Method for manufacturing a cured film, method for manufacturing a polymer optical waveguide, and method for manufacturing an optical component.

Abstract

In manufacturing optical waveguides and display components using a polymer-containing curable composition having reactive functional groups, the present invention provides a manufacturing method that prevents low-molecular-weight components such as oligomers that volatilize during the exposure process from adhering to and contaminating the reflective mirror, lens, or high-voltage generator of the exposure machine, thereby maintaining the functionality of the exposure machine. [Solution] A method for manufacturing a cured film, comprising: a coating step of coating a polymer-containing photocurable composition having reactive functional groups onto a substrate; a reduced-pressure heating step of heating the photocurable composition coated on the substrate under reduced pressure to obtain a film of the photocurable composition; and an exposure step of exposing the film of the photocurable composition to light.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a cured film, a method for manufacturing a polymer optical waveguide, and a method for manufacturing an optical component. [Background technology]

[0002] In recent years, there has been a growing demand for faster, higher-capacity, and lower-power communication and signal transmission. In equipment wiring, technologies that use light for signal transmission instead of conventional electricity are attracting attention. Such short-distance optical communication technologies are called optical interconnects, and their components include replacing some of the copper electrical wiring on printed circuit boards with optical wiring using optical fibers or optical waveguides. The development of such optical-electrical composite substrates is thriving, and for example, optical waveguides that can connect to near-infrared single-mode silica-based optical fibers are required, particularly in data center equipment. Potential materials for fabricating these optical waveguides include, for example, organopolysiloxanes with reactive groups, epoxy resins, and phenolic resins.

[0003] For example, Patent Document 1 discloses the manufacture of an optical waveguide in which an organopolysiloxane composition having polymerizable alkenyl groups as reactive groups is applied to a substrate by spin coating, then pattern-exposed using light irradiation with an exposure machine, and the unexposed areas are dissolved with an organic solvent to obtain a linear cured product which serves as the core, the lower cladding layer being a silicon thermal oxide film, and the upper and side cladding layers being air. Patent Document 2 discloses a resin sheet with a support having a resin composition layer formed of a resin composition containing an epoxy resin and a photopolymerizable resin containing carboxyl groups, and an optical waveguide formed using the resin sheet. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2014-510159 [Patent Document 2] Japanese Patent Publication No. 2024-001786 [Patent Document 3] Japanese Patent Publication No. 2017-105930 [Patent Document 4] Japanese Patent Publication No. 2009-185254 [Overview of the project] [Problems that the invention aims to solve]

[0005] Organopolysiloxanes are produced through equilibrium reactions of siloxane oligomers with acids and alkalis, and regardless of the degree of polymerization, a considerable amount of cyclic or linear siloxanes with a degree of polymerization (i.e., the number of silicon atoms in one molecule) of 10 or less, known as low-molecular-weight siloxanes, are always present. These low-molecular-weight siloxanes volatilize even at room temperature, not just in high-temperature atmospheres, and adhere to the surroundings, causing a wide variety of problems such as clouding and turbidity, contact failure, adhesion inhibition, and surface hydrophobicity.

[0006] As described above, polymerizable organopolysiloxane-containing compositions used as materials for optical waveguides and display components often suffer from problems such as low-molecular-weight siloxanes volatilizing during the exposure process adhering to and contaminating the surfaces of the exposure machine's reflective mirror, lens, or high-voltage generator. This can lead to a decrease in the reflectivity of the mirror and the light transmittance of the lens, as well as spark reduction in the high-voltage generator, frequently impairing the function of the exposure machine. A decrease in the function of the exposure machine leads to a deterioration in resolution, negatively impacts the waveguide, and reduces yield, which is economically undesirable. Furthermore, photosensitive resin-containing compositions, such as epoxy resins and phenolic resin-containing compositions, used in the fabrication of optical waveguides also contain low-molecular-weight components that volatilize during the exposure process, which may lead to the same problems as those associated with the polymerizable organopolysiloxane-containing compositions.

[0007] It is known that low-molecular-weight siloxanes in organopolysiloxanes can be removed by volatilizing them under reduced pressure and high temperature, and various proposals have been made for this purpose.

[0008] For example, Patent Document 3 describes a method in which polymerizable organopolysiloxane is placed in a vacuum-reducing container, the system is vacuum-reduced using a vacuum pump, and distillation is performed at a predetermined temperature for a certain period of time. However, when polymerizable organopolysiloxane or a polymerizable organopolysiloxane-containing composition is purified using this prior art method, there is a problem that it usually takes a long time to reduce the amount of low molecular weight siloxane to below the desired level. As a result, a large amount of energy is required, the distillation load is large, and there is also a large loss of organopolysiloxane. Furthermore, prolonged vacuum distillation may lead to oxidation, decomposition, or deterioration of the polymerizable organopolysiloxane or various additives in the composition, potentially resulting in a decrease in quality, making it impractical. There is a patent document (Patent Document 4) describing the purification of polymerizable organopolysiloxanes by thin-film distillation. However, purifying polymerizable organopolysiloxanes and polymerizable organopolysiloxane-containing compositions using this prior art method may lead to oxidation, decomposition, or alteration of the polymerizable organopolysiloxanes and various additives in the composition, potentially resulting in a decrease in quality. Furthermore, there are concerns about yield due to pipe clogging and other issues, making it impractical.

[0009] Thus, purifying photosensitive resins and photosensitive resin compositions, such as polymerizable organopolysiloxanes and polymerizable organopolysiloxane-containing compositions, using prior art and methods conceivable from prior art is extremely difficult from the standpoint of maintaining the desired quality while preventing various types of damage to the exposure equipment.

[0010] In response to the problems described above, the present invention relates to a manufacturing method for optical waveguides and display components using a polymer-containing curable composition having reactive functional groups, in which low-molecular-weight components such as oligomers that volatilize during the exposure process do not adhere to and contaminate the reflective mirror, lens, or high-voltage generator of the exposure machine, and the function of the exposure machine can be maintained. [Means for solving the problem]

[0011] As a result of intensive studies to solve such problems, the present inventors have found that by providing a reduced-pressure heating step of subjecting a coating film of a polymer-containing curable composition having a reactive functional group to reduced-pressure heat treatment between the coating step and the exposure step, the problems of the present application can be solved. The present invention has been completed based on such findings. That is, the present invention relates to the following.

[0012] (1) A coating step of applying a polymer-containing photocurable composition having a reactive functional group onto a substrate, A reduced-pressure heating step of heating the photocurable composition applied onto the substrate under reduced-pressure conditions to obtain a film of the photocurable composition, An exposure step of exposing the film of the photocurable composition, A method for producing a cured film, comprising the above steps. (2) The method for producing a cured film according to item (1) above, wherein the polymer having a reactive functional group is an organopolysiloxane having a reactive functional group. (3) The method for producing a cured film according to item (2) above, wherein the organopolysiloxane having a reactive functional group is represented by the following [1]. (R 1 R 2 R 3 SiO 1 / 2 ) M1 (R 4 R 5 R 6 SiO 1 / 2 ) M2 (R 7 R 8 SiO 2 / 2 ) D1 (R 9 R 6 SiO 2 / 2 ) D2 (R 10 SiO 3 / 2 ) T1 (R 6 SiO 3 / 2 ) T2 (SiO 4 / 2 ) Q (O 1 / 2 R 11 )Y1 (O 1 / 2 R 6 ) Y2 ···[1] [In formula [1], R 1 ~R 5 , R 7 ~R 11 Each of these is independently one or more groups selected from the group consisting of organic groups and hydrogen atoms. R 1 ~R 3 , R 7 , R 8 , R 10 and R 11 It does not contain reactive functional groups. R 6 This refers to one or more organic groups containing reactive functional groups, and if there are multiple such groups, they may be identical or different from each other. 0≦M1, 0≦D1, 0≦T1, 0≦Y1, 0≦Y2, 0≦Q 0 <M2+D2+T2、 0 <D1+D2+T1+T2+Q M1 + M2 + D1 + D2 + T1 + T2 + Q = 1. A method for manufacturing a cured film according to any one of the above items (1) to (3), further comprising: (4) a curing step of heating the exposed film to obtain a cured film. (5) The exposure step is a step of partially exposing the film of the photocurable composition, A developing step in which the unexposed areas of the partially exposed film are removed with a solvent to obtain a patterned resin film, A method for producing a cured film according to any one of the above items (1) to (4), further comprising a curing step of heating the patterned resin film to obtain a cured film.

[0013] (6) A method for manufacturing a cured film according to any one of the above items (1) to (5), wherein the cured film is manufactured to have a thickness of 100 μm or less. (7) A method for producing a cured film according to any one of items (1) to (6) above, wherein in the reduced pressure heating step, the photocurable composition on the substrate is heated under reduced pressure of 150 Pa or less at a temperature of 50°C or more and 150°C or less. (8) A method for producing a polymer optical waveguide, which is formed using a cured film obtained by any one of the manufacturing methods described in item (1) to (7) above. (9) A method for manufacturing an optical component, which is formed using a cured film obtained by the manufacturing method described in any one of the above items (1) to (7). [Effects of the Invention]

[0014] According to the present invention, when manufacturing optical waveguides and display components using a polymer-containing curable composition having reactive functional groups, it is possible to suppress contamination of the reflective mirror, lens, or high-voltage generator of an exposure machine, and to provide a manufacturing method that maintains the functionality of the exposure machine. [Brief explanation of the drawing]

[0015] [Figure 1] Figure 1 is a simplified diagram of the fabrication of a TOF-SIMS evaluation substrate as described in the example. [Modes for carrying out the invention]

[0016] In this specification, "(meth)acrylic" means "either acrylic or methacrylic, or both." In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0017] The present invention will be described in detail below. While embodiments of the present invention (hereinafter sometimes referred to as "embodiments") will be described in detail, the following description is merely an example of an embodiment of the present invention, and the present invention is not limited to these embodiments.

[0018] The method for producing a cured film according to this embodiment is characterized by comprising: a coating step of coating a polymer-containing photocurable composition having a reactive functional group onto a substrate; a reduced-pressure heating step of heating the photocurable composition coated on the substrate under reduced pressure to obtain a film of the photocurable composition; and an exposure step of exposing the film of the photocurable composition to light.

[0019] [Coating process] In the coating process, a photocurable composition containing a polymer having a reactive functional group, as described later, is coated onto the substrate. As substrates, silicon wafers, silicon wafers with oxide films, polyimide resins, epoxy resins, PEEK resins, liquid crystal polymers, glass, glass epoxy substrates, etc., can be used.

[0020] The above substrate may be subjected to surface treatments such as corona discharge treatment, ozone treatment, or silane coupling agent, as needed.

[0021] There are no particular restrictions on the application method, but known methods include the dip coating method, air knife coating method, curtain coating method, spin coating method, roller coating method, bar coating method, wire bar coating method, gravure coating method, and spray coating method.

[0022] The photocurable polymer-containing polymer having the above-mentioned reactive functional group (hereinafter sometimes simply referred to as "photocurable resin composition") can use various resin materials as the reactive functional group, including organic-inorganic hybrid materials such as organopolysiloxanes having polymerizable functional groups, as well as acrylic resins, methacrylic resins such as polymethyl methacrylate (PMMA), epoxy resins, oxetane resins, phenoxy resins, benzocyclobutene resins, norbornene resins, fluorine resins, silicone resins, phenolic resins, polyester resins, polycarbonate resins, polystyrene resins, polyamide resins, polyimide resins, poly(imide-isoindoquinazolindioneimide) resins, polyetherimide resins, polyetherketone resins, polyesterimide resins, polybenzoxazole resins, and polysilanes. Among these materials, organopolysiloxanes having reactive functional groups are suitable as core and cladding materials because they have high transparency in the near-infrared wavelength band and high heat resistance. Further details will be provided later.

[0023] [Reduced pressure heating process] In this embodiment, the method is characterized by having a reduced-pressure heating step in which the photocurable composition applied to the substrate is heated under reduced pressure before the exposure step to obtain a film of the photocurable composition.

[0024] In the subsequent exposure process, there was a problem where the exposure machine would become contaminated during manufacturing, resulting in reduced exposure or insufficient exposure of the photocurable composition, leading to a decrease in the shape accuracy of the cured film after exposure. Conventionally, to prevent contamination during exposure, vacuum drying was performed after applying the photocurable composition, but the inventors noticed that this process was also insufficient.

[0025] The contamination of the exposure machine is thought to be caused by low molecular weight components (volatile components) contained in the polymer resin composition. For example, the organopolysiloxane, which is suitably used as a polymer having reactive functional groups in this embodiment, is a siloxane containing volatile components. Normally, unlike thermal curing, the exposure process in photocuring cures the material under conditions where not much heat is applied, so it was unlikely that the volatile components contained in the polymer would lead to contamination with the energy of exposure. Furthermore, in the case of manufacturing a cured film by photocuring, if heat treatment is applied before exposure, there is a risk that the photopolymerization initiator contained in the photocurable composition may react, depending on the degree of heat treatment. However, after diligent research, the inventors have found that by adding a reduced-pressure heating step before the exposure step, contamination of the exposure machine's reflective mirror, lens, or high-voltage generator can be suppressed, and the function of the exposure machine can be maintained. Low molecular weight components that become contaminants are often difficult to remove under normal pressure, and if heat is applied to remove the contaminants at high temperatures, problems arise such as thermal cleavage and hardening of components constituting the photocurable composition, such as the photopolymerization initiator. In this embodiment, by providing the reduced-pressure heating step before the exposure step, it is possible to significantly remove the low molecular weight components that are to be removed while suppressing the deterioration of the photocurable composition.

[0026] The pressure conditions for the reduced-pressure heating process are preferably 150 Pa or less, more preferably 130 Pa or less, and even more preferably 100 Pa or less. The lower limit is not limited as long as it does not impair the effects of this embodiment, but for example, it may be 0.05 Pa or more. Within this pressure range, along with the temperature conditions, low molecular weight components can be sufficiently removed without adversely affecting the components contained in the photocurable composition.

[0027] The temperature conditions for the reduced-pressure heating process are preferably 50°C to 150°C. Within this temperature range, low molecular weight components can be sufficiently removed without adversely affecting the components contained in the photocurable composition. The temperature is preferably 60°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 100°C or lower.

[0028] The duration of the reduced-pressure heating step is not limited as long as it is sufficient to perform the main process. For example, it is preferably 1 minute or more and 60 minutes or less. The duration of the reduced-pressure heating step is preferably 2 minutes or more, preferably 50 minutes or less, more preferably 40 minutes or less, and even more preferably 30 minutes or less.

[0029] When a photocurable composition contains an organopolysiloxane having a reactive functional group, the low molecular weight components removed in the reduced-pressure heating step include, for example, highly volatile siloxane compounds such as cyclic siloxanes. By going through this reduced-pressure heating process, a film can be obtained in which low molecular weight components, such as highly volatile siloxane compounds, are reduced.

[0030] [Synthesis process] As described above, an exposure process is performed in which the film, which has undergone a reduced-pressure heating process to remove low molecular weight components, is irradiated (exposed) with active energy rays. Examples of light sources used for active energy rays include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, as well as laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. Examples of exposure machine methods include proximity methods, mirror projection methods, stepper methods, and direct laser writing methods. The exposure step may be a step of partially exposing a film of the photocurable composition by irradiating it with active energy light through a predetermined mask pattern. In this case, the exposed area hardens, the hardened area becomes insoluble or sparingly soluble in the developer, and a patterned resin film can be obtained.

[0031] [Development process] In the development process, the unexposed areas of the partially exposed film are removed with a solvent (developer) to obtain a patterned resin film. There are no restrictions on the solvent or method used in this process; any solvent that can dissolve the photocurable composition may be used, and the photocurable composition in the unexposed areas can be dissolved by any method such as dipping or spraying. In addition, the same process as development described above may be used to remove the uncured layer on the surface of the resin film. After removing the unexposed areas with the solvent, it is preferable to remove the solvent by air drying or heating. This process is preferably performed not only when the exposure method partially exposes the film of the photocurable composition, so-called pattern exposure, but also when the entire surface is exposed. This process can remove defective areas on the surface of the cured film.

[0032] [Curing process] This step involves heating the patterned resin film after the exposure step or development step to obtain a cured film. This curing step is preferably performed not only when the exposure is partial, so-called pattern exposure, of the photocurable composition film, but also when the entire film is exposed. Examples of the heating conditions include a temperature of 50°C to 200°C for several tens of seconds to 60 minutes, or a temperature of 80°C to 150°C for several tens of seconds to 60 minutes.

[0033] For design purposes as an optical waveguide, the thickness of the cured film obtained by the manufacturing method of this embodiment is preferably 100 μm or less.

[0034] The organopolysiloxanes that can be preferably used as polymers having the reactive functional groups in this embodiment will be described in detail below.

[0035] (Organopolysiloxane) The reactive functional groups of organopolysiloxanes do not react substantially during the preparation of the organopolysiloxane itself, but react when external energy is applied, causing crosslinking or chain extension between organopolysiloxane molecules and resulting in higher molecular weight. Examples of external energy include light, heat, and electron beams, and these may be used in combination. When using light (active energy rays) as the external energy, it is preferable to expose the organopolysiloxane and photopolymerization initiator together. Furthermore, by selectively irradiating only the desired area with active energy rays during the exposure process, only the exposed area can be crosslinked or have its molecular weight increased, while the unexposed area can be dissolved and removed in the developer. In addition, if necessary, further crosslinking or higher molecular weight can be achieved by applying external energy such as active energy rays or heat after exposure and development.

[0036] Specific examples of reactive functional groups include vinyl groups, allyl groups, allyloxy groups, methacryloyl(oxy) groups, acryloyl(oxy) groups, vinyloxy groups, ethynyl groups, cyano groups, oxetanyl groups, epoxy groups, and episulfide groups. Vinyl groups, methacryloyl(oxy) groups, acryloyl(oxy) groups, ethynyl groups, oxetanyl groups, and epoxy groups are preferred for their high reactivity and high crosslinking density, with methacryloyl(oxy) groups or acryloyl(oxy) groups being more preferred, and methacryloyl(oxy) groups being the most preferred. Note that methacryloyl(oxy) groups refer to either methacryloyl groups or methacryloyloxy groups. The same applies to acryloyl(oxy) groups. Furthermore, the above-mentioned reactive functional groups also include embodiments having halogen atoms such as fluorine atoms or other substituents.

[0037] <Organopolysiloxanes with reactive functional groups> In this embodiment, the organopolysiloxane (hereinafter sometimes simply referred to as "organopolysiloxane") is preferably represented by the following formula [1]. (R1 R 2 R 3 SiO 1 / 2 ) M1 (R 4 R 5 R 6 SiO 1 / 2 ) M2 (R 7 R 8 SiO 2 / 2 ) D1 (R 9 R 6 SiO 2 / 2 ) D2 (R 10 SiO 3 / 2 ) T1 (R 6 SiO 3 / 2 ) T2 (SiO 4 / 2 ) Q (O 1 / 2 R 11 ) Y1 (O 1 / 2 R 6 ) Y2 ···[1]

[0038] In the above formula [1], R 1 ~R 5 , R 7 ~R 11 Each of these is independently one or more groups selected from the group consisting of organic groups and hydrogen atoms. R 1 ~R 3 , R 7 , R 8 , R 10 and R 11 It does not contain reactive functional groups. R 6 This refers to one or more organic groups containing reactive functional groups, and if there are multiple such groups, they may be identical or different from each other. 0≦M1, 0≦D1, 0≦T1, 0≦Y1, 0≦Y2, 0≦Q 0 <M2+D2+T2、 0 <D1+D2+T1+T2+Q M1 + M2 + D1 + D2 + T1 + T2 + Q = 1.

[0039] In the general formula [1], the coefficients M1, M2, D1, D2, T1, T2, and Q represent the ratios of the respective structures (on a molar basis) when M1 + M2 + D1 + D2 + T1 + T2 + Q = 1. Further, in the general formula [1], the coefficients Y1 and Y2 represent the relative content ratios (on a molar basis) of (O 1 / 2 R 11 ) and (O 1 / 2 R 6 ).

[0040] In the general formula [1], the coefficients M1 and M2 represent the ratio of the so-called M-unit silicon (SiO 1 / 2 ), which has one oxygen atom bonded to the silicon atom (hereinafter sometimes simply referred to as "M-unit"). Similarly, D1 and D2 represent the ratio of the D-unit silicon (SiO 2 / 2 ), which has two oxygen atoms bonded to the silicon atom (hereinafter sometimes simply referred to as "D-unit"). T1 and T2 represent the ratio of the T-unit silicon (SiO 3 / 2 ), which has three oxygen atoms bonded to the silicon atom (hereinafter sometimes simply referred to as "T-unit"). Q represents the ratio of the Q-unit silicon (SiO 4 / 2 ), which has four oxygen atoms bonded to the silicon atom (hereinafter sometimes simply referred to as "Q-unit"). M2, D2, and T2 represent the ratios of the M-unit, D-unit, and T-unit, respectively, in which an organic group containing R 6 , that is, a reactive functional group, is bonded to the silicon atom. Y1 means the content ratio of a structure having a group selected from the group consisting of an organic group and a hydrogen atom that does not contain a reactive functional group, specifically an alkoxy group or a silanol group. Y2 means the content ratio of an organic group containing a reactive functional group bonded to silicon.

[0041] 0 ≦ M1, 0 ≦ D1, 0 ≦ T1, 0 ≦ Y1, 0 ≦ Y2, 0 ≦ Q means that M1, D1, T1, Y1, Y2, and Q are each 0 or more and may be 0, that is, the structural unit may not be present.

[0042] 0 < M2 + D2 + T2 means that the organopolysiloxane has at least one of the M units, D units, and T units to which an organic group containing a reactive functional group, i.e., R, is bonded. 6 That is, it means that the organopolysiloxane has at least one of the M units, D units, and T units to which an organic group containing a reactive functional group is bonded. 0 < D1 + D2 + T1 + T2 + Q means that the organopolysiloxane has at least one of the D units, T units, and Q units. M1 + M2 + D1 + D2 + T1 + T2 + Q = 1 means that the total ratio of the M units, D units, T units, and Q units is 1.

[0043] <M2 + D2 + T2> In the organopolysiloxane represented by formula [1], when 0 < M2 + D2 + T2, the organopolysiloxane contains a reactive functional group, and it becomes possible to easily obtain a cured film using a composition containing a polymerization initiator described later. If the content ratio of the reactive functional group is too small, curing defects may occur during the production of the cured film, and the compatibility with other components added to the organopolysiloxane-containing composition described later may deteriorate. From the above viewpoints, it is preferably 0.10 ≦ M2 + D2 + T2, and more preferably 0.12 ≦ M2 + D2 + T2. On the other hand, there is no particular limitation on the upper limit of M2 + D2 + T2. However, when the ratio of M2 + D2 + T2 is too large, the content of the reactive functional group increases, and the crosslinking density of the cured film becomes high, making it prone to brittleness. Therefore, it is preferably M2 + D2 + T2 ≦ 0.75, and more preferably M2 + D2 + T2 ≦ 0.60. As described above, it is preferably 0.10 ≦ M2 + D2 + T2 ≦ 0.75, and more preferably 0.12 ≦ M2 + D2 + T2 ≦ 0.60.

[0044] <Q unit> The Q unit is the most oxidized form of silicon. By being included in the structure of organopolysiloxane, the heat resistance of the cured film can be enhanced. The Q unit is also contained in quartz. When the organopolysiloxane has the Q unit, a cured film having a refractive index close to that of the core material of a near-infrared single-mode silica optical fiber can be obtained using the composition containing the organopolysiloxane. In the organopolysiloxane represented by Formula [1], the Q unit may or may not be present. From the viewpoint of improving the heat resistance of the cured film of the organopolysiloxane, it is preferable to have the Q unit. On the other hand, from the viewpoint of improving the flexibility of the cured film of the organopolysiloxane, it is more preferable not to have the Q unit.

[0045] When having the Q unit, the coefficient Q is preferably greater than 0, more preferably 0.04 or more. On the other hand, when there are many Q units, it becomes solid or the viscosity becomes high, and the handling property deteriorates. Therefore, the upper limit is usually 0.65 or less, more preferably 0.6 or less, and still more preferably 0.45 or less. As described above, when the organopolysiloxane represented by Formula [1] has the Q unit, its coefficient Q is preferably 0 < Q ≤ 0.65, more preferably 0.04 ≤ Q ≤ 0.6, and still more preferably 0.04 ≤ Q ≤ 0.45.

[0046] <D1 + D2 + T1 + T2 + Q>[[ID=##]] In the organopolysiloxane represented by Formula [1], when 0 < D1 + D2 + T1 + T2 + Q, other structural units than the M unit can be introduced into the organopolysiloxane, which is advantageous from the viewpoints of curability and heat resistance after curing. 0.01 < D1 + D2 + T1 + T2 + Q is preferable, 0.1 < D1 + D2 + T1 + T2 + Q is more preferable, and 0.2 < D1 + D2 + T1 + T2 + Q is still more preferable. The upper limit is not particularly limited, but it is 1 or less from the definition. From the perspective of improving the heat resistance of the cured film of organopolysiloxane, the relational expression "0 < D1 + D2 + T1 + T2 + Q" in Formula [1] is replaced by "0 < Q", that is, it preferably has a Q unit. Formula [2] will be used later.

[0047] <O 1 / 2 R 11 > (O 1 / 2 R 11 ) has no reactive functional group and has a structure having a group selected from the group consisting of an organic group and a hydrogen atom. Specifically, it is an alkoxy group and / or a silanol group bonded to silicon. The viscosity of the organopolysiloxane can be controlled by this structural unit, and it can be adjusted to a viscosity suitable for molding. The silanol group has the effect of increasing the viscosity, and the alkoxy group has the effect of decreasing the viscosity. When the content ratio of the alkoxy group or the silanol group is small, the amount of terminal groups with high mobility is small, and the siloxane skeleton becomes a rigid cage type, so the viscosity increases. Conversely, when the content ratio of the alkoxy group or the silanol group is large, the amount of terminal groups with high mobility is large, and the siloxane skeleton also becomes a flexible random structure rather than a cage type, so the viscosity decreases.

[0048] <Coefficient Y1> (O 1 / 2 R 11 ) The coefficient Y1 indicating the content ratio is 0 or a positive value. In one aspect, Y1 indicates the total content ratio of the silanol group and the alkoxy group in the organopolysiloxane from the definition of R 11 . The range of the coefficient Y1 is preferably 0 or more, more preferably 0.02 or more, still more preferably 0.025 or more, even more preferably 0.03 or more, and even more preferably 0.035 or more, from the perspective of viscosity adjustment required for the synthesis of the organopolysiloxane and the preparation of the organopolysiloxane-containing composition described later. [[ID=:27]] On the other hand, from the viewpoint of storage stability and handling ease, the upper limit of the coefficient Y1 is preferably 0.25 or less, more preferably less than 0.25, even more preferably 0.2 or less, even more preferably 0.20 or less, especially preferably 0.15 or less, and particularly preferably 0.1 or less. Preferred ranges in formula [1] are: 0.02≦Y1≦0.25 preferred, 0.02≦Y1<0.25 more preferred, 0.025≦Y1≦0.2 even more preferred, 0.025≦Y1≦0.20 even more preferred, 0.03≦Y1≦0.15 particularly preferred, and 0.035≦Y1≦0.1 particularly preferred. Y1 represents the relative value to M1+M2+D1+D2+T1+T2+Q=1.

[0049] <Coefficient Y2> Y2 is the percentage of one or more organic groups in the organopolysiloxane that contain a reactive functional group bonded to silicon via an oxygen atom. (O 1 / 2 R 6 The coefficient Y2, which indicates the content of ), is 0 or a positive value, preferably Y2 > 0.25, more preferably Y2 > 0.30, and even more preferably Y2 > 0.35. When Y2 > 0.25, compatibility with other resins is improved. Organic groups containing reactive functional groups are easily hydrolyzed and removed by water, which can lead to high water absorption. Therefore, it is preferable to use a method that is less affected by moisture. On the other hand, in environments affected by moisture, if Y2 is large, the cured film tends to become brittle due to moisture, so Y2 < 0.4 is preferable, Y2 < 0.3 is more preferable, and Y2 < 0.2 is even more preferable. It is also preferable for Y2 to be 0. Y2 represents the relative value to M1+M2+D1+D2+T1+T2+Q=1.

[0050] <Coefficient M1> R containing reactive functional groups 6M units that do not have R6 are not essential constituent elements in organopolysiloxanes, but may be included. Therefore, M1, which is the proportion of M units that do not have R6, may be M1 > 0, and substituting either the alkoxy group or the silanol group of the organopolysiloxane with an M unit tends to improve the storage stability of the organopolysiloxane and lower its viscosity. From the viewpoint of storage stability, it is preferable that the coefficient M1 is 0.09 or more, usually 0.6 or less, preferably 0.5 or less, and more preferably 0.4 or less.

[0051] <Coefficient D1> R containing reactive functional groups 6 While D units without such units are not essential constituent elements in organopolysiloxanes, including them tends to impart toughness to the cured film. That is, from the viewpoint of imparting toughness to the cured film, D1 ≥ 0.2 is preferred, D1 ≥ 0.3 is more preferred, and D1 ≥ 0.4 is even more preferred. On the other hand, R 6 If the content of D units that do not have is too high, the heat resistance of the cured film tends to decrease. In other words, from the viewpoint of suppressing the decrease in heat resistance of the cured film, D1 is preferably D1 ≤ 0.5, more preferably D1 ≤ 0.4, and even more preferably D1 ≤ 0.3.

[0052] <Coefficient T1> R containing reactive functional groups 6 While T units without such units are not essential constituent elements in organopolysiloxanes, including them tends to improve compatibility with other components added to the organopolysiloxane-containing composition described later. From the viewpoint of improving compatibility with other components, T1 ≥ 0.2 is preferred, and T1 ≥ 0.3 is more preferred. On the other hand, R 6 If the content of T units that do not have is too high, steric hindrance of the introduced organic groups can easily lead to poor curing. Therefore, from the viewpoint of curability, T1 ≤ 0.5 is preferable, T1 ≤ 0.4 is more preferable, and T1 ≤ 0.3 is even more preferable.

[0053] From the above, each coefficient in the above formula [1] preferably satisfies 0 < Q ≤ 0.65, 0 < M2 + D2 + T2 ≤ 0.75, 0.02 ≤ Y1 ≤ 0.25, Y2 < 0.4, 0 < M1 ≤ 0.6, D1 ≤ 0.7, T1 ≤ 0.5; more preferably, 0.04 ≤ Q ≤ 0.60, 0.10 ≤ M2 + D2 + T2 ≤ 0.75, 0.025 ≤ Y1 ≤ 0.20, Y2 < 0.3, 0.09 ≤ M1 ≤ 0.5, D1 ≤ 0.6, T1 ≤ 0.4; still more preferably, 0.04 ≤ Q ≤ 0.45, 0.12 ≤ M2 + D2 + T2 ≤ 0.6, 0.03 ≤ Y1 ≤ 0.15, Y2 < 0.2, 0.09 ≤ M1 ≤ 0.4, D1 ≤ 0.3, T1 ≤ 0.3.

[0054] <R 6 > R 6 is one or more organic groups containing a reactive functional group. Specifically, R 6 can contain a reactive alkenyl group as the reactive functional group. Examples of the reactive alkenyl group include those having an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, etc. Preferred examples of R 6 are organic groups containing at least one functional group selected from the group represented by the following formulas [i] to [iv] in one molecule.

[0055]

Chemical formula

[0056] More preferably, R 6 has at least one functional group selected from the group consisting of an acryloyloxypropyl group, an acryloyloxyoctyl group, a methacryloyloxypropyl group, and a methacryloyloxyoctyl group in one molecule, and among them, it is particularly preferred to have an acryloyloxypropyl group and / or a methacryloyloxypropyl group in one molecule.

[0057] In formulas [ii] and [iv], X is a divalent organic group and may include a branched structure and / or a cyclic structure. In addition to carbon and hydrogen, X may include any element selected from the group consisting of oxygen, nitrogen, phosphorus, sulfur, and halogens. When a silicon atom is bonded to X, the terminal atom of X that is directly bonded to silicon is preferably a carbon atom. When an oxygen atom directly bonded to silicon is bonded to X, the terminal atom of X that is directly bonded to oxygen is preferably a carbon atom. For example, hydrocarbon groups having 1 to 20 carbon atoms and including divalent branched or cyclic structures, or polyalkylene glycols, are suitably used.

[0058] In the organopolysiloxane represented by formula [1], the units constituting the M unit, D unit, and T unit do not all need to be identical. For example, the unit with a proportion of M1 (R 1 R 2 R 3 SiO 1 / 2 ) For example, within a certain R 1 is a hydrogen atom, and a certain R 1 It may have a different structure, such as a methyl group. This is also true for the other R and X elements.

[0059] <R 1 ~R 5 , R 7 ~R 11 > R 1 ~R 5 , R 7 ~R 11 Each of these is independently one or more groups selected from the group consisting of organic groups and hydrogen atoms. R 1 ~R 5 , R 7 ~R 11If it is an organic group, it is preferably an organic group having 1 to 20 carbon atoms, more specifically, it is preferably a linear, segmented, or cyclic alkyl group having 1 to 20 carbon atoms, or an aromatic ring group having 6 to 20 carbon atoms, more specifically, it is preferably an alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, or cyclohexyl group, or a polyether group such as a polyalkylene glycol group, and is particularly preferably a methyl group.

[0060] The organopolysiloxane having the reactive alkenyl group can also preferably be represented by the following formula [2]. (R 1 R 2 R 3 SiO 1 / 2 ) M1 (R 4 R 5 R 6 SiO 1 / 2 ) M2 (R 7 R 8 SiO 2 / 2 ) D1 (R 9 R 6 SiO 2 / 2 ) D2 (R 10 SiO 3 / 2 ) T1 (R 6 SiO 3 / 2 ) T2 (SiO 4 / 2 ) Q (O 1 / 2 R 11 ) Y1 (O 1 / 2 R 6 ) Y2 ···[2]

[0061] In the general formula [2], the coefficients M1, M2, D1, D2, T1, T2, and Q represent the ratios of the respective structures (based on the number of moles) when M1 + M2 + D1 + D2 + T1 + T2 + Q = 1. Also, in the general formula [2], the coefficients Y1 and Y2 represent the relative content ratios (based on the number of moles) of (O 1 / 2 R 11 ) and (O 1 / 2 R 6 ).

[0062] The organopolysiloxane having a reactive alkenyl group represented by formula [2] is an organopolysiloxane with 0 < Q. That is, it is characterized by having Q units. By having Q units, the heat resistance of the cured film of the organopolysiloxane can be improved. Except for Q = 0, the possible ranges of the coefficients M1, M2, D1, D2, T1, T2, and Q include preferred combinations and are as described in the above formula [1]. The structural units represented by each coefficient are also as described in the above formula [1].[[]]

[0063] It is also preferable that the organopolysiloxane having the reactive functional group is represented by the following formula [3].[[]] (R 1 R 2 R 3 SiO 1 / 2 ) M1 (R 4 R 5 R 6 SiO 1 / 2 ) M2 (R 7 R 8 SiO 2 / 2 ) D1 (R 9 R 6 SiO 2 / 2 ) D2 (R 10 SiO 3 / 2 ) T1 (R 6 SiO 3 / 2 ) T2 (O 1 / 2 R11 ) Y1 (O 1 / 2 R 6 ) Y2 ...[3]

[0064] In the above formula [3], R 1 ~R 5 , R 7 ~R 11 Each of these is independently selected from the group consisting of organic groups and hydrogen atoms, comprising one or more groups. R 1 ~R 3 , R 7 , R 8 , R 10 and R 11 It does not contain reactive functional groups. R 6 This refers to one or more organic groups containing reactive functional groups, and if there are multiple such groups, they may be identical or different from each other. 0≦M1, 0≦D1, 0≦T1, 0≦Y1, 0≦Y2, 0 <D1+D2+T1+T2、 0 <M2+D2+T2 M1 + M2 + D1 + D2 + T1 + T2 = 1.

[0065] Equation [3] represents an organopolysiloxane in which the coefficient Q in equation [1] is 0, i.e., an organopolysiloxane that does not contain Q units. R in equation [3] 1 ~R 11 This is similar to formula [1], and the preferred group is also similar. M1, M2, D1, D2, T1, T2, Y1, Y2 are the same as in equation [1], and the preferred numerical ranges for each coefficient are also the same.

[0066] <D1+D2+T1+T2> In the organopolysiloxane represented by the formula [3], when 0 < D1 + D2 + T1 + T2, it is possible to introduce a structural unit other than the M unit into the organopolysiloxane, which is advantageous from the viewpoints of curability and heat resistance after curing. D1 + D2 + T1 + T2 is preferably 0.01 < D1 + D2 + T1 + T2, more preferably 0.1 < D1 + D2 + T1 + T2, and even more preferably 0.2 < D1 + D2 + T. The upper limit is not particularly limited and is 1 or less from the definition. From the viewpoint of introducing a flexible site into the organopolysiloxane and improving the crack resistance of its cured film, it is preferable that 0 < D1 + D2. More preferably, D1 + D2 ≥ 0.05, and even more preferably D1 + D2 ≥ 0.1. Further, from the viewpoint of suppressing the thermal expansion of the cured film of the organopolysiloxane, it is preferable that D1 + D2 ≤ 0.9, and more preferably D1 + D2 ≤ 0.8.

[0067] From the viewpoint of improving the heat resistance of the cured film of the organopolysiloxane, it is preferable that 0 < T1 + T2. More preferably, T1 + T2 ≥ 0.05, and even more preferably T1 + T2 ≥ 0.1. From the viewpoint of suppressing the curing shrinkage of the cured film of the organopolysiloxane, it is preferable that T1 + T2 ≤ 0.9, and more preferably T1 + T2 ≤ 0.8. That is, from the viewpoint of achieving both crack resistance and heat resistance of the cured film of the organopolysiloxane, it is preferable that 0 < D1 + D2 and 0 < T1 + T2.

[0068] From the above, the respective ratios in the above formula [3] are preferably 0 < M2 + D2 + T2 ≤ 0.9, 0.02 ≤ Y1 ≤ 0.25, Y2 < 0.4, 0 < M1 ≤ 0.6, D1 ≤ 0.5, T1 ≤ 0.5, more preferably 0.10 ≤ M2 + D2 + T2 ≤ 0.8, 0.025 ≤ Y1 ≤ 0.20, Y2 < 0.3, 0.09 ≤ M1 ≤ 0.5, D1 ≤ 0.4, T1 ≤ 0.4, and even more preferably 0.12 ≤ M2 + D2 + T2 ≤ 0.6, 0.03 ≤ Y1 ≤ 0.15, Y2 < 0.2, 0.09 ≤ M1 ≤ 0.4, D1 ≤ 0.3, T1 ≤ 0.3.

[0069] In this embodiment, to suppress the increase in the refractive index of the cured film, it is also preferable to use an organopolysiloxane having a reactive functional group that does not contain an aromatic structure as the photocurable composition.

[0070] [Method for producing organopolysiloxanes having reactive functional groups] The method for producing an organopolysiloxane having a reactive functional group is not particularly limited as long as it can produce the organopolysiloxanes represented by formulas [1], [2], and [3], respectively. For example, any of the following manufacturing methods may be used: a method of condensing disiloxane compounds, disilazane compounds and their hydrolysates, alkoxysilane compounds and their hydrolysates, or partially hydrolyzed condensates, either individually or in combination with multiple other products; a method of condensing chlorosilane compounds and their hydrolysates, or partially hydrolyzed condensates; a method of ring-opening polymerization of cyclic siloxane compounds; or chain polymerization including anionic polymerization. Multiple manufacturing methods can also be used in combination. Furthermore, there are no particular limitations on the method of introducing reactive functional groups. Any method may be used, such as condensing one type of alkoxysilane compound, disiloxane compound, disilazane compound, or their hydrolysates or partial hydrolysis condensates, or a method of converting reactive organic groups introduced into organopolysiloxanes into reactive functional groups by chemical means. These methods may also be used in combination. The following are examples of raw materials that can be used to produce organopolysiloxanes having reactive functional groups by hydrolysis condensation.

[0071] (M unit source) Examples of M unit sources include trimethylsilanol, trimethylmethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, dimethylsilanol, dimethylmethoxysilane, tetramethyldisiloxane, tetramethyldisilazane, dimethylvinylsilanol, dimethylvinylmethoxysilane, 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetramethyldisilazane, 3-(meth)acryloyloxypropyldimethylsilanol, 3-(meth)acryloyloxypropyldimethylmethoxysilane, 1,3-bis((meth)acryloyloxypropyl)-1,1,3,3-tetramethyldisiloxane, methoxytriphenylsilane, triphenylsilanol, 1,3-diphenyl Tramethyldisiloxane, 1,3-diphenyltetramethyldisilazane, dimethylphenylsilanol, dimethylmethoxyphenylsilane, 1,4-bis(dimethylmethoxysilyl)benzene, 1,4-bis(dimethylethoxysilyl)benzene, 2-(3,4-epoxycyclohexyl)ethyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyldimethylethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, and, among the compounds listed above, those containing a silanol hydroxyl group or alkoxy group, can be replaced with compounds to which a halogen is bonded instead. Hexamethyldisiloxane is particularly suitable as the M unit source.

[0072] (D unit source) Examples of D-unit sources include dimethyldisilanol, dimethyldimethoxysilane, tetramethyldisiloxane, dimethylsiloxane oligomer, 3-(meth)acryloyloxypropyldimethoxymethylsilane, methyldimethoxyphenylsilane, diethoxymethylphenylsilane, methylphenyldisilanol, 1,4-bis(methyldimethoxysilyl)benzene, 1,4-bis(methyldiethoxysilyl)benzene, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and compounds in which halogens are bonded in place of the silanol hydroxyl group or alkoxy group of the listed compounds, as well as polymers thereof. Dimethyldimethoxysilane can be used particularly favorably.

[0073] (T unit source) Examples of T-unit sources include trimethoxysilanes modified with long-chain C1-C20 alkoxy groups such as trimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane, as well as vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 1,4-bis(trimethoxysilyl)benzene, p-styryltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane. In addition to these methoxysilane compounds, alkoxysilane compounds such as ethoxysilane, silanol compounds, chlorosilane compounds, hydrosilylsilane compounds, and polymers thereof can be used. In particular, 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 8-acryloyloxyoctyltrimethoxysilane, and decyltrimethoxysilane can be suitably used.

[0074] (Q unit source) Examples of Q unit sources include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, triethoxymonomethoxysilane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane, triethoxymonopropoxysilane, diethoxydipropoxysilane, tripropoxymonopropoxysilane, dimethoxymonoethoxymonobutoxy Alkoxysilanes such as sisilane, diethoxymonomethoxymonoboxysilane, diethoxymonopropoxymonoboxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonoboxysilane, dipropoxymonoethoxymonoboxysilane, dipropoxymonomethoxymonoboxysilane, dipropoxymonoethoxymonoboxysilane, dibutoxymonomethoxymonoethoxysilane, dibutoxymonoethoxymonoboxysilane, monomethoxymonoethoxymonoboxysilane, or aryloxysilanes and tetramethoxysilane oligomers such as methyl silicate MS51, MS56, MS57, MS60 manufactured by Mitsubishi Chemical Corporation, and ethyl silicate oligomers ES40, ES48 manufactured by Tama Chemical Industry Co., Ltd. can be used as tetraethoxysilane oligomers, with methyl silicate MS51 being particularly preferred. The above-mentioned M, D, T, and Q unit sources can each be used in combination of one or more types.

[0075] Acid catalysts, base catalysts, or inorganic salts can be used as catalysts for hydrolysis and condensation of these silicon raw materials, and acid catalysts are particularly suitable. Examples of acid catalysts include hydrochloric acid, sulfuric acid, trifluoroacetic acid, acetic acid, methacrylic acid, and acrylic acid, with hydrochloric acid being particularly suitable. Examples of base catalysts that can be used include ammonia, hexamethyldisilazane, triethylamine, tetraethylammonium hydroxide, diazabicycloundecene, potassium hydroxide, sodium hydroxide, barium hydroxide, potassium carbonate, and sodium carbonate, with potassium hydroxide being particularly preferred. As inorganic salts, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, etc. can be used, with sodium chloride being particularly preferred.

[0076] Examples of solvents used in the hydrolysis condensation reaction include tetrahydrofuran, toluene, methanol, ethanol, isopropanol, hexane, and heptane. Tetrahydrofuran is particularly preferred, and two or more solvents may be used depending on the solubility of the product. A mixture of toluene and methanol, or a mixture of tetrahydrofuran and methanol, is particularly preferred.

[0077] Alkoxy and silanol groups that remain after hydrolysis condensation may be substituted with organic acids or alcohols as needed. Examples of organic acids include acetic acid, acrylic acid, and methacrylic acid. Examples of alcohols that do not contain reactive alkenyl groups include methanol, ethanol, propanol, butyl alcohol, pentanol, hexanol, heptanol, and their structural isomers. Examples of alcohols that do contain reactive alkenyl groups include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, with 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate being preferred from the viewpoint of stability.

[0078] If the organopolysiloxane has a rigid structure such as a perfectly caged silsesquioxane, the cured film will be hard and brittle; therefore, it is preferable that it does not have a perfectly caged structure. It does not need to be a perfectly caged silsesquioxane; for example, it may include a random structure or a ladder structure as a higher-order structure, as long as it does not impair the effects of the present invention.

[0079] <Water> The amount of water used for hydrolysis is preferably 0.5 equivalents or more, more preferably 0.8 equivalents or more, and even more preferably 1.1 equivalents or more, relative to the total amount of alkoxy groups contained in the MDTQ unit source. The water is not particularly limited and may be water contained in commercially available hydrochloric acid, or water purified by distillation or ion exchange resin may be used.

[0080] [Organopolysiloxane composition having reactive functional groups] The organopolysiloxane-containing composition having a reactive functional group used in this embodiment (hereinafter sometimes simply referred to as "organopolysiloxane-containing composition") is more preferably an organopolysiloxane-containing composition having a reactive alkenyl group. In addition to the organopolysiloxane described above, the composition may contain monofunctional reactive alkenyl compounds, polyfunctional reactive alkenyl compounds, and / or alkenyl polymers, etc., to the extent that they do not impair the properties of the cured film obtained from the composition.

[0081] Furthermore, a polymerization initiator may be included to polymerize and cure the organopolysiloxane and polymerizable alkenyl compound. Although it is possible to cure the organopolysiloxane or organopolysiloxane-containing resin composition by electron beam irradiation or the like without using a polymerization initiator, a large amount of energy is required for curing. Therefore, a preferred embodiment of the organopolysiloxane-containing composition in the present invention is one that contains at least a polymerization initiator in addition to the organopolysiloxane described above. Other components that can be included in the composition include sensitizers, chain transfer agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, rheology modifiers, adhesion aids such as silane coupling agents, dyes, defoamers, other components, solvents, etc., to the extent that they do not impair the properties of the cured film obtained from the composition as described below. The following describes the components that may be included in the organopolysiloxane-containing composition.

[0082] <Monofunctional polymerizable alkenyl compounds> Specific examples of monofunctional polymerizable alkenyl compounds include (meth)acrylates containing carboxyl groups, such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, and 2-(meth)acryloyloxyethyl hexahydrophthalate; Hydroxylated (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate; Alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, tert-butyl(meth)acrylate, pentyl(meth)acrylate, heptyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, isooctyl(meth)acrylate, n-nonyl(meth)acrylate, isononyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, etc. (Meth)acrylates containing alicyclic structures such as cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, and 4-tert-butylcyclohexyl (meth)acrylate; (meth)acrylates containing aromatic ring structures such as phenyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxydiethylene glycol(meth)acrylate, phenoxypolyethylene glycol(meth)acrylate, nonylphenoxypolyethylene glycol(meth)acrylate, phenoxypolypropylene glycol(meth)acrylate, phenylphenyl(meth)acrylate, phenylphenoxyethyl(meth)acrylate, phenoxybenzyl(meth)acrylate, phenylbenzyl(meth)acrylate, naphthyl(meth)acrylate, and (1-naphthyl)methyl(meth)acrylate; (Meth)acrylates containing heterocyclic structures such as tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acryloylmorpholine; Alkoxy(meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and butoxyethyl (meth)acrylate; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(meth)acryloyloxyethyl acid phosphate, trifluoroethyl (meth)acrylate and heptadecafluorodecyl (meth)acrylate, 2-(meth)acryloyloxyethyl isocyanate; Styrene, α-methylstyrene, 2-vinylpyridine, 4-vinylpyridine, 1,1-diphenylethylene, and styrene derivatives such as aromatic ring hydrogen-substituted derivatives thereof; Examples include vinyl acetate, vinyl octanoate, vinyl decanoate, vinyl hexanoate, acrylonitrile, vinyl benzoate, and other vinyl compounds. Furthermore, since the refractive index of the cured film becomes high, it is preferable to use materials that do not contain aromatic structures.

[0083] <Polyfunctional polymerizable alkenyl compounds> Specific examples of polyfunctional polymerizable alkenyl compounds include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; Polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate; Di(meth)acrylates containing alicyclic structures such as cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated hydrogenated bisphenol A di(meth)acrylate, and adamantanediol di(meth)acrylate; Difunctional (meth)acrylates such as polycarbonate diol di(meth)acrylate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene, and polyurethane di(meth)acrylate; Trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, and ε-caprolactone-modified tris((meth)acrooxyethyl)isocyanurate; Tetrafunctional (meth)acrylates such as ditrimethylolpropanetetra(meth)acrylate; Penta-functional (meth)acrylates such as dipentaerythritol penta(meth)acrylate; Polyfunctional monomers such as hexafunctional (meth)acrylates, including dipentaerythritol hexa(meth)acrylate; Examples include 1,4-divinylbenzene and 1,3-divinylbenzene. Furthermore, since the refractive index of the cured film becomes high, it is preferable to use materials that do not contain aromatic structures.

[0084] <Alkenyl polymers> Alkenyl polymers are polymers containing 50% by mass or more of alkenyl monomer units in their composition. In this specification, "unit" refers to the repeating unit that constitutes the polymer. Polymerizable alkenyl compounds may be monofunctional or polyfunctional. Furthermore, it is preferable to use compounds that do not contain aromatic structures, as this would result in a high refractive index. The alkenyl monomer units contained in the alkenyl polymer may be one type or two or more types. The polymerization method for obtaining alkenyl polymers is not particularly limited, and polymerization can be carried out by known methods such as solution polymerization, suspension polymerization, emulsion polymerization, and partial polymerization. In the present invention, suspension polymerization is preferred because it allows for relatively easy control of the polymerization reaction and separation of the resulting polymer.

[0085] As an alkenyl polymer, a modified version may be used, which has been chemically modified to introduce a functional group containing a double bond, such as a (meth)acryloyl group or a vinyl group, into the side chain. Examples of chemical modification methods include the reaction of a carboxyl group with a glycidyl group or the reaction of a hydroxyl group with an isocyanate group. When using a chemical modification method involving the reaction of a carboxyl group and a glycidyl group, for example, an alkenyl polymer containing alkenyl monomer units having a carboxyl group is produced, and the resulting alkenyl polymer is reacted with a compound having a glycidyl group and a double bond, such as glycidyl (meth)acrylate.

[0086] In the reaction between an alkenyl polymer containing alkenyl monomer units having a carboxyl group and a compound having a double bond with a glycidyl group, it is preferable to use a reaction catalyst to shorten the reaction time. Examples of reaction catalysts include quaternary ammonium salts such as tetrabutylammonium bromide, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, and phosphine compounds such as triphenylphosphine. Quaternary ammonium salts are particularly preferred because the organopolysiloxane composition of this embodiment is less likely to discolor.

[0087] The weight-average molecular weight (Mw) of the alkenyl polymer is preferably 5,000 to 500,000, and more preferably 10,000 to 200,000. A weight-average molecular weight of 5,000 or higher results in good strength of the cured film. A weight-average molecular weight of 500,000 or lower reduces the viscosity of the organopolysiloxane composition, resulting in improved workability, for example, during the coating process.

[0088] <Polymerization initiator> Examples of polymerization initiators include photopolymerization initiators, thermal polymerization initiators, and peroxides used in redox polymerization. The type of polymerization initiator can be appropriately selected depending on the polymerization method.

[0089] (Photopolymerization initiator) Photopolymerization initiators are radical polymerization initiators used in photopolymerization. Specific examples of photopolymerization initiators include benzophenone-type compounds such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl 2-benzoylbenzoate, and 4-phenylbenzophenone; anthraquinone-type compounds such as tert-butylanthraquinone and 2-ethylanthraquinone; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyldimethylketal, and 1 Alkylphenone-type compounds such as -hydroxycyclohexylphenyl ketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one; thioxanthone-type compounds such as 2-benzyl-2-dimethylamino-4'-morpholinobylophenone, diethylthioxanthone, isopropylthioxanthone; 2,4,6-tri Acylphosphine oxide type compounds such as methylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; phenylglyoxylate type compounds such as phenylglyoxylic acid methyl ester; N-acetoxy-N-{4-acetoxyimino-4-[9-ethyl-6-(o-toluyl)-9H-carbazole-3-yl]butane-2- Examples include oxime ester compounds such as yl acetamide, N-acetoxy-N-{3-(acetoxyimino)-3-[9-ethyl-6-(1-naphthoyl)-9H-carbazole-3-yl]-1-methylpropyl}acetamide, 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-5-oxopentanoate methyl, and 4-acetoxyimino-5-oxo-5-(4-(phenylthio)phenyl)pentanoate methyl, as well as combinations thereof.

[0090] Among these, alkylphenone-type compounds are preferred in that they can suppress discoloration of the cured film, and 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenyl ketone are more preferred. Acylphosphine oxide-type compounds are preferred in that they facilitate sufficient curing to the interior of the cured film, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferred in that it can suppress discoloration of the cured film. Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 4-acetoxyimino-5-oxo-5-(4-(phenylthio)phenyl)pentanoate methyl are more preferred due to their high sensitivity to longer wavelength light. 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone is also preferred from the viewpoint of high reactivity to light around 365 nm. These photopolymerization initiators may be used individually or in combination of two or more.

[0091] In this embodiment, since the organopolysiloxane composition (hereinafter sometimes simply referred to as "curable composition") is cured by photopolymerization to obtain a cured film, the wavelength of light irradiated onto the curable composition is not particularly limited, but it is preferable to irradiate it with ultraviolet light with a wavelength of 200 to 500 nm. Specific examples of ultraviolet light sources include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps, UV-LED lamps, chemical lamps, and black lights. After photopolymerization of the curable composition, after-curing may be performed. This can reduce the amount of unreacted polymerizable alkenyl groups remaining in the cured film, thereby increasing the strength of the cured film. After-curing conditions include temperatures of 50°C to 230°C for several tens of seconds to 60 minutes, or temperatures of 80°C to 200°C for several tens of seconds to 60 minutes.

[0092] (Thermal polymerization initiator) Thermal polymerization initiators are radical polymerization initiators used in thermal polymerization. Examples of thermal polymerization initiators include organic peroxides and azo compounds. Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, and 1,1-di(tert-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; and dicumyl peroxide, di-tert-butyl peroxide, etc. Examples include dialkyl peroxides; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-tert-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; and peroxyesters such as tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate.

[0093] Specific examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitride, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane)dihydrochloride.

[0094] These thermal polymerization initiators may be used individually or in combination of two or more. Organic peroxides are preferred as thermal polymerization initiators because they are less likely to cause bubbles in the cured film. Considering the balance between the curing time and pot life of the curable composition, the 10-hour half-life temperature of the organic peroxide is preferably 35 to 80°C, more preferably 40 to 75°C, and even more preferably 45 to 70°C. If the 10-hour half-life temperature is 35°C or higher, the curable composition is less likely to gel at room temperature, resulting in a good pot life. On the other hand, if the 10-hour half-life temperature is 80°C or lower, the curing time of the curable composition can be shortened.

[0095] Examples of such organic peroxides include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, and di(4-tert-butylcyclohexyl)peroxydicarbonate. A commercially available example of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate is Perocta-O (trade name, manufactured by NOF Corporation, 10-hour half-life temperature: 65.3°C). A commercially available example of tert-butylperoxy-2-ethylhexanoate is Perbutyl-O (trade name, manufactured by NOF Corporation, 10-hour half-life temperature: 72.1°C). A commercially available example of di(4-tert-butylcyclohexyl)peroxydicarbonate is Perloyl TCP (trade name, manufactured by NOF Corporation, 10-hour half-life temperature: 40.8°C).

[0096] When a curable composition is cured by thermal polymerization to obtain a cured film, the curing conditions are not particularly limited, but from the viewpoint of obtaining a resin for optical components with suppressed discoloration, the curing temperature is preferably 40 to 200°C, and more preferably 60 to 150°C. The curing time (heating time) also varies depending on the curing temperature, but is preferably 1 to 120 minutes, and more preferably 1 to 60 minutes. After thermal polymerization of the curable composition, it is preferable to perform an after-curing process. Examples of after-curing conditions include a temperature of 50°C to 200°C for several tens of seconds to 60 minutes, or a temperature of 80°C to 150°C for several tens of seconds to 60 minutes.

[0097] <Chain movement agent> When curing an organopolysiloxane composition in air, oxygen traps active radicals as peroxide radicals, inhibiting polymerization. However, by adding a hydrogen-donating chain transfer agent, polymerization inhibition by oxygen can be suppressed. As the above chain transfer agent, for example, as a thiol compound, methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolethanetris(3-mercaptopropionate Trimethylolethanetris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), Mercaptocarboxylic acid esters such as tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate and tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate; alkylthiols such as ethanethiol, 2-methylpropane-2-thiol, n-dodecanethiol, 2,3,3,4,4,5-hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, and benzylthiol. Examples include aromatic thiols such as benzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzimidazole-2-thiol, and benzothiazole-2-thiol; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; and silane-containing thiols such as 3-(trimethoxysilyl)propane-1-thiol and 3-(triethoxysilyl)propane-1-thiol. Among these, secondary thiol compounds are preferred from the viewpoint of the reactivity and storage stability of the curable composition. When adding a chain transfer agent, it may be used alone or in a mixture of two or more types. The amount added is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total amount of polymerizable components. When using a mixture of two or more types, the total amount of chain transfer agents will be within the above range.

[0098] <Solvent> A solvent may be included for the purpose of diluting organopolysiloxanes and their compositions. The type of solvent is not particularly limited as long as it does not impair the physical properties required for the cured film of the organopolysiloxane and its composition, but good solubility is good, such as aromatic hydrocarbons (e.g., toluene, xylene, ethyl benzoate, ethylbenzene, benzyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, ethyl lactate, methyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, γ-butyrolactone), ethers (e.g., Alternatively, isopropyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, 1,4-dioxane, methyl-tert-butyl ether, tetrahydrofuran), alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, butanol, sec-butanol, tert-butanol, n-pentanol), halogenated solvents (e.g., methylene chloride, trichloroethylene, tetrachloroethylene, bromopropane, chloroform), and others (e.g., dimethyl sulfoxide, N,N-dimethylformamide, water) may be used, and two or more solvents may be used.

[0099] The content is not particularly limited as long as it does not impair the physical properties desired for the cured film of the organopolysiloxane and its composition. However, if it is desired to reduce viscosity while keeping the volatile content to a minimum, it is preferable that the content be more than 0% by mass and 25% by mass or less relative to the entire organopolysiloxane or its composition. Furthermore, if it is desired to obtain a thin cured film, it is preferable that the content be 75% by mass or more and less than 100% by mass relative to the entire organopolysiloxane or its composition.

[0100] (Antioxidant) The curable composition preferably further contains an antioxidant. The inclusion of an antioxidant in the curable composition suppresses discoloration caused by heat, such as heating during soldering of the cured film or heat generation from the device. Specific examples of antioxidants include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc. Examples of antioxidants include: ol-based antioxidants; phosphorus-based antioxidants such as triphenyl phosphite, trisisodecyl phosphite, tristridecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and tetra(C12~15 alkyl)-4,4'-isopropylidenediphenyl diphosphite; and sulfur-based antioxidants such as dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, disteryl-3,3'-thiodipropionate, and pentaerythritol tetrakis(β-laurylthiopropionate). These antioxidants may be used individually or in combination of two or more.

[0101] (Other ingredients) The above curable composition may also contain other components such as fillers, curing control agents, and viscosity modifiers. These components can be included as appropriate, within a range that does not affect the transmission loss, heat resistance, and refractive index of the cured film of the organopolysiloxane composition according to this embodiment.

[0102] According to this embodiment, by removing low molecular weight components through a reduced-pressure heating process, contamination of the reflective mirror, lens, or high-voltage generator of the exposure machine can be suppressed, and a manufacturing method is provided that can maintain the functionality of the exposure machine.

[0103] [Polymer Optical Waveguide] The cured film obtained by the manufacturing method of this embodiment can be used as a polymer optical waveguide. Furthermore, optical waveguides having a cured film obtained by the manufacturing method of this embodiment and optical transmission members comprising at least the optical waveguide are also within the scope of the present invention.

[0104] In this embodiment, the optical waveguide comprises at least a core and / or cladding formed by curing the organopolysiloxane composition, and may also comprise a substrate (also referred to as a "substrate"). In embodiments using the organopolysiloxane composition, the optical waveguide is suitable for a near-infrared optical waveguide. The optical waveguide of this embodiment preferably comprises a core and cladding made using a cured film obtained by the manufacturing method of this embodiment. The cladding may consist of a lower cladding and an upper cladding. In addition to the near-infrared optical waveguide described above, the near-infrared optical transmission member of this embodiment may also include optical fibers such as mirrors and connectors, and connection members for silicon photonics optical circuits, etc.

[0105] The refractive index of the cured film can be controlled, for example, by changing the proportion of constituent units of the organopolysiloxane. For example, increasing the value of M2+D2+T2 in the above-mentioned formulas [1], [2], or [3], that is, increasing the content of polymerizable alkenyl groups, increases the density of the resulting cured film and thus the refractive index. Conversely, decreasing the value of M2+D2+T2, that is, decreasing the content of polymerizable alkenyl groups, reduces the density of the resulting cured film and thus the refractive index. The refractive index of the cured film can also be controlled by changing the component proportions of the organopolysiloxane composition.

[0106] Furthermore, the refractive index can be controlled by adjusting the content (volume %) of polymerizable alkenyl groups in the organopolysiloxane composition described above, and / or alkenyl polymers, thereby controlling the crosslinking density of the cured film, similar to the case described above. In addition, in one embodiment of this organopolysiloxane, the refractive index can be increased by increasing the aromatic group content (volume %) of the cured film, and decreased by increasing the fluorine content (volume %). Moreover, the refractive index of the cured film can also be controlled by combining these methods.

[0107] This manufacturing method can be extended to highly productive manufacturing methods. Multiple optical waveguides can be manufactured simultaneously on a single substrate. Furthermore, this method can also utilize conventional wafer manufacturing techniques (e.g., coating, exposure, development, curing) and equipment. Optical waveguides manufactured according to this method have superior microfabrication capabilities compared to optical waveguides containing other known materials, and can reduce heat resistance, low transmission loss at target wavelengths such as near-infrared, and connection loss due to reflection at the optical fiber / optical waveguide interface.

[0108] [Optical components] An optical component having an optical waveguide obtained by the manufacturing method of this embodiment is also within the scope of the present invention. In addition to the aforementioned optical waveguide and near-infrared optical waveguide, the optical component may also include connection members such as mirrors and connectors for optical fibers and silicon photonic optical circuits. Furthermore, the cured film obtained by the manufacturing method of this embodiment can be used not only for the above-mentioned applications but also in the manufacture of optical components that constitute various electronic devices such as organic thin-film transistors, sensors, touch panels, liquid crystal displays, and organic LED displays. In particular, it can be suitably used as an insulating film and protective film for displays such as liquid crystal displays and organic LED displays. [Examples]

[0109] Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[0110] <Evaluation Method 1> (1) 1 Method for measuring H-NMR • Equipment: Bruker Japan Co., Ltd. AVANCE NEO 400, BBFO Probe (5mm diameter) Measurement conditions: Pulse repetition time / 5 seconds, Number of scans / 16, Measurement mode / Single pulse, Measurement temperature / 25°C, Flip angle / 30°, Spin / 20Hz, Measurement temperature 25°C • Sample preparation: 60 mg of the organopolysiloxane to be measured was weighed, and 12 mg of N,N-dimethylformamide was added as an internal standard. Deuterated chloroform was then added to dissolve the sample until the total mass was 1 g, and the sample was placed in an NMR sample tube. • Calculation of functional group content: The functional group content was estimated based on the ratio of the signal intensity of each component to the signal intensity of the internal standard N,N-dimethylformamide, and the weighed value.

[0111] (2) 29 Method for measuring SiNMR • Sample preparation: Add tris(2,4-pentanedionato)chromium(III) to deuterated chloroform to a concentration of 0.5% by mass. 29A solvent for Si-NMR measurement was obtained. 1.5 g of the organopolysiloxane to be measured was weighed, and the above 29 2.5 ml of Si-NMR solvent was added to dissolve the sample, and it was then placed into the NMR sample tube. (2)-1: The organopolysiloxane a-1 described below 29 Si-NMR measurement • Equipment: JEOL Ltd. JNM-ECS400, TUNABLE Probe (10mm diameter): Si-free, AT10 probe Measurement conditions: Pulse repetition time / 16 seconds, Number of scans / 1024, Measurement mode / Non-gated decoupled pulse method (NNE), Flip angle / 90°, Spin / None, Measurement temperature / 25°C (2)-2: The organopolysiloxane a-2 described below 29 Si-NMR measurement • Equipment: Bruker Japan Co., Ltd., AVANCE NEO 600, BBO Cryo Probe (5mm diameter) Measurement conditions: Pulse repetition time / 16 seconds, Number of scans / 1024 times, Measurement mode / Inverse gate decoupling measurement, Flip angle / 90°, Spin / None, Measurement temperature / 25°C <Calculation of constituent units> The signal intensity of each unit of silicon was measured, and the above 1 The composition ratio of silicon units was calculated from the ratio of the signal intensity measured by 1H-NMR and the ratio of the functional group content.

[0112] [Organopolysiloxane a-1] Referring to Japanese Patent Publication No. 2014-510159, organopolysiloxane a-1 was obtained using 3-methacryloyloxypropyltrimethoxysilane KBM503 manufactured by Shin-Etsu Chemical Co., Ltd. and diphenylsilanediol manufactured by Tokyo Chemical Industry Co., Ltd. as organopolysiloxane raw materials. The composition ratio of silicon units is shown in Table 1.

[0113] [Organopolysiloxane a-2] Organopolysiloxane a-2 was synthesized by the following method. As organopolysiloxane raw materials, 115.00 g of 3-methacryloyloxypropyltrimethoxysilane KBM503 and 103.53 g of dimethyldimethoxysilane KBM22, both manufactured by Shin-Etsu Chemical Co., Ltd., were used. As solvents, 109.27 g of toluene and 109.27 g of methanol were used. As catalyst and water, a mixture of 63.94 g of 1N hydrochloric acid and 63.94 g of methanol was used. Hydrolysis condensation was carried out while maintaining a temperature of 15°C to 40°C. After that, the reaction solution was neutralized, washed with desalted water, the solvent and water were removed, and the mixture was filtered to obtain 194 g of the target liquid organopolysiloxane a-2. The composition ratio of silicon units is shown in Table 1. Organopolysiloxane a-2 is a polymer that has reactive functional groups.

[0114] [Table 1]

[0115] [Photopolymerization Initiator-1] 2-Benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone (Omnirad 369, manufactured by IGM Resins BV) [Solvent-1] Propylene glycol monomethyl ether acetate

[0116] [Method for preparing an organopolysiloxane-containing composition] To 100 parts by mass of organopolysiloxane, photopolymerization initiator-1 and solvent-1 were added in the amounts shown in Table 1, and the mixture was stirred at room temperature to obtain organopolysiloxane-containing curable compositions 1 to 9.

[0117] <Evaluation Method 2> [Fabrication of TOF-SIMS evaluation substrates] The explanation will be given with reference to Figure 1. An organopolysiloxane-containing curable composition was applied to a glass substrate 3 using a spinner to a thickness of 20 μm after curing and development. The solvent was then removed from the resulting substrate by drying it at 25°C for 1 minute under reduced pressure of 50 Pa. Subsequently, for Examples 1 to 6, reduced-pressure heat treatment was performed under the conditions described in Table 1, while for Reference Example 1 and Comparative Examples 1 and 2, substrates 4 with a film 2 containing organopolysiloxane were obtained without reduced-pressure heat treatment. The longitudinal ends of the substrate with the obtained organopolysiloxane-containing film were wiped with a nonwoven fabric soaked in an organic solvent, and a 200 μm thick PET film was placed as a spacer 21 on the wiped area. Then, the glass substrate with the ITO film (ITO substrate) 1 and the substrate with the organopolysiloxane-containing film 4 were placed facing each other, as shown in Figure 1. Next, in Examples 1-6 and Comparative Examples 1 and 2, a manual exposure machine (MA-1100) manufactured by Dainippon Kaken Co., Ltd. was used, and a high-pressure mercury lamp with wavelengths below 330 nm cut off was used, with an exposure dose of 1000 mJ / cm². 2 A substrate coated with an organopolysiloxane film was fully exposed from the glass side of the ITO substrate, as indicated by the arrow in the figure, at an exposure time of 22.2 seconds. The light intensity at a wavelength of 365 nm at this time was 45 mW / cm². 2 In Reference Example 1, no exposure was performed, and the sample was left to stand for 22.2 seconds, the same exposure time as in the other examples and comparative examples. Finally, the ITO substrate was removed without contact with the film containing organopolysiloxane, and the removed ITO substrate was used as the substrate for TOF-SIMS evaluation.

[0118] [Evaluation of volatile component emissions using TOF-SIMS] • Equipment: IONTOF M6 manufactured by JEOL Ltd. Mass spectroscopy: Primary ion Bi3 2+ Acceleration voltage 30kV, positive and negative ion detection, Flood Gun used, Spectrometry mode / All-Purpose mode, Beam defining aperture 400μm, Beam scanning 500μm square, 256×256, 15 integrations, Flood Gun used • Measurement samples: The TOF-SIMS evaluation substrate and ITO substrate (reference) • Volatile component A: SiC3H9+ (m / z 73.0494) • Volatile component B: Si5C5H 15 O7+ (m / z 326.9592) • Calculation of the ionic intensity ratio of volatile components A and B: ITO substrate (reference) 13 The ratio of the ionic strengths of volatile components A and B from the TOF-SIMS evaluation substrate to the ionic strength of In was calculated. Furthermore, the volatile components are those with high sensitivity (SiC3H9+) and those with the largest molecular weight (Si5C5H9+) from among the volatile components derived from organopolysiloxane. 15 The O7+ components were designated as volatile components A and B, respectively. Furthermore, the volatile components used to calculate the ionic strength ratio were appropriately selected depending on the type of polymer used in the composition.

[0119] Table 1 shows the results of the evaluation of volatile components A and B derived from low molecular weight siloxanes. If the ionic intensity ratio of volatile component A is less than 1% and the ionic intensity ratio of volatile component B is less than 0.05%, it is classified as "A," and if the ionic intensity ratio of volatile component A is 1% or more, or the ionic intensity ratio of volatile component B is 0.05% or more, it is classified as "X."

[0120] [Table 2]

[0121] Examples 1 to 6 show that heating a substrate coated with an organopolysiloxane-containing composition having reactive functional groups under reduced pressure can suppress the generation of volatile components A and B. This is thought to be because volatile components (low molecular weight components) can be efficiently reduced in the reduced pressure heating process, and the amount of volatile components from the organopolysiloxane-containing film decreases during exposure.

[0122] In Reference Example 1, which did not include a reduced-pressure heating process or an exposure process, it was found that the amount of volatile components A and B generated was small. This is because the exposure process was not performed, and it is thought that there were fewer volatile components from the film containing organopolysiloxane.

[0123] In Comparative Example 1, where exposure was performed without a reduced-pressure heating process, volatile components A and B were generated in large quantities, and in Comparative Example 2, a large amount of volatile component B was generated. It was confirmed that these components could adhere to the reflective mirror, lens, or high-voltage generator of the exposure machine, contaminating their surfaces, which could lead to problems such as a decrease in the reflectivity of the mirror and the light transmittance of the lens, or a decrease in sparks in the high-voltage generator, potentially impairing the function of the exposure machine. Comparing the examples, reference examples, and comparative examples, it can be seen that even with the amount of energy used in the exposure process, the amount of volatile components generated from the film containing organopolysiloxane increases significantly, leading to contamination of the exposure machine. [Explanation of symbols]

[0124] 1 ITO board 2. Resist film 21 Spacers 3. Glass substrate 4. Substrate with film

Claims

1. A coating step of applying a photocurable composition containing a polymer having reactive functional groups onto a substrate, A vacuum heating step involves heating the photocurable composition coated on the substrate under reduced pressure to obtain a film of the photocurable composition, An exposure step of exposing the film of the photocurable composition, A method for manufacturing a cured film, comprising the following features.

2. The method for producing a cured film according to claim 1, wherein the polymer having the reactive functional group is an organopolysiloxane having the reactive functional group.

3. The method for producing a cured film according to claim 2, wherein the organopolysiloxane having the reactive functional group is shown in [1] below. (R １ R ２ R ３ SiO １／２ ) Ｍ１ (R ４ R ５ R ６ SiO １／２ ) Ｍ２ (R ７ R ８ SiO ２／２ ) Ｄ１ (R ９ R ６ SiO ２／２ ) Ｄ２ (R １０ SiO ３／２ ) Ｔ１ (R ６ SiO ３／２ ) Ｔ２ (SiO ４／２ ) Ｑ (O １／２ R １１ ) Ｙ１ (O １／２ R ６ ) Ｙ２ ・・・[1] [In formula [1], R １ ~R ５ , R ７ ~R １１ Each of these is independently one or more groups selected from the group consisting of organic groups and hydrogen atoms. R １ ~R ３ , R ７ , R ８ , R １０ and R １１ It does not contain reactive functional groups. R ６ This refers to one or more organic groups containing reactive functional groups, and if there are multiple such groups, they may be identical or different from each other. 0≦M1, 0≦D1, 0≦T1, 0≦Y1, 0≦Y2, 0≦Q 0<M2+D2+T2, 0<D1+D2+T1+T2+Q M1 + M2 + D1 + D2 + T1 + T2 + Q = 1.

4. A method for manufacturing a cured film according to claim 1, further comprising a curing step of heating the exposed film to obtain a cured film.

5. The exposure step is a step of partially exposing the film of the photocurable composition, A developing step in which the unexposed areas of the partially exposed film are removed with a solvent to obtain a patterned resin film, The method for producing a cured film according to claim 1, further comprising a curing step of heating the patterned resin film to obtain a cured film.

6. The method for manufacturing a cured film according to claim 1, wherein the cured film is manufactured such that the thickness of the cured film is 100 μm or less.

7. The method for producing a cured film according to claim 1, wherein in the reduced-pressure heating step, the photocurable composition on the substrate is heated under a reduced pressure of 150 Pa or less at a temperature of 50°C or more and 150°C or less.

8. A method for producing a polymer optical waveguide, using a cured film obtained by the manufacturing method described in any one of claims 1 to 7.

9. A method for manufacturing an optical component, comprising forming it using a cured film obtained by the manufacturing method described in any one of claims 1 to 7.

Images