JP5320182B2 - Hybrid cured body and resin composition, and composite transparent sheet using them - Google Patents

Description

  The present invention relates to a hybrid cured body and a resin composition, and a composite transparent sheet in which the hybrid cured body or resin composition and a filler are combined.

  Epoxy resins are used as epoxy resin compositions in combination with curing agents. The epoxy resin composition is excellent in workability, and the cured product of the resin composition is excellent in heat resistance, electrical properties, adhesiveness, mechanical properties, and the like. Therefore, such a cured body is widely used in the fields of various electric / electronic parts, structural materials, adhesives and paints. Further, with the recent development of the electric / electronic field, a curable resin having improved heat resistance, suppression of coloring, and excellent moldability has been demanded.

  In recent years, glass substrates used for display element substrates such as liquid crystal display elements and organic EL display elements, color filter substrates, touch panel substrates, and solar cell substrates are difficult to break, flexible, and have a small specific gravity. Attempts have been made to replace plastic substrates that can be reduced in weight. For example, a transparent resin substrate for a liquid crystal display element (for example, Patent Documents 1 and 2) composed of a cured product obtained by curing an epoxy resin composition containing an epoxy resin, an acid anhydride curing agent, and a curing catalyst has been proposed. . However, these resin single materials have a higher coefficient of linear expansion than glass plates, causing problems such as warpage and disconnection of aluminum wiring in the manufacturing process of the display element substrate, and are difficult to use in these applications. . Accordingly, there is a demand for a plastic sheet that satisfies the transparency and heat resistance required for display element substrates, particularly active matrix display element substrates, and has a low coefficient of linear expansion.

  Examples of the method for improving the heat resistance of the epoxy resin include a method for increasing the crosslink density of the cured product by increasing the functional group density in the epoxy resin, and a method for introducing a rigid skeleton into the resin skeleton. However, a method using such a structure of the epoxy resin itself does not provide a sufficient improvement effect.

  As a heat resistance improving method other than the method of improving the structure of the epoxy resin itself, a method of using a silane-modified epoxy resin having an alkoxy group obtained by dealcoholizing a bisphenol A type epoxy resin and a hydrolyzable alkoxysilane ( For example, Patent Document 3) has been proposed. However, for the dealcoholization reaction, an excess of alkoxy groups relative to the hydroxyl groups in the epoxy resin is required. For this reason, the resin composition has a large amount of alkoxy groups. Alkoxy groups react with moisture (such as moisture) in the air and produce alcohol as a by-product, which causes defects such as voids during curing. Also in the cured body, there is a possibility that a similar reaction may proceed due to moisture. Furthermore, when there are a large amount of alkoxy groups or silanol groups generated by hydrolysis, condensation reactions will also occur. When the condensation reaction occurs, the degree of cure shrinkage increases, and there is a problem that cracks and the like are likely to occur due to strain. These problems are particularly prominent when acid and base epoxy curing agents that serve as catalysts for hydrolysis and condensation reactions are used.

  On the other hand, a method (for example, Patent Document 4 and Non-Patent Document 1) for improving the heat resistance of an epoxy resin using a silicone having a small residual alkoxy group has also been proposed. However, these methods utilize the interaction between the hydroxyl group generated in the epoxy resin by the reaction between the amine curing agent and the epoxy group and the silanol group in the silicone. Indispensable. However, when an amine-based curing agent is used, there is a problem that coloring during curing is unavoidable.

  On the other hand, a cage silica and epoxy resin composition (for example, Patent Document 5) using a photocationic curing agent to suppress coloring has also been proposed. However, the document does not mention or suggest any heat resistance. As described above, there is no method capable of improving the heat resistance of the epoxy resin while avoiding the generation of alcohol by side reactions, the problem of voids, and the problem of coloring.

  In order to reduce the linear expansion coefficient of the resin sheet, it is often performed to make an inorganic filler such as glass fiber in the resin. However, a transparent composite material cannot usually be obtained by combining these resins and inorganic fillers. The main cause is that the light transmitted through the resin is scattered at the interface between the resin and the inorganic filler because the refractive index of the resin and the refractive index of the inorganic filler are different. In order to solve such a problem, various methods (for example, Patent Documents 6 to 9) of making the resin transparent by matching the refractive index of the resin with the refractive index of the inorganic filler have been studied.

JP-A-6-337408 JP-A-7-120740 JP 2001-59013 A JP 2004-43696 A JP 2004-189840 A JP-A-6-256604 JP-A-6-305077 JP 2004-231934 A JP 2004-51960 A

Journal of Polymer Science: Part B: Polymer Physics, Vol.39, 1074-1084 (2001) M.Ochi, R.Takahashi, (Phase structure and thermo-mechanical Properties of primary and tertiary amine-cured epoxy / silica hybrids,)

  However, when based on the technique disclosed in the above Patent Documents 6 to 9, the resin used for forming the transparent composite material together with the inorganic filler is inferior in heat resistance, and the elastic modulus is lowered at the glass transition temperature or higher. Therefore, expansion and deformation occur in the sheet by heating, and it is difficult to produce a stable and uniform laminated structure when the inorganic layer is laminated.

  Therefore, an object of the present invention is to provide a cured product and a resin composition that are excellent in heat resistance, transparency, adhesion, and stress relaxation properties, and have no defects such as voids and cracks. The present invention also provides a smooth transparent resin sheet that is excellent in heat resistance and optical properties, has a low coefficient of linear expansion, has a small change in elastic modulus with changes in temperature, and can replace a glass substrate. Also aimed.

  The present inventors have intensively studied to solve the above problems. As a result, the size of the phase separation structure determined by the Guiner plot of the scattering profile measured using the X-ray small angle scattering method (SAXS) is 50 nm or less, and satisfies the relaxation index of 1.2 to 10. It has been found that a hybrid cured product of silicone and epoxy resin having a specific structure is excellent in heat resistance, transparency, adhesion and stress relaxation. Furthermore, the present invention has been completed by finding that a sheet formed by combining silicone and epoxy resin having a specific structure and a filler has a low coefficient of linear expansion and excellent heat resistance, optical characteristics and smoothness.

  That is, the present invention is as follows.

In one embodiment of the present invention, (i) the size (Rg) of a phase separation structure determined by a Guiner plot of a scattering profile measured using a small-angle X-ray scattering method (SAXS) is 50 nm or less, (Ii) Formula (1) below:
(Equation 1)
Relaxation index = (T2 at 200 ° C.) / (T2 at 25 ° C.) (1)
(In the formula, T2 is a relaxation time obtained by the solid echo method of solid state ¹ H-NMR)
Is a hybrid cured product that contains silicone, satisfying that the relaxation index represented by the formula is 1.2 to 10 and (iii) the yellowness (YI) is 30 or less.

  Another aspect of the present invention is a method for producing the above hybrid cured product, comprising (iv) a silicone having a reactive functional group and an organic compound having an epoxy group, which is different from silicone, and (V) An epoxy equivalent of 100 to 20,000 g / eq, containing a cycloaliphatic epoxy group, and curing the resin composition with heat or energy rays. It is a manufacturing method.

  In the method for producing a hybrid cured product, the resin composition preferably further contains an acid generator.

In the method for producing the hybrid cured body, the silicone has an average composition represented by the following formula (2), and the condensation ratio of the silicone represented by the following formula (3) is 30 to 99%. Is preferred.
(Chemical formula 1)
R ¹ _a Si (OX) _b O _{(4-ab) / 2} (2)
(Equation 2)
Condensation rate = 100 × {(4-ab) / (4-a)} (3)

Here, in the above formula, R ¹ represents the same or different organic group, OX represents the same or different hydrolyzable group or hydroxyl group, and a and b are each independently an integer of 0 to 3. .

  Still another embodiment of the present invention is the above resin composition, comprising (iv) a silicone having a reactive functional group and an organic compound having an epoxy group different from silicone, and (v) It is a resin composition having an epoxy equivalent of 100 to 20,000 g / eq and having a cycloaliphatic epoxy group.

The resin composition preferably has an average composition of the silicone represented by the following formula (2), and the condensation ratio of the silicone represented by the following formula (3) is 30 to 99%.
(Chemical formula 2)
R ¹ _a Si (OX) _b O _{(4-ab) / 2} (2)
(Equation 3)
Condensation rate = 100 × {(4-ab) / (4-a)} (3)

Here, in the above formula, R ¹ represents the same or different organic group, OX represents the same or different hydrolyzable group or hydroxyl group, and a and b are each independently an integer of 0 to 3.

Still another embodiment of the present invention is a method for producing the above resin composition, wherein the structural unit of D-form represented by the following formula (4) is 5-99 mol% (ratio of structural units of D-form). This is a method for producing a resin composition, comprising hydrolyzing and condensing an alkoxysilane containing to obtain a silicone, and mixing the silicone with an organic compound.
(Chemical formula 3)
R ¹ R ² Si (OX) ₂ (4)

Here, in the above formula, R ¹ and R ² each independently represent the same or different organic group, and OX represents the same or different hydrolyzable group or hydroxyl group. In addition, the ratio of the structural unit of the said D body is calculated | required by the method of 29Si-NMR.

  Moreover, the other aspect of this invention is a composite transparent sheet containing the said hybrid hardened | cured material and a filler.

  Yet another embodiment of the present invention is a method for producing a composite transparent sheet, comprising mixing the resin composition and a filler, and pressing the sheet into a sheet while curing with heat or energy rays.

  In the method for producing the composite transparent sheet, it is preferable that the resin composition further contains an acid generator.

  According to the present invention, a cured product and a resin composition that are excellent in heat resistance, transparency, adhesiveness, and stress relaxation properties and are free from defects such as voids and cracks can be obtained. In addition, a smooth transparent resin sheet that is excellent in heat resistance and optical properties, has a low coefficient of linear expansion, has a small change in elastic modulus accompanying a change in temperature, and can replace a glass substrate can be obtained.

It is a graph which shows the small angle X-ray scattering profile of a hybrid hardening body. It is a graph which shows the linear approximation of the low angle part of the Guinier plot with respect to a small angle scattering profile based on the Guinier rule of the small angle X-ray scattering profile shown by FIG. It is the schematic which shows the evaluation criteria regarding the softness | flexibility of the resin sheet of Examples 14 and 15 and the comparative example 8. FIG. It is a graph which shows the result of the dynamic viscoelasticity measurement of a (hybrid) hardening body. It is a graph which shows the measurement result of a linear expansion coefficient. 10 is an optical micrograph showing the observation results of voids in Comparative Example 8.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not restrict | limited to the following embodiment, In the range of the summary, various deformation | transformation can be implemented.

  [First embodiment: Hybrid cured body]

The hybrid cured body according to the first embodiment is (i) the size (Rg) of the phase separation structure determined by the Guiner plot of the scattering profile measured using the X-ray small angle scattering method (SAXS). Is 50 nm or less, (ii) the following formula (1):
(Equation 4)
Relaxation index = (T2 at 200 ° C.) / (T2 at 25 ° C.) (1)
(In the formula, T2 is a relaxation time obtained by the solid echo method of solid state ¹ H-NMR)
And (iii) yellowness (YI) is 30 or less, and contains silicone.

  The present inventors satisfy a phase separation structure obtained by a specific measurement method, and a hybrid cured body having a specific molecular mobility index is excellent in stress relaxation, not colored, and excellent in heat resistance. It has been found that it is optimal for use in IC encapsulants, epoxy resin laminates, paints, adhesives, and coating agents for electrical and electronic materials. Moreover, when combined with the said hardening body and filler, it discovered that there was no optical defect, it was excellent in smoothness, it was hard to break, it was excellent in heat resistance, and a composite transparent sheet (optical sheet) with small thermal expansion was obtained. . Hereinafter, the first embodiment will be described in detail.

  The hybrid cured body (hereinafter also simply referred to as “cured body”) according to the present embodiment is a cured body containing at least silicone and an organic compound. Here, the “cured product” in the present specification means a product obtained by curing a liquid resin composition by a crosslinking reaction. The type of the cross-linking reaction is not limited to the following, but may be, for example, a chemical bond or a pseudo cross-link formed by interaction. Here, “silicone” in the present specification contains an organic group (a non-reactive group such as an alkyl group and an aryl group, and a reactive functional group composed of an organic compound such as a reactive organic functional group), and And a compound that may contain a hydroxyl group (silanol) directly bonded to a silicon atom.

  The siloxane bond present in the main chain skeleton of silicone in this embodiment is advantageous in that it has excellent heat resistance. Siloxane bonds are also excellent in relaxation because they have good micro mobility, and the main chain skeleton and side chains of silicone can be phase-separated microscopically to suppress the movement of organic groups. It is advantageous. Further, when the silicone contains a hydrogen group (silanol), it is preferable because it becomes easier to form a denser and stronger structure by hydrogen bonding or the like.

  In the present embodiment, the ratio of silicone in the resin composition is not limited to the following, but is preferably 1 to 99% by mass, more preferably 10 to 95% by mass, and 20 to 85% by mass. Is more preferable, and it is still more preferable that it is 30-80 mass%. When it is within the above range, the heat resistance can be improved and the toughness is excellent. In addition, the ratio of silicone to the resin composition in the present specification (hereinafter also simply referred to as “silicone ratio”) can be calculated by comprehensively judging the results of 29Si-NMR and GPC.

  Moreover, in this Embodiment, although the ratio of the inorganic component in a hardening body is not restrict | limited to the following, It is preferable that it is 1-99 mass%, It is more preferable that it is 2-75 mass%, 5-50 It is more preferable that it is mass%, and it is still more preferable that it is 10-25 mass%. In addition, the ratio of the inorganic component in the present specification (hereinafter, also simply referred to as “inorganic ratio”) is the mass after the organic compound is completely carbonized with respect to the mass of the resin composition using thermogravimetric analysis. It can be obtained as a percentage. In addition, the “inorganic component” in this specification means a component including other than silicon.

  Silicone and organic compounds are essentially incompatible, and a cured product containing them usually forms a phase-separated structure. Here, the phase separation structure means that a component derived from silicone or an organic compound is locally present. When the localization of the organic compound-derived component is significant, it exhibits a glass transition due to molecular motion accompanying a temperature rise, leading to a decrease in elastic modulus. On the other hand, by suppressing the phase separation between the silicone and the organic compound and suppressing the molecular motion of the organic component with the silicone, it is possible to effectively prevent the decrease in the elastic modulus. Usually, the phase separation structure can be directly observed with a transmission electron microscope (TEM) or the like. However, no direct correlation is observed between the size of the phase separation structure by direct observation and the heat resistance of the organic compound. This is considered to be because the observation result does not reflect the state of the interface between the organic component and the inorganic component.

  The present inventors have determined the size of a phase separation structure determined by a Guiner plot of a scattering profile (hereinafter, also referred to as “small angle X-ray scattering profile”) measured using an X-ray small angle scattering method (SAXS). It was found that (Rg) gave information on the phase separation structure including the interface between the silicone and the organic compound, and as a result, the Rg was correlated with heat resistance. Hereinafter, the small-angle X-ray scattering profile and Rg will be described in detail.

  FIG. 1 is a graph showing a small-angle X-ray scattering profile of a hybrid cured body. FIG. 1 is a small-angle X-ray scattering (SAXS) profile of a cured product, where s on the horizontal axis indicates the magnitude of the scattering vector in the inverse space, and has a dimension of the reciprocal of the length. Furthermore, s satisfies the relational expression of s = 2 sin θ / λ using the wavelength (λ) and the diffraction angle (θ). The vertical axis indicates the scattering intensity.

  FIG. 2 is a graph showing a linear approximation of the low angle portion of the Guinier plot for the small angle scattering profile based on the Guinier rule for the small angle X-ray scattering profile shown in FIG. FIG. 2 shows a linear approximation of the low angle portion of the Guinier plot for the small angle scattering profile based on the Guinier rule of the SAXS profile shown in FIG. The phase separation structure size can be obtained from the “slope” and “intercept” of the straight line obtained thereby. The relationship between the scattering intensity I (q) and the phase separation structure size (radius of inertia) Rg satisfies the relational expression I (q) ≈exp [− {Rg (2/3)} q2].

  Rg is 50 nm or less, preferably 30 nm or less, more preferably 20 nm or less, and still more preferably 10 nm or less. Rg within the above range is preferable because the heat resistance of the hybrid cured body is further improved.

Here, “the heat resistance of the hybrid cured product is excellent” in the present specification means that the decrease in the elastic modulus accompanying the temperature increase is small. When the difference between the low-temperature elastic modulus near room temperature and the elastic modulus during heating is small, it is preferable because the cured body can be processed with high accuracy. As an example of an index representing heat resistance, temperature dependency of storage elastic modulus in dynamic viscoelasticity measurement can be mentioned. For example, the elastic modulus ratio represented by the following formula (5) is preferably 15 or less, more preferably 12 or less, further preferably 9 or less, and even more preferably 6 or less. .
(Equation 5)
Elastic modulus ratio = E0,25 ′ / E0,250 ′ (5)

  In the above formula, E0,25 'is the storage elastic modulus of the cured body at 25 ° C by dynamic viscoelasticity measurement, and E0,250' is the storage elastic modulus of the cured body at 250 ° C by dynamic viscoelasticity measurement.

  An example of an index representing heat resistance is the maximum value of tan δ in 25 to 250 ° C. in dynamic viscoelasticity measurement. tan δ is preferably 0.075 or less, more preferably 0.065 or less, further preferably 0.060 or less, and even more preferably 0.050 or less.

Next, the “relaxation index” in the present embodiment is a parameter related to the molecular mobility of the organic component and is represented by the following formula (1).
(Equation 6)
Relaxation index = (T2 at 200 ° C.) / (T2 at 25 ° C.) (1)
In the above formula, T2 is a relaxation time obtained by the solid echo method of solid state ¹ H-NMR.

  The shorter the relaxation time T2 obtained by the solid echo method, the slower the movement (for example, a polymer crystal or a glass state), while the longer T2, the better the mobility. The solid echo method is suitable for measuring a component having a short relaxation time in consideration of the dead time. In the present embodiment, when a plurality of relaxation times are measured, the shortest relaxation time is adopted as T2. The relaxation index is 1.2 to 10, preferably 1.3 to 9, more preferably 1.4 to 7, still more preferably 1.5 to 5, and 1.7 to Even more preferred is 3. When the relaxation index is within the above range, the molecular mobility is excellent, so that distortion due to curing or thermal shock is not easily applied. It is preferable that distortion is difficult to occur because voids and cracks hardly occur. Moreover, when the relaxation index is within the above range, the heat resistance of the hybrid cured product can be improved. Further, when the mobility is excellent, the viscosity is lower and the stress relaxation property is excellent. Thus, the cured body according to the present embodiment and the resin composition to be described later are further excellent in stress relaxation properties when satisfying a specific relaxation index of the above range.

  The yellowness degree (YI) in the present embodiment means a value obtained by measuring a 3 mm thick sample using SPECTROTOPOMETER CM-3600d manufactured by Konica Minolta. YI is 30 or less, preferably 20 or less, more preferably 12 or less, still more preferably 8 or less, and even more preferably 5 or less. When YI is within the above range, it is not determined to be so high that it is colored (in other words, it can be determined that the transparency is high). Therefore, the hybrid cured body according to the present embodiment can be used for various applications.

  The hybrid cured body according to the present embodiment is preferably excellent in moisture resistance. In the present embodiment, the moisture resistance can be judged by a change in appearance and a change in weight after the cured body is heated in water at 100 ° C. for 2 hours and then vacuum-dried at 100 ° C. to completely remove moisture. The weight change is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less, and even more preferably 3% or less.

If alkoxy groups are present in the silicone, the alcohol can be liberated by hydrolysis. Therefore, the alkoxy ratio represented by the following formula (6) of the cured body is preferably 50% or less, more preferably 35% or less, further preferably 20% or less, and more preferably 10% or less. Even more preferably. When the alkoxy ratio is within the above range, moisture resistance is good and alcohol is hardly liberated, which is preferable.
(Equation 7)
Alkoxy ratio = (number of Si—O—C bonds) / (number of Si—O—X bonds) (6)
In the above formula, Si represents a silicon atom, O represents an oxygen atom, C represents a carbon atom, and X represents an arbitrary atom.

  The number of Si—O—C bonds and Si—O—X bonds can be measured by NMR, IR, and NIR, and the highest measured value among them is adopted in this embodiment. In other words, the number of bonds is measured by NMR, IR, and NIR, respectively, and the largest number of bonds (measured value) is adopted. The reason is that almost the same results are generally obtained by any of the methods of NMR, IR, and NIR, but on the other hand, it may be difficult to measure by overlapping with other peaks. This is because the value may be small. Therefore, the largest value is adopted in order to increase the reliability of measurement as much as possible.

  The method for curing the hybrid cured body according to the present embodiment is not limited to the following, but may be, for example, a sequential polymerization type or a chain polymerization type. Further, it may be cured by a single reaction or may be cured by combining a plurality of reactions, but at least a chain polymerization type reaction is preferably used. This is because chain polymerization generally has a higher speed than sequential polymerization, and therefore chain polymerization tends to significantly suppress phase separation. Among these, cationic polymerization using an acid generator is preferable from the viewpoint of not being affected by oxygen. Thus, the hybrid cured body according to the present embodiment is more preferably cured by a chain polymerization type reaction (more preferably cationic polymerization) using an acid generator.

  The “acid generator” in the present specification means a compound that initiates polymerization by generating cationic species by heat or energy rays. Examples of the compound include, but are not limited to, various onium salts such as a quaternary ammonium salt, a sulfonium salt, a phosphonium salt, and an aromatic onium salt. These may be used alone or in combination of two or more.

  Examples of the quaternary ammonium salt include, but are not limited to, for example, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p -Toluenesulfonate, N, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyltrifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroan Moneto, and N, N- diethyl -N- (4- methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

  Examples of the sulfonium salt include, but are not limited to, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroalcinate, tris (4-methoxyphenyl) sulfonium hexafluoroalcinate, And diphenyl (4-phenylthiophenyl) sulfonium hexafluoroarsinate.

  Examples of the phosphonium salt include, but are not limited to, ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

  Examples of the aromatic onium salt include, but are not limited to, compounds disclosed in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, and Japanese Patent Publication No. 52-14279.

  The hybrid cured body according to the present embodiment is preferably obtained by curing a liquid resin composition with heat or energy rays from the viewpoint of improving moldability. Here, the “liquid” means fluidity. The viscosity serving as the fluidity index is preferably 1 to 1,000,000 mPa · s, more preferably 1 to 100,000 mPa · s, and 1 to 20,000 mPa · s. Is more preferable, and even more preferably 1 to 5,000 mPa · s. Within the above range, the moldability is significantly improved, which is preferable. The “viscosity” in this specification is measured using an E-type viscometer.

  In the above curing by heat or energy rays, the organic compound may cause a crosslinking reaction, the silicone may cause a crosslinking reaction, or both reactions may occur. From the viewpoint of further reducing the phase separation size, it is preferable that the organic compound and silicone both undergo a crosslinking reaction. The functional group in the resin composition may cause a crosslinking reaction by heat or energy rays, or a curing agent that reacts with heat or energy rays may coexist. Among these, from the viewpoint of controlling the structure of the cured body, it is preferable to use a curing agent that reacts with heat or energy rays.

  The temperature for curing with heat is not limited to the following, but is preferably 30 to 300 ° C, more preferably 80 to 250 ° C, and still more preferably 120 to 220 ° C. When it is within the above range, the decomposition of organic substances can be prevented and the time required for curing can be significantly shortened. In general, in thermosetting of an epoxy resin or the like, curing by a stepwise increase in temperature from a low temperature can be employed to suppress abnormal reactions. However, in the present embodiment, since it is necessary to suppress phase separation between the organic component and the inorganic component, it is preferable that the curing rate is high, and it is also preferable to set the initial temperature to a high temperature. In particular, when a silanol group (one type of reactive functional group) is present in the silicone described later, the initial temperature is preferably set to 100 ° C. or more from the viewpoint of facilitating the dehydration reaction. Preferably, it is cured at 120 ° C. or higher. In the case where two or more kinds of reactive functional groups are present, it is preferable to set the initial temperature above the temperature at which the functional group having the lowest reactivity reacts from the viewpoint of further promoting the reaction. Moreover, it becomes easy to suppress phase separation by uniformly curing the system. The reaction temperature of the functional group can be determined by differential scanning calorimetry (DSC measurement).

  The atmosphere at the time of curing is not limited to the following, but includes air, an inert gas such as nitrogen, and vacuum. Among these, an inert gas or a vacuum atmosphere is preferable from the viewpoint of suppressing the oxidation reaction by oxygen.

  Although it does not restrict | limit as a heating method below, a hot air, infrared rays, electromagnetic waves, etc. can be utilized suitably.

  The energy rays in the present embodiment are not limited to the following, but are, for example, light such as ultraviolet rays, near ultraviolet rays, visible rays and near infrared rays, and electron beams. From the viewpoint that side reactions are unlikely to occur, the type of energy beam is preferably light, and more preferably ultraviolet light.

  Sources of energy rays are not limited to the following, but for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion Examples of the light source include laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, excimer laser, light emitting diode, CRT light source, plasma light source, and electron beam irradiator.

  The method of curing with energy rays is not particularly limited, but usually a process in which a polymerization initiator is generated due to decomposition of the polymerization initiator by energy ray stimulation and the polymerizable functional group of the target substance is polymerized. Follow.

  The polymerization initiator used for curing with energy rays is not limited to the following, but can be broadly classified into the following three types depending on the difference in the generated active species. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  1. Those that generate radicals when irradiated with energy rays.

  2. Those that generate cations when irradiated with energy rays (called photoacid generators when the energy rays are light).

  3. Those that generate anions upon irradiation with energy rays (when the energy rays are light, they are called photobase generators).

  Specific examples of the polymerization initiator used for curing with energy rays include, but are not limited to, benzoins and benzoin alkyl ethers (benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, etc.); acetophenones (acetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl)- 2-monoforino-propan-1-one, N, N-dimethylaminoacetophenone, etc.); anthraquinones (2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroa Thioxanthones (2,4-dimethylthiosantone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.); ketals (acetophenone) Dimethyl ketals, benzyl dimethyl ketals, etc.); benzophenones (benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, etc.); xanthones; benzoates (ethyl 4-dimethylaminobenzoate) 2- (dimethylamino) ethyl benzoate, etc.); amines (triethylamine, triethanolamine, etc.); and iodonium salt compounds, sulfonium salt compounds, ammonium Compounds, phosphonium salt compounds, arsonium salt compound, a stibonium salt compound, an oxonium salt compound, a selenonium salt compound, and stannonium salt compounds.

  [Second Embodiment: Resin Composition]

  The resin composition according to the second embodiment is liquid, and is cured by heat or energy rays to form a silicone-containing hybrid resin composition that generates the hybrid cured body according to the first embodiment. In other words. That is, the resin composition according to the present embodiment is a raw material for the hybrid cured body, and the resin composition and the hybrid cured body have almost common characteristics. The resin composition according to the present embodiment may contain a curing agent. The curing agent in the present embodiment is a substance used for curing the resin composition, and is not limited to the following. For example, an acid anhydride compound, an acid generator, a base generator, and an amine compound , Amide compounds, and phenol compounds. From the viewpoint of reducing colorability (improving transparency), an acid generator or an acid anhydride compound is preferable, and an acid generator is more preferable. These curing agents may be used alone or in combination of two or more.

  Among the acid anhydride compounds, carboxylic acid anhydrides are preferable from the viewpoint of improving reactivity. The above acid anhydride compounds include alicyclic acid anhydrides. Among the carboxylic acid anhydrides, alicyclic carboxylic acid anhydrides are preferable from the viewpoint of reducing coloring during heating.

  Specific examples of the alicyclic carboxylic acid anhydride include, but are not limited to, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride (existence ratio: 70/30), 4-methylhexahydrophthalic anhydride, and methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid Anhydride / bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride.

  Specific examples of alicyclic acid anhydrides other than the alicyclic carboxylic acid anhydride include, but are not limited to, tetrapropenyl succinic anhydride, octenyl succinic anhydride, phthalic anhydride, succinic anhydride, trimellitic anhydride Examples include acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

Specific examples of the acid generator are as described above. On the other hand, the base generator is not limited to the following. Ammonium compounds such as quaternary ammonium tetraphenylborate, benzoin compounds, dimethoxybenzyl urethane compounds, orthonitrobenzyl urethane compounds, aromatic sulfonamides, α-lactams, N- (2-arylethenyl) amides, N -Substituted 4- (o-nitrophenyl) dihydroxypyridine, N- (2-nitrobenzyloxycarbonyl) piperidine,
1,3-bis (N- (2-nitrobenzyloxycarbonyl) -4-piperidyl) propane, N, N'-bis (2-nitrobenzyloxycarbonyl) dihexylamine, and o-benzylcarbonyl-N- (1 -Phenylethylidene) hydroxylamine and the like.

  Further specific examples of those listed above include, but are not limited to, for example, 2-hydroxy-2-phenylacetophenone N-cyclohexyl carbamate, nitrobenzyl N-cyclohexyl carbamate, 3,5-dimethoxybenzyl N-cyclohexyl carbamate, dibenzoin isophorone dicarbamate, 1- (2-nitrophenyl) ethyl cyclohexyl carbamate, 2,6-dinitrobenzyl cyclohexyl carbamate, 1- (2,6-dinitrophenyl) ethyl cyclohexyl carbamate, 1- (3 , 5-dimethoxyphenyl) -1-methylethyl cyclohexyl carbamate, 1-benzoyl-1-phenylmethyl cyclohexyl carbamate, 2-benzoyl-2-hydroxy-2-pheny Ruethyl cyclohexyl carbamate, 1,2,3-benzenetriyl tris (cyclohexyl carbamate), 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, 1,1-dimethyl-2-phenylethyl-N-isopropyl carbamate, α- (cyclohexylcarbamoyloxyimino) -α- (4-methoxyphenyl) acetonitrile, N- (cyclohexylcarbamoyloxy) succinimide, N-cyclohexyl-2-naphthalenesulfonamide, N-cyclohexyl p-toluenesulfonamide And N-cyclohexyl-4-methylphenylsulfonamide.

  Further, among the above curing agents, specific examples of amine compounds, amide compounds and phenol compounds are not limited to the following, but include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, Tetraethylenepentamine, dimethylbenzylamine, ketimine compound, polyamide resin synthesized from dimer of linolenic acid and ethylenediamine, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxy Naphthalene etc.) and polycondensates of various aldehyde compounds, polymers of phenols and various diene compounds, polycondensation of phenols and aromatic dimethylol. Condensates of bismethoxymethyl biphenyl and naphthol or phenols, and biphenols, and modified products thereof, imidazole derivatives, boron trifluoride - amine complex, and include guanidine derivatives.

  Here, when a curing agent containing an amine compound (hereinafter, simply referred to as “amine curing agent”) is used, it is preferable to use a trace amount of the amine compound rather than a considerable amount. This is because, when only a small amount of an amine compound is used, coloring of the hybrid cured product according to the present embodiment can be effectively avoided, and a small amount of the amine compound can assist and accelerate curing. . The “trace amount” is preferably 3,000 ppm or less in the resin composition from the viewpoint of sufficiently exhibiting the above effects.

  Moreover, the resin composition according to the present embodiment may contain a curing accelerator. The said hardening accelerator means the curing catalyst used for the purpose of acceleration | stimulation of hardening reaction, may be used individually by 1 type, or may be used in combination of 2 or more types. Although the said hardening accelerator is not restrict | limited in particular, It is preferable to select a tertiary amine and its salt from a viewpoint of the balance of reactivity and coloring at the time of a heating.

  Specific examples of the curing accelerator include, but are not limited to, the following.

  1. Tertiary amines include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine.

  2. As imidazoles, 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4 , 5-Di (hydroxymethyl) imidazole, 1- (2- Anoethyl) -2-phenyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) ) -2-Phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′) )] Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ′)] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, and 2 4-diamino-6- [2'-methylimidazolyl- - (1 ')] isocyanuric acid adduct of ethyl -s- triazine.

  3. Examples of organophosphorus compounds include diphenylphosphine, triphenylphosphine, and triphenyl phosphite.

  4). As quaternary phosphonium salts, benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide Id, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butyl Examples thereof include phosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate.

  5. Examples of the diazabicycloalkenes include 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof.

  6). Examples of the organometallic compound include zinc octylate, tin actylate, and aluminum acetylacetone complex.

  7). Examples of quaternary ammonium salts include tetraethylammonium bromide and tetra-n-butylammonium bromide.

  8). Examples of the metal halogen compound include boron compounds such as boron trifluoride and triphenyl borate, zinc chloride, and stannic chloride.

  The resin composition according to the present embodiment is excellent in heat resistance and has an epoxy which is different from a silicone having a reactive functional group and a silicone having the reactive functional group from the viewpoint of easily forming a homogeneous structure. It is preferable to contain an organic compound having a group. The mass composition ratio of the silicone having a reactive functional group and the organic compound having an epoxy group is preferably 5:95 to 99: 1, more preferably 15:85 to 95: 5, and still more preferably. It is 20: 80-90: 10, More preferably, it is 30: 70-85: 15. When it is within the above range, the heat resistance and toughness of the resin composition can be improved.

  The resin composition according to the present embodiment preferably has an epoxy equivalent of 100 to 20,000 g / eq, more preferably 100 to 10,000 g / eq, and 100 to 5,000 g / eq. Is more preferable, and it is still more preferable that it is 100-2,000 g / eq. When it is within the above range, the curing rate can be further increased.

  Since the resin composition according to the present embodiment is highly reactive among epoxy groups, it preferably has a cycloaliphatic epoxy group from the viewpoint that the phase separation size can be further reduced. If it says in detail about the said viewpoint, it can segment into the following three points. The first point is that the curing rate is fast and the phase can be fixed before phase separation proceeds. The second point is that the silicone can react when it contains a silanol group. The third point is that water is likely to be added, and a hydroxyl group generated thereby can form a hydrogen bond with a silanol group in silicone. Here, the cycloaliphatic epoxy group is, for example, a polycyclic epoxy group composed of an aliphatic ring and an epoxy ring, and is generally obtained by epoxidizing a cyclic body having an unsaturated group. It is done. Examples of the cycloaliphatic epoxy group include, but are not limited to, a cyclohexene oxide group, a tricyclodecene oxide group, and a cyclopentene oxide group.

  In the resin composition according to the present embodiment, it is preferable that at least one of silicone having a reactive functional group and an organic compound having an epoxy group has a cyclic aliphatic epoxy group. However, it may further have an epoxy group other than the cycloaliphatic epoxy group. Examples of such epoxy groups include, but are not limited to, glycidyl ether groups, glycidyl ester groups, glycidyl amine groups, and heterocyclic epoxy groups. The ratio of cycloaliphatic epoxy groups to all epoxy groups is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%, and 75 to 100 mol%. Even more preferably.

  In applying to various uses, it is also possible to use a polyol in combination with the resin composition. Such a polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-hexanediol, 1 , 6-hexanediol and the like.

The silicone having a reactive functional group preferably contains silicon, oxygen, carbon, and hydrogen as constituent elements from the viewpoint of improving compatibility with an organic compound. Further, a metal such as titanium, zirconium, germanium, aluminum or indium may be included as a further constituent element. Among these, silicone is more preferable from the viewpoint of abundant types of raw materials and a high degree of freedom in structural design. Examples of reactive functional groups include, but are not limited to, cyclic ether groups, vinyl groups, mercapto groups, isocyanate groups, hydroxyl groups, carboxyl groups, and amino groups. Further, the reactive functional group is not limited to the following, but is Si-OOCR (R is acryloxy group, acetyl group, acetoxy group, carboxyl group, adipate group, etc.), Si-NR (amino group), Si-H. , Si—O—Ph (phenoxy group), Si—O—N═C (oxime group), Si—N═C—O (amide group), Si—O—BO ₂ (borate), Si—OSO _2- (sulfonate group), Si—O—PO ₃ (phosphate), Si—PO ₃ (phosphite group), Si—F, Si—Cl, Si—I, Si—Br, Si—C≡C, Si— (O—C ₂ H ₄ ) ₃ —N (silacytone), Si—NHCOO (carbamate group), Si—C (═CH ₂ ) —COO—, and Si—NH—CO—NH (urea group) are also included. Illustratively.

  Among the above, silicone having a cyclic ether group is preferable from the viewpoint of high reactivity. The cyclic ether group means an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3-6 membered ring structure. Among them, from the viewpoint of high ring strain energy and high reactivity, a 3-membered or 4-membered cyclic ether group is preferable, a 3-membered cyclic ether group is more preferable, and a 3-membered epoxy group is more preferable. . Examples of the cyclic ether group include, but are not limited to, for example, glycidoxy bonded with oxyglycidyl groups having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, and γ-glycidoxybutyl. Alkyl group, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- ( C5-C8 cycloalkyl having an oxirane group such as 3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, and β- (3,4-epoxycyclohexyl) pentyl group And an alkyl group substituted with a group.

Among these, C ₁ -C such as β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group and the like from the viewpoint of easy availability of raw materials at low cost. C ₅ -C ₈ cycloalkylalkyl group having 3 or less carbon atoms substituted with groups having ₃ glycidoxy group and an oxirane group-oxy glycidyl group is bonded to an alkyl group.

  Moreover, it is preferable that the silicone which has said reactive functional group has a silanol group. The silanol group means a hydroxyl group directly bonded to a Si atom. A silanol group is preferable because it binds to a surface of metal or the like and has excellent adhesion. In addition, silanol groups can react with organic compounds to form crosslinks. This is preferable because the heat resistance of the hybrid cured body according to the first embodiment described above can be improved.

  The silicone having a silanol group is preferably synthesized by a hydrolysis reaction and a condensation reaction from the viewpoint that introduction of the silanol group is easy. Furthermore, it is more preferable to synthesize alkoxysilane as a raw material from the viewpoint that the reaction proceeds slowly and is easy to control.

Silane as a raw material for the hydrolysis reaction and the condensation reaction can be represented by the following formula (7).
(Chemical formula 4)
R ¹ _a Si (OX) _4-a (7)
In the above formula, R ¹ represents the same or different organic group, OX represents the same or different hydrolyzable group or hydroxyl group, and a is an integer of 0 to 3. )

R ¹ representing the organic group is not particularly limited, and examples thereof include an aryl group, a hydrogen atom, and an alkyl group in addition to the organic group that is the reactive functional group described above.

  Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n-propyl group, i-propyl group, butyl group (n-butyl, i-butyl, t-butyl, sec-butyl), Pentyl group (n-pentyl, i-pentyl, neopentyl etc.), hexyl group (n-hexyl, i-hexyl etc.), heptyl (n-heptyl, i-heptyl etc.), octyl group (n-octyl, i-octyl etc.) , T-octyl etc.), nonyl (n-nonyl, i-nonyl etc.), decyl group (n-decyl, i-decyl etc.), and dodecyl group (n-dodecyl, i-dodecyl etc.) Or a branched alkyl group. Among these, from the viewpoint that the ratio of the inorganic component does not become too low, an alkyl group having 10 or less carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group are preferred. Is more preferable. In addition, some or all of these hydrogen atoms or main chain skeletons are ether groups, ester groups, carbonyl groups, siloxane groups and halogen atoms such as fluorine, methacryl groups, acrylic groups, mercapto groups, amino groups and hydroxyl groups. It may be substituted with one or more groups selected from the group consisting of

  The aryl group means a functional group or substituent derived from an aromatic hydrocarbon (simple aromatic ring or polycyclic aromatic hydrocarbon). The aryl group is not particularly limited as long as it fits this meaning, but a phenyl group or a benzyl group is preferable in consideration of steric hindrance in a higher order structure.

  The hydrolyzable group which is one option of the above OX is not limited to the following, and examples thereof include an alkoxy group, a chloro group, an acetoxy group, an isopropenoxy group, and an amino group. Among these, an alkoxy group is preferable from the viewpoint that the reaction is mild and easy to control. Among the alkoxy groups, an alkoxy group having 1 to 8 carbon atoms is more preferable, and a methyl group and an ethyl group are more preferable.

  Among the alkoxysilanes, the proportion of the silane having a reactive functional group is preferably 5 to 100 mol%, more preferably 10 to 99 mol%, still more preferably 20 to 98 mol%, More preferably, it is 30-95 mol%.

  Examples of the alkoxysilane include, but are not limited to, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxy Silane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2 , 3-epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 2 (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, Methoxytrimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, bis ( -Chloroethoxy) methylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltriethoxysilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, ethoxydimethylvinylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxy Methylsilane, methyltris (ethylmethylketoxime) silane, trimethylpropoxysilane, trimethoxyisopropoxysilane, diethoxydimethylsilane, 3- [dimethoxy (methyl) silyl] propane-1-thiol, trimethoxy (propyl) silane, (3 -Mercaptopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, diethoxymethylvinylsilane, butoxytrimethylsilane, butyltrimethoxysilane, Methyltriethoxysilane, methoxyltriethoxysilane, triethoxyvinylsilane, diethoxydiethylsilane, dimethoxyldipropoxysilane, ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, allyltriethoxysilane 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, hexyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-ureidopropyltriethoxysilane, methoxytripropyl Lan, dibutoxydimethylsilane, methyltripropoxysilane, methyltriisopropoxysilane, octyloxytrimethylsilane, pentyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, hexyltriethoxysilane, 3-methacryl Examples include loxypropyltriethoxysilane, octyltriethoxysilane, dodecyloxytrimethylsilane, and diethoxydodecylmethylsilane. Further, tetramethoxysilane and tetraethoxysilane, and partial condensates thereof can also be suitably used. These may be used alone or in combination of two or more.

  Silicone is obtained by hydrolysis and condensation of alkoxysilane, but the reaction temperature at that time is not particularly limited, but is preferably 130 ° C. or less, more preferably 0 to 120 ° C., and still more preferably 0. ~ 100 ° C. When it is within the above range, the resin composition can be effectively prevented from being altered. The reaction time for hydrolysis and condensation is not particularly limited, and is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. When it is within the above range, the remaining amount of the unreacted substance can be effectively reduced.

The amount of water added during the hydrolysis and condensation, is not particularly limited, it is preferable that with respect to OX ² in the formula (8), a 1~5,000mol%, 10~500mol% It is more preferable that it is 20-200 mol%, and it is still more preferable that it is 40-80 mol%. Within the above range, the reaction is likely to proceed, and even if there is a functional group that reacts with water in the system, the occurrence of side reactions can be prevented, thereby effectively reducing the energy cost during dehydration. This is preferable.
(Chemical formula 5)
R ¹ _a Si (OX ² ) _4-a (8)
In the above formula, R ¹ represents the same or different organic group, OX ² represents the same or different hydrolyzable group or hydroxyl group, and a is an integer of 0 to 3.

  The method for adding water during the hydrolysis reaction and the condensation reaction is not particularly limited, and may be added all at once or continuously. When a large amount of water is used, a raw material such as silane may be introduced into the water.

  Water is consumed in the hydrolysis reaction and produced in the condensation reaction. Along with this, the amount of water in the system and the concentration of alcohol generated by hydrolysis change, which may result in a heterogeneous structure of silicone. From the viewpoint of avoiding such a situation, it is preferable to add water little by little in accordance with the rate of hydrolysis reaction and condensation reaction. Alcohol or the like produced by hydrolysis may be returned to the system, but is preferably removed from the system from the viewpoint of increasing the reaction rate and increasing the productivity.

  In the present embodiment, hydrolysis and condensation can be performed in the absence of a solvent or in a solvent. When it is desired to strictly control the reaction temperature, the reaction is preferably carried out under reflux using a solvent. On the other hand, when the reaction rate is desired to be increased as much as possible, the reaction is preferably carried out without a solvent.

  The solvent is not particularly limited as long as it is a solvent that is inactive with respect to the functional group contained in the silane compound. When synthesizing a silicone having a more random structure, it is preferable to use a silane compound to be used, a hydrolyzate thereof, and a solvent capable of dissolving water. Moreover, when it is desired to have a bias in the composition of the silicone, a solvent that does not dissolve any of the silane compound, the hydrolyzate thereof, and water, but phase-separates may be used. Examples of such solvents include, but are not limited to, hydrocarbons such as hexane and cyclohexane, aromatics such as benzene, toluene and xylene, ethers such as dimethyl ether, tetrahydrofuran and dioxane, and methanol, ethanol, butanol and isopropanol. And alcohols such as n-butanol.

  The amount of the solvent added is not particularly limited, but is preferably 20 times or less, more preferably 15 times or less, and even more preferably 10 times the total amount (in terms of mass) of the silane compound. It is as follows. When it is within the above range, the molecular weight tends to be larger, which is preferable from the viewpoint of energy cost.

  In the present embodiment, it is preferable to perform the reaction in the state where an organic compound such as an organic compound having an epoxy group coexists. That is, it is preferable to manufacture the resin composition according to the present embodiment by mixing the silicone and the organic compound. When it is difficult to mix homogeneously due to the high viscosity of the organic compound or silicone to be synthesized, it is preferable to react using a solvent in the presence of both, but it is possible to mix homogeneously later. In some cases, it is preferable to carry out the reaction without adding an organic compound because the reaction rate is likely to increase. In particular, when a hydroxyl group is present in the organic compound, a condensation reaction occurs between the hydroxyl group of the organic compound and the silicone in competition with the hydrolysis and condensation reaction of silicone, and a Si—O—C bond can be generated. When the Si—O—C bond remains, the moisture resistance decreases, so it is preferable not to allow a compound having a hydroxyl group to coexist. When a compound having a hydroxyl group needs to coexist, it is preferable to completely hydrolyze the Si—O—C bond by adding water.

  In the present embodiment, a catalyst that contributes to the hydrolysis reaction and the condensation reaction may be added. The catalyst is not limited to the following as long as it promotes a conventionally known hydrolysis reaction and condensation reaction. For example, metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, Zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium , Zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases ( Magnesium oxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base ( Ammonia, tetramethylammonium hydroxide, etc.), inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, etc.), and organic acids (acetic acid, formic acid, glycolic acid, etc.). Among these, acids and organic metals are preferable from the viewpoint of high hydrolysis reactivity and easy control of higher order structures, more preferably organic acids, inorganic solid acids and organic tins, and more preferably tin organic acids. Salts and inorganic solid acids.

  These catalysts may be used alone or in combination of two or more. For example, after reacting with an organic acid, an organic acid salt such as tin may be added to accelerate the reaction. It is also possible to treat with an inorganic base after reacting with an organic acid salt such as tin. As the inorganic base in this case, a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide is preferable from the viewpoint that it can be easily removed by filtration or the like. The final treatment with an inorganic base is preferable because the condensation rate can be easily increased. On the other hand, it is preferable to avoid the reaction with only an inorganic base from the beginning if possible because the hydrolysis reaction can proceed somewhat slowly. In addition, the condensation with a base catalyst is usually an equilibrium reaction and settles into an energetically stable structure, so that it may be difficult to control the higher order structure. In the case of a short time treatment with an inorganic base after reacting with another catalyst in advance, the condensation reaction proceeds more preferentially than the decomposition reaction of the siloxane bond, so condensation is performed while maintaining the higher-order structure formed with the first catalyst. The rate can be improved, which is preferable.

  The above organic tin refers to one in which at least one organic group is bonded to a tin atom. Examples of the structure include monoorganotin, diorganotin, triorganotin, and tetraorganotin. Among them, diorganotin is preferable from the viewpoint of easily controlling the reaction. In addition, organic tin carboxylates are preferable among the organic tins from the viewpoints that the opening of the oxirane ring during hydrolysis and condensation can be suppressed and that the molecular weight of the resin composition is easily controlled.

  Examples of the organic tin include, but are not limited to, for example, tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin dioxide. Acetate, dibutyltin dioctate, dibutyltin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate Dibutyltin bis (acetylacetonate), dibutyltin bis (ethyl maleate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmaleate) G), dibutyltin bis (stearyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin bis (2-ethylhexyl mercaptopropionate), dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, Dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctate, dioctyltin didodecylmercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethylmalate), dioctyltin bis ( Octylmalate), dioctyltin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyl Examples include tin dibutoxide, tin octylate, and tin stearate. Of these, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin diacetate are preferable from the viewpoint of easy control of the reaction.

  Examples of the solid acid catalyst include, but are not limited to, Amberlyst 15 (trade name, manufactured by Organo), Diaion PK (trade name, manufactured by Mitsubishi Chemical) and Purolite CT (trade name, manufactured by Purolite). Ion-exchange resins such as Nafion (trade name, manufactured by DuPont), activated clay, activated clay, zirconia sulfate, and zeolite. Among these, activated clay is preferable from the viewpoint of price, and ion exchange resin is preferable from the viewpoint of ease of handling. The solid acid catalyst can be preferably used because it can be removed from the reaction system after the reaction. By removing the catalyst, an unintended condensation reaction can be suppressed. The method for removing the solid acid catalyst is not limited to the following, and examples thereof include vacuum filtration, pressure filtration, and atmospheric pressure filtration.

  The amount of the catalyst added is not particularly limited, but is preferably 0.0005 to 50 mol%, more preferably 0.001 to 5 mol%, more preferably 0.001 mol% with respect to the silane compound. It is more preferable that it is 005-3 mol%, and it is still more preferable that it is 0.01-1 mol%. When it is within the above range, the effect of adding the catalyst can be sufficiently obtained, and the control of the reaction can be facilitated.

Regarding the resin composition according to the present embodiment, which is a raw material of the hybrid cured product, the average composition of silicone synthesized by hydrolysis and condensation of alkoxysilane is represented by the following formula (2).
(Chemical formula 6)
R ¹ _a Si (OX) _b O _{(4-ab) / 2} (2)
In the above formula, R ¹ represents the same or different organic group, OX represents the same or different hydrolyzable group or hydroxyl group, and a and b are each independently an integer of 0 to 3. )

At that time, the condensation rate of the silicone is represented by the following formula (3).
(Equation 8)
Condensation rate = 100 × {(4-ab) / (4-a)} (3)

  The condensation ratio of the silicone represented by the formula (3) is preferably 30 to 99%, more preferably 50 to 98%, still more preferably 70 to 97%, and 85 to 96%. Even more preferably. When the amount is within the above range, the remaining amount of hydrolyzable groups and silanol groups can be significantly reduced, so that generation of voids and the like during molding can be effectively prevented. In addition, the adhesive force due to silanol groups can be significantly improved. From the viewpoint of adhesiveness, the proportion of hydroxyl groups (OH) in OX in the general formula (3) is preferably 30% or more, more preferably 45% or more, and 60% or more. More preferably, it is still more preferably 75% or more.

In addition, regarding the production of the resin composition according to the present embodiment, which is a raw material for the hybrid cured body, the structural unit of the D body represented by the following formula (4) is included in the total amount of the alkoxysilane that is the raw material. It is preferably 5 to 99 mol%, more preferably 10 to 95 mol%, still more preferably 20 to 90 mol%, still more preferably 30 to 90 mol%. Since the structural unit of the D body is excellent in mobility, the viscosity is lower, the stress relaxation property is excellent, and as a result, hardening strain is easily eliminated. In particular, from the viewpoint of mobility, R ¹ R ² preferably contains at least one of a methyl group and an ethyl group, and more preferably R ¹ R ² contains a methyl group. The amount of alkoxysilane in which R ¹ R ² is a methyl group is preferably 5 to 70 mol%, more preferably 5 to 50 mol%, and further preferably 5 to 30 mol% of all alkoxysilanes. .
(Chemical formula 7)
R ¹ R ² Si (OX) ₂ (4)
In the above formula, R ¹ and R ² represent the same or different organic groups, and OX represents the same or different hydrolyzable groups or hydroxyl groups.

  Thus, it is possible to obtain a silicone by hydrolyzing and condensing an alkoxysilane containing the structural unit of D-form represented by the above formula (4) in the above-described range, and mixing this silicone with an organic compound. It is suitable for producing the resin composition according to the embodiment.

  The resin composition according to the present embodiment is preferably excellent in storage stability. The storage stability in the present embodiment is represented by a change in viscosity when the resin composition is stored in a sealed container at 60 ° C. for 72 hours. The ratio of the viscosity after 72 hours to the initial viscosity, which represents the storage stability, is preferably 0.90 to 3.0, more preferably 0.95 to 2.0, and 0.99. It is more preferable that it is -1.5, and it is still more preferable that it is 1.0-1.1. In the above range, as a result of effectively suppressing the release of low molecules, the amount of volatile components can be significantly reduced, and in addition, changes in physical properties over time can be prevented.

  The method for improving the storage stability is not limited to the following, but firstly, a method of removing and deactivating the catalyst, and secondly, a method of sealing silanol can be considered. As the first method, when a solid catalyst is used, means such as filtration is effective. When an acid catalyst or a base catalyst is used, a means such as neutralization is effective. It is also possible to adsorb and remove the catalyst with activated carbon or the like. As the second method, any compound that reacts with a silanol group can be used without particular limitation, but it is preferably a group that is not easily hydrolyzed after the silanol is sealed. For example, higher alcohols are preferable for alcohols, and trisubstituted silicon compounds are preferable.

  Although it does not restrict | limit to the following as a substituent of the said 3 substituted silicon compound, For example, an alkyl group, an aryl group, and various reactive groups are mentioned. Specifically, when it is desired to increase hydrophobicity, an alkyl group is preferable, and when it is desired to increase compatibility with an organic compound before curing, an aryl group is preferable, and in order to suppress phase separation during curing. It is preferable to introduce a reactive group capable of reacting with an organic compound.

  The means for introducing a trisubstituted silicon compound is not limited to the following, but generally a compound called a silylating agent can be preferably used. Examples of the silylating agent include, but are not limited to, trimethylsulfoxonium iodide, 2,2,2-trifluoro-1-trimethylsiloxy-N-trimethylsilylethaneimine, N, O-bis (trimethylsilyl) acetamide N-methyl-N-trimethylsilyltrifluoroacetamide, trimethylsilyldimethylamine, trimethylsilyldiethylamine, N-methyl-N-trimethylsilylacetamide, trimethylchlorosilane, hexamethyldisilazane, hexamethyldisiloxane, trimethylsilanol, and methoxytrimethylsilane Can be mentioned. The silylating agent is a compound for introducing a trimethylsilyl group, but a similar compound having an aryl group or a reactive functional group can also be used as the “silylating agent”. These compounds (reagents) may be used alone or in combination of two or more. The synthesized silicone may be treated with these reagents, or may be used during the hydrolysis reaction and condensation reaction in order to adjust the molecular weight. In that case, you may use the catalyst for promoting a hydrolysis reaction and a condensation reaction.

  Here, the conditions for the hydrolysis reaction and the condensation reaction are not limited to the following, but it is preferable to carry out these reactions after removing water or a solvent. When water is present, a silanol body of a trisubstituted silicon compound may be generated as an impurity. In the presence of a solvent, the reaction efficiency may decrease. When the resin composition has a high viscosity, it is preferable to recover the remaining silylating agent after silylation using an excessive amount of the reaction reagent.

  Although the organic compound which has an epoxy group as a reactive functional group is not restrict | limited to the following, what is necessary is just to have an oxirane ring in the molecule | numerator. In order to form a highly crosslinked structure, it is preferable that two or more oxirane rings are contained in one molecule. The organic compound having an epoxy group may be used alone or in combination of two or more. Although not limited to the following, for example, an epoxy resin obtained by a crosslinking curing reaction, an epoxy group-containing (meth) acrylate resin, an epoxy group-containing thermosetting polyimide resin, an epoxy group-containing urea resin, an epoxy group-containing melamine resin, and an epoxy group A contained unsaturated polyester resin is mentioned. Among these, from the viewpoint of high reactivity and easy control of the phase separation structure, an epoxy resin and an epoxy group-containing (meth) acrylate resin are preferable, and an epoxy resin is more preferable.

  The epoxy equivalent in the epoxy resin is preferably 100 to 1,000 g / eq, more preferably 100 to 700 g / eq, still more preferably 100 to 500 g / eq, and even more preferably 100 to 300 g / eq. It is. Within the above range, the molecular mobility is excellent and the curing rate can be increased. In addition, the measuring method of the said epoxy equivalent is the same method as what was used in the Example mentioned later.

  The epoxy resin is preferably a liquid having a viscosity at 25 ° C. of 1,000,000 mPa · s or less, more preferably 100,000 mPa · s or less, and still more preferably 10,000 mPa · s. The following liquid, and even more preferably a liquid of 1,000 mPa · s or less. When the amount is within the above range, it is possible to avoid the limitation of the manufacturing conditions, and it is preferable because the manufacturing becomes easier.

  The type of the epoxy resin is not limited to the following, for example, a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound, a cyclic aliphatic epoxy resin, a polyfunctional epoxy resin that is a glycidyl etherified product of various novolak resins, and an aromatic Examples thereof include a nuclear hydride of an aliphatic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, and an epoxy resin obtained by glycidylating a halogenated phenol. Among them, from the viewpoint of being easily available and imparting good physical properties as a cured product, a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound and a cyclic aliphatic epoxy resin are preferable, and a cyclic aliphatic is preferable. An epoxy resin is more preferable. Moreover, these epoxy resins may be used individually by 1 type, or may be used in combination of 2 or more type.

  The cycloaliphatic epoxy resin is not particularly limited as long as it is an epoxy resin having a cycloaliphatic epoxy group. For example, a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, etc. The epoxy resin which has is mentioned. The cycloaliphatic epoxy group is as described above. Examples of cycloaliphatic epoxy resins include, but are not limited to, for example, 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexylcarboxylate, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane. And 1,2,8,9-diepoxy limonene.

  The polyfunctional epoxy resin that is a glycidyl etherified product of the above polyphenol compound is not particularly limited. The skeleton of such a polyfunctional epoxy resin is not limited to the following, but examples include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol. F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1- Bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-t) -Butylphenol), trishydroxyphenyl Phenols having a skeleton such as tan, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, and diisopropylidene; having a fluorene skeleton such as 1,1-di (4-hydroxyphenyl) fluorene Phenols; and phenolic polybutadiene. Among the above, glycidyl of phenols having a bisphenol A skeleton from the viewpoint that many of the types excellent in transparency and fluidity are commercially available and are available at low cost and have excellent thermal shock resistance when cured. A polyfunctional epoxy resin which is an etherified product is preferred.

  As the epoxy resin, the repeating unit in the case of using the polyfunctional epoxy resin which is a glycidyl etherified product of the polyphenol compound described above is not limited to the following, but is preferably less than 50, more preferably 0.001 to 5, more preferably Is 0.01-2. When it is within the above range, the fluidity is further improved, which is practically advantageous.

  Examples of the polyfunctional epoxy resin that is a glycidyl etherified product of the novolak resin include, but are not limited to, for example, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherified products of novolak resins made from various phenols such as thiols, and various types such as phenol novolac resins containing xylylene skeletons, phenol novolac resins containing dicyclopentadiene skeletons, phenol novolac resins containing biphenyl skeletons, and phenol novolac resins containing fluorene skeletons Examples thereof include glycidyl etherified products of novolak resins.

  Examples of the nuclear hydride of the aromatic epoxy resin include, but are not limited to, glycidyl etherified products of phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.), various phenols (phenol, Cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and the hydrogenated glycidyl ethers of novolak resins. .

  Examples of the aliphatic epoxy resin include, but are not limited to, polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, and xylylene glycol derivatives. Of glycidyl ethers.

  Although it does not restrict | limit as said heterocyclic epoxy resin below, For example, the heterocyclic epoxy resin which has heterocyclic rings, such as an isocyanuric ring and a hydantoin ring, is mentioned.

  The glycidyl ester-based epoxy resin is not limited to the following, and examples thereof include epoxy resins made of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.

  Examples of the glycidylamine epoxy resin include, but are not limited to, for example, epoxy resins obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Is mentioned.

  Examples of the epoxy resin obtained by glycidylating the halogenated phenols include, but are not limited to, for example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, and chlorinated bisphenol. S and epoxy resins obtained by glycidyl etherification of halogenated phenols such as chlorinated bisphenol A can be mentioned.

  The resin composition (second embodiment) and its cured body (first embodiment) according to the present embodiment are used for the purpose within a range that does not impair the desired effect of the present embodiment. Appropriately add various organic resins, inorganic fillers, leveling agents, lubricants, surfactants, silicone compounds, reactive diluents, non-reactive diluents, antioxidants, light stabilizers, etc. Can do. Other general additives for resins (plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial and antifungal agents, conductive fillers, antifogging agents, crosslinking agents, etc.) What is marketed as may be mix | blended.

  Here, the organic resin is not limited to the following, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. Among these, an epoxy resin is preferable from the viewpoint that one having a highly reactive organic group is advantageous.

  Examples of the leveling agent include, but are not limited to, oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, and water. There are added castor oil and a titanium coupling agent. These leveling agents may be used alone or in combination of two or more.

  Examples of the inorganic filler include, but are not limited to, silicas (fused crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, Calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, titanic acid Examples include barium, glass fiber, carbon fiber, and molybdenum disulfide. Among these, silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, and calcium silicate are preferable. Considering the physical properties of the cured product, silicas are more preferable.

  Examples of the lubricant include, but are not limited to, hydrocarbon lubricants such as paraffin wax, microwax, and polyethylene wax, and higher fatty acid systems such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Lubricants, stearylamide, palmitylamide, oleylamide, higher fatty acid amide type lubricants such as methylenebisstearoamide, ethylene bisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, Higher fatty acid ester lubricants such as di-, tri-, or tetra-stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic Natural waxes such as metal soaps such as magnesium, calcium, cadmium, barium, zinc and lead such as acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid and naphthenic acid, carnauba wax, candelilla wax, beeswax and montan wax Kind. These lubricants may be used alone or in combination of two or more.

  The above surfactant means an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. To do. In addition, the type is not limited to the following, and examples thereof include silicone surfactants and fluorine surfactants. Surfactants may be used alone or in combination of two or more.

  Examples of the silicone compound include, but are not limited to, silicone resins, silicone condensates, silicone partial condensates, silicone oils, silane coupling agents, silicone oils, and polysiloxanes. Or what modified | denatured by introduce | transducing an organic group into a side chain is also contained. Examples of the modification method include, but are not limited to, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, poly Examples include ether modification, polyether methoxy modification, and diol modification.

  Examples of the reactive diluent include, but are not limited to, alkyl glycidyl ether, alkylphenol monoglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, and ethylene glycol. Examples include diglycidyl ether and propylene glycol diglycidyl ether. On the other hand, examples of the non-reactive diluent include, but are not limited to, high boiling solvents such as benzyl alcohol, butyl diglycol, and propylene glycol monomethyl ether.

  Examples of the antioxidant include, but are not limited to, organic phosphorus-based antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic sulfur-based compounds such as distearyl-3,3′-thiodipropinate. Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.

  Examples of the light stabilizer include, but are not limited to, UV absorbers such as benzotriazole, benzophenone, salicylate, cyanoacrylate, nickel, and triazine, and hindered amine light stabilizers. It is done.

  As described so far, the resin composition and the cured product thereof according to the present embodiment are extremely advantageous in that they are excellent in heat resistance, transparency, adhesion, and stress relaxation properties and are free from defects such as voids and cracks. Demonstrate the effect. From such a viewpoint, the use of the resin composition and the cured product thereof is not limited to the following. For example, electronic materials (such as castings such as insulators, AC transformers, switchgears, circuit units, various parts) Packaging materials, sealing materials for ICs, LEDs, semiconductors, generators, rotating coils for motors, winding impregnation, printed wiring boards, insulation boards, medium-sized insulators, coils, connectors, terminals, various cases, electricity Parts), paint (corrosion resistant paint, maintenance, marine paint, corrosion resistant lining, primer for automobiles and home appliances, beverage / beer cans, outer surface lacquer, extruded tube paint, general corrosion resistant paint, maintenance halfway, lacquer for woodworking products, Automotive electrodeposition primer, other industrial electrodeposition coatings, beverage / beer can inner surface lacquer, coil coating, drum / can inner surface coating, acid resistance Inning, wire enamel, insulation paint, automotive primer, exterior and anticorrosion coating of various metal products, pipe interior and exterior coating, electrical component insulation coating, etc.), composite materials (chemical plant pipes and tanks, aircraft materials, automotive parts, etc.) , Various sporting goods, carbon fiber composite materials, aramid fiber composite materials, etc.), civil engineering and building materials (floor materials, paving materials, membranes, anti-slip / thin layer pavement, concrete jointing / uplifting, anchor embedded adhesion, precast concrete joining , Tile adhesion, crack repair of concrete structures, grouting and leveling of pedestals, anticorrosion and waterproofing of water and sewage facilities, corrosion resistant laminated lining of tanks, anticorrosion coating of iron structures, mastic coating of exterior walls of buildings, etc.), adhesion Agent (same or different of metal, glass, ceramics, cement concrete, wood, plastic, etc.) Adhesives of materials, adhesives for assembling automobiles, railway vehicles, aircraft, etc., adhesives for manufacturing prefabricated composite panels, etc .: including one-part, two-part, and sheet types), aircraft, automobile, plastic molding Jigs (resin molds such as press dies, stretched dies, matched dies, vacuum molding / blow molding molds, master models, casting patterns, laminated jigs, various inspection jigs, etc.), modifiers / stabilizers (fiber Resin processing, stabilizers for polyvinyl chloride, additives to synthetic rubber, etc.) and the like (semiconductor applications, light emitting diode (LED) applications, liquid crystal applications).

  The said sealing material means the material for sealing so that substances (foreign substances), such as a liquid and gas, may not enter the inside of components. The substance (foreign matter) includes physical impacts such as temperature, humidity and dust.

  In these applications, other members made of epoxy resin, silicone resin, epoxy silicone resin, acrylic resin, urethane resin, urea resin, imide resin, glass, or the like may be used in combination.

  In addition, the resin composition and the cured product thereof according to the present embodiment are semiconductor / LED peripheral materials (lens material, substrate material, die bond material, chip coating material, laminated plate, optical fiber, optical waveguide, optical filter, for electronic components) Adhesives, coating materials, sealing materials, insulating materials, photoresists, encap materials, potting materials, light transmission layers and interlayer insulating layers of optical disks, printed wiring boards, laminates, light guide plates, antireflection films, etc.) It can also be used for applications.

  Examples of the lens material include, but are not limited to, lenses for optical devices, automobile lamp lenses, eyeglass lenses, pickup lenses such as CD / DVD, and projector lenses.

  The use of the LED sealing material is not limited to the following, but is a display, an electric display panel, a traffic light, a display backlight (organic EL display, mobile phone, mobile PC, etc.), automobile interior / exterior certification, illumination, lighting equipment And can be deployed in a wide range of fields such as flashlights.

  Other substances may be added to the resin composition and the cured body thereof according to the present embodiment as long as the effects of the present embodiment are not impaired. Examples of such other substances include, but are not limited to, solvents, oils and fats, processed oils, natural resins, synthetic resins, pigments, dyes, dyes, release agents, preservatives, adhesives, deodorizers, and agglomerates Agent, cleaning agent, deodorant, pH adjuster, photosensitive material, ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agricultural chemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant Agent, rust preventive agent, metal compound, filler, cosmetics / pharmaceutical raw material, dehydrating agent, desiccant, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, defoaming agent Agent, curing agent, reducing agent, flux agent, film treatment agent, casting raw material, mineral, acid / alkali, shot agent, antioxidant, surface coating agent, additive, oxidizing agent, explosives, fuel, bleaching agent, light emission Element, fragrance, concrete, fiber (carbon fiber, aramid fiber, glass Cellulose fiber, etc.), glass, metal, excipients, disintegrants, binders, fluidizing agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, and include thickeners.

  [Third Embodiment: Composite Transparent Sheet]

  The composite transparent sheet according to the third embodiment contains the hybrid cured body and the filler according to the first embodiment. Moreover, the said composite transparent sheet is obtained by mixing the said resin composition and a filler, and pressing to a sheet form, hardening with a heat | fever or an energy ray.

  Each of the cured product and the resin composition is excellent in heat resistance and moldability. Therefore, by compounding with a filler, the thermal expansion coefficient is low, the change in elastic modulus with temperature change is small, and the smoothness is excellent. A composite transparent sheet is obtained. From the viewpoint of improving transparency, the filler is preferably a filler having a wavelength smaller than the visible light wavelength or a filler having no absorption in the visible light region.

  Since the resin composition of this Embodiment mentioned above contains an inorganic component, there exists an advantage that a filler is easy to disperse | distribute uniformly. Therefore, the composite transparent sheet according to the present embodiment is formed with a high degree of composite, has a low coefficient of thermal expansion, a small change in elastic modulus due to a temperature change, excellent smoothness, and a high light transmittance. In addition, there is little variation in the in-plane optical properties.

  Examples of the filler include, but are not limited to, carbon fibers, celluloses, inorganic compounds, and glass. Among these, from the viewpoint of excellent heat resistance, inorganic compounds and glass are preferable, and glass is more preferable. The shape of the filler is not limited to the following, but can be freely selected from, for example, a particulate shape, an indefinite shape, a fiber shape, and a mesh shape. Further, from the viewpoint of reducing the linear expansion coefficient (described later) of the sheet plane, the filler preferably forms a continuous phase, and specifically, a fibrous or network shape is preferably used. These fillers may be used alone or in combination of two or more. It is preferable that content of the said filler is 1-90 mass% with respect to the composite transparent sheet obtained, More preferably, it is 10-80 mass%, More preferably, it is 30-70 mass%. When it is within the above range, the effect of low linear expansion by compounding becomes large, and the moldability can be significantly improved.

  Examples of the inorganic compound include, but are not limited to, silicas (fused crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, carbonic acid Calcium, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate Glass fiber, carbon fiber, and molybdenum disulfide. Silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, and calcium silicate are preferable. Considering the physical properties of the cured product, silicas are more preferable.

  Examples of the glass filler include, but are not limited to, glass fiber, glass cloth, glass nonwoven fabric, glass beads, glass flakes, glass powder, and middle glass. Among these, glass fiber, glass cloth, and glass nonwoven fabric are preferable, and glass cloth is more preferable from the viewpoint that the effect of reducing the linear expansion coefficient (described later) is even higher. Although it does not restrict | limit to the kind of glass below, For example, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, and quartz glass are mentioned. Among these, S glass, T glass, and NE glass are preferable from the viewpoint of easy control of the refractive index as a resin and easy availability. The thickness, weave density and texture of the glass cloth can be selected according to the intended silicone-epoxy hybrid glass cloth composite sheet. Further, from the viewpoint of improving resin impregnation property and surface unevenness, it is a preferable and effective technique to physically open the yarn bundle of the glass cloth.

  Since the surface of the filler is treated with a silane coupling agent, various surfactants, and washing with an inorganic acid, the wettability, affinity, and adhesion at the interface between the filler and the resin are increased. preferable.

  Since the composite transparent sheet according to the present embodiment can be used as a display element substrate as its specific application, it is preferable that the composite transparent sheet is excellent in transparency as one of practical performances. Therefore, it is preferable that the difference in refractive index between the cured body or the resin composition and the filler is as small as possible. Here, as the refractive index, a value (nD) measured using sodium D-line (wavelength 589.2 nm) is used. The difference in refractive index between the cured body or resin composition and the filler is preferably 0.02 or less, and more preferably 0.01 or less. If it is within the above range, the transparency can be improved.

The Abbe number of the hybrid cured body according to the first embodiment is preferably 40 or more from the viewpoint of minimizing chromatic aberration of the sheet. Here, the relationship between the Abbe number and chromatic aberration is attributed to the dispersibility or spectral property of the light wavelength caused by the difference in refractive index between the cured body constituting the sheet and the filler. The larger the chromatic aberration is, the more the image seen through the sheet becomes “colored”, and the performance as a display substrate is remarkably deteriorated. Therefore, the Abbe number is used as an index of the degree of such chromatic aberration. The Abbe number V is expressed by the following formula (9), and has a relationship that the higher the Abbe number, the smaller the chromatic aberration.
(Equation 9)
Abbe number (V) = (nD-1) / (nF-nC) (9)
In the above formula, nD, nF, and nC are refractive indexes for light having a material wavelength of D-589.2 nm, F-486.1 nm, and C-656.3 nm, respectively.

  In order to adjust the refractive index and Abbe number of the above-mentioned hybrid cured product, it is not limited to the following, but the structure of the organic compound, the structure of the silicone, the molecular volume, and the additive are added. A combination of these means can be executed. In particular, in order to adjust the refractive index so as to obtain a glass having a high refractive index, it is preferable to add high refractive fine particles such as titanium and zirconium, and condensation with alkoxysilane using titanium alkoxide, zirconium alkoxide, etc. It is also preferable that

  The transparency exhibited by the composite transparent sheet according to the present embodiment means that the light transmittance in the wavelength region of visible light is 60% or more, preferably 80% or more. The wavelength region of the visible light is 400 to 800 nm.

The composite transparent sheet has higher heat resistance because a cured body excellent in heat resistance and adhesiveness and a filler are highly complexed. Here, “heat resistance of the composite transparent sheet” means that the change in the storage elastic modulus in the dynamic viscoelasticity measurement is small, for example, satisfying the following formula (10).
(Equation 10)
E1'25 / E1'250 ≦ 1.8 (10)
In the above formula, E1′25 represents the storage elastic modulus of the transparent resin sheet at 25 ° C. in the dynamic viscoelasticity measurement, and E1′250 represents the storage elastic modulus of the transparent resin sheet at 250 ° C in the dynamic viscoelasticity measurement. Represent.

  That the dynamic viscoelasticity of the transparent resin sheet satisfies the above relational expression indicates that the decrease in the strength of the sheet due to temperature change is small. As a result, the degree of expansion and deformation of the sheet due to heating is reduced.

  The composite transparent sheet according to the present embodiment preferably has no optical defect, that is, has excellent optical characteristics. The optical defect means a void generally called a void or a foreign substance having a different refractive index. As for the cause of voids, the first cause is air mixed when the resin composition and the filler before curing are mixed, the second cause is a gas generated at the time of curing, and the third cause is curing. Distortions that occur when subjected to time or temperature cycles are considered. The first cause can be reduced by increasing the temperature when mixing the resin composition and the filler to lower the viscosity or performing vacuum defoaming. About a 2nd cause, it can reduce by methods, such as removing the excess volatile matter from a resin composition, or suppressing the side reaction which generate | occur | produces gas. In particular, when a large amount of alkoxy groups remain in the silicone, voids generated due to the second cause can be a problem, and thus the above method is particularly effective. The third cause can be reduced by adjusting the temperature condition during curing and the temperature cycle condition, or introducing a stress relaxation component in the resin. The above cured body and resin composition are further excellent in stress relaxation when the specific relaxation index described above is satisfied. Therefore, the composite transparent sheet is less likely to generate voids.

  The transparent resin sheet according to the present embodiment preferably has a small linear expansion coefficient. The “linear expansion coefficient” in the present embodiment refers to an average linear expansion coefficient at 25 to 250 ° C. The linear expansion coefficient is preferably 1 to 40 ppm, more preferably 1 to 30 ppm, further preferably 1 to 20 ppm, and even more preferably 1 to 12 ppm. The hybrid cured body according to the first embodiment has a strong interface with the filler because it contains silicone and suppresses phase separation. The resin composition according to the second embodiment has the specific relaxation index described above, and can flexibly change the interface between the resin composition and the filler. From these characteristics, when the hybrid cured product is combined with a filler, the linear expansion coefficient can be significantly reduced.

  In addition, the coefficient of thermal expansion usually changes rapidly before and after the glass transition temperature. However, if a thermal history that crosses the glass transition temperature is added, problems such as disconnection are likely to occur, which is not preferable. The difference in linear expansion coefficient before and after the glass transition temperature of the composite transparent sheet is preferably 20 ppm or less, more preferably 15 ppm or less, further preferably 10 ppm or less, and preferably 5 ppm or less. Even more preferred. The above-mentioned hybrid cured body is preferable because the change in elastic modulus due to heat is small and the change in thermal expansion coefficient due to heat tends to be small.

  When the composite transparent sheet according to the present embodiment is used as a circuit board or a display element substrate, the thickness of these substrates is preferably 5 to 2,000 μm, more preferably 10 to 1,000 μm. More preferably, it is 15-200 micrometers, More preferably, it is 15-80 micrometers. When the thickness of the substrate is within the above range, the flatness is excellent, and the weight of the substrate can be reduced as compared with a glass substrate or the like. Thus, the composite transparent sheet can replace the glass substrate.

  Crack resistance is also important when processing sheets. Since the above-mentioned hybrid cured body has the specific relaxation index described above, not only heat but also physical impact can be reduced. In addition, since the interface between the filler and the cured body is strong, as a result, the hybrid cured body is extremely excellent in crack resistance.

  For applications such as liquid crystals, the birefringence of the sheet is also important. The in-plane birefringence of the sheet is preferably 5 nm or less, more preferably 3 nm or less, still more preferably 2 nm or less, and even more preferably 1 nm or less. In the case of a cured resin, birefringence is caused by strain due to stress. On the other hand, since the hybrid cured product is excellent in stress relaxation and has a very small degree of distortion, the occurrence of birefringence can be effectively suppressed.

  The method for producing the composite transparent sheet according to the present embodiment is not particularly limited, but from the viewpoint of easily obtaining a uniform molded product with few foreign substances such as bubbles, the resin composition and the filler are used. It is preferable to have a step of mixing and a step of curing the resin. Although not limited to the following, for example, a method in which a resin composition and a filler are directly mixed and cast after being cast into a required mold, and the resin composition is dissolved in a solvent, the filler is dispersed, and after the casting is crosslinked And a method of crosslinking after impregnating a glass cloth or a glass nonwoven fabric with the resin composition.

  Moreover, depending on the case, it is also preferable to smooth the sheet | seat surface by mixing a resin composition and a filler and pressing into a sheet form, hardening with a heat | fever or an energy ray. Here, when an epoxy group is present, deterioration due to oxygen generally tends to occur at a high temperature. Therefore, it is preferable to perform the press working under a vacuum or an inert gas not containing oxygen.

  Further, the composite transparent sheet according to the present embodiment can be applied to various substrates (display element substrates) having excellent transparency. At that time, for the purpose of improving the surface roughness, and also for the purpose of protection from mechanical or chemical damage in the assembly process, a cured film obtained by applying and curing a curable resin varnish on the surface of the substrate is used. It may be formed. Examples of the curable resin varnish include, but are not limited to, photocurable resins containing acrylic esters such as epoxy acrylate, urethane acrylate and polyester acrylate, epoxy resins such as o-cresol novolac type and bisphenol type, Examples thereof include thermosetting resins containing urethane, acrylic acid esters and unsaturated polyesters, and electron beam curable resins. Among these, from the viewpoint of improving productivity and the like, a photocurable resin is preferable. The cured film is preferably substantially transparent and optically isotropic. The method for forming the cured film on the substrate is not limited to the following, and examples thereof include a gravure coating method, a reverse roll coating method, and a kiss roll coating method. If necessary, a resin coating layer, a gas barrier layer against water vapor or oxygen, a transparent electrode layer, and the like may be provided on the composite transparent sheet.

  Moreover, when manufacturing the said composite transparent sheet, as above-mentioned, it is preferable that the said resin composition further contains an acid generator from a viewpoint of reducing colorability (improving transparency).

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to only these examples. The present invention will be described based on examples, but the present invention is not limited to the following examples.

  First, evaluation of physical properties in Examples and Comparative Examples will be described below.

  [Evaluation of physical properties]

  <Measurement of phase separation structure size using X-ray small angle scattering method (SAXS)>

  The X-ray small angle scatter measurement apparatus generally includes a block collimator optical system for achieving a small angle resolution, an all-vacuum chamber that eliminates air scattering, and a direct beam position and a beam intensity after transmission through a detector. In general, it is composed of a semi-transmission beam stopper or the like that measures simultaneously. However, the above configuration was appropriately selected depending on the measurement object and its properties, the scale of the measurement object, and the like.

  (Measurement and data handling)

The intensity at which X-rays are scattered with respect to the sample to be measured is obtained by integrating all the existing electron densities, and is represented by the following formula (11).
(Equation 11)
(11)
In the above formula, q is a scattering vector, where θ is the scattering angle, and is represented by the following formula (12).
(Equation 12)
q = 4πsin (θ / 2) / λ (12)
In the above formula (11), r is the distance in real space, δρ is the density of the phase separation region portion such as particles, and ρ _ave is the average density. Capillaries or solvents that fill or support the sample can be a medium that scatters X-rays. Therefore, the capillary or solvent was measured in advance as a blank, and after performing absorption correction, it was subtracted from the scattering intensity (that is, equivalent to subtracting the first term on the right side in the above equation (11)). For example, in a dilute system with a sample concentration of 1% by mass or less, there is no need to consider the interaction between the phase separations of the sample, and it can be regarded as if only the phase separation components are dispersed in the vacuum. It becomes possible to discuss the phase separation structure (shape) in comparison with a typical scattering profile.

  (Data analysis method based on Guinier's law)

By using this method, the average size of the phase separation structure including the interface information was estimated. The density inside the scatterer was assumed to be uniform, the shape (sphere, rod, plate, etc.) was assumed, and the phase separation structure was assumed to be monodisperse. Then, linear linear approximation was performed for the low-angle part of the obtained data (scattering profile). Specifically, when this analysis method is applied to the scattering profile obtained by the calculation described above, an approximated straight line is obtained, and the inertia radius (Rg) is calculated from the inclination. When it is assumed that the phase separation structure is a sphere between the real space distance (r) and the inertial radius (Rg), the following relational expression (13) is established.
(Equation 13)
r = Rg × (5/3) ^1/2 (13)

  <Measurement of relaxation time and calculation of relaxation index>

The relaxation time of ¹ H nuclei was measured by the following method.

  Using a JNM-MU25A nuclear magnetic resonance apparatus (manufactured by JEOL), relaxation time T2 at room temperature and 200 ° C. was measured using a pulse of SolidEcho method. The relaxation index was calculated by applying the measured value of T2 to the above equation (1).

  <Epoxy equivalent (WPE)>

  It was measured according to JIS K 7236: 2001 (how to obtain epoxy equivalent of epoxy resin).

  <Measurement of dynamic viscoelastic spectrum of hybrid cured product>

  Using an EXSTAR6000 manufactured by Seiko Instruments Inc., a 2 mm thick sample was measured at a rate of 5 ° C. per minute from −120 ° C. to 300 ° C. and measured in a bending mode.

  <Heat resistance of hybrid cured product>

  As above-mentioned, the temperature dependence of the storage elastic modulus in a dynamic viscoelasticity measurement is mentioned as a heat resistant parameter | index of a hybrid hardening body. Therefore, the heat resistance of the hybrid cured body was determined by calculating the elastic modulus ratio represented by the above formula (5).

  <Yellowness (YI)>

  YI was measured on a 3 mm thick sample using SPECTROPHOTOMETER CM-3600d manufactured by Konica Minolta. In that case, it calculated | required according to "ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics".

  <Measurement of refractive index>

  A refractive index of 589 nm was measured at 23 ° C. using an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.

  <Measurement of dynamic viscoelastic spectrum of composite transparent sheet>

  Using a rheometric RSAII, the temperature was increased from 20 ° C. to 300 ° C. at a rate of 5 ° C. per minute, and the storage elastic modulus E ′ of the sheet sample was measured. The distance between chucks was 20 to 30 mm, the sample width was 2 to 4 mm, the measurement frequency was 1 Hz, the strain amount was 0.05%, and the measurement was performed in the tensile mode.

  <Measurement of linear expansion coefficient of composite transparent sheet>

Using TMA / SS120 manufactured by Seiko Instruments Inc., the temperature was increased from 30 ° C. to 330 ° C. at a rate of 5 ° C. per minute, and the linear expansion coefficient was measured. The distance between chucks was 10 mm, the sample width was 2 mm, and the load was 10 g. According to the following formula (14), the change rate ΔL of the average sample length between 50 ° C. and 300 ° C. was defined as the linear expansion coefficient.
(Equation 14)
ΔL = {(L300−L50) / L50} / (300−50) (14)
In the above formula, the sample length at 50 ° C. was L50, and the sample length at 300 ° C. was L300.

  <Measurement of total light transmittance>

  It measured based on JIS K-7105.

  <Observation of optical defects>

  Using a microscope, the scattered light reflected from the oblique direction was observed.

  <Flexibility>

  The feeling of folding the sheet was evaluated. Here, as shown in Table 4 below, the evaluation of flexibility is performed with ◯ and ×. “○” corresponds to the evaluation when the sheet is bent as a whole when it is bent with both ends of the sheet, and “X” indicates that the sheet is bent locally at the ends when it is bent with both ends of the sheet, or This corresponds to the evaluation in the case of breaking and cracking. Moreover, the evaluation criteria regarding the softness | flexibility of a resin sheet, such as "(circle)" and "x", were shown visually and schematically as FIG. That is, FIG. 3 is a schematic diagram showing evaluation criteria relating to the flexibility of the resin sheets of Examples 14 and 15 and Comparative Example 8 described later.

  [raw materials]

  Next, the raw material used in each of “Production Example” for producing the resin composition according to the present invention, “Example” for producing the hybrid cured product according to the present invention, and “Comparative Example” which is a control section thereof. Will be described in the following 1-9.

  1. Epoxy resin

  (1) Epoxy resin A: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “BisA”)

AER manufactured by Asahi Kasei Epoxy Corporation was used. Moreover, the epoxy equivalent (WPE) and viscosity measured by said method were as follows.
Epoxy equivalent (WPE): 187 g / eq
Viscosity (25 ° C.): 14.3 Pa · s

  (2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (hereinafter referred to as "alicyclic epoch")

Ceroxide 2021P manufactured by Daicel Chemical Industries, Ltd. was used. Moreover, the epoxy equivalent (WPE) and viscosity measured by said method were as follows.
Epoxy equivalent (WPE): 131 g / eq
Viscosity (25 ° C.): 227 mPa · s

  (3) Epoxy resin C: hydrogenated poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “hydrogenated BisA”)

YX8000 manufactured by Japan Epoxy Resin Co., Ltd. was used. Moreover, the epoxy equivalent (WPE) and viscosity measured by said method were as follows.
Epoxy equivalent (WPE): 205 g / eq
Viscosity (25 ° C.): 1,150 mPa · s

  2. Alkoxysilane compounds

  (1) Alkoxysilane compound A: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”)

  KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  (2) Alkoxysilane compound B: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as “ECETMS”)

  KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  (3) Alkoxysilane compound C: 3-glycidoxypropylmethyldimethoxysilane (hereinafter referred to as “GPMDMS”)

  KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  (4) Alkoxysilane compound D: phenyltrimethoxysilane (hereinafter referred to as “PTMS”)

  KBM-103 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  (5) Alkoxysilane compound E: Diphenyldimethoxysilane (hereinafter referred to as “DPDMS”)

  KBM-202SS manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  (6) Alkoxysilane compound F: phenylmethyldimethoxysilane (hereinafter referred to as “PMDMS”)

  SIP 6740 manufactured by Asmax Co., Ltd. was used.

  (7) Alkoxysilane compound G: Dimethyldimethoxysilane (hereinafter referred to as “DMDMS”)

  KBM-22 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  (8) Alkoxysilane compound H: tetraethoxysilane (hereinafter referred to as “TEOS”)

  KBE-04 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  3. solvent

  Tetrahydrofuran (stabilizer-free type, manufactured by Wako Pure Chemical Industries, Ltd.) was used (hereinafter referred to as “THF”).

  4). Hydrolysis and condensation catalysts

  (1) Dibutyltin diacetate (trade name: dibutyltin diacetate, manufactured by Tokyo Chemical Industry Co., Ltd.) was used (hereinafter referred to as “DBTDA”).

  (2) Wako Pure Chemical Industries, Ltd. was used as acetic acid.

  (3) An ion exchange resin (AMBERLYST 15DRY, manufactured by Organo Corporation) was used as the solid acid catalyst.

  (4) Barium hydroxide (trade name: anhydrous barium hydroxide, manufactured by Wako Pure Chemical Industries, Ltd.) was used.

(5) A titanium catalyst (Ti (OPr) ₄ ) (trade name: tetraisopropyl orthotitanate, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

  (6) A product manufactured by Wako Pure Chemical Industries, Ltd. was used as dibutyltin dilaurate (hereinafter referred to as “DBTDL”).

  5. Hardener

  (1) A thermal cationic curing agent (CP-77, manufactured by ADEKA Corporation) was used.

  (2) A photocationic curing agent (SP-170 manufactured by ADEKA Corporation) was used.

  (3) An amine curing agent (4,4'-diaminodiphenylmethane, manufactured by Wako Pure Chemical Industries, Ltd.) was used (hereinafter referred to as "DDM").

  6). Silylating agent

  (1) Trimethylsilanol (LS-310, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

  (2) Hexamethyldisilazane (Strem Chemicals Inc.) was used.

  Next, “Production Example” for producing the resin composition will be described in detail.

  [Production Example 1]

  150 g of GPTMS, 142.5 g of PMDMS, 146.3 g of THF and 1.21 g of barium hydroxide were placed in a flask containing a stirrer, set in an oil bath, and mixed and stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing began, 75 g of water was added in one batch and refluxing was continued for 10 hours. After cooling to room temperature, barium hydroxide was filtered through a 0.2 μm filter. The obtained filtrate was evaporated at 80 ° C. for 5 hours, and the solvent, methanol and water were removed to obtain silicone 1.

  [Production Example 2]

  75 g of GPTMS, 71.25 g of PMDMS, 73.13 g of THF and 1.243 g of DBTDA were placed in a flask containing a stirrer, set in an oil bath, and mixed and stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing began, 37.49 g of water was added in one batch and refluxing was continued for 7 hours. Evaporation was performed at 80 ° C. for 5 hours, and the solvent, methanol and water were removed to obtain silicone 2.

  [Production Example 3]

  75 g of GPTMS, 71.25 g of PMDMS, 73.13 g of THF and 1.243 g of DBTDA were placed in a flask containing a stirrer, set in an oil bath, and mixed and stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing began, 37.49 g of water was added in one batch and refluxing was continued for 7 hours. 0.909 g of barium hydroxide was added and stirring was continued for another 20 minutes. After cooling to room temperature, barium hydroxide was filtered through a 0.2 μm filter. The obtained filtrate was evaporated at 80 ° C. for 5 hours, and the solvent, methanol and water were removed to obtain silicone 3.

  [Production Example 4]

  Silicone 4 was obtained in the same manner as in Production Example 3, except that 20 g of trimethylsilanol was added simultaneously with barium hydroxide.

  [Production Example 5]

  150 g of GPTMS, 14.25 g of PMDMS, 10 g of ion exchange resin (AMBERLYST 15DRY), and 125 g of water were placed in a flask and set in an evaporator. The temperature of the oil bath was set to 80 ° C., and the reaction was performed for 7 hours while distilling off methanol produced at 100 kPa, and then the ion exchange resin was removed by filtration. The obtained filtrate was evaporated at 80 ° C. for 5 hours, and the remaining methanol and water were removed to obtain silicone 5.

  [Production Example 6]

24.25 g of GPTMS, 23.00 g of PMDMS, and 22.76 g of ethanol were placed in a flask containing a stirring bar, and mixed and stirred at room temperature. After the solution was uniformly mixed, 5.05 g of 0.1M hydrochloric acid was added to start the hydrolysis reaction. After 1.5 hours, 29Si-NMR of the reaction solution was measured to confirm that the hydrolysis reaction had progressed. In advance, 10.75 g of Ti (OPr) ₄ was weighed in another container and diluted with the same mass of ethanol, and this diluted solution was slowly added to the hydrolyzed solution at room temperature over 20 minutes. The solution was added dropwise and stirred at room temperature for 22 hours. Using an evaporator, the resulting liquid was concentrated at room temperature for 1.5 hours to obtain silicone 6.

  [Production Example 7]

  GPTMS 55g, PMDMS 52g, THF 53.5g and acetic acid 0.31g were put into a flask charged with a stirrer, set in an oil bath, and mixed and stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing began, 22.86 g of water was added in one batch and continued to reflux for 7 hours. Then, it evaporated at 80 degreeC for 5 hours, the solvent, methanol, and water were removed, and the silicone 7 was obtained.

  [Production Example 8]

  75 g of GPTMS, 71.25 g of PMDMS, and 1.243 g of DBTDA were placed in a flask containing a stirrer, set in an oil bath, and mixed and stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. 32 g of water was added over 5 hours and the reaction was continued for 10 hours while removing the methanol formed. Further, the mixture was evaporated at 80 ° C. for 5 hours to remove the remaining methanol and water. Thereafter, 30 g of hexamethyldisilazane was added and reacted at 80 ° C. for 5 hours while removing the generated ammonia. Thereafter, the mixture was evaporated at 80 ° C. for 8 hours, and the remaining hexamethyldisilazane was removed to obtain silicone 8.

  [Production Example 9]

  45 g of ECETMS, 13.12 g of DMDMS, and 0.92 g of DBTDA were placed in a flask charged with a stir bar, set in an oil bath, and mixed and stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing began, 9 g of water was added in one portion and refluxing was continued for 4 hours. After cooling to room temperature, 41 g of alicyclic epoch was added and stirred until homogeneous. Thereafter, the mixture was evaporated at 80 ° C. for 2 hours, and the solvent, methanol and water were removed to obtain silicone 9.

  [Production Example 10]

  205 g of GPTMS, 9.61 g of GPDMMS, 58.7 g of PTMS, 258 g of PMDMS, 64.8 g of TEOS, 408 g of alicyclic epoch, 8.46 g of DBTDL, and 288 g of THF were placed in a flask charged with a stir bar and set in an oil bath. The mixture was stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing began, 155 g of water was added in one batch and refluxing was continued for 9 hours. Thereafter, the mixture was evaporated at 80 ° C. for 10 hours, and the solvent, methanol and water were removed to obtain silicone 10.

  [Production Example 11]

  ECETMS 38.73g, DPDMS 37.65g, DMDMS 29.16g, PMDMS 18.06g, DBTDA 1.14g and THF 62.16g were put in a flask charged with a stir bar, set in an oil bath, and mixed and stirred at room temperature. did. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing started, 20 g of water was added in one batch and refluxing was continued for 9 hours. Then, it cooled to room temperature, 54 g of alicyclic epoxies were thrown in, and it mixed uniformly, Then, it evaporated at 80 degreeC for 7 hours, the solvent, methanol, and water were removed, and the silicone 11 was obtained.

  [Production Example 12]

  GPDMMS (50 g), DBTDA (0.32 g) and THF (20 g) were placed in a flask containing a stirring bar, set in an oil bath, and mixed and stirred at room temperature. After the solution was mixed uniformly, the oil bath was heated to 80 ° C. After refluxing began, 4 g of water was added in one batch and refluxing was continued for 9 hours. Thereafter, the mixture was evaporated at 80 ° C. for 7 hours, and the solvent, methanol and water were removed to obtain silicone 12.

The physical properties of each silicone (1-12) obtained in the above Production Examples 1-12 are summarized in Table 1 below.

  In Table 1, the condensation rate is a value obtained using the above-described formula (3). The storage stability is represented by a change in viscosity when the resin composition is stored in a closed container at 60 ° C. for 72 hours as described above. Specifically, the storage stability value is the ratio of the viscosity after 72 hours to the initial viscosity. Moreover, the ratio of the structural unit of D body was calculated | required by 29Si-NMR.

  Next, the Example which manufactured the hybrid hardening body and its comparative example are demonstrated in detail.

  [Examples 1-8, 12]

  As shown in Table 2 below, the silicone obtained in Production Examples 1 to 9 and the epoxy resin were mixed thoroughly. At that time, when it was difficult to mix the silicone and the epoxy resin, THF was distilled off after dissolving and mixing in THF. A predetermined curing agent was added to the obtained resin composition (see Table 2). Thereafter, it was poured into a mold and cured under predetermined conditions shown in Table 2. The physical properties of the hybrid cured product obtained in each of the above examples are shown in Table 3 below.

  [Examples 9 to 11, 13]

  As shown in Table 1 above, the “silicone” obtained in the above Production Examples 9 to 11 contains silicone and an epoxy resin and can be said to be a resin composition. Therefore, the epoxy resin was not added again in the examples (see Table 2). A predetermined curing agent was added to the resin composition (see Table 2). Thereafter, it was poured into a mold and cured under predetermined conditions shown in Table 2. The physical properties of the hybrid cured product obtained in each of the above examples are shown in Table 3 below.

  [Comparative Examples 1-6]

  In Comparative Examples 2, 4, and 6, as shown in Table 2 below, the silicone of Production Example (2, 12) and the epoxy resin were completely mixed. When it was difficult to mix, THF was distilled off after dissolving and mixing in THF. On the other hand, in Comparative Examples 1, 3, and 5, as shown in Table 1 above, silicone is not used in the first place.

  A predetermined curing agent was added to the obtained resin composition (Comparative Examples 2, 4 and 6) or epoxy resin (Comparative Examples 1, 3 and 5) (see Table 2). Thereafter, it was poured into a mold and cured under predetermined conditions shown in Table 2. The physical properties of the cured products obtained in the above comparative examples are shown in Table 3 below.

  Comparative Example 1 was only an alicyclic epoxy, and was confirmed to be inferior in heat resistance. Moreover, the relaxation index was small, and some cured bodies had cracks.

  In Comparative Example 2, since the size (Rg) of the phase separation structure between silicone and epoxy resin was extremely large, it was confirmed that the effect of improving heat resistance by silicone was very small.

  Comparative Example 3 was only BisA epoxy, and was confirmed to be inferior in heat resistance.

  Comparative Example 4 was amine curing and confirmed that it was strongly colored. It was also confirmed that the alicyclic epoxy had poor reactivity with the amine-based curing agent, phase-separated, and poor heat resistance.

  Comparative Example 5 was only hydrogenated BisA epoxy, and was confirmed to be inferior in heat resistance. Furthermore, it was confirmed that coloring was conspicuous as compared with Comparative Example 2.

Comparative Example 6 was amine curing and confirmed that it was markedly colored.

  Furthermore, the heat resistance of the (hybrid) cured bodies obtained in Example 9 and Comparative Example 1 was compared in detail. FIG. 4 is a graph showing the results of dynamic viscoelasticity measurement of a (hybrid) cured body. That is, the relationship between the storage elastic modulus E ′ (left vertical axis) and tan δ (right vertical axis) with respect to temperature (horizontal axis) was shown. As can be seen from FIG. 4, in the high temperature region, E 'is more stable and higher in Example 9, and tan δ is stably lower in value. In Comparative Example 1, it can be seen that E ′ decreases and tan δ increases rapidly in the high temperature region.

  [Comparative Example 7]

  10 g of Composeran E202C (Arakawa Chemical Co., Ltd.) and 1 g of CP77 were mixed. Then, when a vacuum defoaming was attempted, a large amount of foam was generated. Defoaming was stopped after 10 minutes because the generation of foam did not stop, and the foam was poured into a mold and cured at 90 ° C. for 1 hour, then at 180 ° C. for 1 hour, and then at 200 ° C. for 10 minutes. As a result, since the remaining amount of methoxy groups was large, foaming was intense and a cured product suitable for measurement could not be obtained.

  [Examples 14 and 15]

  The resin composition (liquid material before curing) in Example 10 (for Example 14) and Example 11 (for Example 15) was converted into a T glass-based glass cloth (manufactured by Nittobo; glass fiber diameter: 5 μm and the number of focusings). : 200 woven fabrics obtained by plain weaving with a weaving density of 60/25 mm in length and 46/25 mm in width and 100 μm in thickness were subjected to fiber opening treatment and cationic silane coupling treatment; refractive index 1.520 ) Was impregnated respectively. Next, these were thermally cured at 150 ° C. for 1 hour and then at 200 ° C. for 1 hour while maintaining the pressure at 5 MPa in the press. The thermosetting will be described. The curing agent used in Example 10 in Example 14 and the curing agent used in Example 11 in Example 15 were added to the resin composition, respectively. Thereafter, it was poured into a mold and cured under the corresponding conditions shown in Table 2 above. In this way, a resin sheet (composite transparent sheet) was obtained. Each of the obtained resin sheets had a thickness of 100 μm, a refractive index of 1.524, and was transparent. The linear expansion coefficient tended to be smaller when the resin composition in Example 11 having a larger relaxation index was used. The measurement results of the physical properties of the resin sheet are shown in Table 4 below. FIG. 5 also shows this tendency.

  FIG. 5 is a graph showing the measurement results of the linear expansion coefficient (TMA) of the composite transparent sheet. The slope corresponds to the linear expansion coefficient. From the figure, it can be seen that the linear expansion coefficient tends to be smaller in Example 14 over the entire temperature range.

  [Comparative Example 8]

  A resin sheet was obtained in the same manner as in Example 14 using the resin composition (liquid material before curing) obtained in Comparative Example 1. Since the relaxation index was small, voids were generated during molding, and it was confirmed that the appearance was whitish (FIG. 6). The measurement results of the physical properties of the resin sheet are shown in Table 4 below. FIG. 6 is an optical micrograph showing the observation results of the voids of Comparative Example 8. The dots that appear white indicate voids. The scale shown in FIG. 6 is 50.00 μm.

  [Comparative Example 9]

Using the resin composition (liquid before curing) obtained in Example 9, a resin sheet was obtained in the same manner as in Example 14. Since the refractive indexes did not match, the glass was visible and opaque.

  The resin composition and the hybrid cured product thereof according to the present invention include, for example, electronic materials (insulators, AC transformers, switchgear and other castings and circuit units, various component packages, ICs, LEDs, semiconductors, etc.) Materials, generators, motors and other rotating machine coils, winding impregnations, printed wiring boards, insulation boards, medium-sized insulators, coils, connectors, terminals, various cases, electrical components, etc.) it can.

  The composite transparent sheet according to the present invention can be applied to a wide range of fields centering on substitutes for glass substrates, taking advantage of the properties of excellent transparency, heat resistance and dimensional stability.

  Namely, plastic lens, array substrate, anisotropic conductive film, polarizing film, polarizing plate, optical filter, optical film, vehicle monitor panel, electrode substrate, electronic paper, liquid crystal display device substrate, organic EL display device substrate, It can be suitably used in the fields of color filter substrates, backplane substrates, touch panel substrates, and solar cell substrates. More specifically, plastic transmissive diffraction grating lenses, micro lenses, f-θ lenses, collimator lenses, photoelectric switch lenses, imaging / projection lenses, Fresnel lenses, linear Fresnel lenses, lenticular lenses, prism plates, fly Eye lens, lens array, plano-concave lens, plano-convex lens, hemispherical lens, cylindrical lens, cylinder Fresnel lens, aspheric lens, aspheric condenser lens, color filter, bandpass filter, etalon filter, cold filter, dichroic filter, ultraviolet transmission Visible cut filter, ultraviolet cut visible transmission filter, band pass filter, dielectric multilayer filter, ND filter, visibility filter, band stop filter, color temperature conversion filter Color correction filter, polarizing filter, interference filter, diffusion filter, color filter for liquid crystal display, contact type / complete contact type image sensor / cover glass, reduction type image sensor / cover glass, cover glass for solid-state image sensor such as CCD, CMOS, Cover glass with coating, cover glass for image sensors for mobile phones, glass powder for PDP sealing / ceramics sealing sealing, laser diode / cover glass, UV reflection / visible transmission mirror, cold mirror, hot mirror, laser mirror, visible gas laser Mirror, mirror for white laser, mirror for semiconductor laser, mirror for YAG laser, mirror for excimer laser, total reflection mirror for communication equipment, UV reflection mirror, dual wavelength total reflection mirror, metal film mirror, half mirror, multilayer film steam Wearable dichroic mirror, laser mirror, high-precision flat mirror, dichroic mirror, laser mirror, wire grid polarizing film, light control film (peep prevention film), laser guard film, polarizing film protective film, polarizing plate surface protective film, lead Optical plate, retardation film for liquid crystal display, film for FPC, antireflection (AR / LR) film, diffusion film for liquid crystal display, transparent conductive film, reflective film for liquid crystal display, hard coat film, polarizing film protective film, viewing angle Magnifying film, liquid crystal alignment film, anti-glare (AG) film, AG / AR film, reflective film for liquid crystal backlight, reflective film for liquid crystal display, retardation film for liquid crystal display, reflective film, Bright conductive film, brightness enhancement film (reflection type polarizing plate), cast film for ceramic layer thin film production, carrier film for ceramic layer thin film production, electromagnetic wave shielding film, near infrared absorption / shielding film, release film, adhesive Agent layer protective film, antistatic film, antifouling film, optical compensation film, adhesive / adhesive tape substrate, viewing angle adjustment film, beam splitter, polarizing beam splitter, plate type dielectric beam splitter, cube type dielectric beam Splitter, Plate type polarizing beam splitter, Cube type polarizing beam splitter, Plate type non-polarizing beam splitter, Cube type non-polarizing beam splitter, Anti-reflective coating, Normal / Visible ultra-low reflection coating, Non-polarization anti-reflection coating, YAG laser Anti-reflection coating, anti-reflection coating for excimer laser, lens anti-reflection coating for optical fiber, anti-reflection coating for communication equipment, fly-eye lens anti-reflection coating, near-red ultra-wide anti-reflection coating, liquid crystal alignment film, multilayer polarizer, wire Grid polarizer hologram element, plastic optical element, diffractive optical element, reflector, finder system prism, micro prism, multiple interference type spectroscopic element, planar prism, rear screen (for rear projection TV etc.), Fresnel wrench screen, Fresnel with diffusion layer Wrench screen, low-melting glass preform, connector, optical waveguide, multi-step diffraction grating, blazed and relief diffraction grating, sub-wavelength grating, transmission / reflection diffraction grating, microcapillary, quartz wave plate, absorption polarizing plate, Infrared signal transmission window material (color ), Cover glass, shield glass, optical window, prism, diffusion plate, optical flat panel, strobe panel, dry film resist base material, prism sheet for liquid crystal display, light guide plate for liquid crystal backlight, diffusion sheet for liquid crystal display, prism Sheet (brightness enhancement film), protective diffusion sheet, embossed carrier tape, back grind tape, dicing tape, thermosetting interlayer insulation material, transfer layer substrate, optical film protective material, LCD module surface protective material, It can be suitably used for an elliptically polarizing plate, a condensing material and the like.

Claims (6)

A hybrid cured product containing silicone,
(I) Guinier (G) of the scattering profile measured using the X-ray small angle scattering method (SAXS)
(uiner) The size (Rg) of the phase separation structure determined by plotting is 50 nm or less,
(Ii) Formula (1) below:
(Equation 1)
Relaxation index = (T2 at 200 ° C.) / (T2 at 25 ° C.) (1)
(Where T2 is the relaxation time obtained by the solid echo method of solid state ¹ H-NMR)
That the relaxation index represented by the formula is 1.2 to 10, and (iii) the yellowness (YI) is 30 or less,
Satisfied,
A hybrid cured product obtained by a production method including curing a liquid resin composition satisfying (iv) to (ix) with heat or energy rays.
(Iv) containing a silicone having a reactive functional group and an organic compound having an epoxy group different from silicone;
(V) having an epoxy equivalent of 100 to 20,000 g / eq and containing a cycloaliphatic epoxy group;
(Vi) The mass composition ratio of the silicone having the reactive functional group and the organic compound having the epoxy group is 15:85 to 95: 5,
(Vii) the silicone having the reactive functional group contains a silicone having a cyclic ether group;
(Viii) further containing an acid generator ,
(Ix) The silicone having the reactive functional group has a silanol group, has an average composition of the silicone represented by the following formula (2), and condensation of the silicone represented by the following formula (3) The rate is 30-99%.
(Chemical formula 1)
R ¹ _a Si (OX) _b O _{(4-ab) / 2} (2)
(Equation 2)
Condensation rate = 100 × {(4-ab) / (4-a)} (3)
(Wherein R ¹ represents the same or different organic group, OX represents the same or different hydrolyzable group or hydroxyl group, and a and b are each independently an integer of 0 to 3) is there.) The silicone comprises a silicone obtained by alkoxysilane containing 5～99Mol% structural units of D-represented by the following formula (4) hydrolysis and condensation, the hybrid cured product according to claim 1.
(Chemical formula 3)
R ¹ R ² Si (OX) ₂ (4)
Here, in the above formula, R ¹ and R ² each independently represent the same or different organic group,
OX represents the same or different hydrolyzable groups or hydroxyl groups.   A composite transparent sheet comprising the hybrid cured product according to claim 1 and a filler. A liquid resin composition satisfying (iv) to (ix) ,
(Iv) containing a silicone having a reactive functional group and an organic compound having an epoxy group different from silicone;
(V) having an epoxy equivalent of 100 to 20,000 g / eq and containing a cycloaliphatic epoxy group;
(Vi) The mass composition ratio of the silicone having the reactive functional group and the organic compound having the epoxy group is 15:85 to 95: 5,
(Vii) the silicone having the reactive functional group contains a silicone having a cyclic ether group;
(Viii) further containing an acid generator,
(Ix) The silicone having the reactive functional group has a silanol group, has an average composition of the silicone represented by the following formula (2), and condensation of the silicone represented by the following formula (3) The rate is 30-99%.
(Chemical formula 2)
R ¹ _a Si (OX) _b O _{(4-ab) / 2} (2)
(Equation 3)
Condensation rate = 100 × {(4-ab) / (4-a)} (3)
(Wherein R ¹ represents the same or different organic group, OX represents the same or different hydrolyzable group or hydroxyl group, and a and b are each independently an integer of 0 to 3) is there.)
A cured product obtained by curing the resin composition with heat or energy rays,
(I) Guinier (G) of the scattering profile measured using the X-ray small angle scattering method (SAXS)
(uiner) The size (Rg) of the phase separation structure determined by plotting is 50 nm or less,
(Ii) Formula (1) below:
(Equation 1)
Relaxation index = (T2 at 200 ° C.) / (T2 at 25 ° C.) (1)
(Where T2 is the relaxation time obtained by the solid echo method of solid state ¹ H-NMR)
That the relaxation index represented by the formula is 1.2 to 10, and (iii) the yellowness (YI) is 30 or less,
A resin composition satisfying The resin composition of Claim 4 in which the said silicone contains the silicone obtained by hydrolyzing and condensing the alkoxysilane which contains 5-99 mol% of D structural units represented by following formula (4).
(Chemical formula 3)
R ¹ R ² Si (OX) ₂ (4)
Here, in the above formula, R ¹ and R ² each independently represent the same or different organic group,
OX represents the same or different hydrolyzable groups or hydroxyl groups. A method for producing a composite transparent sheet, comprising mixing the resin composition according to claim 4 or 5 and a filler, and pressing into a sheet shape while being cured with heat or energy rays.