Organopolysiloxane, organopolysiloxane-containing curable resin composition and cured product of the same, near-infrared optical waveguide, and near-infrared optical transmission member

Abstract

To provide an organopolysiloxane material excellent in both reflow resistance and a low coefficient of linear thermal expansion, which are required when used as an optical member.SOLUTION: An organopolysiloxane containing at least one substituent selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, wherein the substituent is directly bonded to a silicon atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organopolysiloxane, an organopolysiloxane-containing curable resin composition and a cured product thereof, a near-infrared light waveguide, and a near-infrared light transmission component. [Background technology]

[0002] Plastic materials have a wide range of applications due to their light weight, high moldability, and high productivity, and in recent years, they have increasingly been used in place of inorganic materials for optical components. In particular, organopolysiloxanes have attracted attention for their use as optical components because they offer a high degree of freedom in structural design and have high optical transparency.

[0003] For example, Patent Document 1 discloses a curable resin composition containing a silicone resin having a specific structure, and reports that the cured product is excellent as an optical lens or prism material. Patent Document 2 discloses a silicone resin composition containing an organopolysiloxane having a specific structure, and reports that the composition is useful as an encapsulating material for optical devices. [Prior art documents] [Patent documents]

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-133375 Patent Document 2: Japanese Patent Application Laid-Open No. 2015-101645 Summary of the Invention [Problem to be solved by the invention]

[0005] There are several physical properties that become problematic when organopolysiloxanes are used in optical components, and specific examples include reflow resistance and coefficient of linear thermal expansion. Since mounting optical components often involves a solder reflow process, improved reflow resistance is required. In addition, optical components often use inorganic materials with extremely low linear thermal expansion coefficients, so the material must have a low linear thermal expansion coefficient that does not adversely affect bonding with inorganic materials.

[0006] Although Patent Document 1 also mentions heat resistance, it is still insufficient and no study has been made on the coefficient of linear thermal expansion. The silicone resin composition of Patent Document 2 also aims to improve heat resistance, but it is still insufficient and no detailed study has been made on the coefficient of linear thermal expansion.

[0007] In response to the above-mentioned problems, an object of the present invention is to provide an organopolysiloxane material that has both excellent reflow resistance and a low coefficient of linear thermal expansion, which are problems when used as optical components. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve these problems, and as a result have found that the above problems can be solved by using an organopolysiloxane having a specific structure, which has led to the completion of the present invention. That is, the present invention provides the following.

[0009] [1] An organopolysiloxane containing at least one substituent selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, wherein the substituent is directly bonded to a silicon atom. [2] The organopolysiloxane according to the above item [1], wherein the substituent directly bonded to the silicon atom is at least one group selected from the group consisting of an acryloyloxymethyl group and a methacryloyloxymethyl group. [3] The organopolysiloxane according to the above item [1], which is represented by the following general formula [1]: (R 1 R 2 R 3SiO 1 / 2 ) M1 (R 4 R 5 R 6 SiO 1 / 2 ) M2 (R 7 R 8 R 9 SiO 1 / 2 ) M3 (R 10 R 11 SiO 2 / 2 ) D1 (R 12 R 6 SiO 2 / 2 ) D2 (R 13 R 9 SiO 2 / 2 ) D3 (R 14 SiO 3 / 2 ) T1 (R 6 SiO 3 / 2 ) T2 (R 9 SiO 3 / 2 ) T3 (SiO 4 / 2 ) Q (O 1 / 2 R 15 ) Y1 (O 1 / 2 R 6 ) Y2 (O 1 / 2 R 9 ) Y3 [1] [In formula [1], R 1 ~R 5 , R 7 ~R 8 , R 10 ~R 15 are each independently one or more groups selected from the group consisting of an organic group, a reactive functional group, and a hydrogen atom. R 1 ~R 3 , R 10 , R 11 , R 14 and R 15 does not contain a polymerizable alkenyl group. 6is at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, and when there are a plurality of them, they may be the same as or different from each other. R 9 is the above R 6 is an acryloyloxyalkyl group or a methacryloyloxyalkyl group other than the above, and when there are a plurality of them, they may be the same as or different from each other. 0≦M1, 0≦M3, 0≦D1, 0≦D3, 0≦T1, 0≦T3, 0≦Q, 0≦Y1, 0≦Y2, 0≦Y3. 0 < M2 + D2 + T2. M1 + M2 + M3 + D1 + D2 + D3 + T1 + T2 + T3 + Q = 1. [4] In the above formula [1], R 6 is at least one group selected from the group consisting of an acryloyloxymethyl group and a methacryloyloxymethyl group represented by the following formulas [2] and [3], and the organopolysiloxane according to the above item [3]. [Chemical formula] (In the above formula, * represents a bond.) [5] In the above formula [1], 0 < M2 + D2 + T2 < 1, and the organopolysiloxane according to the above item [3] or [4]. [6] An organopolysiloxane-containing curable resin composition containing the organopolysiloxane according to any one of the above items [1] to [5] and at least a polymerization initiator. [7] A cured product obtained by curing the organopolysiloxane-containing curable resin composition according to the above item [6]. [8] A near-infrared optical waveguide produced using the organopolysiloxane-containing curable resin composition according to the above item [6]. [9] A near-infrared light transmission member including at least the near-infrared optical waveguide according to the above item [8]. [Advantages of the Invention]

[0010] According to the present invention, it is possible to provide an organopolysiloxane, an organopolysiloxane-containing curable resin composition, and a cured product thereof, which are excellent in both reflow resistance and a low coefficient of linear thermal expansion. Because the organopolysiloxane provided by the present invention has excellent reflow resistance and a low coefficient of linear thermal expansion, it is particularly useful as a near-infrared optical waveguide and a near-infrared optical transmission component. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, an embodiment of the present invention (hereinafter sometimes referred to as "the present embodiment") will be described in detail, but the following description is an example of an embodiment, and the present invention is not limited to these in any way.

[0012] [Organopolysiloxane] The organopolysiloxane of this embodiment must contain at least one substituent selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. The organopolysiloxane of this embodiment preferably contains at least one substituent selected from the group consisting of an acryloyloxymethyl group and a methacryloyloxymethyl group. In the following description, when "(meth)acryloyl" is used, it means both "acryloyl" and "methacryloyl".

[0013] Many siloxane compounds that have been studied for use in optical components have alkyl or aromatic groups with three or more carbon atoms as spacers. There have been virtually no attempts to reduce the number of carbon atoms in the spacer connecting the (meth)acryloyloxy group and the silicon atom. While this is thought to be due to synthesis reasons, it is also thought that a smaller carbon number generally has a negative impact on heat resistance, such as reflow resistance, making the compound more susceptible to cracking at high temperatures. As a result of extensive research, the present inventors have found that organopolysiloxanes in which (meth)acryloyloxy groups are bonded to silicon atoms via methyl groups having at most two carbon atoms, preferably one carbon atom, have excellent reflow resistance, such as being less susceptible to cracking at high temperatures, and also have a low coefficient of linear thermal expansion.

[0014] In this embodiment, the organopolysiloxane preferably contains either (meth)acryloyloxymethyl groups or (meth)acryloyloxyethyl groups in a proportion (based on the number of moles) of preferably 0.2 or more, more preferably 0.25 or more, even more preferably 0.3 or more, still more preferably 0.4 or more, and preferably less than 1, more preferably 0.95 or less, even more preferably 0.9 or less, and still more preferably 0.8 or less. When the amount of either the (meth)acryloyloxymethyl group or the (meth)acryloyloxyethyl group is within the above range, an organopolysiloxane having excellent reflow resistance and a low coefficient of linear thermal expansion can be obtained.

[0015] As described above, the organopolysiloxane of this embodiment contains at least one substituent selected from the group consisting of acryloyloxymethyl, methacryloyloxymethyl, acryloyloxyethyl, and methacryloyloxyethyl groups, and may contain a substituent in which a (meth)acryloyloxy group is bonded via a spacer having 3 or more carbon atoms. An example of a (meth)acryloyloxyalkyl group having a spacer having 3 or more carbon atoms is a (meth)acryloyloxypropyl group. When the organopolysiloxane contains such a (meth)acryloyloxyalkyl group having a spacer having 3 or more carbon atoms, the proportion of the (meth)acryloyloxyalkyl group is not particularly limited and can be set as desired within a range that ensures sufficient curing during production of a cured product and good compatibility with other components added to the organopolysiloxane-containing composition described below.

[0016] More specifically, the organopolysiloxane of this embodiment can be one having the following structural formula: (R 1 R 2 R 3 SiO 1 / 2 ) M1 (R 4 R 5 R 6 SiO 1 / 2 ) M2 (R 7 R 8 R 9 SiO 1 / 2 ) M3 (R 10 R 11 SiO 2 / 2 ) D1 (R 12 R 6 SiO 2 / 2 ) D2 (R 13 R 9 SiO 2 / 2 ) D3 (R 14 SiO 3 / 2 ) T1 (R 6 SiO 3 / 2 ) T2 (R 9 SiO 3 / 2 ) T3 (SiO 4 / 2 ) Q (O 1 / 2 R 15 ) Y1 (O 1 / 2 R 6 ) Y2 (O 1 / 2 R 9 ) Y3 [1] [In formula [1], R 1 ~R 5 , R 7 ~R 8 , R 10 ~R 15 are each independently one or more groups selected from the group consisting of an organic group, a reactive functional group, and a hydrogen atom. R 1 ~R 3 , R 10 , R 11 , R 14 and R 15 does not contain a polymerizable alkenyl group. 6represents at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, and when a plurality of groups are present, they may be the same or different, R 9 is the above R 6 and when a plurality of acryloyloxyalkyl groups or methacryloyloxyalkyl groups are present, they may be the same or different, 0≦M1, 0≦M3, 0≦D1, 0≦D3, 0≦T1, 0≦T3, 0≦Q, 0≦Y1, 0≦Y2, 0≦Y3, 0 <M2+D2+T2であり、 M1+M2+M3+D1+D2+D3+T1+T2+T3+Q=1. In the general formula [1], the coefficients M1, M2, M3, D1, D2, D3, T1, T2, T3, and Q indicate the proportions (based on the number of moles) of each structure when M1 + M2 + M3 + D1 + D2 + D3 + T1 + T2 + T3 + Q = 1. Also, in the general formula [1], the coefficients Y1, Y2, and Y3 indicate the proportions (based on the number of moles) of each structure when M1 + M2 + M3 + D1 + D2 + D3 + T1 + T2 + T3 + Q = 1. 1 / 2 R 15 ), (O 1 / 2 R 6 ) and (O 1 / 2 R 9 ) indicates the relative content ratio.

[0017] In the general formula [1], M1, M2, and M3 are so-called M units (SiO 1 / 2 ) (hereinafter sometimes referred to simply as "M units"). Similarly, D1, D2, and D3 represent the proportion of D units (SiO 2 / 2 ) (hereinafter sometimes simply referred to as "D units"), and T1, T2, and T3 represent the proportion of T units (SiO 3 / 2 ) (hereinafter sometimes simply referred to as "T units"), and Q represents the proportion of Q units (SiO 4 / 2(hereinafter sometimes simply referred to as "Q unit").

[0018] M2, D2, and T2 are at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group bonded to a silicon atom. R 6 It shows the ratio of the M unit, D unit, and T unit to which the group is bonded, respectively. Y1 has no polymerizable alkenyl group and has a structure having a group selected from the group consisting of an organic group, a reactive functional group, and a hydrogen atom. Specifically, it shows the content ratio of an alkoxy group or a silanol group bonded to a silicon atom. Y2 is at least one group selected from a (meth)acryloyloxymethyl group and a (meth)acryloyloxyethyl group bonded to silicon through an oxygen atom (O 1 / 2 R 6 ) represents the content ratio, and Y3 represents the content ratio of a (meth)acryloyloxyalkyl group other than R 6 bonded to a silicon atom (O 1 / 2 R 9 ).

[0019] 0≦M1, 0≦M3, 0≦D1, 0≦D3, 0≦T1, 0≦T3, 0≦Q, 0≦Y1, 0≦Y2, 0≦Y3 means that M1, M3, D1, D3, T1, T3, Q, Y1, Y2, and Y3 are each 0 or more and may be zero. That is, it means that the organopolysiloxane may not contain these structural units. 0<M2 + D2 + T2 means that the organopolysiloxane necessarily contains at least one of the units of M2, D2, and T2. The preferred range of M2 + D2 + T2 is as described above.

[0020] In this embodiment, it is not necessary for all the units constituting the M unit, D unit, and T unit to be the same. For example, among the units having a ratio of M1 (R 1 R 2 R 3 SiO 1 / 2 ), for example, a certain R1 is a hydrogen atom, and as long as each R 1 satisfies the definition of each R, such as being a methyl group, it may have a different structure. This is also common to the other R 2 ~R 15 as well.

[0021] <R 6 > In the present embodiment, the R 6 group is at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. When there are a plurality of them, they may be the same as or different from each other. In the present embodiment, the R 6 group more preferably has at least one functional group selected from the group consisting of an acryloyloxymethyl group and a methacryloyloxymethyl group represented by the following formulas [2] and [3] in one molecule.

[0022]

Chemical formula

[0023] (The (meth)acryloyloxy group is bonded to the silicon atom by a methyl group having 1 carbon atom, so that an organopolysiloxane having more excellent reflow resistance and a lower coefficient of thermal expansion can be obtained.)

[0024] <Coefficient M2 + D2 + T2> M2, D2, and T2 respectively represent the ratios of the M unit, D unit, and T unit to which R 6 is bonded to the silicon atom. R 6 represents the ratios of the M unit, D unit, and T unit to which at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group is bonded, as described above, and it is necessary that 0 < M2 + D2 + T2.

[0025] If 0 < M2 + D2 + T2, there is no particular limitation on the value of M2 + D2 + T2. However, the organopolysiloxane of the present embodiment preferably contains either a (meth)acryloyloxymethyl group or a (meth)acryloyloxyethyl group in the above-mentioned ratio. Therefore, M2 + D2 + T2 is preferably 0.2 or more, more preferably 0.25 or more, still more preferably 0.3 or more, even more preferably 0.4 or more, and preferably less than 1, more preferably 0.95 or less, still more preferably 0.9 or less, even more preferably 0.8 or less. Specifically, for example, within the range of 0 < M2 + D2 + T2 < 1, the above-mentioned preferred values can be selected. By setting the range of M2 + D2 + T2 within the above range, an organopolysiloxane can be obtained that achieves both more excellent reflow resistance and a low coefficient of thermal expansion.

[0026] <R 9 > In the present embodiment, the R 9 group is a (meth)acryloyloxyalkyl group other than the above R 6 group, and when there are a plurality of them, they may be the same or different from each other. That is, examples of the R 9 group include groups in which the (meth)acryloyloxy group has an alkyl group with 3 or more carbon atoms. Examples of the R 9 group having an alkyl group with 3 or more carbon atoms include, for example, a (meth)acryloyloxypropyl group.

[0027] <Coefficients M3, D3, T3> M3, D3, and T3 respectively represent the ratios of the M units, D units, and T units to which R 9 is bonded to the silicon atom. M3, D3, and T3 are each 0 or a positive value. The coefficients M3, D3, and T3 can be arbitrarily set within a range that allows for sufficient curing during the production of the cured product and good compatibility with other components added to the organopolysiloxane-containing composition described later. On the other hand, from the viewpoint of handleability and suppressing warpage of the obtained cured product, the upper limit of each of the coefficients M3, D3 and T3 is usually 0.25 or less, preferably less than 0.25, more preferably 0.2 or less, even more preferably 0.20 or less, still more preferably 0.15 or less, and even more preferably 0.1 or less.

[0028] In one aspect of this embodiment, in formula [1], M3 is preferably 0≦M3≦0.25, more preferably 0.02≦M3≦0.25, even more preferably 0.02≦M3<0.25, still more preferably 0.025≦M3≦0.2, even more preferably 0.025≦M3≦0.20, still more preferably 0.03≦M3≦0.15, and particularly preferably 0.035≦M3≦0.1.

[0029] In one aspect of this embodiment, in formula [1], D3 is preferably 0≦D3≦0.25, more preferably 0.02≦D3≦0.25, even more preferably 0.02≦D3<0.25, even more preferably 0.025≦D3≦0.2, even more preferably 0.025≦D3≦0.20, even more preferably 0.03≦D3≦0.15, and particularly preferably 0.035≦D3≦0.1.

[0030] In one aspect of this embodiment, in formula [1], T3 is preferably 0≦T3≦0.25, more preferably 0.02≦T3≦0.25, even more preferably 0.02≦T3<0.25, still more preferably 0.025≦T3≦0.2, even more preferably 0.025≦T3≦0.20, still more preferably 0.03≦T3≦0.15, and particularly preferably 0.035≦T3≦0.1.

[0031] <O 1 / 2 R 15 > (O 1 / 2 R 15) is a structure that does not contain a polymerizable alkenyl group but contains a group selected from the group consisting of an organic group, a reactive functional group, and a hydrogen atom, specifically an alkoxy group or silanol group bonded to silicon. This structural unit allows the viscosity of the organopolysiloxane to be controlled, making it possible to adjust the viscosity to a level suitable for molding. The silanol group has the effect of increasing viscosity, and converting the silanol group to an alkoxy group has the effect of decreasing viscosity. When the content of alkoxy groups and silanol groups is low, the amount of highly mobile terminal groups is low and the siloxane skeleton becomes a rigid cage structure, resulting in an increased viscosity. Conversely, when the content of alkoxy groups and silanol groups is high, the amount of highly mobile terminal groups is high and the siloxane skeleton becomes a flexible random structure rather than a cage structure, resulting in a decreased viscosity.

[0032] <Coefficient Y1> (O 1 / 2 R 15 Y1, which indicates the content ratio of R 15 From the definition of (1), it represents the total content of silanol groups and alkoxy groups in the organopolysiloxane. From the viewpoint of the synthesis of organopolysiloxane and the viscosity adjustment required for preparing the organopolysiloxane-containing composition described below, the range of coefficient Y1 is usually 0 or more, preferably 0.02 or more, more preferably 0.025 or more, even more preferably 0.03 or more, and even more preferably 0.035 or more. On the other hand, from the viewpoint of storage stability and handling, the upper limit of the coefficient Y1 is usually 0.25 or less, preferably less than 0.25, more preferably 0.20 or less, even more preferably 0.15 or less, and even more preferably 0.1 or less. In one aspect of this embodiment, in formula [1], when Y1 is not zero, it is preferably 0.02≦Y1≦0.25, more preferably 0.02≦Y1<0.25, even more preferably 0.025≦Y1≦0.2, even more preferably 0.025≦Y1≦0.20, still more preferably 0.03≦Y1≦0.15, and particularly preferably 0.035≦Y1≦0.1.

[0033] <Coefficient Y2> Y2 is the content ratio of at least one group (O 1 / 2 R 6 ) selected from (meth)acryloyloxymethyl group and (meth)acryloyloxyethyl group bonded to silicon through an oxygen atom in the organopolysiloxane. Y2 is 0 or a positive value. Preferably, 0.25 < Y2, more preferably 0.30 < Y2, still more preferably 0.35 < Y2. When 0.25 < Y2, the compatibility with other resins is improved. Since the group having a polymerizable (meth)acryloyloxy group is hydrolyzed by water and is likely to be desorbed, the water absorption rate may increase. Therefore, it is preferably used in a manner less affected by moisture. On the other hand, in an environment affected by moisture, when Y2 is large, the cured product is likely to become brittle due to moisture. Therefore, Y2 < 0.4 is preferred, Y2 < 0.3 is more preferred, and Y2 < 0.2 is still more preferred. Also, Y2 being 0 is also preferred.

[0034] <Coefficient Y3> Y3 is the content ratio of a (meth)acryloyloxyalkyl group other than R 6 bonded to silicon through an oxygen atom (O 1 / 2 R 9 ). Y3 is 0 or a positive value. Preferably, 0.25 < Y3, more preferably 0.30 < Y3, still more preferably 0.35 < Y3. When 0.25 < Y3, the compatibility with other resins is improved. Since the organic group containing a polymerizable (meth)acryloyloxy group is hydrolyzed by water and is likely to be desorbed, the water absorption rate may increase. Therefore, it is preferably used in a manner less affected by moisture. On the other hand, in an environment affected by moisture, when Y3 is large, the cured product is likely to become brittle due to moisture. Therefore, Y3 < 0.4 is preferred, Y3 < 0.3 is more preferred, and Y3 < 0.2 is still more preferred. Also, Y3 being 0 is also preferred.

[0035] <Coefficient M1> The M unit without a coincident alkenyl group is not an essential component in the organopolysiloxane of this embodiment, but it may be included. That is, 0 < M1 may be satisfied. By substituting either the alkoxy group or the silanol group of the organopolysiloxane with the M unit, the storage stability of the organopolysiloxane can be improved and the viscosity can be reduced to a low viscosity. From the viewpoint of storage stability, preferably 0.09 ≤ M1, more preferably 0.10 ≤ M1, still more preferably 0.20 ≤ M1, and even more preferably 0.25 ≤ M1. Also, usually M1 ≤ 0.6, preferably M1 ≤ 0.55, more preferably M1 ≤ 0.5, and still more preferably M1 ≤ 0.4.

[0036] <Coefficient D1> In the organopolysiloxane of this embodiment, the D unit without a polymerizable alkenyl group is not an essential component, but by containing such a unit, toughness can be imparted to the cured product. That is, 0 < D1 may be satisfied, and when 0 < D1, preferably 0.01 ≤ D1, more preferably 0.05 ≤ D1, and still more preferably 0.1 ≤ D1. On the other hand, when the proportion of the D unit without a polymerizable alkenyl group is too high, the coefficient of thermal expansion of the cured product tends to increase. Therefore, the proportion D1 of the D unit without a polymerizable alkenyl group is preferably D1 ≤ 0.7, more preferably D1 ≤ 0.6, and still more preferably D1 ≤ 0.5.

[0037] <Coefficient T1> In the organopolysiloxane of this embodiment, the T unit without a polymerizable alkenyl group is not an essential component, but by containing such a unit, the compatibility with other components added to the organopolysiloxane-containing resin composition described later can be improved. That is, 0 < T1 may be satisfied, and when 0 < T1, preferably 0.01 ≤ T1, more preferably 0.05 ≤ T1, and still more preferably 0.1 ≤ T1. On the other hand, if the proportion of T units without a polymerizable alkenyl group is too high, curing defects are likely to occur due to the steric hindrance of the introduced organic groups. Therefore, the proportion T1 of T units without a polymerizable alkenyl group is preferably T1≦0.5, more preferably T1≦0.4, and even more preferably T1≦0.3.

[0038] <Coefficient Q> In the organopolysiloxane of the present embodiment, the Q unit is not an essential constituent, but it is the most oxidized form of silicon, and by being included in the structure of the organopolysiloxane, the heat resistance of the cured product can be increased. The Q unit is also included in quartz. For example, when the cured product is used as a near-infrared optical waveguide, a cured product having a refractive index close to that of the core material of a near-infrared single-mode silica optical fiber can be obtained by using an organopolysiloxane-containing curable resin composition having a Q unit. As described above, the organopolysiloxane of the present embodiment may or may not have a Q unit, but from the viewpoint of improving the heat resistance of the cured product of the organopolysiloxane, it is preferable to have a Q unit. On the other hand, from the viewpoint of improving the flexibility of the cured product of the organopolysiloxane, it is preferable not to have a Q unit. The coefficient Q indicating the proportion of the Q unit may be 0 or may be 0 or more, that is, Q≧0. When having a Q unit, the coefficient Q is preferably Q≧0.04, more preferably Q≧0.10, even more preferably Q≧0.15, and even more preferably Q≧0.20. On the other hand, when the amount of the Q unit is too large, it tends to become solid or have a high viscosity, resulting in a decrease in handling properties. Therefore, usually Q≦0.65, preferably Q≦0.6, more preferably Q≦0.45, and even more preferably Q≦0.40. As described above, when having a Q unit, it is preferable that 0<Q≦0.65, more preferably 0.04≦Q≦0.6, and even more preferably 0.04≦Q≦0.45.

[0039] From the above, each coefficient in the above formula [1] is preferably such that each of M3, D3, T3, M1, D1, T1, Y1 and Y2 is within any of the above-described preferred ranges within the range of 0 < M2 + D2 + T2 < 1, more preferably each of M3, D3, T3, M1, D1, T1, Y1 and Y2 is within any of the above-described preferred ranges within the range of 0.2 ≦ M2 + D2 + T2 ≦ 0.95, still more preferably each of M3, D3, T3, M1, D1, T1, Y1 and Y2 is within any of the above-described preferred ranges within the range of 0.25 ≦ M2 + D2 + T2 ≦ 0.9, and even more preferably each of M3, D3, T3, M1, D1, T1, Y1 and Y2 is within any of the above-described preferred ranges within the range of 0.3 ≦ M2 + D2 + T2 ≦ 0.8.

[0040] <R 1 ~R 5 、R 7 ~R 8 、R 10 ~R 15 > R 1 ~R 5 、R 7 ~R 8 、R 10 ~R 15 are each independently one or more groups selected from the group consisting of an organic group, a reactive functional group, and a hydrogen atom. R 1 ~R 5 、R 7 ~R 8 、R 10 ~R 15 When R~R are organic groups, they are preferably organic groups having 1 to 20 carbon atoms, specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, polyether groups such as furanyl group, polyalkylene glycol group, and more preferably methyl group.

[0041] R 1 ~R 5 、R 7 ~R 8 、R 10 ~R15 When R is a reactive functional group, it is preferably a hydrogen atom, a hydroxyl group such as an alcohol, a carboxyl group, an aldehyde group, an epoxy group, or the like. 1 ~R 3 , R 10 , R 11 , R 14 and R 15 does not contain a polymerizable alkenyl group as a reactive functional group. 1 ~R 3 When is an organic group containing a polymerizable alkenyl group, it becomes difficult to distinguish between the M1 proportion and the M2 proportion, and therefore this is specified as such. On the other hand, the R in the M2 proportion part 4 , R 5 and R in the M3 proportion part 7 , R 8 Since such a problem does not occur even when the organic group contains a polymerizable alkenyl group, the D1 fraction, the T1 fraction, and the Y1 fraction are not subject to this limitation. For the same reason, in this embodiment, R 10 , R 11 , R 14 and R 15 is defined as not containing polymerizable alkenyl groups.

[0042] <Method for producing organopolysiloxane> The method for producing the organopolysiloxane of this embodiment is not particularly limited as long as it can produce an organopolysiloxane containing at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. Among these, it is preferable to produce an organopolysiloxane represented by the above formula [1]. For example, any of the production methods may be used, such as a method of simultaneously condensing one or more disiloxane compounds, disilazane compounds, and their hydrolysates, alkoxysilane compounds, and their hydrolysates, and partial hydrolyzed condensates; a method of condensing a chlorosilane compound, and its hydrolysates, and partial hydrolyzed condensates; a method of ring-opening polymerization of a cyclic siloxane compound; or chain polymerization such as anionic polymerization, or a combination of several production methods. The method for introducing the polymerizable alkenyl group is not particularly limited, and any method may be used, such as a method of simultaneously condensing one or more alkoxysilane compounds, disiloxane compounds, or disilazane compounds having a polymerizable alkenyl group, or their hydrolysates or partial hydrolysis condensates, or a method of converting a reactive organic group introduced into an organopolysiloxane into a polymerizable alkenyl group by a chemical method, or a combination of these methods. Examples of raw materials that can be used in the production of organopolysiloxane by hydrolysis and condensation in this embodiment are given below.

[0043] (M unit source) Examples of sources of M units include trimethylsilanol, trimethylmethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, dimethylsilanol, dimethylmethoxysilane, tetramethyldisiloxane, tetramethyldisilazane, dimethylvinylsilanol, dimethylvinylmethoxysilane, 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetramethyldisilazane, 3-(meth)acryloyloxypropyldimethylsilanol, 3-(meth)acryloyloxypropyldimethylmethoxysilane, 1,3-bis((meth)acryloyloxypropyl)-1,1,3,3-tetramethyldisiloxane, (meth)acryloyloxymethyldimethylmethoxysilane, Examples of suitable silanes include silane, 2-(meth)acryloyloxyethyldimethylmethoxysilane, (meth)acryloyloxymethyldiphenylmethoxysilane, 2-(meth)acryloyloxyethyldiphenylmethoxysilane, methoxytriphenylsilane, triphenylsilanol, 1,3-diphenyltetramethyldisiloxane, 1,3-diphenyltetramethyldisilazane, dimethylphenylsilanol, dimethylmethoxyphenylsilane, 1,4-bis(dimethylmethoxysilyl)benzene, 1,4-bis(dimethylethoxysilyl)benzene, dimethylglycidyloxypropylmethoxysilane, and 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane. Furthermore, among the compounds listed above, those containing a silanol hydroxyl group or an alkoxy group can be replaced with a compound group in which a halogen is bonded instead of the silanol hydroxyl group or the alkoxy group. Hexamethyldisiloxane is particularly suitable as the source of M units.

[0044] (D unit source) Examples of D unit sources that can be used include dimethyldisilanol, dimethyldimethoxysilane, tetramethyldisiloxane, 3-glycidoxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane, (meth)acryloyloxymethyldimethoxysilane, 2-(meth)acryloyloxyethyldimethoxysilane, (meth)acryloyloxymethylphenyldimethoxysilane, 2-(meth)acryloyloxyethylphenyldimethoxysilane, methyldimethoxyphenylsilane, diethoxymethylphenylsilane, methylphenyldisilanol, diphenyldisilanol, dimethoxydiphenylsilane, 1,4-bis(methyldimethoxysilyl)benzene, 1,4-bis(methyldiethoxysilyl)benzene, dimethoxy(methyl)(3,3,3-trifluoropropyl)silane, and compounds in which halogen is bonded instead of the silanol hydroxyl group or alkoxy group in the above-listed compounds, as well as polymers thereof. In particular, dimethyldimethoxysilane can be preferably used.

[0045] (T unit source) Examples of T unit sources include trimethoxysilane, trimethoxysilanes modified with a C1 to C20 long-chain alkoxy group such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane, vinyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, (meth)acryloyloxymethyltrimethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, and 3-(meth)acryloyloxypropyl Alkoxysilane compounds such as trimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 1,4-bis(trimethoxysilyl)benzene, p-styryltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ethoxysilane, silanol compounds, chlorosilane compounds, hydrosilylsilane compounds, and polymers thereof can be used. In particular, methacryloyloxymethyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, acryloyloxymethyltrimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, and decyltrimethoxysilane can be preferably used.

[0046] (Q unit source) Examples of Q unit sources include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, triethoxymonomethoxysilane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane, triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymono Examples of alkoxysilanes that can be used include monoethoxybutoxysilane, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dibutoxymonomethoxymonoethoxysilane, dibutoxymonoethoxymonopropoxysilane, and monomethoxymonoethoxymonopropoxymonobutoxysilane, as well as aryloxysilanes and tetramethoxysilane oligomers such as Methyl Silicate MS51, MS56, MS57, and MS60 manufactured by Mitsubishi Chemical Corporation, and tetraethoxysilane oligomers such as Ethyl Silicate Oligomer ES40 and ES48 manufactured by Tama Chemicals Co., Ltd. Methyl Silicate MS51 is particularly preferred. The above M, D, T and Q unit sources may each be used alone or in combination of two or more.

[0047] The catalyst for hydrolyzing and condensing these silicon raw materials may be an acid catalyst, a base catalyst, or an inorganic salt, with an acid catalyst being particularly preferred. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, trifluoroacetic acid, acetic acid, methacrylic acid, acrylic acid, etc. Hydrochloric acid is particularly suitable. Examples of the base catalyst include ammonia, hexamethyldisilazane, triethylamine, tetraethylammonium hydroxide, diazabicycloundecene, potassium hydroxide, sodium hydroxide, barium hydroxide, potassium carbonate, sodium carbonate, etc. Potassium hydroxide is particularly preferred. Examples of inorganic salts include sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, etc. Sodium chloride is particularly preferred.

[0048] Examples of solvents used during hydrolysis and condensation include tetrahydrofuran, toluene, methanol, ethanol, isopropanol, hexane, and heptane. Tetrahydrofuran is particularly preferred. Depending on the solubility of the product, two or more solvents may be used, and a mixture of toluene and methanol, or a mixture of tetrahydrofuran and methanol is particularly preferred.

[0049] The alkoxy groups and silanol groups remaining without hydrolysis and condensation may be substituted with an organic acid or alcohol, if necessary. Examples of organic acids that can be used include acetic acid, acrylic acid, and methacrylic acid. Examples of alcohols that do not contain a polymerizable alkenyl group include methanol, ethanol, propanol, butyl alcohol, pentanol, hexanol, heptanol, and structural isomers thereof. Examples of alcohols that contain a polymerizable alkenyl group include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. From the viewpoint of stability, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

[0050] If the organopolysiloxane has a rigid structure such as a complete cage silsesquioxane, the cured product will be hard and brittle, so it is preferable that the organopolysiloxane does not have a complete cage structure. As long as it is not a complete cage silsesquioxane, for example, it may contain a random structure or ladder structure as a higher-order structure within a range that does not impair the effects of the present invention.

[0051] <Water> The amount of water used for hydrolysis is preferably 0.5 equivalents or more, more preferably 0.8 equivalents or more, and even more preferably 1.1 equivalents or more, based on the total amount of alkoxy groups contained in the MDTQ unit source. The water is not particularly limited, and may be water contained in commercially available hydrochloric acid or water purified by distillation or ion exchange resin.

[0052] [Organopolysiloxane-containing curable resin composition] The organopolysiloxane-containing curable resin composition of this embodiment can be suitably used for forming optical components such as lenses, light guide plate sealing materials, and near-infrared optical waveguides. In addition to the organopolysiloxane described above, the composition can contain a monofunctional polymerizable alkenyl compound, a polyfunctional polymerizable alkenyl compound, and / or an alkenyl polymer, etc., within a range that does not impair the properties of the cured product obtained from the composition, which will be described later. Furthermore, a polymerization initiator can be contained to polymerize and easily cure the organopolysiloxane and polymerizable alkenyl compound. Although it is possible to cure the organopolysiloxane or the organopolysiloxane-containing curable resin composition by electron beam irradiation or the like without using a polymerization initiator, a large amount of energy is required for curing. Therefore, in a preferred aspect of this embodiment, the organopolysiloxane-containing curable resin composition contains the organopolysiloxane and at least a polymerization initiator. The curable resin composition of the present embodiment may contain chain transfer agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, rheology modifiers, adhesion aids such as silane coupling agents, other components such as dyes, antifoaming agents, and sensitizers, solvents, and the like, within a range that does not impair the properties of the cured product described below. Components that may be contained in the organopolysiloxane-containing curable resin composition will be described below.

[0053] <Monofunctional polymerizable alkenyl compound> Specific examples of the monofunctional polymerizable alkenyl compound include (meth)acrylates containing a carboxy group, such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, and 2-(meth)acryloyloxyethyl hexahydrophthalate; (meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate; (meth)acrylates containing an alicyclic structure, such as cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, and 4-tert-butylcyclohexyl (meth)acrylate; (meth)acrylates containing an aromatic ring structure, such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, phenylphenyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylbenzyl (meth)acrylate, naphthyl (meth)acrylate, and (1-naphthyl)methyl (meth)acrylate; (meth)acrylates containing a heterocyclic structure, such as tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acryloylmorpholine; Alkoxy(meth)acrylates such as methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate, and butoxyethyl(meth)acrylate; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(meth)acryloyloxyethyl acid phosphate, trifluoroethyl (meth)acrylate and heptadecafluorodecyl (meth)acrylate, 2-(meth)acryloyloxyethyl isocyanate; styrene, α-methylstyrene, 2-vinylpyridine, 4-vinylpyridine, 1,1-diphenylethylene, and styrene derivatives such as aromatic ring hydrogen-substituted derivatives thereof; Examples of the vinyl compounds include vinyl acetate, vinyl octanoate, vinyl decanoate, vinyl hexanoate, acrylonitrile, and vinyl benzoate. When a near-infrared optical waveguide is produced using the curable resin composition, the refractive index of the cured product at wavelengths of 589 nm (visible light region) and 1300 nm (near-infrared wavelength region) is preferably 1.4 to 1.5 for reasons described below. Therefore, from the viewpoint of making the refractive index of the cured product lower than 1.5, it is preferable to use a composition that does not contain an aromatic structure.

[0054] <Polyfunctional polymerizable alkenyl compounds> Specific examples of the polyfunctional polymerizable alkenyl compound include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate; Di(meth)acrylates containing an alicyclic structure, such as cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated hydrogenated bisphenol A di(meth)acrylate, and adamantanediol di(meth)acrylate; bifunctional (meth)acrylates such as polycarbonate diol di(meth)acrylate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene, and polyurethane di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, and ε-caprolactone-modified tris((meth)acryloxyethyl)isocyanurate; tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate; Pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate; polyfunctional monomers such as hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Examples include 1,4-divinylbenzene and 1,3-divinylbenzene. From the viewpoint of making the refractive index of the cured product lower than 1.5 at wavelengths of 589 nm and 1300 nm, it is preferable to use one that does not contain an aromatic structure.

[0055] <Alkenyl polymer> An alkenyl polymer is a polymer containing 50% by mass or more of alkenyl monomer units. In this specification, the term "unit" refers to a repeating unit that constitutes a polymer. The alkenyl polymer may be monofunctional or polyfunctional, and preferably does not contain an aromatic structure, from the viewpoint of making the refractive index of the cured product lower than 1.5 at wavelengths of 589 nm and 1300 nm and preventing the cured product from becoming brittle. The alkenyl monomer unit contained in the alkenyl polymer may be of one type alone or two or more types. The polymerization method for obtaining the alkenyl polymer is not particularly limited, and can be a known method such as solution polymerization, suspension polymerization, emulsion polymerization, partial polymerization, etc. In the present embodiment, suspension polymerization is preferred because it is relatively easy to control the polymerization reaction and to separate the produced polymer.

[0056] The alkenyl polymer may be modified by introducing a double bond-containing functional group, such as a (meth)acryloyl group or a vinyl group, into the side chain by chemical modification. Examples of chemical modification methods include a reaction between a carboxy group and a glycidyl group, or a reaction between a hydroxyl group and an isocyanate group. When a reaction between a carboxy group and a glycidyl group is used as a chemical modification method, for example, an alkenyl polymer containing an alkenyl monomer unit having a carboxy group is produced, and the obtained alkenyl polymer is reacted with a compound having a glycidyl group and a double bond, such as glycidyl (meth)acrylate.

[0057] In order to shorten the reaction time, it is preferable to use a reaction catalyst when reacting an alkenyl polymer containing an alkenyl monomer unit having a carboxy group with a compound having a glycidyl group and a double bond. Examples of the reaction catalyst include quaternary ammonium salts such as tetrabutylammonium bromide, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, and phosphine compounds such as triphenylphosphine. Quaternary ammonium salts are particularly preferred because they are less likely to discolor the organopolysiloxane-containing curable resin composition of this embodiment.

[0058] The weight-average molecular weight (Mw) of the alkenyl polymer is preferably 5,000 to 500,000, more preferably 10,000 to 200,000, and even more preferably 20,000 to 150,000. When the weight-average molecular weight is 5,000 or more, the strength of the cured product is improved. When the weight-average molecular weight is 500,000 or less, the viscosity of the organopolysiloxane-containing curable resin composition of this embodiment is reduced, thereby improving workability.

[0059] <Polymerization initiator> Examples of the polymerization initiator include a photopolymerization initiator, a thermal polymerization initiator, a peroxide used in redox polymerization, etc. The type of polymerization initiator can be appropriately selected depending on the polymerization method.

[0060] (Photopolymerization initiator) The photopolymerization initiator is a radical polymerization initiator used in photopolymerization. Specific examples of the photopolymerization initiator include benzophenone-type compounds such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl 2-benzoylbenzoate, and 4-phenylbenzophenone; anthraquinone-type compounds such as tert-butylanthraquinone and 2-ethylanthraquinone; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, and benzyl dimethyl ketone. alkylphenone-type compounds such as methyl ether, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one; thioxanthone-type compounds such as 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, diethylthioxanthone, and isopropylthioxanthone; Acylphosphine oxide compounds such as 4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; phenylglyoxylate compounds such as phenylglyoxylic acid methyl ester; N-acetoxy-N-{4-acetoxyimino-4-[9-ethyl-6-(o-toluoyl)-9H-carbazol-3-yl] oxime ester compounds such as N-acetoxy-N-{3-(acetoxyimino)-3-[9-ethyl-6-(1-naphthoyl)-9H-carbazol-3-yl]-1-methylpropyl}acetamide, N-acetoxy-N-{3-(acetoxyimino)-3-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate, and methyl 4-acetoxyimino-5-oxo-5-(4-(phenylthio)phenyl)pentanoate.

[0061] Among these, alkylphenone-type compounds are preferred in terms of their ability to suppress discoloration of the cured product, and 2-hydroxy-2-methyl-1-phenylpropan-1-one or 1-hydroxycyclohexyl phenyl ketone is more preferred. Acylphosphine oxide-type compounds are preferred in terms of their ability to facilitate sufficient curing deep into the cured product, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferred in terms of their ability to suppress discoloration of the cured product. Furthermore, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and methyl 4-acetoxyimino-5-oxo-5-(4-(phenylthio)phenyl)pentanoate are more preferred in terms of their increased sensitivity to light with longer wavelengths. 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone is also preferred in terms of its high reactivity to light with a wavelength of around 365 nm. These photopolymerization initiators may be used alone or in combination of two or more.

[0062] In this embodiment, when the organopolysiloxane-containing curable resin composition (hereinafter sometimes simply referred to as "curable resin composition") is cured by photopolymerization to obtain a cured product, the wavelength of the light irradiated onto the curable resin composition is not particularly limited, but it is preferable to irradiate it with ultraviolet light having a wavelength of 200 to 500 nm. Specific examples of ultraviolet light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, high-power metal halide lamps, UV-LED lamps, chemical lamps, and black lights. After photopolymerization of the curable resin composition, an after-cure may be further performed. By performing the after-cure, the amount of unreacted polymerizable alkenyl groups remaining in the cured product can be reduced, and the strength of the cured product can be further increased. The after-cure conditions are preferably 70 to 200°C for 0.01 to 24 hours, more preferably 80 to 180°C for 0.1 to 10 hours.

[0063] (thermal polymerization initiator) The thermal polymerization initiator is a radical polymerization initiator used in thermal polymerization, and examples of the thermal polymerization initiator include organic peroxides and azo compounds. Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, and 1,1-di(tert-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; dicumyl peroxide, di-tert-butyl peroxide, and the like. diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-tert-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; and peroxyesters such as tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate.

[0064] Specific examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane) dihydrochloride.

[0065] These thermal polymerization initiators may be used alone or in combination of two or more. As the thermal polymerization initiator, organic peroxides are preferred because they are less likely to generate bubbles in the cured product. In consideration of the balance between the curing time and pot life of the curable resin composition, the 10-hour half-life temperature of the organic peroxide is preferably 35 to 80°C, more preferably 40 to 75°C, and even more preferably 45 to 70°C. If the 10-hour half-life temperature is 35°C or higher, the curable resin composition is less likely to gel at room temperature, resulting in a good pot life. On the other hand, if the 10-hour half-life temperature is 80°C or lower, the curing time of the curable resin composition can be shortened.

[0066] Examples of such organic peroxides include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, and di(4-tert-butylcyclohexyl)peroxydicarbonate. Commercially available 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate includes, for example, Perocta O (trade name, manufactured by NOF Corporation, 10-hour half-life temperature: 65.3°C). Commercially available tert-butylperoxy-2-ethylhexanoate includes, for example, Perbutyl O (trade name, manufactured by NOF Corporation, 10-hour half-life temperature: 72.1°C). Commercially available di(4-tert-butylcyclohexyl)peroxydicarbonate includes, for example, Peroyl TCP (trade name, manufactured by NOF Corporation, 10-hour half-life temperature: 40.8°C).

[0067] When the curable resin composition is cured by thermal polymerization to obtain a cured product, the curing conditions are not particularly limited, but from the viewpoint of easily obtaining a resin for optical components with suppressed coloration, the curing temperature is preferably 40 to 200° C., more preferably 60 to 150° C. The curing time (heating time) varies depending on the curing temperature, but is preferably 1 to 120 minutes, more preferably 1 to 60 minutes. After the curable resin composition is thermally polymerized, it is preferable to further carry out after-curing. The after-cure conditions are preferably 70 to 200° C. for 0.1 to 10 hours, and more preferably 80 to 180° C. for 0.2 to 5 hours.

[0068] (redox polymerization) Redox polymerization usually uses a redox polymerization initiator. The redox polymerization initiator is a polymerization initiator that uses a peroxide and a reducing agent in combination. Examples of peroxides used in redox polymerization include dibenzoyl peroxide and hydroperoxide. These peroxides may be used alone or in combination of two or more. When the above-mentioned peroxides are used as redox polymerization initiators, examples of combinations with reducing agents are as follows: (1) A combination of dibenzoyl peroxide (peroxide) and an aromatic tertiary amine (reducing agent) such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, or N,N-bis(2-hydroxypropyl)-p-toluidine. (2) A combination of hydroperoxide (peroxide) and metal soaps (reducing agents). (3) A combination of hydroperoxide (peroxide) and thiourea (reducing agent).

[0069] When a curable resin composition is cured by redox polymerization to obtain a cured product, the use of a redox polymerization initiator allows curing at a temperature of 5 to 40° C. The curing temperature is preferably 15 to 40° C., since this can reduce the amount of unreacted (meth)acryloyl groups remaining in the obtained cured product and further increase the strength of the cured product. A preferred method for curing involves dissolving a reducing agent in a curable resin composition in advance and then adding a peroxide to the curable resin composition, since the curable resin composition is less likely to gel and can be handled stably. When curing the curable resin composition, it is preferable to cure the curable resin composition in a sealed state in order to suppress curing inhibition by oxygen. Examples of a method for sealing the curable resin composition include a method of sandwiching the curable resin composition between glass or PET film.

[0070] <Chain transfer agent> When a curing reaction of a curable resin composition is carried out in air, active radicals are trapped by oxygen as peroxide radicals, inhibiting polymerization. However, by adding a chain transfer agent that donates hydrogen, polymerization inhibition by oxygen can be suppressed. Examples of the chain transfer agent include methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolethane tris(3-mercaptopropionate), trimethylol Trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), tris[2-(3- mercaptocarboxylic acid esters such as tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate and tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate; alkyl thiols such as ethanethiol, 2-methylpropane-2-thiol, n-dodecanethiol, 2,3,3,4,4,5-hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, and benzylthiol; benzenethiol Examples of thiol compounds include aromatic thiols such as 2-mercaptoethanol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzimidazole-2-thiol, and benzothiazole-2-thiol; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; and silane-containing thiols such as 3-(trimethoxysilyl)propane-1-thiol and 3-(triethoxysilyl)propane-1-thiol. When a chain transfer agent is added, one type of chain transfer agent may be used alone, or two or more types may be used in combination. The amount added is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total amount of polymerizable components. When two or more types are used in combination, the total amount of chain transfer agents falls within the above range.

[0071] <Solvent> The curable resin composition of this embodiment may contain a solvent for the purpose of diluting the organopolysiloxane and the curable resin composition. The type of solvent is not particularly limited as long as it does not impair the physical properties required for the cured product of the organopolysiloxane and the curable resin composition. Examples of solvents that have good solubility include aromatic hydrocarbons (e.g., toluene, xylene, ethyl benzoate, ethylbenzene, benzyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, ethyl lactate, methyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, γ-butyrolactone), and ethers (e.g., isopropyl ether, ethylene glycol). Examples of solvents that can be used include propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, 1,4-dioxane, methyl tert-butyl ether, and tetrahydrofuran, alcohols (e.g., methanol, ethanol, normal propanol, isopropanol, butanol, sec-butanol, tert-butanol, and normal pentanol), halogenated solvents (e.g., methylene chloride, trichloroethylene, tetrachloroethylene, bromopropane, and chloroform), and others (e.g., dimethyl sulfoxide, N,N-dimethylformamide, and water). One type of solvent may be used alone, or two or more types may be used.

[0072] The content of the solvent in the curable resin composition is not particularly limited as long as it does not impair the physical properties required for the cured product of the organopolysiloxane and the curable resin composition, but when it is desired to reduce the viscosity while keeping the volatile content low, it is preferably more than 0% by mass and not more than 25% by mass of the organopolysiloxane or the curable resin composition as a whole. Furthermore, when a thin-film cured product is to be obtained, it is preferably 75% by mass or more and less than 100% by mass of the curable resin composition as a whole.

[0073] (antioxidant) The curable resin composition preferably further contains an antioxidant. When the curable resin composition contains an antioxidant, discoloration of the cured product due to heat, such as heating during soldering of the cured product or heat generation in a device, can be suppressed. Specific examples of antioxidants include phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Examples of the antioxidants include phosphorus-based antioxidants such as triphenyl phosphite, tris-isodecyl phosphite, tris-tridecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and tetra(C12-15 alkyl)-4,4'-isopropylidenediphenyl diphosphite; and sulfur-based antioxidants such as dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearic-3,3'-thiodipropionate, and pentaerythritol tetrakis(β-laurylthiopropionate). These antioxidants may be used alone or in combination of two or more.

[0074] (Other ingredients) The curable resin composition of the present embodiment may contain other components such as a filler, a curing regulator, a viscosity modifier, etc. These components may be appropriately contained within a range that does not affect the reflow resistance, low coefficient of linear thermal expansion, or refractive index of the cured product of the organopolysiloxane-containing curable resin composition of the present embodiment.

[0075] <Curing of Organopolysiloxane-Containing Curable Resin Composition> In another embodiment of the present invention, there is provided a cured product obtained by curing the above-described organopolysiloxane-containing curable resin composition with heat or light. The curing conditions for the organopolysiloxane-containing curable resin composition of this embodiment are not particularly limited, and curing can be carried out under the conditions that are appropriately used for curing silicone resins, depending on the type of polymerization initiator, etc.

[0076] <Characteristics of the cured product> When an organopolysiloxane containing at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, and a curable resin composition containing the organopolysiloxane are cured as described above, a cured product having the following properties can be obtained.

[0077] Reflow resistance The cured product obtained in this embodiment is characterized by excellent reflow resistance, such as being less susceptible to cracking at high temperatures. Without being bound by any particular theory, excellent reflow resistance can be achieved by using a curable resin composition containing an organopolysiloxane in which an acryloyloxy group is bonded to a silicon atom via an alkyl group having either 1 or 2 carbon atoms, i.e., at least one of a methyl group and an ethyl group. The "reflow resistance" in this invention is evaluated by the method described in the examples below. Mounting optical components often involves a solder reflow process. The cured product of this embodiment has excellent reflow resistance, which can alleviate stresses that occur during the solder reflow process and sufficiently suppress defects such as cracks, making it suitable for mounting.

[0078] Coefficient of linear thermal expansion (CTE) The cured product of this embodiment has a low coefficient of linear thermal expansion (CTE). Many inorganic materials, such as quartz, with low CTE are used for optical components, and it is preferable to use a component that has little adverse effect on bonding with these inorganic materials. The CTE of the cured product of this embodiment is preferably 150 ppm / K or less, more preferably 140 ppm / K or less, even more preferably 130 ppm / K or less, even more preferably 120 ppm / K or less, even more preferably less than 110 ppm / K, and particularly preferably 100 ppm / K or less. In the present invention, the CTE of the cured product can be measured by the method described in the Examples below.

[0079] The cured product of this embodiment can be particularly useful as a near-infrared optical waveguide. Photocurable organic-inorganic hybrid materials are often used as optical waveguide materials due to their high degree of freedom in structural design and high optical transparency. The introduction of inorganic components makes the material hard and brittle, which can lead to the problem of cracks occurring during heating processes such as reflow processes. Furthermore, it is also necessary to reduce the CTE, which is important when connecting to optical fibers. As described above, the cured product of this embodiment has excellent reflow resistance and a low CTE, and therefore can be particularly preferably used as a near-infrared optical waveguide.

[0080] As described above, the curable resin composition containing the organopolysiloxane of this embodiment has excellent reflow resistance, excellent compatibility with manufacturing processes, and a low CTE, and therefore can be preferably used for optical components. The optical components can be used as various optical components such as camera lenses, pickup lenses, eyeglass lenses, plastic lenses such as Fresnel lenses and prism lenses, optical waveguides, holograms, prism lenses, optical components for optical semiconductors, and light guide plate sealants, and among these, the optical components can be used particularly as near-infrared optical waveguides.

[0081] [Near-infrared optical waveguide and near-infrared optical transmission component] A near-infrared optical waveguide produced using the above-described organopolysiloxane-containing curable resin composition and a near-infrared optical transmission component comprising at least the near-infrared optical waveguide also fall within the scope of the present invention. As will be described later, the scope of the present invention also includes a near-infrared light waveguide having a cured product obtained by curing the above-mentioned organopolysiloxane-containing curable resin composition, and a near-infrared light transmission component comprising at least the near-infrared light waveguide. The near-infrared optical waveguide of the present invention comprises at least a core and / or a clad formed by curing the organopolysiloxane-containing curable resin composition, and may also comprise a base material (also referred to as a "substrate"). The near-infrared light transmission component of this embodiment may include, in addition to the near-infrared light waveguide described above, a connecting component such as a mirror or a connector for connecting to an optical fiber or a silicon photonics optical circuit.

[0082] The organopolysiloxane-containing curable resin composition described above can be used as both a cladding material for forming the cladding portion of an optical waveguide and a core material for forming the core portion, provided that the refractive index of the core material for forming the core portion is higher than the refractive index of the cladding material for forming the cladding portion.

[0083] The refractive index of the cured product can be controlled by changing the proportion of organopolysiloxane structural units contained in the organopolysiloxane-containing curable resin composition. For example, by increasing the value of M2 + D2 + T2 in the above formula [1], i.e., by increasing the proportion of polymerizable alkenyl groups, the density of the resulting cured product can be increased and the refractive index can be raised. Conversely, by decreasing the value of M2 + D2 + T2, i.e., by decreasing the proportion of polymerizable alkenyl groups, the density of the resulting cured product can be decreased and the refractive index can be lowered. Alternatively, the refractive index of the cured product can be controlled by changing the component ratio of the organopolysiloxane-containing curable resin composition. Alternatively, the refractive index can be controlled by adjusting the content (volume %) of polymerizable alkenyl groups in the polymerizable alkenyl compound and / or alkenyl polymer contained in the organopolysiloxane-containing curable resin composition, thereby controlling the crosslink density of the cured product in the same manner as described above. Additionally, the refractive index can be increased by increasing the aromatic group content (volume %) of the cured product, or decreased by increasing the fluorine content (volume %). Furthermore, the refractive index of the cured product can also be controlled by combining these methods. These methods can be applied within a range that does not significantly impair the effects of the present invention. In the case of a near-infrared single-mode optical signal, the refractive index difference between the core material and the cladding material at near-infrared wavelengths is preferably 0.01 to 0.05, more preferably 0.01 to 0.04, even more preferably 0.01 to 0.03, and even more preferably 0.01 to 0.02.

[0084] When connecting to a near-infrared single-mode silica-based optical fiber in a device, a smaller difference in refractive index between the core material of the silica-based optical fiber and the core material of the optical waveguide reduces interfacial reflection of light at the connection portion and can further reduce connection loss. Generally, the refractive index of the core material of a near-infrared single-mode silica-based optical fiber at near-infrared wavelengths is 1.4 to 1.5. If the refractive index of the core material of the optical waveguide at a wavelength of 1,300 nm is preferably 1.400 to 1.500, more preferably 1.420 to 1.480, even more preferably 1.425 to 1.480, still more preferably 1.440 to 1.480, and particularly preferably 1.450 to 1.480, the difference in refractive index between the two materials becomes smaller, and connection loss can further be reduced. Furthermore, even if the refractive index of the core material at a wavelength of 589 nm is preferably 1.400 to 1.510, more preferably 1.410 to 1.510, even more preferably 1.430 to 1.490, still more preferably 1.435 to 1.490, particularly preferably 1.450 to 1.490, and particularly preferably 1.460 to 1.490, the difference in refractive index between the two materials at near-infrared wavelengths will be small, and the connection loss may be small.

[0085] The method for producing the near-infrared optical waveguide according to this embodiment is not particularly limited. For example, the optical waveguide can be formed through a process of curing the above-described organopolysiloxane-containing curable resin composition by exposure (photocuring) or heating (thermal curing). As a typical example, an optical waveguide can be formed by using a lithography technique with a photomask, followed by an etching step and a development step. When an optical waveguide is produced by photolithography, it is preferable to use a curable resin composition containing at least an organopolysiloxane and a photopolymerization initiator, and if necessary, a curable resin composition to which a solvent, a chain transfer agent, etc. are further added can be used. Alternatively, the optical waveguide can be produced by a method such as nanoimprinting. The above-mentioned method of forming an optical waveguide by photolithography is particularly preferable because it allows the fabrication of an optical waveguide with a small line width and pitch.

[0086] The substrate of the near-infrared optical waveguide can be a silicon wafer, a silicon wafer with an oxide film, a polyimide resin, an epoxy resin, a PEEK resin, a liquid crystal polymer, glass, a glass epoxy substrate, or the like. When using photolithography, the core of the optical waveguide can be prepared on the substrate by a coating process in which a curable resin composition is applied to the substrate, an exposure process through a photomask, and a washing process in which the unexposed composition is washed away with a solvent. Furthermore, an overclad can be prepared by applying and curing an organopolysiloxane or an organopolysiloxane-containing resin composition to the core prepared on the substrate. Before preparing the core, an underclad can be prepared in advance by applying and curing an organopolysiloxane-containing composition to the substrate. Alternatively, after preparing the core and clad of the optical waveguide on the substrate, the waveguide can be peeled off from the substrate. [Example]

[0087] The present invention will be described in more detail by the following examples, but the present invention is not limited thereto.

[0088] [Evaluation method] (1) 1 H-NMR measurement method Equipment: AVANCE NEO 600 (manufactured by Bruker Japan) BBO type Cryo Probe (5mm diameter) (manufactured by Bruker Japan, registered trademark) Measurement conditions: Pulse repetition time / 10 seconds, number of scans / 16, single pulse measurement, flip angle / 30°, spin / none, measurement temperature / 25°C Sample preparation: 60 mg of the organopolysiloxane to be measured was weighed out, and 12 mg of N,N-dimethylformamide was added as an internal standard. Deuterated chloroform was then added to dissolve the organopolysiloxane to a total mass of 1 g, and the solution was placed in an NMR sample tube. Calculation of functional group content: The functional group content was estimated from the ratio of the signal intensity of each component to the signal intensity of the internal standard N,N-dimethylformamide, and the weighed value.

[0089] (2) 29 Si-NMR measurement method (Organopolysiloxanes of Examples 1 and 2 and Comparative Example 2 29 Si-NMR measurement equipment and measurement conditions Equipment: AVANCE NEO 600 (manufactured by Bruker Japan), BBO type Cryo Probe (5 mm diameter) (manufactured by Bruker Japan, registered trademark) Measurement conditions: Pulse repetition time / 16 seconds, Scan count / 1024 times, Inverse gate decoupling measurement, Flip angle / 90°, Spin / None, Measurement temperature / 25°C (Organopolysiloxane of Comparative Example 1 29 Apparatus and conditions used for Si-NMR measurement: JNM-ECS400 manufactured by JEOL Ltd., TUNABLE Probe (10 mm diameter): Si-free, AT10 probe Measurement conditions: Pulse repetition time / 16 seconds, number of scans / 1024, measurement mode / non-gated decoupled pulse method (NNE), flip angle / 90°, spin / none, measurement temperature / 25°C <Sample preparation and calculation of constituent units> Sample preparation: Tris(2,4-pentanedionato)chromium(III) was added to deuterated chloroform to a concentration of 0.5% by mass. 29 A solvent for Si-NMR measurement was obtained. 1.5 g of the organopolysiloxane to be measured was weighed out and 29 2.5 ml of a solvent for Si-NMR measurement was added to dissolve the sample, which was then placed in an NMR sample tube. Calculation of constituent units: Measure the signal intensity of each silicon unit and calculate the above 1 The composition ratio of silicon units was calculated from the ratio to the signal intensity measured by H-NMR and the ratio to the functional group content.

[0090] (3) CTE measurement Preparation of cured product: 100 parts by mass of the organopolysiloxane obtained in each Example and Comparative Example and 2 parts by mass of 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (Omnirad 369, manufactured by IGM Resins BV) were placed in a container and stirred for 2 hours to obtain a photocurable resin composition. This resin composition was sandwiched between two glass plates, with a 1 mm thick silicone rubber sheet with a 5 mm diameter hole inserted between them as a spacer, and then heated at room temperature with an LED light source with a wavelength of 365 nm and an irradiation energy of 300 mW / cm. 2 The cured product was exposed to light at 100°C for 20 seconds, yielding a cylindrical cured product with a diameter of 10 mm and a thickness of 1 mm. The dimensional change of the resulting cured product was measured under the following conditions using a thermomechanical analyzer TMA7100 (manufactured by Hitachi High-Tech Science Corporation). From the measurement results, the dimensional change rate in the third step from 30 to 120°C was taken as the linear thermal expansion coefficient of each cured product. <Measurement conditions> Measurement mode: Compression mode Atmosphere: 200 mL / min nitrogen flow Heating rate: 5℃ / min ·Measurement temperature: 1st step: 30~120℃ 2nd step: 120~30℃ 3rd step: 30~120℃ 4th step: 120~30℃

[0091] (4) Evaluation of reflow resistance Preparation of cured product: 100 parts by weight of the organopolysiloxane obtained in each Example and Comparative Example and 2 parts by weight of 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (Omnirad 369, IGM Resins BV) were placed in a container and stirred for 2 hours to obtain a photocurable resin composition. This resin composition was sandwiched between two glass plates with a 1 mm thick silicone rubber sheet inserted as a spacer, and then exposed to a cumulative light dose of 6000 mJ using a 365 nm LED light source to obtain a cured product approximately 4 cm square. The reflow resistance of the obtained cured product was evaluated under the following conditions. Equipment: Shinapex Co., Ltd. Desktop reflow equipment SVO-1 Solder reflow heat resistance test conditions: Based on JPCA-PE02-05-01S, the heat resistance test was carried out using the temperature profile shown in Figure 6.3.1 of "6.3 Other Tests 6.3.1 Heat Resistance Test" of the standard. The peak temperature (maximum reached temperature) was set to 260°C and held for 10 seconds. Evaluation: After the test, the cured product was observed for warping and cracks. Evaluation was performed as follows: A: No warping or cracks in the cured product B: The cured product has slight warping and / or slight cracks. C: Cured product has warpage and cracks

[0092] [Method for synthesizing organopolysiloxane] Example 1 Using 98.00 g of methacryloyloxymethyltrimethoxysilane (X-12-1303MS, manufactured by Shin-Etsu Chemical Co., Ltd.) and 53.55 g of dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as organopolysiloxane raw materials, 75.78 g of toluene and 75.78 g of methanol as solvents, and a mixture of 54.88 g of 1N hydrochloric acid and 54.88 g of methanol as catalyst and water, hydrolysis and condensation were carried out while maintaining the temperature at 15° C. to 40° C. The reaction solution was then neutralized and washed with demineralized water, after which the solvent and water were removed and the mixture was filtered, yielding 88.9 g of the desired organopolysiloxane.

[0093] Example 2 The target organopolysiloxane was obtained in the same manner as in Example 1, except that the amount of methacryloyloxymethyltrimethoxysilane was changed to 74.00 g and the amount of dimethoxydimethylsilane was changed to 75.10 g.

[0094] Comparative Example 1 Using 210.00 g of 3-methacryloyloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) and 101.80 g of dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as organopolysiloxane raw materials, 155.90 g of toluene and 155.90 g of methanol as solvents, and a mixture of 104.33 g of 1N hydrochloric acid and 104.33 g of methanol as catalyst and water, hydrolysis and condensation were carried out while maintaining the temperature between 15° C. and 40° C. The reaction liquid was then neutralized and washed with demineralized water, after which the solvent and water were removed and the mixture was filtered, yielding 199.96 g of organopolysiloxane.

[0095] Comparative Example 2 An organopolysiloxane was obtained in the same manner as in Comparative Example 1, except that the amount of 3-methacryloyloxypropyltrimethoxysilane was changed to 100.00 g and the amount of dimethoxydimethylsilane was changed to 90.03 g.

[0096] Regarding the organopolysiloxanes obtained in each of the Examples and Comparative Examples, 1 H-NMR and 29 The molecular composition ratio of the organopolysiloxane calculated by Si-NMR measurement and the physical properties of the cured product are shown in Table 1. The values ​​of the coefficients M1, M2, M3, D2, D3, T1, Q, Y2, and Y3 were 0, and therefore not shown in Table 1.

[0097] [Table 1]

[0098] From the examples, it was confirmed that organopolysiloxanes containing methacryloyloxymethyl groups as substituents directly bonded to silicon atoms have low CTE and excellent reflow resistance. On the other hand, from the comparative examples, it was confirmed that the organopolysiloxanes of the comparative examples, which did not contain at least one substituent selected from the group consisting of acryloyloxymethyl groups, methacryloyloxymethyl groups, acryloyloxyethyl groups, and methacryloyloxyethyl groups as substituents directly bonded to silicon atoms, exhibited significant warpage in the cured films prepared for the reflow resistance test, and it was confirmed that a low CTE and high reflow resistance could not be achieved at the same time.

Claims

1. An organopolysiloxane comprising at least one substituent selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, wherein the substituent is directly bonded to a silicon atom.

2. 2. The organopolysiloxane according to claim 1, wherein the substituent bonded directly to the silicon atom is at least one substituent selected from the group consisting of an acryloyloxymethyl group and a methacryloyloxymethyl group.

3. 2. The organopolysiloxane according to claim 1, which is represented by the following general formula [1]: (R １ R ２ R ３ SiO １／２ ) Ｍ１ (R ４ R ５ R ６ SiO １／２ ) Ｍ２ (R ７ R ８ R ９ SiO １／２ ) Ｍ３ (R １０ R １１ SiO ２／２ ) Ｄ１ (R １２ R ６ SiO ２／２ ) Ｄ２ (R １３ R ９ SiO ２／２ ) Ｄ３ (R １４ SiO ３／２ ) Ｔ１ (R ６ SiO ３／２ ) Ｔ２ (R ９ SiO ３／２ ) Ｔ３ (SiO ４／２ ) Ｑ (O １／２ R １５ ) Ｙ１ (O １／２ R ６ ) Ｙ２ (O １／２ R ９ ) Ｙ３ ・・・[1] [In formula [1], R １ ~R ５ , R ７ ~R ８ , R １０ ~R １５ are each independently one or more groups selected from the group consisting of an organic group, a reactive functional group, and a hydrogen atom. R １ ~R ３ , R １０ , R １１ , R １４ and R １５ does not contain a polymerizable alkenyl group. ６ represents at least one group selected from the group consisting of an acryloyloxymethyl group, a methacryloyloxymethyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, and when a plurality of groups are present, they may be the same or different, R ９ is the above R ６ and when a plurality of acryloyloxyalkyl groups or methacryloyloxyalkyl groups are present, they may be the same or different, 0≦M1, 0≦M3, 0≦D1, 0≦D3, 0≦T1, 0≦T3, 0≦Q, 0≦Y1, 0≦Y2, 0≦Y3, 0<M2+D2+T2, M1 + M2 + M3 + D1 + D2 + D3 + T1 + T2 + T3 + Q = 1.

4. In the formula [1], R ６ is at least one group selected from the group consisting of acryloyloxymethyl groups and methacryloyloxymethyl groups represented by the following formulas [2] and [3]: 【Chemical 1】 (In the above formula, * indicates a bond.)

5. 5. The organopolysiloxane according to claim 3, wherein in the formula [1], 0<M2+D2+T2<1.

6. An organopolysiloxane-containing curable resin composition comprising the organopolysiloxane according to claim 1 or 3 and at least a polymerization initiator.

7. A cured product obtained by curing the organopolysiloxane-containing curable resin composition according to claim 6.

8. A near-infrared optical waveguide produced using the organopolysiloxane-containing curable resin composition according to claim 6.

9. A near-infrared light transmission component comprising at least the near-infrared light waveguide according to claim 8 .

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