JP2007302825A - Epoxy-modified silicone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy-modified silicone usable in applications such as light-emitting device sealing materials for which transparency, heat resistance, light resistance and heat discoloration resistance are required, and to provide a method for producing the epoxy-modified silicone. <P>SOLUTION: The epoxy-modified silicone is such as to be obtained by adding an epoxy group-bearing vinyl compound to the SiH units of an organohydrogensilicone by hydrosilylating reaction. In this epoxy-modified silicone, the residual amount of a C=C bond-bearing compound is 2 mass% or less. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an epoxy-modified silicone useful as a light-emitting device sealing agent and a method for producing the same.

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 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.

  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, the epoxy-modified silicone is produced by adding a compound containing a vinyl compound having an epoxy group and an alkene having 6 or more carbon atoms to the organohydrogensilicone by a hydrosilylation reaction. A method is disclosed.
Japanese Patent Laid-Open No. 5-105758 JP-A-7-18078

However, as disclosed in Patent Document 1 and Patent Document 2, an epoxy-modified silicone produced by adding a vinyl compound having an epoxy group to an organohydrogen silicone by a hydrosilylation reaction has a cured product that is light or light. There is a problem that it is easily colored or discolored by heat, and improvement of this point is required for use in applications where transparency is required, such as a sealant for a light emitting element.
Then, an object of this invention is to provide the epoxy modified silicone with few coloring and discoloration by light and a heat | fever, and its manufacturing method.

As a result of intensive studies to solve the above problems, the present inventors have obtained light and heat from a cured product of an epoxy-modified silicone produced by adding a vinyl compound having an epoxy group to an organohydrogen silicone by a hydrosilylation reaction. It has been found that coloring and discoloration due to carbon is due to a compound having a carbon-carbon double bond, and that coloring and discoloration can be prevented by making the residual amount below a certain value, leading to the completion of the present invention. It was.
That is, the present invention is as follows.
An epoxy-modified silicone obtained by adding a vinyl compound having an epoxy group to a SiH unit of an organohydrogensilicone by a hydrosilylation reaction, wherein the residual amount of the compound having a carbon-carbon double bond is changed to the epoxy-modified silicone. Epoxy-modified silicone that is 2% by mass or less.

Also in the prior art, unreacted components of the solvent and vinyl compound are distilled off under heating and reduced pressure conditions.
However, an epoxy-modified silicone obtained by adding a vinyl compound to an organohydrogen silicone by a hydrosilylation reaction becomes a viscous product. It is difficult to completely distill off low molecular weight components from such a viscous material. For example, when a vertical stirring tank is used, with increasing scale, the ratio of the evaporation area to the liquid volume usually decreases and the liquid depth increases. For this reason, even if the degree of vacuum is increased, the lower part of the stirring tank has a liquid depth, so that the pressure is substantially high and it is difficult to efficiently distill off the low molecular weight component.
For this reason, simple distillation such as that performed in the prior art does not actually sufficiently remove unreacted components of the vinyl compound.

Furthermore, when the present inventors investigated in detail about the hydrosilylation reaction of organohydrogensilicone and a vinyl compound, as a side reaction, the vinyl group of the vinyl compound undergoes internal transfer, has a higher boiling point than the vinyl compound, and the hydrosilylation reaction. It has been found that by-products are produced that are very insensitive to. Such a by-product has a carbon-carbon double bond, but is difficult to evaporate due to its high boiling point.
For this reason, the above-mentioned by-products are not distilled off only by performing distillation for the unreacted portion of the solvent or vinyl compound as in the past, and as a result, in the epoxy-modified silicone, A compound with many carbon-carbon double bonds remains.

Thus, in the prior art which does not pay special attention to the residual amount of the compound having a carbon-carbon double bond, a compound having many carbon-carbon double bonds remains in the epoxy-modified silicone.
On the other hand, in the present invention, paying attention to the compound having a carbon-carbon double bond in the epoxy-modified silicone, the raw material to be used, or when distilling off, so that the residual amount becomes a specific value or less. By selecting operating conditions such as temperature, pressure, time, etc., the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone vinyl compound is reduced, and thereby the light resistance and heat discoloration resistance of the cured product are reduced. Improved.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the epoxy modified silicone suitable for the light emitting element sealing material use which has transparency and heat resistance, and there are few coloring and discoloration by light and a heat | fever, and its manufacturing method.

Hereinafter, the present invention will be described in detail.
The epoxy-modified silicone of the present invention preferably has an epoxy value in the range of 0.15 to 0.5.
Here, the epoxy value in the present invention refers to the number of epoxy units present in 100 g of the epoxy-modified silicone, and is specifically 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.
Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W)
[W, V, N, and F represent the following values, respectively.
W: Mass 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 epoxy-modified silicone of the present invention is used as a cured product, it is preferable that the epoxy value of the epoxy-modified silicone is 0.15 or more because the heat resistance of the cured product is increased. Furthermore, in order to increase the strength of the cured product and avoid damage to the surface during mounting or use, the epoxy value is more preferably 0.17 or more, further preferably 0.19 or more, 0 .21 or more is particularly preferable.
On the other hand, since the light resistance of the cured product obtained using the epoxy-modified silicone of the present invention increases, the epoxy value of the epoxy-modified silicone is preferably 0.5 or less, more preferably 0.48 or less, and 46 or less is further preferable, and 0.44 or less is particularly preferable.

The epoxy-modified silicone in the present invention is preferably obtained by adding a vinyl compound having an epoxy group to the SiH unit of the organohydrogen silicone represented by the average composition formula (1).
[Wherein R ¹ independently represents an aliphatic carbonized group comprising 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 a hydrogen unit and having 1 to 24 carbon atoms and 0 to 5 oxygen atoms, and D) an unsubstituted or substituted aromatic hydrocarbon unit, which is necessary And having an aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of a chain, a branched chain and a ring, which are unsubstituted or substituted according to the above, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. It represents at least one organic group selected from the group consisting of the following monovalent aromatic organic groups.
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 above 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 repeating unit present in 1 mole of the organohydrogensilicone, and a, b, c, d , E, f, and g are numerical values of 0 or more, respectively, and b, d, and f are numerical values that satisfy the following formula (1).
b + d + f> 0 Formula (1)

When the above c, d, e, f, and g satisfy the following equations (2), (3), and (4), respectively, a, b, e, f, and g are , A numerical value selected from a range satisfying the formula (5).
c + d ≠ 0 Formula (2)
e + f ≠ 0 Formula (3)
g ≠ 0 Formula (4)
0 ≦ a + b ≦ e + f + 2g + 2 Formula (5)

Furthermore, when the above e, f, and g satisfy the following formula (6) and formula (7), respectively, the above a and b are numerical values selected from the range satisfying the following formula (8). is there.
e + f = 0 Formula (6)
g = 0 Formula (7)
0 ≦ a + b ≦ 2 Formula (8)

In addition, when the above e, f, and g satisfy the following equations (3) and (7), respectively, the above a and b are numerical values selected from the range that satisfies the following equation (9). is there.
e + f ≠ 0 Formula (3)
g = 0 Formula (7)
0 ≦ a + b ≦ e + f + 2 Equation (9)

Furthermore, when e, f, and g simultaneously satisfy the following mathematical formulas (6) and (4), a and b are numerical values selected from a range that satisfies the following mathematical formula (10).
e + f = 0 Formula (6)
g ≠ 0 Formula (4)
0 ≦ a + b ≦ 2g + 2 Formula (10)

  The structure of the organohydrogensilicone represented by the average composition formula (1) is not particularly limited as long as an epoxy-modified silicone can be produced after adding a vinyl compound having an epoxy group by hydrosilylation reaction. The structure may be any shape such as a ring shape, a ring shape, a branched shape, a ladder shape, and a bowl shape, and may be a mixture of two or more of these. Further, each structural unit may have a block-like chain structure, may be randomly dispersed, or a mixture thereof.

The organic group R ¹ is a carbon selected from the group consisting of chain, branched and cyclic with respect to the total number of moles of all Si units from the viewpoint of improving the light resistance or stability of the epoxy-modified silicone obtained by the present invention. -Organic compounds containing carbon double bond hydrocarbon units, hydroxyl units, alkoxy units, acyl units, carboxyl units, alkenyloxy units, acyloxy units, halogen atoms, or ester bonds, and also heteroatoms other than oxygen and silicon The total number of moles of silicon atoms to which groups are bonded is preferably selected to be 30% or less, more preferably 10% or less, even more preferably 1% or less, and particularly preferably not contained at all.

Furthermore, the organic group R ¹ is a saturated monovalent group having 1 to 20 carbon atoms and 1 or less oxygen atoms having a hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic. The aliphatic organic group is desirable. Examples of such an organic group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. A chain organic group composed of hydrocarbon 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; 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.
Among these, a chain organic group made of hydrocarbon and an organic group made of hydrocarbon containing a cyclic unit are particularly desirable.

  The number of moles of each repeating unit constituting 1 mole of the organohydrogensilicone represented by the average composition formula (1) is such that the values of c and d are 5,000 or less in order to improve the solubility in a solvent. It is preferable that e, f each satisfy the range of 100 or less, and g is the range of 100 or less at the same time. The hydrosilylation reaction can be stably performed with good reproducibility by reducing steric hindrance. In order to proceed, it is preferred that g is 0, g is 0, and (e + f) / (a + b + c + d + e + f) is more preferably 0.02 or less, g is 0, and (e + f) / ( It is more preferable that (a + b + c + d + e + f) is 0.01 or less, and it is particularly preferable that the values of g and (e + f) / (a + b + c + d + e + f) are zero.

  The epoxy-modified silicone of the present invention is produced by adding a vinyl compound having an epoxy group to the SiH unit of the organohydrogen silicone.

  The vinyl compound having an epoxy group that can be used in the present invention is not particularly limited. For example, 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, glycidyl methacrylate, glycidyl acrylate, 4-vinylcyclohexene oxide, 1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethyl-4-vinylcyclohexene oxide, vinyl norbornene oxide, etc. Can be mentionedThese can be used as one kind or a mixture of two or more kinds.

Among these, it is preferable to use an epoxycycloalkane having a vinyl group represented by the following chemical formula (2) because the curing rate of the epoxy-modified silicone and the light resistance of the cured product are increased.
[Wherein 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 (2) include 4-vinylcyclohexene oxide, 1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethyl-4-vinylcyclohexene oxide, vinyl norbornene oxide, and the like. Preferably, 4-vinylcyclohexene oxide is used.

  In the present invention, if an epoxy-modified silicone can be produced, a vinyl compound other than a vinyl compound having an epoxy group may be added to the organohydrogen silicone by a hydrosilylation reaction.

As such a vinyl compound other than the vinyl compound having an epoxy group, for example,
(A) An aliphatic hydrocarbon unit that does not contain an epoxy group, has a vinyl group as an essential constituent unit, and has one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic group A compound having 3 to 24 carbon atoms and an oxygen number of 0 to 5
(A) An aromatic hydrocarbon unit that does not contain an epoxy group and has a vinyl group as an essential constituent unit, and an unsubstituted or substituted aromatic hydrocarbon unit, and an optionally substituted or substituted chain, branched, or cyclic A compound having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of carbon number of 8 to 24 and oxygen number of 0 to 5;
(C) a silane containing one or more vinyl groups without containing an epoxy group in the molecule represented by the following chemical formula (3);
[However, each R ³ is independently a carbon having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of a) a halogen atom, b) an unsubstituted or substituted chain, branched, and cyclic group. A monovalent and / or divalent aliphatic organic group having a number of 1 to 10 and an oxygen number of 0 to 5, or c) an unsubstituted or substituted aromatic hydrocarbon unit, and optionally A monovalent monovalent carbon having 6 to 10 carbon atoms and an oxygen number of 0 to 5 and having an aliphatic hydrocarbon unit of one or more structures selected from the group consisting of substituted or substituted chain, branched and cyclic groups It represents at least one organic group selected from the group consisting of aromatic 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 no epoxy group in the molecule represented by the following average composition formula (4) and containing one or more vinyl groups,
[Wherein R ⁴ is independently a monovalent aliphatic group having at least one structure selected from the group consisting of a) a vinyl group, b) a chain, branched, or cyclic group having 1 to 10 carbon atoms. An organic group, c) an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted aromatic hydrocarbon unit and an optionally substituted or substituted chain, branched or cyclic group A monovalent aromatic organic group having 6 to 10 carbon atoms and 0 to 5 oxygen atoms having a hydrogen unit. Here, at least one of R4 is an organic group having a vinyl group.
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 the average composition formula (4), p, q, r, and s represent the number of moles of each repeating unit present in 1 mole of siloxane containing one or more vinyl groups in the molecule, and 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 never zero at the same time.

In addition, when q, r, and s satisfy the following formula (11), formula (12), and formula (13), respectively, p, r, and s satisfy formula (14). A number selected from a range.
q ≠ 0 Formula (11)
r ≠ 0 Formula (12)
s ≠ 0 Formula (13)
0 ≦ p ≦ r + 2s + 2 Equation (14)

Furthermore, when the above r and s satisfy the following mathematical expressions (15) and (16), the above p is a numerical value selected from the range satisfying the following mathematical expression (17).
r = 0 Formula (15)
s = 0 Formula (16)
0 ≦ p ≦ 2 Equation (17)

Moreover, when said r and s satisfy | fill the following numerical formula (12) and numerical formula (16) simultaneously, said p and r are numerical values selected from the range which satisfies numerical formula (18), respectively.
r ≠ 0 Formula (12)
s = 0 Formula (16)
0 ≦ p ≦ r + 2 Equation (18)

Further, when r and s satisfy the following expressions (15) and (13), respectively, p and r are numerical values selected from a range satisfying the expression (19).
r = 0 Formula (13)
s ≠ 0 Formula (15)
0 ≦ p ≦ 2s + 2 Equation (19)

  The siloxane containing one or more vinyl groups 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, ladder-like, Any structure such as a shape may be used, and 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. 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 above ranges. Heteroatoms such as nitrogen, phosphorus and sulfur other than atoms may be contained.

  Specific examples of the above (a) include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1 -Tridedecene, 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 Pills ether, allyl methyl ether, allyl ethyl ether, allyl propyl ether, and the like methoxy polyethylene glycol allyl ether (polymerization degree of 1 to 4 ethylene glycol units) and the like. These can be used as one kind or a mixture of two or more kinds.

  On the other hand, specific examples of (i) include styrene, 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.

  Specific examples of (c) include, for example, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinyltriisopropoxysilane, Aliphatic vinylalkoxysilane having one vinyl group such as vinyltri-t-butoxysilane and vinyltriisopropenoxysilane; one vinyl group such as vinylphenylmethylmethoxysilane, vinylphenyldiethoxysilane and vinyldiphenylethoxysilane Aliphatic vinyl alkoxysilane having two or more vinyl groups such as aromatic vinylalkoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, trivinylmethoxysilane, and trivinylethoxysilane. Aromatic vinylalkoxysilane having two or more vinyl groups such as divinyldiphenoxysilane and trivinylphenoxysilane; vinyltrimethylsilane, vinylethyldimethylsilane, vinyldiethylmethylsilane, vinyltriethylsilane, vinyltripropylsilane, vinyl Triisopropylsilane, vinyltributylsilane, vinyltri-t-butylsilane, vinyl-t-butyldimethylsilane, vinyltripentylsilane, vinyltrihexylsilane, vinyltricyclohexylsilane, vinyltriheptylsilane, vinyltrioctylsilane, vinyltrinonyl Vinylalkylsilanes having one vinyl group such as silane, vinyltridecylsilane, vinylmethylsilacyclopentane, etc .; vinylphenyldimethylsilane, vinylphenol Vinyl arylsilanes having one vinyl group such as rudiethylsilane, vinyldiphenylmethylsilane, vinyltriphenylsilane, vinyltritolylsilane; vinylbenzyldimethylsilane, vinylbenzyldiethylsilane, vinyldibenzylmethylsilane, vinyltribenzylsilane Vinyl aralkyl silane having one vinyl group such as vinyltriphenethylsilane; vinylalkyl having two or more vinyl groups such as divinyldimethylsilane, divinyldiethylsilane, divinylethylmethylsilane, trivinylmethylsilane, trivinylethylsilane Silane; vinylarylsilane having two or more vinyl groups such as divinyldiphenylsilane, divinylditolylsilane, trivinylphenylsilane, trivinyltolylsilane; vinyl (chloro A vinyl halo-substituted alkylsilane having a halogen-substituted hydrocarbon group having one vinyl group, such as methyl) dimethylsilane, vinyl (trifluoromethyl) dimethylsilane, vinyl (3,3,3-trifluoropropyl) dimethylsilane; Vinyldimethylfluorosilane, vinyldimethylchlorosilane, vinylmethyldichlorosilane, vinyltrichlorosilane, vinylethyldichlorosilane, vinyloctyldichlorosilane, vinyl (bromomethyl) dichlorosilane, vinylphenyldichlorosilane, vinyldiphenylchlorosilane, vinylphenylmethylchlorosilane, etc. A vinyl halosilane having one vinyl group and at least one halogen atom bonded to a silicon atom; a vinyl group such as divinyldichlorosilane or trivinylchlorosilane; A FOB, a halogen atom and vinyl halo silane bonded to the silicon atom. Silanes containing one or more vinyl groups in these molecules can be used as one kind or a mixture of two or more kinds.

Furthermore, b) Specific examples of the monovalent aliphatic organic group having at least one structure selected from the group consisting of a chain, a branched chain, and a ring having 1 to 10 carbon atoms in the organic group R ⁴ of (d) Examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n- A saturated hydrocarbon group such as a nonyl group, a cyclohexyl group, a methylcyclohexyl group or a norbornyl group; a saturated hydrocarbon group substituted with a halogen atom such as a chloromethyl group or a 3,3,3-trifluoropropyl group; Carbon having an unsubstituted or substituted aromatic hydrocarbon unit and an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of a linear, branched, or cyclic group that is unsubstituted or substituted as necessary number Specific examples of the monovalent aromatic organic group having 10 or less and an oxygen number of 0 or more and 5 or less include, for example, aromatic hydrocarbon groups such as phenyl group, tolyl group and benzyl group; 4-chlorobenzyl group and the like An aromatic hydrocarbon group substituted with a halogen atom and the like can be mentioned.

  Of these, from the viewpoint of improving light resistance, hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, aromatic hydrocarbon unit, halogen atom, ester bond, and oxygen atom (A), (U), and (E) that do not contain a heteroatom other than are preferably used.

As (a), 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene is used from the viewpoint of improving the handleability of the vinyl compound or from the viewpoint of facilitating the distillation of the excess compound. 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, as (c), vinyltrimethylsilane, vinylethyldimethylsilane, vinyldiethylmethylsilane, and vinyltriethylsilane are more preferably used because it makes it easy to distill off excess compounds.

In addition, as (d), q is in the range of 50 or less, and r is 10 or less because it is easy to relieve steric hindrance and facilitate the hydrosilylation reaction with good reproducibility. And s preferably satisfies the range of 10 or less simultaneously, more preferably s is zero, q is a range of 20 or less, r is a range of 5 or less, s is zero, and r / (P + q + r) is more preferably 0.02 or less, q is 15 or less, r is 3 or less, s is zero, and r / (p + q + r) is 0.01 or less Particularly preferred are those in which q is in the range of 10 or less and the values of s and r / (p + q + r) are zero.
For example, a siloxane having a dimethylvinylsiloxy group at one end of a molecular chain such as vinylpentamethyldisiloxane or vinylheptamethyltrisiloxane and the other substituent is an alkyl group; vinylmethylbis (trimethylsiloxy) silane Such as a siloxane having a dimethylvinylsiloxy group in the molecular chain, one vinyl group in the molecule, and the other substituent being a saturated hydrocarbon group; 1,3-divinyl-tetramethyldisiloxane, etc. Siloxane having two vinyl groups in the molecule in which both ends are dimethylvinylsiloxy groups and the other substituent is a saturated hydrocarbon group; 1,3,5-trivinyl-1,1,3,5,5 -Pentamethyltrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane tris (vinyldimethylsiloxy) Molecules such as methylsilane, 1.3.5.7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1.3.5.7-tetravinyl-1,3,5,7-tetraethylcyclotetrasiloxane, etc. Examples thereof include siloxane containing 3 or more vinyl groups and other organic groups being saturated hydrocarbon groups.

  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 to be subjected to the hydrosilylation reaction,
(Iii) a by-product generated when a carbon-carbon double bond in the vinyl compound added to be subjected to the hydrosilylation reaction undergoes an internal transition during the hydrosilylation reaction,
Etc.

  Specific examples of the impurities having a carbon-carbon double bond contained in the vinyl compound added for the (ii) hydrosilylation reaction include 4-epoxy contained in 4-vinylcyclohexene oxide. And ethyl-cyclohexene.

The (iii) by-product produced by the internal transition 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 or the like is used, and for example, vinylcyclohexane is used as the vinyl compound. Examples of by-products include ethylidenylcyclohexane.
Furthermore, as a vinyl compound, for example, (a-1) 4-vinylcyclohexene oxide, (a-2) 1-methyl-4-isopropenylcyclohexene oxide, (a-3) 1,4-dimethyl-4-vinylcyclohexene oxide (A-4) When an epoxycycloalkane having a vinyl group such as vinyl norbornene oxide is used, as by-products corresponding to (a-1) to (a-4), (b-1) 4-ethylidenylcyclohexene oxide, (b-2) 1-methyl-4-isoproperenyl cyclohexene oxide, (b-3) 1,4-dimethyl-4-ethylidenylcyclohexene oxide, (b-4) ethyl Examples include lidenyl norbornene oxide.

In the present invention, the residual amount of the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone needs to be 2% by mass or less based on the epoxy-modified silicone.
Here, when the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone is composed of two or more components, the residual amount of the compound having a carbon-carbon double bond in the present invention is the residual amount. This means the total value of each component.
When the residual amount of the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone exceeds 2% by mass with respect to the epoxy-modified silicone, when the epoxy-modified silicone is used as a cured product, the cured product becomes light or heat. Color and discolor by.

  Furthermore, in order to further improve the light resistance and heat discoloration of the epoxy-modified silicone, the residual amount of the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone is 1.5% by mass or less. Is preferably 1% by mass or less, more preferably 0.75% by mass or less, particularly preferably 0.5% by mass or less, and 0.3% by mass or less. Is desirable.

  The residual amount of the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone is better, but setting the residual amount to 0 is more effective in reducing coloring and discoloration than time and labor are required. Is small. Therefore, from the viewpoint of cost effectiveness, it is realistic that the residual amount of the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone is reduced to about 0.003% by mass.

In addition, among the compounds having carbon-carbon double bonds remaining in the epoxy-modified silicone, the residual amount of the compound having an epoxy group is reduced in the epoxy-modified silicone in order to reduce coloring and discoloration of the cured product by light and heat. On the other hand, it is preferably 1.5% by mass or less, more preferably 1% by mass or less, further preferably 0.6% by mass or less, and particularly preferably 0.3% by mass or less. .
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.

Furthermore, among the compounds having a carbon-carbon double bond remaining in the epoxy-modified silicone, a carbon-carbon double bond of a vinyl compound having an epoxy group added for use in the hydrosilylation reaction is caused by internal transition. The residual amount of the by-product is preferably 0.5% by mass or less, and 0.3% by mass or less with respect to the epoxy-modified silicone in order to reduce coloring and discoloration of the cured product due to light and heat. Is more preferable.
Here, when there are two or more by-products generated in the carbon-carbon double bond of the vinyl compound having an epoxy group added to be used for the hydrosilylation reaction remaining in the epoxy-modified silicone and causing internal transition. The residual amount of the by-product generated by the internal transition of the carbon-carbon double bond of the vinyl compound having an epoxy group added for the hydrosilylation reaction is the total amount of each remaining component. means.

In the epoxy-modified silicone of the present invention, there may be a case where the hydrosilylation catalyst used at the time of manufacture or the metal component eluted from the reaction apparatus remains. For example, when SUS316 alloy is used, metal elements such as Fe, Ni, Cr, and Mo may be eluted. In order to maintain the light resistance of the cured product of the epoxy-modified silicone at a high level, the residual amount of the transition metal component corresponding to Group 3 to Group 11 of the periodic table with respect to the epoxy-modified silicone is 20 ppm or less in terms of element. It is preferably 10 ppm or less, more preferably 5 ppm or less.
In addition, when there are two or more transition metal components remaining, the residual amount of the transition metal component means the total value of the residual amounts of the respective components.

  In the epoxy-modified silicone of the present invention, the solvent used during production may remain. In order to suppress the generation of bubbles in the cured product of the epoxy-modified silicone, the amount of the remaining solvent is preferably 0.1% by mass or less, and 0.08% by mass or less based on the epoxy-modified silicone. Is more preferable, and it is further more preferable that it is 0.06 mass% or less.

There is no limitation in particular in the manufacturing method of the organohydrogen silicone represented by average compositional formula (1), For example, a conventionally well-known method, for example,
(C-1) Hydrolysis of alkoxysilanes and / or chlorosilanes containing at least SiH units and having other organic groups as required in the presence or absence of a catalyst, and if necessary, polycondensation And / or a method of sealing the terminal in the presence of a terminal sealing agent represented by hexamethyldisiloxane, 1,1,3,3-hexamethyldisiloxane, and the like,
(C-2) Silicone having SiH units obtained by hydrolysis of alkoxysilanes and / or chlorosilanes having at least SiH units, if necessary, in the presence or absence of a catalyst, if necessary Polycondensation and / or A and silicone B having SiH units obtained by hydrolyzing alkylalkoxysilanes and / or chlorosilanes in the presence or absence of a catalyst. A method of sealing the ends in the presence of a terminal blocking agent represented by hexamethyldisiloxane, 1,1,3,3-hexamethyldisiloxane, etc., if necessary after re-equilibration by a siloxane exchange reaction ,
(C-3) Hexamethyldisiloxane in the presence of silicone having at least one structure selected from the group consisting of cyclic, chain, and branched, containing at least SiH units and having other organic groups as necessary. A method of re-equilibrating by ring-opening polymerization and / or siloxane exchange reaction in the presence or absence of a terminal capping agent represented by 1,1,3,3-tetramethyldisiloxane and the like in the presence of a catalyst,
(C-4) Subsequent to the method described in (c-1) to (c-3) above, or (c-5) the method described in (c-4) above, or (c-5) A method for further separating and purifying the components recovered by distillation,
Etc. can be manufactured.

  In the present invention, when adding a vinyl compound having an epoxy group to the SiH unit of the organohydrogensilicone by a hydrosilylation reaction, it is preferable to add a hydrosilylation catalyst. In the absence of a hydrosilylation catalyst, the hydrosilylation reaction between the SiH unit of the organohydrogensilicone and the vinyl compound is usually slow.

Examples of the hydrosilylation catalyst that can be used in the present invention include those in Periodic Table 8
Examples thereof include simple metals belonging to the genus, those obtained by supporting these metal solids on a carrier such as alumina, silica, and carbon black, and salts and complexes of these metals. As the metal of Group 8 of the periodic table, platinum, rhodium, and ruthenium are preferable, and platinum is particularly preferable. Examples of the hydrosilylation reaction catalyst using platinum include chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, and ketone complexes, platinum-vinylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, and dicarbonyl. Examples include dichloroplatinum and dicyclopentadienyldichloroplatinum.
The amount of catalyst is not particularly limited because it varies greatly depending on the type of organohydrogensilicone, vinyl compound, and solvent represented by the average composition formula (1), but is usually a periodic table with respect to the mass of the organohydrogensilicone. The metal atom of Group 8 is used in the range of 1 ppm to 1,000 ppm. When the amount of catalyst is less than 1 ppm, the hydrosilylation reaction may not proceed. On the other hand, when the amount exceeds 1,000 ppm, the vinyl compound having a vinyl group and an epoxy group subjected to the hydrosilylation reaction may be significantly modified. There is. In order to perform the hydrosilylation reaction at a reproducible rate and / or to produce a polyorganosiloxane containing an organic functional group with good reproducibility, it is preferably in the range of 2 ppm to 500 ppm, more preferably 3 ppm to 100 ppm. The range is more preferably 5 ppm or more and 50 ppm or less.

  In the present invention, the reaction temperature at the time of hydrosilylation reaction is the type and molecular weight of organohydrogen silicone, the type of vinyl compound having an epoxy group, and further, batch type, semi-batch type, continuous type, etc. Although it varies depending on the reaction mode, there is no particular limitation, but in order to increase the reaction rate and complete the reaction efficiently, a range of 0 ° C to 150 ° C is preferable, and a range of 10 ° C to 140 ° C is more preferable. The range of 20 ° C. or higher and 130 ° C. or lower is more preferable, and the range of 30 ° C. or higher and 120 ° C. or lower 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 during the reaction.

  In the present invention, when the hydrosilylation reaction is performed, the heat of reaction due to the hydrosilylation reaction is removed to suppress excessive modification of the resulting epoxy-modified silicone, or to suppress an increase in the viscosity of the reaction system due to the addition reaction. It is preferable to use a solvent.

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, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as hexane, cyclohexane, heptane, octane, and isooctane; toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene Aromatic hydrogen solvents such as: Ester solvents such as ethyl acetate and butyl acetate; Alcohols such as butyl cellosolve and butyl carbitol System solvents. These solvents can be used as one kind or a mixture of two or more kinds.
Of these, ether solvents, ketone solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents are preferred from the viewpoints of improving hydrosilylation reaction rate, solubility of raw materials and / or solvent recoverability, and ethers. More preferred is a solvent containing 50% by mass or more of a system solvent, and at least one or more selected from the group consisting of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether having a boiling point of 110 ° C. or less at atmospheric pressure. The mixed solvent is more preferable.

  The amount of the solvent varies depending on the type of organohydrogensilicone, the type of vinyl compound, etc., and is not particularly limited. Usually, the total mass of the organohydrogensilicone and vinyl compound relative to the total mass of the reaction system is 0.01. The amount is in the range of from mass% to 99 mass%, preferably from 5 mass% to 80 mass%, more preferably from 10 mass% to 70 mass%. When the total mass of the organohydrogensilicone and the vinyl compound with respect to the total mass is less than 0.01% by mass, the hydrosilylation reaction rate tends to decrease, whereas when it exceeds 99% by mass, the reaction heat It may be difficult to remove heat, and the epoxy-modified silicone obtained by local heating may be modified.

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 an inert gas or a lower saturated hydrocarbon gas having 1 to 4 carbon atoms, more preferably an inert gas, and still more preferably nitrogen.

  In the present invention, the reaction method for carrying out the hydrosilylation reaction is not particularly limited. For example, the organohydrogensilicone represented by the average composition formula (1) and the vinyl compound having an epoxy group are batch-type, semi-batch. Examples include a method of reacting sequentially, continuously, or at a time depending on a method of combination of one or more selected from the group of formula and continuous. Further, when the vinyl compound having an epoxy group is composed of a plurality of types of compounds, a composition in which all vinyl compounds having an epoxy group are mixed together is used for the reaction, or a part or all of the vinyl compounds are sequentially added. It is also possible to react.

  At that time, the method for adding the hydrosilylation reaction catalyst is not particularly limited, and a method for adding the catalyst to the organohydrogensilicone containing the solvent in advance, if necessary, a part or all of the solvent containing the solvent. A method of adding to a vinyl compound, a method of adding to both an organohydrogensilicone containing a solvent as needed and a vinyl compound containing a solvent as needed, and a method of adding the organohydrogensilicone containing a solvent. A method of adding to a mixture of a part or all of the vinyl compound is used.

  After completion of the reaction of adding a vinyl compound having an epoxy group to the SiH unit of the organohydrogensilicon represented by the average composition formula (1) by a hydrosilylation reaction, the number of carbon atoms is 1 or more and 20 or less as necessary. It is also possible to perform a treatment for reducing or eliminating unreacted SiH units with an alcohol selected from the group consisting of:

The reaction mixture containing the epoxy-modified silicone after completion of the hydrosilylation reaction or the treatment of unreacted SiH with alcohol is subjected to a step of separating the compound having a solvent and a carbon-carbon double bond, and the epoxy-modified silicone is recovered. Is done.
In order to suppress the modification of the epoxy-modified silicone when separating the solvent and the compound having a carbon-carbon double bond from the reaction mixture, the number of unreacted SiH units relative to the total number of Si contained in the epoxy-modified silicone is: It is preferably 2% or less, more preferably 1.5% or less, and further preferably 1% or less.

In addition, prior to the step of separating the solvent and the compound having a carbon-carbon double bond, it is also preferable to reduce or remove metal components such as a catalyst used in the hydrosilylation reaction.
Examples of a method for reducing or removing a metal component such as a catalyst used in a hydrosilylation reaction include, for example, a metal such as a hydrosilylation catalyst through an adsorbent such as activated carbon, celite, silica gel, alumina powder, or an ion exchange resin. A method of adsorbing and removing components; a method of deactivating a conventionally known hydrosilylation catalyst such as dodecyl mercaptan and 2-mercaptobenzothiazole to deactivate the catalyst, and the like.
Among these methods, a method of reducing or removing a metal component such as a catalyst using activated carbon and / or celite is particularly preferable because a colored component and the like can be removed at the same time.

A method for separating a solvent and a compound having a carbon-carbon double bond from a reaction mixture containing an epoxy-modified silicone will be described.
There is no particular limitation on the method for separating the solvent and the compound having a carbon-carbon double bond from the reaction mixture containing the epoxy-modified silicone. For example, the solvent and the carbon-carbon double bond are separated from the reaction mixture containing the epoxy-modified silicone. And a method of recovering the epoxy-modified silicone by distilling off the compound having the above. When the epoxy-modified silicone has high volatility, the epoxy-modified silicone may be separated and recovered by distillation.
At this time, separation of the epoxy-modified silicone from the solvent and the compound having a carbon-carbon double bond may be performed simultaneously or individually. Furthermore, the separation operation can be carried out at once or repeatedly under the same or different conditions.

  Setting the residual amount of the compound having a carbon-carbon double bond to 2% by mass or less with respect to the epoxy-modified silicone means that the operating conditions such as temperature, pressure, time, etc. when distilling / distilling are changed. It can be carried out by determining based on the common general technical knowledge while confirming the residual amount of the compound having a bond.

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

  The temperature at which the solvent and the compound having a carbon-carbon double bond are separated from the reaction mixture containing the epoxy-modified silicone includes the epoxy-modified silicone, the solvent, the vinyl group subjected to the hydrosilylation reaction, and the compound having the epoxy group. Although it differs depending on the type of vinyl compound, it is preferably 0 ° C. or more and 150 ° C. or less in order to efficiently separate the solvent and the compound having a carbon-carbon double bond and suppress the modification of the epoxy-modified silicone. The range is preferably 5 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 70 ° C. or lower, and further preferably 15 ° C. or higher and 50 ° C. or lower. Within such a range, the temperature at which the solvent and the compound having a carbon-carbon double bond are separated from the reaction mixture containing the epoxy-modified silicone does not have to be a constant temperature. It is also possible to change.

  The apparatus used for separating the solvent and the compound having a carbon-carbon double bond from the reaction mixture containing the epoxy-modified silicone is used when the solvent content is reduced and the viscosity of the mixture containing the epoxy-modified silicone is increased. In the apparatus, an apparatus capable of efficiently separating a solvent and a compound having a carbon-carbon double bond, for example, a vertical stirring tank, a surface renewal stirring tank reactor, a surface renewal biaxial kneading reactor, a biaxial horizontal type Devices such as a stirring reactor, a wet wall reactor, a free-falling perforated plate reactor, and a reactor that distills volatile components while dropping a compound along a support are preferable.

  The epoxy-modified silicone of the present invention has an excellent color tone suitable for applications requiring transparency, and has excellent light resistance, heat discoloration resistance, and heat resistance. / Or it can mix | blend the hardening | curing agent for epoxy resins, and can use it as a sealing agent for light emitting elements. Furthermore, conventionally known additives such as curing accelerators, modifiers, inorganic fillers, silane coupling agents, antifoaming agents, colorants, phosphors, anti-discoloring agents, light diffusing agents, and heat conductive fillers are added as necessary. An agent 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, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol A. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrafluorobisphenol A; epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) Epoxy resin obtained by glycidylation of trisphenols such as phenyl) ethylidene) bisphenol; epoxy resin obtained by glycidylation of tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol novolac, cresol Examples thereof include novolak type epoxy resins obtained by glycidylating novolaks such as novolak, bisphenol A novolak, brominated phenol novolak and brominated bisphenol A novolak.

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 glycidyl hexahydrophthalate, glycidyl amines such as triglycidyl isocyanurate; linear aliphatic epoxies such as epoxidized soybean oil and epoxidized polybutadiene Compounds and the like.

  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 preferably 50% by mass or less, and 30% by mass from the viewpoint of improving light resistance. More preferably, it is more preferably 10% by mass or less, and particularly preferably an epoxy resin containing no aromatic epoxy resin is used.

  It is preferable that the usage-amount of an epoxy resin is 0.1-100 mass parts with respect to 100 mass parts of epoxy-modified silicones, More preferably, it is 1-100 mass parts, More preferably, it is 1-80 mass parts.

  Examples of the epoxy resin curing agent include aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, and isophoronediamine; metaphenylenediamine, paraphenylenediamine, 3 , 3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenol sulfone, 4,4'-diaminodiphenol methane, 4,4'-diaminodiphenol ether, etc .; mercaptopropionic acid ester , Mercaptans such as terminal mercapto compounds of epoxy resins; bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol A , Tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4 Phenol resins such as-(1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak; Polyols obtained by hydrogenating aromatic rings of resins; polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro anhydride Phosphoric acid, 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- Alicyclic acid anhydrides such as dicarboxylic acid anhydrides; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride; 2-methylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-phenylimidazole and salts thereof, amine amines obtained by reaction of the above aliphatic amines, aromatic amines, and / or imidazoles with epoxy resins; hydrazines such as adipic acid dihydrazide; dimethyl Tertiary amines such as benzylamine, 1,8-diazabicyclo [5,4,0] undec-7-ene; Organic phosphines such as enylphosphine; dicyandiamide and the like.

  Of these, alicyclic acid anhydrides and aromatic acid anhydrides are preferable because the curing rate is increased, and light resistance of the cured product is further increased, and alicyclic acid anhydrides are more preferable. Methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, and methyl-norbornane-2,3-dicarboxylic anhydride are 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.

  The light emitting element sealing agent may contain a curing accelerator as necessary. Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; tertiary amines such as 1,8-diazabicyclo [5,4,0] undec-7-ene. And phosphines such as triphenylphosphine; phosphonium salts such as triphenylphosphonium bromide; aminotriazoles; tin such as tin octylate and dibutyltin dilaurate; zinc such as zinc octylate; aluminum, chromium, Metal catalysts such as acetylacetonate such as cobalt and zirconium are used. These curing accelerators can be used as one kind or a mixture of two or more kinds.

  The light emitting element sealing agent may contain a modifier as necessary. Examples of the modifier include polyols containing two or more hydroxyl groups in one molecule, and aliphatic polyols such as ethylene glycol and glycerin are 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 light emitting element sealant may contain an inorganic filler as necessary. The inorganic filler that is preferably used has an average particle diameter equal to or smaller than the wavelength of the LED to be used in order to avoid an adverse effect on permeability, and more preferably, the average particle diameter is 100 nm or less. Inorganic fillers may improve, for example, mechanical properties or thermal conductivity.

  The light emitting element sealing agent may contain a silane coupling agent as necessary. The silane coupling agent preferably used is a compound having no aromatic group or halogen atom.

A known method can be used as a method for curing the light-emitting element sealant. Among known techniques, a method of curing by heating or a method of curing by irradiating with ultraviolet rays (UV) is a method generally used as a method for curing an epoxy resin, and can be mentioned as a preferable method. The temperature for curing by heating is not particularly limited because it depends on the epoxy resin or curing agent used, but is usually in the range of 80 to 200 ° C.
The curing reaction can be cured 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. . 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 can be formed by sealing a light emitting element using the light emitting element sealing agent obtained by using the epoxy-modified silicone of the present invention.
The emission wavelength of the light-emitting element obtained by sealing with the light-emitting element sealant obtained by using the epoxy-modified silicone of the present invention can be widely used from infrared to red, green, blue, purple and ultraviolet. In addition, the conventional sealant can be used practically to light having a wavelength of 250 nm to 550 nm, which is deteriorated 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.

Specific examples of the light-emitting element that can be used include a light-emitting element formed by stacking semiconductor materials over a substrate. 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 can also be used.

The light-emitting element can be sealed only with the light-emitting element sealant obtained by using the epoxy-modified silicone of the present invention, but can be sealed with another sealant.
When other sealants are used in combination, after sealing with the light emitting device sealant obtained using the epoxy-modified silicone of the present invention, the periphery is sealed with other sealants, or other sealants are sealed. After sealing with a stopper, the periphery can be sealed with a light emitting device sealant obtained using the epoxy-modified silicone of 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 sealant, for example, a method of injecting a curable composition in advance into a mold mold and immersing a lead frame or the like on which the light emitting element is fixed, followed by curing. For example, a method of injecting a light-emitting element sealing agent into a mold frame in which the light-emitting element is inserted and curing it may be used. 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 on 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 light emitting device sealing agent obtained by using the epoxy-modified silicone of the present invention can also be used as a die bond material for fixing the light emitting device to a lead terminal or a package, a passivation film on the light emitting device, 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 using the epoxy-modified silicone of 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 light emitting element after sealing with hard material, Method of inserting light emitting diode into through hole and fixing, Light emitting element connected to 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 of 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 lamp, a display lamp, and a display device It is useful as a light source for a planar light emitter, a display, a decoration, various lights, and the like.

Specific examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following examples.
In Examples and Comparative Examples, measurement and evaluation were performed by the following methods.
(1) Calculation of ratio of average composition of silicone and ratio of contained organic group A solution dissolved in deuterated chloroform solvent at a ratio of 1 ml per 30 mg of silicone was used as a measurement sample. Using this measurement sample, 1H-NMR measurement of 400 MHz (manufactured by JASCO Corporation α-400) was performed at 200 integration times, and the obtained results were analyzed to determine the average composition in one molecule of the modified polysiloxane. Asked.
A solution in which 8 wt% of Cr (acac) 3 was added to silicone was dissolved in 0.15 g of silicone in a deuterated chloroform solvent at a rate of 1 g. Using this measurement sample, 29Si-NMR measurement at 400 MHz (manufactured by JASCO Corporation α-400) was performed at an integration number of 4,000 times, and the obtained results were analyzed and averaged in one molecule of the modified polysiloxane. The composition was determined.
By analyzing the results obtained by the above two methods, the ratio of contained organic groups was calculated.

(2) Measurement of residual amount and residual solvent amount of compound having carbon-carbon double bond in epoxy-modified silicone Using Shimadzu Gas Chromatography Analyzer GC-14B, the amount was determined under the following conditions.
After measuring about 0.5 g of epoxy-modified silicone and 0.015 g of n-octane as an internal standard in a 5 ml volumetric flask, a solution diluted to 5 ml with dehydrated THF or dehydrated 1,4-dioxane was 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 raising condition: After holding at 50 ° C. for 5 minutes, the temperature was raised from 50 ° C. to 300 ° C. at 10 ° C./min.
From the obtained results, the content of each component contained in the epoxy-modified silicone was quantified and summed using a separately prepared calibration curve by an internal standard method. In addition, a numerical value is represented with the mass ratio with respect to epoxy-modified silicone.

(3) Epoxy value Determined by the following operation and calculation method.
The resin sample was dissolved with benzyl alcohol and 1-propanol. A potassium iodide aqueous solution and a bromophenol blue indicator were added to this solution, followed by titration with 1N hydrochloric acid, and the point where the reaction system turned from blue to yellow was defined as the equivalent point. From the equivalent point, the epoxy value of the epoxy-modified silicone was 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: Mass of the sample (g)
V; titration volume (ml)
N: Normality of hydrochloric acid used for titration (N)
F: Factor of hydrochloric acid used for titration

(4) Element content The platinum content was analyzed using a quadrupole ICP mass spectrometer (manufactured by Thermo Elemental: X7-ICP-MS).
(5) Transparency Using a cured product having a thickness of 2 mm, the light transmittance at 350 nm, 400 nm, and 450 nm in the thickness direction was 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 ×.
(6) Light resistance It set so that UV light could be irradiated to the hardened | cured material of thickness 2mm in the constant temperature dryer made 100 degreeC constant from UV irradiation apparatus (product made from Ushio Electric: SP-7) via the optical fiber.
Using a 365 nm band pass filter, light of 330 to 410 nm was irradiated so as to be 2 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.

(7) 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 an index of heat resistance. Tg of the cured product was 120 ° C. or more, ◯, 100 ° C. or more and less than 120 ° C., and 50 ° C. or more and less than 100 ° C., Δ.
(8) Heat-resistant discoloration Using a cured product having a thickness of 2 mm, a light transmittance of 400 nm in the thickness direction was measured by JASCO V-550 manufactured by JASCO Corporation. Next, the cured product is put into a mold made of SUS316, subjected to heat treatment at 250 ° C. for 20 minutes in the air, and then rapidly cooled with ice-cold water, and then the light transmittance at 400 nm in the thickness direction of the sample is measured again. Then, the value of the light transmittance of 400 nm in the sample after the heat treatment with respect to the light transmittance of 400 nm in the sample before the heat treatment is calculated, and the light transmittance of the sample after the heat treatment with respect to the light transmittance of the sample before the heat treatment Was calculated as the light transmission retention rate. The light transmission retention was 92% or more, ◎, 90% or more and less than 92%, ◯, 88% or more and less than 90%, or less than 88%.

Example 1
<Manufacture of epoxy-modified silicone (1a)>
A 1.5 liter reactor with reflux condenser, thermometer and stirrer was purged with nitrogen. Pure 1,3,5,7-tetramethylcyclotetrasiloxane obtained by dehydrating and purifying 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) under nitrogen in the apparatus. 70 g, 31.55 g of pure 1,3-divinyltetramethyldisiloxane obtained by dehydrating and purifying 1,3-divinyltetramethyldisiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.) under nitrogen, 4- 4-vinylcyclohexene containing 1.3% by mass of 4-epoxyethyl-cyclohexene obtained by dehydrating and purifying epoxyethyl-cyclohexene (Daicel Chemical Industries, Ltd .: Celoxide 2000) under nitrogen. After charging 107.0 g of oxide and 820 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen under nitrogen, the atmosphere was dried at atmospheric pressure. The temperature of the mixture reached 60 ℃ under care. To this, 1.6 g of a 1,4-dioxane solution of a platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum element was added under nitrogen, followed by reaction for 4 hours. Under the present circumstances, reaction temperature was 60 to 100 degreeC with reaction heat.
After completion of the reaction, the temperature of the reaction solution was lowered to 30 ° C., and 300 g of activated carbon (manufactured by Wako Pure Chemicals: Granular Special Grade) heated and dried at 120 ° C. for 3 hours under a dry nitrogen stream was added to the reaction solution After the stirring treatment was continued for 24 hours at a temperature of 30 ° C. to 40 ° C., the activated carbon was filtered.
The obtained treatment solution was heated using an evaporator under the conditions of a heating temperature of 45 ° C. and a pressure of 10 kPa for 1.5 hours, the pressure was sequentially reduced, and the pressure was lowered to 30 Pa for 3 hours. The compound having a bond was distilled off to obtain an epoxy-modified silicone. About 140 g of the obtained epoxy-modified silicone was put in a glass tube having an inner diameter of 65 mmφ and a length of 250 mm, and set in a glass tube oven (GTO-350 manufactured by Shibata Kagaku) so that the long axis of the glass tube was horizontal. While rotating the glass tube around the major axis direction at a rotation speed of about 15 times / min, dry nitrogen was introduced into the interior at a flow rate of 3 ml / min under atmospheric pressure conditions, and the system was depressurized to 40 Pa. . The glass tube is heated to 45 ° C. with an external surface heater, and the residual solvent and the compound having a carbon-carbon double bond contained in the epoxy-modified silicone are distilled off over 1 hour to obtain an epoxy-modified silicone (1a). Got.
1,4-Dioxane remaining in the epoxy-modified silicone (1a) is 300 ppm, and compounds having a carbon-carbon double bond and an epoxy group include 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -Cyclohexene remained at 0.45 mass%, 0.68 mass%, and 0.3 mass%, respectively, and the total amount was 1.43 mass%. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (1a) is 1.43% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 1.43% by mass. The residual amount of by-products generated by the internal transition of the carbon-carbon double bond of the compound having a vinyl group and an epoxy group was 0.68% by mass.
Further, the epoxy value of the epoxy-modified silicone (1a) is 0.40, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 3 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone (1a) is mixed with 60.5 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate under nitrogen until the whole becomes uniform. After stirring, defoaming was performed to obtain a curable composition. The curable composition was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

(Example 2)
<Production of epoxy-modified silicone (2a)>
Except that the operation time for distilling off the solvent in the epoxy-modified silicone and the compound having a carbon-carbon double bond contained in the epoxy-modified silicone with a glass tube oven was 2 hours, Epoxy-modified silicone (2a) was obtained.
1,4-dioxane remaining in the epoxy-modified silicone (2a) is 200 ppm, and compounds having a carbon-carbon double bond and an epoxy group include 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -Cyclohexene remained 0.21 mass%, 0.42 mass%, and 0.17 mass%, respectively, and the total amount was 0.8 mass%. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (2a) is 0.8% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.8%. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.42 mass%.
Moreover, the epoxy value of the epoxy-modified silicone (2a) is 0.39, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 3 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
90 parts by mass of the resulting epoxy-modified silicone (2a), 10 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanedicarboxylate, 53.1 parts by mass of methylhexahydrophthalic anhydride, diaza 1 part by mass of bicycloundecenoctylate was mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

(Example 3)
<Production of epoxy-modified silicone (3a)>
The same procedure as in Example 1 except that the operation time for distilling off the residual solvent and the compound having a carbon-carbon double bond contained in the epoxy-modified silicone in the epoxy-modified silicone by a glass tube oven was set to 3 hours. Thus, an epoxy-modified silicone (3a) was obtained.
1,4-Dioxane remaining in the epoxy-modified silicone (3a) is 100 ppm, and compounds having a carbon-carbon double bond and an epoxy group are 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -0.03 mass%, 0.08 mass%, and 0.04 mass% of cyclohexene remained, respectively, and the total amount was 0.15 mass%. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (3a) is 0.15% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.15%. The residual amount of the by-product generated by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.08 mass%.
Moreover, the epoxy value of the epoxy-modified silicone (3a) is 0.39, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 2 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
The curable composition and curing were carried out in the same manner as in Example 1 except that the epoxy-modified silicone (3a) was used instead of the epoxy-modified silicone (1a) and 59 parts by mass of methylhexahydrophthalic anhydride was used. I got a thing. Table 1 shows the performance of the obtained cured product.

Example 4
<Production of epoxy-modified silicone (4a)>
The same as in Example 1 except that the operation time for distilling off the residual solvent and the compound having a carbon-carbon double bond contained in the epoxy-modified silicone in the epoxy-modified silicone by a glass tube oven was set to 4 hours. Thus, an epoxy-modified silicone (4a) was obtained.
1,4-Dioxane remaining in the epoxy-modified silicone (4a) is 20 ppm or less, and compounds having a carbon-carbon double bond and an epoxy group include 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxy. Ethyl-cyclohexene remained at 0.003%, 0.004%, and 0.004% by mass, respectively, and the total amount was 0.011% by mass. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone (4a) is 0.011% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.011. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.004 mass%.
Further, the epoxy value of the epoxy-modified silicone (4a) is 0.39, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 2 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition and a cured product were obtained in the same manner as in Example 3 except that the epoxy-modified silicone (4a) was used instead of the epoxy-modified silicone (3a). Table 1 shows the performance of the obtained cured product.

(Comparative Example 1)
<Production of epoxy-modified silicone (1b)>
After carrying out the hydrosilylation reaction in the same manner as in Example 1, activated carbon was added and stirred, and then the activated carbon was filtered to obtain a treatment liquid. The obtained treatment liquid was heated using an evaporator at a heating temperature of 45 ° C. and a pressure of 10 kPa for 1.5 hours, the pressure was reduced successively, and finally the pressure was reduced to 30 Pa and the solvent and carbon-carbon doubled over 1 hour. The compound having a bond was distilled off to obtain an epoxy-modified silicone (1b).
The 1,4-dioxane remaining in the epoxy-modified silicone (1b) is 1,000 ppm, as a compound having a carbon-carbon double bond and an epoxy group, 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4- Epoxyethyl-cyclohexene remained in 0.91% by mass, 1.45% by mass, and 0.64% by mass, respectively, and the total amount was 3% by mass. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone (1b) is 3% by mass, the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 3% by mass, vinyl. The residual amount of by-products generated by the internal transition of the carbon-carbon double bond of the compound having a group and an epoxy group was 1.45% by mass.
Further, the epoxy value of the epoxy-modified silicone (1b) is 0.40, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 2 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the epoxy-modified silicone (1b) was used instead of the epoxy-modified silicone (1a). Table 1 shows the performance of the obtained cured product.

(Comparative Example 2)
<Production of epoxy-modified silicone (2b)>
After carrying out the hydrosilylation reaction in the same manner as in Example 1, activated carbon was added and stirred, and then the activated carbon was filtered to obtain a treatment liquid. The obtained treatment liquid was heated using an evaporator under the conditions of a heating temperature of 45 ° C. and a pressure of 10 kPa for 1.5 hours, successively reducing the pressure to a final pressure of 30 Pa, and the solvent and carbon-carbon double over 4 hours. The compound having a bond was distilled off to obtain an epoxy-modified silicone (2b).
1,4-dioxane remaining in the epoxy-modified silicone (2b) is 700 ppm, and 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl as a compound having a carbon-carbon double bond and an epoxy group. -Cyclohexene remained 0.76% by mass, 1.21% by mass, and 0.53% by mass, respectively, and the total amount was 2.5% by mass. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone (2b) is 2.5% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 2.5%. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 1.21 mass%.
Further, the epoxy value of the epoxy-modified silicone (2b) is 0.40, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 3 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the epoxy-modified silicone (2b) was used instead of the epoxy-modified silicone (1a). Table 1 shows the performance of the obtained cured product.

(Comparative Example 3)
<Production of epoxy-modified silicone (3b)>
After carrying out the hydrosilylation reaction in the same manner as in Example 1, activated carbon was added and stirred, and then the activated carbon was filtered to obtain a treatment liquid. The obtained treatment solution was heated using an evaporator under the conditions of a heating temperature of 45 ° C. and a pressure of 10 kPa for 1.5 hours, the pressure was successively reduced, and finally the pressure was reduced to 30 Pa and the solvent and carbon-carbon double were taken over 7 hours. The compound having a bond was distilled off to obtain an epoxy-modified silicone (3b).
1,4-Dioxane remaining in the epoxy-modified silicone (3b) is 100 ppm, and compounds having a carbon-carbon double bond and an epoxy group are 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -Cyclohexene remained in 0.72 mass%, 1.19 mass%, and 0.49 mass%, respectively, and the total amount was 2.4 mass%. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Thus, the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone (3b) is 2.4% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 2.4. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 1.19 mass%.
Moreover, the epoxy value of the epoxy-modified silicone (3b) is 0.40, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 3 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the epoxy-modified silicone (3b) was used instead of the epoxy-modified silicone (1a). Table 1 shows the performance of the obtained cured product.

(Comparative Example 4)
<Production of epoxy-modified silicone (4b)>
After carrying out the hydrosilylation reaction in the same manner as in Example 1, activated carbon was added and stirred, and then the activated carbon was filtered to obtain a treatment liquid. The obtained treatment solution was heated using an evaporator under the conditions of a heating temperature of 45 ° C. and a pressure of 10 kPa for 1.5 hours, the pressure was sequentially reduced, and the pressure was lowered to 30 Pa for 3 hours. The compound having a bond was distilled off to obtain an epoxy-modified silicone.
Carbon-carbon double contained in the residual solvent and the epoxy-modified silicone under the following conditions using the obtained epoxy-modified silicone with a thin film evaporator (model: MS-300 type) manufactured by Shibata Chemical Co., Ltd. The compound having a bond was distilled off to obtain an epoxy-modified silicone (4b).
Epoxy-modified silicone heating temperature: 70 ° C
Pressure: 30Pa
Internal condenser temperature: 0 ° C
Feed rate of epoxy-modified silicone: 3 g / min 1,4-dioxane remaining in epoxy-modified silicone (4b) is 600 ppm, as a compound having a carbon-carbon double bond and an epoxy group, 4-vinylcyclohexene oxide, 4- Ethylidenylcyclohexene oxide and 4-epoxyethyl-cyclohexene remained in 0.77% by mass, 1.28% by mass and 0.59% by mass, respectively, and the total amount was 2.64% by mass. It was. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone (4b) is 2.64% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 2.64. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 1.28 mass%.
Further, the epoxy value of the epoxy-modified silicone (4b) is 0.40, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 3 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the epoxy-modified silicone (4b) was used instead of the epoxy-modified silicone (1a). Table 1 shows the performance of the obtained cured product.

(Example 5)
<Production of epoxy-modified silicone (5a)>
30 g of pure 1,3,5,7-tetramethylcyclotetrasiloxane was used, and α-vinyldimethylsilyl containing 1.64 mmol of vinyl group in 1 g instead of pure 1,3-divinyltetramethyldisiloxane Oxy-ω-vinyldimethylsilyl-polydimethylsiloxane [average degree of polymerization of dimethylsiloxane units is 14. 152.4 g used, 35.65 g 4-vinylcyclohexene oxide containing 1.3% by mass of 4-epoxyethyl-cyclohexene, 1,4-dioxane purified by dehydration distillation (Wako Pure) Example 4 except that 855 g of a reagent manufactured by Yakuhin Co., Ltd. was used, and 1.7 g of a 1,4-dioxane solution of a platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum element was used. In the same manner as above, an epoxy-modified silicone (5a) was obtained.
The 1,4-dioxane remaining in the epoxy-modified silicone (5a) is 500 ppm, and compounds having a carbon-carbon double bond and an epoxy group are 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -0.64 mass%, 0.18 mass%, and 0.08 mass% of cyclohexene remained, and the total amount was 0.9 mass%. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (5a) was 0.9% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group was 0.9%. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.18 mass%.
Moreover, the epoxy value of the epoxy-modified silicone (5a) is 0.1, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.7%, and the transition metal component contained is only platinum, The content of the component was 2 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
Use of epoxy-modified silicone (5a) instead of epoxy-modified silicone (1a), use of 15.1 parts by weight of methylhexahydrophthalic anhydride, curing reaction at 60 ° C. for 4 hours, and further at 70 ° C. for 4 hours Except having performed, it carried out similarly to the Example, and obtained curable composition- and hardened | cured material. Table 1 shows the performance of the obtained cured product.

(Example 6)
<Production of epoxy-modified silicone (6a)>
Pure 1,3-divinyltetramethyldisiloxane was not used, 151.23 g of 4-vinylcyclohexene oxide containing 1.3% by mass of 4-epoxyethyl-cyclohexene was used, and purified by dehydration distillation. For 1.7 g of 1,4-dioxane solution of platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum element, using 870 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) Except that, epoxy-modified silicone (6a) was obtained in the same manner as in Example 3.
1,4-dioxane remaining in the epoxy-modified silicone (6a) is 200 ppm, and compounds having a carbon-carbon double bond and an epoxy group are 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -0.02% by mass, 0.09% by mass, and 0.04% by mass of cyclohexene remained, and the total amount was 0.15% by mass. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (6a) is 0.15% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.15%. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.09 mass%.
Further, the epoxy value of the epoxy-modified silicone (6a) is 0.54, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.7%, and the transition metal component contained is only platinum, The content of the component was 2 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition in the same manner as in Example 1 except that the epoxy-modified silicone (6a) was used instead of the epoxy-modified silicone (1a) and that 81.7 parts by mass of methylhexahydrophthalic anhydride was used. And a cured product was obtained. Table 1 shows the performance of the obtained cured product.

(Example 7)
<Production of epoxy-modified silicone (7a)>
The same procedure as in Example 1 except that the operation time for distilling off the residual solvent and the compound having a carbon-carbon double bond contained in the epoxy-modified silicone in the epoxy-modified silicone by a glass tube oven was set to 5 hours. Thus, an epoxy-modified silicone (7a) was obtained.
1,4-dioxane remaining in the epoxy-modified silicone (7a) is 20 ppm or less, and only 4-ethylidenylcyclohexene oxide is detected as a compound having a carbon-carbon double bond and an epoxy group, and is 0.002% by mass. It remained. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (7a) is 0.002% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.002. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.002 mass%.
Further, the epoxy value of the epoxy-modified silicone (7a) is 0.39, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 2 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition and a cured product were obtained in the same manner as in Example 3 except that the epoxy-modified silicone (7a) was used instead of the epoxy-modified silicone (3a). Table 1 shows the performance of the obtained cured product.

(Example 8)
<Production of epoxy-modified silicone (8a)>
15.16 g of pure 1,3-divinyltetramethyldisiloxane was used, 130.7 g of 4-vinylcyclohexene oxide containing 1.3% by mass of 4-epoxyethyl-cyclohexene was used, dehydration distillation 1. Using 845 g of purified 1,4-dioxane (a reagent manufactured by Wako Pure Chemical Industries, Ltd.), and a 1,4-dioxane solution of a platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum element. Epoxy-modified silicone (8a) was obtained in the same manner as in Example 4 except that 66 g was used.
1,4-Dioxane remaining in the epoxy-modified silicone (8a) is 100 ppm, and compounds having a carbon-carbon double bond and an epoxy group are 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -0.03 mass%, 0.08 mass%, and 0.04 mass% of cyclohexene remained, respectively, and the total amount was 0.15 mass%. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (8a) is 0.15% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.15%. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.08 mass%.
Further, the epoxy value of the epoxy-modified silicone (8a) is 0.48, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.5%, and the transition metal component contained is only platinum, The content of the component was 1 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
The curable composition was the same as in Example 1 except that the epoxy-modified silicone (8a) was used instead of the epoxy-modified silicone (1a) and that 72.6 parts by mass of methylhexahydrophthalic anhydride was used And a cured product was obtained. Table 1 shows the performance of the obtained cured product.

Example 9
<Production of epoxy-modified silicone (9a)>
45 g of pure 1,3,5,7-tetramethylcyclotetrasiloxane was used, and α-vinyldimethylsilyl containing 3.17 mmol of vinyl group in 1 g instead of pure 1,3-divinyltetramethyldisiloxane Oxy-ω-vinyldimethylsilyl-polydimethylsiloxane [average degree of polymerization of dimethylsiloxane units is 6. ] 117.88 g was used, 51.74 g of 4-vinylcyclohexene oxide containing 1.3% by mass of 4-epoxyethyl-cyclohexene was used, 1,4-dioxane purified by dehydration distillation (Wako Pure Chemical Industries, Ltd.) Example 4 except that 840 g of a reagent manufactured by Yakuhin Co., Ltd. was used, and 1.66 g of a 1,4-dioxane solution of platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum element was used. In the same manner as above, an epoxy-modified silicone (9a) was obtained.
1,4-Dioxane remaining in the epoxy-modified silicone (9a) is 100 ppm, and compounds having a carbon-carbon double bond and an epoxy group are 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -Cyclohexene remained in 0.12% by mass, 0.02% by mass and 0.05% by mass, respectively, and the total amount was 0.19% by mass. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone (9a) is 0.19% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.19%. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.02 mass%.
Further, the epoxy value of the epoxy-modified silicone (9a) is 0.17, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.4%, and the transition metal component contained is only platinum, The content of the component was 1 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
The epoxy-modified silicone (9a) was used in place of the epoxy-modified silicone (1a), 25.7 parts by mass of methylhexahydrophthalic anhydride was used, and the curing reaction was carried out at 80 ° C. for 2 hours and further at 100 ° C. for 4 hours. A curable composition and a cured product were obtained in the same manner as in Example 1 except that the test was performed for a long time. Table 1 shows the performance of the obtained cured product.

(Example 10)
<Production of epoxy-modified silicone (10a)>
In a 1.5 liter reactor having a reflux condenser, a thermometer, and a stirring device, 17.56 g of norbornene (special grade reagent manufactured by Tokyo Chemical Industry Co., Ltd.) is charged and purged with nitrogen. Subsequently, 4-epoxyethyl-cyclohexene (produced by Daicel Chemical Industries, Ltd .: Celoxide 2000) was purified by dehydration distillation under nitrogen. -77.66 g of vinylcyclohexene oxide and 305 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen were charged under nitrogen, and then stirred under an atmospheric pressure dry nitrogen atmosphere. The temperature was raised to 80 ° C. To this was added 1.95 g of a 1,4-dioxane solution of a platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum, and then α-trimethylsilyloxy-ω-trimethylsilyl-poly (dimethylsiloxane). -Co-hydrogen methylsiloxane) [The degree of polymerization of the total of dimethylsiloxane units and hydrogenmethylsiloxane units is 38, and it has an average of 19 SiH units in one molecule. ] A solution obtained by dissolving 110 g and 280 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) under nitrogen has a liquid temperature in a 1.5 liter reaction vessel in a range of 80 ° C to 83 ° C. It was dripped at a speed. Reaction was performed at 80 degreeC after completion | finish of dripping for 4 hours.
After completion of the reaction, the temperature of the reaction solution was lowered to 30 ° C., and 240 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular special grade) heated and dried at 120 ° C. for 3 hours under a dry nitrogen stream was added to the reaction solution After continuing the stirring treatment at a temperature of 30 ° C. to 40 ° C. for 30 hours, the activated carbon was filtered. The obtained treatment solution was heated using an evaporator under the conditions of a heating temperature of 45 ° C. and a pressure of 10 kPa for 1.5 hours, the pressure was sequentially reduced, and the pressure was lowered to 30 Pa for 3 hours. The compound having a bond was distilled off to obtain an epoxy-modified silicone.
About 140 g of the obtained epoxy-modified silicone was put into a glass tube having an inner diameter of 65 mmφ and a length of 250 mm, and set in a glass tube oven (GTO-350 manufactured by Shibata Kagaku) so that the long axis of the glass tube was horizontal. While rotating the glass tube around the major axis at a rotation speed of about 15 times / min, dry nitrogen is introduced into the interior at a flow rate of 3 ml / min under atmospheric pressure, and the system is depressurized to 40 Pa. . The glass tube is heated to 45 ° C. with an external surface heater, and the residual solvent and the compound having a carbon-carbon double bond contained in the epoxy-modified silicone are distilled off over 6 hours to obtain an epoxy-modified silicone (10a). Got.
1,4-Dioxane remaining in the epoxy-modified silicone (10a) is 150 ppm, and compounds having a carbon-carbon double bond and an epoxy group include 4-vinylcyclohexene oxide, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl. -0.13 mass%, 0.05 mass%, and 0.02 mass% of cyclohexene remained, respectively, and the total amount was 0.2 mass%. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond in the epoxy-modified silicone (10a) is 0.2% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.2%. The residual amount of the by-product generated by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.05 mass%.
Further, the epoxy value of the epoxy-modified silicone (10a) is 0.27, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.6%, and the transition metal component contained is only platinum, The content of the component was 3 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition in the same manner as in Example 1 except that the epoxy-modified silicone (10a) was used instead of the epoxy-modified silicone (1a) and that 40.9 parts by mass of methylhexahydrophthalic anhydride was used. And a cured product was obtained. Table 1 shows the performance of the obtained cured product.

(Example 11)
<Production of epoxy-modified silicone (11a)>
To a 1.5 liter reactor with reflux condenser, thermometer and stirrer, add α-trimethylsilyloxy-ω-trimethylsilyl-poly (dimethylsiloxane-co-hydrogenmethylsiloxane) [dimethylsiloxane units and hydrogenmethylsiloxane units. The total degree of polymerization is 38, and it has an average of 19 SiH units in one molecule. ] 110 g is charged and replaced with nitrogen. Subsequently, 305 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen was charged under nitrogen, and then heated to 60 ° C. with stirring in an atmospheric pressure dry nitrogen atmosphere. To this, 1.97 g of a 1,4-dioxane solution of a platinum divinyltetramethyldisiloxane complex containing 1,000 ppm of platinum in terms of platinum element was added, and then as a first step, 4-epoxyethyl-cyclohexene 77.66 g of 4-vinylcyclohexene oxide containing 1.3% by mass of 4-epoxyethyl-cyclohexene obtained by dehydrating and purifying (Daicel Chemical Industries, Ltd .: Celoxide 2000) under nitrogen was dehydrated. A solution dissolved under nitrogen in 240 g of distilled and purified 1,4-dioxane (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added all at once, and the reaction was continued for 2 hours. Subsequently, as a second step, a solution prepared by dissolving 17.56 g of norbornene (Tokyo Kasei reagent special grade) in 50 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) under nitrogen was added at once. The reaction is continued for 3 hours. Subsequently, as a third step, 12.18 g of pure 4-vinylcyclohexane obtained by dehydrating and purifying 4-vinylcyclohesacene (a reagent made by Aldrich) under nitrogen was added all at once and reacted for 4 hours. Went.
After completion of the reaction, the same procedure as in Example 8 was conducted except that the operation time for distilling off the compound having a carbon-carbon double bond contained in the residual solvent and the epoxy-modified silicone was 7 hours in a glass tube oven. The operation was carried out to obtain an epoxy-modified silicone (11a).
1,4-dioxane remaining in the epoxy-modified silicone (11a) is 100 ppm, and as a compound having a carbon-carbon double bond and an epoxy group, 4-ethylidenylcyclohexene oxide, 4-epoxyethyl-cyclohexene is Remaining 0.02% by mass and 0.01% by mass, respectively, and the total amount was 0.03% by mass. In addition, as a compound having a carbon-carbon double bond other than a compound having a carbon-carbon double bond and an epoxy group, vinylcyclohexane and ethylidenylcyclohexane remain 0.06% by mass and 0.02% by mass, respectively. The total amount was 0.08% by mass.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (11a) is 0.11% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.03%. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.02 mass%.
Further, the epoxy value of the epoxy-modified silicone (11a) is 0.29, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.7%, and the transition metal component contained is only platinum, The content of the component was 3 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
A curable composition in the same manner as in Example 1 except that the epoxy-modified silicone (11a) was used instead of the epoxy-modified silicone (1a) and that 43.9 parts by mass of methylhexahydrophthalic anhydride was used. And a cured product was obtained. Table 1 shows the performance of the obtained cured product.

(Example 12)
<Production of epoxy-modified silicone (12a)>
To a 1.5 liter reactor with reflux condenser, thermometer and stirrer, add α-trimethylsilyloxy-ω-trimethylsilyl-poly (dimethylsiloxane-co-hydrogenmethylsiloxane) [dimethylsiloxane units and hydrogenmethylsiloxane units. The total degree of polymerization is 38, and it has an average of 19 SiH units in one molecule. 110 g was charged and the atmosphere was replaced with nitrogen. Subsequently, 220 g of tetrahydrofuran (stabilizer-free product: reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration and distillation under nitrogen was charged under nitrogen, and then the temperature was raised to 66 ° C. with stirring in an atmospheric pressure dry nitrogen atmosphere. did. To this was added 1.96 g of a platinum divinyltetramethyldisiloxane complex tetrahydrofuran solution containing 1,000 ppm of platinum in terms of platinum element. Then, as a first step, 4-epoxyethyl-cyclohexene (Daicel Chemical Industries, Ltd.) 72.44 g of 4-vinylcyclohexene oxide containing 1.3% by mass of 4-epoxyethyl-cyclohexene obtained by dehydration distillation purification under nitrogen: A solution of 220 g of tetrahydrofuran dissolved in nitrogen was added all at once, and the reaction was continued for 2 hours. Subsequently, as a second step, a solution prepared by dissolving 6.94 g of norbornene (special grade reagent manufactured by Tokyo Chemical Industry Co., Ltd.) in 62 g of tetrahydrofuran was added at a time under nitrogen, and the reaction was continued for 3 hours.
Further, as a third step, pure vinyltrimethylsilane 22 obtained by reducing the reaction temperature to 50 ° C. and subsequently purifying vinyltrimethylsilane (Tokyo Kasei Reagent Special Grade) as a third step by dehydration distillation purification under nitrogen. .15 g was added at once, and the reaction was performed for 24 hours.
After completion of the reaction, the temperature of the reaction solution was lowered to 30 ° C., and 240 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular special grade) heated and dried at 120 ° C. for 3 hours under a dry nitrogen stream was added to the reaction solution After continuing the stirring treatment at a temperature of 30 ° C. to 40 ° C. for 35 hours, the activated carbon was filtered. The obtained treatment liquid was heated using an evaporator under the conditions of a heating temperature of 45 ° C. and a pressure of 22 kPa for 1.5 hours, the pressure was successively reduced, and finally the pressure was lowered to 30 Pa and the solvent and carbon-carbon double were taken over 3 hours. The compound having a bond was distilled off to obtain an epoxy-modified silicone.
Subsequently, an operation similar to that in Example 9 was carried out to distill off the residual solvent and the compound having a carbon-carbon double bond contained in the epoxy-modified silicone in a glass tube oven, and the epoxy-modified silicone (12a )
Tetrahydrofuran remaining in the epoxy-modified silicone (12a) is 50 ppm, and 4-ethylidenylcyclohexene oxide and 4-epoxyethyl-cyclohexene are each 0.07 as a compound having a carbon-carbon double bond and an epoxy group. % By mass and 0.03% by mass remained, and the total amount was 0.1% by mass. In addition, the compound which has carbon-carbon double bonds other than the compound which has a carbon-carbon double bond and an epoxy group was not contained.
Accordingly, the residual amount of the compound having a carbon-carbon double bond of the epoxy-modified silicone (12a) is 0.1% by mass, and the residual amount of the compound having a carbon-carbon double bond and an epoxy group is 0.1% by mass. The residual amount of the by-product produced by the internal transition of the carbon-carbon double bond of the compound having a mass%, vinyl group and epoxy group was 0.07 mass%.
Moreover, the epoxy value of the epoxy-modified silicone (12a) is 0.28, the amount of Si atoms constituting the residual SiH unit with respect to all Si atoms is 0.8%, and the transition metal component contained is only platinum, The content of the component was 2 ppm in terms of platinum element.

<Manufacture and characteristic evaluation of cured product>
<Production and properties of cured product> described in Example 1 except that epoxy-modified silicone (12a) was used instead of epoxy-modified silicone (1a) and that 42.4 parts by mass of methylhexahydrophthalic anhydride was used. Evaluation> The curable composition and the cured product were obtained in the same manner. Table 1 shows the performance of the obtained cured product.

(Reference Example 1)
The curable composition obtained in Example 3 was injected into a bullet-shaped mold form 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 after degassing in vacuum A curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours 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.
(Reference Example 2)
A light emitting diode was obtained in the same manner as in Reference Example 1 except that the curable composition obtained in Example 9 was used and the curing reaction was set at 80 ° C. for 2 hours and further at 100 ° C. for 4 hours. 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.
(Reference Example 3)
Using the curable composition obtained in Example 12, a light emitting diode was obtained in the same manner as in Reference 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.
(Reference Example 4)
The epoxy-modified silicones (3a), (4a), and (7a) produced in Example 3, Example 4, and Example 7 were subjected to a storage stability acceleration test. The results are shown in Table 1.

  From Table 1, it is understood that the heat discoloration resistance and light resistance of the epoxy-modified silicone are improved by setting the residual amount of the compound having a carbon-carbon double bond to 2% by mass or less.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the epoxy modified silicone which has transparency, heat resistance, light resistance, heat discoloration resistance, and storage stability, and is used suitably for a light emitting element sealing material use.

Claims (10)

  An epoxy-modified silicone obtained by adding a vinyl compound having an epoxy group to a SiH unit of an organohydrogen silicone by a hydrosilylation reaction, wherein the residual amount of the compound having a carbon-carbon double bond is changed to the epoxy-modified silicone. Epoxy-modified silicone that is 2% by mass or less.   The epoxy-modified silicone according to claim 1, wherein the residual amount of the vinyl compound having an epoxy group is 1.5% by mass or less based on the epoxy-modified silicone.   The residual amount of the by-product produced by causing an internal transition of the carbon-carbon double bond of the vinyl compound having an epoxy group is 0.5% by mass or less based on the epoxy-modified silicone. Epoxy-modified silicone.   The vinyl compound having an epoxy group is an epoxy cycloalkane having a vinyl group, and the product in which a carbon-carbon double bond of the vinyl compound having an epoxy group is internally transferred is an epoxy cycloalkane having an ethylidenyl group. The epoxy-modified silicone according to claim 3.   The epoxy-modified silicone according to claim 1, wherein the residual amount of the compound having a carbon-carbon double bond is 0.3% by mass or less based on the epoxy-modified silicone. The epoxy-modified silicone according to any one of claims 1 to 5, wherein the organohydrogen silicone is represented by the following average composition formula (1).
[Wherein R ¹ independently represents an aliphatic carbonized group comprising 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 a hydrogen unit and having 1 to 24 carbon atoms and 0 to 5 oxygen atoms, and D) an unsubstituted or substituted aromatic hydrocarbon unit, which is necessary And having an aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of a chain, a branched chain and a ring, which are unsubstituted or substituted according to the above, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms. It represents at least one organic group selected from the group consisting of the following monovalent aromatic organic groups.
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 above carbon number and oxygen number. May be included. Moreover, the hetero atom except oxygen, such as nitrogen, phosphorus, and sulfur, may be included. ]   The epoxy-modified silicone according to any one of claims 1 to 6, which has an epoxy value of 0.15 or more and 0.5 or less.   The epoxy-modified silicone according to any one of claims 1 to 7, wherein the hydrosilylation reaction is performed in the presence of a hydrosilylation catalyst and a solvent.   After adding a vinyl compound containing a compound having an epoxy group to the SiH unit of the organohydrogensilicon represented by the average composition formula (1), the reaction mixture is subjected to a temperature of 0 ° C. or higher and 100 ° C. or lower, The method for producing an epoxy-modified silicone according to any one of claims 1 to 8, comprising a step of distilling off the solvent and the compound having a carbon-carbon double bond.   The light emitting element sealing agent containing the epoxy modified silicone of any one of Claim 1 to 9.