JP5110630B2 - Method for producing epoxy-modified silicone - Google Patents

Description

  The present invention relates to a method for producing a modified silicone suitable for producing an epoxy-modified silicone useful as a light-emitting device encapsulation.

  In recent years, the performance of optical semiconductors has increased, and higher performance has been required for sealing resins. Epoxy-modified silicones having a siloxane skeleton as a repeating unit and having an epoxy group as a substituent combine excellent curing characteristics of epoxy resins with excellent properties such as heat resistance based on high Tg, light resistance and transparency of silicones. Since it is expected to have, it attracts attention as a high-performance sealing material.

  Examples of the method for producing the epoxy-modified silicone include a method in which an olefin group-containing siloxane is reacted with a peroxide, and a method in which a chlorosilane or an acetoxysilane compound is reacted with glycidol to produce a glycidyl silicone ether. However, none of these methods has been put to practical use because the yield is low and the operation is complicated.

  In contrast, a method of adding a compound having at least a vinyl group and an epoxy group to an organohydrogensilicone having a SiH unit in the molecule by a hydrosilylation reaction is the introduction of an epoxy functional group or an organic functional group other than an epoxy group. Therefore, it is widely used as a method for producing epoxy-modified silicone, and there are many disclosures.

  For example, Patent Document 1 has an epoxy group for an epoxy-modified silicone having a Q structure as a unit structure and having an alkoxysilylalkyl group as a substituent, and an organohydrogen silicone having a SiH unit. A method for producing the epoxy-modified silicone by adding a vinyl compound by a hydrosilylation reaction is disclosed.

In addition, for example, Patent Document 2 discloses an epoxy modification comprising a monofunctional siloxane unit and a tetrafunctional siloxane unit each having at least one epoxy group-containing organic group and an alkyl group having 6 or more carbon atoms in one molecule. In the presence of silicone and hydrosilylation reaction catalyst, a compound containing an epoxy group-containing vinyl compound and an alkene having 6 or more carbon atoms is added to the organohydrogen silicone by a hydrosilylation reaction to produce the epoxy-modified silicone. A method is disclosed.
Furthermore, for example, Patent Document 3 discloses a modified silicone resin composition in which an alicyclic hydrocarbon group and an epoxy unit are introduced into a side chain of a siloxane skeleton by a hydrosilylation reaction.

  According to these publications, it is disclosed that a cured product obtained by using an epoxy-modified silicone in which an epoxy unit is introduced into a side chain of a siloxane skeleton has light resistance and excellent heat resistance. However, the cured product obtained by using the epoxy-modified silicone tends to decrease the heat resistance when trying to improve the light resistance, and tends to decrease the light resistance when trying to improve the heat resistance. In addition, cracks may occur due to the cold cycle, and further improvement has been demanded in order to satisfy all of light resistance, heat resistance, and crack resistance required for a light emitting device sealant. Regarding the siloxane skeleton, there are descriptions on various substituents and copolymerization ratios. However, the effect of the chain distribution of the copolymerized units of the resulting epoxy-modified silicone on the properties of the cured product and the copolymerization of organohydrogensilicones. There is no description or description of unit chain distribution and hydrosilylation reaction conditions.

  On the other hand, silicones that specify the chain distribution of the siloxane skeleton have also been proposed. For example, Patent Document 4 proposes a block-like hydrogen-modified silicone in which the number average chain length of dialkylsiloxy units and alkylhydrogensiloxy units is in the range of 5 or more and 3000 or less. It is described that a modified silicone can be derived into a desired modified silicone by a hydrosilylation reaction with an olefin. Furthermore, the modified silicone obtained has a segmented silicone part and modified part compared to those obtained by modifying a conventional random hydrogen-modified silicone. It can be used as a synthetic intermediate for raw materials such as cosmetics, mold release agents, lubricants, etc. There is a statement to that effect. However, there is no specific description of reacting with a compound having a carbon-carbon double bond and an epoxy group, and no description or description regarding hydrosilylation reaction conditions.

Japanese Patent Laid-Open No. 5-105758 JP-A-7-18078 JP 2004-155865 A JP-A-9-208702

  The present invention provides an epoxy-modified silicone having excellent transparency and heat resistance, and crack resistance in a heating / cooling cycle accompanying the on / off cycle of an LED, at a high reaction rate, and stable. It aims at providing the method of manufacturing with sufficient reproducibility.

The method of producing a modified silicone by adding a compound having a vinyl group to an organohydrogen silicone having a SiH unit in the molecule by a hydrosilylation reaction can introduce various organic functional groups including an epoxy group. Therefore, it is widely used.
As a method for marking the structure of the organohydrogensilicone, usually, the unit constituting the silicone, specifically, (R ₃ SiO _1/2 ) unit, (R ₂ HSiO _1/2 ) unit, (R ₂ SiO) _2/2 ) units, (RHSiO _2/2 ) units, (RSiO _3/2 ) units, (HSiO _3/2 ) units, (SiO _4/2 ) units, and the following average composition formula (2): It is marked as follows.
(R ₃ SiO _1/2 ) _t (R ₂ HSiO _1/2 ) _u (R ₂ SiO _2/2 ) _v
(RHSiO _2/2 ) _w (RSiO _3/2 ) _x (HSiO _3/2 ) _y (SiO _4/2 ) _z (2)

These can be seen as a block copolymer at first glance, but t, u, v, w, x, y, and z do not represent the way of the chain distribution. It merely represents the component ratio or total number of each unit described.
In general, the siloxane skeleton has a high main chain exchange reactivity, and when an organohydrogensilicone having a SiH unit and a unit not containing SiH in the molecule is easily produced, an equilibrium reaction occurs easily. It is considered that the structure has a random structure depending on the copolymer composition.

  The organohydrogen silicone used as the raw material for the epoxy-modified silicone of Patent Documents 1 to 3 is considered to have a random structure as well, and such an organohydrogen silicone is converted to a hydrosilylation reaction or the like. Even if it is modified by the above, it is considered that the site of introducing the functional group is randomly distributed in the resulting modified silicone, which may deteriorate the characteristics of the modified silicone.

In response, the inventors of the present invention produce (R ₂ SiO _2/2 ) units and (RHSiO _2/2 ) units constituting the organohydrogen silicone as a raw material when producing an epoxy-modified silicone by hydrosilylation reaction. As a result of intensive studies on the average chain length and the performance of the epoxy-modified silicone obtained, the light resistance is improved by setting the average chain length of (R ₂ SiO _2/2 ) units and (RHSiO _2/2 ) units to specific ranges, respectively. It was previously found that an epoxy-modified silicone satisfying the heat resistance and further the crack resistance required for a light-emitting device sealant can be obtained.

However, a compound having a carbon-carbon double bond and an epoxy group is used for a block-type organohydrogen silicone having an average chain length of specific (R ₂ SiO _2/2 ) units and (RHSiO _2/2 ) units. When adding by hydrosilylation reaction, formation of a high molecular weight part derived from the ring opening of the epoxy group is observed in the epoxy-modified silicone obtained depending on the conditions, and the epoxy-modified silicone is produced stably and reproducibly. However, the development of the technology was desired.
In view of these points, the present inventors added as a result of intensive investigations on conditions for adding a compound having a carbon-carbon double bond and an epoxy group to a block-type organohydrogensilicone by a hydrosilylation reaction. The inventors have found that the above problem can be solved by setting the ratio of the added amount of the vinyl compound and the total amount of SiH units in the block-type organohydrogensilicone to a specific range, and the present invention has been completed.

That is, the present invention is as follows.
[1] A carbon-carbon double bond in the presence of a hydrosilylation catalyst for a block-type organohydrogensilicone represented by the following average composition formula (1) that simultaneously satisfies the following <A> and <B> requirements: And a vinyl compound (b) that coexists with the total number of moles of SiH units when producing an epoxy-modified silicone by adding a vinyl compound (b) containing a compound (a) having an epoxy group by a hydrosilylation reaction. The total number of moles of all vinyl groups is 5 times or more and 100 times or less, and a method for producing an epoxy-modified silicone.
<A>: The average chain length of (R ¹ ₂ SiO _2/2 ) units is 3 or more and 100 or less.
<B>: The average chain length of (R ¹ HSiO _2/2 ) units is 2 or more and 20 or less.
(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ HSiO _1/2 ) _b (R ¹ ₂ SiO _2/2 ) _c
(R ¹ HSiO _2/2 ) _d (R ¹ SiO _3/2 ) _e (HSiO _3/2 ) _f (SiO _4/2 ) _g (1)
[However, each R ¹ independently represents a fat having at least one structure selected from the group consisting of A) hydroxyl group, B) halogen atom, C) unsubstituted or substituted chain, branched and cyclic. A monovalent or divalent aliphatic organic group having an aromatic hydrocarbon unit and having a carbon number of 1 to 24 and an oxygen number of 0 to 5, D) an unsubstituted or substituted aromatic hydrocarbon unit, , Having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of a chain, a branched chain and a ring, which are unsubstituted or substituted as necessary, having 6 to 24 carbon atoms and an oxygen number Represents at least one organic group selected from the group consisting of monovalent aromatic organic groups of 0 or more and 5 or less.
The above organic group has a hydroxyl group, an alkoxy group, an acyl group, a carboxyl group, an alkenyloxy group, an acyloxy group, a halogen atom, or an ester bond as long as it is within the range of the carbon number and oxygen number. May be included. Moreover, the hetero atom except oxygen may be included.
Moreover, a, b, c, d, e, f, and g in the average composition formula (1) represent the number of moles of each unit present in 1 mole of the organohydrogensilicone, and a, b, e, f, Each g is 0 or more, c is 3 or more, and d is 2 or more.
Further, when e, f, and g satisfy the following expressions (1) and (2), respectively, a, b, e, f, and g satisfy the expression (3). It is a numerical value selected from the range.
e + f ≠ 0 Formula (1)
g ≠ 0 Formula (2)
0 ≦ a + b ≦ e + f + 2g + 2 Formula (3)
Further, when the above e, f, and g satisfy the following formulas (4) and (5), respectively, the above a and b are numerical values selected from the range satisfying the following formula (6). It is.
e + f = 0 Formula (4)
g = 0 Formula (5)
0 ≦ a + b ≦ 2 Formula (6)
When the above e, f, and g satisfy the following formulas (1) and (5), respectively, the above a and b are numerical values selected from the range that satisfies the following formula (7). It is.
e + f ≠ 0 Formula (1)
g = 0 Formula (5)
0 ≦ a + b ≦ e + f + 2 Formula (7)
Furthermore, when e, f, and g satisfy the following expressions (4) and (2), respectively, a and b are numerical values selected from a range that satisfies the following expression (8). .
e + f = 0 Formula (4)
g ≠ 0 Formula (2)
0 ≦ a + b ≦ 2g + 2 (formula (8))
[2] The number of Si bonded to a monovalent aliphatic organic group having 5 to 20 carbon atoms and having a hydrocarbon unit composed of one or more structures selected from a chain, branched, and cyclic structure group The method for producing an epoxy-modified silicone according to [1], which is in a range of 5% to 95% with respect to the total Si.
[3] The average chain length of the (R ¹ HSiO _2/2 ) unit of the organohydrogensilicone represented by the average composition formula (1) is 2.2 or more and less than 5, [1] or [ [2] The method for producing an epoxy-modified silicone according to [2].
[4] The (b + d + f) / (a + b + c + d + e + f + g) value of the block type organohydrogen silicone represented by the average composition formula (1) is in the range of 0.100 to 0.800 [1] To [3]. The method for producing an epoxy-modified silicone according to any one of [3].
[5] The block type organohydrogen silicone represented by the average composition formula (1) has a value of (e + f + g) of zero, according to any one of [1] to [4] Production method of epoxy-modified silicone.
[6] The block type organohydrogen silicone represented by the average composition formula (1), wherein the value of b / (a + b) is 0.5 or more, and any one of [1] to [5] 2. A method for producing an epoxy-modified silicone according to item 1.
[7] The content of the component having a molecular weight of 1,000 or less contained in the block-type organohydrogen silicone represented by the average composition formula (1) is 15% or less, [1] to [6 ] The manufacturing method of the epoxy-modified silicone of any one of.
[8] The compound (a) having a carbon-carbon double bond and an epoxy group by hydrosilylation reaction with respect to the total number of moles of SiH units of the block type organohydrogen silicone represented by the average composition formula (1). The method for producing an epoxy-modified silicone according to any one of [1] to [7], wherein the mole fraction of SiH units to be added is 70% or more.
[9] The total number of moles of SiH units of the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction, in which the number of moles of the catalyst used in the hydrosilylation reaction is represented by the average composition formula (1) The method for producing an epoxy-modified silicone according to any one of [1] to [8], wherein the range is from 1 / 5,000,000 to 1 / 1,200.
[10] A vinyl compound (b) containing a compound (a) having a carbon-carbon double bond and an epoxy group is hydrosilylated with respect to the SiH unit of the organohydrogen silicone represented by the average composition formula (1). After the addition, the method for producing an epoxy-modified silicone according to any one of [1] to [9], including a step of subjecting the mixture to a temperature of 0 ° C. to 200 ° C. to separate and recover the epoxy-modified silicone.
[11] Any one of [1] to [10], wherein the number of residual SiH units is 2% or less with respect to the total number of Si contained in the epoxy-modified silicone subjected to the separation and recovery step. A process for producing an epoxy-modified silicone as described in 1.

  According to the present invention, an epoxy-modified silicone that is suitably used for applications that require transparency, light resistance, heat resistance, and crack resistance, such as a light emitting device sealant, is industrially efficient and stable. It is possible to provide a method for manufacturing with good performance.

In the present invention, the organohydrogensilicone used as a raw material is a block-type organohydrogensilicone represented by an average composition formula (1) that simultaneously satisfies the following <A> and <B> requirements.
<A>: The average chain length of (R ¹ ₂ SiO _2/2 ) units is 3 or more and 100 or less.
<B>: The average chain length of (R ¹ HSiO _2/2 ) units is 2 or more and 20 or less.
(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ HSiO _1/2 ) _b (R ¹ ₂ SiO _2/2 ) _c
(R ¹ HSiO _2/2 ) _d (R ¹ SiO _3/2 ) _e (HSiO _3/2 ) _f (SiO _4/2 ) _g (1)
[However, each R ¹ independently represents a fat having at least one structure selected from the group consisting of A) hydroxyl group, B) halogen atom, C) unsubstituted or substituted chain, branched and cyclic. A monovalent or divalent aliphatic organic group having an aromatic hydrocarbon unit and having a carbon number of 1 to 24 and an oxygen number of 0 to 5, D) an unsubstituted or substituted aromatic hydrocarbon unit, , Having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of a chain, a branched chain and a ring, which are unsubstituted or substituted as necessary, having 6 to 24 carbon atoms and an oxygen number Represents at least one organic group selected from the group consisting of monovalent aromatic organic groups of 0 or more and 5 or less.
The above organic group has a hydroxyl group, an alkoxy group, an acyl group, a carboxyl group, an alkenyloxy group, an acyloxy group, a halogen atom, or an ester bond as long as it is within the range of the carbon number and oxygen number. May be included. Moreover, the hetero atom except oxygen, such as nitrogen, phosphorus, and sulfur, may be included. ]

In addition, a, b, c, d, e, f, and g in the average composition formula (1) represent the number of moles of each unit present in 1 mole of the organohydrogensilicone, and a, b, e, f, Each g is 0 or more, c is 3 or more, and d is 2 or more.
Further, when e, f, and g satisfy the following expressions (1) and (2), respectively, a, b, e, f, and g satisfy the expression (3). It is a numerical value selected from the range.
e + f ≠ 0 Formula (1)
g ≠ 0 Formula (2)
0 ≦ a + b ≦ e + f + 2g + 2 Formula (3)
Further, when the above e, f, and g satisfy the following formulas (4) and (5), respectively, the above a and b are numerical values selected from the range satisfying the following formula (6). It is.
e + f = 0 Formula (4)
g = 0 Formula (5)
0 ≦ a + b ≦ 2 Formula (6)
When the above e, f, and g satisfy the following formulas (1) and (5), respectively, the above a and b are numerical values selected from the range that satisfies the following formula (7). It is.
e + f ≠ 0 Formula (1)
g = 0 Formula (5)
0 ≦ a + b ≦ e + f + 2 Formula (7)
Furthermore, when e, f, and g satisfy the following expressions (4) and (2), respectively, a and b are numerical values selected from a range that satisfies the following expression (8). .
e + f = 0 Formula (4)
g ≠ 0 Formula (2)
0 ≦ a + b ≦ 2g + 2 (8)

The average chain length of (R ¹ ₂ SiO _2/2 ) units and (R ¹ HSiO _2/2 ) units in the present invention is a value determined by ²⁹ Si-NMR. Specifically, Cr (acac) ₃ is added to the organohydrogensilicone in a solution obtained by dissolving the organohydrogensilicone represented by the average composition formula (1) in a deuteride such as chloroform. After adding 10% by mass and dissolving the solution, a solution obtained by further adding 10 microliters of tetramethylsilane as a standard substance was subjected to ²⁹ Si-NMR measurement under proton complete decoupling conditions, and from the obtained spectrum pattern. Based on the calculated integration values, the average chain lengths of the (R ¹ ₂ SiO _2/2 ) units and (R ¹ HSiO _2/2 ) units (hereinafter referred to as γ and δ, respectively) obtained by calculation. ).
The calculation method of the average chain length of each unit is described below.

^(R ₁ 2 _{SiO 2/2)} average chain length of the unit (gamma) was obtained as determined by ²⁹ Si-NMR method mentioned ^above, adjacent that _(R 1 _{2 SiO 2/2)} units, 2 the sum of integral values of peaks derived from the chain and [alpha] ^1, the sum of _(R 1 _{2 SiO 2/2)} units and ^(R 1 _{HSiO 2/2)} the integral value of the peak of the unit and is neighboring two chain-derived silicon Is a value calculated by Equation (9), where β is β.
γ = 1 + α1 / β (9)

On the other ^hand, (R 1 _{HSiO 2/2)} average chain length of the unit ([delta]) are obtained by measuring by ²⁹ Si-NMR method mentioned ^above, adjacent that (R 1 _{HSiO 2/2)} units, 2 The sum of the integral values of the peaks derived from the chain is α2, and the sum of the integral values of the peaks of the silicon derived from the two chains in which the (R ¹ HSiO _2/2 ) unit and the (R ¹ ₂ SiO _2/2 ) unit are adjacent to each other. Is a value calculated by equation (10), where β is β.
δ = 1 + α2 / β (10)

Here, the integrated value of each peak refers to the integrated value of the portion surrounded by the peak and the base line derived from the corresponding unit structure. When the peak derived from the corresponding unit structure partially overlaps with another peak, the baseline is formed from the peak of the convex portion formed by the peak derived from the unit structure and the other peak. This is the integrated value of the part surrounded by the peak, the perpendicular and the base line.
Hereinafter, the method for calculating the average chain length will be specifically described by taking as an example the case where all of R ¹ are methyl groups. In the present invention, dimethylsiloxy units represented by (R ¹ ₂ SiO _2/2 ) units are represented by (D), while in the present invention, hydrogen methylsiloxy units represented by (R ¹ HSiO _2/2 ) units are represented by (H ), The chemical shift values of silicon located in the center corresponding to the three chains of D and H are as follows based on silicon of tetramethylsilane.

-D-D-D-: -21.8 ppm
-D-D-H-: -20.5 ppm
-H-D-H-: -18.8 ppm
-H-H-H-: -35.0 ppm
-H-H-D-: -36.2 ppm
-D-H-D-: -37.5 ppm

-D-D-D- unit, -D-D-H- unit, -H-D-H- unit, -H-H-H- unit, -H-H-D- unit, -D- Assuming that the integrated values of peaks corresponding to HD units are A (DDD), A (DDH), A (HDH), A (HHH), A (HHD), and A (DHD), dimethylsiloxy units The average chain length (γD) and hydrogen methylsiloxy (δD) can be calculated by the following formulas (11) and (12), respectively.
γD = 1 + A (DDD) / {A (DDH) + A (HDH)} (11)
δD = 1 + {A (HHH) + A (HHD)} / A (DHD) (12)

In the organohydrogen silicone represented by the average composition formula (1) used in the present invention, when the average chain length of the (R ¹ ₂ SiO _2/2 ) unit is less than 3, the resulting epoxy-modified silicone is cured. The cured product obtained in this manner is not preferable because it causes cracks due to temperature changes. On the other hand, when it exceeds 100, the hardness of the cured product becomes insufficient, and when the cured product is mounted on a light emitting element or a light emitting component is used, the surface becomes sticky and foreign matter adheres, or the Since the surface of the light emitting component is damaged, it is not preferable. In order to stably satisfy sufficient heat resistance and hardness, the average chain length of (R ¹ ₂ SiO _2/2 ) units is preferably in the range of 4 to 70, more preferably in the range of 4 to 50, A range of 4 to 25 is particularly preferable.

Moreover, in the organohydrogen silicone represented by the average composition formula (1), when the average chain length of the (R ¹ HSiO _2/2 ) unit is less than 2 or exceeds 20, the resulting epoxy-modified Since the heat resistance of the hardened | cured material obtained by hardening | curing silicone becomes inadequate, or the said hardened | cured material produces a crack by a temperature change, it is unpreferable.
The cured product obtained by curing the resulting epoxy-modified silicone has sufficient heat resistance and suppresses the occurrence of cracks due to temperature changes, and also reproduces the epoxy group by preventing side reactions during the hydrosilylation reaction. When producing an epoxy-modified silicone with good properties, the average chain length of the (R ¹ HSiO _2/2 ) unit is preferably 2.2 or more and less than 5, more preferably 2.3 or more and less than 4.5. Preferably, it is 2.4 or more and less than 4.

  In the present invention, the block type organohydrogen silicone represented by the average composition formula (1) is not particularly limited as long as it satisfies the above requirements <A> and <B> at the same time. Any structure such as a shape, a ladder shape, or a bowl shape may be used. Even if it is a mixture of two or more kinds, it can be used if the mixture satisfies the above requirements <A> and <B> simultaneously.

The number of moles of each unit constituting 1 mol of the block type organohydrogensilicone represented by the average composition formula (1) used in the present invention is such that the solubility in a solvent during the hydrosilylation reaction is improved. , D each satisfying a range of 5,000 or less, and e, f, and g each satisfying a range of 100 or less at the same time, reducing the steric hindrance to stabilize the hydrosilylation reaction, and In order to proceed with good reproducibility, it is more preferable that g is 0, g is 0, the value of (e + f) / (a + b + c + d + e + f) is 0.02 or less, and the values of c and d are 3, respectively. More preferably, it is in the range of 000 or less, g is 0, the value of (e + f) / (a + b + c + d + e + f) is 0.01 or less, and the values of c and d are each 2,000 or less. Particularly preferred, (g + e + f) value of zero, and, c, it is desirable that the value of d are each 1,000 or less.
On the other hand, since the crack resistance of the cured product using the epoxy-modified silicone obtained by hydrosilylation reaction of the block type organohydrogen silicone represented by the average composition formula (1) used in the present invention is improved, c The value of is preferably 4 or more.

Moreover, since the heat resistance of the hardened | cured material using the epoxy-modified silicone obtained by hydrosilylating the block type | mold organohydrogen silicone represented by the average compositional formula (1) used in this invention increases, the value of d Is preferably 4 or more.
In the present invention, a vinyl compound (b) containing a compound (a) having a carbon-carbon double bond and an epoxy group is subjected to a hydrosilylation reaction with respect to the block type organohydrogen silicone represented by the average composition formula (1). Since the stickiness of the surface of the cured product obtained by curing the epoxy-modified silicone obtained by addition is suppressed, b / (a + b) of the block type organohydrogen silicone represented by the average composition formula (1) The value is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 0.9 or more, and particularly preferably 0.95 or more.

  The number of SiH units in the block-type organohydrogen silicone represented by the average composition formula (1) used in the present invention increases the heat resistance of a cured product using an epoxy-modified silicone obtained after the hydrosilylation reaction. The value of (b + d + f) / (a + b + c + d + e + f + g) of the block type organohydrogen silicone represented by the average composition formula (1) is preferably 0.100 or more, more preferably 0.120 or more, 0 More preferably, it is 150 or more. On the other hand, since the gelation at the time of hydrosilylation reaction of the block-type organohydrogensilicone represented by the average composition formula (1) can be suppressed, an epoxy-modified silicone can be obtained stably and with good reproducibility. (B + d + f) The value of / (a + b + c + d + e + f + g) is preferably 0.800 or less, more preferably 0.700 or less, and still more preferably 0.600 or less.

Here, the calculation method of ag in the block type | mold organohydrogen silicone represented by average composition formula (1) is demonstrated. For the calculation of a to g, calculation is performed using ²⁹ Si-NMR measurement, gel permeation chromatography (GPC) measurement, and, if necessary, results obtained by ¹ H-NMR measurement. Specifically, first, ²⁹ Si-NMR measurement of the block-type organohydrogensilicone represented by the average composition formula (1) was performed using the above (R ¹ ₂ SiO _2/2 ) units and (R ¹ HSiO _{2 / 2} ) The average chain length of the unit is measured in the same manner as that for calculating the unit, and the content fraction of a to g is calculated as a percentage based on the integral value calculated from the obtained spectrum pattern.

When the block-type organohydrogensilicone represented by the average composition formula (1) has various substituents, for each substituent, based on the integrated value calculated from the spectrum pattern obtained by ¹ H-NMR measurement. The percentage of each structural unit is calculated as a percentage.
Using the obtained abundance ratio of each structural unit and the theoretical formula amount of each structural unit, an average formula amount of the structural unit is calculated.

  The number average molecular weight obtained by GPC measurement of the block type organohydrogen silicone represented by the average composition formula (1) is the molecular weight per mole of the block type organohydrogen silicone represented by the average composition formula (1). Each unit constituting the block type organohydrogen silicone represented by the average composition formula (1) divided by the average formula amount considering the abundance of the terminal group, hydrogen alkyl unit and dialkylsiloxy unit calculated above The total number of moles of is calculated. The block represented by the average composition formula (1) from the total number of moles of each unit constituting the block type organohydrogen silicone represented by the obtained average composition formula (1) and the abundance of each unit. The number of moles of each unit constituting 1 mol of the type organohydrogensilicone can be calculated.

  The number average molecular weight of the block-type organohydrogensilicone represented by the average composition formula (1) is a monodisperse polypolystyrene standard substance having a known molecular weight and styrene monomer (molecular weight 104) as a standard substance with chloroform as an eluent. Is a value obtained by gel permeation chromatography (GPC) measurement. Specifically, a calibration curve obtained from the elution time by RI detection is prepared in advance, and the number average molecular weight calculated using the above calibration curve from the elution time and detection intensity of the measurement sample solution.

As the organic group R ¹ , the light resistance of the epoxy-modified silicone of the present invention is improved, or the stability during storage is increased, so that the block type organohydrogen silicone represented by the average composition formula (1) is used. Carbon-carbon double bond hydrocarbon unit, hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit selected from a chain, branched and cyclic structure group with respect to the total number of moles of all Si units The total number of moles of silicon atoms bonded with halogen atoms or ester bonds, and further organic groups containing hetero atoms other than oxygen and silicon are preferably 30% or less, more preferably 10% or less, more preferably Is selected to be 1% or less, particularly preferably not contained at all.

Further, the organic group R ¹ is saturated having 1 to 20 carbon atoms and 1 or less oxygen atoms having a hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group. The monovalent aliphatic organic group is preferably selected from the group consisting of: Examples of such an organic group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, and nonyl group. Chain organic groups consisting of hydrocarbons such as decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc., cyclopentyl group, methylcyclopentyl group, cyclohexyl group, Examples thereof include an organic group composed of a hydrocarbon containing a cyclic unit such as a methylcyclohexyl group, an ethynylcyclohexyl group and a norbornyl group, and an organic group containing an ether bond such as a methoxyethyl group and an ethoxyethyl group. These may be a mixture of one or more organic groups.
Of these, chain-like organic groups composed of hydrocarbons and organic groups composed of hydrocarbons containing cyclic units are particularly desirable.

As the organic group R ¹ , the light resistance of the epoxy-modified silicone of the present invention is improved, or the stability during storage is increased, so that the block type organohydrogen silicone represented by the average composition formula (1) is used. Carbon-carbon double bond hydrocarbon unit, hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit selected from a chain, branched and cyclic structure group with respect to the total number of moles of all Si units The total number of moles of silicon atoms bonded with halogen atoms or ester bonds, and further organic groups containing hetero atoms other than oxygen and silicon are preferably 30% or less, more preferably 10% or less, more preferably Is selected to be 1% or less, particularly preferably not contained at all.

Further, the organic group R ¹ is saturated having 1 to 20 carbon atoms and 1 or less oxygen atoms having a hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group. The monovalent aliphatic organic group is preferably selected from the group consisting of: Examples of such an organic group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, and nonyl group. Chain organic groups consisting of hydrocarbons such as decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc., cyclopentyl group, methylcyclopentyl group, cyclohexyl group, Examples thereof include an organic group composed of a hydrocarbon containing a cyclic unit such as a methylcyclohexyl group, an ethynylcyclohexyl group and a norbornyl group, and an organic group containing an ether bond such as a methoxyethyl group and an ethoxyethyl group. These may be a mixture of one or more organic groups.
Of these, chain-like organic groups composed of hydrocarbons and organic groups composed of hydrocarbons containing cyclic units are particularly desirable.

The epoxy-modified silicone of the present invention comprises a vinyl compound (b) containing a compound (a) having a carbon-carbon double bond and an epoxy group with respect to the block-type organohydrogen silicone represented by the average composition formula (1). An epoxy-modified silicone obtained by addition, the primary structure of the epoxy-modified silicone is (i) a block unit of siloxane to which a vinyl compound containing a compound having a carbon-carbon double bond and an epoxy group is added; And a siloxane block unit having a (R ¹ ₂ SiO _2/2 ) structure. For this reason, the obtained epoxy-modified silicone may become cloudy depending on the proportion of the compound having a carbon-carbon double bond and an epoxy group in the vinyl compound. In order to improve the transparency of the epoxy-modified silicone, the block-type organohydrogen silicone represented by the average composition formula (1) has at least one structure selected from a chain, branched, and cyclic structure group. The total number of Si units in the block-type organohydrogensilicone in which the number of organic groups R ¹ , which is a monovalent aliphatic organic group having 5 to 20 carbon atoms and having a hydrocarbon unit, is represented by the average composition formula (1) The total number of moles is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more.

On the other hand, in order to complete the hydrosilylation reaction stably and with good reproducibility, the number of carbon atoms having 5 or more hydrocarbon units composed of one or more structures selected from the chain, branched and cyclic structure groups is 5 The number of organic groups R ¹ , which is a monovalent aliphatic organic group of 20 or less, is 95 with respect to the total number of moles of all Si units of the block type organohydrogen silicone represented by the average composition formula (1). % Or less, more preferably 90% or less, and even more preferably 85% or less.
Furthermore, the organic group R which is a monovalent aliphatic organic group having 5 to 20 carbon atoms and having a hydrocarbon unit composed of one or more structures selected from the chain, branched and cyclic structure groups. ^{When 1} is a monovalent alicyclic unit, it is particularly preferably used because light resistance is improved. Examples of such monovalent alicyclic units include a cyclopentyl group and a cyclohexyl group.

The production method of the block type organohydrogen silicone represented by the average composition formula (1) used in the present invention is not particularly limited, and a conventionally known method can be used.
For example, [A-1] a polydialkylsiloxane (a-1) having at least a dialkylsiloxy unit and a polyhydrogenalkylsiloxane (a-2) having at least a hydrogenalkylsiloxy unit are required in the presence of a conventionally known catalyst. Depending on the solvent, and / or in the presence of a terminal blocking agent typified by hexamethyldisiloxane, 1,1,3,3-hexamethyldisiloxane, etc., it is subjected to an equilibration reaction so as to have a predetermined average chain length. The method of manufacturing by this is mentioned.

Further, for example, as another method [A-2], a polydialkylsiloxane (a) having a (R ¹ ₂ SiO _2/2 ) unit having a hydroxyl group at the terminal and an average chain length of 3 or more and 100 or less. -3) and a polyhydrogenalkylsiloxane (a-4) containing a (R ¹ HSiO _2/2 ) unit having a hydroxyl group at the terminal and an average chain length of 2 to 20, Polycondensation in the presence of a catalyst, if necessary in the presence of a solvent, or the polycondensate is subsequently capped in the presence of the above-mentioned end capping agent in the presence of a conventionally known catalyst. Is also possible.
Said (a-1)-(a-4) can be manufactured with the following method, for example.

The above (a-1) has, for example, an aliphatic hydrocarbon unit composed of one or more structures selected from an unsubstituted or substituted chain, branched, and cyclic structure group, and has a carbon number. A monovalent or divalent aliphatic organic group having 1 to 24 and an oxygen number of 0 to 5 or an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary. A monovalent fragrance having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic structures, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms Alkoxysilanes in which two organic groups of the same or different types selected from the group consisting of group organic groups and two alkoxy groups are bonded to silicon atoms and / or two chlorine atoms instead of the two alkoxy groups. Is bonded to a silicon atom. Silanes, conventionally known catalyst presence, or after the hydrolysis in the absence, it can be obtained by polycondensation as needed.
When performing the above hydrolysis, the organohydrogensilicone obtained by the reaction described in [A-1] coexists with the following 1) to 3) in an amount that does not depart from the present invention. It is also possible to make it.
1) having 1 to 24 carbon atoms and 0 or more oxygen atoms having an aliphatic hydrocarbon unit composed of one or more structures selected from a structure group consisting of unsubstituted, substituted, branched, and cyclic structures 5 or less monovalent or divalent aliphatic organic group, or an unsubstituted or substituted aromatic hydrocarbon unit, which is composed of a chain, a branched chain or a ring which is unsubstituted or substituted as necessary. Selected from the group consisting of monovalent aromatic organic groups having an aliphatic hydrocarbon unit composed of at least one structure selected from the structural group and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms Alkoxysilanes in which three organic groups of the same or different types and one alkoxy group are bonded to a silicon atom, and / or chlorosilanes in which one chlorine atom is bonded to a silicon atom instead of the one alkoxy group.
2) Tetraalkoxysilane and / or tetrachlorosilane.
A polyhydrogenalkylsiloxane having at least a hydrogen alkylsiloxy unit obtained by the above hydrolysis or obtained by polycondensation after the hydrolysis is continuously produced in the presence of a conventionally known catalyst. The terminal may be sealed in the presence.
Further, polydialkylsiloxane having at least a dialkylsiloxy unit obtained by the above-mentioned hydrolysis or obtained by polycondensation after hydrolysis is subsequently converted into hexamethyldisiloxane, 1 in the presence of a conventionally known catalyst. It is also possible to seal the terminal in the presence of a terminal blocking agent typified by 1,3,3-hexamethyldisiloxane.

Another method is, for example, having an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched and cyclic, and having 1 to 24 carbon atoms and A monovalent or divalent aliphatic organic group having an oxygen number of 0 or more and 5 or less, or an unsubstituted or substituted aromatic hydrocarbon unit which is optionally substituted or substituted in a chain or branched form A monovalent aromatic organic group having an aliphatic hydrocarbon unit consisting of one or more structures selected from a structural group consisting of a ring and a ring, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, A group consisting of a cyclic siloxane having a structure in which at least two of the same or different organic groups selected from the group are bonded to a silicon atom, a conventionally known catalyst, and water, alcohols, and the above end-capping agent. 1 or more types selected from Presence of the compound, in the presence of a solvent, if necessary, can be prepared by ring opening.
When carrying out the above ring-opening reaction, the following 3) and 4) in an amount in which the organohydrogensilicone obtained by the reaction described in [A-1] does not depart from the present invention, if necessary. It is possible to coexist.
3) having 1 to 24 carbon atoms and 0 or more oxygen atoms having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of unsubstituted, substituted chain, branched and cyclic structures 5 or less monovalent or divalent aliphatic organic group, or an unsubstituted or substituted aromatic hydrocarbon unit, which is composed of a chain, a branched chain or a ring which is unsubstituted or substituted as necessary. Selected from the group consisting of monovalent aromatic organic groups having an aliphatic hydrocarbon unit composed of at least one structure selected from the structural group and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms Alkoxysilanes in which three organic groups of the same or different types and one alkoxy group are bonded to a silicon atom.
4) Tetraalkoxysilane.
In the case where a polydialkylsiloxane having at least a dialkylsiloxy unit is produced by carrying out the ring-opening reaction in the presence of water, the reaction is continued in the presence of the above-mentioned end-capping agent in the presence of a conventionally known catalyst. It is also possible to seal the ends.

The above (a-2) has, for example, an aliphatic hydrocarbon unit composed of one or more structures selected from a structural group consisting of an unsubstituted or substituted chain, branched and cyclic structure, and a carbon number of 1 A monovalent or divalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, or an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary. Monovalent aromatic having 6 to 24 carbon atoms and 0 to 5 oxygen atoms having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group One organic group selected from the group consisting of an organic group, one hydrogen atom, and alkoxysilanes in which two alkoxy groups are bonded to a silicon atom, and / or a chlorine atom instead of the two alkoxy groups. Are bonded to silicon atoms. Roshiran such conventionally known catalyst presence, or after the hydrolysis in the absence, it can be obtained by polycondensation as needed. When performing the above hydrolysis, the following 5) to 7) in an amount not departing from the present invention can be allowed to coexist if necessary.
5) having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure, having 1 to 24 carbon atoms and 0 or more oxygen atoms 5 or less monovalent or divalent aliphatic organic group, or an unsubstituted or substituted aromatic hydrocarbon unit, which is composed of a chain, a branched chain or a ring which is unsubstituted or substituted as necessary. Selected from the group consisting of monovalent aromatic organic groups having an aliphatic hydrocarbon unit composed of at least one structure selected from the structural group and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms Alkoxysilanes in which two organic groups of the same or different types and one hydrogen atom and one alkoxy group are bonded to a silicon atom, and / or one chlorine atom is a silicon atom instead of the one alkoxy group Chloro bound to Orchids.
6) Tetraalkoxysilane and / or tetrachlorosilane.
The polyhydrogenalkylsiloxane having at least a hydrogen alkylsiloxy unit obtained by the above hydrolysis or obtained by polycondensation after the hydrolysis continues to be hexamethyldisiloxane, 1 in the presence of a conventionally known catalyst. , 1,3,3-hexamethyldisiloxane and the like may be sealed at the end in the presence of a terminal blocking agent.

Another method is, for example, having an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched and cyclic, and having 1 to 24 carbon atoms and A monovalent or divalent aliphatic organic group having an oxygen number of 0 or more and 5 or less, or an unsubstituted or substituted aromatic hydrocarbon unit which is optionally substituted or substituted in a chain or branched form A monovalent aromatic organic group having an aliphatic hydrocarbon unit consisting of one or more structures selected from a structural group consisting of a ring and a ring, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, A cyclic siloxane comprising a hydrogen alkylsiloxy unit in which one organic group selected from the group and one hydrogen atom are bonded to a silicon atom, a conventionally known catalyst, water, alcohols, and the above end-capping agent Chosen from the group The presence of one or more compounds, in the presence of a solvent, if necessary, can be prepared by ring opening.
When carrying out the above ring-opening reaction, the following 7) and 8) in an amount in which the organohydrogensilicone obtained by the reaction described in [A-1] does not depart from the present invention, if necessary. It is possible to coexist.
7) having an aliphatic hydrocarbon unit composed of one or more structures selected from a structure group consisting of unsubstituted or substituted chain, branched and cyclic, having 1 to 24 carbon atoms and 0 or more oxygen atoms 5 or less monovalent or divalent aliphatic organic group, or an unsubstituted or substituted aromatic hydrocarbon unit, which is composed of a chain, a branched chain or a ring which is unsubstituted or substituted as necessary. Selected from the group consisting of monovalent aromatic organic groups having an aliphatic hydrocarbon unit composed of at least one structure selected from the structural group and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms Alkoxysilanes in which two organic groups of the same or different types, one hydrogen atom, and one alkoxy group are bonded to a silicon atom.
8) Tetraalkoxysilane.
In the case where a polyhydrogenalkylsiloxane having at least a hydrogen alkylsiloxy unit is produced by carrying out the above ring-opening reaction in the presence of water, the presence of the above-mentioned end capping agent is continued in the presence of a conventionally known catalyst. It is also possible to seal the ends underneath.

The above (a-3) has, for example, an aliphatic hydrocarbon unit composed of one or more structures selected from a structural group consisting of an unsubstituted or substituted chain, branched and cyclic structure, and a carbon number of 1 A monovalent or divalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, or an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary. Monovalent aromatic having 6 to 24 carbon atoms and 0 to 5 oxygen atoms having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group By hydrolyzing alkoxysilanes and / or chlorosilanes having two organic groups of the same kind or different kinds selected from the group consisting of organic groups in the presence or absence of a catalyst, and then by polycondensation as necessary Is possible to get
When performing the above hydrolysis, if necessary, the above 1) and 2) in such an amount that the average chain length of the dialkylsiloxy unit of the polydialkylsiloxane obtained is in the range of 3 or more and 100 or less are allowed to coexist. Is also possible.

Further, as another method, for example, the aliphatic hydrocarbon unit having one or more kinds of structures selected from the structural group consisting of an unsubstituted or substituted chain, branched, and cyclic structure, having 1 to 24 carbon atoms. Or a monovalent or divalent aliphatic organic group having an oxygen number of 0 or more and 5 or less, or an unsubstituted or substituted aromatic hydrocarbon unit, which is optionally substituted or unsubstituted chain A monovalent aromatic organic group having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of branched and cyclic structures A cyclic siloxane having a structure in which two organic groups of the same or different types selected from the group consisting of are bonded to a silicon atom, a conventionally known catalyst, and one or more compounds selected from the group consisting of water and alcohols In the presence of In the presence of a solvent Te, it can be prepared by ring opening.
When performing the above ring-opening reaction, the above 3) and 4) in an amount such that the average chain length of the dialkylsiloxy units of the obtained polydialkylsiloxane is in the range of 3 to 100 is coexisted as necessary. It is also possible.

The above (a-4) has, for example, an aliphatic hydrocarbon unit composed of one or more structures selected from a structural group consisting of an unsubstituted or substituted chain, branched and cyclic structure, and a carbon number of 1 A monovalent or divalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, or an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary. Monovalent aromatic having 6 to 24 carbon atoms and 0 to 5 oxygen atoms having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group One organic group selected from the group consisting of an organic group, one hydrogen atom, and alkoxysilanes in which two alkoxy groups are bonded to a silicon atom, and / or a chlorine atom instead of the two alkoxy groups. Are bonded to silicon atoms. Roshiran such conventionally known catalyst presence, or after the hydrolysis in the absence, it can be obtained by polycondensation as needed.
When performing the above hydrolysis, if necessary, coexistence of 5) and 6) in an amount such that the average chain length of the hydrogen alkylsiloxy unit of the resulting polyhydrogenalkylsiloxane is in the range of 2 to 20 inclusive. It is also possible to make it.

Further, as another method, for example, the aliphatic hydrocarbon unit having one or more kinds of structures selected from the structural group consisting of an unsubstituted or substituted chain, branched, and cyclic structure, having 1 to 24 carbon atoms. Or a monovalent or divalent aliphatic organic group having an oxygen number of 0 or more and 5 or less, or an unsubstituted or substituted aromatic hydrocarbon unit, which is optionally substituted or unsubstituted chain A monovalent aromatic organic group having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of branched and cyclic structures And a cyclic siloxane composed of a hydrogen alkylsiloxy unit in which one organic group selected from the group consisting of and one hydrogen atom bonded to a silicon atom is selected from the group consisting of conventionally known catalysts and water and alcohols. One or more Presence of the compound, in the presence of a solvent, if necessary, can be prepared by ring opening.
When carrying out the above ring-opening reaction, the above 7) and 8) in an amount such that the average chain length of the hydrogen alkylsiloxy units of the resulting polyhydrogenalkylsiloxane is in the range of 2 to 20, if necessary. It is possible to coexist.

  In the block-type organohydrogensilicone produced by the above method or the like, the catalyst used in producing the block-type organohydrogensilicone may remain. When the catalyst remains in the block-type organohydrogensilicone, the cyclic product formed as a by-product is removed by subjecting it to a heat-reduced pressure condition and / or the like and / or the desolvation operation is performed. In some cases, the equilibration reaction of the silicone may proceed during storage of the block type organohydrogen silicone. In order to stably produce the block-type organohydrogensilicone of the present invention, one or more kinds selected from solid-liquid separation, neutralization, water washing and the like after [A-1] or [A-2]. It is preferable to remove or deactivate by this operation.

  Subsequent to the reaction of [A-1] or [A-2] described above, an operation for separating or reducing a cyclic product, an excessive end-capping agent, or the like can also be performed. In addition, when a solvent is used when the reaction [A-1] or [A-2] is performed, an operation for separating or reducing the solvent can be performed subsequently. Of course, the operation for separating or reducing the above-mentioned annular product, excess terminal blocking agent and the like and the operation for separating or reducing the solvent can be performed simultaneously or in combination.

  The method for separating or reducing the cyclic product, excess end-capping agent, etc., or the solvent is particularly suitable if the block-type organohydrogensilicone represented by the average composition formula (1) of the present invention is obtained. There is no limitation, for example, in the case of a cyclic product, an excess end-capping agent, a method of distilling off the solvent, or in the case where the block type organohydrogen silicone is a highly volatile compound, the block type organohydro For example, a method for separating and recovering gen-silicone. At this time, the block-type organohydrogensilicone and the cyclic product, excess end-capping agent, etc., separation from the solvent, a method of simultaneously performing, the cyclic product, the surplus end-capping agent, and the like, You may implement by the method of isolate | separating each from a solvent separately, or the method which mixed these. Furthermore, the separation operation can be performed at once, or can be performed repeatedly under the same or different conditions.

  The atmosphere at the time of separating the cyclic product, excess end-capping agent, etc., and the solvent is inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, carbon number of 1 or more and 4 It can be performed under an atmosphere of at least one gas selected from the group consisting of the following lower saturated hydrocarbon gases and air, under circulation, under reduced pressure or under pressure, under bubbling, or under a combination of these. These gases can be used as one kind or a mixture of two or more kinds. Among these, a preferable gas is the inert gas, a lower saturated hydrocarbon gas having 1 to 4 carbon atoms, more preferably the inert gas, and more preferably nitrogen.

  The temperature at the time of separating the cyclic product, the excess end-capping agent, etc., and the solvent is such that the cyclic product, the excess end-capping agent, etc., the solvent are separated, and the block type organohydrogen is separated. In order to suppress silicone modification, it is preferably in the range of 0 ° C. or higher and 400 ° C. or lower, preferably in the range of 5 ° C. or higher and 350 ° C. or lower, more preferably in the range of 30 ° C. or higher and 320 ° C. or lower. Within the above range, the temperature does not have to be constant, and can be changed midway.

  In the step of separating the cyclic product, excess end-capping agent, etc., and the solvent, the cyclic product, excessive end-capping agent, etc., when the solvent content is reduced and the viscosity is increased However, it is preferable to use a device that can efficiently separate a ring, an excess end-capping agent, and the like, and a solvent. Examples of such devices include vertical stirring tanks, surface renewal stirring tank reactors, surface renewal biaxial kneading reactors, biaxial horizontal stirring reactors, wet wall reactors, free fall perforated plates Examples thereof include a type reactor, and a reactor in which volatile components are distilled off while dropping a compound along a support. These apparatuses can be used alone or in combination of two or more.

  By the above method or the like, it is possible to obtain a block type organohydrogensilicone represented by the average composition formula (1) in which the content of the cyclic product, the excess end-capping agent and the like is reduced. When a cured product is produced using the epoxy-modified silicone obtained by the method of the present invention, the compatibility with the curing agent used is increased and the curing operation is facilitated, and therefore, it is represented by the average composition formula (1). The amount of the component having a molecular weight of 1,000 or less contained in the block type organohydrogen silicone is preferably 15% or less, more preferably 10% or less, and still more preferably 5% or less.

  Here, the content of the component having a molecular weight of 1,000 or less contained in the block type organohydrogen silicone represented by the average composition formula (1) will be described. The content of the component having a molecular weight of 1,000 or less contained in the block type organohydrogen silicone represented by the average composition formula (1) of the present invention is determined by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard substance. ) In the elution curve obtained by the measurement, the elution peak area (peak area 1) obtained by connecting the elution start point and elution end point of the block type organohydrogensilicone represented by the average composition formula (1) A numerical value expressed as a percentage of the peak area (peak area 2) corresponding to a molecular weight of 1,000 or less calculated from the standard substance in the eluted peak area [ie, (peak area 2) / (peak area 1)] X100 (%)].

  In the present invention, a vinyl compound (b) containing a compound (a) having a carbon-carbon double bond and an epoxy group is hydrosilylated with respect to the SiH unit of the block type organohydrogen silicone represented by the average composition formula (1). The present invention relates to a method for producing an epoxy-modified silicone by addition by a oxidization reaction. In the present invention, all of the vinyl compound (b) may be a compound (a) having a carbon-carbon double bond and an epoxy group, and a part of the vinyl compound (b) is a carbon-carbon double bond. And a compound (a) having an epoxy group.

  The compound (a) having a carbon-carbon double bond and an epoxy group that can be used in the present invention is not particularly limited. For example, the compound having an epoxy group and a carbon-carbon double bond as essential structural units, unsubstituted or Examples include compounds having 3 to 24 carbon atoms and an oxygen number of 0 to 5 and having an aliphatic hydrocarbon unit composed of one or more structures selected from a substituted chain, branched, and cyclic structure group it can. Examples of such compounds include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, butenyl glycidyl ether, 1,2-epoxy-3-butene, 1,2-epoxy-4-pentene, 1 , 2-epoxy-5-hexene, 1,2-epoxy-6-heptene, 1,2-epoxy-7-octene, 1,2-epoxy-8-nonene, 1,2-epoxy-9-decene, 1, , 2-epoxy-10-undecene, 1,2-epoxy-11-dodecene, 1,2-epoxy-12-tridecene, 1,2-epoxy-13-tetradecene, 1,2-epoxy-14-pentadecene, , 2-epoxy-15-hexadecene, 1,2-epoxy-16-heptadecene, 1,2-epoxy-17-octadecene, 1, -Epoxy-18-nonadecene, glycidyl methacrylate, glycidyl acrylate, 4-vinylcyclohexene oxide, 1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethyl-4-vinylcyclohexene oxide, vinyl norbornene oxide, etc. . These can be used as one kind or a mixture of two or more kinds. Furthermore, when an optical isomer exists, it can be used as a mixture of two or more.

Among these, since the curing rate when curing the resulting epoxy-modified silicone is increased, or the light resistance of the cured product obtained using the epoxy-modified silicone is increased, 1,2-epoxy-3-butene, 1,2-epoxy-4-pentene, 1,2-epoxy-5-hexene, 1,2-epoxy-6-heptene, 1,2-epoxy-7-octene, 1,2-epoxy-8-nonene, 1,2-epoxy-9-decene, 1,2-epoxy-10-undecene, 1,2-epoxy-11-dodecene, 1,2-epoxy-12-tridecene, 1,2-epoxy-13-tetradecene, 1,2-epoxy-14-pentadecene, 1,2-epoxy-15-hexadecene, 1,2-epoxy-16-heptadecene, 1,2-epoxy-17-octadecene It is preferable to use at least one epoxycycloalkane having a carbon-carbon double bond selected from the group represented by 1,2-epoxy-18-nonadecene and the following chemical formula (3). It is more preferable to use at least one epoxycycloalkane having a carbon-carbon double bond consisting of the group represented by:
^{_{CH 2 = CR 2 -EPO ··· (}} 3)
[However, R ² represents hydrogen or a linear or branched monovalent hydrocarbon group having 1 to 4 carbon atoms. EPO represents an epoxycycloalkyl group having 10 or less carbon atoms, and may have a chain or branched hydrocarbon group as a substituent as long as the carbon number is within the above range. ]

  Examples of the compound represented by the chemical formula (3) include 4-vinylcyclohexene oxide, 1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethyl-4-vinylcyclohexene oxide, and vinyl norbornene oxide. More preferably, 4-vinylcyclohexene oxide is used.

Examples of vinyl compounds other than the compound (a) having a carbon-carbon double bond and an epoxy group that can be used in the vinyl compound (b) include:
(A) It comprises one or more structures selected from the group consisting of unsubstituted, substituted, chain-like, branched, and cyclic, containing no epoxy group and having a carbon-carbon double bond as an essential constituent unit. A compound having 3 to 24 carbon atoms and an oxygen number of 0 to 5 having an aliphatic hydrocarbon unit,
(A) A structure comprising a carbon-carbon double bond as an essential constituent unit, an unsubstituted or substituted aromatic hydrocarbon unit, and an optionally substituted or substituted chain, branched and cyclic structure A compound having an aliphatic hydrocarbon unit having at least one structure selected from the group and having a carbon number of 8 to 24 and an oxygen number of 0 to 5;
(C) a silane containing one or more carbon-carbon double bonds in the molecule represented by the following chemical formula (4);
CH ₂ = CH-SiR ³ ₃ (4)
[However, each R ³ independently represents an aliphatic hydrocarbon unit having at least one structure selected from the group consisting of a) a halogen atom, b) an unsubstituted or substituted chain, branched, and cyclic structure. A monovalent aliphatic organic group having 1 to 10 carbon atoms and 0 to 5 oxygen atoms, or c) an unsubstituted or substituted aromatic hydrocarbon unit, and optionally substituted or substituted A monovalent fragrance having 6 to 10 carbon atoms and 0 to 5 oxygen atoms having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group Represents at least one organic group selected from the group consisting of group organic groups.
The organic group may contain a hydroxyl group, an acyl group, an alkenyloxy group, an acyloxy group, or a halogen atom as the organic group as long as it is within the range of the carbon number and the oxygen number. ]

(D) Siloxane containing one or more carbon-carbon double bonds in the molecule represented by the following average composition formula (5):
(R ⁴ ₃ SiO _1/2 ) _p (R ⁴ ₂ SiO _2/2 ) _q (R ⁴ SiO _3/2 ) _r (SiO _4/2 ) _s (5)
[However, each R ⁴ independently comprises at least one structure selected from a) a carbon-carbon double bond, and b) a chain, branched, and cyclic structure having 1 to 10 carbon atoms. 1 or more types selected from the group consisting of monovalent aliphatic organic groups, c) unsubstituted or substituted aromatic hydrocarbon units, and optionally substituted or substituted chain, branched and cyclic structures It is a monovalent aromatic organic group having 6 to 10 carbon atoms and an oxygen number of 0 to 5 having an aliphatic hydrocarbon unit having the structure: Here, at least one of R ⁴ is an organic group having a carbon-carbon double bond.
The organic group includes a hydroxyl group, an alkoxy group, an acyl group, a carboxyl group, an alkenyloxy group, an acyloxy group, a halogen atom, or an ester bond as long as it is within the range of the carbon number and the oxygen number. Also good. Moreover, the hetero atom except oxygen, such as nitrogen, phosphorus, and sulfur, may be included. ]
Etc. can be used.

In addition, p, q, r, and s in the average composition formula (5) represent the number of moles of each unit present in 1 mole of siloxane containing one or more carbon-carbon double bonds in the molecule, q is a numerical value of 0 or more, r is a numerical value of 0 or more, s is a numerical value of 0 or more, and p, q, and r are not simultaneously zero.
In addition, when q, r, and s satisfy the following expressions (13), (14), and (15), respectively, p, r, and s satisfy expression (16). A number selected from a range.
q ≠ 0 Formula (13)
r ≠ 0 Formula (14)
s ≠ 0 Expression (15)
0 ≦ p ≦ r + 2s + 2 (16)

Further, when the above r and s satisfy the following expressions (17) and (18), the above p is a numerical value selected from the range satisfying the following expression (19).
r = 0 Formula (17)
s = 0 Formula (18)
0 ≦ p ≦ 2 Formula (19)

When r and s satisfy the following expressions (14) and (18), respectively, p and r are numerical values selected from a range satisfying the expression (20).
r ≠ 0 Formula (14)
s = 0 Formula (18)
0 ≦ p ≦ r + 2 Formula (20)

Further, when r and s satisfy the following expressions (17) and (15), respectively, p and r are numerical values selected from a range satisfying the expression (21).
r = 0 Formula (17)
s ≠ 0 Expression (15)
0 ≦ p ≦ 2s + 2 Formula (21)

  The siloxane containing one or more carbon-carbon double bonds in the molecule is not particularly limited as long as it is a structure represented by the average composition formula (4), and is linear, cyclic, branched, or ladder. Any structure such as a shape or a bowl shape, or a mixture of two or more of these may be used. Further, each structural unit may have a block-like chain structure, may be randomly dispersed, or a mixture thereof.

  The compounds (a) to (d) can be used as one kind or a mixture of two or more kinds. In addition, these compounds have a hydroxyl group, an acyl group, a carboxyl group, an alkenyloxy group, an acyloxy group, a halogen atom, an ester bond, or an oxygen bond, as long as the carbon number and the oxygen number are within the ranges described above. Heteroatoms such as nitrogen, phosphorus and sulfur other than atoms may be contained.

  One or more structures selected from the group consisting of unsubstituted or substituted chain, branched and cyclic, which do not contain an epoxy group (a) and have a carbon-carbon double bond as an essential constituent unit Specific examples of the compound having an aliphatic hydrocarbon unit and having 3 to 24 carbon atoms and 0 to 5 oxygen atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, cyclopentene, cyclohexene, methylcyclohexene , Norbornene, vinylcyclohexane, vinyldecahydronaphthalene, dicyclopentadiene, norbornadiene, 1 2,4-trivinylcyclohexane, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycerin diacrylate, glycerin dimethacrylate, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, allyl methyl ether, allyl Examples include ethyl ether, allyl propyl ether, methoxy polyethylene glycol allyl ether (degree of polymerization of ethylene glycol unit of 1 to 4), and the like. These can be used as one kind or a mixture of two or more kinds.

  On the other hand, (i) an aromatic hydrocarbon unit having a carbon-carbon double bond as an essential constituent unit, an unsubstituted or substituted aromatic hydrocarbon unit, and an optionally substituted or substituted chain, branched and cyclic Specific examples of the compound having an aliphatic hydrocarbon unit composed of one or more structures selected from the structural group consisting of carbon number of 8 to 24 and oxygen number of 0 to 5 are, for example, styrene, Examples include 3-methylstyrene, 4-methylstyrene, α-methylstyrene, cinnamic acid, and the like. These can be used as one kind or a mixture of two or more kinds.

  (C) Specific examples of silanes containing one or more carbon-carbon double bonds in the molecule include, for example, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane. Aliphatic having one carbon-carbon double bond such as vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane, vinyltriisopropenoxysilane Aromatic vinylalkoxysilanes having one carbon-carbon double bond, such as vinylalkoxysilane, vinylphenylmethylmethoxysilane, vinylphenyldiethoxysilane, vinyldiphenylethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, tribi Fragrances having two or more carbon-carbon double bonds such as aliphatic vinylalkoxysilane, divinyldiphenoxysilane and trivinylphenoxysilane having two or more carbon-carbon double bonds such as rumethoxysilane and trivinylethoxysilane. Vinyl alkoxysilane, vinyltrimethylsilane, vinylethyldimethylsilane, vinyldiethylmethylsilane, vinyltriethylsilane, vinyltripropylsilane, vinyltriisopropylsilane, vinyltributylsilane, vinyltri-t-butylsilane, vinyl-t-butyldimethylsilane , Vinyltripentylsilane, vinyltrihexylsilane, vinyltricyclohexylsilane, vinyltriheptylsilane, vinyltrioctylsilane, vinyltrinonylsilane, vinyltridecylsilane, Carbon-carbon such as vinylalkylsilane, vinylphenyldimethylsilane, vinylphenyldiethylsilane, vinyldiphenylmethylsilane, vinyltriphenylsilane, vinyltritolylsilane, etc. having one carbon-carbon double bond such as nylmethylsilacyclopentane Vinyl aralkyl having one carbon-carbon double bond such as vinylarylsilane, vinylbenzyldimethylsilane, vinylbenzyldiethylsilane, vinyldibenzylmethylsilane, vinyltribenzylsilane, vinyltriphenethylsilane, etc. having one double bond Vinylalkylsilanes having two or more carbon-carbon double bonds such as silane, divinyldimethylsilane, divinyldiethylsilane, divinylethylmethylsilane, trivinylmethylsilane, trivinylethylsilane, and divinyli Vinylarylsilanes having two or more carbon-carbon double bonds such as rudiphenylsilane, divinylditolylsilane, trivinylphenylsilane, trivinyltolylsilane, vinyl (chloromethyl) dimethylsilane, vinyl (trifluoromethyl) dimethyl Vinylhalo-substituted alkylsilanes having a halogen-substituted hydrocarbon group having one carbon-carbon double bond such as silane, vinyl (3,3,3-trifluoropropyl) dimethylsilane, vinyldimethylfluorosilane, vinyldimethylchlorosilane , Vinylmethyldichlorosilane, vinyltrichlorosilane, vinylethyldichlorosilane, vinyloctyldichlorosilane, vinyl (bromomethyl) dichlorosilane, vinylphenyldichlorosilane, vinyldiphenylchlorosilane, vinylphenol 2 carbon-carbon double bonds such as vinylhalosilane, divinyldichlorosilane, trivinylchlorosilane, etc. having one carbon-carbon double bond such as rumethylchlorosilane and at least one halogen atom bonded to silicon atom. Examples thereof include vinylhalosilane having at least one and a halogen atom bonded to a silicon atom. Silanes containing one or more carbon-carbon double bonds in these molecules can be used as one kind or a mixture of two or more kinds.

Furthermore, (d) as a siloxane containing one or more carbon-carbon double bonds in the molecule, the organic group R ⁴ b) a structural group consisting of chain, branched and cyclic having 1 to 10 carbon atoms A monovalent aliphatic organic group having at least one structure selected from, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, n -Saturated hydrocarbon groups such as pentyl group, n-hexyl group, n-octyl group, n-nonyl group, cyclohexyl group, methylcyclohexyl group, norbornyl group, chloromethyl group, 3,3,3-trifluoropropyl group, etc. A saturated hydrocarbon group substituted with a halogen atom, etc., c) an unsubstituted or substituted aromatic hydrocarbon unit, and optionally substituted or substituted chain, branched and cyclic Construction A monovalent aromatic organic group having 6 to 10 carbon atoms and an oxygen number of 0 to 5 having an aliphatic hydrocarbon unit having at least one structure selected from the group is, for example, a phenyl group, a tolyl group, An aromatic hydrocarbon group such as a benzyl group, an aromatic hydrocarbon group substituted with a halogen atom such as a 4-chlorobenzyl group, and the like can be given.

  Among these, since the light resistance of the cured product obtained using the epoxy-modified silicone obtained after the hydrosilylation reaction is enhanced, the vinyl compound (b) includes a hydroxyl unit, an alkoxy unit, an acyl unit, a carboxyl unit, an alkenyloxy. Units, acyloxy units, aromatic hydrocarbon units, halogen atoms, or ester bonds, and further do not contain heteroatoms other than oxygen atoms (a) do not contain epoxy groups and must contain carbon-carbon double bonds The unit has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure, having 3 to 20 carbon atoms and 0 oxygen number 5 or less compounds, (c) silane containing one or more carbon-carbon double bonds in the molecule, and (d) one in the molecule. Carbon above - at least one compound selected from the siloxane group consisting containing carbon double bond is preferably used.

  (A) It comprises one or more structures selected from the group consisting of unsubstituted, substituted, chain-like, branched, and cyclic, containing no epoxy group and having a carbon-carbon double bond as an essential constituent unit. As a compound having 3 to 20 carbon atoms and an oxygen number of 0 to 5 having an aliphatic hydrocarbon unit, the handleability of the vinyl compound is increased, or the excess compound can be easily distilled off. 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- Octadecene, cyclopentene, cyclohexene, methylcyclohexene, norbornene, and vinylcyclohexane are more preferably used.

  On the other hand, (c) As a silane containing one or more carbon-carbon double bonds in the molecule, it is easy to distill off excess compounds, so that vinyltrimethylsilane, vinylethyldimethylsilane, vinyldiethylmethyl Silane and vinyltriethylsilane are more preferably used.

  In addition, (d) siloxanes containing one or more carbon-carbon double bonds in the molecule can ease steric hindrance and facilitate the hydrosilylation reaction stably and with good reproducibility. Therefore, it is preferable that q is in the range of 50 or less, r is in the range of 10 or less, s is in the range of 10 or less, more preferably s is zero, and q is in the range of 20 or less. More preferably, r is in the range of 5 or less, s is zero, and r / (p + q + r) is 0.02 or less, q is in the range of 15 or less, and r is in the range of 3 or less, s Is particularly preferred, and r / (p + q + r) is preferably 0.01 or less, q is preferably in the range of 10 or less, and s and r / (p + q + r) are zero, for example, Vinyl pentamethyldisiloxane, Nylheptamethyltrisiloxane and other molecular chains have a dimethylvinylsiloxy group at one end, and other substituents are alkyl groups such as siloxane and vinylmethylbis (trimethylsiloxy) silane. Siloxy group-containing siloxane having one carbon-carbon double bond in the molecule and other substituents being saturated hydrocarbon groups, both ends of 1,3-divinyl-tetramethyldisiloxane etc. are dimethyl 1,3,5-trivinyl-1,1,3,5,5, a siloxane having two carbon-carbon double bonds in the molecule which is a vinylsiloxy group and the other substituent is a saturated hydrocarbon group -Pentamethyltrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane tris (vinyldimethylsiloxy) methylsilane; 5.7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1.3.5.7-tetravinyl-1,3,5,7-tetraethylcyclotetrasiloxane, etc. 3 or more in the molecule And a siloxane having another organic group that is a saturated hydrocarbon group.

  The value of p to s of the siloxane containing one or more carbon-carbon double bonds in the molecule represented by the average composition formula (5) is the block type organohydrogen represented by the average composition formula (1). It can be calculated by the same method as that used for silicone.

In the present invention, a vinyl compound (b) containing a compound (a) having a carbon-carbon double bond and an epoxy group is added to a block type organohydrogen silicone represented by the average composition formula (1) to form an epoxy. The present invention relates to a method for producing a modified silicone.
A carbon-carbon double bond to a random organohydrogensilicone having the same composition as the block-type organohydrogensilicone represented by the average composition formula (1) and each unit structure arranged in a random form And an epoxy-modified silicone obtained by adding a compound (a) having an epoxy group and a vinyl compound other than the compound (a) having a carbon-carbon double bond and an epoxy group, the average composition formula (1 Other than the compound (a) having a carbon-carbon double bond and an epoxy group and the compound (a) having a carbon-carbon double bond and an epoxy group with respect to the SiH unit of the block type organohydrogen silicone represented by Since the heat resistance of the epoxy-modified silicone obtained by adding the vinyl compound is significantly increased, the average composition formula (1) The fraction of the number of moles of SiH units to which the compound (a) having a carbon-carbon double bond and an epoxy group is added is 70% or more with respect to the total number of moles of SiH units of the block type organohydrogen silicone It is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.

The epoxy-modified silicone of the present invention is obtained by hydrosilylating a vinyl compound containing a compound having a carbon-carbon double bond and an epoxy group with respect to the SiH unit of the block type organohydrogen silicone represented by the average composition formula (1) of the present application. It can be obtained by addition by a hydrosilylation reaction in the presence of an oxidation catalyst.
In the absence of a hydrosilylation catalyst, a hydrosilylation reaction between the SiH unit of the block type organohydrogen silicone represented by the average composition formula (1) and a vinyl compound containing a compound having a carbon-carbon double bond and an epoxy group Does not progress.

  As the hydrosilylation catalyst that can be used in the present invention, a conventionally known catalyst can be used. Examples of such a hydrosilylation catalyst include a simple substance of Group 8 metal, a metal solid supported on a support such as alumina, silica, and carbon black, a salt of the metal, Examples include complexes. Of these, platinum, rhodium, and ruthenium, which are metals of Group 8 of the periodic table, which have high hydrosilylation reaction activity and are unlikely to cause side reactions, are preferred, and platinum is particularly preferred. Examples of the hydrosilylation reaction catalyst using platinum include chloroplatinic acid, complexes of chloroplatinic acid and alcohol, aldehyde, ketone, platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, dicarbonyldichloro. Platinum, dicyclopentadienyl dichloro platinum, etc. are mentioned.

  The number of moles in terms of metal atoms of the catalyst used for the hydrosilylation reaction is usually the total number of moles of SiH units in the block type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, it is in the range of 1 / 50,000,000 times or more and 1/20 times or less. The number of moles in terms of metal atom of the catalyst used when the hydrosilylation reaction is performed is based on the total number of moles of SiH units in the block type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. When the ratio is less than 1 / 50,000,000, the hydrosilylation reaction may not proceed. On the other hand, when the ratio exceeds 1/20, the vinyl compound containing a compound having a carbon-carbon double bond and an epoxy group for the hydrosilylation reaction may be significantly modified, or the reaction system may be markedly colored and transparent epoxy The modified silicone may not be recovered.

  In order to suppress the ring opening of the epoxy group during the hydrosilylation reaction and produce an epoxy-modified silicone with good reproducibility, the number of moles of the catalyst used in the hydrosilylation reaction in terms of metal atoms is the same as that before the hydrosilylation reaction. The total number of moles of SiH units in the block type organohydrogen silicone represented by the average composition formula (1) is preferably 1 / 1,200 times or less, and preferably 1 / 6,000 times or less. Is more preferable, and it is still more preferable to set it as 1 / 25,000 times or less.

On the other hand, when the hydrosilylation reaction is performed at a reproducible rate, the number of moles in terms of metal atom of the catalyst used when the hydrosilylation reaction is performed is represented by the average composition formula (1) before the hydrosilylation reaction. It is preferably 1 / 5,000,000 times or more, more preferably 1 / 1,000,000 times or more, and more preferably 1/800 times the total number of moles of SiH units of the type organohydrogensilicone. More preferably, it should be 1,000 times or more.
When adding a vinyl compound (b) containing a compound (a) having a carbon-carbon double bond and an epoxy group to the SiH unit of the block type organohydrogen silicone represented by the average composition formula (1) The amount of the catalyst used is not necessarily constant as long as it is within the above range, and may be changed at the initial stage of the reaction or during the reaction.

In the present invention, in the hydrosilylation reaction, the total number of vinyl groups of the vinyl compound (b) to be coexisted with respect to the total number of moles of SiH units of the block type organohydrogen silicone represented by the average composition formula (1). The total number of moles is in the range of 5 to 100 times.
Here, “all vinyl groups of the vinyl compound (b) to be coexisted” refers to all vinyl groups that can be hydrosilylated with the organohydrogensilicone contained in the vinyl compound (b) coexisting in the reaction system. This includes silicon compounds having one or more vinyl groups in the molecule, but organohydrogensilicones are not included even if they have vinyl groups.

  When the total number of moles of all vinyl groups of the vinyl compound (b) to be coexisted is less than 5 times the total number of moles of SiH units in the block type organohydrogen silicone represented by the average composition formula (1) The epoxy group of the compound (a) having an added carbon-carbon double bond and an epoxy group is ring-opened to produce an epoxy-modified silicone containing a high molecular weight product, and the epoxy-modified silicone is stably reproducible. It cannot be manufactured. On the other hand, when the total number of moles of all vinyl groups in the coexisting vinyl compound (b) increases with respect to the total number of moles of SiH units in the block type organohydrogen silicone represented by the average composition formula (1), hydrosilylation occurs. Although the reaction rate tends to increase, the total of all vinyl groups of the vinyl compound (b) to be coexisted with respect to the total number of moles of SiH units of the block type organohydrogen silicone represented by the average composition formula (1) Even if the number of moles exceeds 100 times, the effect of increasing the reaction rate is lost, or in some cases, the hydrosilylation reaction rate is lowered if the hydrosilylation reaction catalyst is stabilized by the coexisting vinyl compound (b). The reaction mixture containing the epoxy-modified silicone obtained by the method of the present invention. , The load on the step of separating and recovering the epoxy-modified silicone increases, undesirable.

  Vinyl which coexists with the total number of moles of SiH units of the block type organohydrogensilicone represented by the average composition formula (1) for producing epoxy-modified silicone with a high reaction rate with good reproducibility. The total number of moles of all vinyl groups in the compound (b) is preferably in the range of 6 to 50 times, more preferably in the range of 7 to 30 times, and particularly preferably in the range of 7 to 20 times. The total number of moles of all vinyl groups in the coexisting vinyl compound (b) with respect to the total number of moles of SiH units in the block type organohydrogen silicone represented by the average composition formula (1) should be within the above range. For example, it is not necessary to be constant, and it may be changed at the beginning of the reaction or during the reaction.

  By making the total number of moles of all vinyl groups in the coexisting vinyl compound (b) 5 times or more with respect to the total number of moles of SiH units in the block type organohydrogen silicone represented by the average composition formula (1) The reason for inhibiting the ring opening of the epoxy group during the hydrosilylation reaction is not clear, but the residual amount of the hydrogen alkylsiloxy unit in the block-type organohydrogensilicone in the hydrosilylation reaction process and the hydrosilylation reaction It is presumed that the presence state of the catalyst is related.

Specifically, the formation of the high molecular weight portion is assumed to be caused by the following <I>.
<I> The SiH unit at a site where the hydrogen alkylsiloxy unit has 3 or more chains tends to cause a ring-opening addition reaction with an epoxy group in the presence of a hydrosilylation reaction catalyst, and the hydrogen alkylsiloxy unit has 3 or more chains. The SiH unit at the site reacts with the epoxy group present by adding the compound (a) having a carbon-carbon double bond and an epoxy group to different molecular chains.

On the other hand, the amount of the vinyl compound (b) to coexist with the total number of moles of SiH units of the block-type organohydrogen silicone represented by the average composition formula (1) is about 1 to 2 times the amount usually used. It can be presumed that the following <II> is the reason why the formation of the high molecular weight part can be suppressed by increasing the amount to the range of the present invention.
<II> By increasing the vinyl group concentration in the hydrosilylation reaction system, the amount of the vinyl compound (b) coordinated to the hydrosilylation catalyst increases, and the hydrosilylation reaction catalyst oxidizes to the Si—H bond. After the addition, the addition reaction proceeds preferentially without causing side reactions such as ring opening of the epoxy group.

  In the present invention, the reaction temperature at the time of hydrosilylation reaction has the type and molecular weight of the block type organohydrogen silicone represented by the average composition formula (1) used, or has a carbon-carbon double bond and an epoxy group. Although it depends on the type of vinyl compound including the compound, and also the reaction mode such as batch, semi-batch, or continuous, it is 0 ° C. or higher and 250 ° C. or lower from the viewpoint of increasing the reaction rate and completing the reaction efficiently. The range of 10 ° C to 200 ° C is more preferable, the range of 20 ° C to 150 ° C is more preferable, and the range of 30 ° C to 120 ° C is particularly preferable. The reaction temperature does not need to be constant as long as it is within the above range, and may be changed at the initial stage of the reaction or during the reaction.

  In the present invention, when the hydrosilylation reaction is carried out, it is possible to remove the heat of reaction due to the hydrosilylation reaction, suppress the modification of the resulting epoxy-modified silicone and / or suppress the increase in the viscosity of the reaction system due to the addition reaction, Since the hydrosilylation reaction is enhanced by suppressing phase separation between the organosilicone being modified during the hydrosilylation reaction and the vinyl compound (b) containing the compound (a) having a carbon-carbon double bond and an epoxy group, Is preferably used.

  Examples of the solvent used include dimethyl ether, diethyl ether, diisopropyl ether, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and anisole. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, isooctane, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, etc. Aromatic hydrogen solvents, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as butyl cellosolve and butyl carbitol Medium, and the like. These solvents can be used as one kind or a mixture of two or more kinds.

Among these, the hydrosilylation reaction rate is relatively high, and ether solvents, ketone solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents are preferable from the viewpoints of solubility of raw materials and / or solvent recoverability. Further, a solvent containing 50% by mass or more of an ether solvent is more preferable, and at least one or two selected from the group consisting of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether having a boiling point at atmospheric pressure of 120 ° C. or lower. More than one kind of mixed solvent is more preferably used.
The amount of the solvent used varies depending on the type of block type organohydrogensilicone used, the type of vinyl compound, etc., but usually the mass of the solvent relative to the total mass of the mixture is 0.1% by mass at the start of the hydrosilylation reaction. The range is 99.9% by mass or less, preferably 10% by mass or more and 95% by mass or less, and more preferably 20% by mass or more and 90% by mass or less.

  In the present invention, the atmosphere during the hydrosilylation reaction is an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or a lower saturated hydrocarbon gas having 1 to 4 carbon atoms. It can be carried out under an atmosphere such as air, under circulation, under reduced pressure or under pressure. These gases can be used as one kind or a mixture of two or more kinds. Among these, a preferable gas is the inert gas, a lower saturated hydrocarbon gas having 1 to 4 carbon atoms, more preferably the inert gas, and more preferably nitrogen.

  In the present invention, the reaction method for carrying out the hydrosilylation reaction is not particularly limited. For example, the block type organohydrogen silicone represented by the average composition formula (1) of the present application, a carbon-carbon double bond, and an epoxy group. Exemplified is a method of reacting a vinyl compound containing a compound having a compound sequentially, continuously, or at a time with a method of one or a combination of two or more selected from the group of batch, semi-batch, and continuous it can.

  As a supply method of a vinyl compound containing a block type organohydrogen silicone represented by the average composition formula (1) of the present application and a compound having a carbon-carbon double bond and an epoxy group, the present application contains a solvent as necessary. A method of supplying a vinyl compound containing a compound having a carbon-carbon double bond containing a solvent and an epoxy group, if necessary, to the block-type organohydrogensilicone represented by the average composition formula (1) of A block type represented by the average composition formula (1) of the present application containing a solvent as needed for a vinyl compound containing a compound having a carbon-carbon double bond and an epoxy group containing a solvent as necessary. A method for supplying organohydrogensilicone, and a block type organ represented by the average composition formula (1) of the present application containing a solvent as necessary. Hydrogen silicone and carbon - the method for supplying premixed and vinyl compounds containing a compound having a double bond and an epoxy group having a carbon may be exemplified.

When the vinyl compound containing a compound having a carbon-carbon double bond and an epoxy group is composed of a plurality of types of compounds, all the vinyl compounds containing the compound having a carbon-carbon double bond and an epoxy group are collectively included. It is also possible to subject the mixed composition to the reaction or to react some or all of the vinyl compounds sequentially.
At that time, the method for adding the hydrosilylation reaction catalyst is not particularly limited. If necessary, a method of adding a catalyst to the block-type organohydrogensilicone containing a solvent is included, and if necessary, a solvent is contained. A method of adding to some or all vinyl compounds, a method of adding to both the block type organohydrogensilicone containing a solvent as necessary, and a vinyl compound containing a solvent as needed, containing a solvent A method of adding to a mixture of the block type organohydrogen silicone and a part or all of the vinyl compound is used.

  When the vinyl compound (b) containing the compound (a) having a carbon-carbon double bond and an epoxy group is added to the SiH unit of the organohydrogensilicone by a hydrosilylation reaction, the moisture in the system affects. May affect. In order to maintain the hydrosilylation reaction rate or suppress the ring-opening reaction of the epoxy group, the water content of the reaction system is preferably 2% by mass or less based on the mass of the reaction system, preferably 1% by mass or less. More preferably, it is more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably 0.01% by mass or less. Although the water content of the reaction system should be low, setting the water content to 0 maintains the hydrosilylation reaction rate or suppresses the ring-opening reaction of the epoxy group compared to the time and labor required. Small effect. Therefore, from the viewpoint of cost effectiveness, it is realistic to reduce the water content of the reaction system to about 0.001% by mass.

  Prior to separating and recovering the epoxy-modified silicone from the reaction mixture, the alcohol is brought into contact with or mixed with the reaction mixture to reduce or eliminate unreacted SiH units, and a conventionally known hydrosilylation catalyst deactivator. Alternatively, the catalyst is deactivated or deactivated by contacting or mixing the deactivator with the reaction mixture, or the reaction mixture is contacted, mixed, or distributed to the adsorbent to form a metal such as a hydrosilylation catalyst. Performing the treatment to remove or reduce components, coloring components, etc., or performing a combination of these treatments is to suppress the modification of the epoxy-modified silicone when the epoxy-modified silicone is separated and recovered from the reaction mixture. It is a method preferably used.

  Examples of the alcohol used at this time include at least one alcohol selected from a chain, branched and cyclic structure group having 1 to 4 carbon atoms. Examples of the deactivator for hydrosilylation catalyst used at this time include sulfur-containing compounds such as dodecyl mercaptan and 2-mercaptobenzothiazole, acetonitrile, acrylonitrile, 2-pentenylolyl, 3-pentenenitrile and the like. Nitriles, 1-heptin, 1-octyne, 1-decyne, 3-methyl-1-pentyne, 2-propyn-1-ol, 3-butyn-1-ol, 2-pentyn-1-ol, 4-pentyne -1-ol, 4-pentyn-2-ol, 2-methyl-3-butyn-1-ol, 3-methyl-1-pentyn-3-ol, 3-methyl-1-hexyn-3-ol, 3 , 5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, 2, -Dimethyl-3-hexyne-2,5-diol, 1,1-dimethyl-2-propynylamine, 3-methyl-3- (trimethylsiloxy) -1-butyne, dimethyl-bis (1,1-dimethyl-2) -Propynoxy) -silane, 3-methyl-3- (trimethylsiloxy) -1-pentyne, 3,5-dimethyl-3- (trimethylsiloxy) -1-hexyne, 3-ethyl-3- (trimethylsiloxy) -1 -Acetylene type compounds, such as pentyne, methyl propionate, and ethyl propionate, etc. are mentioned. Examples of the adsorbent that removes or reduces a metal component such as a hydrosilylation catalyst, a coloring component, and the like include activated carbon, celite, silica gel, alumina powder, and ion exchange resin.

  Prior to separating and recovering the epoxy-modified silicone from the reaction mixture, an operation in which alcohols are contacted or mixed with the mixture before the epoxy-modified silicone is separated and recovered to reduce or eliminate unreacted SiH units, conventionally known The deactivating agent deactivator of the hydrosilylation catalyst is contacted or mixed with the mixture before the epoxy-modified silicone is separated and recovered to deactivate or deactivate the catalyst, and the adsorbent contains the epoxy-modified silicone. When the mixture before separation / recovery is contacted, mixed, or distributed to perform a process for adsorbing or removing metal components such as hydrosilylation catalyst or colored components, or a combination thereof. The atmosphere is an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, 1 to 4 carbon atoms Of a lower saturated hydrocarbon gas, at least one gas selected from air comprising the group atmosphere, distribution, reduced pressure or under pressure, bubbling under, or can be carried out under the conditions of a combination of these. These gases can be used as one kind or a mixture of two or more kinds. Among these, a preferable gas is the inert gas, a lower saturated hydrocarbon gas having 1 to 4 carbon atoms, more preferably the inert gas, and more preferably nitrogen.

An operation for reducing or eliminating the unreacted SiH units by contacting or mixing the mixture before the separation and recovery of the epoxy-modified silicone with alcohols, and a conventionally known hydrosilylation catalyst deactivator or deactivator. An operation of deactivating or deactivating the catalyst by contacting or mixing with the mixture before separating and recovering the epoxy-modified silicone, contacting, mixing, or mixing the mixture before separating and recovering the epoxy-modified silicone with the adsorbent, or The temperature at the time of carrying out the treatment for removing or reducing the metal component such as the hydrosilylation catalyst or the coloring component, or the operation of the combination of these, is to suppress the modification of the epoxy-modified silicone. , Preferably in the range of 0 ° C to 200 ° C, preferably in the range of 5 ° C to 150 ° C, more preferably in the range of 10 ° C to 100 ° C Range, more preferably in the range of 15 ℃ above 80 ° C. or less. If it is in the said range, it is not necessary to be constant temperature, and it is also possible to change temperature on the way.
It is used for the process of isolate | separating an epoxy modified silicone from the mixture containing the obtained epoxy modified silicone, and the epoxy modified silicone of this invention is collect | recovered.

In the present invention, the number of residual SiH units relative to the total number of Si contained in the epoxy-modified silicone to be subjected to the separation / recovery step for suppressing the modification of the epoxy-modified silicone when separating and collecting the epoxy-modified silicone from the mixture Is preferably 2% or less, more preferably 1.5% or less, still more preferably 1% or less, and particularly preferably 0.5% or less.
In the present invention, the compound having a carbon-carbon double bond, and the deactivator or deactivator of the hydrosilylation catalyst used as necessary are collectively referred to as a low boiling point compound and used as necessary. Solvents and alcohols used in processing operations to reduce or eliminate unreacted SiH units as needed are collectively referred to as volatile compounds.

Next, a method for separating the epoxy-modified silicone from the mixture containing the epoxy-modified silicone will be described.
The method for separating the epoxy-modified silicone from the mixture containing the epoxy-modified silicone is not particularly limited as long as the epoxy-modified silicone of the present invention can be obtained. For example, from the mixture containing the epoxy-modified silicone, the low boiling point compound and the volatile compound And a method of recovering the epoxy-modified silicone by distilling off, or a method of separating and recovering the epoxy-modified silicone by distillation when the epoxy-modified silicone is a highly volatile compound.

  When recovering the epoxy-modified silicone from the mixture containing the epoxy-modified silicone by distilling off the low-boiling compound and the volatile compound, the respective compounds constituting the low-boiling compound and the volatile compound are distilled off simultaneously. It can be carried out by a method, a method in which each compound constituting a low boiling point compound and a volatile compound is individually separated, or a method in which these are combined. When the epoxy-modified silicone is separated and recovered by distillation, a method of separating and recovering the epoxy-modified silicone in one step, or one or more compounds that once constitute a low-boiling compound and a volatile compound and the epoxy-modified silicone The epoxy-modified silicone is subsequently separated in one step or sequentially from one or more compounds constituting the low boiling point compound and / or volatile compound and the epoxy-modified silicone under the same or different conditions. It can implement by the method to do or the method by these combination.

  The atmosphere for separating the epoxy-modified silicone from the mixture containing the epoxy-modified silicone is an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or a lower saturated hydrocarbon having 1 to 4 carbon atoms. The reaction can be performed under an atmosphere of at least one gas selected from the group consisting of a system gas and air, under circulation, under reduced pressure or under pressure, under bubbling, or under a combination of these. These gases can be used as one kind or a mixture of two or more kinds. Among these, a preferable gas is the inert gas, a lower saturated hydrocarbon gas having 1 to 4 carbon atoms, more preferably the inert gas, and more preferably nitrogen.

  The temperature at which the epoxy-modified silicone is separated from the mixture containing the epoxy-modified silicone varies depending on the types of the epoxy-modified silicone, the low boiling point compound, and the volatile compound. The range is from 0 ° C. to 200 ° C., preferably from 5 ° C. to 150 ° C., more preferably from 10 ° C. to 100 ° C., and even more preferably from 15 ° C. to 80 ° C. If it is in the said range, the temperature at the time of isolate | separating an epoxy-modified silicone from the mixture containing an epoxy-modified silicone does not need to be a fixed temperature, and it is also possible to change temperature on the way.

  The step of separating the epoxy-modified silicone from the mixture containing the epoxy-modified silicone is effective even when the content of the low-boiling compound and the volatile compound is reduced and the viscosity of the mixture containing the epoxy-modified silicone is increased. It is preferable to use an apparatus capable of separating low boiling compounds and volatile compounds. Examples of such devices include vertical stirring tanks, surface renewal stirring tanks, thin film evaporators, surface renewal biaxial kneaders, biaxial horizontal stirrers, wet wall reactors, free-falling perforated plates Examples thereof include a type reactor, and a reactor in which volatile components are distilled off while dropping a compound along a support. These apparatuses can be used alone or in combination of two or more.

  The epoxy-modified silicone obtained by the method of the present invention includes the compound (a) having a carbon-carbon double bond and an epoxy group, which was used in producing the epoxy-modified silicone used in producing the epoxy-modified silicone. A low boiling point compound and / or a volatile compound such as a compound having a carbon-carbon double bond or a solvent derived from the vinyl compound (b) to be contained may remain.

Here, the “compound having a carbon-carbon double bond” in the present invention will be described. The compound having a carbon-carbon double bond in the present invention refers to a compound other than silicone and having one or more carbon-carbon double bonds in the molecule. Therefore, organohydrogen silicone and epoxy-modified silicone are not included even if they have a carbon-carbon double bond in the molecule.
As a compound having such a carbon-carbon double bond, for example,
(I) excess or unreacted vinyl compound added to be subjected to hydrosilylation reaction,
(Ii) Impurities having a carbon-carbon double bond contained in the vinyl compound added for use in the hydrosilylation reaction,
(Iii) a by-product generated by an internal transition of the carbon-carbon double bond in the vinyl compound added for use in the hydrosilylation reaction, during the hydrosilylation reaction;
Etc.

  As a specific example of the impurity having a carbon-carbon double bond contained in the vinyl compound added for use in the (ii) hydrosilylation reaction, it may be contained in, for example, 4-vinylcyclohexene oxide. 4-epoxyethyl-cyclohexene and the like can be mentioned.

  The (iii) by-product produced by the internal transfer of the carbon-carbon double bond in the vinyl compound added for use in the hydrosilylation reaction during the hydrosilylation reaction includes the type of vinyl compound used, Although depending on the hydrosilylation reaction conditions, for example, as a by-product when 1-hexene is used as the vinyl compound, 2-hexene, 3-hexene, etc. are used, and, for example, vinylcyclohexane is used as the vinyl compound. Examples of by-products include ethylidenylcyclohexane.

  Furthermore, as the vinyl compound, for example, (a-1) 4-vinylcyclohexene oxide, (a-2) 1-methyl-4-isopropenylcyclohexene oxide, (a-3) 1,4-dimethyl-4-vinyl When epoxycycloalkanes having a vinyl group such as cyclohexene oxide and (a-4) vinyl norbornene oxide are used, by-products corresponding to (a-1) to (a-4) are respectively (b- 1) 4-ethylidenylcyclohexene oxide, (b-2) 1-methyl-4-isoproperenyl cyclohexene oxide, (b-3) 1,4-dimethyl-4-ethylidenylcyclohexene oxide, (b- 4) Ethylidenyl norbornene oxide and the like. Further, for example, when (a-5) 1,2-epoxy-5-hexene is used as a compound having a carbon-carbon double bond and an epoxy group, carbon in the vinyl compound corresponding to (a-5) -By-products generated by internal transfer of carbon double bond during hydrosilylation reaction include 1,2-epoxy-4-hexene, 1,2-epoxy-3-hexene, 1,2-epoxy- 2-hexene and the like can be mentioned.

  The heat discoloration and light resistance of the cured product using the epoxy-modified silicone obtained by the method of the present invention are improved, and the heat discoloration and light resistance of the cured product using the epoxy-modified silicone obtained by the method of the present invention are improved. From the viewpoint of improvement, the total amount of low boiling point compounds remaining in the epoxy-modified silicone obtained by the method of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less. More preferably, it is more preferably no more than 0.75% by mass, particularly preferably no more than 0.75% by mass, and more preferably no more than 0.5% by mass, and particularly preferably no more than 0.3% by mass.

In the present invention, when the low-boiling compound is composed of two or more components, the total amount of low-boiling compounds remaining in the epoxy-modified silicone in the present invention is the total of each component remaining in the epoxy-modified silicone. Mean value.
The total amount of low-boiling compounds remaining in the epoxy-modified silicone should be small, but reducing the total amount of low-boiling compounds to 0 reduces coloring and discoloration compared to the time and labor required. The effect to do is small. Therefore, from the viewpoint of cost effectiveness, it is realistic that the total amount of low boiling point compounds remaining in the epoxy-modified silicone is reduced to about 0.003% by mass.

  In addition, among the low-boiling compounds remaining in the epoxy-modified silicone, the residual amount of the compound having a carbon-carbon double bond is less than that of the epoxy-modified silicone in order to reduce coloring or discoloration of the cured product by light or heat. It is preferably 1.5% by mass or less, more preferably 1% by mass or less, still more preferably 0.75% by mass or less, particularly preferably 0.5% by mass or less, 0 It is desirably 3% by mass or less, and particularly desirably 0.1% by mass or less.

In the present invention, when the compound having a carbon-carbon double bond is composed of two or more components, what is the residual amount of the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone in the present invention? Means the total value of each component remaining in the epoxy-modified silicone.
Of the compounds having a carbon-carbon double bond remaining in the epoxy-modified silicone, the residual amount of the compound having an epoxy group is the same as that of the epoxy-modified silicone in order to reduce the coloration or discoloration of the cured product by light or heat. It is preferably 1% by mass or less, more preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. 0.05 mass% or less is desirable.
Here, when there are two or more compounds having a carbon-carbon double bond and an epoxy group remaining in the epoxy-modified silicone, the residual amount of the compound having a carbon-carbon double bond and an epoxy group is: It means the total amount of each remaining component.

  Further, among the compounds having a carbon-carbon double bond remaining in the epoxy-modified silicone, the carbon-carbon double bond of the compound (a) having an epoxy group added for use in the hydrosilylation reaction causes an internal transition. The residual amount of by-products generated in this way is preferably 0.5% by mass or less, and 0.3% by mass or less, based on the epoxy-modified silicone, in order to reduce coloration or discoloration of the cured product by light or heat. More preferably, it is more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

  Here, the carbon-carbon double bond of the compound (a) having the carbon-carbon double bond and the epoxy group added to be used for the hydrosilylation reaction remaining in the epoxy-modified silicone was produced by causing an internal transition. When there are two or more by-products, the residual amount of by-products generated by the internal transition of the carbon-carbon double bond of the vinyl compound having an epoxy group added for use in the hydrosilylation reaction Means the total amount of each remaining component.

  In addition, in the compound (a) having a carbon-carbon double bond and an epoxy group added for use in the hydrosilylation reaction, the carbon-carbon 2 of the compounds already having the carbon-carbon double bond and the epoxy group is included. When a compound having a different heavy bond position is contained, the compound having a different carbon-carbon double bond position is a compound having a carbon-carbon double bond and an epoxy group in the present invention (a). Of carbon-carbon double bonds are not included in by-products generated by internal transition.

Further, in the present invention, when the hydrosilylation catalyst deactivator or deactivator is brought into contact with or mixed with the reaction mixture to deactivate or deactivate the catalyst, the hydrosilylation used in the treatment is used. The residual amount of the catalyst deactivator or deactivator is preferably 0.5% by mass or less based on the epoxy-modified silicone in order to reduce coloration or discoloration of the cured product by light or heat. The content is more preferably 3% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.
In the present invention, when the hydrosilylation catalyst deactivator or deactivator comprises two or more components, the hydrosilylation catalyst deactivator or deactivation remaining in the epoxy-modified silicone in the present invention The residual amount of the agent means the total value of each component remaining in the epoxy-modified silicone.

  The epoxy-modified silicone obtained in the present invention is used for processing to reduce or eliminate unreacted SiH units by contacting or mixing the solvent or reaction mixture used in producing the epoxy-modified silicone with alcohols. Volatile compounds may remain. When the epoxy-modified silicone of the present invention is used as a cured product, the total amount of volatile compounds remaining in the epoxy-modified silicone of the present invention is 1% by mass or less in order to suppress the generation of bubbles in the cured product. It is preferable that it is 0.1 mass% or less, and it is still more preferable that it is 0.05 mass% or less.

In the present invention, when the volatile compound is composed of two or more components, the total amount of the volatile compound remaining in the epoxy-modified silicone in the present invention is the total of each component remaining in the epoxy-modified silicone. Mean value.
The total amount of volatile compounds remaining in the epoxy-modified silicone should be small, but reducing the total amount of remaining volatile compounds to 0 reduces the coloration and discoloration compared to the time and labor required. The effect to do is small. Therefore, from the viewpoint of cost effectiveness, it is realistic that the total amount of volatile compounds remaining in the epoxy-modified silicone is reduced to about 0.0005% by mass.

  The amount of SiH units remaining in the epoxy-modified silicone obtained by the present invention is such that the number of residual SiH units is 2% with respect to the total number of Si contained in the epoxy-modified silicone in order to improve the storage stability modification of the epoxy-modified silicone. Or less, more preferably 1.5% or less, still more preferably 1% or less, and particularly preferably 0.5% or less.

  Since the heat resistance of the cured product obtained using the epoxy-modified silicone obtained by the present invention is increased, the epoxy value of the epoxy-modified silicone obtained by the present invention is preferably 0.10 or more, and 0.12 or more. More preferred is 0.14 or more. On the other hand, since the light resistance of the cured product obtained using the epoxy-modified silicone obtained after the hydrosilylation reaction is increased, the epoxy value is preferably 0.5 or less, more preferably 0.48 or less, and 0.46 or less. Is more preferable.

The epoxy value in the present invention refers to the number of epoxy units present in 100 g of epoxy-modified silicone, and specifically refers to a value measured by the following method.
<Method for measuring epoxy value>
The resin sample is dissolved with benzyl alcohol and 1-propanol. To this solution, an aqueous potassium iodide solution and a bromophenol blue indicator are added, followed by titration with 1N hydrochloric acid, and the point where the reaction system turns from blue to yellow is taken as the equivalent point. From the equivalent point, the epoxy value of the epoxy-modified silicone is calculated according to the following formula (22).
Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W) Formula (22)
[W, V, N, and F represent the following values, respectively.
W: weight of sample (g),
V: titer (ml),
N: Normality of hydrochloric acid used for titration (N),
F: Factor of hydrochloric acid used for titration]

  When the cured product is prepared using the epoxy-modified silicone obtained by the present invention, it is included in the epoxy-modified silicone obtained by the present invention because the compatibility with the curing agent used is increased and the curing operation is facilitated. The content of components having a molecular weight of 1,000 or less is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less.

  Here, the content of components having a molecular weight of 1,000 or less contained in the epoxy-modified silicone obtained by the present invention will be described. The content of the component having a molecular weight of 1,000 or less contained in the epoxy-modified silicone obtained by the present invention is determined by gelation permeation chromatography (GPC) measurement using monodisperse polystyrene as a standard substance in the modified polycrystal. The area of a peak corresponding to a molecular weight of 1,000 or less calculated from a standard substance within the elution peak area with respect to the elution peak area (peak area 1) obtained by connecting the elution start point and elution end point of siloxane ( It is a numerical value [that is, a numerical value represented by (peak area 2) / (peak area 1) × 100 (%)] in which the ratio of peak area 2) is expressed as a percentage.

  The epoxy-modified silicone obtained by the present invention may contain a residue of a catalyst such as a hydrosilylation catalyst used when producing the epoxy-modified silicone or a metal component eluted from the reaction apparatus. For example, when SUS316 alloy is used, metal elements such as Fe, Ni, Cr, and Mo may be eluted. These metals, especially transition metal components, may affect the light resistance of the cured product when the epoxy-modified silicone obtained by the present invention is cured. In the point which maintains the light resistance of this hardened | cured material at a high level, the total amount of the transition metal component applicable to the periodic table group 3-11 group contained in the epoxy modified silicone of this invention is 20 ppm in element conversion. Is preferably 10 ppm or less, more preferably 5 ppm or less.

  Examples of the method for reducing the content of the transition metal component include a method in which the reaction solution after the hydrosilylation reaction is passed through an adsorbent such as activated carbon, silica gel, alumina powder, or ion exchange resin to adsorb and remove the metal component. it can. In addition, for example, considering the amount of the transition metal element eluted from the reaction apparatus in the step of producing the epoxy-modified silicone of the present application, the total amount of transition metal components contained in the epoxy-modified silicone of the present application is not more than the above range. Similarly, a method for reducing the amount of the catalyst used for the hydrosilylation reaction is also exemplified as a preferred method.

  The epoxy-modified silicone obtained by the present invention has excellent transparency that can be used in applications where transparency is required, and also has excellent light resistance, heat resistance, and crack resistance. Sealants for elements, eyeglass lenses, lenses for optical devices, lenses for picking up CDs and DVDs, lenses for automobile headlamps, lenses for projectors, optical fibers, optical waveguides, optical filters, optical adhesives, optical disks It can be used as various optical members such as a substrate, a display substrate, and a coating material such as an antireflection film.

  When used in the above applications, the epoxy-modified silicone obtained by the present invention, and epoxy resin and / or epoxy resin curing agent, curing accelerator, cationic polymerization catalyst, modifier, inorganic filler, silane coupling agent, if necessary, Conventionally known additives such as an antifoaming agent, a colorant, a phosphor, a discoloration preventing agent, a light diffusing agent, and a heat conductive filler can be appropriately blended.

  Examples of the epoxy resin used include glycidyl ethers obtained by hydrogenating aromatic rings of aromatic epoxy resins represented by conventionally known aromatic glycidyl ethers, alicyclic epoxy resins, and other epoxy resins. It is done. These can be used as one kind or a mixture of two or more kinds.

Examples of the aromatic glycidyl ether include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, and tetrachloro. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as bisphenol A and tetrafluorobisphenol A, and epoxy obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Resin, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methyl ester) Epoxy resin obtained by glycidylation of trisphenol such as l) phenyl) ethylidene) bisphenol, epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane, phenol novolac Novolak type epoxy resins obtained by glycidylating novolaks such as cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, and the like.
The hydrogenation reaction of the aromatic ring of the aromatic glycidyl ether can be carried out by a conventionally known method using, for example, a ruthenium-based catalyst or a rhodium-based catalyst.

  Examples of the alicyclic epoxy resins include conventionally known compounds such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 2,2-bis (hydroxymethyl) -1-butanol. , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct, bis (3,4-epoxycyclohexylmethyl) adipate, and the like.

Other epoxy resins include glycidyl esters such as dimer acid glycidyl ester and hexahydrophthalic acid glycidyl ester, glycidyl amines such as triglycidyl isocyanurate, linear aliphatic epoxies such as epoxidized soybean oil and epoxidized polybutadiene. A compound etc. can be illustrated.
When an aromatic epoxy resin is used as the epoxy resin, the ratio of the aromatic epoxy resin to the total mass of the epoxy resin used is 50% by mass or less in that light resistance is improved. The content is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably an epoxy resin containing no aromatic epoxy resin as the epoxy resin.
The amount of the epoxy resin used is preferably 0.1 to 100 parts by weight, more preferably 1 to 100 parts by weight, and still more preferably 1 to 80 parts by weight with respect to 100 parts by weight of the epoxy-modified silicone obtained by the present invention. Part by mass.

  Examples of the curing agent for epoxy resin that can be used in the present invention include polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, and 5-norbornene-2. , 3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride, etc. Aromatic acid anhydrides such as formula acid anhydrides, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, silicones having two or more acid anhydride-containing functional groups in a molecule as substituents, Etc.

Among these, since the light resistance of the cured product obtained by curing the epoxy-modified silicone of the present invention is increased, alicyclic acid anhydrides are substituted with two or more acid anhydride-containing functional groups in one molecule. Silicones having a group are more preferable, and methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, and methyl-norbornane-2,3-dicarboxylic anhydride are more preferably used.
These curing agents can be used as one kind or a mixture of two or more kinds.
The amount of the epoxy resin curing agent used is preferably 1 part by mass or more and 200 parts by mass or less, and more preferably 2 parts by mass or more and 100 parts by mass or less, with respect to 100 parts by mass of the epoxy-modified silicone obtained by the present invention. .

    The curable composition obtained by using the epoxy-modified silicone obtained by the present invention may contain a curing accelerator as necessary. Examples of the curing accelerator used include imidazole compounds, quaternary ammonium salts, phosphonium salts, amine compounds, aluminum chelate compounds, organic phosphine compounds, metal carboxylates and acetylacetone chelate compounds. These curing accelerators can be used as one kind or a mixture of two or more kinds.

  Specific examples of these compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo (5,4,0) undecene-7, trimethylamine, benzyldimethylamine, triethylamine, dimethyl Amine compounds such as benzylamine, 2,4,6-trisdimethylaminomethylphenol and salts thereof, quaternary ammonium salts such as tetramethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium bromide, aluminum chelate, tetra-n- Organic phosphine compounds such as butylphosphonium benzotriazolate, tetra-n-butylphosphonium-0,0-diethyl phosphorodithioate, chromium (III) tricarboxylate, tin octylate, chromium Metal carboxylates and acetylacetone chelate compounds such acetylacetonate can be exemplified. Moreover, as a commercial item, U-CAT SA1, U-CAT 2026, U-CAT 18X etc. can be illustrated from a San Apro company. Among these, an imidazole compound, a quaternary ammonium salt, a phosphonium salt, an organic phosphine compound, and the like are preferably used because they give a cured product with less coloring.

  The blending amount of these curing accelerators is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, in order to increase the curing rate with respect to 100 parts by mass of the epoxy-modified silicone. It is particularly preferably 1 part by mass or more. On the other hand, from the viewpoint of moisture resistance, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

The epoxy-modified silicone of the present invention can be made into a curable composition by blending a conventionally known cationic polymerization catalyst.
Examples of cationic polymerization catalysts that can be used include Lewis acid catalysts typified by BF ₃ · amine complexes, PF ₅ , BF ₃ , AsF ₅ , SbF ₅ , phosphonium salts, quaternary ammonium salts, sulfonium salts, benzylammonium. Salt, benzylpyridinium salt, benzylsulfonium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, thermosetting cationic polymerization catalyst represented by amine imide, diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate And UV curable cationic polymerization catalysts represented by the above.
Among these, a thermosetting cationic polymerization catalyst is preferably used because a transparent cured product having a high glass transition temperature and excellent solder heat resistance and adhesion and less coloring can be obtained.

Examples of such thermosetting cationic polymerization catalysts include sulfonium salt-based cationic polymerization initiators SI-100L, SI-60L (above, manufactured by Sanshin Chemical Industries), CP-66, CP-77 (above. Asahi Denka Kogyo).
The blending amount of these cationic polymerization catalysts is usually preferably 0.001 part by mass or more and more preferably 0.005 part by mass or more for increasing the curing rate with respect to 100 parts by mass of the epoxy-modified silicone. More preferably, the content is 0.01 parts by mass or more. On the other hand, from the viewpoint of moisture resistance, the range is preferably 10 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 parts by mass or less, and 0.2 parts by mass or less. It is particularly preferred.

The curable composition obtained by using the epoxy-modified silicone obtained by the present invention may contain a modifier as necessary. Examples of the modifier used include polyols containing two or more hydroxyl groups in one molecule, and aliphatic polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, neopentyl glycol, glycerin and the like, and silicones having a silanol group at the terminal are more preferably used. These modifiers can be used as one kind or a mixture of two or more kinds. The modifier may impart flexibility to the cured product and improve peel adhesion.
The blending amount of polyols containing two or more hydroxyl groups in one molecule is 0.1 parts by mass or more from the viewpoint of improving adhesion to 100 parts by mass of epoxy-modified silicone, and from the viewpoints of heat resistance and moisture resistance. To 50 parts by mass or less. A more preferable blending amount is 1 to 30 parts by weight, further preferably 3 to 20 parts by weight, and particularly preferably 5 to 10 parts by weight.

The inorganic filler that is preferably used in the curable composition obtained by using the epoxy-modified silicone obtained by the present invention has an average particle diameter equal to or smaller than the wavelength to be used in order to avoid adverse effects on permeability, and more preferably Has an average particle diameter of 100 nm or less. Inorganic fillers may improve, for example, mechanical properties or thermal conductivity. The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.1 nm or more because the viscosity of the resin composition is lowered and the moldability is improved.
The silane coupling agent preferably used for the curable composition obtained by using the epoxy-modified silicone obtained by the present invention is a compound having no aromatic group or halogen atom.

As a curing method for the curable composition obtained using the epoxy-modified silicone obtained by the present invention, a known method can be used.
Among the above-mentioned known techniques, the method of curing by heating or the method of curing by irradiating with ultraviolet rays (UV) is a method generally used as a method for curing an epoxy resin, and is a preferable method in the present invention. It can be illustrated. The temperature for curing by heating is not particularly limited because it depends on the epoxy resin and curing agent used, but is usually in the range of 20 to 200 ° C.
The curing reaction is performed under an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or an atmosphere such as a lower saturated hydrocarbon gas or air, under reduced pressure or under pressure. Can do. These gases can be used as one kind or a mixture of two or more kinds. Of these, the preferred gas is nitrogen.

A light emitting diode is formed by sealing a light emitting element using the curable composition obtained by using the epoxy-modified silicone obtained by the present invention.
The emission wavelength of the light-emitting element obtained by sealing with the curable composition obtained using the epoxy-modified silicone obtained by the present invention should be widely used from infrared to red, green, blue, purple and ultraviolet. The conventional sealant can be practically used for light having a wavelength of 250 nm to 550 nm, which deteriorates due to insufficient light resistance. As a result, a white light-emitting diode having a long life, high energy efficiency, and high color reproducibility can be obtained. Here, the emission wavelength refers to the main emission peak wavelength.

  As a specific example of the light emitting element to be used, for example, a light emitting element formed by stacking semiconductor materials on a substrate can be exemplified. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. If necessary, a buffer layer may be formed between the substrate and the semiconductor material. Examples of these buffer layers include GaN and AlN.
The method for laminating the semiconductor material on the substrate is not particularly limited, but for example, MOCVD method, HDVPE method, liquid phase growth method and the like are used.
Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. A single or multiple quantum well structure may also be used.

  A light emitting diode can be manufactured with the light emitting element obtained by sealing using the light emitting element sealing agent obtained using the epoxy modified silicone obtained by this invention. In this case, the light-emitting element can be sealed only with a light-emitting element sealant obtained by using the epoxy-modified silicone obtained according to the present invention, but it may be sealed together with other sealants. Is possible. When other sealants are used in combination, after sealing with a light emitting device sealant obtained using the epoxy-modified silicone obtained by the present invention, the periphery is sealed with another sealant, or other It is also possible to seal the periphery with a light emitting element sealant obtained by using the epoxy-modified silicone obtained by the present invention. Examples of other sealants include epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, and glass.

  As a method of sealing a light emitting element with a light emitting element sealing agent obtained by using the epoxy-modified silicone obtained by the present invention, for example, a curable composition is injected into a mold mold in advance, and the light emitting element is inserted there. Examples include a method in which a fixed lead frame or the like is immersed and cured, and a method in which a light emitting element sealant is injected into a mold frame in which the light emitting element is inserted and cured. At this time, as a method for injecting the light-emitting element sealing agent, injection by a dispenser, transfer molding, injection molding and the like can be mentioned. Further, as other sealing methods, a light emitting device sealant is dropped onto the light emitting device, stencil printing, screen printing, or a method of applying and curing through a mask, a cup having a light emitting device disposed in the lower part, etc. For example, a method of injecting a light-emitting element sealing agent with a dispenser or the like and curing it.

The curable composition obtained by using the epoxy-modified silicone obtained by the present invention can also be used as a die bond material for fixing a light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.
Examples of the shape of the sealing portion include a bullet-shaped lens shape, a plate shape, and a thin film shape.

  The performance of the light-emitting diode obtained by using the epoxy-modified silicone obtained by the present invention can be improved by a conventionally known method. As a method for improving the performance, for example, a method of providing a light reflecting layer or a condensing layer on the back surface of the light emitting device, a method of forming a complementary colored portion on the bottom, a layer that absorbs light having a wavelength shorter than the main light emitting peak is used. Method of providing on top, method of molding the light emitting element after sealing with a hard material, method of inserting the light emitting diode into the through hole and fixing it, connecting the light emitting element to the lead member etc. by flip chip connection etc. And a method of extracting light from the light source.

  The light-emitting diode obtained by using the epoxy-modified silicone obtained by the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal light, an indicator light, It is useful as a display device, a light source for a planar light emitter, a display, decoration, various lights, and the like.

<Example>
The present invention will be specifically described below.
The average chain length, composition, and characteristics of silicone are determined by the following method.
(1) Calculation of average chain length of organohydrogensilicone
^It is determined by ²⁹ Si-NMR measurement.
0.15 g of silicone is dissolved in 1 g of deuterated chloroform. Ten microliters of tetramethylsilane is further added to a solution obtained by adding 0.015 g of Cr (acac) ₃ to the organohydrogensilicone and dissolving the solution in the solution to obtain an NMR measurement solution. Using the NMR measurement solution, measurement of ²⁹ Si-NMR under proton complete decoupling conditions was performed with 4,000 times of integration (apparatus: α-400 manufactured by JASCO Corporation), and calculated from the obtained spectrum pattern. The integrated value is analyzed to calculate the average composition of each modified polysiloxane molecule and the average chain length of each of (R ¹ ₂ SiO _2/2 ) units and (R ¹ HSiO _2/2 ) units.
Here, the block type organohydrogen silicone produced in the synthesis example, specifically, the case where the constituent unit excluding the terminal of the silicone is a cyclohexylmethylsiloxy unit, a dimethylsiloxy unit, and a hydrogen methylsiloxy unit is described as an example. The method for calculating the average chain length will be specifically described below.

When the cyclohexylmethylsiloxy unit and the dimethylsiloxy unit are dialkylsiloxy units (D1), and the hydrogenmethylsiloxy unit is (H1), the chemical shift value of silicon located at the center corresponding to the three chains of D1 and H1 is The following ranges are obtained based on tetramethylsilane silicon.
-D1-D1-D1-: -26.5 ppm excess -23.9 ppm or less -D1-D1-H1-: -23.9 ppm excess -21.5 ppm or less -H1-D1-H1-: -38.5 ppm excess- 37.4 ppm or less -H1-H1-H1-: -35.5 ppm excess-33.0 ppm or less -H1-H1-D1-: -37.4 ppm excess-35.5 ppm or less-D1-H1-D1-: -21 More than 5ppm-19.5ppm or less

-D1-D1-D1-unit, -D1-D1-H1-unit, -H1-D1-H1-unit, -H1-H1-H1-unit, -H1-H1-D1-unit, -D1- Assuming that the integrated values of the peaks corresponding to the H1-D1-unit are A (D1D1D1), A (D1D1H1), A (H1D1H1), A (H1H1H1), A (H1H1D1), A (D1H1D1), dimethylsiloxy units The average chain length (γD1) and hydrogen methylsiloxy (δD1) can be calculated by the following formulas (23) and (24), respectively.
γD1 = 1 + A (D1D1D1) / {A (D1D1H1) + A (H1D1H1)}
... Formula (23)
δD1 = 1 + {A (H1H1H1) + A (H1H1D1)} / A (D1H1D1)
... Formula (24)

(2) Calculation of the number average molecular weight of the high molecular weight side peak of polydialkylsiloxane and calculation of the high molecular weight side peak area area ratio Using a Tosoh gel permeation chromatography (GPC) analyzer 8020 GPC system, the following conditions are used. .
A 0.5 mass% tetrahydrofuran solution of polydialkylsiloxane is prepared, and then filtered through a 0.45 μm filter as a measurement sample solution.
At a column temperature of 40 ° C., eluent (tetrahydrofuran) was added under the condition of a flow rate of 1 ml / min. [The column configuration was Tsquardcolumn H time-H (registered trademark) manufactured by Tosoh Corp. as a guard column. ) Tskel (registered trademark) G5000H time manufactured by Tosoh Co., Ltd., Tskel (registered trademark) G3000H time manufactured by Tosoh Corporation, and Tskel (registered trademark) G1000H time manufactured by Tosoh Corporation are arranged in series. Laboratories molecular weights 7,500,000, 2,560,000, 841,700, 320,000, 148,000, 59,500, 28,500, 10,850, 2,930, 580, known molecular weights Monodisperse polypolystyrene reference material and styrene monomer (molecule A calibration curve obtained from the elution time by RI detection of the amount 104) is prepared in advance. The number average molecular weight is calculated from the elution time and detection intensity of the measurement sample solution.
When the elution curve obtained by the analysis is a multimodal peak, a vertical line is drawn from the apex of the lower convex portion formed between each peak to the baseline, and the elution curve, the vertical line and the baseline The number average molecular weight of the portion surrounded by is the number average molecular weight of each peak. The content of each peak component is calculated from the ratio of the total peak area based on polyalkylsiloxane and the peak area based on each peak component.

(3) Molecular weight measurement of polyhydrogenmethylsiloxane, measurement of content of components having molecular weight of 1,000 or less in block type organohydrogen silicone and epoxy-modified silicone Gel Permeation Chromatography (GPC) Analyzer 8020GPC system manufactured by Tosoh Corporation Use the following conditions.
A 5% by mass chloroform solution of the modified polysiloxane is prepared, and then filtered through a 0.45 μm filter as a measurement sample solution.
The column temperature was 40 ° C. and the eluent (chloroform) was flowed at a flow rate of 1 ml / min. [The column configuration was Tsquardcolumn H time-H (registered trademark) manufactured by Tosoh Corp. as a guard column. ) Tskel (registered trademark) G5000H time manufactured by Tosoh Co., Ltd., Tskel (registered trademark) G3000H time manufactured by Tosoh Corporation, and Tskel (registered trademark) G1000H time manufactured by Tosoh Corporation are arranged in series. Laboratories molecular weights 7,500,000, 2,560,000, 841,700, 320,000, 148,000, 59,500, 28,500, 10,850, 2,930, 580, known molecular weights Monodisperse polypolystyrene standard substance and styrene monomer (molecular weight 10 A calibration curve obtained from the elution time by RI detection in 4) is prepared in advance. From the elution time and detection intensity of the measurement sample solution, the molecular weight is calculated using the above calibration curve.
On the other hand, the content of components having a molecular weight of 1,000 or less is obtained by connecting the elution start point and the elution end point for each of the epoxy-modified silicone or the block-type organohydrogen silicone in the elution curve obtained by measurement. The ratio of the peak area (peak area 2) corresponding to a molecular weight of 1,000 or less calculated from the standard substance in the eluted peak area to the eluted peak area (peak area 1) was calculated and expressed as a percentage. [That is, a numerical value represented by (peak area 2) / (peak area 1) × 100 (%)].

(4) Composition of organohydrogen silicone
It calculates using the result obtained by < ²⁹ > Si-NMR measurement, a gel permeation chromatography (GPC) measurement, and also < ¹ > H-NMR measurement.
Specifically, first, an integrated value calculated from a spectrum pattern obtained by ²⁹ Si-NMR measurement of the block type organohydrogensilicone represented by the average composition formula (1) performed in the above (1) is used. Analysis is performed to calculate the percentage content of terminal groups, hydrogen alkyl units, and dialkylsiloxy units as a percentage.
Furthermore, based on the integrated value calculated from the spectrum pattern obtained by ¹ H-NMR measurement described below, the abundance of dialkylsiloxy units having each substituent is calculated as a percentage.
Using the obtained abundance ratio of each structural unit and the theoretical formula amount of each structural unit, an average formula amount of the structural unit is calculated.
Next, the block type represented by the average composition formula (1) is the number average molecular weight obtained by the GPC measurement of the block type organohydrogen silicone represented by the average composition formula (1) carried out in the above (3). The molecular weight per mole of the organohydrogensilicone is represented by the average composition formula (1) divided by the average formula weight considering the abundance of the terminal groups, hydrogen alkyl units and dialkylsiloxy units calculated above. The total number of moles of each unit constituting the block type organohydrogensilicone is calculated. The block represented by the average composition formula (1) from the total number of moles of each unit constituting the block type organohydrogen silicone represented by the obtained average composition formula (1) and the abundance of each unit. The number of moles of each unit constituting 1 mol of the type organohydrogensilicone was calculated.
^<1 H-NMR measurement method>
A solution dissolved in deuterated chloroform solvent at a rate of 1 ml per 30 mg of silicone is used as a measurement sample. Using this measurement sample, ¹ H-NMR measurement at 400 MHz (manufactured by JASCO Corporation α-400) is performed at 200 integration times.

(5) Measurement of low-boiling compound amount and volatile compound amount remaining in epoxy-modified silicone Using a gas chromatography analyzer GC-14B manufactured by Shimadzu Corporation, the following conditions are used.
In a 5 ml volumetric flask, about 0.5 g of epoxy-modified silicone and 0.015 g of n-octane as an internal standard are weighed, and a solution diluted to 5 ml with chloroform is used as a measurement sample.
Column: DB-1 (registered trademark) manufactured by J & W Scientific,
Length 30m, inner diameter 0.25mm, liquid film 1μm
Carrier gas: Helium Detector: FID
Injection temperature: 250 ° C
Detector temperature: 300 ° C
Temperature rising condition: After holding at 50 ° C. for 5 minutes, from 50 ° C. to 300 ° C.
The temperature is raised at 10 ° C / min.
From the obtained results, the content of each component contained in the epoxy-modified silicone is quantified and summed up using a separately prepared calibration curve by an internal standard method. In addition, a numerical value is represented with the mass fraction with respect to epoxy-modified silicone.

(6) Epoxy value Determined by the following procedure and calculation method.
The resin sample is dissolved with benzyl alcohol and 1-propanol. To this solution, an aqueous potassium iodide solution and a bromophenol blue indicator are added, followed by titration with 1N hydrochloric acid, and the point where the reaction system turns from blue to yellow is taken as the equivalent point. From the equivalent point, the epoxy value of the epoxy-modified silicone is calculated according to the following formula.
Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W)
[W, V, N, and F represent the following values, respectively.
W: Weight of sample (g)
V; titration volume (ml)
N: Normality of hydrochloric acid used for titration (N)
F: Factor of hydrochloric acid used for titration

(7) Element content The platinum content is analyzed using a quadrupole ICP mass spectrometer (manufactured by Thermo Elemental: X7-ICP-MS).
(8) Transparency Using a cured product having a thickness of 3 mm, the light transmittance at 350 nm, 400 nm, and 450 nm in the thickness direction is measured by JASCO V-550 manufactured by JASCO Corporation. The initial light transmittance of 80% or more was evaluated as ◎, 70% or more and less than 80% as ○, 50% or more and less than 70% as Δ, and less than 50% as ×.
(9) Heat resistance Tg of the pulverized cured product was measured with a DSC220C manufactured by Seiko Instruments Inc. under a temperature rising rate of 10 ° C / min, and used as a heat resistance index. The Tg of the cured product was 120 ° C. or higher, ◯, 100 ° C. or higher and lower than 120 ° C., 80 ° C. or higher and lower than 100 ° C., and 80 ° C. or lower.

(10) Light resistance It is set so that UV light can be irradiated to a cured product having a thickness of 3 mm in a constant temperature dryer kept constant at 100 ° C. from a UV irradiation device (USHIO: SP-7) via an optical fiber. Using a 365 nm band pass filter, the light of 330-410 nm is irradiated so that it may become 3 W / cm <2>.
After the start of irradiation, ◎ indicates that the cured product is not colored for 250 hours or more, ○ indicates that the cured product is colored in 200 hours or more and less than 250 hours, and × indicates that the cured product is colored in less than 200 hours.
(11) Heat-resistant discoloration Using a cured product having a thickness of 3 mm, a light transmittance of 400 nm in the thickness direction is measured by JASCO V-550 manufactured by JASCO Corporation. Next, the cured product is put into a mold made of SUS316, subjected to heating conditions at 150 ° C. for 100 hours under air, and then allowed to cool at room temperature. Thereafter, the light transmittance at 400 nm in the thickness direction of the sample is measured again, and the value of the light transmittance at 400 nm in the sample after the heat treatment is calculated with respect to the light transmittance at 400 nm in the sample before the heat treatment. The ratio of the light transmittance of the sample after the heat treatment to the light transmittance of the sample is calculated as the light transmission retention rate. The light transmission retention was 90% or more, ◎, 88% or more and less than 90%, ○, 85% or more and less than 88%, or less than 85%.

(12) Crack resistance A silicon chip of 5 mm × 5 mm × 0.2 mm is placed in a 10 mm × 10 mm × 2 mm size mold, and the resin composition is cast and heated to obtain a test piece. The obtained cured product was taken out from the mold and held at −40 ° C. for 15 minutes in a cooling cycle test (TSE-11-A manufactured by Espec Corp.), and then the temperature was raised to 120 ° C. in an average of 3 minutes. The test is held for 15 minutes, and then tested in a cycle in which the temperature is lowered to -40 ° C in an average of 3 minutes, and the presence or absence of cracks is visually observed. The case where cracks did not occur for 40 cycles or more was rated as ◎, the case where cracks occurred after 20 cycles or more and less than 40 cycles was rated as ◯, and the case where cracks occurred after less than 5 cycles was marked as x.
(13) Surface hardness It implemented based on JIS-K-5600-5-4.
The test results were evaluated as 以上 for HB or more, ◯ for B to 2B, and x for 3B or less.

[Example of catalyst synthesis]
Under a nitrogen atmosphere, in a 50 ml two-necked flask equipped with a reflux tube and a stirrer bar, 8.34 g of phosphorus pentachloride (Wako Pure Chemicals reagent), 1.06 g of ammonium chloride (Wako Pure Chemicals reagent special grade) and tetra After charging 20 ml of chloroethane (aldrich reagent), the reaction was carried out at 160 ° C. for 15 hours while flowing atmospheric nitrogen at 20 ml / min to obtain a yellow solution. After completion of the reaction, 20 ml of petroleum ether (Wako Pure Chemicals Reagent) was added to the system while stirring under an atmospheric pressure of nitrogen atmosphere to precipitate a solid. Subsequently, the obtained solid was filtered under reduced pressure in a nitrogen atmosphere, washed with 100 ml of n-hexane (dehydrated grade for reagent organic synthesis manufactured by Wako Pure Chemical Industries, Ltd.), and then filtered again under nitrogen. Thereafter, it was dried under reduced pressure to obtain 7.1 g of a phosphazene compound as a pale yellow powder. In Reference Examples 1 to 3 below, a solution in which 60 mg of the obtained phosphazene compound was dissolved per 1 g of dichloromethane (dehydrated grade for reagent organic synthesis manufactured by Wako Pure Chemical Industries, Ltd.) was used as the phosphazene solution.

[Reference Example 1]
<Synthesis of hydrolyzate>
After charging 1500 g of distilled water into a separable flask with a baffle having an internal volume of 3 liters equipped with a stirring blade, the inside is heated to 60 ° C. While rotating the stirring blade of the separable flask at 600 rpm, a solution in which 400 g of cyclohexylmethyldichlorosilane (Shin-Etsu Chemical Co., Ltd. reagent) and 65.5 g of dimethyldichlorosilane are uniformly mixed is dropped at 2 g / min. . After completion of dropping, the reaction is continued for 2 hours, heating and stirring are stopped, the inner solution is phase-separated, and the water tank is discarded. Next, at room temperature, 500 g of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 1 liter of 0.02 mol / liter sodium formate aqueous solution were added, and the stirring blade was rotated at 600 rpm, and stirring was stopped. Phase separate the inner solution and discard the water bath. Subsequently, 1 liter of distilled water is added at room temperature, the stirring blade is rotated at 600 rpm, the stirring is stopped, the inner solution is phase-separated, and the aqueous phase is discarded twice. A toluene solution was recovered from the separable flask, and toluene was distilled off at 65 ° C. under reduced pressure using an evaporator to obtain hydrolyzate 1.

<Synthesis of polydialkylsiloxane>
A 500 ml separable flask equipped with a distillation tube and a stirring blade is charged with 300 g of the obtained hydrolyzate and 1 g of the phosphazene solution obtained in the catalyst synthesis example, and then the inside of the system is purged with nitrogen under reduced pressure. Subsequently, the system is heated to 120 ° C. and subjected to a polycondensation reaction at a pressure of 150 torr for 45 minutes, and then the reaction system is returned to atmospheric pressure with nitrogen and cooled to 60 ° C. Next, 7 g of 1,1,3,3-tetramethyl-disiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.) purified by distillation under dry nitrogen was added to the system under a nitrogen atmosphere, and stirring was continued for 3 hours. After end-capping reaction, cool to room temperature. The contents were dissolved and recovered using a total of 500 ml of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.), and the toluene was distilled off from the resulting solution with an evaporator at 65 ° C. under reduced pressure to obtain a polydialkylsiloxane. It was.
All terminal structures of the obtained polydialkylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the composition other than the terminal groups was 20 mol% of dimethylsiloxy units and 80 mol% of cyclohexylmethylsiloxy units. It was. As a result of molecular weight measurement, the elution curve was bimodal, the number average molecular weight of the peak on the high molecular weight side was 11,700, and the area area was 65% with respect to all peaks.
If necessary, the above synthesis operation was repeated to obtain a polydialkylsiloxane, which was used in the following reaction.

[Reference Example 2]
<Synthesis of hydrolyzate>
Hydrolyzate 2 was obtained in the same manner as in Reference Example 1 except that the amounts of cyclohexylmethyldichlorosilane and dimethyldichlorosilane were changed to 430 g and 31.3 g, respectively.
<Synthesis of polydialkylsiloxane>
Instead of using hydrolyzate 1, hydrolyzate 2 was used, the polycondensation reaction time was 2 hours, and 4 g of 1,1,3,3-tetramethyl-disiloxane was used. A polydialkylsiloxane was obtained in the same manner as in Reference Example 1.
All terminal structures of the obtained polydialkylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the composition other than the terminal groups was 10 mol% of dimethylsiloxy units and 90 mol% of cyclohexylmethylsiloxy units. It was. As a result of molecular weight measurement, the elution curve was bimodal, the number average molecular weight of the peak on the high molecular weight side was 20,400, and the area area was 60% with respect to all peaks.
If necessary, the above synthesis operation was repeated to obtain a polydialkylsiloxane, which was used in the following reaction.

[Reference Example 3]
<Synthesis of hydrolyzate>
Hydrolyzate 3 was obtained in the same manner as in Reference Example 1 except that the amounts of cyclohexylmethyldichlorosilane and dimethyldichlorosilane used were 320 g and 139.7 g, respectively.
<Synthesis of polydialkylsiloxane>
Instead of using hydrolyzate 1, hydrolyzate 3 was used, 0.5 g of the phosphazene solution obtained in the catalyst synthesis example was used, the polycondensation reaction time was 1 hour, 1, 1, A polydialkylsiloxane was obtained in the same manner as in Reference Example 1 except that 15.6 g of 3,3-tetramethyl-disiloxane was used.
All terminal structures of the obtained polydialkylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the composition other than the terminal groups was 40 mol% dimethylsiloxy units and 60 mol% cyclohexylmethylsiloxy units. It was. As a result of the molecular weight measurement, the elution curve was bimodal, the number average molecular weight of the peak on the high molecular weight side was 5,300, and the area area was 32% with respect to the total peak.
If necessary, the above synthesis operation was repeated to obtain a polydialkylsiloxane, which was used in the following reaction.

[Reference Example 4]
In a 0.5 liter reactor equipped with a reflux condenser, thermometer and stirrer bar, 1,3,5,7-tetramethylcyclotetrasiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.) purified by distillation under dry nitrogen was added. 270 g, 108 g of 1,1,3,3-tetramethyl-disiloxane purified by distillation under nitrogen (reagent manufactured by Shin-Etsu Chemical Co., Ltd.), activated clay (TONSIL OPTIMUM 230FF) dried at 110 ° C. for 5 hours under vacuum Zood Chemie Co., Ltd.) was charged in an amount of 0.38 g, and the reaction was performed at 65 ° C. under nitrogen for 24 hours under stirring. The obtained reaction solution was passed through a 1 μm filter under dry nitrogen to remove the catalyst, and then the low molecular weight oligomer was distilled off over 2 hours at 50 ° C. and 1.3 kPa to remove polyhydrogenmethylsiloxane. Obtained.
All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 800.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Reference Example 5]
190 g of 1,1,3,3-tetramethyl-disiloxane was used, 0.46 g of activated clay was used, and low molecular weight oligomers were distilled off under conditions of 2.7 kPa over 3 hours. Except for the above, polyhydrogenmethylsiloxane was obtained in the same manner as in Reference Example 4.
All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 500.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Reference Example 6]
Polyhydrogenmethylsiloxane was obtained in the same manner as in Reference Example 4 except that 115 g of 1,1,3,3-tetramethyl-disiloxane was used and 0.39 g of activated clay was used.
All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 750.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Reference Example 7]
Except for using 145 g of 1,1,3,3-tetramethyl-disiloxane, using 0.42 g of activated clay, and distilling off the low molecular weight oligomer over 2 hours under the condition of 2 kPa. In the same manner as in Reference Example 4, polyhydrogenmethylsiloxane was obtained.
All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 600.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Reference Example 8]
Using 58 g of 1,1,3,3-tetramethyl-disiloxane, using 0.33 g of activated clay, and distilling off low molecular weight oligomers under conditions of 75 ° C. and 0.7 kPa over 3 hours. A polyhydrogenmethylsiloxane was obtained in the same manner as in Reference Example 4 except that it was performed.
All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 1,400.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Reference Example 9]
38 g of 1,1,3,3-tetramethyl-disiloxane was used, 0.31 g of activated clay was used, and low molecular weight oligomers were distilled off at 100 ° C. and 0.7 kPa over 3 hours. A polyhydrogenmethylsiloxane was obtained in the same manner as in Reference Example 4 except that it was performed.
All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 2,000.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Reference Example 10]
The use of 23.6 g of 1,1,3,3-tetramethyl-disiloxane, the use of 0.29 g of activated clay, and the distillation of low molecular weight oligomers at 150 ° C. and 0.1 kPa for 3 hours. A polyhydrogenmethylsiloxane was obtained in the same manner as in Reference Example 4 except that the procedure was carried out.
All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 3,150.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Synthesis Example 1]
<Equilibration reaction>
A 300 separable flask equipped with a stirring blade was charged with 100 g of the polydialkylsiloxane obtained in Reference Example 1 and 129.7 g of the polyhydrogenmethylsiloxane obtained in Reference Example 4 under dry nitrogen. The system is cooled to 20 ° C. After the system is uniformly mixed and dispersed, trifluoromethanesulfonic acid (special grade product manufactured by Wako Pure Chemical Industries, Ltd.) is mixed with polydialkylsiloxane and polyhydrogenmethylsiloxane under dry nitrogen conditions while continuing stirring under dry nitrogen. After adding 0.25 wt% with respect to the total weight of the mixture and performing the equilibration reaction for 45 minutes, add equimolar amount of triethylamine (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) equivalent to the added trifluoromethanesulfonic acid. Then, stirring is continued for 30 minutes. After 30 minutes, stirring is stopped, the reaction system is brought to room temperature, and the contents are dissolved and recovered using a total of 600 ml of toluene (special grade product manufactured by Wako Pure Chemical Industries, Ltd.). The recovered solution is transferred to a 2 liter separatory funnel, and 700 ml of a 0.02 mol / liter sodium hydrogen carbonate aqueous solution is added for separation and washing, followed by phase separation and discarding of the aqueous phase. Subsequently, 700 ml of distilled water is added for separation and washing, and then the phase separation is performed and the aqueous phase is discarded twice. The toluene solution was recovered, and toluene was distilled off at 65 ° C. under reduced pressure using an evaporator to obtain silicone.

<Evaporation of low molecular weight components>
Into a glass tube oven [GTO-350RG manufactured by Shibata Kagaku Co., Ltd.], the silicone obtained above is charged into a cylindrical tube made of Pyrex (registered trademark) glass having an inner diameter of 70 mm and an effective length of 200 mm. I set it. After replacing the interior with nitrogen under room temperature conditions, the internal cylindrical tube started to rotate, and under a pressure of 0.1 kPa, the temperature was raised to 200 ° C. for 1 hour, and then the temperature was raised to 250 ° C. The low molecular weight component was distilled off for 3 hours. After completion of the low boiling point distillation, after cooling to room temperature, the pressure was changed to atmospheric pressure with dry nitrogen to obtain a block type organohydrogen silicone.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 4,800, and the content of components having a molecular weight of 1,000 or less was 10%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 2.2 mol%, hydrogen methylsiloxy units 21.7 mol% dimethylsiloxy units 22.0 mol%, cyclohexylmethyl siloxy units 54.1 mol%, dialkylsiloxy units And the average chain lengths of the hydrogen methylsiloxy units were 9.8 and 3.8, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.239, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 33.5 and 9.6, respectively, in 1 g of block type organohydrogen silicone. Contained 2.19 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.
If necessary, the above synthesis operation was repeated to obtain a block type organohydrogen silicone, which was used in the following reaction.

[Synthesis Example 2]
A block type organohydrogensilicone was prepared in the same manner as in Synthesis Example 1 except that the equilibration reaction was performed for 60 minutes, and the low molecular weight component was distilled off at a pressure of 0.27 kPa and a temperature of 200 ° C. for 2 hours. Obtained.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 2,400, and the content of components having a molecular weight of 1,000 or less was 13%.
All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 3.0 mol%, hydrogen methylsiloxy units 24.2 mol% dimethylsiloxy units 8.3 mol%, cyclohexylmethyl siloxy units 64.5 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 5.8 and 2.7, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.272, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 15.0 and 5.0, respectively, in 1 g of block type organohydrogen silicone. Contained 2.34 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 3]
The conditions for distilling off the low molecular weight component were the pressure of 0.1 kPa, the temperature was raised to 200 ° C. for 1 hour, the temperature was raised to 250 ° C. for 3 hours, and the temperature was further raised to 300 ° C. A block type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the time was 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 6,000, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 2.6 mol%, hydrogen methylsiloxy units 22.4 mol% dimethylsiloxy units 23.9 mol%, cyclohexylmethyl siloxy units 51.1 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 12.2 and 3.2, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.250, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 42.0 and 12.5, respectively, in 1 g of block type organohydrogen silicone. Contained 2.33 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 4]
110 g of the polydialkylsiloxane obtained in Reference Example 2 was used in place of the polydialkylsiloxane obtained in Reference Example 1, and that obtained in Reference Example 5 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4. Using 21.4 g of polyhydrogenmethylsiloxane, carrying out the equilibration reaction for 60 minutes, raising the temperature of the low molecular weight component to 200 ° C. under the pressure of 0.1 kPa and continuing for 1 hour. A block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 250 ° C. for 3 hours, and subsequently raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block-type organohydrogensilicone was 5,200, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 3.1 mol%, hydrogen methylsiloxy units 22.3 mol% dimethylsiloxy units 9.2 mol%, cyclohexylmethyl siloxy units 65.4 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 58 and 2.3, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.254, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 33.1 and 9.9, respectively, in 1 g of block type organohydrogen silicone. Contained 2.17 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 5]
115 g of the polydialkylsiloxane obtained in Reference Example 2 was used instead of the polydialkylsiloxane obtained in Reference Example 1, and that obtained in Reference Example 6 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4. 15.3 g of polyhydrogenmethylsiloxane was used, the equilibration reaction was carried out at 30 ° C. for 90 minutes, the low molecular weight component was distilled off under a pressure of 0.1 kPa and the temperature was raised to 200 ° C. to 1 A block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 250 ° C. for 3 hours, and then further raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 4,000, and the content of components having a molecular weight of 1,000 or less was 3%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 3.4 mol%, hydrogen methylsiloxy units 17.4 mol% dimethylsiloxy units 15.0 mol%, cyclohexylmethyl siloxy units 64.2 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 37 and 2.6, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] was 0.208, and dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 27.0 and 5.9, respectively, in 1 g of block type organohydrogen silicone. Contained 1.77 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 6]
The use of 31.3 g of the polyhydrogenmethylsiloxane obtained in Reference Example 7 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4, the equilibration reaction for 17 minutes, and the distillation conditions for the low molecular weight component Except that the temperature was raised to 200 ° C. for 1 hour under the condition of a pressure of 0.1 kPa, then the temperature was raised to 250 ° C. for 3 hours, and further raised to 300 ° C. for 3 hours. In the same manner as in Synthesis Example 1, a block type organohydrogen silicone was obtained.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 3,800, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 3.7 mol%, hydrogen methylsiloxy units 23.1 mol% dimethylsiloxy units 14.9 mol%, cyclohexylmethyl siloxy units 58.3 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 21 and 2.7, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.268, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 24.7 and 7.8, respectively, in 1 g of block type organohydrogen silicone. Contained 2.38 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 7]
95 g of the polydialkylsiloxane obtained in Reference Example 2 was used instead of the polydialkylsiloxane obtained in Reference Example 1, and that obtained in Reference Example 7 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4. Using 35.1 g of polyhydrogenmethylsiloxane, carrying out the equilibration reaction for 15 minutes, evaporating the low molecular weight components under a pressure of 0.1 kPa, raising the temperature to 200 ° C. and continuing for 1 hour, A block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 250 ° C. for 3 hours, and subsequently raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 7,200, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 2.3 mol%, hydrogen methylsiloxy units 29.3 mol% dimethylsiloxy units 14.2 mol%, cyclohexylmethyl siloxy units 54.2 mol%, dialkylsiloxy units The average chain lengths of the hydrogen methylsiloxy units were 40 and 4.3, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.316, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 45.5 and 19.5, respectively, in 1 g of block type organohydrogen silicone. Contained 2.92 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 8]
Using 31.3 g of the polyhydrogenmethylsiloxane obtained in Reference Example 7 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4, carrying out the equilibration reaction for 7 minutes, and the conditions for distilling off the low molecular weight component Except that the temperature was raised to 200 ° C. for 1 hour under the condition of a pressure of 0.1 kPa, then the temperature was raised to 250 ° C. for 3 hours, and further raised to 300 ° C. for 3 hours. In the same manner as in Synthesis Example 1, a block type organohydrogen silicone was obtained.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 4,400, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 3.3 mol%, hydrogen methylsiloxy units 22.2 mol% dimethylsiloxy units 17.4 mol%, cyclohexylmethyl siloxy units 57.1 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 60 and 4.8, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.255, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 29.3 and 8.8, respectively, in 1 g of block type organohydrogen silicone. Contained 2.29 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 9]
115 g of the polydialkylsiloxane obtained in Reference Example 3 was used instead of the polydialkylsiloxane obtained in Reference Example 1, and that obtained in Reference Example 8 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4. 16.3 g of polyhydrogenmethylsiloxane was used, the equilibration reaction was carried out at 10 ° C. for 50 minutes, and the low molecular weight component was distilled off under a pressure of 0.1 kPa at a temperature of 200 ° C. A block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 250 ° C. for 3 hours, and then further raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 3,500, and the content of components having a molecular weight of 1,000 or less was 1%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 5.1 mol%, hydrogen methylsiloxy units 14.2 mol% dimethylsiloxy units 17.6 mol%, cyclohexylmethyl siloxy units 63.1 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 3.2 and 2.2, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.193, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 23.9 and 4.2, respectively, in 1 g of block type organohydrogen silicone. Contained 1.64 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 10]
Instead of the polydialkylsiloxane obtained in Reference Example 1, 98 g of the polydialkylsiloxane obtained in Reference Example 2 was used, and instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4, it was obtained in Reference Example 8. 31.9 g of polyhydrogenmethylsiloxane was used, the equilibration reaction was carried out at 10 ° C. for 10 minutes, the low molecular weight component was distilled off under a pressure of 0.1 kPa and the temperature was raised to 200 ° C. to 1 A block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 250 ° C. for 3 hours, and then further raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 5,900, and the content of components having a molecular weight of 1,000 or less was 4%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 2.1 mol%, hydrogen methylsiloxy units 26.4 mol% dimethylsiloxy units 12.8 mol%, cyclohexylmethyl siloxy units 58.7 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 90 and 15, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.285, and dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 37.8 and 14.0, respectively, in 1 g of block type organohydrogen silicone. Contained 2.56 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 11]
75 g of the polydialkylsiloxane obtained in Reference Example 1 was used, 55.9 g of the polyhydrogenmethylsiloxane obtained in Reference Example 9 was used instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4, The reaction was carried out at 5 ° C. for 8 minutes, the low molecular weight component was distilled off under a pressure of 0.1 kPa, the temperature was raised to 200 ° C. for 1 hour, and then the temperature was raised to 250 ° C. A block type organohydrogen silicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was further raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 4,000, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 2.8 mol%, hydrogen methylsiloxy units 53.5 mol% dimethylsiloxy units 14.5 mol%, cyclohexylmethyl siloxy units 29.2 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 6 and 18, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.563, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 19.9 and 24.3, respectively, in 1 g of block type organohydrogen silicone. Contained 6.40 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 12]
115 g of the polydialkylsiloxane obtained in Reference Example 3 was used instead of the polydialkylsiloxane obtained in Reference Example 1, and that obtained in Reference Example 8 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4. 16.3 g of polyhydrogenmethylsiloxane was used, the equilibration reaction was carried out at 10 ° C. for 65 minutes, the conditions for distilling off the low molecular weight components were raised to 200 ° C. under a pressure of 0.1 kPa, and A block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 250 ° C. for 3 hours, and then further raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 2,100, and the content of components having a molecular weight of 1,000 or less was 1%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 8.0 mol%, hydrogen methylsiloxy units 14.7 mol% dimethylsiloxy units 16.1 mol%, cyclohexylmethyl siloxy units 61.2 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 2 and 1.6, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.227, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 13.7 and 2.6, respectively, in 1 g of block type organohydrogen silicone. Contained 1.92 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 13]
Using 31.4 g of the polyhydrogenmethylsiloxane obtained in Reference Example 8 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4, carrying out the equilibration reaction for 60 minutes, and the conditions for distilling off the low molecular weight component Except that the temperature was raised to 200 ° C. for 1 hour under the condition of a pressure of 0.1 kPa, then the temperature was raised to 250 ° C. for 3 hours, and further raised to 300 ° C. for 3 hours. In the same manner as in Synthesis Example 1, a block type organohydrogen silicone was obtained.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 3,700, and the content of components having a molecular weight of 1,000 or less was 1%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 4.0 mol%, hydrogen methylsiloxy units 21.6 mol% dimethylsiloxy units 9.1 mol%, cyclohexylmethyl siloxy units 65.3 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 2 and 4, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.256, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 23.4 and 6.8, respectively, in 1 g of block type organohydrogen silicone. Contained 2.17 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 14]
115 g of the polydialkylsiloxane obtained in Reference Example 2 was used instead of the polydialkylsiloxane obtained in Reference Example 1, and that obtained in Reference Example 6 instead of the polyhydrogenmethylsiloxane obtained in Reference Example 4. 15.3 g of polyhydrogenmethylsiloxane was used, the equilibration reaction was carried out at 30 ° C. for 55 minutes, and the conditions for distilling off the low molecular weight component were raised to 200 ° C. under a pressure of 0.1 kPa and 1 A block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 250 ° C. for 3 hours, and then further raised to 300 ° C. for 3 hours.
As a result of molecular weight measurement, the number average molecular weight of the obtained block-type organohydrogensilicone was 6,100, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 2.9 mol%, hydrogen methylsiloxy units 15.5 mol% dimethylsiloxy units 13.6 mol%, cyclohexylmethyl siloxy units 68.0 mol%, dialkylsiloxy units And the average chain lengths of the hydrogen methylsiloxy units were 110 and 4, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.184, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 41.5 and 7.9, respectively, in 1 g of block type organohydrogen silicone. Contained 1.54 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Synthesis Example 15]
In place of the polyhydrogenmethylsiloxane obtained in Reference Example 4, 32.3 g of the polyhydrogenmethylsiloxane obtained in Reference Example 10 was used, the equilibration reaction was carried out at 15 ° C. for 12 minutes, The distillation conditions were a pressure of 0.1 kPa and the temperature was raised to 200 ° C. for 1 hour, then the temperature was raised to 250 ° C. for 3 hours, and subsequently the temperature was raised to 300 ° C. for 3 hours. Except for this, a block-type organohydrogensilicone was obtained in the same manner as in Synthesis Example 1.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogen silicone was 6,200, and the content of components having a molecular weight of 1,000 or less was 2%.

All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [H—Si ( CH _{3) 2} -O _1/2 -] units 2.7 mol%, hydrogen methylsiloxy units 22.4 mol% dimethylsiloxy units 16.0 mol%, cyclohexylmethyl siloxy units 58.9 mol%, dialkylsiloxy units And the average chain length of the hydrogen methylsiloxy units were 8 and 23, respectively.
The content ratio of SiH units to the total Si constituting the block type organohydrogen silicone [value of (b + d + f) / (a + b + c + d + e + f + g) in the present invention] is 0.251, and the dialkyl constituting 1 mol of the block type organohydrogen silicone. The number of moles of siloxy units [value of c in the present invention] and the number of moles of hydrogen alkylsiloxy units [value of d in the present invention] are 41.3 and 12.3, respectively, in 1 g of block type organohydrogen silicone. Contained 2.23 mmol of SiH units.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

<Production 1a of epoxy-modified silicone>
A 1 liter reactor with reflux condenser, thermometer and stirrer is replaced with dry nitrogen. Under dry nitrogen conditions, 60 g of the block-type organohydrogensilicone produced in Synthesis Example 1 was added to the above apparatus, and 163.4 g of 4-vinylcyclohexene oxide (reagent manufactured by Aldrich) purified by dehydration distillation under dry nitrogen. (1315.9 mmol), 305.8 g of tetrahydrofuran (reagent grade manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration and distillation under nitrogen was added, and the temperature was raised to 66 ° C. with stirring in an atmospheric pressure dry nitrogen atmosphere. . The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 131.55 mmol.
To this, 0.31 g of a tetrahydrofuran solution of a platinum divinyltetramethyldisiloxane complex containing 500 ppm of platinum in terms of platinum element is added under dry nitrogen, and the hydrosilylation reaction is allowed to react for 20 hours. After the reaction for 20 hours, 0.15 g of the tetrahydrofuran solution of the platinum divinyltetramethyldisiloxane complex is added under dry nitrogen, and the reaction is continued for another 20 hours. Further, 0.15 g of the above-mentioned platinum divinyltetramethyldisiloxane complex tetrahydrofuran solution was added under dry nitrogen and the reaction was carried out for 24 hours. As a result, the hydrosilylation reaction progressed quantitatively, and the reaction was unreacted. No SiH unit was detected. Subsequently, the heating of the reaction solution was stopped and the mixture was allowed to cool to room temperature.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. In contrast, the value at the end of the reaction when the catalyst was added was 1 / 84,015 times.

  After cooling the reaction solution, 170 g of activated carbon (manufactured by Wako Pure Chemicals: Granular Special Grade) heated and dried at 150 ° C. for 3 hours under a dry nitrogen stream is added, and activated carbon treatment is performed for 48 hours under a dry nitrogen atmosphere. Then, the activated carbon was filtered using a PTFE membrane filter having a pore size of 1 micron to collect the filtrate. Furthermore, the separated activated carbon was washed with 600 ml of tetrahydrofuran, and the activated carbon was similarly filtered using a membrane filter to collect the washing solution, which was mixed with the previously obtained filtrate. The recovered tetrahydrofuran solution was evaporated using an evaporator under reduced pressure at a heating temperature of 40 ° C. to obtain an epoxy-modified silicone.

The obtained epoxy-modified silicone is put into a Pyrex (registered trademark) glass cylindrical tube having an inner diameter of 70 mm and an effective length of 200 mm, and set in a glass tube oven (GTO-350 manufactured by Shibata Kagaku). After starting rotation of the internal cylindrical tube and substituting the inside with dry nitrogen at room temperature, dry nitrogen at a flow rate of 10 ml / min in terms of atmospheric pressure at a temperature of 50 ° C. and a pressure of 0.2 kPa. Was added for 70 hours to obtain 54 g of epoxy-modified silicone (1a) with reduced low boiling point compounds.
All terminal structures of the resulting epoxy-modified silicone (1a) are modified to a trialkylsiloxy group by hydrosilylation reaction, and the composition excluding the terminal group is a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit. They were 22.2 mol%, dimethylsiloxy unit 22.5 mol%, and cyclohexylmethylsiloxy unit 55.3 mol%. As a result of molecular weight measurement, the peak content with a molecular weight of 1,000 or less was 8%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.

Only tetrahydrofuran remaining in the epoxy-modified silicone (1a) was detected, and the total amount of remaining volatile compounds was 0.002% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.004% by mass and 0.003% by mass, respectively. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.007% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.007% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.007% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.003% by mass.
Moreover, the epoxy value of the epoxy-modified silicone (1a) was 0.172, the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 1a>
100 parts by mass of the resulting epoxy-modified silicone (1a), 28.9 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-1a. The curable composition-1a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 2a of epoxy-modified silicone>
52 g of epoxy-modified silicone (2a) with reduced low-boiling compounds was obtained in the same manner as in Example 1 except that 89.8 g (723.2 mmol) of 4-vinylcyclohexene oxide was used during the hydrosilylation reaction. It was. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 131.55 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 5.5 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. In contrast, the value at the end of the reaction when the catalyst was added was 1 / 84,015 times.

All terminal structures of the resulting epoxy-modified silicone (2a) are modified to a trialkylsiloxy group by hydrosilylation reaction, and the composition excluding the terminal group is a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit. They were 22.2 mol%, dimethylsiloxy unit 22.5 mol%, and cyclohexylmethylsiloxy unit 55.3 mol%. As a result of molecular weight measurement, the peak content with a molecular weight of 1,000 or less was 8%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only tetrahydrofuran remaining in the epoxy-modified silicone (2a) was detected, and the total amount of remaining volatile compounds was 0.002% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.004 mass% and 0.002 mass%, respectively. Other compounds were not detected. From this, the total amount of the low-boiling compounds remaining in the epoxy-modified silicone in the present invention is 0.006% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.006% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.006% by mass; the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.002% by mass.
The epoxy value of the epoxy-modified silicone (2a) was 0.172, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 2a>
100 parts by mass of the resulting epoxy-modified silicone (2a), 28.9 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-2a. The curable composition-2a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 3a of epoxy-modified silicone>
During the hydrosilylation reaction, a 1.5 liter reactor was used, 1470.2 g (11840.2 mmol) of 4-vinylcyclohexene oxide was used, and the processing time in the glass tube oven was 90 hours. Except that, 53 g of epoxy-modified silicone (3a) in which the low boiling point compound was reduced was obtained in the same manner as in Example 1. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 131.55 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 90 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. In contrast, the value at the end of the reaction when the catalyst was added was 1 / 84,015 times.

All terminal structures of the resulting epoxy-modified silicone (3a) have been modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 22.2 mol%, dimethylsiloxy unit 22.5 mol%, and cyclohexylmethylsiloxy unit 55.3 mol%. As a result of molecular weight measurement, the peak content with a molecular weight of 1,000 or less was 8%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (3a) was detected, and the total amount of the remaining volatile compounds was 0.001% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.005 mass% and 0.002 mass%, respectively. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.007% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.007% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.007% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.002% by mass.
The epoxy value of the epoxy-modified silicone (3a) was 0.172, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 3a>
100 parts by mass of the resulting epoxy-modified silicone (3a), 28.9 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-3a. The curable composition-3a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 4a of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 2 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 174.0 g (1401) of 4-vinylcyclohexene oxide was used. .3 mmol) and using 310 g of tetrahydrofuran were obtained in the same manner as in Example 1 to obtain 52 g of an epoxy-modified silicone (4a) having a reduced low boiling point compound. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 140.11 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 89,576 times.

All terminal structures of the resulting epoxy-modified silicone (4a) are modified to a trialkylsiloxy group by hydrosilylation reaction, and the composition excluding the terminal group is a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit. They were 24.9 mol%, dimethylsiloxy unit 8.6 mol%, and cyclohexylmethylsiloxy unit 66.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 13%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (4a) was detected, and the total amount of the remaining volatile compounds was 0.001% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.002 mass% and 0.002 mass%, respectively. Other compounds were not detected. From this, the total amount of the low-boiling compounds remaining in the epoxy-modified silicone in the present invention is 0.004% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.004% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.004% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.002% by mass.
Moreover, the epoxy value of the epoxy-modified silicone (4a) was 0.181, and the transition metal component contained was only platinum, and the content of this component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 4a>
90 parts by mass of the resulting epoxy-modified silicone (4a), 10 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanedicarboxylate, 27.4 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 3-propanediol and 0.25 parts by mass of diazabicycloundecene octylate are mixed under nitrogen, stirred until the whole becomes uniform, and then defoamed to obtain a curable composition-4a. It was. The curable composition-4a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 5a of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 3 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 173.8 g (1399) of 4-vinylcyclohexene oxide was used. Example 1 except that 0.9 g of tetrahydrofuran was used, 310 g of tetrahydrofuran was used, and 0.93 g of a tetrahydrofuran solution of a platinum divinyltetramethyldisiloxane complex containing 500 ppm of platinum in terms of platinum at the start of the reaction. In the same manner as above, 55 g of an epoxy-modified silicone (5a) with reduced low boiling point compounds was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 139.94 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 44,372 times.

All terminal structures of the resulting epoxy-modified silicone (5a) are modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 23.0 mol%, dimethylsiloxy unit 24.5 mol%, and cyclohexylmethylsiloxy unit 52.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (5a) was detected, and the total amount of the remaining volatile compounds was 0.003% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.005% by mass and 0.004% by mass, respectively. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.009% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.009% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.009% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.004% by mass.
Moreover, the epoxy value of the epoxy-modified silicone (5a) was 0.181, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 5a>
100 parts by mass of the resulting epoxy-modified silicone (5a), 30.4 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-5a. The curable composition-5a was poured into a mold having a depth of 3 mm under nitrogen and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 6a of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 4 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 129.1 g (1039) of 4-vinylcyclohexene oxide was used. .7 mmol), the use of 306 g of tetrahydrofuran, and the amount of activated carbon used during the activated carbon treatment was changed to 160 g. ) 54 g was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 129.95 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 8 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 83,082 times.

All terminal structures of the resulting epoxy-modified silicone (6a) were modified to trialkylsiloxy groups by a hydrosilylation reaction, and the composition excluding the terminal groups was a unit in which vinylcyclohexene oxide was added to hydrogen methylsiloxy units. They were 23.0 mol%, dimethylsiloxy unit 9.5 mol%, and cyclohexylmethylsiloxy unit 67.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (6a) was detected, and the total amount of the remaining volatile compounds was 0.003% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.015 mass% and 0.01 mass%, respectively. Other compounds were not detected. From this, the total amount of the low-boiling compounds remaining in the epoxy-modified silicone in the present invention is 0.025% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.025% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.025% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.01% by mass.
Moreover, the epoxy value of the epoxy-modified silicone (6a) was 0.171, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture and characteristic evaluation 6a of cured product>
100 parts by mass of the resulting epoxy-modified silicone (6a), 28.7 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-6a. The curable composition-6a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 7a of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 5 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 158.5 g (1276) of 4-vinylcyclohexene oxide was used. .5 mmol), 294 g of tetrahydrofuran, 160 g of activated carbon used in the activated carbon treatment, and the amount of activated carbon used in the treatment was changed to 160 g. ) 51 g was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 106.34 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 12 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 67,990 times.

All terminal structures of the resulting epoxy-modified silicone (7a) are modified to a trialkylsiloxy group by hydrosilylation reaction, and the composition excluding the terminal group is a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit. They were 18.0 mol%, dimethylsiloxy unit 15.5 mol%, and cyclohexylmethylsiloxy unit 66.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 5%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Tetrahydrofuran remaining in the epoxy-modified silicone (7a) is 0.005% by mass or less, and only tetrahydrofuran is detected as a compound having a carbon-carbon double bond, and the total amount of remaining volatile compounds is 0.003% by mass. Met. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.006% by mass and 0.004% by mass, respectively. Other compounds were not detected. From this, the total amount of the low-boiling compounds remaining in the epoxy-modified silicone in the present invention is 0.01% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.01% by mass, and the remaining carbon -The total amount of the compound having a carbon double bond and an epoxy group is 0.01% by mass. The total amount of by-products generated by the internal transition of the carbon double bond was 0.004% by mass.
The epoxy value of the epoxy-modified silicone (7a) was 0.145, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 7a>
100 parts by mass of the resulting epoxy-modified silicone (7a), 24.4 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-7a. The curable composition-7a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 140 ° C. for 2 hours, and then at 160 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture of epoxy-modified silicone 8a>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 6 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 177.4 g (1428) of 4-vinylcyclohexene oxide was used. 0.7 mmol), and using 313 g of tetrahydrofuran was carried out in the same manner as in Example 1 to obtain 55 g of epoxy-modified silicone (8a) with reduced low boiling point compounds. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 142.87 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 191,737 times, and 1 / 191,342 times.

All terminal structures of the resulting epoxy-modified silicone (8a) are modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 24.0 mol%, dimethylsiloxy unit 15.5 mol%, and cyclohexylmethylsiloxy unit 60.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Tetrahydrofuran remaining in the epoxy-modified silicone (8a) is 0.005% by mass or less, and only tetrahydrofuran is detected as a compound having a carbon-carbon double bond, and the total amount of remaining volatile compounds is 0.002% by mass. Met. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.004 mass% and 0.002 mass%, respectively. Other compounds were not detected. From this, the total amount of the low-boiling compounds remaining in the epoxy-modified silicone in the present invention is 0.006% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.006% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.006% by mass; the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.002% by mass.
The epoxy value of the epoxy-modified silicone (8a) was 0.184, the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture and characteristic evaluation 8a of cured product>
100 parts by mass of the resulting epoxy-modified silicone (8a), 30.9 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-8a. The curable composition-8a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 9a of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 7 was used in place of the block type organohydrogen silicone produced in Synthesis Example 1, and 217.8 g (1754) of 4-vinylcyclohexene oxide was used. 0.0 mmol), 328 g of tetrahydrofuran was used, 0.15 g of a tetrahydrofuran solution of a platinum divinyltetramethyldisiloxane complex containing 500 ppm of platinum in terms of platinum was used at the start of the reaction, and used during activated carbon treatment. Except that the amount of activated carbon was 180 g, 57 g of an epoxy-modified silicone (9a) with reduced low boiling point compounds was obtained in the same manner as in Example 1. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 175.37 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value was 1 / 427,464 times, and the value at the end of the reaction in which the catalyst was added was 1 / 148,683 times.

All terminal structures of the resulting epoxy-modified silicone (9a) are modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 30.0 mol%, dimethylsiloxy unit 14.5 mol%, and cyclohexylmethylsiloxy unit 55.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Tetrahydrofuran remaining in the epoxy-modified silicone (9a) is 0.005% by mass or less, and only tetrahydrofuran is detected as a compound having a carbon-carbon double bond, and the total amount of remaining volatile compounds is 0.003% by mass. Met. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.006% by mass and 0.003% by mass, respectively. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.009% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.009% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.009% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.003% by mass.
Moreover, the epoxy value of the epoxy-modified silicone (9a) was 0.214, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture and characteristic evaluation 9a of cured product>
100 parts by mass of the resulting epoxy-modified silicone (9a), 36.0 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-9a. The curable composition-9a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 10a of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 8 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 170.4 g (1372) of 4-vinylcyclohexene oxide was used. .3 mmol) and using 310 g of tetrahydrofuran were carried out in the same manner as in Example 1 to obtain 54 g of an epoxy-modified silicone (10a) having a reduced low boiling point compound. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 137.24 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 87,744 times.

All terminal structures of the obtained epoxy-modified silicone (10a) are modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 23.0 mol%, dimethylsiloxy unit 18.0 mol%, and cyclohexylmethylsiloxy unit 59.0 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (10a) was detected, and the total amount of the remaining volatile compounds was 0.002% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.005% by mass and 0.004% by mass, respectively. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.009% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.009% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.009% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.004% by mass.
The epoxy value of the epoxy-modified silicone (10a) was 0.178, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 10a>
100 parts by mass of the resulting epoxy-modified silicone (10a), 29.9 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed under and stirred until the whole became uniform, and then defoamed to obtain a curable composition-10a. The curable composition-10a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 1 shows the performance of the obtained cured product.

<Manufacture 11a of epoxy-modified silicone>
During the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 9 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and dry nitrogen was used instead of 4-vinylcyclohexene oxide. 1,2-Epoxy-5-hexene (reagent made by Aldrich) 96.5 g (983.3 mmol) purified by dehydration distillation was used, 284 g of tetrahydrofuran was used, and the amount of activated carbon used during the activated carbon treatment In the same manner as in Example 1 except that the amount was changed to 160 g, 50 g of an epoxy-modified silicone (11a) with reduced low boiling point compounds was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 98.33 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 62,866 times.

All terminal structures of the resulting epoxy-modified silicone (11a) were modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups was 1,2-epoxy-5 in hydrogen methylsiloxy units. The amount of units added with -hexene was 15.0 mol%, the dimethylsiloxy unit was 18.5 mol%, and the cyclohexylmethylsiloxy unit was 66.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 2%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (11a) was detected, and the total amount of the remaining volatile compounds was 0.002% by mass. The low boiling point compounds are 1,2-epoxy-5-hexene and by-products generated by the internal transition of the carbon-carbon double bond of the aforementioned 1,2-epoxy-5-hexene. 1,2-epoxy-4-hexene, 1,2-epoxy-3-hexene and 1,2-epoxy-2-hexene were detected, and the residual amounts thereof were 0.003% by mass and 0.002% by mass, respectively. 0.002 mass% and 0.002 mass%. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.009% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.009% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.009% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.006% by mass.
Moreover, the epoxy value of the epoxy-modified silicone (11a) was 0.141, the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 11a>
100 parts by mass of the resulting epoxy-modified silicone (11a), 23.7 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-11a. The curable composition-11a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 140 ° C. for 2 hours, and subsequently at 160 ° C. for 1 hour to obtain a cured product. . Table 2 shows the performance of the obtained cured product.

<Manufacture 12a of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 10 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 190.6 g (1535) of 4-vinylcyclohexene oxide was obtained. 0.0 mmol) and 317 g of tetrahydrofuran were used, and in the same manner as in Example 1, 56 g of epoxy-modified silicone (12a) with reduced low boiling point compounds was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 153.46 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 198,116 times, and 1 / 198,116 times.

All terminal structures of the resulting epoxy-modified silicone (12a) have been modified to trialkylsiloxy groups by a hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 27.0 mol%, dimethylsiloxy unit 13.0 mol%, and cyclohexylmethylsiloxy unit 60.0 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 5%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (12a) was detected, and the total amount of the remaining volatile compounds was 0.004% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.02% by mass and 0.015% by mass, respectively. Other compounds were not detected. From this, the total amount of the low boiling point compound remaining in the epoxy-modified silicone in the present invention is 0.035% by mass, the total amount of the remaining compound having a carbon-carbon double bond is 0.035% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.035% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of carbon double bonds was 0.015% by mass.
The epoxy value of the epoxy-modified silicone (12a) was 0.194, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 12a>
100 parts by mass of the resulting epoxy-modified silicone (12a), 32.6 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-12a. The curable composition-12a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 2 shows the performance of the obtained cured product.

<Manufacture 13a of epoxy-modified silicone>
The use of a 1.5 liter reactor during the hydrosilylation reaction, the use of the block type organohydrogensilicone produced in Synthesis Example 11 instead of the block type organohydrogensilicone produced in Synthesis Example 1, Use of 476.5 g (3837.5 mmol) of 4-vinylcyclohexene oxide, use of 435 g of tetrahydrofuran, and a tetrahydrofuran solution of a platinum divinyltetramethyldisiloxane complex containing 500 ppm of platinum in terms of platinum at the start of the reaction 0.43 g was added under dry nitrogen and the hydrosilylation reaction was allowed to react for 20 hours, then 0.22 g of the above platinum divinyltetramethyldisiloxane complex tetrahydrofuran solution was added under dry nitrogen for another 20 hours. Continue the reaction, and Subsequently, 0.22 g of a tetrahydrofuran solution of the above platinum divinyltetramethyldisiloxane complex was added under dry nitrogen, and the reaction was carried out for 24 hours, except that the amount of activated carbon used during the activated carbon treatment was 300 g. Was obtained in the same manner as in Example 1 to obtain 76 g of an epoxy-modified silicone (13a) having a reduced low boiling point compound. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 383.74 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the number of unreacted SiH units relative to the total number of Si contained in the epoxy-modified silicone was 0.2%.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 173,563 times.

All terminal structures of the resulting epoxy-modified silicone (13a) were modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups was 0.2 mol% hydrogen methylsiloxy units, hydrogen They were 54.8 mol% of units in which vinylcyclohexene oxide was added to methylsiloxy units, 15.0 mol% of dimethylsiloxy units, and 30.0 mol% of cyclohexylmethylsiloxy units. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (13a) was detected, and the total amount of the remaining volatile compounds was 0.004% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.01% by mass and 0.008% by mass, respectively. Other compounds were not detected. Accordingly, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.018% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.018% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.018% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated through the internal transition of the carbon double bond was 0.008% by mass.
Moreover, the epoxy value of the epoxy-modified silicone (13a) was 0.356, the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 13a>
100 parts by mass of the resulting epoxy-modified silicone (13a), 59.8 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-13a. The curable composition-13a was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 2 shows the performance of the obtained cured product.

[Comparative Example 1]
<Manufacture of epoxy-modified silicone 1b>
51 g of epoxy-modified silicone (1b) with reduced low boiling point compounds was obtained in the same manner as in Example 1 except that 73.5 g (591.9 mmol) of 4-vinylcyclohexene oxide was used during the hydrosilylation reaction. It was. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 131.55 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 4.5 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. In contrast, the value at the end of the reaction when the catalyst was added was 1 / 84,015 times.

  All terminal structures of the resulting epoxy-modified silicone (1b) have been modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 22.2 mol%, dimethylsiloxy unit 22.5 mol%, and cyclohexylmethylsiloxy unit 55.3 mol%. As a result of molecular weight measurement, the peak content with a molecular weight of 1,000 or less was 8%, but a peak not observed before was observed in the vicinity of a molecular weight of 100,000 to 1,000,000. Formation of a molecular weight part was observed. In the GPC elution curve of the obtained epoxy-modified silicone (1b), the ratio of the area area of the peak observed this time to the elution peak area obtained by connecting the elution start point and the elution end point is about 5%. there were.

[Comparative Example 2]
<Manufacture 2b of epoxy-modified silicone>
The reaction was conducted in the same manner as in Example 1 except that a 3 liter reactor was used during the hydrosilylation reaction, and 1796.9 g (14471.3 mmol) of 4-vinylcyclohexene oxide was used. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 131.55 mmol.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 110 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. In contrast, the value at the end of the reaction when the catalyst was added was 1 / 84,015 times.
When the reaction solution after the reaction for a predetermined time was sampled, about 4% of the total mole number of SiH units contained in the charged block type organohydrogensilicone remained, and the hydrosilylation reaction was not completed.

[Comparative Example 3]
<Manufacture 3b of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 12 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 143.0 g (1151) of 4-vinylcyclohexene oxide was used. 0.6 mmole), the use of 300 g of tetrahydrofuran, and the amount of activated carbon used in the activated carbon treatment was changed to 180 g. ) 52 g was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 115.19 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 173,647 times, 1 / 144,919 times.

All terminal structures of the obtained epoxy-modified silicone (3b) are modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit. It was 16.0 mol%, dimethylsiloxy unit 17.5 mol%, and cyclohexylmethylsiloxy unit 66.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 2%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (3b) was detected, and the total amount of the remaining volatile compounds was 0.001% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.002 mass% and 0.002 mass%, respectively. Other compounds were not detected. From this, the total amount of the low-boiling compounds remaining in the epoxy-modified silicone in the present invention is 0.004% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.004% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.004% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.002% by mass.
The epoxy value of the epoxy-modified silicone (3b) was 0.155, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 3b>
100 parts by mass of the resulting epoxy-modified silicone (3b), 26.0 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-3b. The curable composition-3b was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 2 shows the performance of the obtained cured product.

[Comparative Example 4]
<Manufacture 4b of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 13 was used instead of the block type organohydrogen silicone produced in Synthesis Example 1, and 162.0 g (1304) of 4-vinylcyclohexene oxide was used. .7 mmol), the use of 306 g of tetrahydrofuran, and the amount of activated carbon used in the activated carbon treatment was changed to 165 g. ) 54 g was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 130.43 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 182,740 times.

All terminal structures of the resulting epoxy-modified silicone (4b) were modified to trialkylsiloxy groups by a hydrosilylation reaction, and the composition excluding the terminal groups was a unit in which vinylcyclohexene oxide was added to hydrogen methylsiloxy units. They were 22.5 mol%, dimethylsiloxy unit 9.5 mol%, and cyclohexylmethylsiloxy unit 68.0 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (4b) was detected, and the total amount of the remaining volatile compounds was 0.002% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.006% by mass and 0.004% by mass, respectively. Other compounds were not detected. From this, the total amount of the low-boiling compounds remaining in the epoxy-modified silicone in the present invention is 0.01% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.01% by mass, and the remaining carbon -The total amount of the compound having a carbon double bond and an epoxy group is 0.01% by mass. The total amount of by-products generated by the internal transition of the carbon double bond was 0.004% by mass.
The epoxy value of the epoxy-modified silicone (4b) was 0.171, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 4b>
100 parts by mass of the resulting epoxy-modified silicone (4b), 28.7 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed under and stirred until the whole became uniform, and then defoamed to obtain a curable composition-4b. The curable composition-4b was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 2 shows the performance of the obtained cured product.

[Comparative Example 5]
<Manufacture 5b of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 14 was used in place of the block type organohydrogen silicone produced in Synthesis Example 1, and 114.7 g (923) of 4-vinylcyclohexene oxide was obtained. 0.7 mmol), using 287 g of tetrahydrofuran, and changing the amount of activated carbon used during the activated carbon treatment to 160 g. ) 50 g was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 92.35 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction when the catalyst was added was 1 / 159,041 times.

All terminal structures of the resulting epoxy-modified silicone (5b) have been modified to trialkylsiloxy groups by a hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 16.0 mol%, dimethylsiloxy unit 14.0 mol%, and cyclohexylmethylsiloxy unit 70.0 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (5b) was detected, and the total amount of the remaining volatile compounds was 0.003% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.005% by mass and 0.004% by mass, respectively. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.009% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.009% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.009% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.004% by mass.
The epoxy value of the epoxy-modified silicone (5b) was 0.129, the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 5b>
100 parts by mass of the resulting epoxy-modified silicone (5b), 21.7 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-5b. The curable composition-5b was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 130 ° C. for 2 hours, and further at 150 ° C. for 1 hour to obtain a cured product. . Table 2 shows the performance of the obtained cured product.

[Comparative Example 6]
<Manufacture 6b of epoxy-modified silicone>
In the hydrosilylation reaction, the block type organohydrogen silicone produced in Synthesis Example 15 was used in place of the block type organohydrogen silicone produced in Synthesis Example 1, and 166.1 g (1337) of 4-vinylcyclohexene oxide was used. .7 mmol), 307 g of tetrahydrofuran, and 165 g of activated carbon used in the activated carbon treatment were used in the same manner as in Example 1 except that the low-boiling compound was reduced. ) 54 g was obtained. The total number of moles of SiH units contained in the prepared block type organohydrogensilicone was 133.78 mmol.
When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.
At the start of the reaction, the total number of moles of all vinyl groups in the coexisting vinyl compound was 10 times the total number of moles of SiH units in the block type organohydrogensilicone.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms is the total number of moles of SiH units in the block-type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. On the other hand, the value at the end of the reaction in which the catalyst was added was 1 / 185,130 times, 1 / 185,130 times.

All terminal structures of the obtained epoxy-modified silicone (6b) are modified to trialkylsiloxy groups by hydrosilylation reaction, and the composition excluding the terminal groups is a unit in which vinylcyclohexene oxide is added to hydrogen methylsiloxy units. They were 23.0 mol%, dimethylsiloxy unit 16.5 mol%, and cyclohexylmethylsiloxy unit 60.5 mol%. As a result of measuring the molecular weight, the content of a peak having a molecular weight of 1,000 or less was 3%. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.
Only the tetrahydrofuran remaining in the epoxy-modified silicone (6b) was detected, and the total amount of the remaining volatile compounds was 0.003% by mass. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.006% by mass and 0.003% by mass, respectively. Other compounds were not detected. Thus, the total amount of the low boiling point compounds remaining in the epoxy-modified silicone in the present invention is 0.009% by mass, the total amount of the remaining compounds having a carbon-carbon double bond is 0.009% by mass, and the remaining carbon. -The total amount of the compound having a carbon double bond and an epoxy group is 0.009% by mass, the carbon of the compound (a) having a carbon-carbon double bond and an epoxy group added to be used for the remaining hydrosilylation reaction- The total amount of by-products generated by the internal transition of the carbon double bond was 0.003% by mass.
Further, the epoxy value of the epoxy-modified silicone (6b) was 0.175, and the transition metal component contained was only platinum, and the content of the component was 1 ppm or less in terms of platinum element.

<Manufacture of cured product and characteristic evaluation 6b>
100 parts by mass of the resulting epoxy-modified silicone (6b), 29.4 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate were added to nitrogen. The mixture was mixed at the bottom, stirred until the whole became uniform, and then defoamed to obtain a curable composition-6b. The curable composition-6b was poured into a mold having a depth of 3 mm under nitrogen, and cured at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and subsequently at 170 ° C. for 1 hour to obtain a cured product. . Table 2 shows the performance of the obtained cured product.

[Production Example 1]
The curable composition-1a obtained in Example 1 was poured into a bullet-shaped mold mold having a diameter of 4 mm, and a lead frame on which a light-emitting element having an emission wavelength of 400 nm was fixed was immersed therein and removed in a vacuum. After foaming, a curing reaction was performed at 120 ° C. for 1 hour, further at 150 ° C. for 2 hours, and at 170 ° C. for 1 hour to obtain a light emitting diode. Even when the light-emitting diode obtained by this operation was energized at 50 mA at room temperature for 200 hours, peeling between the element and the sealing portion and reduction in luminance were not observed.

[Production Example 2]
A light emitting diode was obtained in the same manner as in Production Example 1 using the curable composition-4a obtained in Example 4. Even when the light-emitting diode obtained by this operation was energized at 50 mA at room temperature for 200 hours, peeling between the element and the sealing portion and reduction in luminance were not observed.

[Production Example 3]
Except that the curable composition-11a obtained in Example 11 was used and the curing conditions were 120 ° C. for 1 hour, 140 ° C. for 2 hours and 160 ° C. for 1 hour, the same method as in Production Example 1 A light emitting diode was obtained. Even when the light-emitting diode obtained by this operation was energized at 50 mA at room temperature for 200 hours, peeling between the element and the sealing portion and reduction in luminance were not observed.

[Production Example 4]
Using the curable composition-13a obtained in Example 11, a light-emitting diode was obtained in the same manner as in Production Example 1. Even when the light-emitting diode obtained by this operation was energized at 50 mA at room temperature for 200 hours, peeling between the element and the sealing portion and reduction in luminance were not observed.

  According to the present invention, it is possible to provide a method for stably and reproducibly producing an epoxy-modified silicone having transparency, light resistance, heat resistance, and crack resistance and suitable for use in a light emitting device sealing material. It becomes possible.

Claims (11)

In the presence of a hydrosilylation catalyst, a carbon-carbon double bond and an epoxy group with respect to a block-type organohydrogensilicone represented by the following average composition formula (1) that simultaneously satisfies the following <A> and <B> requirements: When vinyl compound (b) containing a compound (a) having a hydrogen atom is added by a hydrosilylation reaction to produce an epoxy-modified silicone, the total vinyl of the vinyl compound (b) to be coexisted with respect to the total number of moles of SiH units A method for producing an epoxy-modified silicone, wherein the total number of moles of groups is 5 to 100 times.
<A>: The average chain length of (R ¹ ₂ SiO _2/2 ) units is 3 or more and 100 or less.
<B>: The average chain length of (R ¹ HSiO _2/2 ) units is 2 or more and 20 or less.
(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ HSiO _1/2 ) _b (R ¹ ₂ SiO _2/2 ) _c
(R ¹ HSiO _2/2 ) _d (R ¹ SiO _3/2 ) _e (HSiO _3/2 ) _f (SiO _4/2 ) _g (1)
[However, each R ¹ independently represents a fat having at least one structure selected from the group consisting of A) hydroxyl group, B) halogen atom, C) unsubstituted or substituted chain, branched and cyclic. A monovalent or divalent aliphatic organic group having an aromatic hydrocarbon unit and having a carbon number of 1 to 24 and an oxygen number of 0 to 5, D) an unsubstituted or substituted aromatic hydrocarbon unit, , Having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of a chain, a branched chain and a ring, which are unsubstituted or substituted as necessary, having 6 to 24 carbon atoms and an oxygen number Represents at least one organic group selected from the group consisting of monovalent aromatic organic groups of 0 or more and 5 or less.
The above organic group has a hydroxyl group, an alkoxy group, an acyl group, a carboxyl group, an alkenyloxy group, an acyloxy group, a halogen atom, or an ester bond as long as it is within the range of the carbon number and oxygen number. May be included. Moreover, the hetero atom except oxygen may be included.
Moreover, a, b, c, d, e, f, and g in the average composition formula (1) represent the number of moles of each unit present in 1 mole of the organohydrogensilicone, and a, b, e, f, Each g is 0 or more, c is 3 or more, and d is 2 or more.
Further, when e, f, and g satisfy the following expressions (1) and (2), respectively, a, b, e, f, and g satisfy the expression (3). It is a numerical value selected from the range.
e + f ≠ 0 Formula (1)
g ≠ 0 Formula (2)
0 ≦ a + b ≦ e + f + 2g + 2 Formula (3)
Further, when the above e, f, and g satisfy the following formulas (4) and (5), respectively, the above a and b are numerical values selected from the range satisfying the following formula (6). It is.
e + f = 0 Formula (4)
g = 0 Formula (5)
0 ≦ a + b ≦ 2 Formula (6)
When the above e, f, and g satisfy the following formulas (1) and (5), respectively, the above a and b are numerical values selected from the range that satisfies the following formula (7). It is.
e + f ≠ 0 Formula (1)
g = 0 Formula (5)
0 ≦ a + b ≦ e + f + 2 Formula (7)
Furthermore, when e, f, and g satisfy the following expressions (4) and (2), respectively, a and b are numerical values selected from a range that satisfies the following expression (8). .
e + f = 0 Formula (4)
g ≠ 0 Formula (2)
0 ≦ a + b ≦ 2g + 2 (formula (8))   The number of Si bonded to a monovalent aliphatic organic group having 5 to 20 carbon atoms and having a hydrocarbon unit composed of one or more structures selected from a chain, branched, and cyclic structure group is the total Si The method for producing an epoxy-modified silicone according to claim 1, wherein the content is in the range of 5% to 95%. The average chain length of the (R ¹ HSiO _2/2 ) unit of the organohydrogensilicone represented by the average composition formula (1) is 2.2 or more and less than 5, Production method of epoxy-modified silicone.   The value of (b + d + f) / (a + b + c + d + e + f + g) of the block type organohydrogen silicone represented by the average composition formula (1) is in the range of 0.100 or more and 0.800 or less. The manufacturing method of the epoxy-modified silicone of any one.   The block-type organohydrogen silicone represented by the average composition formula (1) has a value of (e + f + g) of zero, wherein the epoxy-modified silicone according to any one of claims 1 to 4 is produced. Method.   The block-type organohydrogensilicone represented by the average composition formula (1) has a value of b / (a + b) of 0.5 or more, according to any one of claims 1 to 5. Production method of epoxy-modified silicone.   The content of the component having a molecular weight of 1,000 or less contained in the block-type organohydrogensilicone represented by the average composition formula (1) is 15% or less. The manufacturing method of the epoxy-modified silicone as described in a term.   SiH in which a compound (a) having a carbon-carbon double bond and an epoxy group is added to the total number of moles of SiH units of the block-type organohydrogensilicone represented by the average composition formula (1) by a hydrosilylation reaction. The method for producing an epoxy-modified silicone according to any one of claims 1 to 7, wherein the mole fraction of units is 70% or more.   The number of moles in terms of metal atom of the catalyst used when the hydrosilylation reaction is performed is based on the total number of moles of SiH units in the block type organohydrogensilicone represented by the average composition formula (1) before the hydrosilylation reaction. The method for producing an epoxy-modified silicone according to any one of claims 1 to 8, wherein the range is from 1 / 5,000,000 to 1 / 1,200.   After the vinyl compound (b) containing the compound (a) having a carbon-carbon double bond and an epoxy group is added to the SiH unit of the organohydrogen silicone represented by the average composition formula (1) by a hydrosilylation reaction. The method for producing an epoxy-modified silicone according to any one of claims 1 to 9, further comprising a step of subjecting the mixture to a temperature of 0 ° C to 200 ° C to separate and recover the epoxy-modified silicone.   11. The epoxy modification according to claim 1, wherein the number of residual SiH units with respect to the total number of Si contained in the epoxy-modified silicone to be subjected to the separation and recovery step is 2% or less. Production method of silicone.