JP2006213763A - Resin composition for sealing light-emitting element, light-emitting part, and display device given by using the light-emitting part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for sealing a light-emitting element, having excellent light resistance and excellent adhesion to the light-emitting element which is served to be exposed to open air or to be continuously used for a long time, capable of preventing damage to a light-emitting surface due to adhesion of waste, dust, etc., in case of being mounted or used, and capable of inhibiting occurrence of a crack, and to provide a light-emitting diode capable of preventing the element from being released from a sealant, scarcely causing deterioration in luminance for a long period, and therefore excellent. <P>SOLUTION: This thermosetting composition for sealing the light-emitting element contains the modified polysiloxane which has two or more organic groups having an epoxy unit in a molecule thereof, wherein the modified polysiloxane simultaneously satisfies requisites (A), (B), and (C) as follows: (A) a molecular weight peak value Mp of the modified polysiloxane is not less than 1,000; (B) an epoxy equivalent WPE is not less than 320; and (C) a content of low molecular weight fraction having a molecular weight of not more than 1,000 is not more than 5% in the modified polysiloxane. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an epoxy-modified polysiloxane that exhibits excellent light resistance and excellent adhesiveness and is useful for sealing a light emitting device.

With respect to blue or ultraviolet light emitting diodes (hereinafter referred to as “LEDs”) having an emission wavelength of 250 nm to 550 nm, high brightness products using GaN-based compound semiconductors such as GaN, GaAlN, InGaN and InAlGaN have recently been obtained. In combination with red and green light emitting LEDs, high-quality full-color images can be formed. In addition, white light-emitting LEDs are also obtained by combining blue light-emitting LEDs, ultraviolet light-emitting LEDs, and phosphors, and demand is expected to increase for backlights and general lighting for liquid crystal displays.
Conventionally, as a sealant for a light emitting element of a red or green light emitting LED, an epoxy resin containing an acid anhydride curing agent having high adhesiveness and excellent mechanical durability has been widely used. However, the epoxy resin-based sealant has low light transmittance for light in the low wavelength region from blue to ultraviolet, and is liable to be colored due to light deterioration, and has low light resistance to light in the low wavelength region. Had.

In order to solve these problems, some proposals using alicyclic hydrocarbon-based epoxy resins have been made (for example, Patent Document 1, Patent Document 2, and Patent Document 3). Was not enough.
On the other hand, a method using a silicone resin has been proposed as a sealant having high light resistance to light in a low wavelength region. However, the conventionally known silicone resin-based sealant has low adhesiveness. For example, in a light-emitting element that often receives a large thermal history depending on ON / OFF during light emission and extinction, installation conditions of the device, etc., thermal expansion The element and the sealing agent were peeled off due to the difference in the rate, and there was a tendency to cause intrusion of moisture, deterioration of the element, and the like.

Furthermore, for the purpose of improving adhesiveness, a proposal has been made to use not only a silicone resin alone but also the silicone resin and an epoxy resin excellent in adhesiveness as a sealant (for example, Patent Document 4). However, for applications exposed to the outside air, such as white LEDs, backlights for liquid crystal displays, and general lighting, or for applications that are used continuously for a long time, the adhesion is still not sufficient, and further improvements are made. Was demanded.
On the other hand, a method using a modified silicone having a skeleton in which an epoxy unit is bonded to a silicone skeleton has also been proposed. As these methods, for example, a method using a modified silicone having a skeleton in which an aromatic hydrocarbon epoxy unit is bonded to a silicone skeleton (Patent Document 5, Patent Document 6, Patent Document 7, etc.), for example, a silicone skeleton A method using a modified silicone resin composition in which an alicyclic hydrocarbon group and an epoxy unit are introduced into the side chain (Patent Document 8, Patent Document 9, etc.) is disclosed.

According to these publications, a cured product obtained by thermosetting a composition containing a modified silicone resin having an epoxy unit introduced into the side chain of a silicone skeleton and a curing agent has light resistance and heat resistance. It is disclosed that it is excellent and does not soften during use.
In particular, the composition containing a modified silicone resin in which an alicyclic hydrocarbon group and an epoxy unit are introduced into a side chain of a silicone skeleton and a curing agent is used for the above-described white LED, backlight of a liquid crystal display, outside air such as general illumination. It is described that the adhesiveness to a light emitting device for use exposed to the above or for a use continuously used for a long time is improved.
However, the cured product obtained by thermosetting the composition may cause stickiness on the surface of the cured product (that is, has surface tackiness), and the stickiness may cause foreign matters to adhere during mounting or use. As a result, the surface of the light emitting component may be damaged. In some cases, cracks may occur due to thermal stress or the like when a light-emitting diode is produced or used using the cured composition. However, in this publication, there is no description or suggestion regarding a method for suppressing the stickiness or a method for preventing the occurrence of cracks.

JP 11-274571 A JP 2000-196151 A JP 2002-226551 A JP 2002-324920 A Japanese Patent Laid-Open No. 2-028211 Japanese Patent Laid-Open No. 4-034908 Japanese Patent No. 3283606 JP 2004-155865 A JP 2004-289102 A

  The present invention has excellent adhesion to light emitting devices for excellent light resistance, applications exposed to the outside air, or applications that are used continuously for a long period of time. A light emitting device encapsulating a light-emitting element containing a modified silicone resin in which an organic group having an epoxy unit is introduced into a side chain of a silicone skeleton capable of suppressing damage to the light emitting surface due to adhesion of dust or the like and preventing occurrence of cracks. The thermosetting composition for fixing, and the element and the sealing agent formed using the composition are not peeled off, the luminance is hardly lowered over a long period of time, and the light emitting surface is damaged during mounting or use. An object of the present invention is to provide an excellent light-emitting diode in which the light emission is reduced.

In general, silicones are produced by hydrolyzing an organopolysiloxane containing a condensation-reactive group such as an organohalosilane or an organoalkoxysilane, followed by a condensation reaction, or in the presence or absence of a solvent. In the presence of a siloxane in the presence of a ring-opening polymerization method of a cyclic organosiloxane, and a method of synthesizing a compound obtained by the above-described method by a re-equilibration reaction. However, at this time, it is known that a relatively low molecular weight polymer containing cyclic siloxanes remains in the silicone in a large amount.
As a result of intensive studies to solve the above problems, the present inventors have found that the modified silicone has an organic group having a specific amount of epoxy units in the side chain of the silicone skeleton and a specific molecular weight peak value. By limiting the epoxy value of the modified silicone and the content of components having a specific molecular weight or less, there is no surface tackiness, and furthermore, the occurrence of cracks due to thermal stress or the like in the cured product can be prevented. The present invention has been completed.

That is, the present invention is as follows.
[1] A thermosetting composition for sealing a light-emitting element, comprising a modified polysiloxane having two or more organic groups having an epoxy unit in one molecule, wherein the modified polysiloxane has the following (A ) To (C) are satisfied at the same time, a thermosetting composition for sealing a light emitting device.
(A) The molecular weight peak value Mp of the modified polysiloxane is 1,000 or more.
(B) Epoxy equivalent WPE is 320 or more.
(C) Low molecular weight content of molecular weight 1,000 or less in the modified polysiloxane is 5% or less.
[2] The thermosetting composition for sealing a light-emitting element according to [1], wherein the modified polysiloxane has at least one organic group having an alicyclic hydrocarbon unit in one molecule.
[3] The thermosetting composition for sealing a light-emitting device according to [1] or [2], wherein the modified polysiloxane has a viscosity at 25 ° C. of 50,000 mPa · s or less.
[4] Any of the above [1] to [3], wherein the epoxy unit is at least one selected from the group consisting of an ethynylcyclohexene oxide unit, a glycidyl unit, an ethynylglycidyl unit, and a propylonylglycidyl unit. The thermosetting composition for light emitting element sealing as described in one.
[5] The thermosetting composition for sealing a light-emitting element according to any one of [1] to [4], wherein the alicyclic hydrocarbon unit is a cyclohexyl unit and / or a norbornyl unit.
[6] The modified polysiloxane is characterized in that the organic group having an epoxy unit and the polysiloxane are bonded through a Si—C bond, according to any one of the above [1] to [5] A thermosetting composition for sealing a light emitting device.
[7] The modified polysiloxane according to any one of [1] to [5], wherein the organic group having an epoxy unit thereof and the polysiloxane are bonded via a Si—O bond. A thermosetting composition for sealing a light emitting device.
[8] The thermosetting composition for sealing a light-emitting element according to any one of [1] to [7], wherein the modified polysiloxane has an APHA color number of 50 or less.
[9] The thermosetting composition for sealing a light emitting device, wherein the total of transition metal components contained therein is 20 ppm or less in terms of element, any one of [1] to [8] The thermosetting composition for sealing a light-emitting element according to 1.
[10] 100 parts by mass of the modified polysiloxane according to any one of [1] to [9], 0.1 part by mass or more and 100 parts by mass or less of an epoxy resin, 1 part by mass or more and 200 parts by mass of a curing agent for epoxy resin A thermosetting composition for sealing a light-emitting element, which is contained at the following ratio.
[11] A light-emitting component produced by sealing a light-emitting element using the thermosetting composition for sealing a light-emitting element according to any one of [1] to [10], and the light-emitting component were used. Display equipment.

According to the present invention, it is easy to handle, in particular, has excellent light resistance to light of 250 to 550 nm, has high adhesiveness, and can suppress damage to the light emitting surface due to stickiness of the cured product surface. A curable composition for sealing a light emitting element can be obtained.
Moreover, the light-emitting diode manufactured by sealing the light-emitting element using the curable composition for sealing a light-emitting element of the present invention can prevent generation of cracks in the sealant part due to thermal stress during lighting. It is an excellent light-emitting diode in which the element and the sealant do not peel off even for uses that are less likely to decrease in luminance over a long period of time and that are exposed to the outside air or that are used continuously for a long time. Furthermore, since the light-emitting diode manufactured by sealing the light-emitting element using the curable composition for sealing a light-emitting element of the present invention can suppress stickiness of the surface of the light-emitting component, it can be mounted or used. Thus, an excellent light-emitting diode capable of avoiding damage to the surface of the light-emitting component due to adhesion of dust, dust, etc.
Further, the light-emitting diode obtained by the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal light, a display light, a display device, and a planar light emitter It is useful as a light source, display, decoration, and various lights.

Hereinafter, the present invention will be described in detail.
The modified polysiloxane of the present invention needs to have two or more organic groups having an epoxy unit in one molecule. When the modified polysiloxane has less than 2 epoxy units, a cured product having sufficient strength cannot be obtained. The modified polysiloxane preferably contains 3 or more organic groups having an epoxy unit, more preferably 4 or more, in terms of improving the heat resistance of the cured product.
The molecular weight peak value (hereinafter abbreviated as Mp) of the modified polysiloxane of the present invention needs to be 1,000 or more. When Mp is less than 1,000, the thermosetting reaction takes a long time and the strength of the cured product is remarkably lowered. Mp in the present invention refers to a molecular weight value corresponding to the peak top of an elution curve obtained by gel permeation chromatography (GPC) measurement using monodisperse polystyrene as a standard substance.

In the elution curve obtained by the GPC measurement, when there are a plurality of peaks, Mp in the present invention refers to the maximum molecular weight of the plurality of peaks.
The preferable range of Mp is 1,200 or more, more preferably 1,500 or more, more preferably 2,000 or more, particularly preferably 2,500 or more, in that the strength of the cured product obtained after curing is increased. It is a range. The upper limit of Mp is not particularly limited because it varies depending on the primary structure of the modified polysiloxane, or a mixture of two or more kinds, but it is usually 5,000,000 or less, which is caused by fluidity and the like. In order to improve the handleability and workability, it is preferably 100,000 or less, more preferably 50,000 or less, more preferably 15,000 or less, and particularly preferably 10,000 or less.

  The content of the component having a molecular weight of 1,000 or less contained in the modified polysiloxane of the present invention is in the range of 5% or less. The content of the component having a molecular weight of 1,000 or less in the present invention is the elution start point and elution end point of the modified polysiloxane in the elution curve obtained by gel permeation chromatography (GPC) measurement using monodisperse polystyrene as a standard substance. The ratio of the peak area (peak area 2) corresponding to a molecular weight of 1,000 or less calculated from the standard substance in the elution peak area to the elution peak area (peak area 1) obtained by linking The numerical value expressed [that is, the numerical value represented by (peak area 2) / (peak area 1) × 100 (%)]. When the content of the component having a molecular weight of 1,000 or less exceeds 5%, it is not preferable because stickiness occurs on the outermost surface of the cured product after curing. The content of the component having a molecular weight of 1,000 or less is in the range of 4.5% or less in order to stably suppress the stickiness of the surface even in the use environment of the light-emitting diode obtained by sealing the light-emitting element. Preferably, the range is 4% or less, more preferably 3.5% or less. A method for reducing the content of components having a molecular weight of 1,000 or less contained in the modified polysiloxane of the present invention will be described later.

Epoxy equivalent of the modified polysiloxane of the present invention [mass (g) of modified silicone having 1 equivalent of epoxy unit, hereinafter abbreviated as WPE. ] Is 320 or more. If the WPE is less than 320, it is not preferable because cracking of the sealant portion, which is estimated to be caused by, for example, thermal stress, is likely to occur during long-time lighting or the like. WPE is the mass (g) of an epoxy-containing compound having 1 equivalent of an epoxy unit, and can be determined according to JIS K-7236. There is no particular limitation on the upper limit of WPE, but since it contains at least two epoxy units in one molecule of the modified siloxane, it is usually 2,500,000 or less, but is sufficient in the cured product obtained after curing. In view of improving the properties such as light resistance and heat resistance, it is preferably 3,000 or less, more preferably 2,000 or less, more preferably 1,500 or less, and particularly preferably 1, 000 or less, desirably 700 or less.
The structure of the modified polysiloxane having two or more organic groups having an epoxy unit in one molecule of the present invention may be linear, cyclic, branched, or ladder-shaped. Specific examples of the structure of the modified polysiloxane (hereinafter, the average composition formula is shown in the present application) are the structures represented by the following general formula (1). It may be a mixture of seeds or more.

  [The above Ra to Rg can be independently selected in a plurality of similar structural units, and each of Ra to Rg independently represents hydrogen, a hydroxyl group, a halogen atom, an unsubstituted or substituted carbon number. Is an organic group not containing an epoxy unit consisting of a linear and / or branched alkyl unit of 1 to 25 and an oxygen atom number of 0 to 5, an unsubstituted or substituted cyclic group of 4 to 25 carbon atoms Selected from the group consisting of an alkyl group and an organic group not containing an epoxy unit having 0 to 5 oxygen atoms, a chain, branched or cyclic group having 2 to 25 carbon atoms that are unsubstituted or substituted. Organic group not containing an epoxy unit consisting of one or more alkenyl units and an oxygen atom number of 0 to 5, and an unsubstituted or substituted aryl unit of 6 to 19 carbon atoms An organic group containing no epoxy unit consisting of 0 to 5 oxygen atoms, an epoxy unit as an essential constituent unit, and an unsubstituted or substituted aryl unit having 6 to 19 carbon atoms, unsubstituted or substituted An organic group composed of a chain and / or branched alkyl unit having 2 to 12 carbon atoms and an oxygen atom number of 1 to 5 and a carbon number of 3 to 25 containing an epoxy unit as an essential constituent unit. Hereinafter, it represents a monovalent aliphatic organic group having one or more structures selected from the group consisting of a chain, a branch, and a ring, which are unsubstituted or substituted, each having 1 to 5 oxygen atoms. M, D, T, and Q are integers of 0 or more each representing the number of corresponding structural units. The above Ra to Rg, and M, D, T, and Q have two or more organic groups having one epoxy molecule in the molecule, and satisfy Mp and WPE of the modified polysiloxane of the present invention. In addition, the content is appropriately selected from a range that satisfies the content of the component having a molecular weight of 1,000 or less in the modified polysiloxane of the present invention. ]

  Here, the organic group has a chain and / or branched alkyl group, a chain and / or branched alkenyl group, an aryl as the organic group, as long as the number of carbon atoms and the number of oxygen atoms is within the above ranges. Group, a halogen atom, a hydroxyl group, an alkoxyl group, an acyl group, an alkenyloxy group, an acyloxy group, a cyano group, an amino group, and an amide group, an aminoxy group in the structure of the above organic group, A mercapto group, an acid anhydride group, a carbonyl group, a saccharide, an oxazoline group, an isocyanate group and the like may be contained.

As the modified polysiloxane used in the present invention, the solubility of the curing agent necessary for making a cured product is increased, the heat resistance of the sealing agent after curing is improved, or the adhesiveness as a sealing agent. In order to improve this, it is preferable to have at least one organic group having an alicyclic hydrocarbon unit in one molecule. Here, the organic group having an alicyclic hydrocarbon unit in the present invention is a monovalent organic group containing an alicyclic hydrocarbon unit and not containing an epoxy unit, or an alicyclic hydrocarbon group. This is what it is.
As the modified polysiloxane used in the present invention, the total number of Ra to Rg containing aryl units, aralkyl units or alkenyl units with respect to the total number of Ra to Rg is 50 in that light resistance is good. % Or less, more preferably 30% or less, more preferably 10% or less, and particularly preferably not contained at all.

As the modified polysiloxane used in the present invention, a modified polysiloxane in which an organic group having an epoxy unit and a polysiloxane are bonded via a Si-C bond because of excellent light resistance or heat resistance, and A modified polysiloxane in which an organic group having an epoxy unit and a polysiloxane are bonded via a Si-C bond is preferred, and an organic group having an epoxy unit and the polysiloxane are bonded via a Si-C bond. More preferred are modified polysiloxanes.
In the present invention, the modified polysiloxane in which an organic group having an epoxy unit and a polysiloxane are bonded via a Si—C bond is represented by the chemical formula (2), the chemical formula (3), or the chemical formula (4). Preferred examples of the modified polysiloxane include linear, cyclic, or branched compounds.

[However, each R ¹ independently contains hydrogen, a hydroxyl group, a chain and / or branched aliphatic hydrocarbon having 1 to 25 carbon atoms, and an epoxy unit having 0 to 5 oxygen atoms. Each monovalent organic group, R ² is independently a chain, branched, or cyclic structure having an epoxy unit as an essential constituent unit and having 3 to 25 carbon atoms and 1 to 5 oxygen atoms. A monovalent aliphatic organic group (excluding an alkoxy group) having at least one structure selected from the group consisting of R ³ each independently having an alicyclic hydrocarbon unit having 4 to 15 carbon atoms and a carbon number Is a monovalent organic group containing no chain unit and / or branched aliphatic hydrocarbon of 0 to 12 and an epoxy unit having 0 to 5 oxygen atoms. R ⁴ , R ⁵ and R ⁶ are each independently any group of R ¹ , R ² and R ³ . p to u are each an integer of 0 or more representing the number of corresponding structural units, and when R ⁴ , R ⁵ , and R ⁶ are not R ² and r is 0, q, The total amount of s (q + s) is an integer of 2 or more, and when R ⁴ , R ⁵ , R ⁶ are not R ² and r is an integer of 1 or more, the total amount of q and s (Q + s) is an integer of 0 or more. When any of R ⁴ , R ⁵ , and R ⁶ is R ² , the total amount (q + r) of q and r is an integer of 0 or more. When all of R ⁴ , R ⁵ , and R ⁶ are not R ³ , the total amount of s to u (s + t + u) is an integer of 1 or more. When any of R ⁴ , R ⁵ , and R ⁶ is R ³ , the total amount (s + t + u) of s to u is an integer of 0 or more. p to u are the total amount (p + q + r + s + t + u) satisfying the Mp of the modified polysiloxane of the present invention, and the WPE of the present invention and the content of components having a molecular weight of 1,000 or less in the modified polysiloxane of the present invention. It is an integer selected from a satisfactory range. ]

[However, each R ¹ independently contains hydrogen, a hydroxyl group, a chain and / or branched aliphatic hydrocarbon having 1 to 25 carbon atoms, and an epoxy unit having 0 to 5 oxygen atoms. Each monovalent organic group, R ² is independently a chain, branched, or cyclic structure having an epoxy unit as an essential constituent unit and having 3 to 25 carbon atoms and 1 to 5 oxygen atoms. A monovalent aliphatic organic group (excluding an alkoxy group) having at least one structure selected from the group consisting of R ³ each independently having an alicyclic hydrocarbon unit having 4 to 15 carbon atoms and a carbon number Is a monovalent organic group containing no chain unit and / or branched aliphatic hydrocarbon of 0 to 12 and an epoxy unit having 0 to 5 oxygen atoms. p to u are integers of 0 or more each representing the number of corresponding structural units. When r is 0, the total amount of q and s (q + s) is an integer of 2 or more, and r is 1 or more. In the case of an integer, the total amount (q + s) of q to s is an integer of 0 or more. The total amount (s + t + u) of s, t, and u is an integer of 1 or more. p to u are the total amount (p + q + r + s + t + u) satisfying the Mp of the modified polysiloxane of the present invention, and the WPE of the present invention and the content of components having a molecular weight of 1,000 or less in the modified polysiloxane of the present invention. It is an integer selected from a satisfactory range. ]

[However, R ′ is at least one selected from the group consisting of the following chemical formula (5), chemical formula (6), and chemical formula (7); Is an integer. R ⁷ is independently selected from any group of R ¹ , R ² and R ³ so as to satisfy the following conditions (a) to (d) at the same time.
(A) The condition that at least R ² is 2 or more and at least R ³ is 1 or more is satisfied.
(B) Satisfying the conditions satisfying the WPE of the present invention.
(C) Both v and w are integers of 0 or more, and the value of (v + w) is an integer of 1 or more.
(D) The total amount (v + w + x) of v, w, x is an integer selected from the range satisfying the Mp of the present invention and the content of components having a molecular weight of 1,000 or less in the modified polysiloxane of the present invention. is there. ]

[However, R ⁷ is each independently a group of R ¹ , R ² , or R ³ . ]

As the modified polysiloxane of the present invention, the compounds represented by the chemical formula (2), the chemical formula (3), and the chemical formula (4) can be used alone or as a mixture of two or more. When used as a mixture of two or more kinds, the mixture only needs to satisfy the contents of components having a molecular weight of 1,000 or less in the Mp and WPE of the present invention and the modified polysiloxane of the present invention.
In the case where the modified polysiloxane in the present invention contains the compound of the chemical formula (4), the modified polysiloxane of the chemical formula (4) is v, w, and x in order to improve light resistance, heat resistance, and handleability. , X / (3 × v + 2 × w + x + 2) ranges from 0.1 to 1, w / (3 × v + 2 × w + x + 2) ranges from 0 to 0.4, v / (3 × v + 2 × The value of w + x + 2) preferably satisfies the range of 0 or more and 0.1 or less simultaneously.

When the modified polysiloxane of the present invention is one or a mixture of two or more of chemical formula (2), chemical formula (3), and chemical formula (4), it contains an alicyclic hydrocarbon unit and also contains an epoxy unit. Not containing monovalent organic groups, hydrogen, hydroxyl groups, chain and / or branched aliphatic hydrocarbons having 1 to 25 carbon atoms, and epoxy units having 0 to 5 oxygen atoms the ratio of the total number of monovalent organic groups that do not is expressed by the ratio of the organic base of ^{R 3} (NR ³⁾ and ^{R 1} of the organic groups ^{(NR 1) (NR 3 /} NR 1), in the present invention A value exceeding 0 is preferred. Although it varies depending on the type of organic group and the molecular weight of the modified polysiloxane, the above-mentioned (NR ³ / NR ¹⁾ is required for improving characteristics such as handleability, storage stability, light resistance, and heat resistance. ) Is more preferably greater than 0 and less than or equal to 20, more preferably greater than 0 and less than or equal to 15, particularly preferably greater than 0 and less than or equal to 10, desirably greater than 0 and less than or equal to 5, more desirably 0. Is in the range of more than 1 and less than 1.

When the modified polysiloxane of the present invention is one or a mixture of two or more of the chemical formula (2), the chemical formula (3), and the chemical formula (4), the organic group of R ¹ is more resistant to light. Preferably, it is a chain and / or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a chain and / or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably It is a methyl group. These organic groups may be one type or a mixture of two or more types.
When the modified polysiloxane of the present invention is one or a mixture of two or more of the chemical formula (2), the chemical formula (3), and the chemical formula (4), as R ² , the light resistance and the heat resistance are further improved. It is preferable that it is 1 type, or 2 or more types of organic groups chosen from Chemical formula (8) and Chemical formula (9).

(However, R ⁸ is a divalent aliphatic organic group in which the bond atom to Si is carbon, the carbon number is 1 or more and 10 or less, and the oxygen number is 0 or more and 5 or less.)

R ^6, which may contain an ether bond, or ester bond, for _{example, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -O -, - CH 2 -CH 2 -CH 2 _{-O -, - CH 2 -CH 2} -COO-CH 2 - and the like. The organic group represented by R ² is more preferably an organic group represented by the chemical formula (8), and more preferably an ethynylcyclohexene oxide group. These organic groups may be one type or a mixture of two or more types.
When the modified polysiloxane of the present invention is one or a mixture of two or more of the chemical formula (2), the chemical formula (3), and the chemical formula (4), the organic group of R ³ is necessary for a cured product. An alicyclic hydrocarbon unit having 4 to 15 carbon atoms and a chain and / or branched aliphatic hydrocarbon having 0 to 12 carbon atoms in that the solubility and heat resistance of the curing agent are further increased. And a cyclohexyl group, a norbornyl group, and an ethynylcyclohexyl group are more preferable. These organic groups may be one type or a mixture of two or more types.
In the present invention, the modified polysiloxane in which an organic group having an epoxy unit and a polysiloxane are bonded via a Si—O bond is represented by the chemical formula (10), the chemical formula (11), or the chemical formula (12). Preferred examples of the modified polysiloxane include linear, cyclic, or branched compounds.

[However, each R ⁹ independently contains hydrogen, a hydroxyl group, a chain and / or branched aliphatic hydrocarbon having 1 to 25 carbon atoms, and an epoxy unit having 0 to 5 oxygen atoms. A monovalent organic group, R ¹⁰ is independently a chain, branched, or cyclic group having 3 to 25 carbon atoms and having 2 to 5 oxygen atoms, each containing an epoxy unit as an essential constituent unit. A monovalent alkoxy group having at least one structure selected from the group consisting of: R ¹¹ is independently an alicyclic hydrocarbon unit having 4 to 15 carbon atoms, and 0 to 12 carbon atoms. A linear and / or branched aliphatic hydrocarbon and a monovalent organic group (excluding an alkoxy group) that does not contain an epoxy unit consisting of 0 to 5 oxygen atoms, R ¹² is independently carbon Alicyclic having 4 to 15 An alkoxy group containing no hydrocarbon unit, a chain-like and / or branched aliphatic hydrocarbon having 0 to 12 carbon atoms, and an epoxy unit having 1 to 5 oxygen atoms. R ¹³ , R ¹⁴ and R ¹⁵ are each independently any group of R ⁹ , R ¹⁰ , R ¹¹ and R ¹² . A to j are integers of 0 or more each representing the number of corresponding structural units. Here, when all of R ¹³ , R ¹⁴ , and R ¹⁵ are not R ¹⁰ and c is 0, the total amount (b + d + h) of b, d, and h is an integer of 2 or more, and R ^{When all of 13} , R ¹⁴ , and R ¹⁵ are not R ¹⁰ and c is an integer of 1 or more, the total amount of b, d, and h (b + d + h) is an integer of 0 or more. On the other hand, when any of R ¹³ , R ¹⁴ , and R ¹⁵ is R ¹⁰ , the total amount (b + c + d + h) of b, c, d, and h is an integer of 0 or more. Further, when any of R ¹³ , R ¹⁴ , and R ¹⁵ is not R ¹¹ or R ¹² and f and j are 0 at the same time, the total amount of d, e, g, h, and i (d + e + g + h + i) ) Is an integer of 1 or more, and any of R ¹³ , R ¹⁴ and R ¹⁵ is not R ¹¹ or R ¹² and at least one of f or j is an integer of 1 or more, d , E, g, h, i (d + e + g + h + i) is an integer of 0 or more. On the other hand, when any of R ¹³ , R ¹⁴ , and R ¹⁵ is R ¹¹ or R ¹² , the total amount of d, e, f, g, h, i, and j (d + e + f + g + h + i + j) is an integer of 0 or more. It is. a to j, the total amount (a + b + c + d + e + f + g + h + i + j) satisfies the Mp of the modified polysiloxane of the present invention, and the WPE of the present invention and the content of components having a molecular weight of 1,000 or less in the modified polysiloxane of the present invention. It is an integer selected from a satisfactory range. ]

[However, each R ⁹ independently contains hydrogen, a hydroxyl group, a chain and / or branched aliphatic hydrocarbon having 1 to 25 carbon atoms, and an epoxy unit having 0 to 5 oxygen atoms. A monovalent organic group, R ¹⁰ is independently a chain, branched or cyclic group having 3 to 25 carbon atoms and 2 to 5 oxygen atoms containing an epoxy unit as an essential constituent unit. A monovalent alkoxy group having at least one structure selected from the group consisting of R ¹¹ each independently having an alicyclic hydrocarbon unit having 4 to 15 carbon atoms and having 0 to 12 carbon atoms. A linear and / or branched aliphatic hydrocarbon and a monovalent organic group not containing an epoxy unit consisting of 0 to 5 oxygen atoms (excluding an alkoxy group), each R ¹² independently represents the number of carbon atoms. 4 to 15 alicyclic charcoal It is a monovalent alkoxy group not containing a hydrogen fluoride unit, a chain and / or branched aliphatic hydrocarbon having 0 to 12 carbon atoms, and an epoxy unit having 1 to 5 oxygen atoms. a to j are integers of 0 or more each representing the number of corresponding structural units. Here, when c is 0, the total amount of b, d, and h (b + d + h) is an integer of 2 or more, and when c is an integer of 1 or more, the total amount of b, d, and h (b + d + h). ) Is an integer of 0 or more. When f and j are 0 at the same time, the total amount of d, e, g, h, i (d + e + g + h + i) is an integer of 1 or more, and at least one of f or j is an integer of 1 or more. The total amount (d + e + g + h + i) of d, e, g, h, i is an integer of 0 or more. a to j, the total amount (a + b + c + d + e + f + g + h + i + j) satisfies the Mp of the modified polysiloxane of the present invention, and the WPE of the present invention and the content of components having a molecular weight of 1,000 or less in the modified polysiloxane of the present invention. It is an integer selected from a satisfactory range. ]

[However, R ″ is at least one selected from the group consisting of the following chemical formula (13), chemical formula (14), and chemical formula (15), and k, l, and m are each 0 representing the number of corresponding structural units. It is an integer above. Furthermore. R ¹⁶ is independently selected from any group of R ⁹ , R ¹⁰ , and R ¹¹ and simultaneously satisfies the following conditions (e) to (h).
(E) The condition that at least R ¹⁰ is 2 or more and at least R ¹¹ or R ¹² is 1 or more is satisfied.
(F) Satisfying the condition for satisfying the WPE of the present invention.
(G) k and l are both integers greater than or equal to 0, and the value of (k + l) is an integer greater than or equal to 1.
(H) The total amount (k + l + m) of k, l and m is an integer selected from the range satisfying the Mp of the present invention and the content of components having a molecular weight of 1,000 or less in the modified polysiloxane of the present invention. is there. ]

[However, R ⁷ is each independently a group of R ¹ , R ² , or R ³ . ]

As the modified polysiloxane of the present invention, the compounds represented by the chemical formula (10), the chemical formula (11), and the chemical formula (12) can be used singly or as a mixture of two or more. When used as a mixture of two or more kinds, the mixture only needs to satisfy the contents of components having a molecular weight of 1,000 or less in the Mp and WPE of the present invention and the modified polysiloxane of the present invention.
In the case where the modified polysiloxane in the present invention contains the compound of the chemical formula (4), the modified polysiloxane of the chemical formula (12) is k, l, m in order to improve light resistance, heat resistance, and handleability. , M / (3 × k + 2 × l + m + 2) is in the range of 0.1 to 1, and l / (3 × k + 2 × l + m + 2) is in the range of 0 to 0.4, k / (3 × k + 2 × The value of l + m + 2) preferably satisfies the range of 0 to 0.1 at the same time.

When the modified polysiloxane of the present invention is one or a mixture of two or more of chemical formula (10), chemical formula (11), and chemical formula (12), it contains an alicyclic hydrocarbon unit and also contains an epoxy unit. Not containing monovalent organic groups, hydrogen, hydroxyl groups, chain and / or branched aliphatic hydrocarbons having 1 to 25 carbon atoms, and epoxy units having 0 to 5 oxygen atoms The ratio between the total number of organic groups of R ¹¹ and R ¹² [N (R ¹¹ , R ¹² )] and the number of organic groups of R ⁹ (NR ⁹ ) [N (R ¹¹ , R ¹² ) / NR ⁹ ], and in the present invention, a value exceeding 0 is preferable. Although it depends on the type of organic group and the molecular weight of the modified polysiloxane, [N (R ¹¹ , R ¹² ] can be used to improve properties such as handleability, storage stability, light resistance, and heat resistance. ) / NR ⁹ ] is more preferably more than 0 and 20 or less, more preferably more than 0 and 15 or less, particularly preferably more than 0 but 10 or less, desirably more than 0 but 5 or less, More desirably, it is in the range of more than 0 and 1 or less.

When the modified polysiloxane of the present invention is one or a mixture of two or more of the chemical formula (10), the chemical formula (11), and the chemical formula (12), the organic group of R ⁹ is more light-resistant. Preferably, it is a chain and / or branched aliphatic hydrocarbon having 1 to 20 carbon atoms and a monovalent organic group not containing an epoxy unit having 0 to 5 oxygen atoms, more preferably a carbon number. 1 or more and 8 or less chain and / or branched aliphatic hydrocarbons and monovalent organic groups not containing an epoxy unit having 0 or more and 2 or less oxygen atoms, more preferably n-propyl groups, isopropyl groups, An ethyl group, a methyl group, an n-propoxy group, an isopropoxy group, an ethoxy group, and a methoxy group. These organic groups may be one type or a mixture of two or more types.
When the modified polysiloxane of the present invention is one or a mixture of two or more of the chemical formula (10), the chemical formula (11), and the chemical formula (12), as R ¹⁰ , the light resistance and the heat resistance are further improved. It is preferable that it is 1 type, or 2 or more types of organic groups chosen from Chemical formula (16) and Chemical formula (17).

(Wherein R ¹⁷ is an oxygen atom or a divalent chain and / or branched divalent aliphatic organic group having 1 to 10 carbon atoms and 1 to 5 oxygen atoms, Is an organic group in which the bonding atom is an oxygen atom.)

R ¹⁷ may contain an ether bond or an ester bond, and examples thereof include —O—CH ₂ —, —O—CH ₂ —CH ₂ —, —O—CH ₂ —CH ₂ —O—, —O—. _{CH 2 -CH 2 -CH 2 -O -} , - O-CH 2 -CH 2 -COO-CH 2 -, - O-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -COO-CH 2 - Specifically, as the organic group represented by the chemical formula (16), an oxycyclohexene oxide group, an oxymethylenecyclohexene oxide group, and an oxyethylenecyclohexene oxide group, while the organic group represented by the chemical formula (17) is oxy Examples thereof include a glycidyl group, an oxyethylene glycidyl ether group, and an oxypropylene glycidyl ether group. The organic group for R ¹⁷ is more preferably an organic group represented by the chemical formula (16), and more preferably an oxycyclohexene oxide group or an oxymethylene cyclohexene oxide group. These organic groups may be one type or a mixture of two or more types.

When the modified polysiloxane of the present invention is one or a mixture of two or more of the chemical formula (10), the chemical formula (11), and the chemical formula (12), the organic group of R ¹¹ is necessary to form a cured product. An alicyclic hydrocarbon unit having 4 to 15 carbon atoms and a chain and / or branched aliphatic hydrocarbon having 0 to 12 carbon atoms in terms of further improving the solubility and heat resistance of the curing agent. The monovalent organic group which does not contain the epoxy unit which consists of these is preferable, and a cyclohexyl group and an ethynyl cyclohexyl group are still more preferable. These organic groups may be one type or a mixture of two or more types.
When the modified polysiloxane of the present invention is one or a mixture of two or more of the chemical formula (10), the chemical formula (11), and the chemical formula (12), the light resistance and heat resistance of the organic group of R ¹² are further increased. In that respect, it comprises an alicyclic hydrocarbon unit having 4 to 12 carbon atoms, a chain and / or branched aliphatic hydrocarbon having 0 to 6 carbon atoms, and 1 to 5 oxygen atoms. A monovalent alkoxy group containing no epoxy unit is more preferable, and an oxycyclohexyl group and an oxyethynylcyclohexyl group are more preferable. These organic groups may be one type or a mixture of two or more types.
The viscosity of the modified polysiloxane of the present invention is preferably 50,000 mPa · s or less, more preferably 25,000 mPa · s or less at 25 ° C. in order to improve the handleability and workability due to fluidity and the like. More preferably, it is 15,000 mPa · s or less, particularly preferably 10,000 mPa · s or less. The lower limit of the viscosity of the modified polysiloxane is not particularly limited as long as the Mp of the modified polysiloxane is within the range of the present invention.

  The modified polysiloxane having an epoxy group and an organic group having an alicyclic hydrocarbon unit, if necessary, used in the present invention is a conventionally known method, for example, (a-1) an organo group containing a Si-H group. A method of introducing an organic group having an epoxy unit by a hydrosilylation reaction using a polysiloxane as a substrate, and an organic group having an alicyclic hydrocarbon unit, if necessary, (a-2) organohalosilane, organoalkoxysilane, etc. An organic group having an epoxy unit and an organic group having an alicyclic hydrocarbon unit, if necessary, by subjecting the organosiloxane containing a condensation-reactive group to a substrate, hydrolyzing as necessary, and then subjecting to a condensation reaction. A method of producing a group by introducing a group, and further (a-3) an organic group having an epoxy unit and, if necessary, an alicyclic hydrocarbon unit A method of synthesizing a cyclic organosiloxane containing an organic group by a method of ring-opening polymerization in the presence of a chain siloxane containing or not containing a Si-H group in the molecule, if necessary (a- 4) The modified polysiloxanes obtained by the methods described in the above (a-1), (a-2), and (a-3) can be produced by a method such as synthesis by a re-equilibration reaction. Of these, modified polysiloxanes obtained by the method (a-1) or (a-2) or the method (a-1) and / or (a-2) may be used as necessary (a The method of producing a modified polysiloxane having a structure different from the above by subjecting to a re-equilibration reaction by the method of -3) is a modified polysiloxane having excellent light resistance by a simple operation, specifically, an epoxy unit. This is a preferable method because it is possible to produce a modified polysiloxane in which an organic group having a polysiloxane and a polysiloxane are bonded via Si—C bond and / or Si—O bond.

Among the above, the method of introducing an organic group into the organopolysiloxane containing Si—H group by hydrosilylation reaction is a modification in which an organic group having an epoxy unit and the polysiloxane are bonded via a Si—C bond. This method is preferable in the case of producing a polysiloxane, and a method of introducing an organic group into a condensation-reactive group-containing organopolysiloxane by a condensation reaction is such that an organic group having an epoxy unit and the polysiloxane are bonded via a Si-O bond. This is preferred when producing modified polysiloxanes.
In the hydrosilylation reaction, the Si-H group-containing organopolysiloxane and the vinyl group-containing compound are sequentially or continuously in the presence or absence of a catalyst, in the presence or absence of a solvent, or An example is a method of batch addition and an addition reaction. The vinyl group-containing compound used in the above addition reaction can be used as one kind or a mixture of two or more kinds.

There is no restriction | limiting in particular as organopolysiloxane containing Si-H group used in this invention, It is possible to use the organopolysiloxane which has a structure shown below.
As the organopolysiloxane containing a Si—H group, for example, a chain, cyclic or branched compound represented by chemical formula (18), chemical formula (19), or chemical formula (20) can be used. . These can be used alone or as a mixture of two or more.

[However, each of R ¹⁸ is independently a hydroxyl group, a halogen atom, an unsubstituted or substituted chain and / or branched alkyl unit having 1 to 25 carbon atoms and an oxygen atom number of 0 to 5; An alkenyl unit having at least one structure selected from the group consisting of an organic group containing no epoxy unit, an unsubstituted or substituted carbon group having 2 to 25 carbon atoms, a chain, a branched chain, or a ring, and the number of oxygen atoms An organic group containing no epoxy unit consisting of 0 or more and 5 or less, an unsubstituted or substituted aryl unit having 6 to 19 carbon atoms, and an organic group containing no epoxy unit consisting of 0 to 5 oxygen atoms , Do containing R ¹⁹ is hydrogen, R ²⁰ is an epoxy units each alkyl units and the number of oxygen atoms of the unsubstituted or substituted having 4 to 25 ring carbon independently consists 0 to 5 It is an organic group. R ²¹ , R ²² , R ²³ are each independently any group of R ¹⁸ , R ¹⁹ , R ²⁰ , and A to F are integers of 0 or more each representing the number of corresponding structural units. is there. ]

[However, each of R ¹⁸ is independently a hydroxyl group, a halogen atom, an unsubstituted or substituted chain and / or branched alkyl unit having 1 to 25 carbon atoms and an oxygen atom number of 0 to 5; An alkenyl unit having at least one structure selected from the group consisting of an organic group containing no epoxy unit, an unsubstituted or substituted carbon group having 2 to 25 carbon atoms, a chain, a branched chain, or a ring, and the number of oxygen atoms An organic group containing no epoxy unit consisting of 0 or more and 5 or less, an unsubstituted or substituted aryl unit having 6 to 19 carbon atoms, and an organic group containing no epoxy unit consisting of 0 to 5 oxygen atoms , Do containing R ¹⁹ is hydrogen, R ²⁰ is an epoxy units each alkyl units and the number of oxygen atoms of the unsubstituted or substituted having 4 to 25 ring carbon independently consists 0 to 5 It is an organic group. ]

[However, R ′ ″ is at least one selected from the group consisting of the following chemical formula (21), chemical formula (22), and chemical formula (23), and G, H, and I represent the number of corresponding structural units, respectively. It is an integer of 0 or greater. R ²⁴ is each independently any group of R ¹⁸ , R ¹⁹ , and R ²⁰ . ]

[However, R ²⁴ is each independently a group of R ¹⁸ , R ¹⁹ , or R ²⁰ . ]

Here, the organic group has a chain and / or branched alkyl group, a chain and / or branched alkenyl group, an aryl as the organic group, as long as the number of carbon atoms and the number of oxygen atoms is within the above ranges. Group, a halogen atom, a hydroxyl group, an alkoxyl group, an acyl group, an alkenyloxy group, an acyloxy group, a cyano group, an amino group, and in the structure of the organic group, an amide group, an aminoxy group, A mercapto group, an acid anhydride group, a carbonyl group, a saccharide, an oxazoline group, an isocyanate group and the like may be contained.
The molecular weights of these organopolysiloxanes containing Si-H groups are the same as that of the epoxy unit obtained after the hydrosilylation reaction, and Mp and WPE of the modified polysiloxane having an alicyclic hydrocarbon unit if necessary. There is no particular limitation as long as it is 1,000 or more and 320 or more, which is an essential requirement, and it is usually 700 or more in consideration of an increase in molecular weight due to addition of a vinyl compound.

On the other hand, the content of Si-H groups in one molecule of the organopolysiloxane containing these Si-H groups is modified with epoxy units obtained after the hydrosilylation reaction and, if necessary, alicyclic hydrocarbon units. There is no particular limitation as long as polysiloxane contains 2 or more epoxy units in one molecule, which is an essential constituent of the present invention, and WPE is 320 or more, and usually 2 or more.
Good light resistance among organic groups of organopolysiloxane containing chain-like, cyclic, or branched Si-H groups represented by chemical formula (18), chemical formula (19) or chemical formula (20) in that the, aryl units to the total number of the ^R 18 ^{to R 20,} aralkyl units, or the total number of ^R 18 ^{to R 20} containing alkenyl units is preferably 50% or less, 30% or less More preferably, it is more preferably 10% or less, and particularly preferably not at all, and R ¹⁸ each independently represents a hydroxyl group, a chain having 1 to 25 carbon atoms, and / or branched. aliphatic hydrocarbons and the number of oxygen atoms is a monovalent organic group containing no epoxy units consisting of 0 to 5, and, R ²⁰ carbon atoms each independently from 4 to 15 Monovalent organic group not containing an alicyclic hydrocarbon unit, a chain and / or branched aliphatic hydrocarbon having 0 to 12 carbon atoms, and an epoxy unit having 0 to 5 oxygen atoms It is desirable that

  These organopolysiloxanes are (b-1) other chloro or alkoxysilanes having Si—H groups in the molecule, and other or no Si—H groups in the molecule as required. Silanols are produced by hydrolysis in the presence of chloro or alkoxysilanes, and then these are subjected to a condensation reaction, or (b-2) cyclic siloxanes containing Si-H groups in the molecule are required. Depending on the situation, in the presence of other cyclic siloxanes containing or not containing Si-H groups in the molecule, chain and / or branched siloxanes containing or not containing Si-H groups in the molecule It can be obtained by ring-opening polymerization in the coexistence. Furthermore, the organopolysiloxanes obtained by the above methods (b-1) and (b-2) may be used for re-equilibration reaction. These can be used as one kind or a mixture of two or more kinds.

The vinyl group-containing compound that can be used in the present invention is a compound containing at least one or more epoxy units and at least one vinyl group in the molecule, at least one or more containing no epoxy units in the molecule. The compound containing the vinyl group of these is mentioned. Among these, compounds containing no epoxy unit in the molecule and containing at least one vinyl group can be used as necessary.
Examples of the compound containing at least one epoxy unit and at least one vinyl group in the molecule include vinyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, vinyl cyclohexene oxide, and the like. , Vinyl glycidyl ether, vinylcyclohexene oxide and the like are preferred. A compound containing at least one or more epoxy units and at least one or more vinyl groups in these molecules can be used as one kind or a mixture of two or more kinds.

  The compound containing no epoxy unit in the molecule and containing at least one vinyl group is not particularly limited as long as it is a compound that generates an alicyclic hydrocarbon unit after the reaction. For example, norbornene, norbornadiene, Polycyclic vinyl group-containing hydrocarbons such as dicyclopentadiene and vinyldecahydronaphthalene, monocyclic vinyl group-containing hydrocarbons such as vinylcyclohexane, vinylcyclohexene, cyclohexene, 1,2,4-trivinylcyclohexane, And triallyl isocyanurate. Of these, compounds having one vinyl group in the molecule, such as norbornene, vinylcyclohexane, cyclohexene and the like, are preferably used since they have high light resistance. Cyclohexene is more preferably used. A compound containing no epoxy unit in these molecules and containing at least one vinyl group can be used as one kind or a mixture of two or more kinds.

In the present invention, the composition of the vinyl group-containing compound used in the hydrosilylation reaction, specifically, at least one epoxy unit in the molecule, and a compound containing at least one vinyl group, The mass ratio of the compound containing no epoxy unit in the molecule and containing at least one vinyl group is not particularly limited as long as the modified polysiloxane of the present invention is produced.
Examples of the hydrosilylation reaction catalyst that can be used in the present invention include metals of group 8 of the periodic table, those in which these metal solids are supported on a carrier such as alumina, silica, carbon black, and salts of these metals. And complexes. 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 catalyst amount varies greatly depending on the reactivity of the Si-H-containing organopolysiloxane used and the vinyl group-containing compound used, and is not particularly limited, but is usually 0.0001 ppm or more with respect to the mass of the Si-H-containing organopolysiloxane. It is used in the range of 10% by mass or less. When the catalyst amount is less than 0.0001 ppm in terms of moles relative to the moles of Si—H contained in the Si—H containing organopolysiloxane, the reaction rate tends to decrease. On the other hand, when the amount exceeds 10% by mass, the product after the hydrosilylation reaction is remarkably colored, and the coloring may not be removed. The catalyst can be added to the reaction system sequentially, continuously, or in a lump within the above range.

  In the present invention, the reaction temperature when introducing an organic group into the organopolysiloxane containing Si-H groups by hydrosilylation reaction is the kind and molecular weight of the organopolysiloxane containing Si-H groups used, or vinyl groups. There is no particular limitation because it varies depending on the type of the compound to be contained, and also the reaction mode such as batch, semi-batch, or continuous. However, from the viewpoint of increasing the reaction rate and completing the reaction efficiently, it is 0 ° C. The range of 20 ° C. or lower is preferable, the range of 20 ° C. or higher and 170 ° C. or lower is more preferable, the range of 40 ° C. or higher and 150 ° C. or lower is more preferable, and the range of 50 ° 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 constant or may be changed in the middle.

In the present invention, when an organic group is introduced into an organopolysiloxane containing a Si—H group by a hydrosilylation reaction, it is preferable to use a solvent because the reaction heat can be easily removed by the addition reaction.
Examples of the solvent used include ether solvents such as 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. Ketone solvents, hydrocarbon solvents such as hexane, toluene, xylene and cyclohexane, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as butyl cellosolve and butyl carbitol. Of these, ether solvents, ester solvents, ketone solvents, and hydrocarbon solvents are preferred, and 1,4-dioxane, methyl isobutyl ketone, hexane, toluene, xylene, and butyl acetate are the raw material solubility and solvent recoverability. Is particularly preferred. When a solvent is used for the reaction, the solvent is generally recovered by distillation.

  When the reaction is performed using a vinyl compound in a stoichiometric amount or more with respect to Si-H of the organopolysiloxane containing Si-H groups, the reaction mixture is usually unreacted or the excess vinyl compound is removed, Performed by distillation. In some cases, the liquid-liquid extraction method, specifically, the polarity of the unreacted or surplus vinyl compound and the polarity of the modified polysiloxane obtained by the hydrosilylation reaction are greatly different, and both are dissolved. In the case where the solvent is different and the solutions after dissolution are phase-separated from each other, a liquid-liquid extraction method using a solvent for the unreacted or surplus vinyl compound and the modified polysiloxane obtained by the hydrosilylation reaction. Can also be separated. The solvent used is not limited because it varies depending on the type of vinyl group-containing compound to be subjected to the hydrosilylation reaction, the type of organopolysiloxane containing Si-H groups, and the like. Species solvent systems are mentioned.

As described above, the purification operation to remove unreacted raw materials and catalysts is a storage stability typified by gelation of the modified polysiloxane or the thermosetting composition for sealing a light emitting device of the present invention. This is a preferable method in order to improve the property and to suppress the coloring of the cured product.
In the present invention, a reaction in which a predetermined organic group is introduced by condensation using an organosiloxane containing a condensation reactive group such as an organohalosilane or an organoalkoxysilane in the presence of a solvent in the presence or absence of a catalyst. Examples thereof include a method in which a compound containing a predetermined organic group and a condensation reactive group is added to the condensation reactive group-containing organosiloxane in the presence or absence of the reaction in a sequential, continuous or batchwise manner.

  The condensation-reactive group-containing organopolysiloxane used in the present invention is not particularly limited, but in order to maintain the light transmittance in the ultraviolet to low wavelength region at a high level, hydrocarbon groups and / or alicyclic carbonization. Condensation-reactive group-containing polysiloxane containing a hydrogen group as an organic group, for example, condensation-reactive group-containing polymethylsiloxane, condensation-reactive group-containing polyethylsiloxane, condensation-reactive group-containing polyethylmethylsiloxane, condensation-reactive group Containing polyoctylmethylsiloxane is preferably used. The condensation-reactive group-containing organopolysiloxane may be linear, cyclic, branched, or ladder-shaped. Moreover, the said condensation reactive group containing organopolysiloxane may be used independently, or 2 or more types of mixtures may be sufficient as it.

In the present invention, examples of the condensation reactive group of the condensation reactive group-containing polysiloxane include a halogen group, a hydroxyl group, and a condensation reactive organic group having 1 to 25 carbon atoms. Specific examples of the condensation-reactive organic group include, for example, an alkoxy group such as a methoxy group and an ethoxy group, an acyloxy group such as an acetoxy group, an amino group such as a dimethylamino group, and an oxime group such as a methylethylketoxime group. . As the condensation reactive group, a hydroxyl group, an alkoxyl group, and an acyloxy group are preferable. One or more of these condensation-reactive groups may coexist.
Examples of the hydroxy compound include hydroxy compounds having an epoxy unit and other hydroxy compounds.

Further, examples of the hydroxy compound having an epoxy unit include glycidol, hydroxyethyl glycidyl ether, hydroxymethylcyclohexene oxide, hydroxycyclohexene oxide, and a caprolactone-modified product of the hydroxy compound having the epoxy unit. Hydroxy compounds having units are used.
The other hydroxy compound may be a hydroxy compound that generates an alicyclic hydrocarbon unit after the reaction, and examples thereof include cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, norborneol, and methyl derivatives thereof. It is done. Of these, cyclohexanol is preferably used because of its availability.
Examples of the condensation reaction catalyst that can be used in the present invention include titanate compounds such as tetraisopropyl titanate, aluminum compounds such as tris (acetylacetone) aluminum, zirconium compounds, tin compounds such as dibutyltin dilaurate, and zinc such as zinc octylate. Examples include compounds, lead compounds, ammonium salts and the like.

The reaction temperature when condensing an organopolysiloxane containing a condensation reactive group such as an organohalosilane or an organoalkoxysilane is in the range of 0 ° C. or higher and 200 ° C. or lower in terms of increasing the reaction rate and efficiently completing the reaction. The range of 20 ° C to 170 ° C is more preferable, the range of 40 ° C to 160 ° C is more preferable, and the range of 50 ° C to 140 ° C is particularly preferable. The reaction temperature does not need to be constant as long as it is within the above range, and may be constant or may be changed in the middle.
Examples of the solvent used when condensing an organopolysiloxane containing a condensation reactive group such as an organohalosilane or an organoalkoxysilane include ether solvents such as 1,4-dioxane and 1,3-dioxane, methyl isobutyl, and the like. Examples thereof include ketone solvents such as ketones, hydrocarbon solvents such as toluene and xylene, and ester solvents such as butyl acetate. When a solvent is used for the reaction, the solvent is generally recovered by distillation.

  In the modified polysiloxane of the present invention, the content of the molecular weight of 1,000 or less in the modified polysiloxane needs to be 5% or less. The means for setting the content of the molecular weight of 1,000 or less in the modified polysiloxane to 5% or less is not particularly limited. For example, the modified polysiloxane of the present invention may be an organopolysiloxane containing Si-H groups. In the case of producing the substrate by a method of introducing an organic group having an epoxy unit by a hydrosilylation reaction and, if necessary, an organic group having an alicyclic hydrocarbon unit, (c-1) prior to the hydrosilylation reaction. The catalyst is removed from the organopolysiloxane containing Si-H groups used as a substrate, if necessary, and then subjected to heating and reduced pressure conditions, or nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide gas, etc. Heating in the flow of one or more gases selected from an inert gas, a lower saturated hydrocarbon gas or air, or , A method for reducing the content of the low molecular weight component by subjecting to these mixing conditions, (c-2) after the hydrosilylation reaction, unreacted, or only the surplus vinyl compound is heated and subjected to reduced pressure conditions. Or heating under an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or one or more gases selected from lower saturated hydrocarbon gases or air, or , Not only distilling under these mixing conditions, but also distilling together the modified polysiloxane component having a molecular weight of 1,000 or less,

  (C-3) The method of reducing a low molecular weight component by using 1 type, or 2 or more types of solvent from the modified polysiloxane obtained by hydrosilylation reaction, the method by these combination, etc. are mentioned. On the other hand, the modified polysiloxane of the present invention is subjected to a predetermined organic group in a condensation-reactive group-containing organosiloxane such as organohalosilane or organoalkoxysilane in the presence or absence of a catalyst or in the presence or absence of a solvent. And (c-4) removing the catalyst from the modified polysiloxane as necessary, and then subjecting it to heating and reduced pressure conditions, or Heating under an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or one or more gases selected from lower saturated hydrocarbon gases and air, or A method of reducing the content of a modified polysiloxane component having a molecular weight of 1,000 or less by being subjected to these mixing conditions; and (c-5) the modified policy. The use of one or more solvents from hexane, a method of reducing the low molecular weight component, or method due combinations thereof.

In the present invention, the APHA chromaticity of the modified polysiloxane is preferably 50 or less, more preferably 40 or less, more preferably 30 or less.
A light-emitting diode obtained by sealing a light-emitting element using a modified polysiloxane having an APHA chromaticity of more than 50 as a light-emitting element sealant-curing composition may cause a change in color tone or a decrease in luminance during use.
Here, APHA chromaticity can be measured on the basis of a standard concentration of platinum-cobalt by a measurement method of ASTM-D-1209.
As a method for reducing APHA chromaticity, the epoxy unit of the present invention obtained by a conventionally known method and, if necessary, a modified polysiloxane having an alicyclic hydrocarbon unit, activated carbon, silica gel, alumina powder as necessary Examples thereof include a method of treating with an adsorbent such as an ion exchange resin, a method of removing unreacted raw materials and solvents, and the like.

As the curable composition for sealing a light-emitting device of the present invention, the crosslinking reaction sufficiently proceeds during the curing reaction, excellent in light resistance and heat resistance, low moisture permeability, and excellent in adhesion to the light-emitting device. Therefore, it is preferable to contain an epoxy resin and / or a curing agent for epoxy resin. Furthermore, in addition to the above-described components, a curing accelerator, a modifier, an inorganic filler, a silane coupling agent, an antifoaming agent, a colorant, a phosphor, a discoloration inhibitor, a light diffusing agent, and a heat conductive filler, if necessary. It is also possible to mix conventionally known additives as appropriate.
Examples of the epoxy resin used in the present invention include glycidyl ethers, alicyclic epoxy resins, and other epoxy resins obtained by hydrogenating aromatic rings of aromatic epoxy resins represented by conventionally known aromatic glycidyl ethers. Etc. These can be used as one kind or a mixture of two or more kinds.

  Examples of the aromatic glycidyl ether include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, and tetrachloro. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as bisphenol A and tetrafluorobisphenol A, and epoxy obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Resin, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methyl ester) Epoxy resin obtained by glycidylation of trisphenol such as l) phenyl) ethylidene) bisphenol, epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane, phenol novolac Novolak type epoxy resins obtained by glycidylating novolaks such as cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, and the like.

The aromatic ring hydrogenation reaction of the aromatic glycidyl ether can be carried out by a conventionally known method using, for example, a ruthenium catalyst, a rhodium catalyst, or the like.
Examples of the alicyclic epoxy resins include conventionally known compounds such as 1,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-bis (hydroxymethyl) -1-butanol. Examples include 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. A compound etc. can be illustrated.

When an aromatic epoxy resin is used as the epoxy resin, the ratio of the aromatic epoxy resin to the total mass of the epoxy resin used is 50% by mass or less in that light resistance is improved. The content is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably an epoxy resin containing no aromatic epoxy resin as the epoxy resin.
The amount of the epoxy resin used is preferably 0.1 to 100 parts by mass, more preferably 1 to 100 parts by mass, and still more preferably 1 to 80 parts by mass with respect to 100 parts by mass of the modified polysiloxane.

  Examples of the curing agent for epoxy resin that can be used in the present invention include aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine, and metaphenylenediamine. , Aromatic amines such as paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenolmethane, 4,4′-diaminodiphenol ether , Mercaptans such as mercaptopropionic acid esters, terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, Tramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- ( 1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolak, cresol novolak, bisphenol A novolak,

  Phenol resins such as brominated phenol novolak and brominated bisphenol A novolak, polyols obtained by hydrogenating the aromatic ring of the phenol resin, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydro Phthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl- Alicyclic acid anhydrides such as norbornane-2,3-dicarboxylic acid anhydride, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 2-methylimidazole, 2-ethyl Imidazoles such as -4-methylimidazole and 2-phenylimidazole And salts thereof, amine adducts obtained by the reaction of the above aliphatic amines, aromatic amines, and / or imidazoles with epoxy resins, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine, 1,8-diazabicyclo [ 5.4.0] tertiary amines such as undecene-7, organic phosphines such as triphenylphosphine, dicyandiamide and the like.

Among these, alicyclic acid anhydrides and aromatic acid anhydrides are preferable because the curing speed is increased, and the light resistance of the cured product is further increased, so that alicyclic acid anhydrides are further increased. Preferably, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, and methyl-norbornane-2,3-dicarboxylic anhydride are more preferably used.
These curing agents can be used as one kind or a mixture of two or more kinds.
The amount of the epoxy resin curing agent used is preferably 1 part by mass or more and 200 parts by mass or less, and more preferably 2 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the modified polysiloxane.

  The thermosetting composition for sealing a light emitting device obtained in the present invention may contain a curing accelerator as necessary. Examples of the curing accelerator used include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7. And salts thereof, 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.

Examples of the modifier preferably used in the thermosetting composition for sealing a light emitting device of the present invention include polyols containing two or more hydroxyl groups in one molecule, and aliphatic polyols such as ethylene glycol. And glycerin are more preferably used. These modifiers can be used as one kind or a mixture of two or more kinds. The modifier may impart flexibility to the cured product and improve peel adhesion.
The inorganic filler preferably used in the thermosetting composition for sealing a light emitting device of the present invention has an average particle diameter equal to or less than the wavelength of the LED to be used in order to avoid adverse effects on the transmittance, and more preferably, The average particle diameter is 100 nm or less. Inorganic fillers may improve, for example, mechanical properties or thermal conductivity.

The silane coupling agent preferably used in the thermosetting composition for sealing a light emitting device of the present invention is a compound having no aromatic group or halogen atom.
In the thermosetting composition for sealing a light-emitting element obtained in the present invention, the residue of the hydrosilylation catalyst or condensation reaction catalyst used in producing the modified polysiloxane of the present application, or the metal component eluted from the reaction apparatus Etc. may be mixed. For example, when SUS316 alloy is used, metal elements such as Fe, Ni, Cr, and Mo may be eluted. According to the study by the present inventors, it has been found that these metals, particularly transition metal components, may affect the light resistance of the thermosetting material for sealing a light emitting device. In order to maintain the light resistance of the thermosetting product for sealing a light emitting device at a high level, the residual amount of the transition metal component corresponding to Groups 3 to 11 of the periodic table for the thermosetting composition for sealing a light emitting device is: The total amount of the transition metal component is preferably 20 ppm or less, more preferably 10 ppm or less, more preferably 5 ppm or less in terms of element.

Examples of the method for reducing the transition metal component include a method in which the reaction solution after the reaction is passed through an adsorbent such as activated carbon, silica gel, alumina powder, ion exchange resin, and the like to adsorb and remove the metal component. In addition, the amount of the catalyst used for the production of the modified polysiloxane of the present application, such as hydrosilylation reaction and condensation reaction, is preliminarily emitted in consideration of the amount of the transition metal element eluted from the reaction apparatus after the reaction, if necessary. A preferable method is a method of reducing the residual amount of the transition metal component with respect to the element sealing thermosetting composition so as to be not more than the above range.
A known method can be used as the method for curing the thermosetting composition for sealing a light emitting device of the present invention.

Among the known techniques in the previous period, 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 is a preferable method in the present invention. It can be illustrated. The temperature for curing by heating is not particularly limited because it depends on the epoxy resin and the curing agent used, but is usually in the range of 80 to 200 ° C.
The curing reaction is performed under an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or an atmosphere such as a lower saturated hydrocarbon gas or air, under reduced pressure or under pressure. Can do. These gases can be used as one kind or a mixture of two or more kinds. Of these, the preferred gas is nitrogen.

A light emitting diode is formed by sealing a light emitting element using the curable composition of this invention.
The emission wavelength of the light-emitting element used in the present invention can be widely used from infrared to red, green, blue, purple, and ultraviolet, and the conventional sealant has insufficient light resistance and deteriorates to 250 nm to 550 nm. Can be used practically up to the light of the wavelength. As a result, a white light-emitting diode having a long life, high energy efficiency, and high color reproducibility can be obtained. The emission wavelength in the present invention refers to the main emission peak wavelength.
As a specific example of the light emitting element to be used, for example, a light emitting element formed by stacking semiconductor materials on a substrate can be exemplified. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

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

The light emitting diode of this invention can be manufactured by sealing a light emitting element with the curable composition of this invention. In this case, the light-emitting element can be sealed only with the curable composition of the present invention, but other sealing agents can be used in combination. When other sealants are used in combination, after sealing with the curable composition of the present invention, the periphery is sealed with other sealants, or after being sealed with other sealants, It is also possible to seal the periphery with the curable composition of the present invention. Examples of other sealants include epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, and glass.
As a method for sealing a light emitting element with the curable composition of the present invention, for example, a curable composition is pre-injected into a mold mold, and a lead frame having a light emitting element fixed thereon is immersed therein and cured. And a method of injecting a curable composition into a mold in which a light emitting element is inserted and curing. In this case, examples of the method for injecting the curable composition include injection by a dispenser, transfer molding, injection molding and the like. Further, as other sealing methods, a curable composition is dropped on a light emitting element, stencil printing, screen printing, or a method of applying and curing through a mask, curing to a cup or the like in which a light emitting element is arranged in a lower part. The method of inject | pouring a property composition with a dispenser etc., and making it harden | cure is mentioned.

The curable composition of the present invention can also be used as a die bond material for fixing a light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.
Examples of the shape of the sealing portion include a bullet-shaped lens shape, a plate shape, and a thin film shape.
The light emitting diode of the present invention can be improved in performance 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 as the light emitting device. Method of providing on, method of molding the light emitting element after sealing with a hard material, method of inserting and fixing the light emitting diode into the through hole, connecting the light emitting element to the lead member etc. by flip chip connection etc. And a method of extracting light from the light.
The light emitting diode of the present invention includes, for example, a backlight such as a liquid crystal display, a light source such as illumination, various sensors, a printer and a copier, an instrument light source for vehicles, a signal light, an indicator light, a display device, a light source for a planar light emitter, and a display. Useful as decoration, various lights, etc.

The present invention will be specifically described below.
The characteristics of the modified polysiloxane are measured by the following method.
(1) Molecular weight Using a gel permeation chromatography (GPC) analyzer 8020GPC system manufactured by Tosoh Corporation, the molecular weight is obtained under the following conditions.
A 5% by mass chloroform solution of the modified polysiloxane is prepared, and then filtered through a 0.45 μm filter as a measurement sample solution. At a column temperature of 40 ° C., the eluent (chloroform) was added under the condition of a flow rate of 1 ml / min. ) Tskel (registered trademark) G5000H time manufactured by Tosoh Co., Ltd., Tskel (registered trademark) G3000H time manufactured by Tosoh Corporation, and Tskel (registered trademark) G1000H time manufactured by Tosoh Corporation are arranged in series. Laboratories molecular weights 7,500,000, 2,560,000, 841,700, 320,000, 148,000, 59,500, 28,500, 10,850, 2,930, 580, known molecular weights Monodisperse polypolystyrene standard substance and styrene monomer (molecular weight 10 A calibration curve obtained from the elution time by RI detection in 4) is prepared in advance. Mp is calculated from the elution time and detection intensity of the measurement sample solution, and the molecular weight is 1,000 or less from the ratio of the total area of the peak based on the modified siloxane and the peak area based on the component having a molecular weight of 1,000 or less in the elution curve. The content of the component is calculated.

(2) Calculation of ratio of average composition and modified organic group in modified polysiloxane A solution dissolved in a deuterated chloroform solvent at a ratio of 1 ml per 30 mg of modified silicone is used as a measurement sample. Using this measurement sample, 1H-NMR measurement at 400 MHz (α-400 manufactured by JASCO Corporation) was performed at 1000 times, and the obtained results were analyzed to determine the average composition in one molecule of the modified polysiloxane. Ask. Moreover, the obtained result is analyzed and the ratio of the content organic group is calculated.
(3) Epoxy equivalent (WPE)
The epoxy equivalent is the mass (g) of the modified silicone having 1 equivalent of an epoxy unit, and is determined according to JIS K-7236.
(4) Number of colors The number of colors was determined by visual comparison with an APHA standard solution in accordance with ASTM-D-1209.

(5) Element content The amount of contained metal is analyzed using a quadrupole ICP mass spectrometer (manufactured by Thermo Elemental: X7-ICP-MS).
(6) Initial light transmittance Using a cured product having a thickness of 2 mm, light transmittances of 350 nm, 400 nm, and 450 nm are measured with JASCO V-550 manufactured by JASCO Corporation. A 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 ×.
(7) Light resistance It sets so that UV light may be irradiated to the hardened | cured material of thickness 2mm in the constant temperature dryer made constant at 100 degreeC from UV irradiation apparatus (Ushio Electric make: SP-7) via an optical fiber.
Using a 365 nm band pass filter, the light of 330-410 nm is irradiated so that it may become 2 W / cm <2>. After the start of irradiation, the case where the cured product was not colored for 80 hours or more was evaluated as ◎, the case where it was colored for 40 hours or more and less than 80 hours was evaluated as ○, and the case where it was colored in less than 40 hours was rated as x.

(8) 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. The Tg of the cured product was 120 ° C. or higher, 、, 100 ° C. or higher and lower than 120 ° C., 50 ° C. or higher and lower than 100 ° C.
(9) Surface tackiness After storing a cured product having a thickness of 2 mm under conditions of 23 ° C. and 65% RH for 72 hours, a cello tape (registered trademark) manufactured by Nichiban Co., Ltd. was applied to the cured product surface at room temperature. Apply a weight of 5 kg / cm 2 and leave for 30 minutes. Subsequently, the cello tape was peeled off, and when the cloudy surface was found to be cloudy, there was surface tackiness, and when no cloudiness was observed, it was judged that there was no surface tackiness.

[Synthesis Example 1]
1) Synthesis of Si-H-containing silicone 200 g of octamethylcyclotetrasiloxane (Azmax reagent) purified by distillation under nitrogen in a 0.5 liter reactor equipped with a reflux condenser, thermometer and stirrer bar 18. 108 g of 1,3,5,7-tetramethylcyclotetrasiloxane (Azmax reagent) purified by distillation under nitrogen, and hexamethyldisiloxane (Azmax reagent) purified by distillation under nitrogen. 1.6 g of activated clay (Tonsil Optimum 230FF: manufactured by Sud Chemie) dried at 110 ° C. for 5 hours under vacuum was charged, and the reaction was performed at 65 ° C. under nitrogen for 20 hours under stirring conditions. The obtained reaction solution is passed through a 1 μm filter to remove the catalyst, and dissolved in 650 g of hexane (special grade product of Wako Pure Chemical Industries). The solution is neutralized and washed with 970 g of an aqueous solution containing 0.038 g of sodium hydrogen carbonate (special grade product manufactured by Wako Pure Chemical Industries, Ltd.), and then the aqueous phase is separated. The obtained n-hexane solution is washed with 970 g of pure water, and the aqueous phase separation is repeated until the aqueous phase becomes neutral. Next, 20 g of anhydrous sodium sulfate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) is added, and the mixture is allowed to stand at 20 ° C. for 12 hours to dehydrate the n-hexane phase. Next, from the n-hexane solution after washing with water, the solvent was distilled off over 1.5 hours at 65 ° C. and 26 kPa, and then the pressure was reduced to 670 Pa. The low molecular weight oligomer was distilled off over time to produce a hydrogen methyl-dimethylsiloxane copolymer. The number average molecular weight of the hydrogen methyl-dimethylsiloxane copolymer is 3,400, the content of the component having a molecular weight of 1,000 or less contained in the hydrogen methyl-dimethylsiloxane copolymer is 3.0%, and the Si-H unit The average content was 18.7 / molecule.

2) Synthesis of modified polysiloxane 100 g of the hydrogen methyl-dimethylsiloxane copolymer obtained above and 200 g of dioxane purified by dehydration distillation were placed in a reactor having a reflux condenser, a thermometer and a stirring device. The mixture was heated to 80 ° C. with stirring under a nitrogen atmosphere. After adding 0.6 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex to this, 54.1 g of a 20 mass% dioxane solution of norbornene (manufactured by Wako Pure Chemicals: reagent grade) was added dropwise over 1 hour. Then, stirring was continued at 80 ° C. for 1 hour after the completion of the dropwise addition. 0.4 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex was added thereto, and then 25.7 g of a 20 mass% dioxane solution of vinylcyclohexene oxide (Daicel Chemical Industries, Ltd .: Celoxide 2000) was added. The mixture was added dropwise over a period of time, and stirring was continued at 80 ° C. for 1 hour after the completion of the addition. After completion of this operation, the reaction solution was sampled and decomposed with alkali to confirm the generation of hydrogen gas, thereby confirming that the reaction was proceeding quantitatively.

  This reaction solution was added to an eggplant flask containing 100 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular special grade) and subjected to a treatment for 24 hours, and then the activated carbon was filtered. The obtained treatment liquid was distilled for 1 hour under the conditions of 100 ° C. and 13.3 kPa, and then the pressure was reduced to 5.3 kPa to distill off the solvent over 0.5 hour. Then, the solvent was again dissolved in 168 g of n-hexane, After removing impurities with 336 g of acetonitrile, n-hexane was distilled off at 65 ° C. and 26 kPa for 0.5 hour, then the pressure was reduced to 670 Pa for 0.5 hour, and then the pressure was reduced to 270 Pa over 0.5 hour. Thus, a modified polysiloxane in which an organic group having an epoxy unit and a polysiloxane are bonded via a Si-C bond was obtained.

  The resulting modified polysiloxane had 5,800, epoxy equivalent of 380, and had an average of 14.9 epoxy units in one molecule. In addition, an average of 3.7 norbornyl groups are contained in one molecule as the alicyclic hydrocarbon unit, and the monovalent organic compound contains the alicyclic hydrocarbon unit and does not contain an epoxy unit in the present invention. Monovalent organic compounds containing no radicals, hydrogen, hydroxyl groups, chain and / or branched aliphatic hydrocarbons having 1 to 25 carbon atoms, and epoxy units having 0 to 5 oxygen atoms The ratio to the total number of groups was about 0.05. The resulting modified polysiloxane had a molecular weight of 1,000% or less, 2.0%, the APHA color number of the modified polysiloxane was 45, and the viscosity at 25 ° C. was 2,300 mPa · s. It was. The transition metal component contained in the modified polysiloxane was only platinum, and the content of the component was 3.4 ppm in terms of platinum element.

[Synthesis Example 2]
1) Synthesis of Si-H containing silicone 100 g of octamethylcyclotetrasiloxane was used, 165 g of 1,3,5,7-tetramethylcyclotetrasiloxane was used, and 20.1 g of hexamethyldisiloxane was used , 1.4 g of activated clay, 571 g of dissolved n-hexane, 856 g of an aqueous solution containing 0.033 g of sodium hydrogen carbonate as an aqueous solution for neutralization washing, and a subsequent washing solution for water washing Except that 856 g of pure water was used as the Si-H-containing silicone with a molecular weight of 1,000 or less reduced in the same manner as described in Synthesis Example 1 (1) Si-H silicone synthesis method Was synthesized.
The number average molecular weight of the obtained hydrogen methyl-dimethylsiloxane copolymer is 2,600, the content of the component having a molecular weight of 1,000 or less contained in the hydrogen methyl-dimethylsiloxane copolymer is 4.6%, Si— The content of H units was an average of 24.9 pieces / molecule.

2) Synthesis of modified polysiloxane 100 g of the hydrogen methyl-dimethylsiloxane copolymer obtained above and 200 g of dioxane purified by dehydration distillation were placed in a reactor having a reflux condenser, a thermometer and a stirring device. The mixture was heated to 80 ° C. with stirring under a nitrogen atmosphere. After adding 0.6 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex to this, 236 g of a 20 mass% dioxane solution of norbornene (manufactured by Wako Pure Chemicals: reagent grade) is added dropwise over 2 hours, After completion of the dropwise addition, stirring was continued at 80 ° C. for 2 hours. After adding 0.4 g of a 0.22 mass% dioxane solution of platinum divinyltetramethyldisiloxane complex to this, 21.5 g of a 20 mass% dioxane solution of vinylcyclohexene oxide (Daicel Chemical Industries, Ltd .: Celoxide 2000) was added. The mixture was added dropwise over a period of time, and stirring was continued for 2 hours at 80 ° C. after the completion of the addition. After completion of this operation, the reaction solution was sampled and decomposed with alkali to confirm the generation of hydrogen gas, thereby confirming that the reaction was proceeding quantitatively.

  This reaction solution was added to an eggplant flask containing 100 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular special grade) and subjected to a treatment for 24 hours, and then the activated carbon was filtered. The obtained treatment liquid was distilled at 100 ° C. and 13.3 kPa for 1 hour, then the pressure was reduced to 5.3 kPa and the solvent was distilled off over 0.5 hours. Then, the solvent was again dissolved in 210 g of n-hexane, After removing impurities with 419 g of acetonitrile, n-hexane was distilled off at 65 ° C. and 26 kPa for 0.5 hour, then the pressure was reduced to 670 Pa for 0.5 hour, and then the pressure was reduced to 270 Pa for 0.5 hour. Thus, a modified polysiloxane in which an organic group having an epoxy unit and the polysiloxane are bonded through a Si-C bond was obtained.

  The obtained modified polysiloxane had an Mp of 5,500 and an epoxy equivalent of 430, and had an average of 12.4 epoxy units in one molecule. In addition, 12.4 norbornyl groups are contained in the molecule as an alicyclic hydrocarbon unit on average, the alicyclic hydrocarbon unit in the present invention is contained, and the monovalent organic compound does not contain an epoxy unit. Monovalent organic compounds containing no radicals, hydrogen, hydroxyl groups, chain and / or branched aliphatic hydrocarbons having 1 to 25 carbon atoms, and epoxy units having 0 to 5 oxygen atoms The ratio to the total number of groups was about 0.22. Further, the content of the modified polysiloxane having a molecular weight of 1,000 or less was 3.1%, the APHA color number of the modified polysiloxane was 40, and the viscosity at 25 ° C. was 2,800 mPa · s. It was. The transition metal component contained in the modified polysiloxane was only platinum, and the content of the component was 2.8 ppm in terms of platinum element.

[Synthesis Example 3]
1) Synthesis of Si-H-containing silicone 100 g of octamethylcyclotetrasiloxane as a raw material, 165 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and distilled and purified under nitrogen instead of hexamethyldisiloxane 11.1 g of 1,1,3,3-tetramethyldisiloxane (Azmax reagent) and 23.9 g of tetrakisdimethylsiloxysilane (Azmax reagent) newly purified by distillation under nitrogen were added, The use of 1.5 g of activated clay, the use of 600 g of n-hexane which dissolves after removing the catalyst from the polymerization reaction solution, the neutralization washing, 900 g of sodium bicarbonate containing 0.035 g as an aqueous solution Except for using an aqueous solution and using 900 g of pure water as a subsequent washing solution, Example 1 (1) Si—H-containing silicone having a molecular weight of 1,000 or less was reduced in the same manner as described in the method for synthesizing Si—H silicone.
The number average molecular weight of the obtained hydrogen methyl-dimethylsiloxane copolymer is 3,100, the content of the component having a molecular weight of 1,000 or less contained in the hydrogen methyl-dimethylsiloxane copolymer is 4.8%, Si— the content of H units, the average was 29.0 groups / molecule, a unit structure of _SiO 2/2 contained 1.3 mol% based on the total Si.

2) Synthesis of modified polysiloxane 100 g of the hydrogen methyl-dimethylsiloxane copolymer obtained above and 200 g of dioxane purified by dehydration distillation were placed in a reactor having a reflux condenser, a thermometer and a stirring device. The mixture was heated to 80 ° C. with stirring under a nitrogen atmosphere. After adding 0.6 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex to this, 184.8 g of a 20 mass% dioxane solution of norbornene (manufactured by Wako Pure Chemicals: reagent grade) was added dropwise over 2 hours. Then, after completion of the dropwise addition, stirring was continued at 80 ° C. for 3 hours. 0.4 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex was added thereto, and then 365.7 g of a 20 mass% dioxane solution of vinylcyclohexene oxide (Daicel Chemical Industries, Ltd .: Celoxide 2000) was added. The mixture was added dropwise over 5 hours, and after completion of the addition, stirring was continued at 80 ° C. for 3 hours. After completion of this operation, the reaction solution was sampled and decomposed with alkali to confirm the generation of hydrogen gas, thereby confirming that the reaction was proceeding quantitatively.

  This reaction solution was added to an eggplant flask containing 100 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular special grade) and subjected to a treatment for 24 hours, and then the activated carbon was filtered. The obtained treatment liquid was distilled at 100 ° C. and 13.3 kPa for 1 hour, then the pressure was reduced to 5.3 kPa and the solvent was distilled off over 0.5 hours. Then, the solvent was again dissolved in 210 g of n-hexane, After removing impurities with 419 g of acetonitrile, the pressure was reduced to 65 ° C. and 26 kPa for 0.5 hour, then the pressure was reduced to 670 Pa for 0.5 hour, then the pressure was reduced to 270 Pa and 0.5-hour n-hexane was distilled off, A modified polysiloxane in which an organic group having a unit and a polysiloxane were bonded via a Si-C bond was obtained.

  The resulting modified polysiloxane had an Mp of 6,800 and an epoxy equivalent of 350, and had an average of 17.4 epoxy units in one molecule. Moreover, 11.6 norbornyl groups are contained in one molecule on average as an alicyclic hydrocarbon unit, the alicyclic hydrocarbon unit in this invention is contained, and the monovalent organic which does not contain an epoxy unit Monovalent organic compounds containing no radicals, hydrogen, hydroxyl groups, chain and / or branched aliphatic hydrocarbons having 1 to 25 carbon atoms, and epoxy units having 0 to 5 oxygen atoms The ratio to the total number of groups was about 0.19. Further, the content of the molecular weight of 1,000 or less contained in the obtained modified polysiloxane is 3.5%, the APHA color number of the modified polysiloxane is 45, and the viscosity at 25 ° C. is 6,500 mPa · s. It was. The transition metal component contained in the modified polysiloxane was only platinum, and the content of the component was 2.9 ppm in terms of platinum element.

[Synthesis Example 4]
A 1 liter reactor equipped with a reflux condenser, thermometer and stirring blade was purged with nitrogen, and then 300 g of silanol-terminated polydimethylsiloxane (number average molecular weight 550), 118.5 g of methyltrimethoxysilane purified by dehydration distillation, dehydration distillation After charging 20 g of purified cyclohexanol (reagent manufactured by Wako Pure Chemical Industries, Ltd.), 95 g of 4-hydroxymethylenecyclohexene oxide purified by dehydration distillation and 0.01 g of tetraisopropyl titanate (reagent manufactured by Wako Pure Chemical Industries, Ltd.) under nitrogen, the mixture was refluxed. The temperature of the cooler was set to 80 ° C., and the reaction was performed at 80 ° C. for 1.5 hours with stirring under an atmospheric pressure nitrogen atmosphere. After completion of the reaction, the reaction solution was reacted at 80 ° C. and 50 kPa for 2 hours, and then the pressure was reduced to 15 kPa for 2 hours. After completion of this operation, the reaction solution was sampled and (2) Si—OH group, (a) Grignard method described in the silicone resin handbook (issued August 31, 1990, published by Nikkan Kogyo Shimbun, first edition, p792). Thus, it was confirmed that the reaction proceeded quantitatively and the hydroxyl group disappeared.

By distilling off the by-product methanol, low molecular weight oligomers, etc. over 1 hour at a temperature of 150 ° C. and a pressure of 260 Pa, the resulting reaction solution has Si—O bonds between the organic group having an epoxy unit and the polysiloxane. To obtain a modified polysiloxane bonded thereto.
The resulting modified polysiloxane had an Mp of 6,100, an epoxy equivalent of 600, and an average of 10.0 epoxy units in one molecule. In addition, the alicyclic hydrocarbon unit contains an average of 2.7 cyclohexyl groups in one molecule, the alicyclic hydrocarbon unit in the present invention, and a monovalent organic that does not contain an epoxy unit. Monovalent organic compound containing no radical, hydrogen, hydroxyl group, chain and / or branched aliphatic hydrocarbon having 1 to 25 carbon atoms and epoxy unit having 0 to 5 oxygen atoms The ratio to the total number of groups was about 0.04. The resulting modified polysiloxane had a molecular weight of 1,000% or less. The modified polysiloxane had an APHA color number of 45 and a viscosity at 25 ° C. of 6,500 mPa · s. It was.
The transition metal component contained in the modified polysiloxane was only titanium, and the content of the component was 4.5 ppm in terms of titanium element.

[Comparative Synthesis Example 1]
1) Synthesis of Si-H-containing silicone After the polymerization reaction, washing with pure water and dehydration with anhydrous sodium sulfate were performed. The hydrogen methyl-dimethylsiloxane copolymer was prepared in the same manner as in Synthesis Example 1 except that the low molecular weight oligomer was not distilled off at 150 ° C. and 50 Pa after the solvent was distilled off for 0.5 hours. Manufactured. The number average molecular weight of the hydrogen methyl-dimethylsiloxane copolymer was 1,400, and the content of components having a molecular weight of 1,000 or less contained in the hydrogen methyl-dimethylsiloxane copolymer was 16.0%.

2) Synthesis of modified polysiloxane 100 g of the hydrogen methyl-dimethylsiloxane copolymer obtained above and 200 g of dioxane were placed in a reactor having a reflux condenser, a thermometer, and a stirring device, and after substituting with nitrogen, under an atmospheric pressure nitrogen atmosphere And heated to 80 ° C. with stirring. After adding 0.6 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex to this, 54.1 g of a 20 mass% dioxane solution of norbornene (manufactured by Wako Pure Chemicals: reagent grade) was added dropwise over 1 hour. Then, stirring was continued at 80 ° C. for 1 hour after the completion of the dropwise addition. 0.4 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex was added thereto, and then 25.7 g of a 20 mass% dioxane solution of vinylcyclohexene oxide (Daicel Chemical Industries, Ltd .: Celoxide 2000) was added. The mixture was added dropwise over a period of time, and stirring was continued at 80 ° C. for 1 hour after the completion of the addition. After completion of this operation, the reaction solution was sampled and decomposed with alkali to confirm the generation of hydrogen gas, thereby confirming that the reaction was proceeding quantitatively.

This reaction solution was added to an eggplant flask containing 100 g of activated carbon (manufactured by Wako Pure Chemicals: granular special grade) and subjected to a treatment for 24 hours, and then the activated carbon was filtered. The obtained treatment solution was distilled at 100 ° C. and 13.3 kPa for 1 hour, then the pressure was reduced to 5.3 kPa and the solvent was distilled off over 0.5 hour, and then dissolved in 210 g of n-hexane again. After removing impurities with 419 g of acetonitrile, the pressure was reduced to 65 ° C. and 26 kPa for 0.5 hours, then the pressure was reduced to 670 Pa for 0.5 hours, and then the pressure was reduced to 270 Pa for 0.5 hours to distill off n-hexane. A modified polysiloxane in which an organic group having a unit and a polysiloxane were bonded through a Si-C bond was obtained.
The obtained modified polysiloxane had an Mp of 5,900 and an epoxy equivalent of 340. Further, the content of the molecular weight of 1,000 or less contained in the obtained modified polysiloxane was 6.5%, the APHA color number of the modified polysiloxane was 45, and the viscosity at 25 ° C. was 2,030 mPa · s. It was. The transition metal component contained in the modified polysiloxane was only platinum, and the content of the component was 3.6 ppm in terms of platinum element.

[Comparative Synthesis Example 2]
1) Synthesis of Si-H containing silicone Using a 1.5 liter reactor as a reaction vessel, using 100 g of octamethylcyclotetrasiloxane, 730 g of 1,3,5,7-tetramethylcyclotetrasiloxane Used, 68.8 g of hexamethyldisiloxane, 4.5 g of activated clay, 1800 g of dissolved n-hexane, and 0.104 g of sodium bicarbonate as an aqueous solution for neutralization washing. 1800 g of the aqueous solution contained, 1800 g of pure water was used as the washing solution for subsequent washing, and the n-hexane solution after washing was reduced to 65 ° C. and 26 kPa for 1 hour, and then the pressure was reduced to 670 Pa. After removing the solvent over 5 hours, the removal of low molecular weight oligomers at 150 ° C and 50 Pa was shortened to 20 minutes. Except for the above, a Si—H-containing silicone having a molecular weight of 1,000 or less was synthesized in the same manner as described in Synthesis Example 1 (1) Si—H silicone synthesis method.
The number average molecular weight of the obtained hydrogen methyl-dimethylsiloxane copolymer is 1,700, the content of the component having a molecular weight of 1,000 or less contained in the hydrogen methyl-dimethylsiloxane copolymer is 10.0%, Si— The average content of H units was 22.2 particles / molecule.

2) Synthesis of modified polysiloxane 100 g of the hydrogen methyl-dimethylsiloxane copolymer obtained above and 200 g of dioxane were placed in a reactor having a reflux condenser, a thermometer, and a stirring device, and after substituting with nitrogen, under an atmospheric pressure nitrogen atmosphere And heated to 80 ° C. with stirring. After adding 0.6 g of a 0.22 mass% dioxane solution of a platinum divinyltetramethyldisiloxane complex to this, 244.4 g of a 20 mass% dioxane solution of norbornene (manufactured by Wako Pure Chemicals: reagent grade) was added dropwise over 2 hours. Then, after completion of the dropwise addition, stirring was continued at 80 ° C. for 2 hours. After adding 0.4 g of a 0.22% by mass dioxane solution of a platinum divinyltetramethyldisiloxane complex to this, 526 g of a 20% by mass dioxane solution of vinylcyclohexene oxide (manufactured by Daicel Chemical Industries, Ltd .: Celoxide 2000) was taken over 4 hours. After the dropping, the stirring was continued at 80 ° C. for 3 hours. After completion of this operation, the reaction solution was sampled and decomposed with alkali to confirm the generation of hydrogen gas, thereby confirming that the reaction was proceeding quantitatively.

This reaction solution was added to an eggplant flask containing 200 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular special grade), subjected to a treatment for 24 hours, and then the activated carbon was filtered. After the obtained treatment liquid was distilled at 100 ° C. and 13.3 kPa for 1.5 hours and then the pressure was reduced to 5.3 kPa and the solvent was distilled off over 1 hour, the solvent was again dissolved in 260 g of n-hexane, After removing impurities with 520 g of acetonitrile, the solvent is distilled off for 1 hour at 65 ° C. and 26 kPa, then the pressure is reduced to 670 Pa, then the pressure is reduced to 270 Pa, and the organic compound having an epoxy unit is removed over 1 hour. A modified polysiloxane in which the group and the polysiloxane were bonded via Si-C bonds was obtained.
The resulting modified polysiloxane had an Mp of 6,100 and an epoxy equivalent of 300, and had an average of 13.7 epoxy units in one molecule. Further, the content of the modified polysiloxane having a molecular weight of 1,000 or less was 5%, the APHA color number of the modified polysiloxane was 40, and the viscosity at 25 ° C. was 8,300 mPa · s. Moreover, the transition metal component contained in the modified polysiloxane was only platinum, and the content of the component was 3.0 ppm in terms of platinum element.

[Example 1]
100 parts by mass of the modified polysiloxane obtained in Synthesis Example 1 is mixed with 39.8 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate under nitrogen, and the whole becomes uniform. After stirring until defoaming, curable composition-1 was obtained. The transition metal component contained in the cured composition-1 was only platinum, and the content of the component was 2.4 ppm in terms of platinum element.
The cured composition-1 was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 100 ° C. for 3 hours and further at 120 ° C. for 3 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 2]
90 parts by mass of the modified polysiloxane obtained in Synthesis Example 2, 10 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (epoxy equivalent 134), 43 parts by mass of methylhexahydrophthalic anhydride Then, 1 part by mass of diazabicycloundecene octylate was mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition-2. The transition metal component contained in the cured composition-2 was only platinum, and the content of the component was 1.8 ppm in terms of platinum element. The cured composition-2 was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 100 ° C. for 3 hours and further at 120 ° C. for 3 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 3]
100 parts by mass of the modified polysiloxane obtained in Synthesis Example 3 is mixed with 43.2 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate under nitrogen, and the whole becomes uniform. After stirring, the mixture was defoamed to obtain curable composition-3. The transition metal component contained in the cured composition-3 was only platinum, and the content of the component was 2.0 ppm in terms of platinum element. Curing composition-3 was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 3 hours and further at 140 ° C. for 3 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 4]
100 parts by mass of the modified polysiloxane obtained in Synthesis Example 4 is mixed with 39.2 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate under nitrogen, and the whole becomes uniform. After stirring until defoaming, curable composition-4 was obtained. The transition metal component contained in the cured composition-4 was only platinum, and the content of the component was 3.6 ppm in terms of platinum element. Curing composition-4 was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 80 ° C. for 4 hours and further at 100 ° C. for 3 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Comparative Example 1]
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (epoxy equivalent 134) 50 parts, hydrogenated bisphenol A glycidyl ether (epoxy equivalent 273) 50 parts by mass, methylhexahydrophthalic anhydride 84 parts by mass 1 part by mass of diazabicycloundecene octylate was mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition-5. The curable composition-5 was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 2 hours and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Comparative Example 2]
100 parts by mass of the modified polysiloxane obtained in Comparative Synthesis Example 1 was mixed with 44.5 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate under nitrogen. After stirring until it was defoamed, a curable composition-6 was obtained. The curable composition-6 was poured into a mold having a depth of 2 mm under nitrogen, and a curing reaction was performed at 100 ° C. for 3 hours and further at 120 ° C. for 3 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 5]
The curable composition-1 obtained in Example 1 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 removed in a vacuum. After foaming, a curing reaction was carried out at 100 ° C. for 3 hours and further at 120 ° C. for 3 hours to obtain a light emitting diode. This operation was repeated to manufacture 10 light emitting diodes. None of the light emitting diodes had surface tackiness on the surface of the encapsulated material. Moreover, even if it supplied with electricity at 50 mA at room temperature for 100 hours with respect to the light emitting diode obtained by this operation, neither the light emitting diode nor the reduction | decrease of brightness | luminance was seen for the light emitting diode. Further, the surface of the sealing material of the light emitting diode did not have surface tackiness.

[Example 6]
Ten light emitting diodes were obtained in the same manner as in Example 5 except that the curable composition-2 obtained in Example 2 was used. None of the light emitting diodes had surface tackiness on the surface of the encapsulated material. Moreover, even if it supplied with electricity at 50 mA at room temperature for 100 hours with respect to the light emitting diode obtained by this operation, neither the light emitting diode nor the reduction | decrease of brightness | luminance was seen for the light emitting diode. Further, the surface of the sealing material of the light emitting diode did not have surface tackiness.

[Example 7]
10 light emitting diodes as in Example 5 except that the curable composition-3 obtained in Example 3 was used and the curing conditions were 3 hours at 120 ° C. and 3 hours at 140 ° C. Got. None of the light emitting diodes had surface tackiness on the surface of the encapsulated material. Moreover, even if it supplied with electricity at 50 mA at room temperature for 100 hours with respect to the light emitting diode obtained by this operation, neither the light emitting diode nor the reduction | decrease of brightness | luminance was seen for the light emitting diode. Further, the surface of the sealing material of the light emitting diode did not have surface tackiness.

[Example 8]
10 light-emitting diodes as in Example 5 except that the curable composition-4 obtained in Example 4 was used and the curing conditions were 4 hours at 80 ° C. and 3 hours at 100 ° C. Got. None of the light emitting diodes had surface tackiness on the surface of the encapsulated material. Moreover, even if it supplied with electricity at 50 mA at room temperature for 100 hours with respect to the light emitting diode obtained by this operation, neither the light emitting diode nor the reduction | decrease of brightness | luminance was seen for the light emitting diode. Further, the surface of the sealing material of the light emitting diode did not have surface tackiness.

[Comparative Example 3]
Ten light-emitting diodes were prepared in the same manner as in Example 5 except that the curable composition-5 obtained in Comparative Example 1 was used and the curing conditions were 120 ° C. for 2 hours and further 150 ° C. for 2 hours. Obtained. There was no surface tackiness on the surface of any of the light-emitting diodes, but when the light-emitting diodes were energized for 100 hours at 50 mA at room temperature, the light-emitting diodes were peeled off from the elements and the sealing parts. Was observed, and the luminance was lowered.

[Comparative Example 4]
Ten light emitting diodes were obtained in the same manner as in Example 5 except that the curable composition-6 obtained in Comparative Example 2 was used. When the light-emitting diode obtained by this operation was energized for 100 hours at 50 mA at room temperature, neither the light-emitting diode was peeled off nor the brightness was reduced. Later, the surface of the sealing material had surface tackiness.

[Comparative Example 5]
After mixing 100 parts by mass of the modified polysiloxane obtained in Comparative Synthesis Example 2 with 50.5 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate and stirring until the whole becomes uniform And defoaming to obtain a curable composition-7. Using this cured composition-7, 10 light emitting diodes were obtained in the same manner as in Example 5. None of the light emitting diodes had surface tackiness on the surface of the encapsulated material. However, when 10 light-emitting diodes obtained by this operation were energized at 50 mA at room temperature for 100 hours, cracks were observed at the interface between the element and the sealing portion in the three light-emitting diodes. .

  The present invention has excellent light resistance, a light emitting surface for use that is exposed to the outside air, or a light emitting device for applications that are used continuously for a long time, and a light emitting surface during mounting or use, and A light-emitting diode that is useful as a curable composition for sealing a light-emitting element capable of suppressing damage to the light-emitting portion, and manufactured using the curable composition for sealing a light-emitting element of the present invention, It is an excellent light-emitting diode in which the stopper does not peel off and the luminance is not lowered for a long time.

Claims (11)

A thermosetting composition for sealing a light-emitting device, comprising a modified polysiloxane having two or more organic groups having an epoxy unit in one molecule, wherein the modified polysiloxane comprises the following (A) to ( A thermosetting composition for sealing a light-emitting element, which satisfies C) at the same time.
(A) The molecular weight peak value Mp of the modified polysiloxane is 1,000 or more.
(B) Epoxy equivalent WPE is 320 or more.
(C) Low molecular weight content of molecular weight 1,000 or less in the modified polysiloxane is 5% or less.   The thermosetting composition for sealing a light-emitting element according to claim 1, wherein the modified polysiloxane has one or more organic groups having an alicyclic hydrocarbon unit in one molecule.   The thermosetting composition for sealing a light emitting device according to claim 1 or 2, wherein the modified polysiloxane has a viscosity at 25 ° C of 50,000 mPa · s or less.   The light-emitting device package according to any one of claims 1 to 3, wherein the epoxy unit is at least one selected from the group consisting of an ethynylcyclohexene oxide unit, a glycidyl unit, an ethynylglycidyl unit, and a propyronylglycidyl unit. A thermosetting composition for stopping.   The thermosetting composition for sealing a light emitting device according to any one of claims 1 to 4, wherein the alicyclic hydrocarbon unit is a cyclohexyl unit and / or a norbornyl unit.   6. The thermosetting for sealing a light-emitting element according to claim 1, wherein the modified polysiloxane has an organic group having an epoxy unit and the polysiloxane bonded through an Si—C bond. Sex composition.   6. The thermosetting for sealing a light-emitting element according to claim 1, wherein the modified polysiloxane has an organic group having an epoxy unit and the polysiloxane bonded through an Si—O bond. Sex composition.   The thermosetting composition for sealing a light-emitting element according to any one of claims 1 to 7, wherein the APHA color number of the modified polysiloxane is 50 or less.   9. The heat for sealing a light-emitting element according to claim 1, wherein the total of transition metal components contained in the thermosetting composition for sealing a light-emitting element is 20 ppm or less in terms of element. Curable composition.   It contains 100 parts by mass of the modified polysiloxane according to any one of claims 1 to 9, 0.1 part by mass or more and 100 parts by mass or less of an epoxy resin, 1 part by mass or more and 200 parts by mass or less of a curing agent for epoxy resin. A thermosetting composition for sealing a light emitting device.   The light emitting component manufactured by sealing a light emitting element using the thermosetting composition for light emitting element sealing of any one of Claim 1 to 10, and a display apparatus using this light emitting component.