond (MOM bond) in the structure.
- the metal element M is the same as that described for the condensable inorganic compound.
- the metal element constituting the metalloxane component is 10% by mass or more with respect to 100% by mass of the total amount of the cured molded body. When the content is less than 10% by mass, the content of the metalloxane component in the cured molded body is reduced, and the hardness due to the metalloxane component is not sufficiently increased.
- the cured molded body is colored when used for a long period of time in a high temperature environment of at least ° C. or when used in an environment exposed to ultraviolet light.
- the content of the metal element constituting the metalloxane component is preferably 15% by mass or more, more preferably 20% by mass or more, with respect to 100% by mass of the total amount of the cured molded body.
- the content of the metal element constituting the metalloxane component is preferably 50% by mass or less with respect to 100% by mass of the total amount of the cured molded body. More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
- the number of bonds to the hydrocarbon group is n-1 or n-2 (n is the valence of the metal element, and an integer of 2 or more.
- the content of the metal element is 50 atom% or less with respect to 100 atom% of the total amount of metal elements constituting the metalloxane component.
- the metal element is Si
- the valence n is 4, the total amount of Si constituting the metalloxane component (siloxane component) is 100 with the content of Si having 3 or 2 bonds with the hydrocarbon group. It is 50 atomic% or less with respect to atomic%.
- valence n shall represent the average value of the valence of each metal element.
- hydrocarbon group an alkyl group, an aryl group, an aralkyl group, etc. are suitable, and you may have a substituent.
- the content of the metal element having n-1 or n-2 bonds with the hydrocarbon group exceeds 50 atomic%, the three-dimensional cross-linking structure in the molded body is reduced and the hardness of the molded body is lowered. Scratches are likely to occur in the molded body during molding or use.
- the content of the metal element having n-1 or n-2 bonds with the hydrocarbon group is preferably 40 atom% or less with respect to 100 atom% of the total amount of metal elements constituting the metalloxane component, Preferably, it is 20 atomic% or less. More preferably, it is 10 atomic% or less, and most preferably 0 atomic%, that is, it does not contain the metal element as described above.
- YM represents a metal element.
- Y represents a hydrogen atom, a halogen atom, a hydroxyl group, and an RO group (R represents a hydrocarbon group).
- R represents a hydrocarbon group.
- the content of the metal element having a bond represented by :) is 35 atomic percent or less with respect to 100 atomic percent of the total amount of metal elements constituting the metalloxane component. is there.
- the content of the metal element having a YM bond is preferably 33 atomic percent or less, more preferably 30 atomic percent or less, and still more preferably 25 atomic percent or less.
- the content of the metal element having a YM bond is preferably 0.1 atomic% or more with respect to 100 atomic% of the total amount of metal elements constituting the metalloxane component.
- Y is preferably at least one selected from the group consisting of a hydroxyl group and an RO group.
- R is preferably an alkyl group, an aryl group, or an aralkyl group.
- content of the component which exhibits a particulate form in the said metalloxane component is 50 mass% or less with respect to 100 mass% of total amounts of a metalloxane component.
- “presenting a particulate shape” means that the particle diameter is 10 nm or more.
- the metalloxane component does not contain a particulate component.
- the content of the organic resin component is preferably 0.1 to 60% by mass with respect to 100% by mass of the total amount of the cured molded body. If the content of the organic resin component is too small, the viscosity of the resin composition becomes high, making it difficult to handle, and as a result, it becomes difficult to transfer the mold to the molded body in the primary curing. When the content of the organic resin component is too large, the content of the metalloxane component in the cured molded body is reduced, and the hardness due to the metalloxane component is not sufficiently high, so at the time of secondary curing or when using the cured molded body, The cured molded body is colored when used in a high temperature environment of about 80 ° C.
- content of an organic resin component 1 mass% or more is more preferable, 5 mass% or more is further more preferable, and 10 mass% or more is especially preferable.
- content of an organic resin component 50 mass% or less is more preferable, and 40 mass% or less is still more preferable.
- the cured molded body preferably also includes a carboxylic acid structure and / or an ether skeleton. Since the compatibility of each component of the resin composition and the cured product thereof is improved by hydrogen bonding, the resulting molded article is excellent in transparency. In addition, the strength of the molded body is improved.
- the carboxylic acid structure means a structure including a bond represented by —O— (C ⁇ O) —, and is at least one selected from the group consisting of carboxylic acid, carboxylic acid ester and carboxylate. It is preferable. More preferably, it is at least one of carboxylic acid and carboxylic acid ester.
- the carboxylic acid structure is preferably derived from the structure of the curable organic compound.
- the ether skeleton is a structure including a bond represented by R′—O—R ′′ (R ′ and R ′′ represent the same or different organic groups).
- R′—O—R ′′ R ′ and R ′′ represent the same or different organic groups.
- 10 mol% or more is preferably obtained by ring opening of the oxirane ring. More preferably, it is 50 mol% or more.
- the total amount of oxygen atoms forming the carboxylic acid structure and / or the ether skeleton is 0.1% by mass or more with respect to 100% by mass of the total amount of the cured molded body. More preferably, it is 1 mass% or more, More preferably, it is 5 mass% or more.
- the cured molded body is preferably obtained by curing the curable resin composition. That is, the cured molding is preferably obtained by curing a curable resin composition containing a condensable inorganic compound, a curable organic compound, and a curing agent.
- the metalloxane component is preferably a component derived from the condensable inorganic compound
- the organic resin component is preferably a component derived from the curable organic compound.
- a sheet-like molded body having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm was prepared under the conditions described in each of the examples and comparative examples described later, and this was appropriately cut to measure the composition of the molded body and a sample for evaluation ( Molded body sample).
- the determination method of the metal element which comprises a metalloxane component in the said hardening molded object is demonstrated.
- the obtained molded body sample was subjected to elemental analysis with an elemental analyzer (manufactured by J-SCIENCE LAB., CHN CORDER JM10), and carbon, hydrogen, and nitrogen content were quantified. Further, 5 mg of a molded body sample was placed on a platinum board, a few drops of 50% nitric acid were dropped, and burned at 950 ° C. in an electric furnace, and quantitative measurement of ash was performed. The constituent metal elements contained in the ash were estimated by fluorescent X-ray analysis, and the amount of metal elements was estimated from the oxidation stable state of the metal elements.
- solid-state nuclear magnetic resonance solid-state NMR
- the position (chemical shift) of the nuclear magnetic resonance peak differs depending on the coordination form of the metal element contained in the sample.
- Inherent chemical shifts depending on the number of For example, unique peaks are observed depending on the number of hydrocarbon groups bonded to the metal element, the number of RO groups, and the number of metalloxane bonds.
- solid nuclear magnetic resonance (solid NMR) measurement of a solid sample it is possible to perform qualitative analysis and quantitative analysis of the coordination state of the metal element contained in the sample based on the difference in chemical shift as described above. it can.
- the following analysis was performed using this method. Note that a molded body sample containing silicon as a metal element (that is, a molded body sample having a siloxane bond) was subjected to 29 Si-NMR.
- a measurement sample a molded sample was pulverized, and the measurement apparatus and measurement conditions are as follows.
- FIG. 1 is a diagram showing a 29 Si-NMR spectrum of the molded product obtained in Reference Example 1.
- FIG. 2 is a diagram showing a 29 Si-NMR spectrum of the molded product obtained in Example 1-5.
- the molded body sample is cut to a thickness of 100 nm with a microtome in the thickness direction, and transmission measurement is performed with a field emission type scanning electron microscope (FE-SEM). The presence or absence of particulate matter and its elemental components A qualitative analysis was performed. The particulate component was quantified by elemental analysis, fluorescent X-ray analysis, solid-state NMR and FE-SEM.
- FIG. 3 is a scanning electron micrograph of the molded product obtained in Example 1-5.
- FIG. 4 is a scanning electron micrograph of the molded product obtained in Comparative Example 5. As shown in FIG. 3, it was found that there was no particle of 1 nm or more, and the resin composition was a uniform resin composition. As shown in FIG. 3, it was found that there was no particle of 1 nm or more, and the resin composition was a uniform resin composition. As shown in FIG.
- FT-IR infrared absorption spectrum
- qualitative analysis confirmation of presence or absence
- functional groups such as a carboxylic acid structure, a hydroxyl group, and an ether skeleton.
- Measuring device and measurement conditions FT-IR measuring device Nexus-670 manufactured by Thermo Electron
- the charged composition is known, and the weight concentration of oxygen derived from the carboxylic acid structure and the oxirane ring in the molded body can be estimated.
- oxygen atoms derived from carboxylic acid structures and ether skeletons can be quantified by solid-state NMR, pyrolysis gas chromatogram, elemental analysis, and FT-IR qualitative and quantitative analysis. is there.
- the cured molded body preferably has a parallel line transmittance of 80% or more at 500 nm. More preferably, it is 85% or more, More preferably, it is 90% or more. Moreover, it is preferable that the parallel line transmittance in 400 nm is 75% or more. More preferably, it is 80% or more, More preferably, it is 85% or more. When the parallel line transmittance is low, the loss of light when the molded body is used as an optical material is large, and the color reproducibility is low.
- the cured molded body preferably has a pencil hardness of 1H or more. More preferably, it is 3H or more, More preferably, it is 5H or more, Most preferably, it is 7H or more.
- the pencil hardness is in such a range, scratches and the like are unlikely to occur when the molded body is used or assembled (when assembled). Since the cured molded body of the present invention can obtain the hardness due to the inorganic component (metalloxane component) while maintaining the productivity (moldability) due to the organic resin component, a lens having a high surface hardness can be obtained by using a mold. It became possible to get.
- the cured molded body of the present invention is excellent in various physical properties such as hardness, heat resistance, and optical properties, for example, optical members, mechanical component materials, electrical / electronic component materials, automotive component materials, In addition to civil engineering and building materials and molding materials, it is useful for various applications such as paints and adhesive materials. Especially, it can use suitably for an optical member, an optical device member, a display device member, etc. Specific examples of such applications include eyeglass lenses, (digital) cameras, imaging lenses for cameras such as mobile phones, vehicle cameras, surveillance cameras, and lenses such as light beam condensing lenses and light diffusion lenses.
- Transparent sheets such as watch glass and cover glass for display devices;
- Various optical applications such as filters, diffraction gratings, prisms, light guides; photosensors, photoswitches, LEDs, light emitting elements, optical waveguides, multiplexing
- Opto device applications such as optical devices, duplexers, disconnectors, optical splitters, optical fiber adhesives
- LCD organic EL and PDP display element substrates, color filter substrates, touch panel substrates, display protective films, display backs Applications for display devices such as lights, light guide plates, antireflection films, and antifogging films; applications with physical contact such as touch panels It is suitable.
- an optical member is particularly suitable. That is, the form in which the cured molded body is an optical cured molded body is one of the preferred forms of the present invention.
- a cured molded body for lenses is preferable.
- the lens a camera lens, a light beam condensing lens, and a light diffusion lens are preferable, and a camera lens is more preferable.
- imaging lenses such as an imaging lens for a mobile phone and an imaging lens for a digital camera are preferable.
- the cured molded body as a permeable sheet. Examples of the transmissive sheet include a transmissive display protective sheet that requires high hardness.
- the said hardening molded object has high heat resistance, since vapor deposition temperature can be made high and the performance of a vapor deposition film can be raised as a result, a photoselective sheet (for example, IRCF), a light transmissive conductive sheet (for example, it can also be used as a transparent sheet such as an ITO film used for a touch panel.
- a photoselective sheet for example, IRCF
- a light transmissive conductive sheet for example, it can also be used as a transparent sheet such as an ITO film used for a touch panel.
- the said curable resin composition may contain the other component suitably according to the use of the optical curing molding.
- UV absorber IR cut agent
- reactive diluent pigment
- washing agent antioxidant
- light stabilizer plasticizer
- non-reactive compound chain transfer agent
- thermal polymerization initiator anaerobic polymerization Initiators
- light stabilizers polymerization inhibitors
- antifoaming agents antifoaming agents and the like are suitable.
- the method for producing a cured molded body of the present invention has the above-described configuration, it is an inexpensive manufacturing method that can reduce the shrinkage rate of the molded body during primary curing. Therefore, it is possible to easily produce a cured molded body that is excellent in heat resistance, wear resistance, and releasability, has a small shrinkage rate, and can easily produce a transparent cured molded body that is not colored.
- the cured molded body obtained by such a manufacturing method is an organic / inorganic composite material having a specific composition. Realization of high heat resistance, high hardness, and high transparency makes it possible to withstand the use of solder reflow, continuous use at high temperatures, use in external environments, etc. It can be suitably used for a lens.
- the manufacturing method of the present invention has a high level of wear resistance and heat resistance that can be suitably applied to applications for outdoor use or physical contact, and has transparency and dimensional accuracy.
- a cured molded body that is excellent in mold transferability and the like and useful for various uses such as an optical member can be obtained.
- FIG. 4 is a diagram showing a 29 Si-NMR spectrum of a molded product obtained in Reference Example 1.
- FIG. 4 is a diagram showing a 29 Si-NMR spectrum of a molded product obtained in Example 1-5.
- 6 is a scanning electron micrograph of the molded product obtained in Example 1-5.
- 6 is a scanning electron micrograph of a molded product obtained in Comparative Example 5.
- Production Example 8 (resin composition (8)) 6 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 24 g of PMSQ-E (SR-13) (polymethylsilsesquioxane manufactured by Konishi Chemical Industries, Ltd.), 0.15 g of stearic acid, 0.15 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., 0.06 g of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) was added and mixed under reduced pressure until uniform.
- SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.
- Production Example 10 (resin composition (10)) 5.1 g of YX-8000 (manufactured by Japan Epoxy Resin, hydrogenated epoxy resin) and 3.9 g of Jamaicacid MH-700G (manufactured by Shin Nippon Chemical Co., Ltd., alicyclic acid anhydride) are added, and PMSQ-E (SR -13) Add 21 g (manufactured by Konishi Chemical Industry Co., Ltd., polymethylsilsesquioxane), 0.15 g stearic acid, and 0.15 g propylene glycol monomethyl ether acetate (PGMEA) until uniform at 80 ° C. Mixed.
- resin composition (10) 5.1 g of YX-8000 (manufactured by Japan Epoxy Resin, hydrogenated epoxy resin) and 3.9 g of Jamaicacid MH-700G (manufactured by Shin Nippon Chemical Co., Ltd., alicyclic acid anhydride) are added, and PMSQ-E (SR
- 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd., curing accelerator, 2-ethyl-4-methylimidazole
- Production Example 11 (resin composition (11)) 9 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of PMPSQ-E (SR-3321) (produced by Konishi Chemical Industries, Ltd., polymethylphenylsilsesquioxane), and 0.15 g of stearic acid 0.15 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., 0.06 g of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) was added and mixed under reduced pressure until uniform.
- SR-3321 produced by Konishi Chemical Industries, Ltd., polymethylphenylsilsesquioxane
- stearic acid 0.15 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., 0.
- Comparative Production Example 1 Comparative Production Example 1 (Comparative Resin Composition (1)) 30 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 0.15 g of stearic acid, and 0.15 g of propylene glycol monomethyl ether acetate (PGMEA) were added and mixed at 80 ° C. until uniform. . After cooling to 40 ° C., 0.06 g of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) was added and mixed under reduced pressure until uniform.
- Celoxide 2021P manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin
- PGMEA propylene glycol monomethyl ether acetate
- Comparative Production Example 2 Comparative Production Example 2 (Comparative Resin Composition (2)) 15 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) and 15 g of EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) were added and mixed uniformly at 130 ° C. Thereafter, 0.15 g of stearic acid and 0.15 g of propylene glycol monomethyl ether acetate (PGMEA) were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., 0.06 g of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) was added and mixed under reduced pressure until uniform.
- PGMEA propylene glycol monomethyl ether acetate
- Comparative Production Example 3 (Comparative Resin Composition (3)) 16.8 g of YX-8000 (manufactured by Japan Epoxy Resin, Hydrogenated Epoxy Resin), 13.2 g of Jamaicacid MH-700G (manufactured by Shin Nippon Chemical Co., Ltd., alicyclic acid anhydride) are added, and stearic acid is added in an amount of 0. 15 g and 0.15 g of propylene glycol monomethyl ether acetate (PGMEA) were added and mixed at 80 ° C. until uniform.
- PGMEA propylene glycol monomethyl ether acetate
- 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd., curing accelerator, 2-ethyl-4-methylimidazole
- a curing agent SI-60L, SI-80L or 2E4MZ
- a rotational speed D It was performed under the condition of 1 / s.
- an RC25-1 measuring jig was used, and when the viscosity was less than 20 Pa ⁇ s, an RC50-1 jig was used.
- Example 1-1 (First step) Using two metal plates of SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface No. 800), gaps with an interval of 1 mm were formed, and the resin composition (1) obtained in Production Example 1 was cast. The mold was cured for 2 minutes with a 130 ° C. mold and demolded. (Second step) After curing in the first step, curing treatment was performed under the following conditions under N 2 atmosphere (unless otherwise specified, performed at an oxygen concentration of 0.2 to 0.3% by volume). Condition: 250 ° C.
- the Abbe number was measured for the cured product (1 mm-thick molded product) using a refractometer (DR-M2 manufactured by Atago Co., Ltd.) at 20 ° C.
- ⁇ Surface hardness> Using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho), measurement was performed in accordance with JIS-K5600-5-4 (established in 1999). The load was 1000 g. ⁇ UV resistance (transmittance after UV resistance test)> Using M6T (6 kW horizontal metering weather meter) manufactured by Suga Test Instruments Co., Ltd., the transmittance (wavelength 400 nm, 500 nm) after 100 hours at 1 kW / m 2 (300 to 400 nm) and 50 ° C. was measured.
- Example 1-2 to 1-6 The curing conditions in the second step were 250 ° C. for 6 hours in Example 1-2 (15 ° C./min from room temperature), 300 ° C. for 1 hour in Example 1-3 (15 ° C./min from room temperature), In Example 1-4, 300 ° C. for 6 hours (15 ° C./min from room temperature), in Example 1-5, 330 ° C. for 1 hour (15 ° C./min from room temperature), and in Example 1-6, 350 ° C.
- the curing treatment was performed in the same manner as in Example 1-1 except that the temperature was 10 minutes (temperature rising from room temperature was 15 ° C./min).
- the molded body after curing was cooled to 150 ° C. or lower (about 5 ° C./min lower than the maximum temperature) and released into the air.
- Each of the obtained cured molded bodies was evaluated in the same manner as in Example 1-1. The results are shown in Table 2.
- Example 1-7 The curing conditions in the second step were the same as in Example 1-1 except that the N 2 atmosphere (5% by volume oxygen concentration) was set to 300 ° C. for 1 hour (temperature rising from room temperature to 15 ° C./min). Then, a curing treatment was performed. The obtained cured molded body was evaluated in the same manner as in Example 1-1. The results are shown in Table 2.
- Reference example 1 A curing process (curing process of only the first process) was performed in the same manner as in Example 1-1 except that the second process was not performed. The obtained cured product was evaluated in the same manner as in Example 1-1. The results are shown in Table 2.
- Example 2 and Reference Example 2 In Examples 2-1, 2-2, 2-3, 2-4, 2-5, and Reference Example 2, it was obtained in Production Example 2 instead of the resin composition (1) obtained in Production Example 1.
- a curing treatment was carried out in the same manner as in Examples 1-1, 1-3, 1-5, 1-6, 1-7, and Reference Example 1 except that the resin composition (2) was used. It was.
- Each of the obtained cured molded bodies was evaluated in the same manner as in Example 1-1. The results are shown in Table 3.
- Example 3 Reference Example 3 In Examples 3-1, 3-2, 3-3, 3-4, 3-5, and Reference Example 3, the resin composition (1) obtained in Production Example 1 was used instead of the resin composition (1).
- a curing treatment was performed in the same manner as in Examples 1-1, 1-3, 1-5, 1-6, 1-7, and Reference Example 1 except that the resin composition (3) was used. It was.
- Each of the obtained cured molded bodies was evaluated in the same manner as in Example 1-1. The results are shown in Table 4.
- Examples 4 to 12 Reference Examples 4 to 12 In Examples 4-1, 5-1, 6-1, 7-1, 8-1, 9-1 and 11-1, the resin compositions shown in Tables 5 to 6 were used instead of the resin composition (1), respectively.
- a curing treatment was performed in the same manner as in Example 1-1 except that the product was used.
- Examples 4-2, 5-2, 6-2, 7-2, 8-2, 9-2 and 11-2 the resin compositions shown in Tables 5 to 6 instead of the resin composition (1), respectively.
- the curing treatment was performed in the same manner as in Example 1-6 except that the product was used.
- Reference Examples 4 to 9 and 11 curing treatment was performed in the same manner as Reference Example 1 except that the resin compositions shown in Tables 5 to 6 were used in place of the resin composition (1).
- Example 10-1 Example 1 was used except that the resin composition (10) was used in place of the resin composition (1) and that the curing condition in the first step was 140 ° C. for 1 hour.
- a curing treatment was performed in the same manner as in 1.
- Example 10-2 except that the resin composition (10) was used instead of the resin composition (1), and the curing condition in the first step was 140 ° C. for 1 hour
- Example 1-2 The curing treatment was performed in the same manner as in FIG.
- Reference Example 10 the same procedure as in Reference Example 1 was conducted except that the resin composition (10) was used instead of the resin composition (1) and that the curing condition in the first step was 140 ° C. for 1 hour. The curing process was performed.
- Example 12-1 Example 1- 1 except that the resin composition (12) was used in place of the resin composition (1) and that the curing condition in the first step was 150 ° C. for 1 hour.
- a curing treatment was performed in the same manner as in 1.
- Example 12-2 except that the resin composition (12) was used in place of the resin composition (1), and the curing condition in the first step was 150 ° C. for 1 hour, Example 1-2 The curing treatment was performed in the same manner as in FIG.
- Reference Example 12 it was the same as Reference Example 1 except that the resin composition (12) was used instead of the resin composition (1) and that the curing condition of the first step was 150 ° C. for 1 hour.
- the curing process was performed.
- Each of the obtained cured molded bodies was evaluated in the same manner as in Example 1-1.
- Comparative Examples 1-2 and Comparative Reference Examples 1-2 In Comparative Examples 1-1 and 2-1, a curing treatment was performed in the same manner as in Example 1-1 except that the resin composition shown in Table 7 was used instead of the resin composition (1). . In Comparative Examples 1-2 and 2-2, curing treatment was performed in the same manner as in Example 1-6, except that the resin composition shown in Table 7 was used instead of the resin composition (1). . In Comparative Reference Examples 1 and 2, the curing treatment was performed in the same manner as in Reference Example 1 except that the resin composition shown in Table 7 was used instead of the resin composition (1). Each of the obtained cured molded bodies was evaluated in the same manner as in Example 1-1. The results are shown in Table 7.
- Comparative Example 3-1 First step Using two metal plates of SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface No. 800), a gap with a 1 mm interval was formed, and cast molding was performed on the comparative resin composition (3) obtained in Comparative Production Example 3. It was. It hardened
- Comparative Example 3-2 The curing process was performed in the same manner as in Comparative Example 3-1, except that the curing condition in the second step was 350 ° C. for 10 minutes (temperature rising from room temperature to 15 ° C./min). The obtained cured molded body was evaluated in the same manner as in Example 1-1. The results are shown in Table 7.
- Comparative Reference Example 3 A curing process (curing process of only the first process) was performed in the same manner as Comparative Example 3-1, except that the second process was not performed. The obtained cured product was evaluated in the same manner as in Example 1-1. The results are shown in Table 7.
- Comparative Example 4 When the resin composition (1) obtained in Production Example 1 was cured at 250 ° C., steam was generated and foamed to generate a large amount of bubbles in the cured product.
- Production Example 13 (resin composition (13)) 9 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of Alonoxetane OXT221 (produced by Toagosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (produced by Konishi Chemical Industries, polymethyl) 70 g of silserquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform.
- Production Example 14 (resin composition (14)) 9 g of Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of Aron Oxetane OXT221 (manufactured by Toagosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silserquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform.
- Production Example 17 (resin composition (17)) 10 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 10 g of Celoxide 2081 (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), and 10 g of Aron Oxetane OXT221 (produced by Toa Gosei Co., Ltd.) 70 g of PMSQ-E (SR-13) (manufactured by Konishi Chemical Industry Co., Ltd., polymethylsilcerxoxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform.
- PMSQ-E SR-13
- Example 13-18 The resin compositions (13) to (18) obtained in Production Examples 13 to 18 were cured in the same manner as in Example 1-5. With respect to each of the obtained cured molded bodies, the transmittance and the surface hardness were evaluated by the same evaluation method as in Example 1-1, and the water absorption rate and wet heat resistance were evaluated by the following methods. The results are shown in Table 8. As a control, the evaluation results in Example 1-5 are also shown.
- Example 19-25 As shown in Table 9, 0.1 to 0.5% of various additives based on the weight of the resin composition was added to the resin composition (1) obtained in Production Example 1, and Example 1-5 The curing treatment was performed in the same manner as in the above. With respect to each of the obtained cured molded bodies, the transmittance and the surface hardness were evaluated by the same evaluation method as in Example 1-1, and the wet heat resistance was evaluated by the above evaluation method. The results are shown in Table 9. As a control, the evaluation results in Example 1-5 are also shown.
- Production Example 22 (resin composition (22)) In a 500 mL separable flask having a reflux condenser and a thermometer for measuring internal temperature, 13 g of methyltrimethoxysilane (manufactured by Toray Dow Corning, Z-6366), phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) 37.9 g of KBM-103) and 11.5 g of dimethyldimethoxysilane (manufactured by Dow Corning Toray, Z-6329) were added and stirred at an internal temperature of 25 ° C.
- methyltrimethoxysilane manufactured by Toray Dow Corning, Z-6366
- phenyltrimethoxysilane Shin-Etsu Chemical Co., Ltd.
- KBM-103 dimethyldimethoxysilane
- the solvent was distilled off under reduced pressure at 80 ° C. and 1 kPa for 20 minutes while heating and stirring. 0.26 g of stearic acid was added, and the solvent was stirred at 80 ° C. and 1 kPa for 10 minutes under reduced pressure. While stirring under reduced pressure, the temperature was lowered and at 40 ° C., 0.26 g of propylene glycol monomethyl ether acetate and 0.105 g of a thermal latent cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., SI-60L) were added. The mixture was stirred for 30 minutes under reduced pressure to obtain 57.3 g of a resin composition (22).
- a thermal latent cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd., SI-60L
- the solvent was distilled off under reduced pressure for 30 minutes at 80 ° C. and 1 kPa while stirring with heating.
- Stearic acid (0.39 g) was added, and the solvent was stirred at 80 ° C. and 1 kPa for 10 minutes under reduced pressure.
- the temperature was lowered, and at 40 ° C., 0.39 g of propylene glycol monomethyl ether acetate and 0.16 g of a thermal latent cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., SI-60L) were added.
- the mixture was stirred for 30 minutes under reduced pressure to obtain 88.1 g of a resin composition (23).
- Production Example 24 (resin composition (24)) 3.6 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 8.4 g of PMSQ-E (SR-13) (produced by Konishi Chemical Industries, Ltd., polymethylsilsesquioxane), and stearic acid 0.06 g and 0.06 g of propylene glycol monomethyl ether acetate (PGMEA) were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., 0.024 g of CPI-101A (manufactured by San Apro, photocationic polymerization catalyst) was added and mixed under reduced pressure until uniform.
- CPI-101A manufactured by San Apro, photocationic polymerization catalyst
- Production Example 25 (resin composition (25)) 0.46 g of DPE-6A (manufactured by Light Acrylate, dipentaerythritol hexaacrylate), 1.84 g of SR-502 (manufactured by Sartomer, TMS-9EO addition triacrylate), ADMA (Osaka Organic Chemical Co., Ltd.) 2.3 g of 1-adamantyl methacrylate), 10.73 g of PMPSQ-E (SR-3321) (manufactured by Konishi Chemical Industry Co., Ltd., polymethylphenylsilsesquioxane), 0.074 g of stearic acid, propylene glycol monomethyl 0.074 g of ether acetate (PGMEA) was added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., 0.148 g of Parroyl L (manufactured by Nippon Oil (Nippon Oil Co., Ltd., initiator)) was added and mixed under reduced pressure until
- Production Example 26 (resin composition (26)) 0.563 g of DPE-6A (manufactured by Light Acrylate, dipentaerythritol hexaacrylate), 2.252 g of SR-502 (manufactured by Sartomer, TMS-9EO addition triacrylate), ADMA (Osaka Organic Chemical Co., Ltd.) 1.815 g of 1-adamantyl methacrylate), 13.14 g of PMPSQ-E (SR-3321) (manufactured by Konishi Chemical Co., Ltd., polymethylphenylsilsesquioxane), 0.094 g of stearic acid, propylene glycol monomethyl 0.094 g of ether acetate (PGMEA) was added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., 0.188 g of Irgacure 184 (manufactured by Ciba Japan, initiator) was added and mixed under reduced pressure until uniform.
- Comparative Production Example 4 (Comparative Resin Composition (4)) 168 g of hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) and organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid content 30) %) 240 g was mixed uniformly, and the solvent was distilled off under reduced pressure at 80 ° C. using an evaporator. The yield was 249.7 g and the viscosity was 40 Pa ⁇ s.
- Examples 11-3, 26 to 33, Comparative Example 5 The resin compositions (11), (19) to (23) and the resin composition (25) obtained in Production Examples 11, 19 to 23 and Production Example 25 were cured in the same manner as in Example 1-5. (Examples 11-3, 26 to 30 and 32). The resin compositions (24), (26) and comparative resin composition (4) obtained in Production Examples 24 and 26 and Comparative Production Example 4 were cured by the following method (Examples 31 and 33). And Comparative Example 5). (Curing method of resin composition (24)) In the first step, an ultraviolet curing treatment was performed as follows.
- a UV irradiation machine (eye graphic) having an ultrahigh pressure mercury lamp in which a resin composition is disposed on SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface 800 finish) to a thickness of 1 mm.
- a resin composition is disposed on SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface 800 finish) to a thickness of 1 mm.
- SUS304 manufactured by Nippon Test Panel Co., Ltd., surface 800 finish
- a UV irradiator having an ultrahigh pressure mercury lamp from one quartz glass surface, the resin composition being arranged between the two quartz glasses to be 1 mm thick (Eye Graphics Co., Ltd.) was used, and ultraviolet curing was performed at an irradiation accumulated light amount of 2 J / cm 2 .
- the curing treatment was performed under conditions of 330 ° C. for 1 hour (temperature rising from room temperature: 15 ° C./min).
- the curing process was performed in the same manner as in Example 1-5 except that the curing condition in the second step was 230 ° C. for 1 hour (temperature rising from room temperature to 15 ° C./min).
- Comparative Examples 1 to 3 are examples in which each of the comparative resin compositions (1) to (3) not containing a polysiloxane compound having a condensable group was subjected to curing treatment. 12 compared with Examples 1 to 12, the cured molded bodies obtained in Comparative Examples 1 to 3 have a low transmittance, and the transmittance after the UV resistance test, which is an index of heat resistance, is remarkably inferior. As a result.
- the cured molded bodies obtained in Reference Examples in which only the first step of the curing treatment is performed for each Example are compared.
- the curable resin composition containing a polysiloxane compound having a condensable group, a compound having a ring-opening polymerizable group, and a curing agent to at least two-stage curing treatment of the first step and the second step.
- a cured molded body having excellent physical properties such as heat resistance, abrasion resistance (high surface hardness) and transparency, and an excellent appearance due to low shrinkage can be efficiently obtained.
- Example 3-5 From comparison of each of Example 1-3 and Example 1-7, Example 2-2 and Example 2-5, and Example 3-2 and Example 3-5, the oxygen concentration is lower. It was found that the transparency and surface hardness of the resulting cured molded body can be further improved by performing the second step in an atmosphere.
- the resin compositions (1) to (7) and the comparative resin composition (1) use a compound having the same ring-opening polymerizable group and a polysiloxane compound, and the mixing ratio thereof is changed.
- Resin composition (7) (polysiloxane compound: 95 parts), resin composition (6) (polysiloxane compound: 90 parts), resin composition (8) (polysiloxane compound: 80 parts), resin composition Product (1) (polysiloxane compound: 70 parts), resin composition (2) (polysiloxane compound: 50 parts), resin composition (3) (polysiloxane compound: 30 parts), resin composition (4) ( Polysiloxane compound: 10 parts), resin composition (5) (polysiloxane compound: 5 parts), comparative resin composition (1) (polysiloxane compound: 0 part) in this order, the content ratio of the polysiloxane compound is small.
- the content of the polysiloxane compound is 100% by mass of the total amount of the polysiloxane compound and the compound having a ring-opening polymerizable group.
- the effect of improving the surface hardness and transparency is not simply obtained by increasing the content ratio of the polysiloxane compound, but includes the curing process of the specific first step and the second step.
- the content ratio of the polysiloxane compound is increased (preferably 5 to 95% by mass relative to 100% by mass of the total amount of the polysiloxane compound and the compound having a ring-opening polymerizable group). It turned out to be an effect.
- Example 1-1 and Example 1-2 are compared with Comparative Examples 1-1 and 1-2, in Examples 1-1 and 1-2, the molded body contains a metalloxane component and has a highly crosslinked structure. Therefore, the transparency is improved as compared with the comparative example, and the transmittance after the UV resistance test is also improved (deterioration due to UV is suppressed).
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Abstract
Description
本発明はまた、縮合可能な基を有するポリシロキサン化合物、開環重合性基を有する化合物、及び、硬化剤を含む硬化性樹脂組成物から硬化成型体を製造する方法であって、該製造方法は、該硬化性樹脂組成物を80~200℃で熱硬化させる工程及び/又は活性エネルギー線照射により硬化させる工程からなる第1工程と、該第1工程で得た硬化物を200℃を超え、500℃以下で熱硬化させる第2工程とを含む硬化成型体の製造方法でもある。
本発明は更に、メタロキサン成分と有機樹脂成分とを含む硬化成型体であって、上記メタロキサン成分を構成する金属元素は、硬化成型体の総量100質量%に対して10質量%以上であり、上記メタロキサン成分を構成する金属元素のうち、炭化水素基との結合数がn-1又はn-2(nは、金属元素の原子価であり、2以上の整数を表す。)である金属元素の含有量は、メタロキサン成分を構成する金属元素の総量100原子%に対して50原子%以下であり、上記メタロキサン成分を構成する金属元素のうち、Y-M(Mは金属元素を表す。Yは水素原子、ハロゲン原子、水酸基及びRO基(Rは炭化水素基を表す。)からなる群より選択される少なくとも1種を表す。)で表される結合を有する金属元素の含有量は、メタロキサン成分を構成する金属元素の総量100原子%に対して35原子%以下であり、上記メタロキサン成分中、粒子状を呈する成分の含有量は、メタロキサン成分の総量100質量%に対して50質量%以下であることを特徴とする硬化成型体でもある。
以下に本発明を詳述する。
なお、上記活性エネルギー線照射による硬化工程は、空気中及び/又は不活性ガス中、減圧下、加圧下のいずれの雰囲気下でも行うことができる。
この場合、上記硬化性樹脂組成物を硬化剤及び必要に応じて他の成分を含む1液組成物とし、目的とする硬化成型体の形状に合わせた金型内に該1液組成物を充填(射出・塗出等)して硬化させ、その後、硬化物を金型から取り出す方法が好適に用いられる。
なお、鉛筆硬度は、鉛筆引っかき硬度試験機(安田精機製作所製)を用いて、JIS-K5600-5-4(1999年制定)に準拠し、荷重を1000gとして測定することができる。
上記硬化性樹脂組成物は、縮合性無機化合物、硬化性有機化合物、及び、硬化剤を含むものであるが、これらを必須成分とする限り、更に他の成分を含むものであってもよく、各成分は、それぞれ1種又は2種以上を使用することができる。
上記硬化性樹脂組成物において、縮合性無機化合物とは、縮合可能な基を有する無機化合物を意味する。縮合可能な基とは、熱によって縮合する官能基をいう。このような縮合性無機化合物としては、縮合可能な基を有し、かつ、メタロキサン結合(M-O-M結合、Mは金属元素を表す。)を有する化合物(ポリメタロキサン化合物)であることが好適である。すなわち、本発明の縮合性無機化合物が、縮合可能な基を有するポリメタロキサン化合物であることは、本発明の好適な実施形態の1つである。上記縮合可能な基として具体的には、例えば、M-O-R基(Rは、炭化水素基を表す。)、M-OH基、M-X基(Xは、ハロゲン原子を表す。)、M-H基が好適である。これらの縮合可能な基の中でも、硬化反応性の点で、M-O-R基又はM-OH基が特に好適である。
このように、本発明の縮合性無機化合物が、縮合可能な基を有するポリシロキサン化合物を含むことは、本発明の好適な実施形態の1つである。
なお、本明細書においては、Si、Ge、Sb等の半金属元素も金属元素に含めるものとする。
また、上記縮合性無機化合物が、縮合可能な基を有するポリシロキサン化合物を含む形態において、上記縮合可能な基が、Si-O-R基(Rは、炭化水素基を表す。)、Si-OH基、Si-X基(Xは、ハロゲン原子を表す。)、及び、Si-H基からなる群より選択される少なくとも1種の基である形態も、本発明の好適な形態の1つである。
上記アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、2-エチルへキシル基、n-オクチル基、ラウリル基、ステアリル基等の鎖状アルキル基;シクロプロピル基、シクロブチル基、シクロへキシル基、ビシクロヘキシル基等のシクロアルキル基;鎖状アルキル基の水素原子の一部又は全部が、シクロアルキル基で置換されてなる基;シクロアルキル基の水素原子の一部又は全部が、鎖状アルキル基で置換されてなる基等が挙げられる。
上記アリール基としては、例えば、フェニル基、ナフチル基、アントラニル基等の他、これらの水素原子の一部又は全部がアルキル基等で置換されてなる基(例えば、メチルフェニル基(トルイル基)、ジメチルフェニル基(キシリレン基)、ジエチルフェニル基等)等が挙げられる。
上記アラルキル基としては、ベンジル基等の他、これらの水素原子の一部又は全部がアルキル基等で置換されてなる基(例えば、メチルベンジル基等)等が挙げられる。
上記Rは、置換基を有するものであってもよい。また、鎖状(直鎖状、分岐鎖状)構造であってもよいし、環状構造であってもよい。
また上記Xで表されるハロゲン原子としては、特に限定されないが、フッ素原子が特に好適である。
また上記ポリメタロキサン化合物は常温で液状であってもよいし、固体状のものであってもよい。
なお、本明細書における重量平均分子量は、以下に示す方法により測定した。
(重量平均分子量の測定方法)
樹脂組成物、及び、合成途中の樹脂に対して、ゲルパーミエーションクロマトグラフィー(GPC)測定を行い、重量平均分子量を測定した。
(測定装置)
ゲルパーミエーションクロマトグラフィー(東ソー社製、商品名「HLC-8320GPC」)を用いた。
(測定条件)
カラム:東ソー社製「TSKgel SuperMultipore HZ-N」×2本
溶離液:テトラヒドロフラン(THF)
流速:0.35mL/分
温度:40℃
検量線:ポリスチレン標準サンプル(東ソー社製)を用いて作成。
R1xYyMOz (1)
(Mは、金属元素を表す。R1は、アルキル基、アリール基、アラルキル基、オキシラン環を有する基、アクリル及び/又はメタクリル基を有する基、S(硫黄)原子を有する基、又は、F(フッ素)原子を有する官能基を表す。Yは、縮合基又は縮合原子を表し、Mと結合して上記縮合可能な基を形成するものである。x、y及びzは、それぞれ、Mに対するR1、Y及びOの結合割合の平均値を表し、0≦x≦n-1、0<y≦n、及び、0≦z≦n/2を満たす。nは金属元素Mの原子価(Mが2種以上の金属元素を含む場合には各元素の原子価の平均値)を表す。)で表される化合物が特に好ましい。x、y及びzの範囲としてより好ましくは、0≦x≦n-2、0<y≦n-2、及び、(n-2)/2≦z<n/2である。
R1xYySiOz (2)
(R1は、アルキル基、アリール基、アラルキル基、オキシラン環を有する基、アクリル及び/又はメタクリル基を有する基、S(硫黄)原子を有する基、又は、F(フッ素)原子を有する官能基を表す。Yは、縮合基又は縮合原子を表し、Siと結合して上記縮合可能な基を形成するものである。x、y及びzは、それぞれ、Siに対するR1、Y及びOの結合割合の平均値を表し、0<x<2、0<y<2、1<z<2、0<(x+y)<2、及び、x+y+2z=4を満たす。)で表される化合物が特に好ましい。このようなシルセスキオキサンを用いることによって、耐熱性や機械的特性を向上・改善するとともに、樹脂組成物の経時的な粘度の上昇が抑制されることになる。したがって、上記硬化性樹脂組成物をハンドリング性により優れる一液型樹脂組成物(一液性硬化性樹脂組成物)とすることができ、また、本発明の製造方法による作用効果と相まって、より効率的かつ簡便に、優れた物性を有する硬化成型体を得ることが可能になる。
上記R1は、置換基を有するものであってもよいが、置換基を有さない基であることが特に好ましい。
なお、本明細書中、「アルキル基」には、直鎖状又は分岐鎖状のアルキル基だけでなく、環状のアルキル基(シクロアルキル基)を含むものとする。
上記yは、Siに対するYの結合割合の平均値を表し、0を超えて2未満の数であるが、yが2以上であると、Yの縮合により成型体中に気泡を生じるおそれがある。好ましくは1未満、更に好ましくは0.5未満、特に好ましくは0.3未満である。また、0.001より大きい値であることが好ましい。0.001未満では、第2工程でのシルセスキオキサンの縮合による硬度向上効果が小さくなり、エポキシ樹脂への相溶性も小さいものとなる。より好ましくは0.01より大きい値、更に好ましくは0.05より大きい値、特に好ましくは0.08より大きい値である。
上記x+yは、0より大きく2未満の数であればよい。好ましくは0.4より大きく1.6未満であり、より好ましくは0.7より大きく1.3未満である。
上記xは、y及びx+yが上述した好適な範囲を満たすものとなるように、適宜設定することが好適である。
上記縮合性無機化合物において、硬化成型体中のメタロキサン成分を構成する金属元素の含有量としては、最終的に得られる成型体100質量%中の金属元素含有量に換算して、5質量%以上であることが好ましい。より好ましくは10質量%以上、更に好ましくは15質量%以上、特に好ましくは20質量%以上である。
また、上記縮合性無機化合物がポリシロキサン化合物を含む形態において、硬化成型体中のシロキサン結合の量としては、最終的に得られる成型体100質量%中のSi含有量に換算して、5質量%以上であることが好ましい。より好ましくは10質量%以上、更に好ましくは15質量%以上、特に好ましくは20質量%以上である。
上記硬化性樹脂組成物において、硬化性有機化合物とは、硬化性の官能基を有する有機化合物を意味する。硬化性の官能基とは、熱又は光によって硬化反応する官能基(樹脂組成物を硬化反応させる基)をいう。硬化性の官能基としては、例えば、エポキシ基やオキセタン環、エチレンスルフィド基等の開環重合性基や、アクリル基、メタクリル基、ビニル基等のラジカル硬化性基及び/又は付加硬化性基が挙げられる。上記硬化性有機化合物としては、カチオン硬化により硬化する開環重合性基(エポキシ基やオキセタン基、エチレンスルフィド基等)を有する化合物や、ラジカル硬化により硬化するアクリル基及び/又はメタクリル基を有する化合物、ヒドロシリル化やエンチオール反応等の付加反応により硬化するビニル基であることが好ましい。これらの化合物を用いると、1次硬化(上記第1工程における硬化)までの時間が短時間で生産性が良く、得られる硬化物が耐熱性(耐熱分解性、耐熱着色性)に優れたものとなる。中でも、1次硬化時の収縮率が低いため金型等での形状付与がし易くなるという点で、カチオン硬化により硬化する開環重合性基を有する化合物がより好ましい。開環重合性基を有する化合物としては、1分子中に開環重合性基を1個以上含む化合物であればよいが、開環重合性基を合計2個以上有する化合物、すなわち多官能化合物を必須とすることが好適である。これによって、硬化反応性が更に高まり、硬化性や硬化速度に優れる樹脂組成物となるため、より短時間で硬化成型体を得ることが可能になる。このように上記開環重合性基を有する化合物が多官能化合物を必須とする形態は、本発明の好適な形態の1つである。より好ましくは、開環重合性基を有する化合物の総量100質量%に対し、多官能化合物が50質量%以上である形態であり、更に好ましくは80質量%以上、特に好ましくは100質量%、すなわち開環重合性基を有する化合物として、多官能化合物のみを使用することである。
なお、開環重合性基としては、エポキシ基、オキセタン環等が好ましい。すなわち上記開環重合性基を有する化合物は、エポキシ基及び/又はオキセタン環を有する化合物であることが好適である。中でも、上記開環重合性基を有する化合物が多官能化合物であり、開環重合性基がエポキシ基及び/又はオキセタン環である形態は、本発明の特に好ましい形態の1つである。また、エポキシ基とは、3員環のエーテルであるオキシラン環を含むものであり、狭義のエポキシ基の他、グリシジル基(グリシジルエーテル基及びグリシジルエステル基を含む)を含むものである。
上記芳香族エポキシ化合物とは、分子中に芳香環及びエポキシ基を有する化合物であり、例えば、ビスフェノール骨格、フルオレン骨格、ビフェニル骨格、ナフタレン環、アントラセン環等の芳香環共役系を有するグリシジル化合物であることが好ましい。中でも、より高屈折率を実現させるため、ビスフェノール骨格及び/又はフルオレン骨格を有する化合物であることが好適である。より好ましくは、フルオレン骨格を有する化合物であり、これによって、更に著しく屈折率を高めることができ、また離型性を更に高めることも可能となる。また、芳香族グリシジルエーテル化合物も好適である。また、芳香族エポキシ化合物の臭素化化合物を用いることによっても、より高屈折率を達成できるため好適であるが、アッベ数が若干上がるため、用途に応じて適宜使用することが好ましい。
上記エピビスタイプグリシジルエーテル型エポキシ樹脂としては、例えば、ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール等のビスフェノール類とエピハロヒドリンとの縮合反応により得られるものが好適である。
上記高分子量エピビスタイプグリシジルエーテル型エポキシ樹脂としては、例えば、上記エピビスタイプグリシジルエーテル型エポキシ樹脂を上記ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール等のビスフェノール類と更に付加反応させることにより得られるものが好適である。
上記脂肪族グリシジルエーテル型エポキシ樹脂としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール(PEG600)、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、ポリプロピレングリコール(PPG)、グリセロール、ジグリセロール、テトラグリセロール、ポリグリセロール、トリメチロールプロパン及びその多量体、ペンタエリスリトール及びその多量体、グルコース、フルクトース、ラクトース、マルトース等の単/多糖類等とエピハロヒドリンとの縮合反応により得られるもの、プロピレングリコール骨格、アルキレン骨格、オキシアルキレン骨格を有するもの等が好適である。中でも、中心骨格にプロピレングリコール骨格、アルキレン骨格、オキシアルキレン骨格を有する脂肪族グリシジルエーテル型エポキシ樹脂等が好適である。
耐候性向上の観点では、アクリル基、メタクリル基及びビニル基のうち1種又は2種以上を有する化合物の含有量としては、上記硬化性有機化合物の総量100質量%に対して、50質量%以上であることが好ましい。より好ましくは80質量%以上であり、最も好ましくは100質量%、すなわち硬化性有機化合物がアクリル基、メタクリル基及びビニル基のうち1種又は2種以上を有する化合物のみからなることである。
上記硬化性樹脂組成物において、硬化剤としては、第1工程での硬化反応に応じて適宜選択すればよい。例えば、第1工程で熱硬化を行う場合は、熱潜在性カチオン硬化触媒の他、熱潜在性ラジカル硬化触媒、酸無水物系、フェノール系又はアミン系等の通常使用される硬化剤を用いることができる。中でも、熱潜在性カチオン硬化触媒、熱潜在性ラジカル硬化触媒を用いることが好適である。硬化物の収縮量を低減する目的で、特に熱潜在性カチオン硬化触媒を用いることが好ましい。また、活性エネルギー線照射による硬化を行う場合は、硬化剤として光重合開始剤を用いることができ、中でも光潜在性カチオン硬化触媒、光潜在性ラジカル硬化触媒を用いることが好適である。硬化物の収縮量を低減する目的で、特に光潜在性カチオン硬化触媒を用いることが好ましい。なお、これらの硬化剤は1種又は2種類以上併せて用いることができる。
(R1 aR2 bR3 cR4 dZ)+m(AXn)-m (4)
(式中、Zは、S、Se、Te、P、As、Sb、Bi、O、N及びハロゲン元素からなる群より選ばれる少なくとも一つの元素を表す。R1、R2、R3及びR4は、同一又は異なって、有機基を表す。a、b、c及びdは、0又は正数であり、a、b、c及びdの合計はZの価数に等しい。カチオン(R1 aR2 bR3 cR4 dZ)+mはオニウム塩を表す。Aは、ハロゲン化物錯体の中心原子である金属元素又は半金属元素(metalloid)を表し、B、P、As、Al、Ca、In、Ti、Zn、Sc、V、Cr、Mn、Coからなる群より選ばれる少なくとも一つである。Xは、ハロゲン元素を表す。mは、ハロゲン化物錯体イオンの正味の電荷である。nは、ハロゲン化物錯体イオン中のハロゲン元素の数である。)で表される化合物が好適である。
更に一般式AXn(OH)-で表される陰イオンも用いることができる。また、その他の陰イオンとしては、過塩素酸イオン(ClO4 -)、トリフルオロメチル亜硫酸イオン(CF3SO3 -)、フルオロスルホン酸イオン(FSO3 -)、トルエンスルホン酸イオン、トリニトロベンゼンスルホン酸イオン等が挙げられる。
上記各種イミダゾール類の有機酸塩としては、例えばイミダゾール類と多価カルボン酸等の有機酸との塩類が挙げられる。イミダゾール類としては、例えば、2-メチルイミダゾール、2-フェニルイミダゾール、2-ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-シアノエチル-2-メチルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾール等が挙げられる。好ましいイミダゾール類としては、例えば下記の3級窒素を有する芳香族化合物におけるフェニル基置換イミダゾール類と同じイミダゾール類が挙げられる。
上記硬化促進剤は、1種又は2種類以上併せて用いることができる。硬化促進剤の使用量は、硬化性樹脂組成物の総量100質量%に対し、0.01~5質量%とすることが好ましく、より好ましくは0.03~3質量%である。
上記可撓性成分としては、上記硬化性有機化合物とは異なる化合物であってもよく、上記硬化性有機化合物の少なくとも1種が可撓性成分であってもよい。
このように上記可撓性成分としては、硬化性の官能基を含む化合物を好適に用いることができるが、該化合物としては、エポキシ基を含む化合物であることが好ましく、より好ましくは、オキシブチレン基(-〔-(CH2)4-O-〕m-(mは、同上。))を有する化合物である。
上記化合物はまた、直鎖状、分岐状、環状等のいずれの構造であってもよく、分岐しているものが好ましい。
上記化合物の炭素数としては、8~36の整数であることが好適であるが、これによって、樹脂組成物の透明性や作業性等の機能を損なうことなく優れた剥離性を示す硬化物となる。炭素数としてより好ましくは8~20であり、更に好ましくは10~18である。
なお、上記粘度は、実施例において後述する手法によって測定することができる。
1次硬化における収縮率とは、上記第1工程前後の収縮率である。具体的には、例えば後述する実施例においては、130℃×2分の硬化工程前後の130℃における体積収縮量から求めたものである。上記収縮率は実測により求めることが最も好ましいが、困難な場合には、室温から130℃における線膨張率と密度とを夫々測定することにより計算で推定可能である。
上記硬化成型体は、上述した製造方法によって得られるものであることに起因して、耐熱性及び耐磨耗性に優れ、かつ収縮率が小さいうえ、離型性、低着色性及び透明性に優れ、機械的特性や光学特性を充分に発揮できるものである。このような硬化成型体は、金型成型体であることが好ましいが、フィルム、シート、ペレット等の形状であってもよい。
本発明は更に、メタロキサン成分と有機樹脂成分とを含む硬化成型体であって、上記メタロキサン成分を構成する金属元素は、硬化成型体の総量100質量%に対して10質量%以上であり、上記メタロキサン成分を構成する金属元素のうち、炭化水素基との結合数がn-1又はn-2(nは、金属元素の原子価であり、2以上の整数を表す。)である金属元素の含有量は、メタロキサン成分を構成する金属元素の総量100原子%に対して50原子%以下であり、上記メタロキサン成分を構成する金属元素のうち、Y-M(Mは金属元素を表す。Yは水素原子、ハロゲン原子、水酸基及びRO基(Rは炭化水素基を表す。)からなる群より選択される少なくとも1種を表す。)で表される結合を有する金属元素の含有量は、メタロキサン成分を構成する金属元素の総量100原子%に対して35原子%以下であり、上記メタロキサン成分中、粒子状を呈する成分の含有量は、メタロキサン成分の総量100質量%に対して50質量%以下であることを特徴とする硬化成型体でもある。
このような構成であると、硬化成型体が、硬度、耐熱性、光学特性に優れたものとなる。
メタロキサン成分は、構造中にメタロキサン結合(M-O-M結合)を含む成分である。金属元素Mについては、上記縮合性無機化合物に関して述べたものと同様である。
上記硬化成型体において、メタロキサン成分を構成する金属元素は、硬化成型体の総量100質量%に対して10質量%以上である。10質量%未満であると、硬化成型体中のメタロキサン成分の含有量が少なくなり、メタロキサン成分による硬度が充分に高くならないため、2次硬化時や、硬化成型体の使用時、特に、およそ80℃以上の高温環境下で長期間使用される場合や紫外光に晒される環境下で使用される場合等に、硬化成型体に着色が生じる。メタロキサン成分を構成する金属元素の含有量として好ましくは、硬化成型体の総量100質量%に対して15質量%以上であり、より好ましくは20質量%以上である。
メタロキサン成分を構成する金属元素の含有量としてはまた、硬化成型体の総量100質量%に対して50質量%以下であることが好ましい。より好ましくは40質量%以下であり、更に好ましくは30質量%以下である。メタロキサン成分を構成する金属元素の含有量が多過ぎると、樹脂組成物の粘度が高くなり、取り扱いが困難となる。
炭化水素基との結合数がn-1又はn-2である金属元素の含有量が50原子%を超えると、成型体中の3次元架橋構造が少なくなり、成型体の硬度が低くなるため、成型時や使用時に成型体に傷が発生しやすくなる。
炭化水素基との結合数がn-1又はn-2である金属元素の含有量として、好ましくは、メタロキサン成分を構成する金属元素の総量100原子%に対して40原子%以下であり、より好ましくは、20原子%以下である。更に好ましくは10原子%以下であり、最も好ましくは0原子%、すなわち、上記のような金属元素を含まないことである。
上記Mの好ましい形態については、既に述べたとおりである。上記Yとしては、水酸基及びRO基からなる群より選択される少なくとも1種であることが好ましい。上記Rとしては、アルキル基、アリール基、アラルキル基が好適である。
カルボン酸系構造とは、-O-(C=O)-で表される結合を含む構造を意味し、カルボン酸、カルボン酸エステル及びカルボン酸塩からなる群より選択される少なくとも1種であることが好ましい。より好ましくは、カルボン酸及びカルボン酸エステルのうち少なくとも1種であることである。カルボン酸系構造はまた、上記硬化性有機化合物が有する構造に由来するものであることが好ましい。
エーテル骨格とは、R’-O-R’’(R’及びR’’は同じ又は異なる有機基を表す。)で表される結合を含む構造である。硬化成型体中の全エーテル骨格の総量100mol%のうち、10mol%以上がオキシラン環の開環により得られるものであることが好ましい。より好ましくは50mol%以上である。
また、カルボン酸系構造及び/又はエーテル骨格を形成する酸素原子の合計量が、硬化成型体の総量100質量%に対して0.1質量%以上であることが好ましい。より好ましくは1質量%以上、更に好ましくは5質量%以上である。また、25質量%以下であることが好ましく、20質量%以下であることがより好ましく、15質量%以下であることが更に好ましい。上記酸素原子の含有量が多すぎると、酸化による成型体の耐熱性の劣化(着色したり、透明性が低下したりする等)が大きくなる。上記酸素原子の含有量が少な過ぎると、充分な水素結合が得られず、樹脂組成物やその硬化物の各成分の相溶性が低下し、得られる成型体の透明性や強度が低下する。
後述する各実施例及び比較例に記載した条件で縦100mm、横100mm、厚さ1mmのシート状成型体を作製し、これを適宜切削加工して成型体の組成等の測定及び評価用試料(成型体試料)とした。
得られた成型体試料を元素分析装置(J-SCIENCE LAB.社製、CHN CORDER JM10)により元素分析して、炭素、水素、窒素分を定量した。また、白金ボードに5mgの成型体試料をのせて、50%硫硝酸を数滴滴下して、電気炉にて950℃で燃焼し、灰分の定量測定を行った。灰分に含まれる構成金属元素を蛍光X線分析により見積もり、その金属元素の酸化安定状態より金属元素量を見積もった。
(灰分中の金属含有量の定量(概算))
試料に関し、蛍光X線分析装置にて分析を行った。成型体中の、質量数がNa以上の金属元素に関する元素の定性分析、及び、質量%濃度を測定した。
測定装置:フィリップス社製、PW2404
計算方法:FP法(ファンダメンタル・パラメータ法)
(例.実施例1-5の場合)
H:5.42%、C:28.34%、N:0%、灰分:59.90%
蛍光X線分析より、灰分中の金属元素の99重量%以上がSiであり、95重量%以上であったことから金属元素がSiの単一成分からなると概算した。そして、Siの原子量が28.0855、酸素の原子量が15.9994であることより、灰分中の金属元素量をSi量として、以下のように28.0%と算出した。
59.90×(28.0855/(28.0855+15.9994×2))=28.0%
固体核磁気共鳴(固体NMR)においては、試料に含有される金属元素の配位形態により核磁気共鳴ピークの位置(化学シフト)は異なり、各金属元素に配位する結合や基の種類、それらの数に応じて固有の化学シフトを示す。たとえば、金属元素に結合する炭化水素基の数、RO基の数、メタロキサン結合の数によって、それぞれ固有のピークが観測される。
(金属元素に結合する炭化水素基の数により化学シフトが異なる例)
・テトラアルコキシシランの加水分解縮合物(全てのケイ素原子は、炭化水素基との結合数がn-4である)であれば、化学シフトは-90ppm~-120ppmに観測される。
・メチルトリアルコキシシランの加水分解縮合物(全てのケイ素原子は、炭化水素基との結合数がn-3である)であれば、化学シフトは-40ppm~-90ppmに観測される。
・ジメチルジアルコキシシランの加水分解縮合物(全てのケイ素原子は、炭化水素基との結合数がn-2である)であれば、化学シフトは0ppm~-30pmに観測される。
・トリメチルモノアルコキシシランの加水分解縮合物(全てのケイ素原子は、炭化水素基との結合数がn-1である)であれば、化学シフトは0ppm~30ppm(溶液からの推定)に観測される。
(金属元素に結合する水酸基又はOR基(R:炭化水素基)の有無、結合数により、化学シフトが異なる例)
メチルトリアルコキシシランの加水分解縮合物であれば、化学シフトは以下の位置に観測される。
・2個のOR基を有するものの化学シフトは47ppm付近、
・1個のOR基を有するものは56ppm付近、
・0個のOR基を有するものは65ppm付近に観測される。
(装置)固体NMR測定装置 BRUKER社製、AVANCE400
(条件)測定核種: 29Si(観測核共鳴周波数:79.487MHz)
測定モード:DD-MAS(ダイポールデカップリング/マジックアングルスピニング)法
照射パルス:10~60度パルス
パルス繰り返し時間:120秒以上
積算回数:200~4000回
試料回転数:6kHz
観測温度:300K
外部基準物質:3-(トリメチルシリル)プロパン-1-スルホン酸ナトリウム(化学シフトは1.534ppm)
なお、照射パルスは測定核の緩和時間によって上記範囲内で調整してもよく、積算回数と試料回転数は測定時に用いるサンプルローター径に応じて上記範囲内で調整してもよい。
固体核磁気共鳴(固体NMR)により、成型体試料に含有される金属元素の内、金属元素に結合する炭化水素基の数がn-1個である金属元素、及び、n-2個(n:金属元素の原子価、金属元素がケイ素である場合はn=4)である金属元素の合計量の割合を求めた。具体的には、試料について固体NMRを測定し、結合する炭化水素基数に応じて観測される各ケイ素原子のピークの面積を求め、ピーク面積比より、結合する炭化水素基の数が3個又は2個であるケイ素原子の含有量の合計を算出した。
(Y-Mで表される結合を有する金属元素の定量)
固体核磁気共鳴(固体NMR)により、成型体試料に含有される金属元素の内、金属元素に結合するY基(ここでは、水酸基又はOR基)の数が1個以上である金属元素の合計量の割合を求めた。具体的には、試料について固体NMRを測定し、3個のY基を有するケイ素原子(化学シフト:-41.4ppm(溶液からの推定))、2個のY基を有するケイ素原子(化学シフト:47ppm付近)、1個のY基を有するケイ素原子(化学シフト:56ppm付近)0個のY基を有するケイ素原子(化学シフト:65ppm付近)に帰属される各ケイ素原子のピークの面積を求め、ピーク面積比より、全ケイ素原子に対するY基の数が1個以上であるケイ素原子の含有量を算出した。
図1及び図2に、固体NMRスペクトルの例を示した。図1は、参考例1で得られた成型体の29Si-NMRスペクトルを示す図である。図2は、実施例1-5で得られた成型体の29Si-NMRスペクトルを示す図である。
成型体試料を厚さ方向にミクロトームにより100nmの厚みに切削して、電界放射型の走査型電子顕微鏡(FE-SEM)にて透過測定を行い、粒子状の物質の有無、及び、その元素成分の定性分析を行った。なお、粒子状成分の定量は、元素分析、蛍光X線分析、固体NMR及びFE-SEMにより行った。
(測定装置及び測定条件)
日立ハイテクノロジーズ社製 FE-SEM S-4800(コールド型電界放射銃を装備)
EDAX Genesis2000 EDS検出器を装備
加速電圧25kV、エミッション電流10μA、コンデンサ16、W.D.=8mm
EDS:加速電圧10kV、W.D.=15mm
図3及び図4に、走査型電子顕微鏡写真の例を示した。図3は、実施例1-5で得られた成型体の走査型電子顕微鏡写真である。図4は、比較例5で得られた成型体の走査型電子顕微鏡写真である。
図3に示すように、1nm以上の粒子は存在せず、均一樹脂組成物であることが分かった。
図4に示すように、比較例5の場合、FE-SEMによる元素の定性分析より、写真中の黒色粒中にSiが存在しており、有機樹脂成分中には殆どないことが分かった。元素分析、蛍光X線分析、固体NMR及びFE-SEMにより、4官能のSiO2粒子が成型体中に13.5wt%存在していることが分かった。
本発明においては有機樹脂成分、無機成分の仕込み組成が既知である。1次硬化時点では無機成分の縮合が殆ど進んでいないことも固体NMRから分かっている。また、熱分解ガスクロマトグラフにより、2次硬化時点で揮発する成分としては、無機成分の硬化により発生する水、アルコールが主成分であることが分かっている。従って、2次硬化後の成型体中の有機樹脂成分の概算は可能であり、各実施例で得られた硬化成型体中の有機樹脂成分の含有量は表10記載の値であることが分かった。また、未知組成の成型体であっても、無機成分の定性・定量は固体NMR、元素分析、FT-IR、蛍光X線分析により可能であり、逆算により有機樹脂成分の含有量を求めることも可能である。
(例.実施例1-5の場合)
仕込みにおける硬化性有機樹脂成分の重量濃度:29.644wt%
2次硬化後の重量/1次硬化後の重量:93.3wt%
これらより、硬化成型体中の有機樹脂成分の含有量は、29.644/93.3×100=31.7wt%と算出される。
成型体試料に関し、赤外吸収スペクトル(FT-IR)測定を行い、カルボン酸構造、水酸基、エーテル骨格等の官能基の定性分析(有無の確認)を行った。
測定装置及び測定条件:FT-IR測定装置 サーモエレクトロン社製 Nexus-670
本発明においては仕込み組成が既知であり、成型体中のカルボン酸系構造及びオキシラン環由来の酸素の重量濃度の概算は可能である。未知の物質についても、カルボン酸系構造及びエーテル骨格(または、オキシラン環)に由来する酸素原子の定量は、固体NMR、熱分解ガスクロマトグラム、元素分析、FT-IRの定性・定量分析により可能である。
(例.実施例1-5の場合)
脂環式エポキシ樹脂中のカルボン酸系構造及びオキシラン環に由来する酸素濃度:25.37wt%
2次硬化後の重量/1次硬化後の重量:93.3wt%
これらより、硬化成型体中のカルボン酸系構造及びオキシラン環由来の酸素の重量濃度は、(29.644×0.25366)/93.3×100=8.06wt%と算出される。
上記硬化成型体は、500nmにおける平行線透過率が80%以上であることが好ましい。より好ましくは85%以上、更に好ましくは90%以上である。また、400nmにおける平行線透過率が75%以上であることが好ましい。より好ましくは80%以上、更に好ましくは85%以上である。平行線透過率が低いと、成型体を光学材料として用いた場合の光の損失が大きく、色の再現性も低いものとなる。
上述したように、本発明の硬化成型体は、硬度、耐熱性、光学特性等の各種物性に優れるものであるため、例えば、光学部材、機械部品材料、電気・電子部品材料、自動車部品材料、土木建築材料、成形材料等の他、塗料や接着剤の材料等の各種用途に有用なものである。中でも特に、光学部材、オプトデバイス部材、表示デバイス部材等に好適に用いることができる。このような用途として具体的には、例えば、眼鏡レンズ、(デジタル)カメラや、携帯電話や車裁カメラ、監視カメラ等のカメラ用撮像レンズ、光ビーム集光レンズ、光拡散用レンズ等のレンズ用途;ウォッチガラス、表示装置用のカバーガラス等の透明シート;フィルター、回折格子、プリズム、光案内子等の各種の光学用途;フォトセンサー、フォトスイッチ、LED、発光素子、光導波管、合波器、分波器、断路器、光分割器、光ファイバー接着剤等のオプトデバイス用途;LCDや有機ELやPDP等の表示素子用基板、カラーフィルター用基板、タッチパネル用基板、ディスプレイ保護膜、ディスプレイバックライト、導光板、反射防止フィルム、防曇フィルム等の表示デバイス用途;タッチパネル等の物理的接触のある用途等が好適である。
また、上記硬化成型体を透過性シートとして用いることも好ましい。透過性シートとしては、例えば、高硬度が必要とされる透過性ディスプレイ用保護シートを挙げることができる。また、上記硬化成型体は高い耐熱性を有するため、蒸着温度を高く出来、その結果、蒸着膜の性能を上げることが出来るので、光選択性シート(例えばIRCF)、光透過性導電性シート(例えばタッチパネルに使用されるITOフィルム)等の透過性シートとして用いることもできる。
なお、上記硬化成型体が光学用硬化成型体である場合には、上記硬化性樹脂組成物は、光学用硬化成型体の用途に応じて適宜その他の成分を含んでいてもよい。具体的には、UV吸収剤、IRカット剤、反応性希釈剤、顔料、洗料、酸化防止剤、光安定剤、可塑剤、非反応性化合物、連鎖移動剤、熱重合開始剤、嫌気重合開始剤、光安定剤、重合禁止剤、消泡剤等が好適である。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を9g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を21g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製、熱潜在性カチオン硬化触媒)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を15g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を15g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を21g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を9g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を27g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を3g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を28.5g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を1.5g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を3g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を27g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-80L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を1.5g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を28.5g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-80L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を6g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を24g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を4.5g、EHPE-3150(ダイセル化学工業社製、脂環式エポキシ樹脂)を4.5g添加し、130℃で均一に混合した。その後、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を21g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
YX-8000(ジャパンエポキシレジン社製、水添エポキシ樹脂)を5.1g、リカシッドMH-700G(新日本理化社製、脂環式酸無水物)を3.9g添加し、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を21g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、2E4MZ(四国化成工業社製、硬化促進剤、2-エチル-4-メチルイミダゾール)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を9g、PMPSQ-E(SR-3321)(小西化学工業社製、ポリメチルフェニルシルセスキオキサン)を21g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を9g、PPSQ-E(SR-23)(小西化学工業社製、ポリフェニルシルセスキオキサン)を21g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を30g、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を15g、EHPE-3150(ダイセル化学工業社製、脂環式エポキシ樹脂)を15g添加し、130℃で均一に混合した。その後、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.06g添加し、減圧下で均一になるまで混合した。
YX-8000(ジャパンエポキシレジン社製、水添エポキシ樹脂)を16.8g、リカシッドMH-700G(新日本理化社製、脂環式酸無水物)を13.2g添加し、ステアリン酸を0.15g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.15g添加し、80℃にて均一になるまで混合した。40℃に冷却後、2E4MZ(四国化成工業社製、硬化促進剤、2-エチル-4-メチルイミダゾール)を0.06g添加し、減圧下で均一になるまで混合した。
<粘度>
粘度の測定は、硬化剤(SI-60L、SI-80L又は2E4MZ)を加える前の樹脂組成物について、R/Sレオメーター(米国ブルックフィールド社製)を用いて、40℃、回転速度D=1/sの条件下で行った。なお、粘度20Pa・s以上では、RC25-1の測定治具を使用し、粘度20Pa・s未満では、RC50-1の治具を使用した。また、回転速度D=1/s時点の粘度が測定できないものについては、回転速度D=5~100/sの値を外挿して、樹脂組成物の粘度として評価した。
(第1工程)
SUS304(日本テストパネル社製、表面800番仕上げ)の金属板を2枚用いて、1mm間隔のギャップを形成し、製造例1で得た樹脂組成物(1)について注型成型を行った。130℃の金型で2分硬化して、脱型した。
(第2工程)
第1工程での硬化後、N2雰囲気下(特に断りのない限り、0.2~0.3体積%の酸素濃度で実施した)、以下の各条件で硬化の処理を行った。
条件:250℃1時間(250℃の乾燥機へ直接試料を投入)
得られた硬化成型体について、下記測定方法に従い、透過率、屈折率、アッベ数、表面硬度、耐UV特性を評価した。結果を表2に示す。
吸光度計(島津製作所製、分光光度計UV-3100)を用いて、波長400nm、500nmにおける硬化物の透過率を測定した。
<屈折率、アッベ数の評価>
屈折率及びアッベ数の測定は、JIS K7142に準拠した方法で、下記の方法によりそれぞれ測定を行った。
屈折率は、上記硬化物(1mm厚の成型体)について、屈折率計(アタゴ社製、DR-M2)を用いて、測定波長を486nm、589nm、656nmとして、20℃の条件下で測定した。
アッベ数は、上記硬化物(1mm厚の成型体)について、屈折率計(アタゴ社製、DR-M2)を用いて、20℃の条件下で測定した。
鉛筆引っかき硬度試験機(安田精機製作所製)を用いて、JIS-K5600-5-4(1999年制定)に準拠して測定した。なお、荷重は1000gであった。
<耐UV特性(耐UV試験後の透過率)>
スガ試験機社製のM6T(6kW水平式メタリングウエザーメーター)を用いて、1kW/m2(300~400nm)、50℃で100時間後の透過率(波長400nm、500nm)を測定した。
第2工程の硬化条件を、実施例1-2では250℃6時間(室温より昇温15℃/min)、実施例1-3では300℃1時間(室温より昇温15℃/min)、実施例1-4では300℃6時間(室温より昇温15℃/min)、実施例1-5では330℃1時間(室温より昇温15℃/min)、実施例1-6では350℃10分(室温より昇温15℃/min)、としたこと以外は、実施例1-1と各々同様にして硬化処理を行った。また、硬化後の成型体は150℃以下(最高温度より降温5℃/min程度)まで冷却して、空気中に開放した。得られた硬化成型体の各々について、実施例1-1と同様に評価した。結果を表2に示す。
第2工程の硬化条件を、N2雰囲気下(5体積%の酸素濃度)で、かつ300℃1時間(室温より昇温15℃/min)としたこと以外は、実施例1-1と同様にして硬化処理を行った。得られた硬化成型体について、実施例1-1と同様に評価した。結果を表2に示す。
第2工程を行わなかったこと以外は、実施例1-1と同様にして硬化処理(第1工程のみの硬化処理)を行った。得られた硬化物について、実施例1-1と同様に評価した。結果を表2に示す。
実施例2-1、2-2、2-3、2-4、2-5、及び、参考例2では、製造例1で得た樹脂組成物(1)に代えて製造例2で得た樹脂組成物(2)を用いたこと以外は、各々、実施例1-1、1-3、1-5、1-6、1-7、及び、参考例1と同様にして硬化処理を行った。得られた硬化成型体の各々について、実施例1-1と同様に評価した。結果を表3に示す。
実施例3-1、3-2、3-3、3-4、3-5、及び、参考例3では、製造例1で得た樹脂組成物(1)に代えて製造例3で得た樹脂組成物(3)を用いたこと以外は、各々、実施例1-1、1-3、1-5、1-6、1-7、及び、参考例1と同様にして硬化処理を行った。得られた硬化成型体の各々について、実施例1-1と同様に評価した。結果を表4に示す。
実施例4-1、5-1、6-1、7-1、8-1、9-1及び11-1では、各々、樹脂組成物(1)に代えて表5~6に示す樹脂組成物を用いたこと以外は、実施例1-1と同様にして硬化処理を行った。実施例4-2、5-2、6-2、7-2、8-2、9-2及び11-2では、各々、樹脂組成物(1)に代えて表5~6に示す樹脂組成物を用いたこと以外は、実施例1-6と同様にして硬化処理を行った。参考例4~9及び11では、各々、樹脂組成物(1)に代えて表5~6に示す樹脂組成物を用いたこと以外は、参考例1と同様にして硬化処理を行った。
実施例10-1では、樹脂組成物(1)に代えて樹脂組成物(10)を用いたこと、及び、第1工程の硬化条件を140℃1時間としたこと以外は、実施例1-1と同様にして硬化処理を行った。実施例10-2では、樹脂組成物(1)に代えて樹脂組成物(10)を用いたこと、及び、第1工程の硬化条件を140℃1時間としたこと以外は、実施例1-6と同様にして硬化処理を行った。参考例10では、樹脂組成物(1)に代えて樹脂組成物(10)を用いたこと、及び、第1工程の硬化条件を140℃1時間としたこと以外は、参考例1と同様にして硬化処理を行った。
実施例12-1では、樹脂組成物(1)に代えて樹脂組成物(12)を用いたこと、及び、第1工程の硬化条件を150℃1時間としたこと以外は、実施例1-1と同様にして硬化処理を行った。実施例12-2では、樹脂組成物(1)に代えて樹脂組成物(12)を用いたこと、及び、第1工程の硬化条件を150℃1時間としたこと以外は、実施例1-6と同様にして硬化処理を行った。参考例12では、樹脂組成物(1)に代えて樹脂組成物(12)を用いたこと、及び、第1工程の硬化条件を150℃1時間としたこと以外は、参考例1と同様にして硬化処理を行った。
得られた硬化成型体の各々について、実施例1-1と同様に評価した。結果を表5~6に示す。
なお、樹脂組成物(6)又は(7)を用いた例(実施例6-1~6-2、7-1~7-2、及び、参考例6~7)では、第1工程の硬化過程で硬化体中に泡が発生したため、泡の発生していない箇所で物性測定を行った。
比較例1-1及び2-1では、各々、樹脂組成物(1)に代えて表7に示す樹脂組成物を用いたこと以外は、実施例1-1と同様にして硬化処理を行った。比較例1-2及び2-2では、各々、樹脂組成物(1)に代えて表7に示す樹脂組成物を用いたこと以外は、実施例1-6と同様にして硬化処理を行った。比較参考例1~2では、各々、樹脂組成物(1)に代えて表7に示す樹脂組成物を用いたこと以外は、参考例1と同様にして硬化処理を行った。得られた硬化成型体の各々について、実施例1-1と同様に評価した。結果を表7に示す。
(第1工程)
SUS304(日本テストパネル社製、表面800番仕上げ)の金属板を2枚用いて、1mm間隔のギャップを形成し、比較製造例3で得た比較樹脂組成物(3)について注型成型を行った。140℃の金型で1時間硬化して、脱型した。
(第2工程)
第1工程での硬化後、実施例1-1と同様にして硬化の処理を行い、得られた硬化成型体について、実施例1-1と同様に評価した。結果を表7に示す。
第2工程の硬化条件を、350℃10分(室温より昇温15℃/min)としたこと以外は、比較例3-1と同様にして硬化処理を行った。得られた硬化成型体について、実施例1-1と同様に評価した。結果を表7に示す。
第2工程を行わなかったこと以外は、比較例3-1と同様にして硬化処理(第1工程のみの硬化処理)を行った。得られた硬化物について、実施例1-1と同様に評価した。結果を表7に示す。
製造例1で得た樹脂組成物(1)について、250℃で硬化処理を行ったところ、蒸気が発生し、発泡して硬化体に多量の泡が生じた。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を9g、アロンオキセタンOXT221(東亜合成社製、オキセタン樹脂)を21g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセルキオキサン)を70g、ステアリン酸を0.5g添加し80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.2gとプロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.5gの混合物を添加し、減圧下で均一になるまで混合した。
セロキサイド3000(ダイセル化学工業社製、脂環式エポキシ樹脂)を9g、アロンオキセタンOXT221(東亜合成社製、オキセタン樹脂)を21g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセルキオキサン)を70g、ステアリン酸を0.5g添加し80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.2gとプロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.5gの混合物を添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を15g、アロンオキセタンOXT221(東亜合成社製、オキセタン樹脂)を15g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセルキオキサン)を70g、ステアリン酸を0.5g添加し80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.2gとプロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.5gの混合物を添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を21g、アロンオキセタンOXT221(東亜合成社製、オキセタン樹脂)を9g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセルキオキサン)を70g、ステアリン酸を0.5g添加し80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.2gとプロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.5gの混合物を添加し、減圧下で均一になるまで混合した。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を10g、セロキサイド2081(ダイセル化学工業社製、脂環式エポキシ樹脂)を10g、アロンオキセタンOXT221(東亜合成社製、オキセタン樹脂)を10g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセルキオキサン)を70g、ステアリン酸を0.5g添加し80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.2gとプロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.5gの混合物を添加し、減圧下で均一になるまで混合した。
セロキサイド3000(ダイセル化学工業社製、脂環式エポキシ樹脂)を6g、アロンオキセタンOXT221(東亜合成社製、オキセタン樹脂)を24g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセルキオキサン)を70g、ステアリン酸を0.5g添加し80℃にて均一になるまで混合した。40℃に冷却後、SI-60L(三新化学工業工業社製)を0.2gとプロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.5gの混合物を添加し、減圧下で均一になるまで混合した。
製造例13~18で得られた樹脂組成物(13)~(18)について、実施例1-5と同様に硬化処理を行った。得られた硬化成型体の各々について、透過率及び表面硬度を実施例1-1と同様の評価方法により、吸水率、耐湿熱性を下記の方法により評価した。結果を表8に示す。なお、対照として実施例1-5における評価結果も示した。
50℃の熱風乾燥器に約2gの硬化体を入れ、24時間乾燥させた後、重量を測った。25℃の純水200g中に24時間浸漬させた後、表面の水分を拭き取り、重量を測定した。増加した重量より吸水率を算出した。
<耐湿熱性>
硬化体を恒温恒湿器中(エスペック社製、環境試験器SH-221、試験条件:85℃85%RH)に500時間保持し、湿熱試験を行った。湿熱試験後の波長400nmにおける硬化体の透過率を測定し、湿熱試験による透過率(400nm)の低下率を算出した。
製造例1で得られた樹脂組成物(1)に、表9に示すように樹脂組成物の重量に対して0.1~0.5%の種々の添加剤を加え、実施例1-5と同様に硬化処理を行った。得られた硬化成型体の各々について、透過率及び表面硬度を実施例1-1と同様の評価方法により、耐湿熱性を上記の評価方法により評価した。結果を表9に示す。なお、対照として実施例1-5における評価結果も示した。
還流用の冷却管、及び、内温測定用の温度計を有する500mLセパラブルフラスコ中に、メチルトリメトキシシラン(東レ・ダウコーニング社製、Z-6366)300gを投入し、内温25℃で撹拌した。内温を25℃に維持しながら、ギ酸30.46gを投入し10分間撹拌した。更に内温を25℃に維持しながら、水60.75gを添加して10分間撹拌した。その後、昇温して内温50℃にて1時間撹拌した。その後、セパラブルフラスコから還流用の冷却管を取り外し、常圧留去を行うため、先に溶媒トラップを有する温度計付きのト字管をセパラブルフラスコに取り付け、メチルイソブチルケトン30gを投入し、90℃のオイルバスを用いて、撹拌しながら反応系内を昇温した。ト字管の温度計(留出物温度)が66℃となった後、内温が79℃、留出物量が195gとなった時点で留去を停止する為にオイルバスを外し、水浴にて降温した。内温50℃にて、脂環式エポキシ樹脂(ダイセル化学工業社製、CELL-2021P)63.25gを投入し、撹拌しながら、50℃、10kPaにて溶媒を30分間減圧留去した。その後、撹拌しながら、50℃、1kPaにて溶媒を30分間減圧留去した。更に、昇温して撹拌しながら、80℃、1kPaにて溶媒を30分間減圧留去した。ステアリン酸1.05gを加えて、80℃、1kPaにて溶媒を15分間減圧下で撹拌した。減圧下で撹拌しながら、降温して40℃にてプロピレングリコールモノメチルエーテルアセテート1.05g、熱潜在性カチオン重合開始剤(三新化学工業工業社製、SI-60L)0.42gを投入し、30分減圧下で撹拌し、229.8gの樹脂組成物(19)を得た。無機成分(メタロキサン成分)を含む物質の重量平均分子量11000、有機成分(有機樹脂成分)の分子量100であった。
還流用の冷却管、及び、内温測定用の温度計を有する500mLセパラブルフラスコ中に、メチルトリメトキシシラン(東レ・ダウコーニング社製、Z-6366)25g、フェニルトリメトキシシラン(信越化学工業社製、KBM-103)36.5gを投入し、内温25℃で撹拌した。10分撹拌して均一であることを確認した後に、内温を25℃に維持しながら、ギ酸5.08gを投入し10分間撹拌した。更に内温を25℃に維持しながら、水13.25gを添加して10分間撹拌した。その後、昇温して内温50℃にて1時間撹拌した。その後、セパラブルフラスコから還流用の冷却管を取り外し、常圧留去を行うため、先に溶媒トラップを有する温度計付きのト字管をセパラブルフラスコに取り付け、メチルイソブチルケトン6gを投入し、90℃のオイルバスを用いて、撹拌しながら反応系内を昇温した。ト字管の温度計(留出物温度)が67℃となった後、内温が88℃、ト字管の温度計が60℃にまで下がったところで留去を停止する為にオイルバスを外し、水浴にて降温した。内温50℃にて、脂環式エポキシ樹脂(ダイセル化学工業社製、CELL-2021P)15.5gを投入し、撹拌しながら、50℃、10kPaにて溶媒を20分間減圧留去した。その後、撹拌しながら、50℃、1kPaにて溶媒を20分間減圧留去した。更に、昇温して撹拌しながら、80℃、1kPaにて溶媒を20分間減圧留去した。ステアリン酸0.26gを加えて、80℃、1kPaにて溶媒を10分間減圧下で撹拌した。減圧下で撹拌しながら、降温して40℃にてプロピレングリコールモノメチルエーテルアセテート0.26g、熱潜在性カチオン重合開始剤(三新化学工業社製、SI-60L)0.103gを投入し、30分減圧下で撹拌し、54.5gの樹脂組成物(20)を得た。無機成分を含む物質の重量平均分子量1700、有機成分の重量平均分子量100であった。
還流用の冷却管、及び、内温測定用の温度計を有する500mLセパラブルフラスコ中に、メチルトリメトキシシラン(東レ・ダウコーニング社製、Z-6366)13g、フェニルトリメトキシシラン(信越化学工業社製、KBM-103)37.9g、テトラエトキシシラン(東レ・ダウコーニング社製、Z-6697)19.9gを投入し、内温25℃で撹拌した。10分撹拌して均一であることを確認した後に、内温を25℃に維持しながら、ギ酸5.28gを投入し10分間撹拌した。更に内温を25℃に維持しながら、水11.7gを添加して10分間撹拌した。その後、昇温して内温50℃にて1時間撹拌した。その後、セパラブルフラスコから還流用の冷却管を取り外し、常圧留去を行うため、先に溶媒トラップを有する温度計付きのト字管をセパラブルフラスコに取り付け、メチルイソブチルケトン7gを投入し、90℃のオイルバスを用いて、撹拌しながら反応系内を昇温した。ト字管の温度計(留出物温度)が69℃となった後、内温が87℃、ト字管の温度計が55℃にまで下がったところで留去を停止する為にオイルバスを外し、水浴にて降温した。内温50℃にて、脂環式エポキシ樹脂(ダイセル化学工業社製、CELL-2021P)15.8gを投入し、撹拌しながら、50℃、10kPaにて溶媒を20分間減圧留去した。その後、撹拌しながら、50℃、1kPaにて溶媒を20分間減圧留去した。更に、昇温して撹拌しながら、80℃、1kPaにて溶媒を20分間減圧留去した。ステアリン酸0.26gを加えて、80℃、1kPaにて溶媒を10分間減圧下で撹拌した。減圧下で撹拌しながら、降温して40℃にてプロピレングリコールモノメチルエーテルアセテート0.26g、熱潜在性カチオン重合開始剤(三新化学工業工業社製、SI-60L)0.106gを投入し、30分減圧下で撹拌し、57.2gの樹脂組成物(21)を得た。
還流用の冷却管、及び、内温測定用の温度計を有する500mLセパラブルフラスコ中に、メチルトリメトキシシラン(東レ・ダウコーニング社製、Z-6366)13g、フェニルトリメトキシシラン(信越化学工業社製、KBM-103)37.9g、ジメチルジメトキシシラン(東レ・ダウコーニング社製、Z-6329)11.5gを投入し、内温25℃で撹拌した。10分撹拌して均一であることを確認した後に、内温を25℃に維持しながら、ギ酸5.28gを投入し10分間撹拌した。更に内温を25℃に維持しながら、水10.3gを添加して10分間撹拌した。その後、昇温して内温50℃にて1時間撹拌した。その後、セパラブルフラスコから還流用の冷却管を取り外し、常圧留去を行うため、先に溶媒トラップを有する温度計付きのト字管をセパラブルフラスコに取り付け、メチルイソブチルケトン7gを投入し、90℃のオイルバスを用いて、撹拌しながら反応系内を昇温した。ト字管の温度計(留出物温度)が65℃となった後、ト字管の温度計が58℃にまで下がったところで留去を停止する為にオイルバスを外し、水浴にて降温した。内温50℃にて、脂環式エポキシ樹脂(ダイセル化学工業社製、CELL-2021P)16.4gを投入し、撹拌しながら、50℃、10kPaにて溶媒を20分間減圧留去した。その後、撹拌しながら、50℃、1kPaにて溶媒を20分間減圧留去した。更に、昇温して撹拌しながら、80℃、1kPaにて溶媒を20分間減圧留去した。ステアリン酸0.26gを加えて、80℃、1kPaにて溶媒を10分間減圧下で撹拌した。減圧下で撹拌しながら、降温して40℃にてプロピレングリコールモノメチルエーテルアセテート0.26g、熱潜在性カチオン重合開始剤(三新化学工業工業社製、SI-60L)0.105gを投入し、30分減圧下で撹拌し、57.3gの樹脂組成物(22)を得た。
還流用の冷却管、及び、内温測定用の温度計を有する500mLセパラブルフラスコ中に、メチルトリメトキシシラン(東レ・ダウコーニング社製、Z-6366)15g、フェニルトリメトキシシラン(信越化学工業社製、KBM-103)43.7g、2-(3,4-エポキシシクロヘキシル)エチルトエリメトキシシラン(信越化学工業社製、KBM-303)27.2gを投入し、内温25℃で撹拌した。10分撹拌して均一であることを確認した後に、内温を25℃に維持しながら、ギ酸6.1gを投入し10分間撹拌した。更に内温を25℃に維持しながら、水11.4gを添加して10分間撹拌した。その後、昇温して内温50℃にて1時間撹拌した。その後、セパラブルフラスコから還流用の冷却管を取り外し、常圧留去を行うため、先に溶媒トラップを有する温度計付きのト字管をセパラブルフラスコに取り付け、メチルイソブチルケトン7gを投入し、90℃のオイルバスを用いて、撹拌しながら反応系内を昇温した。ト字管の温度計(留出物温度)が65℃となった後、内温90℃、ト字管の温度計が58℃にまで下がったところで留去を停止する為にオイルバスを外し、水浴にて降温した。内温50℃にて、脂環式エポキシ樹脂(ダイセル化学工業社製、CELL-2021P)23.6gを投入し、撹拌しながら、50℃、10kPaにて溶媒を30分間減圧留去した。その後、撹拌しながら、50℃、1kPaにて溶媒を30分間減圧留去した。更に、昇温して撹拌しながら、80℃、1kPaにて溶媒を30分間減圧留去した。ステアリン酸0.39gを加えて、80℃、1kPaにて溶媒を10分間減圧下で撹拌した。減圧下で撹拌しながら、降温して40℃にてプロピレングリコールモノメチルエーテルアセテート0.39g、熱潜在性カチオン重合開始剤(三新化学工業工業社製、SI-60L)0.16gを投入し、30分減圧下で撹拌し、88.1gの樹脂組成物(23)を得た。
セロキサイド2021P(ダイセル化学工業社製、脂環式エポキシ樹脂)を3.6g、PMSQ-E(SR-13)(小西化学工業社製、ポリメチルシルセスキオキサン)を8.4g、ステアリン酸を0.06g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.06g添加し、80℃にて均一になるまで混合した。40℃に冷却後、CPI-101A(サンアプロ社製、光カチオン重合触媒)を0.024g添加し、減圧下で均一になるまで混合した。
DPE-6A(ライトアクリレート社製、ジペンタエリシリトールのヘキサアクリレート)を0.46g、SR-502(サートマー社製、TMS-9EO付加トリアクリレート)を1.84g、ADMA(大阪有機化学工業社製、1-アダマンチルメタクリレート)を2.3g、PMPSQ-E(SR-3321)(小西化学工業社製、ポリメチルフェニルシルセスキオキサン)を10.73g、ステアリン酸を0.074g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.074g添加し、80℃にて均一になるまで混合した。40℃に冷却後、パーロイルL(日本油脂(現日油)社製、開始剤)を0.148g添加し、減圧下で均一になるまで混合した。
DPE-6A(ライトアクリレート社製、ジペンタエリシリトールのヘキサアクリレート)を0.563g、SR-502(サートマー社製、TMS-9EO付加トリアクリレート)を2.252g、ADMA(大阪有機化学工業社製、1-アダマンチルメタクリレート)を2.815g、PMPSQ-E(SR-3321)(小西化学工業社製、ポリメチルフェニルシルセスキオキサン)を13.14g、ステアリン酸を0.094g、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を0.094g添加し、80℃にて均一になるまで混合した。40℃に冷却後、Irgacure 184(チバ・ジャパン社製、開始剤)を0.188g添加し、減圧下で均一になるまで混合した。
水添ビスフェノールA(ジャパンエポキシレジン社製、エピコート YX-8000、エポキシ当量205、液状水添エポキシ樹脂)168gとオルガノシリカゾル(日産化学工業社製、MEK-ST、粒子径10~15nm、固形分30%)240gを均一になるように混合し、80℃でエバポレーターを用いて溶媒の減圧留去を行った。収量249.7g、粘度40Pa・sであった。その樹脂組成物を30g、水添ビスフェノール(ジャパンエポキシレジン社製、YX-8040、エポキシ当量1000、固形水添エポキシ樹脂)を9g、YX-8000を25gそれぞれ秤量し、80℃で均一になるように混合した。その後、離型剤としてステアリン酸を全重量に対して0.5wt%となるように、80℃で均一混合した。50℃に冷却後、カチオン系重合開始剤(三新化学工業工業社製、サンエイドSI-60L、固形分50%)を全重量に対して1wt%(固形分換算0.5wt%)となるように添加し均一になるように混合した。
製造例11、19~23及び製造例25で得られた樹脂組成物(11)、(19)~(23)及び樹脂組成物(25)について、実施例1-5と同様に硬化処理を行った(実施例11-3、26~30及び32)。製造例24、26及び比較製造例4で得られた樹脂組成物(24)、(26)及び比較樹脂組成物(4)については、以下の方法により硬化処理を行った(実施例31、33及び比較例5)。
(樹脂組成物(24)の硬化方法)
第1工程においては、次のように紫外線硬化処理を行った。シリコーンゴムの枠を利用して、SUS304(日本テストパネル社製、表面800番仕上げ)上に厚さ1mmとなるように樹脂組成物を配置し、超高圧水銀ランプを有するUV照射機(アイグラフィックス株式会社製)を用いて、照射積算光量1J/cm2で紫外線硬化させた。第2工程においては、330℃1時間(室温より昇温15℃/min)の条件で硬化処理を行った。
(樹脂組成物(26)の硬化方法)
第1工程においては、次のように紫外線硬化処理を行った。1mm厚のシリコーンシートをギャップとして利用して、2枚の石英ガラスの間に1mm厚となるように樹脂組成物を配置して、一方の石英ガラス面より、超高圧水銀ランプを有するUV照射機(アイグラフィックス株式会社製)を用いて、照射積算光量2J/cm2で紫外線硬化させた。第2工程においては、330℃1時間(室温より昇温15℃/min)の条件で硬化処理を行った。
(比較樹脂組成物(4)の硬化方法)
第2工程の硬化条件を230℃1時間(室温より昇温15℃/min)とした以外は実施例1-5と同様に硬化処理を行った。
比較例1~3は、縮合可能な基を有するポリシロキサン化合物を含まない比較樹脂組成物(1)~(3)を各々用いて硬化処理を行った例であるが、これらと実施例1~12とを比較すると、比較例1~3で得た硬化成型体は、実施例1~12に比較して透過率が低く、また耐熱性の指標となる耐UV試験後の透過率も著しく劣る結果となった。また、参考例1~12と実施例1~12との各々を比較すると、殆どの例において、各実施例に対し、第1工程の硬化処理しか行っていない参考例で得た硬化成型体の方が、鉛筆硬度が低く、表面硬度、すなわち耐磨耗性が充分とはならないことが分かる。更に、比較例4の結果から、第1工程を経ず、第2工程の硬化処理のみを行うと、多量の泡が生じ、製品として使用できるレベルの硬化物を得ることができないことが分かる。なお、この泡は、ポリシロキサン化合物の縮合反応により副生する水分やアルコール等の気化に起因するものと考えられる。
したがって、縮合可能な基を有するポリシロキサン化合物、開環重合性基を有する化合物及び硬化剤を含む硬化性樹脂組成物を、第1工程及び第2工程の少なくとも2段階の硬化処理に供することによって初めて、耐熱性、耐磨耗性(高表面硬度)及び透明性等の各種物性に優れ、かつ低収縮率のために優れた外観を呈する硬化成型体を効率的に得ることができることが分かった。
これらの樹脂組成物を用い、第1工程及び第2工程(350℃×10分)の硬化処理を行った例(実施例7-2、6-2、8-2、1-6、2-4、3-4、4-2、5-2、比較例1-2)の結果から、ポリシロキサン化合物の含有量を、ポリシロキサン化合物と開環重合性基を有する化合物との総量100質量%に対し、5~95質量%とすることで、表面硬度及び透明性の両方を共に更に高めることができることが分かった。
Claims (17)
- 縮合性無機化合物、硬化性有機化合物、及び、硬化剤を含む硬化性樹脂組成物から硬化成型体を製造する方法であって、
該製造方法は、該硬化性樹脂組成物を80~200℃で熱硬化させる工程及び/又は活性エネルギー線照射により硬化させる工程からなる第1工程と、該第1工程で得た硬化物を200℃を超え、500℃以下で熱硬化させる第2工程とを含むことを特徴とする硬化成型体の製造方法。 - 縮合可能な基を有するポリシロキサン化合物、開環重合性基を有する化合物、及び、硬化剤を含む硬化性樹脂組成物から硬化成型体を製造する方法であって、
該製造方法は、該硬化性樹脂組成物を80~200℃で熱硬化させる工程及び/又は活性エネルギー線照射により硬化させる工程からなる第1工程と、該第1工程で得た硬化物を200℃を超え、500℃以下で熱硬化させる第2工程とを含むことを特徴とする硬化成型体の製造方法。 - 前記縮合可能な基を有するポリシロキサン化合物の含有量は、前記縮合可能な基を有するポリシロキサン化合物と開環重合性基を有する化合物との総量100質量%に対し、5~95質量%であることを特徴とする請求項1又は2に記載の硬化成型体の製造方法。
- 前記開環重合性基を有する化合物は、多官能化合物であり、開環重合性基は、エポキシ基及び/又はオキセタン環であることを特徴とする請求項1~3のいずれかに記載の硬化成型体の製造方法。
- 前記第1工程は、金型を用いた硬化工程であることを特徴とする請求項1~4のいずれかに記載の硬化成型体の製造方法。
- 前記製造方法は、前記第1工程と第2工程との間に、更に脱型工程を含むことを特徴とする請求項5に記載の硬化成型体の製造方法。
- 前記活性エネルギー線照射による硬化工程は、波長180~500nmの紫外線又は可視光線を照射して硬化させる光硬化工程であることを特徴とする請求項1~6のいずれかに記載の硬化成型体の製造方法。
- 前記縮合可能な基は、Si-O-R基(Rは、炭化水素基を表す。)、Si-OH基、Si-X基(Xは、ハロゲン原子を表す。)、及び、Si-H基からなる群より選択される少なくとも1種の基であることを特徴とする請求項1~7のいずれかに記載の硬化成型体の製造方法。
- 請求項1~8のいずれかの製造方法で得られることを特徴とする硬化成型体。
- メタロキサン成分と有機樹脂成分とを含む硬化成型体であって、
該メタロキサン成分を構成する金属元素は、硬化成型体の総量100質量%に対して10質量%以上であり、
該メタロキサン成分を構成する金属元素のうち、炭化水素基との結合数がn-1又はn-2(nは、金属元素の原子価であり、2以上の整数を表す。)である金属元素の含有量は、メタロキサン成分を構成する金属元素の総量100原子%に対して50原子%以下であり、
該メタロキサン成分を構成する金属元素のうち、Y-M(Mは金属元素を表す。Yは水素原子、ハロゲン原子、水酸基及びRO基(Rは炭化水素基を表す。)からなる群より選択される少なくとも1種を表す。)で表される結合を有する金属元素の含有量は、メタロキサン成分を構成する金属元素の総量100原子%に対して35原子%以下であり、
該メタロキサン成分中、粒子状を呈する成分の含有量は、メタロキサン成分の総量100質量%に対して50質量%以下である
ことを特徴とする硬化成型体。 - 前記有機樹脂成分の含有量は、硬化成型体の総量100質量%に対して0.1~60質量%であることを特徴とする請求項10に記載の硬化成型体。
- 前記硬化成型体は、500nmにおける平行線透過率が80%以上であることを特徴とする請求項10又は11に記載の硬化成型体。
- 前記硬化成型体は、カルボン酸系構造及び/又はエーテル骨格を含むことを特徴とする請求項10~12のいずれかに記載の硬化成型体。
- 前記硬化成型体は、縮合性無機化合物、硬化性有機化合物、及び、硬化剤を含む硬化性樹脂組成物を硬化して得られるものであることを特徴とする請求項10~13のいずれかに記載の硬化成型体。
- 前記硬化成型体は、光学用硬化成型体であることを特徴とする請求項9~14のいずれかに記載の硬化成型体。
- 前記硬化成型体は、レンズ用硬化成型体であることを特徴とする請求項9~15のいずれかに記載の硬化成型体。
- 前記硬化成型体は、透過性シートであることを特徴とする請求項9~16のいずれかに記載の硬化成型体。
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