TWI756574B - Addition-hardening polysiloxane compositions, cured polysiloxanes, and optical components - Google Patents

Abstract

(A-2)式(2)表示之直鏈狀有機聚矽氧烷、

(B)有機氫聚矽氧烷、 (C)至少具有1個式(3)表示之基的化合物、

及 (D)含有鉑族金屬的矽氫化觸媒、 的加成硬化型聚矽氧組成物。[Problem] To provide an aryl group-containing addition-curable polysiloxane composition, which can obtain a cured product that does not cause cracks or warps to light and has a small decrease in light transmittance. [Solution] Contains: (A-1) the organopolysiloxane represented by the average composition formula (1),

(A-2) Linear organopolysiloxane represented by formula (2),

(B) organohydrogenpolysiloxane, (C) a compound having at least one group represented by the formula (3),

and (D) an addition-hardening polysiloxane composition containing a platinum group metal hydrosilylation catalyst.

Description

Addition-hardening polysiloxane compositions, cured polysiloxanes, and optical components

The present invention relates to an addition-hardening polysiloxane composition, a cured polysiloxane thereof, and an optical element sealed with the cured polysiloxane.

A device having a light emitting diode (LED) as an optical semiconductor element generally has a structure in which an LED mounted on a substrate is sealed with a sealing material made of a transparent resin. For this sealing material, epoxy resins have been used in the past, but in recent years, due to the miniaturization of semiconductor packages, the increase in the amount of heat generated by the high brightness of LEDs, and the shortening of light wavelengths, cracks and yellowing of the resins have occurred, resulting in Decreased reliability.

Therefore, from the viewpoint of heat resistance and heat discoloration resistance, attention has been paid to polysiloxane resin compositions as sealing materials, and addition reaction hardening type polysiloxane resin compositions can be cured in a short time by heating , so the productivity is high, and it is used as a sealing material for LEDs (Patent Document 1).

High refractive index and vulcanization resistance are required for sealing materials of LEDs. For such applications, it is known that polysiloxane resin compositions having phenylsiloxane in the main skeleton (Patent Documents 2 and 3) can provide high refractive index and high resistance to sulfidation. Vulcanized hardened product.

However, with the high output of LEDs in recent years, such cured products containing aryl groups such as phenyl groups may turn 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 problem of lowering the brightness of the LED. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-292714 [Patent Document 2] Japanese Patent Laid-Open No. 2005-105217 [Patent Document 3] Japanese Patent Laid-Open No. 2010-132795

[The problem to be solved by the invention]

The present invention has been made in view of the above-mentioned circumstances, and aims to provide an addition-curable polysiloxane composition containing an aromatic group, which can obtain a cured product that does not cause cracks or warps to light and that the light transmittance decreases less . [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 an organopolysiloxane containing: (A-1) an organopolysiloxane represented by the following average composition formula (1),

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, and at least 10 mol% of the total R ¹ is an aryl group, and R ² is an alkenyl group. a, b , c, d, e, f, and g are numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, respectively, however, are numbers that satisfy b +c+e>0, e+f+g>0, and a+b+c+d+e+f+g=1.) (A-2) Linear chain represented by the following formula (2) organopolysiloxane,

(in the formula, R ^1' is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, R ³ is a methyl group or a phenyl group, h is a number from 0 to 50, and i is a number from 0 to 50. A number of 100. However, when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. The siloxane units in parentheses in the note h and the siloxane units in the brackets in the note i are mutually can be arranged randomly or in blocks.) (B) Organohydrogen polysiloxane having at least 2 or more silicon atoms-bonded hydrogen atoms in 1 molecule: relative to the aforementioned (A-1) components and (A) -2) One silicon atom-bonded alkenyl group in the component, the number of the silicon atom-bonded hydrogen atom in the aforementioned (B) component is 0.1 to 5.0, and (C) 1 molecule has at least one of the following The compound of the group represented by the formula (3) is 200 to 10,000 ppm relative to the total of the above-mentioned (A-1) component, the above-mentioned (A-2) component, and the above-mentioned (B) component,

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, and the asterisk * is a bond with an adjacent atom. When there are plural bases represented by formula (3) in 1 molecule, R ⁴ in the plural bases can be the same or can be different.) and (D) a platinum group metal-containing hydrosilation catalyst, an addition-hardening polysiloxane composition.

With such an addition-curing polysiloxane composition, a cured product excellent in light transmittance, heat resistance, and light resistance with little light transmittance drop can be obtained without generating cracks or warping with respect to light.

(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 the base represented by following formula (4).

(In the formula, R ¹ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and the asterisk * is a bond with an adjacent atom.)

In this case, the strength, refractive index, and vulcanization resistance of the cured product of the polysiloxane 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 the base represented by following formula (5).

(In the formula, R ^1' is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and the asterisk * is a bond with an adjacent atom.)

In this case, the strength, refractive index, and vulcanization resistance of the cured product of the polysiloxane composition can be improved.

Moreover, it is preferable that the said R1 and R1 ^' are ^a phenyl group or a methyl group.

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 the group represented by following formula (6).

(Asterisks * are bonds to adjacent atoms.)

In this case, high hardness and high vulcanization resistance can be imparted to the cured product of the polysiloxane composition.

(式中，R⁴ 為氫原子、烷基或烷氧基，可為相同亦可為相異。)Moreover, it is preferable that the said (C) component is a compound represented by 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 used suitably as (C)component.

Moreover, in the said (C) component, R< ⁴ > is preferably an alkoxy group.

In this case, light resistance can be effectively imparted to the cured product of the polysiloxane composition.

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

In this case, light resistance can be more effectively imparted to the cured product of the polysiloxane composition.

Further, the present invention provides a cured polysiloxane which is a cured product of the above-mentioned addition-curable polysiloxane composition.

Such a cured polysiloxane product can be used as a semiconductor element, especially a semiconductor element for optical applications, because it does not cause cracks or warpage to light, has less reduction in light transmittance, and is excellent in light transmittance, heat resistance, and light resistance. coating materials or sealing materials, and protective coating materials for electrical and electronic applications.

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

The cured polysiloxane of the present invention does not generate cracks or warps against light, has less reduction in light transmittance, and is excellent in light transmittance, heat resistance, and light resistance. Therefore, the optical element sealed with such a polysiloxane cured product is highly reliable. [Effect of invention]

As described above, in the case of the addition-curable polysiloxane composition of the present invention, a cured product excellent in light transmittance, heat resistance, and light resistance can be obtained without cracking or warping with respect to light and with little decrease in light transmittance. . Therefore, the cured product obtained from the addition-curable polysiloxane composition can be suitably used as an optical element sealing material and the like. [The best form of implementing the invention]

As described above, development of an addition-curable polysiloxane composition capable of obtaining a cured product with little light transmittance reduction without cracking or warping to light, and a highly reliable optical element sealed with the cured product has been sought.

As a result of diligently examining the above-mentioned problems, the inventors of the present invention found that the composition of addition-curable polysiloxane containing the components (A-1), (A-2), (B), (C), and (D) described later The above-mentioned subject 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) an organopolysiloxane represented by the following average composition formula (1),

(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, and at least 10 mol% of the total R ¹ is an aryl group, and R ² is an alkenyl group. a, b , c, d, e, f, and g are numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, respectively, however, are numbers that satisfy b +c+e>0, e+f+g>0, and a+b+c+d+e+f+g=1.) (A-2) Linear chain represented by the following formula (2) organopolysiloxane,

(in the formula, R ^1' is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, R ³ is a methyl group or a phenyl group, h is a number from 0 to 50, and i is a number from 0 to 50. A number of 100. However, when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. The siloxane units in parentheses in the note h and the siloxane units in the brackets in the note i are mutually can be arranged randomly or in blocks.) (B) Organohydrogen polysiloxane having at least 2 or more silicon atoms-bonded hydrogen atoms in 1 molecule: relative to the aforementioned (A-1) components and (A) -2) One silicon atom-bonded alkenyl group in the component, the number of the silicon atom-bonded hydrogen atom in the aforementioned (B) component is 0.1 to 5.0, and (C) 1 molecule has at least one of the following The compound of the group represented by the formula (3) is 200 to 10,000 ppm relative to the total of the above-mentioned (A-1) component, the above-mentioned (A-2) component, and the above-mentioned (B) component,

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, and the asterisk * is a bond with an adjacent atom. When there are plural bases represented by formula (3) in 1 molecule, R ⁴ in the plural bases can be the same or can be different.) and (D) an addition-hardening polysiloxane composition of a platinum group metal-containing hydrosilylation catalyst.

With such an addition-curing polysiloxane composition, a cured product excellent in light transmittance, heat resistance, and light resistance with little light transmittance drop can be obtained without generating cracks or warping with respect to light.

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

[Addition hardening polysiloxane composition] The addition-curable polysiloxane 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。)<Component (A-1)> The component (A-1) in the addition-curable polysiloxane 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 that does not contain an alkenyl group, which may be the same or different, and at least 10 mol% of the total R ¹ is an aryl group, and R ² is an alkenyl group. a, b , c, d, e, f, and g are numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, respectively, however, are numbers that satisfy 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 polysiloxane composition, and contains either or both of SiO _3/2 units and SiO _4/2 units.

(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 of the siloxane units in one molecule. By having it, the strength, refractive index, and vulcanization resistance of the cured product of the polysiloxane composition can be improved.

(In the formula, R ¹ is the same as above, and the asterisk * is the bond with the adjacent atom.)

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

At least 10 mol% of all R ¹ are aryl groups. If the aryl group in 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. The aryl group includes, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like, and a phenyl group is particularly preferred.

In addition, R ¹ is preferably a phenyl group or a methyl group, and if so, it can be used more preferably as the component (A-1).

The above R ² is an alkenyl group, preferably a vinyl group, an allyl group, an ethynyl group with 2 to 10 carbon atoms, more preferably an alkenyl group with a carbon number of 2 to 6, especially a vinyl group.

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

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

(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> (A-2) component is a linear organopolysiloxane represented by following formula (2).

(in the formula, R ^1' is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, R ³ is a methyl group or a phenyl group, h is a number from 0 to 50, and i is a number from 0 to 50. A number of 100. However, when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. The siloxane units in parentheses in the note h and the siloxane units in the brackets in the note i are mutually It can be arranged randomly or in blocks.)

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

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

In 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 ranges, high hardness and vulcanization resistance cannot be imparted to the cured product of the polysiloxane composition of the present invention.

The viscosity of the component (A-2) at 25°C is preferably 10 to 100,000 mPa･s, more preferably 10 to 10,000 mPa･s. If the viscosity is within the above range, this component will not function as a soft segment more than necessary, and the target high hardness can be obtained. In addition, there is no problem that the viscosity of the composition is significantly increased 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 more preferably has the siloxane unit at both molecular terminals. By having it, the strength, refractive index, and vulcanization resistance of the cured product of the polysiloxane composition can be improved.

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

Moreover, it is preferable that R ^1' is a phenyl group or a methyl group, and if it is such, it can be used more suitably as a (A-2) component.

Specific examples of the component (A-2) include, for example, both-end methylphenylvinyl chain-blocked diphenylsiloxane, single-end methylphenylvinyl group-end diphenylvinyl chain-sealed diphenyl Siloxane, both-end diphenyl vinyl chain-blocked diphenyl siloxane, double-end diphenyl vinyl chain-sealed diphenyl siloxane・methylphenyl siloxane copolymer, both ends of diphenyl siloxane Methyl vinyl chain-blocked diphenyl siloxane, single-end dimethyl vinyl single-end methyl phenyl vinyl chain-blocked diphenyl siloxane, two-end dimethyl vinyl chain-blocked methyl phenyl Siloxane, single-end dimethyl vinyl, single-end methyl phenyl vinyl chain-sealed methyl phenyl siloxane, etc. The component (A-2) may be used alone or in combination of two or more.

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

<(B) component> (B) Component is an organohydrogen polysiloxane having at least 2 or more silicon atoms bonded to hydrogen atoms in one molecule of the cross-linking agent by causing a hydrosilylation reaction with the components (A-1) and (A-2). alkyl.

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

The component (B) preferably has at least one aryl group from the viewpoint of compatibility with the components (A-1) and (A-2). As the aryl group, the same ones as those exemplified in the component (A-1) can be exemplified.

The organohydrogenpolysiloxane of the component (B) has at least 2, preferably 3 to 300, particularly preferably 3 to 100 hydrogen atoms bonded to silicon atoms in one molecule (ie, a hydrosilyl group (SiH group)). When the organohydrogenpolysiloxane of the component (B) has a straight-chain structure, these SiH groups may be located only at the end of the molecular chain and in the middle of the molecular chain (non-terminal of the molecular chain), or may be located in both of them .

(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 of the siloxane units in one molecule. By having it, high hardness and high vulcanization resistance can be imparted to the cured product of the polysiloxane composition.

(Asterisks * are bonds to adjacent atoms.)

The number (degree of polymerization) of silicon atoms in one molecule of the component (B) 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。)For the component (B), for example, an organohydrogenpolysiloxane represented by the following average composition formula (7) can be used.

(in the formula, R ⁵ is a bond with the same or different unsubstituted or substituted carbon atoms not containing an alkenyl group, preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8 The monovalent hydrocarbon group bonded to the silicon atom is, for example, the same as R 1 in the (A-1) component and R ^{1 '} in the (A-2) component. Also, j and k preferably satisfy 0.7≦j≦2.1 , 0.001≦k≦1.0, and 0.8≦j+k≦3.0, more preferably, 1.0≦j≦2.0, 0.01≦k≦1.0, and 1.55≦j+k≦2.5.)

Specific examples of the component (B) include, for example, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, gins(hydrogendisiloxane) Methylsiloxy) methylsilane, sine (hydrodimethylsiloxy) phenylsilane, methylhydrocyclopolysiloxane, methylhydrosiloxane・dimethylsiloxane cyclic copolymer , Two-terminal trimethylsiloxy chain-blocked methylhydrogen polysiloxane, two-terminal trimethylsiloxy chain-blocked dimethylsiloxane・methylhydrosiloxane copolymer, two-terminal dimethylsiloxane Hydrosiloxy chain-blocked dimethyl polysiloxane, two-terminal dimethyl hydrosiloxy chain-blocked methyl hydrogen polysiloxane, two-terminal dimethyl hydrosiloxy chain-blocked dimethyl siloxane Alkane・Methylhydrosiloxane Copolymer, Two-Terminal Trimethylsiloxy Chain Blocked Methylhydrosiloxane・Diphenylsiloxane Copolymer, Two-Terminal Trimethylsiloxy Chain Blocked Methyl Hydrogen Siloxane・Diphenylsiloxane・Dimethylsiloxane Copolymer, Two-Terminal Trimethylsiloxy Chain Blocked Methylhydrosiloxane・Methylphenylsiloxane・Dimethylsiloxane Alkane copolymer, both-end dimethylhydrosiloxy chain-blocked methylhydrosiloxane, dimethylsiloxane, diphenylsiloxane copolymer, double-end dimethylhydrosiloxy chain-sealed Hydroxysiloxane・dimethylsiloxane・methylphenylsiloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/2 unit 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 )} ) ₃ SiO _1/2 unit composed of copolymers, etc.

The blending amount of component (B) is 0.1 to 5.0 alkenyl groups bonded to silicon atoms in components (A-1) and (A-2), and the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.1 to 5.0. , preferably in the range of 0.5 to 3.0, more preferably in the range of 0.5 to 2.0. When the compounding quantity of (B) component is outside the said range, high hardness cannot be given to the hardened|cured material of a polysiloxane composition.

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

(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> (C)component is a compound which has at least 1 hindered amine group represented by following formula (3) in 1 molecule.

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, and the asterisk * is a bond with an adjacent atom. When there are plural bases represented by formula (3) in 1 molecule, R ⁴ in the plural bases can be the same or can be different.)

The component (C) is a stabilizer for imparting light resistance to light emitted from an LED in a 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, based on 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 sufficiently exhibited, and if the addition amount exceeds the above addition amount, the component (D) described later has catalyst poison, which is easy to cause discoloration at high temperature in addition to inhibiting curing.

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

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

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

Specific examples of the component (C) include dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 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"'-4-(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 , the reaction product of cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine Reaction product with 2-aminoethanol, bis[2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl] decanedioic acid, bis(2,2,6 ,6-Tetramethyl-1-undecyloxy-4-piperidinyl) sebacate, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, 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 a commercially available product, a hindered amine light stabilizer manufactured by ADEKA Co., Ltd. can be used, and a compound represented by the following formula (9) (product name: ADK STAB LA-81) is suitable.

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

＜(D)component＞ The platinum group metal-containing hydrosilylation catalyst of the component (D) promotes the addition reaction of the alkenyl group in the components (A-1) and (A-2) and the silicon atom in the component (B) bonded to a hydrogen atom Can be any catalyst. Specific examples thereof include platinum group metals such as platinum, palladium, rhodium, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, vinylsiloxanes or acetylene compounds. A platinum group metal compound such as a compound, tetra(triphenylphosphine) palladium, chlorosyn(triphenylphosphine) rhodium, etc., is particularly preferably a platinum compound.

(D) Component may be used alone or in combination of two or more.

The compounding amount of the component (D) may be an effective amount as a catalyst, but relative to the total amount of the components (A-1), (A-2) and (B), it is converted into a catalyst metal element and calculated on a mass basis It is preferably within the range of 1~500ppm, more preferably within the range of 1~100ppm. 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-hardening polysiloxane composition of the present invention, components such as an adhesion promoter or a reaction inhibitor may be added according to the purpose.

In terms of the adhesiveness enhancer, from the viewpoint of self-adhesion to the composition of the present invention of the addition reaction hardening type, organosilicon compounds such as silanes and siloxanes containing functional groups for imparting adhesiveness, non-polymeric Silicon-oxygen organic compounds, etc.

Specific examples of the functional group imparting adhesiveness include, for example, an alkenyl group such as a vinyl group and an allyl group bonded to a silicon atom, or a hydrogen atom; an epoxy group (eg, γ- glycidoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, etc.), acryloxy (eg, γ-acryloyloxypropyl, etc.), or methacryloyloxy (such as γ-methacryloyloxypropyl, etc.); alkoxysilyl group (for example, it can contain 1~2 ester structure, urethane structure, ether structure through the alkyl group bonded to the silicon atom alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, methyldimethoxysilyl, etc.).

As the organosilicon compound containing a functional group that imparts adhesiveness, for example, a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and an organic compound having a reactive organic group introduced with an alkoxy group can be mentioned. Silane-based compounds, etc.

Moreover, as a non-polysiloxane type organic compound, an organic acid allyl ester, an epoxy ring-opening catalyst, an organotitanium compound, an organozirconium compound, an organoaluminum compound etc. are mentioned, for example.

In terms of reaction inhibitors, for example, phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene-based compounds; hydrogen Peroxy compounds; maleic acid derivatives; 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylmethanol, 1,3,5, 7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and other conventional compounds having a hardening inhibitory effect on the hydrosilylation catalyst of the above-mentioned (D) component.

Since the degree of the hardening inhibitory effect caused by the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor, the mixing amount of the reaction inhibitor is preferably adjusted to the optimum amount of each reaction inhibitor used. Preferably it is 0.001-5 mass parts with respect to the total 30 mass parts of (A-1) component, (A-2) component, (B) component, (C) component, and (D) component. When the compounding amount is 0.001 part by mass or more, the long-term storage stability of the composition at room temperature can be sufficiently obtained. If the compounding amount is 5 parts by mass or less, the hardening of the composition will not be hindered.

In addition, in order to enhance the reinforcement, the composition of the present invention can also be combined with inorganic fillers such as micro-powder silica, crystalline silica, hollow fillers, silsesquioxane, etc., and fillers thereof. Fillers for surface hydrophobization treatment with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, low molecular weight siloxane compounds, etc.; polysiloxane rubber powder, polysiloxane resin powder, etc.

In terms of micro-powder silica, the specific surface area (BET method) is preferably 50 m ² /g or more, more preferably 50-400 m ² /g, and particularly preferably 100-300 m ² /g. When the specific surface area is 50 m ² /g or more, sufficient reinforcement can be imparted to the cured product.

In terms of such micro-powdered silica, known ones used as reinforcing fillers for polysiloxane rubber, such as aerosol silica (dry silica), precipitated silica (wet silica) silicon) etc. Although micro-powder silica can be used directly, in order to impart good fluidity to the composition, methylchlorosilanes, dichlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane are used. Treatment of organosilicon compounds such as hexaorganodisilazane, methylpolysiloxane, hexamethyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyldisilazane, etc. whichever is better. Such reinforcing silica may be used alone or in combination of two or more.

[Polysilicone cured product] Furthermore, the present invention provides a cured product (cured polysiloxane) obtained by curing the above-mentioned addition-curable polysiloxane composition.

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

The above-mentioned cured polysiloxane obtained by curing the addition-curable polysiloxane composition of the present invention does not cause cracks or warps to light, and has less decrease in light transmittance, light transmittance, heat resistance, and light resistance. Since it is excellent, it can be used as a coating material or sealing material for semiconductor elements, especially semiconductor elements for optical applications, and as a protective coating material for electrical and electronic applications.

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

As described above, the cured polysiloxane of the present invention does not generate cracks or warps with respect to light, has less reduction in light transmittance, and is excellent in light transmittance, heat resistance, and light resistance. Therefore, the optical element sealed with such a polysiloxane cured product is highly reliable.

[Example]

Hereinafter, the present invention will be specifically described using Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these. In addition, the following viscosity is the value at 25 degreeC measured using a rotational viscometer.

[Synthesis Example 1] Methylphenyl 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, 13 parts by mass of a turpentine solution of 2-ethylhexanoate containing cerium as the main component (content of rare earth elements: 6 mass %) and 13 parts by mass (0.55 part of cerium) and 130 parts by mass of organopolysiloxane were added. 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 sufficiently mixed in advance to obtain a yellowish-white dispersion. The turpentine oil was heated while flowing a small amount of nitrogen gas therein, and then heated at 300° C. for 1 hour to obtain a homogeneous composition of dark brown transparent polyorganometallosiloxane (described later (C-7)). The obtained polyorganometallic siloxane was analyzed by ICP-OES (high-frequency induced coupled plasma emission spectrometry), and the Ce content was 3,200 ppm and the Ti content was 2,700 ppm.

[Synthesis Example 2] The reaction product of platinic acid hexachloride and 1,3-divinyltetramethyldisiloxane was prepared as a methyl alcohol with a viscosity of 700 mPa･s containing 30 mol % of phenyl groups so that the platinum content was 1.0 mass %. A platinum catalyst was prepared by diluting with phenylorganopolysiloxane.

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

(A-1) Component: Amount of vinyl group represented by (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

(A-2) Component: The viscosity represented by (CH ₂ =CH(CH ₃ )(C ₆ H ₅ )SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₃ is 2,000 mPa･s and ethylene Linear phenyl polysiloxane oil with a 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) Hindered amine compound represented by the following formula (10)

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

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

(C-5) 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: 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 components: (E) Reaction inhibitor: ethynylcyclohexanol (F-1) Adhesion enhancer: compound represented by the following formula (15)

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

The following evaluations were performed on the addition-hardening polysiloxane compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 5, and the results are shown in Table 2.

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

[hardness] Each composition was poured into a mold so as to have a thickness of 2 mm, and was hardened under the conditions of 150° C.×4 hours. The Type D 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 sufficiently high hardness.

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

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

[cracks] The presence or absence of cracks on the surface of the cured product after exposure to light for 100 hours was observed. No cracks are "GOOD", and cracks are "NG".

[warping] The cured product after the above 100 hours of light exposure was "GOOD" without deformation, but "NG" with deformation on the contrary.

As shown in Table 2, it can be seen that the cured polysiloxanes of Examples 1 to 6 have favorable optical properties and mechanical properties. In addition, as a result of exposure in the light resistance test for 100 hours, Examples 1 to 6 showed 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, about the heat resistance after 180 degreeC x 300 hours, it was confirmed that the difference from the initial stage was small, and both heat resistance and light resistance were possible.

On the other hand, the cured product of Comparative Example 1, which does not contain the component (C) of the present invention, and the cured product of Comparative Example 4, in which the amount of the component (C) added is insufficient, have good heat resistance, but the light transmittance in the light resistance test is good. The decrease is large, resulting in cracks and warping. On the other hand, 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.

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

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

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

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

Claims (10)

An addition hardening type polysiloxane composition, which is characterized by containing: (A-1) an organopolysiloxane represented by the following average composition formula (1), (R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g ( 1) (in the formula, R ¹ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that can be the same or different, at least 10 mol% of all R ¹ are aryl groups, R ² is an alkenyl group, a , b, c, d, e, f, and g are numbers that satisfy a≧0, b≧0, c≧0, d≧0, e=0, f=0, and g>0, respectively, but are Conform to b+c+e>0, e+f+g>0, and a+b+c+d+e+f+g=1) (A-2) the following formula (2) chain organopolysiloxane,

(in the formula, R ^1' is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, R ³ is a methyl group or a phenyl group, h is a number from 0 to 50, and i is a number from 0 to 50. A number of 100, however, when h is 0, R ³ is a phenyl group, and i is a number from 1 to 100, the siloxane units in the brackets of the note h and the siloxane units in the brackets of the note i are mutually (B) Organohydrogen polysiloxane having at least 2 or more silicon atoms-bonded hydrogen atoms in 1 molecule: relative to the aforementioned (A-1) components and (A- 2) One silicon atom-bonded alkenyl group in the component, the number of the silicon atom-bonded hydrogen atom in the aforementioned (B) component is an amount of 0.1 to 5.0, and (C) 1 molecule has at least one of the following formula The compound of the group represented by (3): 200 to 10,000 ppm with respect to the total of the above-mentioned (A-1) component, the above-mentioned (A-2) component, and the above-mentioned (B) component,

(In the formula, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, the asterisk * is a bond with an adjacent atom, and when there are plural bases represented by formula (3) in one molecule, R ⁴ in the plural bases can be the same or can be different) and (D) a hydrosilation catalyst containing platinum group metals. The addition-curable 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 each without an alkenyl group, and an asterisk * is a bond with an adjacent atom). The addition-curable polysiloxane composition according to claim 1 or claim 2, wherein the component (A-2) has a base represented by the following formula (5),

(In the formula, R ^1' is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, each of which may be the same or different, and an asterisk * is a bond with an adjacent atom). The addition-curable polysiloxane composition according to claim 1 or claim 2, wherein the aforementioned R ¹ and R ^1' are a phenyl group or a methyl group. The addition-curable polysiloxane composition according to claim 1 or claim 2, wherein the component (B) has a base represented by the following formula (6),

(Asterisks * are bonds with adjacent atoms). The addition-curable polysiloxane composition according to claim 1 or claim 2, wherein the 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, which is characterized by being the cured product of the addition-hardening polysiloxane composition according to any one of claim 1 to claim 8. An optical element characterized by being sealed with the cured polysiloxane according to claim 9.