TW202026362A - Addition-curable silicone composition, cured silicone and optical element - Google Patents

Abstract

The invention provides an addition-curable silicone composition which contains an aryl group and which suppliesa cured product that does not crack or warp light and has little decrease in light transmittance. The composition comprises (A-1) an organopolysiloxane represented by average compositional formula (1) (R13SiO1/2)a(R2R12SiO1/2)b(R2R1SiO)c(R12SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g (1); (A-2) a linear organopolysiloxane represented by formula (2); (B) an organohydrogen polysiloxane; (C) a compound having at least one group representedby formula (3); and (D) a hydrosilylation catalyst containing a platinum group metal.

Description

Addition hardening type silicone composition, silicone hardening material, and optical components

The present invention relates to an addition-curing polysilicon composition, its cured polysilicon, and an optical element sealed with the cured polysilicon.

As an optical semiconductor element, a device having a light emitting diode (LED) generally has a structure in which the LED mounted on a substrate is sealed with a sealing material made of transparent resin. As for the sealing material, epoxy resin has been used since the past. However, due to the miniaturization of semiconductor packages in recent years, the increase in heat generation accompanying the increase in brightness of LEDs, or the shortening of light wavelengths, cracking or yellowing of the resin has caused Decrease in reliability.

Therefore, from the viewpoint of heat resistance and heat discoloration resistance, as a sealing material, the silicone resin composition is focused on, and the addition reaction curing type silicone resin composition can be cured in a short time by heating , So it has high productivity and is used as a sealing material for LEDs (Patent Document 1).

LED sealing materials pursue high refractive index and vulcanization resistance. For such applications, it is known that polysiloxane resin compositions with phenylsiloxanes in the main skeleton (Patent Documents 2 and 3) can provide high refractive index and resistance to Vulcanized hardened material.

However, with the high output of LEDs in recent years, such cured products containing aryl groups such as phenyl may yellow or crack due to the light emitted by the LED element, and the cured products are easily deformed, and the light transmittance deteriorates. The brightness of the LED decreases. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2004-292714 A [Patent Document 2] JP 2005-105217 A [Patent Document 3] JP 2010-132795 A

[The problem to be solved by the invention]

The present invention was made in view of the above circumstances, and aims to provide an addition-curing polysiloxy composition that contains an aromatic group and can obtain a cured product that does not cause cracks or warpage to light and has a small decrease in light transmittance. . [Means to solve the problem]

(式中，R¹ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，全R¹ 中至少10莫耳%為芳基，R² 為烯基。a、b、c、d、e、f、及g各自為符合a≧0、b≧0、c≧0、d≧0、e≧0、f≧0、及g≧0的數，但是，為符合b+c+e＞0、e+f+g＞0，且a+b+c+d+e+f+g=1之數。) (A-2)下述式(2)表示之直鏈狀有機聚矽氧烷、

(式中，R^1’ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，R³ 為甲基或苯基，h為0~50的數，i為0~100的數。但是，h為0時，R³ 為苯基，且i為1~100的數。在註記h的括弧內之矽氧烷單位及在註記i的括弧內之矽氧烷單位相互間可隨機配列、亦可嵌段配列。) (B)1分子中具有至少2個以上之矽原子鍵結氫原子的有機氫聚矽氧烷：相對於前述(A-1)成分及(A-2)成分中之矽原子鍵結烯基1個，前述(B)成分中之矽原子鍵結氫原子的數為0.1~5.0個之量、 (C)1分子中具有至少1個下述式(3)表示之基的化合物：相對於前述(A-1)成分、前述(A-2)成分、及前述(B)成分的合計，為200~10,000ppm、

(式中，R⁴ 為氫原子、烷基或烷氧基，星號*為與相鄰原子之鍵結。1分子中式(3)表示之基有複數時，複數基中R⁴ 可為相同亦可相異。) 及 (D)含有鉑族金屬的矽氫化觸媒、 之加成硬化型聚矽氧組成物。In order to solve the above-mentioned problems, the present invention provides: (A-1) Organopolysiloxane represented by the following average composition formula (1),

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other and does not contain an alkenyl group. At least 10 mol% of all R ¹ is an aryl group, and R ² is an alkenyl group. a, b , C, d, e, f, and g are numbers corresponding to a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, but they are in accordance with b +c+e>0, e+f+g>0, and a+b+c+d+e+f+g=1.) (A-2) Straight chain represented by the following formula (2) Organic polysiloxane,

(Wherein, R does not contain an alkenyl group substituted with ^{1 'may} be the same or different are each a substituted or unsubstituted monovalent hydrocarbon group one, R ³ is methyl or phenyl, h is a number from 0 to 50, i is 0 The number of 100. However, when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. The silicone unit in the parentheses of the note h and the silicone unit in the parentheses of the note i are mutually exclusive They can be arranged randomly or in blocks.) (B) Organohydrogen polysiloxanes with at least two silicon atoms bonded to hydrogen atoms in one molecule: Compared to the aforementioned (A-1) component and (A) -2) The silicon atom in the component is bonded to 1 alkenyl group, the silicon atom in the aforementioned (B) component is bonded to the number of hydrogen atoms in the amount of 0.1 to 5.0, (C) 1 molecule has at least 1 of the following The compound of the base represented by the formula (3): 200 to 10,000 ppm with respect to the total of the aforementioned (A-1) component, the aforementioned (A-2) component, and the aforementioned (B) component,

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, and an asterisk * is a bond with an adjacent atom. When the group represented by formula (3) in 1 molecule has a plural number, R ^{4 in the} plural group may be the same Can be different.) and (D) Addition hardening polysiloxane composition containing platinum group metal hydrosilation catalyst.

With such an addition-curing silicone composition, a cured product with excellent light transmittance, heat resistance, and light resistance can be obtained without cracking or warping to light, and with little decrease in light transmittance.

(式中，R¹ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，星號*為與相鄰原子之鍵結。)Moreover, it is preferable that the said (A-1) component has a base represented by following formula (4).

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group that may be the same or different from each other and does not contain an alkenyl group, and the asterisk * is a bond to an adjacent atom.)

If so, the strength, refractive index, and vulcanization resistance of the cured product of the silicone composition can be improved.

(式中，R^1’ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，星號*為與相鄰原子之鍵結。)Moreover, it is preferable that the said (A-2) component has a base represented by following formula (5).

(Wherein, R does not contain an alkenyl group substituted with ^{1 'may} be the same or different are each of one or unsubstituted monovalent hydrocarbon group, and the asterisk * is bonded to adjacent atoms.)

If so, the strength, refractive index, and vulcanization resistance of the cured product of the silicone composition can be improved.

In addition, the R ¹ and R ^{1 'preferably} to phenyl or methyl.

If so, it is more suitable to use as (A-1) component and (A-2) component.

(星號*為與相鄰原子之鍵結。)Moreover, it is preferable that the said (B) component has a base represented by following formula (6).

(The asterisk * is the bond with adjacent atoms.)

If so, high hardness and high vulcanization resistance can be imparted to the cured product of the silicone composition.

(式中，R⁴ 為氫原子、烷基或烷氧基，可為相同亦可為相異。)In addition, the aforementioned component (C) is preferably a compound represented by the following formula (8).

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, which may be the same or different.)

If so, it can be suitably used as (C) component.

In addition, R ⁴ in the aforementioned component (C) is preferably an alkoxy group.

If this is the case, it is possible to effectively impart light resistance to the cured product of the silicone composition.

In addition, the aforementioned alkoxy group is preferably a group represented by -OC ₁₁ H ₂₃ .

If this is the case, the cured product of the silicone composition can be more effectively imparted with light resistance.

Furthermore, the present invention provides a cured polysilicone that is a cured product of the above-mentioned addition-curable polysilicone composition.

If it is such a polysilicon cured product, because it does not crack or warp against light, the light transmittance is less reduced, the light transmittance, heat resistance, and light resistance are excellent, and it can be used as a semiconductor element, especially a semiconductor element for optical applications. Coating materials or sealing materials, protective coating materials for electrical and electronic use.

Furthermore, the present invention provides an optical element sealed with the above-mentioned cured polysiloxane.

The polysilicon cured product of the present invention does not crack or warp to light, has a small decrease in light transmittance, and is excellent in light transmittance, heat resistance, and light resistance. Therefore, the reliability of the optical element sealed with such a silicone cured material is high. [Effects of Invention]

As above, if it is the addition curable silicone composition of the present invention, a cured product with excellent light transmittance, heat resistance, and light resistance can be obtained without cracking or warping to light, and with less decrease in light transmittance. . Therefore, the cured product obtained by adding such an addition-curing silicone composition can be applied to optical element sealing materials and the like. [Best form to implement invention]

As described above, the development of an addition-curing polysiloxy composition that can obtain a cured product that does not cause cracks or warpage to light and has a reduced light transmittance, and a highly reliable optical element sealed with the cured product.

As a result of diligent review of the above-mentioned subject, the inventors found that if it is an addition-curing silicone composition containing the components (A-1), (A-2), (B), (C), and (D) described later The above-mentioned problem can be achieved and the present invention has been completed.

(式中，R¹ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，全R¹ 中至少10莫耳%為芳基，R² 為烯基。a、b、c、d、e、f、及g各自為符合a≧0、b≧0、c≧0、d≧0、e≧0、f≧0、及g≧0的數，但是，為符合b+c+e＞0、e+f+g＞0，且a+b+c+d+e+f+g=1之數。) (A-2)下述式(2)表示之直鏈狀有機聚矽氧烷、

(式中，R^1’ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，R³ 為甲基或苯基，h為0~50的數，i為0~100的數。但是，h為0時，R³ 為苯基，且i為1~100的數。在註記h的括弧內之矽氧烷單位及在註記i的括弧內之矽氧烷單位相互間可隨機配列、亦可嵌段配列。) (B)1分子中具有至少2個以上之矽原子鍵結氫原子的有機氫聚矽氧烷：相對於前述(A-1)成分及(A-2)成分中之矽原子鍵結烯基1個，前述(B)成分中之矽原子鍵結氫原子的數為0.1~5.0個之量、 (C)1分子中具有至少1個下述式(3)表示之基的化合物：相對於前述(A-1)成分、前述(A-2)成分、及前述(B)成分的合計，為200~10,000ppm、

(式中，R⁴ 為氫原子、烷基或烷氧基，星號*為與相鄰原子之鍵結。1分子中式(3)表示之基有複數時，複數基中R⁴ 可為相同亦可相異。) 及 (D)含有鉑族金屬的矽氫化觸媒 之加成硬化型聚矽氧組成物。That is, the present invention contains: (A-1) Organopolysiloxane represented by the following average composition formula (1),

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other and does not contain an alkenyl group. At least 10 mol% of all R ¹ is an aryl group, and R ² is an alkenyl group. a, b , C, d, e, f, and g are numbers corresponding to a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, but they are in accordance with b +c+e>0, e+f+g>0, and a+b+c+d+e+f+g=1.) (A-2) Straight chain represented by the following formula (2) Organic polysiloxane,

(Wherein, R does not contain an alkenyl group substituted with ^{1 'may} be the same or different are each a substituted or unsubstituted monovalent hydrocarbon group one, R ³ is methyl or phenyl, h is a number from 0 to 50, i is 0 The number of 100. However, when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. The silicone unit in the parentheses of the note h and the silicone unit in the parentheses of the note i are mutually exclusive They can be arranged randomly or in blocks.) (B) Organohydrogen polysiloxanes with at least two silicon atoms bonded to hydrogen atoms in one molecule: Compared to the aforementioned (A-1) component and (A) -2) The silicon atom in the component is bonded to 1 alkenyl group, the silicon atom in the aforementioned (B) component is bonded to the number of hydrogen atoms in the amount of 0.1 to 5.0, (C) 1 molecule has at least 1 of the following The compound of the base represented by the formula (3): 200 to 10,000 ppm with respect to the total of the aforementioned (A-1) component, the aforementioned (A-2) component, and the aforementioned (B) component,

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, and an asterisk * is a bond with an adjacent atom. When the group represented by formula (3) in 1 molecule has a plural number, R ^{4 in the} plural group may be the same Can be different.) And (D) Addition hardening polysiloxane composition containing platinum group metal hydrosilation catalyst.

With such an addition-curing silicone composition, a cured product with excellent light transmittance, heat resistance, and light resistance can be obtained without cracking or warping to light, and with little decrease in light transmittance.

The present invention will be described in detail below, but the present invention is not limited to this.

[Addition hardening polysiloxy composition] The addition-curable silicone composition of the present invention contains the following components (A-1), (A-2), (B), (C), and (D). Each component is explained in detail below.

(式中，R¹ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，全R¹ 中至少10莫耳%為芳基，R² 為烯基。a、b、c、d、e、f、及g各自為符合a≧0、b≧0、c≧0、d≧0、e≧0、f≧0、及g≧0的數，但是，為符合b+c+e＞0、e+f+g＞0，且a+b+c+d+e+f+g=1之數。)<(A-1) Component> The (A-1) component in the addition curable silicone composition of the present invention is a branched organopolysiloxane represented by the following average composition formula (1).

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other and does not contain an alkenyl group. At least 10 mol% of all R ¹ is an aryl group, and R ² is an alkenyl group. a, b , C, d, e, f, and g are numbers corresponding to a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, but they are in accordance with b +c+e>0, e+f+g>0, and a+b+c+d+e+f+g=1.)

The component (A-1) is an essential component for obtaining the reinforcement of the cured product of the polysiloxy composition, and contains either or both of SiO _3/2 unit and SiO _4/2 unit.

(式中，R¹ 同上述，星號*為與相鄰原子之鍵結。)The component (A-1) preferably has a siloxane unit represented by the following formula (4), and more preferably has two or more siloxane units in one molecule. By having it, the strength, refractive index, and vulcanization resistance of the cured product of the silicone composition can be improved.

(In the formula, R ^{1 is the} same as above, and the asterisk * is the bond with adjacent atoms.)

Regarding the above-mentioned R ¹ , it is not particularly limited if it does not contain an alkenyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.; cyclopentyl, cyclohexyl, etc. Cycloalkyl; aryl groups such as phenyl, tolyl, xylyl and naphthyl; aralkyl groups such as benzyl and phenethyl; chloromethyl, 3-chloropropyl, 3,3,3-tri Halogenated alkyl groups such as fluoropropyl, etc. usually have an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10, more preferably 1 to 8, especially methyl. .

At least 10 mole% of all R ¹ is aryl. If the aryl group in the total R ¹ is less than 10 mol%, the improvement of the refractive index, the improvement of the light extraction efficiency in the LED package, and the sulfidation resistance for suppressing the blackening of the silver substrate cannot be provided. As for the aryl group, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned, and a phenyl group is particularly preferred.

And, R ¹ to phenyl or methyl preferably, if it is so, could be more appropriate to as (A-1) component.

The above-mentioned R ² is an alkenyl group, preferably a vinyl group, an allyl group, an ethynyl group, and the like, having a carbon number of 2-10, more preferably an alkenyl group having a carbon number of 2-6, and particularly preferably a vinyl group.

(A-1) The component is preferably a waxy or solid three-dimensional network organopolysiloxane resin at 23°C. "Waxy" refers to a gelatinous (raw rubber-like) that does not have its own fluidity at a temperature of 10,000 Pa･s or more at 23°C, especially 100,000 Pa･s or more.

(A-1) A component may be used alone or in combination of two or more kinds.

(式中，R^1’ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，R³ 為甲基或苯基，h為0~50的數，i為0~100的數。但是，h為0時，R³ 為苯基，且i為1~100的數。在註記h的括弧內之矽氧烷單位及在註記i的括弧內之矽氧烷單位相互間可隨機配列、亦可嵌段配列。)<(A-2) component> The (A-2) component is a linear organopolysiloxane represented by the following formula (2).

(Wherein, R does not contain an alkenyl group substituted with ^{1 'may} be the same or different are each a substituted or unsubstituted monovalent hydrocarbon group one, R ³ is methyl or phenyl, h is a number from 0 to 50, i is 0 The number of 100. However, when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. The silicone unit in the parentheses of the note h and the silicone unit in the parentheses of the note i are mutually exclusive It can be arranged randomly or in blocks.)

(A-2) The component has two vinyl groups in one molecule, and is a component that causes stress relaxation after curing of the silicone composition.

(A-2) component of formula (2) in the R ^{1 'is} for example, (A-1) component is the same as those of R ^1.

In the formula (2), h is an integer of 0-50, i is an integer of 0-100, when h is 0, R ³ is a phenyl group, and i is 1-100. If h and i are outside the above range, it is impossible to impart high hardness and vulcanization resistance to the cured product of the silicone composition of the present invention.

(A-2) The viscosity of the component at 25°C is preferably 10~100,000mPa･s, more preferably within the range of 10~10,000mPa･s. If the viscosity is within the above range, this component will not exceed the necessary function as a soft segment, and the target high hardness can be obtained. In addition, there is no problem that the viscosity of the composition increases significantly and the workability is poor.

(式中，R^1’ 同上述，星號*為與相鄰原子之鍵結。)The molecular terminal of the component (A-2) preferably has a siloxane unit represented by the following formula (5), and it is more preferable to have the siloxane unit at both ends of the molecule. By having it, the strength, refractive index, and vulcanization resistance of the cured product of the silicone composition can be improved.

(In the formula, R ^{1'is the} same as above, and the asterisk * is the bond with adjacent atoms.)

And, R ^{1 'preferably} to methyl or phenyl, if it is so, could be more appropriate to as (A-2) component.

(A-2) Specific examples of the component include, for example, two-terminal methylphenylvinyl-blocked diphenylsiloxane, and one-terminal methylphenylvinyl and one-terminal diphenylvinyl-blocked diphenyl. Diphenyl siloxane, two-terminal diphenylvinyl-blocked diphenylsiloxane, two-terminal diphenylvinyl-blocked diphenylsiloxane・methylphenylsiloxane copolymer, two-terminal diphenyl Methyl vinyl chain-blocked diphenylsiloxane, single-terminal dimethyl vinyl and single-terminal methyl phenyl vinyl chain-blocked diphenylsiloxane, two-terminal dimethyl vinyl chain-blocked methyl phenyl Silicone, single-terminal dimethyl vinyl single-terminal methyl phenyl vinyl chain methyl phenyl siloxane, etc. (A-2) A component may be used alone or in combination of two or more kinds.

The ratio of (A-1) and (A-2) components is preferably in the range of (A-1): (A-2) 20:80~80:20. If it is within this range, a cured product having an excellent balance of physical properties such as the strength and vulcanization resistance of the cured product can be obtained.

＜(B) Ingredient＞ The component (B) is an organohydrogen polysiloxane that causes a hydrosilation reaction with components (A-1) and (A-2), and is used as a crosslinking agent that has at least two silicon atoms bonded to hydrogen atoms in one molecule alkyl.

The molecular structure of the component (B) is not particularly limited, and various conventionally manufactured organohydrogenpolysiloxanes such as linear, cyclic, branched, and three-dimensional network structures can be used. Furthermore, the component (B) may be liquid or waxy or solid at 23°C.

From the viewpoint of compatibility with the components (A-1) and (A-2), the component (B) preferably has at least one aryl group. Examples of the aryl group are the same as those exemplified in the component (A-1).

(B) The organohydrogen polysiloxane of the component has at least 2, preferably 3 to 300, and particularly preferably 3 to 100 hydrogen atoms (i.e., hydrogen silyl groups) bonded to silicon atoms in one molecule. (SiH-based)). When the organohydrogen polysiloxane of component (B) has a linear structure, these SiH groups may be located only at the end of the molecular chain and in the middle of the molecular chain (non-end of the molecular chain), or both .

(星號*為與相鄰原子之鍵結。)The component (B) preferably has a siloxane unit represented by the following formula (6), and more preferably has two or more siloxane units in one molecule. By having it, high hardness and high vulcanization resistance can be imparted to the cured product of the silicone composition.

(The asterisk * is the bond with adjacent atoms.)

(B) The number of silicon atoms (polymerization degree) in 1 molecule of the component is preferably 2 to 300, more preferably 3 to 200, and still more preferably 4 to 150.

(式中，R⁵ 為不含烯基的互為相同或相異的未取代或者取代的碳原子數較佳為1~12、更佳為1~10、再更佳為1~8的鍵結於矽原子的一價烴基，例如與(A-1)成分中之R¹ 及(A-2)成分中之R^1’ 相同者。又，j及k較佳為符合0.7≦j≦2.1、0.001≦k≦1.0，且符合0.8≦j+k≦3.0之正數，更佳為符合1.0≦j≦2.0、0.01≦k≦1.0，且符合1.55≦j+k≦2.5之正數。)(B) As for the component, for example, an organohydrogenpolysiloxane represented by the following average composition formula (7) can be used.

(In the formula, R ⁵ is the same or different unsubstituted or substituted carbon atom without alkenyl group. The number of carbon atoms is preferably 1-12, more preferably 1-10, and even more preferably 1-8. monovalent hydrocarbon junction in silicon atoms, for example, (a-1) component of R ¹ and (a-2) component of R ^{1 'are} the same. and, j and k are preferably comply with 0.7 ≦ j ≦ 2.1 , 0.001≦k≦1.0, and meet the positive number of 0.8≦j+k≦3.0, more preferably meet the positive number of 1.0≦j≦2.0, 0.01≦k≦1.0, and meet the positive number of 1.55≦j+k≦2.5.)

(B) Specific examples of the component include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, ginseng (hydrogen two Methylsilyloxy)methylsilane, ginseng(hydrodimethylsilyloxy)phenylsilane, methylhydrosiloxane, methylhydrosiloxane, dimethylsiloxane cyclic copolymer , Two-terminal trimethylsiloxy group-blocked methyl hydrogen polysiloxane, two-terminal trimethylsiloxy group-blocked dimethylsiloxane·methylhydrosiloxane copolymer, two-terminal dimethyl Hydrosiloxane alkoxy chain-blocking dimethyl polysiloxane, two-terminal dimethyl hydrosiloxane chain-blocking methyl hydropolysiloxane II, two-terminal dimethyl hydrosiloxane chain-blocking dimethylsiloxane Alkyl/methylhydrosiloxane copolymer, trimethylsiloxy group-blocked methylhydrosiloxane on both ends, diphenylsiloxane copolymer, trimethylsiloxy group-blocked methyl hydrogen on both ends Silicone, diphenylsiloxane, dimethylsiloxane copolymer, trimethylsiloxy group at both ends, chain methylhydrosiloxane, methylphenylsiloxane, dimethylsiloxane Alkyl copolymer, two-terminal dimethylhydrosiloxane chain-blocking methylhydrosiloxane, dimethylsiloxane, diphenylsiloxane copolymer, two-terminal dimethylhydrosiloxane chain-blocking methyl Hydrogen siloxane, dimethylsiloxane, methylphenylsiloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/2 unit The copolymer composed of (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit, (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit and (C ₆ H ₅ ) Copolymers composed of ₃ SiO _1/2 units, etc.

The amount of component (B) is relative to the silicon atom in components (A-1) and (A-2) that are bonded to one alkenyl group. The silicon atom in component (B) has 0.1 to 5.0 hydrogen atoms. , Preferably the amount is within the range of 0.5 to 3.0, more preferably the amount within the range of 0.5 to 2.0. (B) If the blending amount of the component is outside the above range, it is impossible to impart high hardness to the cured product of the silicone composition.

(B) The organohydrogenpolysiloxane of the component may be used alone or in combination of two or more kinds.

(式中，R⁴ 為氫原子、烷基或烷氧基，星號*為與相鄰原子之鍵結。1分子中式(3)表示之基有複數時，複數基中R⁴ 可為相同亦可相異。)<(C) Component> The (C) component is a compound having at least one hindered amino group represented by the following formula (3) in one molecule.

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, and an asterisk * is a bond with an adjacent atom. When the group represented by formula (3) in 1 molecule has a plural number, R ^{4 in the} plural group may be the same Can be different.)

The component (C) is a stabilizer for imparting light resistance to light emitted from the LED in the cured product of a polysiloxane composition having an aryl group such as a phenyl group.

The amount of (C) component added is 200 to 10,000 ppm, preferably 500 to 5,000 ppm, more preferably 500 to 2,000 ppm relative to the total of (A-1), (A-2), and (B) components . If the addition amount is less than this, the effect as a stabilizer cannot be fully exhibited, and if the addition amount exceeds the above addition amount, there is a catalyst poison to the component (D) described later, and it is likely to cause discoloration at high temperature in addition to inhibiting hardening.

(式中，R⁴ 同上述。)The component (C) is preferably a compound represented by the following formula (8). If so, it can be suitably used as (C) component.

(In the formula, R ^{4 is the} same as above.)

In the component (C), R ⁴ is preferably an alkoxy group, and in terms of an alkoxy group, one having 1 to 11 carbon atoms is more preferable. If so, it can be more suitably used as the (C) component. In particular, if the alkoxy group is a group represented by -OC ₁₁ H ₂₃ , the cured product of the silicone composition can be more effectively imparted with light resistance.

(C) Specific examples of the component include, for example, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensation polymer, poly[ {6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl -4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], poly[{6-morpholinyl- s-Triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6- Tetramethyl-4-piperidinyl)imino}], N,N',N”,N”'-tetra-(4,6-bis-(butyl-(N-methyl-2,2 ,6,6-Tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, bis(1,2, 2,6,6-Pentamethyl-4-piperidinyl)[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butylmalonate , Cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine reaction product Reaction product with 2-aminoethanol, decanedioic acid bis[2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl], bis(2,2,6 ,6-Tetramethyl-1-undecyloxy-4-piperidinyl) sebacate, 1,1-dimethylethyl hydroperoxide and octane reaction product, bis(1 ,2,2,6,6-Pentamethyl-4-piperidinyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate Mixture, bis(1,2,2,6,6-pentamethyl-piperidinyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidinyldecane Diester mixture, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, etc.

As for commercially available products, hindered amine-based photostabilizers manufactured by ADEKA Co., Ltd. can be used, and the compound represented by the following formula (9) (product name: ADK STAB LA-81) is preferred.

(C) The component may be used alone or in combination of two or more, and stabilizers such as other hindered phenols may be added.

＜(D)Component＞ (D) The platinum group metal-containing hydrosilation catalyst promotes the addition reaction of the alkenyl group in the (A-1) and (A-2) components and the hydrogen atom bonded to the silicon atom in the (B) component It can be any catalyst. Specific examples include platinum, palladium, rhodium and other platinum group metals or chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, vinylsiloxane or acetylene compounds Platinum compounds such as palladium (triphenylphosphine) palladium, chloroginseng (triphenylphosphine) rhodium, etc., and platinum compounds are particularly preferred.

(D) A component may be used individually by 1 type, and may use 2 or more types together.

(D) The combined amount of the component is sufficient as the effective amount of the catalyst, but the total amount of the (A-1), (A-2) and (B) components is converted into a catalyst metal element based on mass The range of 1~500ppm is better, and the range of 1~100ppm is more preferred. Within this range, the reaction rate of the addition reaction becomes appropriate, and a cured product having high strength can be obtained.

＜Other ingredients＞ In the addition-curing silicone composition of the present invention, components such as an adhesive enhancer or reaction inhibitor can be added according to the purpose.

Regarding the adhesion enhancer, from the viewpoint of imparting self-adhesiveness to the composition of the present invention of the addition reaction curing type, organosilicon compounds such as silanes, siloxanes, etc. containing functional groups that impart adhesion, non-poly Siloxane-based organic compounds, etc.

Specific examples of the functional group that imparts adhesiveness include, for example, an alkenyl group such as a vinyl group or an allyl group bonded to a silicon atom or a hydrogen atom; an epoxy group bonded to a silicon atom through a carbon atom (such as γ- Glycidoxy propyl, β-(3,4-epoxycyclohexyl) ethyl, etc.), acryloxy (e.g. γ-acryloxypropyl, etc.), or methacryloxy (E.g. γ-methacryloxypropyl, etc.); Alkoxysilyl group (e.g. can contain 1 to 2 ester structure, urethane structure, ether structure, which is bonded to silicon atom through alkylene group The trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc.).

Examples of organosilicon compounds containing adhesive functional groups include silane coupling agents, siloxanes having alkoxysilyl groups and organic functional groups, and organic compounds having reactive organic groups with alkoxy groups. Silane-based compounds, etc.

In addition, examples of non-polysiloxane-based organic compounds include allyl organic acids, epoxy ring-opening catalysts, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds.

In terms of reaction inhibitors, for example, phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, benzotriazole, etc.; sulfur-containing compounds; acetylene-based compounds; hydrogen Peroxy compound; maleic acid derivative; 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylmethanol, 1,3,5, Conventional compounds such as 7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, etc., have a curing inhibitory effect on the hydrosilation catalyst of component (D).

The degree of the hardening inhibitory effect caused by the reaction inhibitor varies with the chemical structure of the reaction inhibitor, so it is better to adjust the amount of the reaction inhibitor to the optimum amount of each reaction inhibitor used. Preferably, it is 0.001 to 5 parts by mass with respect to 30 parts by mass of the total of (A-1) component, (A-2) component, (B) component, (C) component, and (D) component. If the blending amount is 0.001 parts by mass or more, the long-term storage stability of the composition at room temperature can be sufficiently obtained. If the blending amount is 5 parts by mass or less, it will not hinder the hardening of the composition.

In addition, the composition of the present invention can also be used with inorganic fillers such as fine powder silica, crystalline silica, hollow filler, silsesquioxane, etc., in order to enhance the reinforcement, and such fillers. Filling agent for surface hydrophobization treatment with organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, low molecular weight silicone compounds, etc.; silicone rubber powder, polysiloxane Resin powder, etc.

For fine powdered silica, the specific surface area (BET method) is preferably 50 m ² /g or more, more preferably 50 to 400 m ² /g, and particularly preferably 100 to 300 m ² /g. If the specific surface area is 50 m ² /g or more, sufficient reinforcement can be provided to the hardened product.

With regard to such fine powdered silica, the known ones used as reinforcing fillers for silicone rubber, such as aerosol silica (dry silica), precipitated silica (wet silica) Silicon) etc. Although the fine powder silicon dioxide can be used directly, in order to give the composition good fluidity, it is necessary to use methylchlorosilanes and dichlorosilanes that have been passed through trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, etc. Treatment of organosilicon compounds such as methyl polysiloxane, hexamethyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyldisilazane, etc. The one is better. Such reinforcing silica can be used alone or in combination of two or more.

[Polysiloxy hardened material] Furthermore, the present invention provides a cured product (cured polysilicone) obtained by curing the above-mentioned addition-curable silicone composition.

Regarding the curing method and conditions of the silicone composition of the present invention, conventional curing methods and conditions can be used. As an example, it can be cured at 100 to 180°C for 10 minutes to 5 hours.

The above-mentioned cured polysilicone obtained by curing the addition-curing polysilicon composition of the present invention does not crack or warp to light, reduces light transmittance, decreases light transmittance, heat resistance, and light resistance It is excellent, so it can be used as a coating material or sealing material for semiconductor elements, especially semiconductor elements for optical applications, and a protective coating material for electrical and electronic applications.

[Optical element] Furthermore, the present invention provides an optical element sealed with the above-mentioned cured polysiloxane.

As described above, the silicone cured product of the present invention does not cause cracks or warpage to light, reduces light transmittance, and is excellent in light transmittance, heat resistance, and light resistance. Therefore, an optical element sealed with such a silicone cured material is highly reliable.

[Example]

Hereinafter, synthesis examples, examples, and comparative examples are used to specifically describe the present invention, but the present invention is not limited to these. In addition, the following viscosity is the value measured at 25°C using a rotary viscometer.

[Synthesis example 1] Methyl phenyl group with a viscosity of 400 mPa･s represented by ((CH ₃ ) ₃ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) _3.9 ((CH ₃ ) ₂ SiO) _8.6 130 parts by mass of organopolysiloxane, and 13 parts by mass (0.55 parts of cerium) of a turpentine solution of 2-ethylhexanoate containing cerium as the main component (rare earth element content of 6 mass%) and 2.7 parts by mass of tetra-n-butyl titanate (the mass of titanium is 0.3 times the mass of cerium in the above-mentioned 2-ethylhexanoate) was thoroughly mixed in advance to obtain a yellowish white dispersion. The turpentine was heated while flowing a small amount of nitrogen gas to flow out the turpentine, and then heated at 300°C for 1 hour to obtain a dense yellow-brown transparent polyorganometallic siloxane composition (described later (C-7)). The obtained polyorganometallic siloxane was analyzed by ICP-OES (High Frequency Induced Plasma Emission Spectroscopy), and the Ce content was 3,200 ppm and the Ti content was 2,700 ppm.

[Synthesis Example 2] The reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane has a platinum content of 1.0% by mass, and a phenyl group containing 30 mol% of phenyl groups with a viscosity of 700 mPa･s Dilute with base phenyl organopolysiloxane to prepare platinum catalyst.

[Examples 1 to 6, Comparative Examples 1 to 5] The following ingredients were mixed in the amounts shown in Table 1 to prepare an addition-curing silicone composition. In addition, the values of each component in Table 1 are parts by mass (for (C-1) to (C-6) are the total parts by mass relative to the components (A-1), (A-2), and (B)) The mass ppm is indicated). The value of [Si-H]/[Si-Vi] is relative to the hydrogen bonded to the silicon atom in the (A-1) component and (A-2) component which is bonded to all silicon atoms in the alkenyl group. The molar ratio of the atom.

(A-1) Ingredients: (CH ₂ =CH(CH ₃ )(C ₆ H ₅ )SiO _1/2 ) _0.20 ((C ₆ H ₅ ) ₂ SiO) _0.38 (SiO ₂ ) _0.42 0.20mol/100g branched phenyl polysiloxane resin

(A-2) Composition: (CH ₂ =CH(CH ₃ )(C ₆ H ₅ )SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₃ with a viscosity of 2,000 mPa･s and ethylene Linear phenyl polysiloxane oil with base weight of 0.22mol/100g

(B) Component: _{Organohydrogen} polysiloxane represented by (H(CH ₃ )(C ₆ H ₅ )SiO _1/2 ) ₃ ((C ₆ H ₅ )SiO _3/2 ) ₁

(C-2)以下述式(10)表示之受阻胺化合物

(C-3)以下述式(11)表示之受阻胺化合物

(C-4)以下述式(12)表示之受阻胺化合物

(C-5)以下述式(13)表示之受阻胺化合物

(C) Component: (C-1) Hindered amine compound represented by the following formula (9)

(C-2) A hindered amine compound represented by the following formula (10)

(C-3) A hindered amine compound represented by the following formula (11)

(C-4) A hindered amine compound represented by the following formula (12)

(C-5) A hindered amine compound represented by the following formula (13)

(C-7)合成例1所得到的聚有機金屬矽氧烷Comparative component: (C-6) Hindered phenol compound represented by the following formula (14)

(C-7) Polyorganometallic siloxane obtained in Synthesis Example 1

(D) Component: the platinum catalyst obtained in Synthesis Example 2

(F-2)接著性提升劑：下述式(16)表示之化合物

Other ingredients: (E) Reaction inhibitor: ethynyl cyclohexanol (F-1) Adhesion enhancer: a compound represented by the following formula (15)

(F-2) Adhesion enhancer: a compound represented by the following formula (16)

The addition curable silicone compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated as follows. The results are shown in Table 2.

[Exterior] Each composition was cured by heating at 150°C for 2 hours, and the appearance of the obtained cured product was visually confirmed.

[hardness] Each composition was poured into a mold to a thickness of 2 mm, and cured under the conditions of 150° C.×4 hours. The TypeD hardness of the cured product was measured in accordance with JIS K6253. If TypeD hardness is 50 or more, it can be judged as a material with high enough hardness.

[Heat resistance] Each composition was poured into a mold to have a thickness of 2 mm, and cured under the conditions of 150° C.×4 hours. The wavelength of the initial cured in a straight line 400nm the light transmittance T ₀ in a spectrophotometer U-3900 (Hitachi High-Tech Science Corporation) was measured. Furthermore, after exposing the cured product under the conditions of 180°C for 300 hours (heat resistance test), the linear light transmittance T at a wavelength of 400 nm was measured. The smaller the difference between the initial light transmittance and the initial light transmittance (|TT ₀ |) is, the more it is evaluated as a material with excellent heat discoloration resistance.

[Light resistance] Each composition was poured into a mold to a thickness of 2 mm, and cured under the conditions of 150° C.×4 hours. The wavelength of the cured product of the initial straight line 400nm the light transmittance T ₀ ^'to a spectrophotometer U-3900 (Hitachi High-Tech Science Corporation) was measured. Furthermore, the hardened product was subjected to a light exposure test (light resistance test) with an irradiation intensity of 18 mW/cm ² at 120°C using a light resistance tester DAIPLA METAL WEATHER (manufactured by KATO Co., Ltd.) type KW-R6TP-A. After 100 hours of exposure, the linear transmittance T'at a wavelength of 400 nm was measured. The smaller the difference between the initial light transmittance and the initial light transmittance (|T'-T ₀ ^' |) is, the better the light resistance is.

[Crack] Observe whether there are cracks on the surface of the cured product after 100 hours of light exposure. No cracks are "GOOD", and cracks are "NG".

[Warpage] The cured product after 100 hours of light exposure is "GOOD" without deformation, but "NG" if there is deformation.

As shown in Table 2, it can be seen that the silicone cured products of Examples 1 to 6 have good optical properties and mechanical properties. In addition, as a result of the 100-hour light resistance test exposure, Examples 1 to 6 had little difference in transmittance from the initial stage, and the cured product after the test had no cracks or warpage, and had good light resistance. Furthermore, regarding the heat resistance after 180° C.×300 hours, it was confirmed that the difference from the initial stage was small, and the heat resistance and light resistance were compatible.

On the other hand, the cured product of Comparative Example 1 that does not contain the (C) component of the present invention and the cured product of Comparative Example 4 in which the addition amount of the (C) component is insufficient, although the heat resistance is good, the light transmittance in the light resistance test The reduction is large, causing cracks and warping. In contrast to this, the cured product of Comparative Example 5 in which the component (C) was excessively added had good light resistance, but the light transmittance in the heat resistance test decreased greatly.

In addition, in Comparative Example 2 in which hindered phenol was added as a stabilizer other than the component (C) of the present invention, the generation of cracks and warpage after the light resistance test could not be suppressed.

Furthermore, in Comparative Example 3 in which an organometallic siloxane containing Ce was used as an additive, although the effect of improving the heat resistance was seen, the effect was not exerted on the light resistance, and the light transmittance was reduced and cracks and warpage occurred.

From the above, it has been confirmed that the addition-curing polysiloxane composition of the present invention is more suitable than ever as a sealing material for LEDs or a coating material for optical semiconductor elements with excellent light transmittance, heat resistance, and light resistance. Protective coating material for electrical and electronic.

In addition, the present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiments are examples, and those having substantially the same structure as the technical idea described in the scope of patent application of the present invention and achieving the same effects are all included in the technical scope of the present invention.

Claims (10)

An addition-hardening polysiloxane composition characterized by: (A-1) Organopolysiloxane represented by the following average composition formula (1),

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other and does not contain an alkenyl group. At least 10 mol% of all R ¹ is an aryl group, R ² is an alkenyl group, a, b , C, d, e, f, and g are the numbers that conform to a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, but they conform to b +c+e＞0, e+f+g＞0, and a+b+c+d+e+f+g=1) (A-2) Linear form expressed by the following formula (2) Organopolysiloxane,

(Wherein, R does not contain an alkenyl group substituted with ^{1 'may} be the same or different are each a substituted or unsubstituted monovalent hydrocarbon group one, R ³ is methyl or phenyl, h is a number from 0 to 50, i is 0 The number of 100, but when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. The silicone unit in the parentheses of the note h and the silicone unit in the parentheses of the note i are mutually exclusive Can be arranged randomly or in blocks) (B) Organohydrogen polysiloxanes having at least two silicon atoms bonded to hydrogen atoms in one molecule: Compared with the aforementioned (A-1) component and (A- 2) The silicon atom in the component is bonded to one alkenyl group. The number of hydrogen atoms bonded to the silicon atom in the aforementioned (B) component is 0.1 to 5.0. (C) At least one molecule has the following formula (3) The compound represented by the group: 200 to 10,000 ppm with respect to the total of the aforementioned (A-1) component, the aforementioned (A-2) component, and the aforementioned (B) component,

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, and an asterisk * is a bond with an adjacent atom. When the group represented by formula (3) in 1 molecule has a plural number, R ^{4 in the} plural group may be the same Can be different) and (D) Hydrosilation catalyst containing platinum group metals. The addition-curing polysiloxane composition according to claim 1, wherein the component (A-1) has a base represented by the following formula (4),

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group that may be the same or different from each other and does not contain an alkenyl group, and the asterisk * is a bond with adjacent atoms). The addition-curing polysiloxane composition described in claim 1 or claim 2, wherein the aforementioned component (A-2) has a base represented by the following formula (5),

(Wherein, R does not contain a substituted alkenyl group ^"may be the same or different are each of ^a one or unsubstituted monovalent hydrocarbon group, and the asterisk * is bonded to adjacent atoms). The requested item 1 or item 2 requests an addition curable silicon oxide described in the polyethylene composition, wherein the R ¹ and R ^{1 'is} phenyl or methyl. The addition-curing polysiloxane composition according to claim 1 or claim 2, wherein the aforementioned component (B) has a base represented by the following formula (6),

(Asterisk * is the bond with adjacent atoms). The addition curable polysiloxane composition according to claim 1 or claim 2, wherein the aforementioned component (C) is a compound represented by the following formula (8),

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, which may be the same or different). The addition curable polysiloxane composition according to claim 1 or claim 2, wherein R ⁴ in the component (C) is an alkoxy group. The addition curable polysiloxane composition according to claim 7, wherein the alkoxy group is a group represented by -OC ₁₁ H ₂₃ . A cured polysiloxane characterized by a cured product of an addition-curing polysiloxane composition as described in any one of Claims 1 to 8. An optical element characterized by being sealed with a polysiloxy hardened material as described in claim 9.