JP2012193235A - Coating material for optical semiconductor device and optical semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material to be used for forming a coating layer on the surface of an optical semiconductor element, which can enhance color stability of light emitted from an optical semiconductor device.SOLUTION: This coating material for the optical semiconductor device is used for forming a coating layer 4 on the surface of the optical semiconductor element 3. The coating material includes a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, a silicon oxide particle and a catalyst for the hydrosilylation reaction. The optical semiconductor device 1 includes the optical semiconductor element 3 and the coating layer 4 disposed on the surface 3a of the optical semiconductor element 3. The coating layer 4 is formed from the coating material for the optical semiconductor device.

Description

  The present invention relates to an optical semiconductor device coating material used for forming a coating layer on the surface of an optical semiconductor element in an optical semiconductor device, and an optical semiconductor device using the optical semiconductor device coating material.

  An optical semiconductor device such as a light emitting diode (LED) device has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  When an optical semiconductor element (for example, an LED), which is a light emitting element used in an optical semiconductor device, is in direct contact with the atmosphere, the light emission characteristics of the optical semiconductor element rapidly deteriorate due to moisture in the atmosphere or floating dust. For this reason, the said optical semiconductor element is normally sealed with the sealing compound for optical semiconductor devices.

  A curable organopolysiloxane composition used as a sealant or the like in an optical semiconductor device is described in Patent Document 1 below. The curable organopolysiloxane composition described in the following Patent Document 1 is represented by the following average unit formula (101), and has the following average polyorganosiloxane having at least two aliphatic unsaturated groups in one molecule: An organohydrogenpolysiloxane represented by the unit formula (102) having at least two silicon-bonded hydrogen atoms in one molecule, a specific radical copolymer, and a hydrosilylation reaction catalyst are included.

R _a SiO _{(4-a) / 2} Formula (101)

  In the above formula (101), R is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a is a positive number of 0.5 ≦ a ≦ 2.2, 20 mol% or more of the total R is a phenyl group.

R ¹ _b H _c SiO _{(4-b-c) / 2} Formula (102)

In the above formula (102), R ¹ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b and c are 0.002 <c <1, 1.0 <b <2, respectively. .2 and 1.0 <(b + c) <3.0.

JP 2006-63092 A

  In Patent Document 1, since the refractive index and light transmittance of the curable organopolysiloxane composition are high, an optical semiconductor element, an optical semiconductor member sealant, an adhesive, a potting agent, a protective coating agent, an underfill It is described that it is useful as an agent or the like. On the other hand, Patent Document 1 does not particularly describe a specific method of using the protective coating agent. Specifically, Patent Document 1 merely describes the use of a curable organopolysiloxane composition as an encapsulant for optical semiconductor devices.

  In a conventional optical semiconductor device using a curable organopolysiloxane composition as described in Patent Document 1 as a sealant, the color of light emitted from the optical semiconductor device may be partially different.

  An object of the present invention is to form a coating layer on the surface of an optical semiconductor element, and to improve the stability of the color of light emitted from the optical semiconductor device. An optical semiconductor device using a coating material for a semiconductor device is provided.

  A limited object of the present invention is to provide a coating material for a semiconductor device that can hardly cause cracking or peeling in a coating layer formed of the coating material even when used in a harsh environment, and the optical semiconductor device. An optical semiconductor device using a coating material is provided.

  According to a wide aspect of the present invention, there is provided a coating material for an optical semiconductor device used for forming a coating layer on the surface of an optical semiconductor element, the first organopolysiloxane having an alkenyl group, and a silicon atom. There is provided a coating material for an optical semiconductor device comprising a second organopolysiloxane having bonded hydrogen atoms, silicon oxide particles, and a hydrosilylation reaction catalyst.

  In a specific aspect of the coating material for an optical semiconductor device according to the present invention, a phosphor is further included.

  In another specific aspect of the coating material for an optical semiconductor device according to the present invention, an organic solvent is further included. The organic solvent is preferably an aromatic hydrocarbon organic solvent.

  In another specific aspect of the coating material for an optical semiconductor device according to the present invention, the first organopolysiloxane is a first organopolysiloxane having an aryl group and an alkenyl group, and the second organopolysiloxane. Is a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom.

  In still another specific aspect of the coating material for an optical semiconductor device according to the present invention, the first organopolysiloxane is represented by the following formula (1) and has an aryl group and an alkenyl group. It is siloxane, and the second organopolysiloxane is a second organopolysiloxane represented by the following formula (51) and having a hydrogen atom bonded to an aryl group and a silicon atom.

  In the above formula (1), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one aryl group, at least one represents an alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

  In the above formula (51), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represent at least one aryl group, at least one represents a hydrogen atom bonded to a silicon atom, and R51 to R51 other than an aryl group and a hydrogen atom bonded to a silicon atom R56 represents a hydrocarbon group having 1 to 8 carbon atoms.

  In still another specific aspect of the coating material for an optical semiconductor device according to the present invention, the content ratios of aryl groups obtained from the following formula (X) in the first organopolysiloxane and the second organopolysiloxane are respectively 30 mol% or more and 70 mol% or less.

  Aryl group content ratio (mol%) = (average number of aryl groups per molecule of the first organopolysiloxane or the second organopolysiloxane × the molecular weight of the aryl group / the first organopolysiloxane) Number average molecular weight of siloxane or second organopolysiloxane) × 100 Formula (X)

  In another specific aspect of the coating material for an optical semiconductor device according to the present invention, silicon oxide particles are further included.

  The coating material for an optical semiconductor device according to the present invention is used for forming a coating layer on the surface of an optical semiconductor element, and the coating layer is a coating material for an optical semiconductor device sealed with a sealing agent. Is preferred. In addition, the coating material for an optical semiconductor device according to the present invention is preferably a coating material for an optical semiconductor device used for forming a coating layer having a thickness of 5 μm or more and 200 μm or less on the surface of the optical semiconductor element. Furthermore, the coating material for an optical semiconductor device according to the present invention is a coating material for an optical semiconductor device that is spray-coated on the surface of the optical semiconductor element and used to form a coating layer on the surface of the optical semiconductor element. Is preferred.

  An optical semiconductor device according to the present invention includes an optical semiconductor element and a coating layer disposed on the surface of the optical semiconductor element, and the coating layer is configured according to the present invention. It is formed by.

  In a specific aspect of the optical semiconductor device according to the present invention, a sealing agent that seals the optical semiconductor element and the coating layer is further provided.

  A coating material for an optical semiconductor device according to the present invention includes a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, silicon oxide particles, and a hydrosilylation reaction. And the formation of a coating layer on the surface of the optical semiconductor element using the coating material for an optical semiconductor device according to the present invention can improve the stability of the color of light emitted from the optical semiconductor device. it can.

FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of an optical semiconductor device for explaining an angle dependency evaluation method in Examples and Comparative Examples.

  Details of the present invention will be described below.

  A coating material for an optical semiconductor device according to the present invention includes a first organopolysiloxane having an alkenyl group, a second organopolysiloxane having a hydrogen atom bonded to a silicon atom, silicon oxide particles, and a hydrosilylation reaction. And a catalyst.

  By forming a coating layer on the surface of the optical semiconductor element using the coating material for an optical semiconductor device having the above composition, the stability of the color of light emitted from the optical semiconductor device can be enhanced.

  The coating material for an optical semiconductor device according to the present invention is used for forming a coating layer on the surface of an optical semiconductor element, and the coating layer is a coating material for an optical semiconductor device sealed with a sealing agent. Is preferred. After the coating layer is formed, the color of light emitted from the optical semiconductor device can be further stabilized by sealing the optical semiconductor element and the coating layer with a sealing agent.

  In addition, the coating material for an optical semiconductor device according to the present invention is preferably a coating material for an optical semiconductor device used for forming a coating layer having a thickness of 5 μm or more and 200 μm or less on the surface of the optical semiconductor element. When the coating layer having such a thickness is formed, the stability of the color of light emitted from the optical semiconductor device can be further improved. The thickness of the coating layer is more preferably 10 μm or more, and more preferably 150 μm or less.

  Furthermore, the coating material for an optical semiconductor device according to the present invention is a coating material for an optical semiconductor device that is spray-coated on the surface of the optical semiconductor element and used to form a coating layer on the surface of the optical semiconductor element. Is preferred. By forming the coating layer by such spray application, it becomes easy to form the coating layer uniformly and without unevenness. As a result, the stability of the color of light emitted from the optical semiconductor device can be further enhanced. In general, the sealant for sealing the optical semiconductor element is not sprayed. The coating material for optical semiconductor devices according to the present invention is different from the encapsulant for optical semiconductor devices.

  From the viewpoint of enhancing the gas barrier property of the coating layer and further making the coating layer less susceptible to cracking or peeling even when used in a harsh environment where the optical semiconductor device is repeatedly subjected to heating and cooling, the first organo The polysiloxane is preferably a first organopolysiloxane having an aryl group and an alkenyl group. From the viewpoint of enhancing the gas barrier property of the coating layer and further making it difficult to generate cracks or peeling in the coating layer even when the optical semiconductor device is used in harsh environments that are repeatedly subjected to heating and cooling, the second organo The polysiloxane is preferably a second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom.

  Even if the optical semiconductor device is used in a harsh environment that is repeatedly subjected to heating and cooling, the first organopolysiloxane and the second organopolysiloxane are used from the viewpoint of making the coating layer more difficult to crack or peel off. It is preferable that the content ratio of the aryl group calculated | required from the following formula (X) in siloxane is 30 mol% or more and 70 mol% or less, respectively.

  Aryl group content ratio (mol%) = (average number of aryl groups per molecule of the first organopolysiloxane or the second organopolysiloxane × the molecular weight of the aryl group / the first organopolysiloxane) Number average molecular weight of siloxane or second organopolysiloxane) × 100 Formula (X)

(First organopolysiloxane)
The first organopolysiloxane contained in the coating material for an optical semiconductor device according to the present invention has an alkenyl group. The first organopolysiloxane preferably has an aryl group and an alkenyl group from the viewpoint of enhancing the gas barrier property and making the coating layer more difficult to crack or peel even when used in a harsh environment. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned. As for 1st organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

  The first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom. The first organopolysiloxane does not have a hydrogen atom bonded to a silicon atom and preferably has an alkenyl group, does not have a hydrogen atom bonded to a silicon atom, and has an aryl group and an alkenyl group. It is more preferable.

  The first organopolysiloxane is represented by the following formula (1) from the viewpoint of enhancing the gas barrier properties and making the coating layer more difficult to crack or peel even when used in a harsh environment. A first organopolysiloxane having an aryl group and an alkenyl group is preferred. However, as the first organopolysiloxane, a first organopolysiloxane other than the first organopolysiloxane represented by the following formula (1) may be used.

In the above formula (1), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 each represents at least one aryl group, R4 to R6 each represents at least one alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group. In the above formula (1), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) each may have an alkoxy group, You may have.

  The above formula (1) shows an average composition formula. The hydrocarbon group in the above formula (1) may be linear or branched. R1 to R6 in the above formula (1) may be the same or different.

In the above formula (1), the oxygen atom part in the structural unit represented by (R4R5SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R6SiO _3/2 ) each form a siloxane bond. An oxygen atom part, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

  In general, in each structural unit of the above formula (1), the content of alkoxy groups is small, and the content of hydroxy groups is also small. Generally, when an organosilicon compound such as an alkoxysilane compound is hydrolyzed and polycondensed to obtain a first organopolysiloxane, most of the alkoxy groups and hydroxy groups are converted into a partial skeleton of siloxane bonds. It is to be done. That is, most of oxygen atoms of the alkoxy group and oxygen atoms of the hydroxy group are converted into oxygen atoms forming a siloxane bond. When each structural unit of the above formula (1) has an alkoxy group or a hydroxy group, it indicates that a slight amount of unreacted alkoxy group or hydroxy group that has not been converted into a partial skeleton of a siloxane bond remains. The same applies to the case where each structural unit of formula (51) described later has an alkoxy group or a hydroxy group.

  In the above formula (1), examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further enhancing the gas barrier properties, the alkenyl group in the first organopolysiloxane and the alkenyl group in the above formula (1) are preferably vinyl groups or allyl groups, and more preferably vinyl groups. .

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (1), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, Examples thereof include n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group and cyclohexyl group.

  The content ratio of the aryl group calculated | required from the following formula (X1) in the said 1st organopolysiloxane becomes like this. Preferably it is 30 mol% or more, Preferably it is 70 mol% or less. When the content ratio of the aryl group is 30 mol% or more, the gas barrier property is further improved, and cracks and peeling are less likely to occur in the coating layer. When the content ratio of the aryl group is 70 mol% or less, the coating layer is more difficult to peel off. From the viewpoint of further enhancing the gas barrier properties, the content ratio of the aryl group is more preferably 35 mol% or more. From the viewpoint of making peeling more difficult, the aryl group content is more preferably 65 mol% or less.

  Aryl group content ratio (mol%) = (average number of aryl groups contained in one molecule of the first organopolysiloxane × molecular weight of the aryl group / number average molecular weight of the first organopolysiloxane) × 100・ Formula (X1)

  When the first organopolysiloxane represented by the above formula (1) is used as the first organopolysiloxane, in the above formula (X1), the “first organopolysiloxane” “The first organopolysiloxane represented by the above formula (1)” is shown.

  When the aryl group in the first organopolysiloxane is a phenyl group, the aryl group in the formula (X1) represents a phenyl group, and the content ratio of the aryl group represents the content ratio of the phenyl group.

In the first organopolysiloxane represented by the above formula (1), the structural unit represented by (R4R5SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following formula (1-2). Or a structure in which one of the oxygen atoms bonded to the silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group.

(R4R5SiXO _1/2 ) (Formula (1-2))

The structural unit represented by (R4R5SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-b), and is further represented by the following formula (1-2b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R4 and R5 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R4R5SiO _2/2 ). Specifically, when the alkoxy group is converted into a partial skeleton of a siloxane bond, the structural unit represented by (R4R5SiO _2/2 ) is a broken line of the structural unit represented by the following formula (1-b) The part enclosed by is shown. When an unreacted alkoxy group remains, or when the alkoxy group is converted to a hydroxy group, the structural unit represented by (R4R5SiO _2/2 ) having the remaining alkoxy group or hydroxy group has the following formula: The part enclosed with the broken line of the structural unit represented by (1-2-b) is shown. In the structural unit represented by the following formula (1-b), the oxygen atom in the Si—O—Si bond forms a siloxane bond with the adjacent silicon atom, and the adjacent structural unit and oxygen atom Sharing. Accordingly, one oxygen atom in the Si—O—Si bond is defined as “O _1/2 ”.

  In the above formulas (1-2) and (1-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R4 and R5 in the above formulas (1-b), (1-2) and (1-2b) are the same groups as R4 and R5 in the above formula (1).

In the first organopolysiloxane represented by the above formula (1), the structural unit represented by (R6SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (1-3) or ( 1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a silicon atom in a trifunctional structural unit. One of the bonded oxygen atoms may contain a structure constituting a hydroxy group or an alkoxy group.

(R6SiX ₂ O _1/2 ) Formula (1-3)
(R6SiXO _2/2 ) Formula (1-4)

The structural unit represented by (R6SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-c), and further includes the following formula (1-3-c) or (1 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R6 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R6SiO _3/2 ).

  In the above formulas (1-3), (1-3-c), (1-4) and (1-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R6 in the above formulas (1-c), (1-3), (1-3-c), (1-4) and (1-4-c) is the same as R6 in the above formula (1). It is the basis of.

  The above formulas (1-b) and (1-c), formulas (1-2) to (1-4), and formulas (1-2b), (1-3-c) and (1-4- In c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, and an isobutoxy group. , Sec-butoxy group and t-butoxy group.

In the above formula (1), a / (a + b + c) is 0 or more and 0.50 or less. When a / (a + b + c) is less than or equal to the above upper limit, the heat resistance of the coating layer is further increased, and peeling of the coating layer can be further suppressed. In the above formula (1), a / (a + b + c) is preferably 0.45 or less, more preferably 0.40 or less. When a is 0 and a / (a + b + c) is 0, there is no structural unit of (R1R2R3SiO _1/2 ) in the above formula (1).

  In said formula (1), b / (a + b + c) is 0.40 or more and 1.0 or less. When b / (a + b + c) is not less than the above lower limit, the coating layer does not become too hard and cracks are hardly generated in the coating layer. In the above formula (1), b / (a + b + c) is preferably 0.50 or more.

In the above formula (1), c / (a + b + c) is 0 or more and 0.50 or less. When c / (a + b + c) is not more than the above upper limit, it is easy to maintain an appropriate viscosity of the coating material, and the adhesiveness is further enhanced. In the above formula (1), c / (a + b + c) is preferably 0.45 or less, more preferably 0.40 or less, and still more preferably 0.35 or less. In addition, when c is 0 and c / (a + b + c) is 0, the structural unit of (R6SiO _3/2 ) does not exist in the above formula (1).

  C / (a + b + c) in the above formula (1) is preferably 0. That is, the first organopolysiloxane represented by the above formula (1) is preferably the first organopolysiloxane represented by the following formula (1A). Thereby, cracks are less likely to occur in the coating layer, and peeling of the coating layer is further less likely to occur.

  In the above formula (1A), a and b satisfy a / (a + b) = 0 to 0.50 and b / (a + b) = 0.50 to 1.0, and at least one of R1 to R5 is aryl. Represents at least one alkenyl group, and R1 to R5 other than an aryl group and an alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms.

  A / (a + b) in the formula (1A) is preferably 0.45 or less, more preferably 0.40 or less. In the above formula (1A), b / (a + b) is preferably 0.55 or more, more preferably 0.60 or more.

When the first organopolysiloxane was subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation was observed depending on the type of substituent, The peak corresponding to the structural unit represented by (R1R2R3SiO _1/2 ) in formula (1) appears in the vicinity of +10 to −5 ppm, and (R4R5SiO _2/2 ) and (1-2) in formula (1) above. Each peak corresponding to the bifunctional structural unit of appears in the vicinity of −10 to −50 ppm, (R6SiO _3/2 ) in the above formula (1), and the trifunctional structure of (1-3) and (1-4) Each peak corresponding to the unit appears in the vicinity of −50 to −80 ppm.

Therefore, ²⁹ Si-NMR is measured, and the ratio of each structural unit in the above formula (1) can be measured by comparing the peak areas of the respective signals.

However, in the case where the structural unit in the above formula (1) cannot be identified by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also the ¹ H-NMR measurement result. Can be used to distinguish the proportion of each structural unit in the above formula (1).

(Second organopolysiloxane)
The second organopolysiloxane contained in the coating material for an optical semiconductor device according to the present invention has hydrogen atoms bonded to silicon atoms. The hydrogen atom is directly bonded to the silicon atom. From the viewpoint of enhancing the gas barrier property and making the coating layer less susceptible to cracking or peeling even when used in harsh environments, the second organopolysiloxane contains hydrogen atoms bonded to aryl groups and silicon atoms. It is preferable to have. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned. As for 2nd organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

  The second organopolysiloxane is represented by the following formula (51) from the viewpoint of enhancing the gas barrier property and making the coating layer less liable to crack or peel even when used in a harsh environment. A second organopolysiloxane having an aryl group and a hydrogen atom bonded to a silicon atom is preferred. However, as the second organopolysiloxane, a second organopolysiloxane other than the second organopolysiloxane represented by the following formula (51) may be used.

In the above formula (51), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represent at least one aryl group, at least one represents a hydrogen atom bonded to a silicon atom, and R51 to R51 other than an aryl group and a hydrogen atom bonded to a silicon atom R56 represents a hydrocarbon group having 1 to 8 carbon atoms. In the above formula (51), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) may each have an alkoxy group, and have a hydroxy group. You may have.

  The above formula (51) represents an average composition formula. The hydrocarbon group in the above formula (51) may be linear or branched. R51 to R56 in the above formula (51) may be the same or different.

In the above formula (51), the oxygen atom part in the structural unit represented by (R54R55SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R56SiO _3/2 ) each form a siloxane bond. An oxygen atom part, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (51), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, vinyl group and allyl group Is mentioned.

  The content ratio of the aryl group calculated | required from the following formula (X51) in the said 2nd organopolysiloxane becomes like this. Preferably it is 30 mol% or more, Preferably it is 70 mol% or less. When the content ratio of the aryl group is 30 mol% or more, the gas barrier property is further improved, and cracks and peeling are less likely to occur in the coating layer. When the content ratio of the aryl group is 70 mol% or less, the coating layer is more difficult to peel off. From the viewpoint of further enhancing the gas barrier properties, the content ratio of the aryl group is more preferably 35 mol% or more. From the viewpoint of making peeling more difficult, the aryl group content is more preferably 65 mol% or less.

  Content ratio of aryl group (mol%) = (average number of aryl groups contained in one molecule of second organopolysiloxane × molecular weight of aryl group / number average molecular weight of second organopolysiloxane) × 100・ Formula (X51)

  When the first organopolysiloxane represented by the formula (51) is used as the second organopolysiloxane, in the formula (X51), the “second organopolysiloxane” “The second organopolysiloxane represented by the above formula (51)” is shown.

  When the aryl group in the second organopolysiloxane is a phenyl group, the aryl group in the formula (X51) represents a phenyl group, and the content ratio of the aryl group represents the content ratio of the phenyl group.

In the second organopolysiloxane represented by the above formula (51), the structural unit represented by (R54R55SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following formula (51-2). Or a structure in which one of the oxygen atoms bonded to the silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group.

(R54R55SiXO _1/2 ) Formula (51-2)

The structural unit represented by (R54R55SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-b), and is further represented by the following formula (51-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R54 and R55 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R54R55SiO _2/2 ).

  In the above formulas (51-2) and (51-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R54 and R55 in the above formulas (51-b), (51-2) and (51-2-b) are the same groups as R54 and R55 in the above formula (51).

In the second organopolysiloxane represented by the above formula (51), the structural unit represented by (R56SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (51-3) or ( 51-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a silicon atom in a trifunctional structural unit. One of the bonded oxygen atoms may contain a structure constituting a hydroxy group or an alkoxy group.

(R56SiX ₂ O _1/2 ) (Formula (51-3)
(R56SiXO _2/2 ) Formula (51-4)

The structural unit represented by (R56SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-c), and further includes the following formula (51-3-c) or (51 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R56 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R56SiO _3/2 ).

  In the above formulas (51-3), (51-3-c), (51-4) and (51-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R56 in the above formulas (51-c), (51-3), (51-3-c), (51-4) and (51-4-c) is the same as R56 in the above formula (51). It is the basis of.

  The above formulas (51-b) and (51-c), formulas (51-2) to (51-4), and formulas (51-2-b), (51-3-c) and (51-4-) In c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, and an isobutoxy group. , Sec-butoxy group and t-butoxy group.

  In said formula (51), p / (p + q + r) is 0.05-0.50. When p / (p + q + r) is less than or equal to the above upper limit, the heat resistance of the coating layer is further increased, and peeling of the coating layer can be further suppressed. In said formula (51), p / (p + q + r) becomes like this. Preferably it is 0.10 or more, Preferably it is 0.45 or less.

  In the above formula (51), q / (p + q + r) is 0.05 or more and 0.50 or less. When q / (p + q + r) is not less than the above lower limit, the coating layer does not become too hard and cracks are hardly generated in the coating layer. When q / (p + q + r) is not more than the above upper limit, the gas barrier property of the coating layer is further enhanced. In said formula (51), q / (p + q + r) becomes like this. Preferably it is 0.10 or more, More preferably, it is 0.45 or less.

  In said formula (51), r / (p + q + r) is 0.20 or more and 0.80 or less. When r / (p + q + r) is equal to or greater than the above lower limit, the hardness of the coating layer is increased, scratches and dust can be prevented, the heat resistance of the coating layer is increased, and the thickness of the coating layer is unlikely to decrease in a high temperature environment. Become. When r / (p + q + r) is less than or equal to the above upper limit, it is easy to maintain an appropriate viscosity of the coating material, and adhesion is further enhanced.

When the second organopolysiloxane was subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although some variation was observed depending on the type of substituent, The peak corresponding to the structural unit represented by (R51R52R53SiO _1/2 ) in formula (51) appears in the vicinity of +10 to −5 ppm, and (R54R55SiO _2/2 ) and (51-2) in formula (51) above. Each peak corresponding to the bifunctional structural unit of appears in the vicinity of −10 to −50 ppm, (R56SiO _3/2 ) in the above formula (51), and the trifunctional structure of (51-3) and (51-4) Each peak corresponding to the unit appears in the vicinity of −50 to −80 ppm.

Therefore, the ratio of each structural unit in the above formula (51) can be measured by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the structural unit in the formula (51) cannot be distinguished by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also the ¹ H-NMR measurement result Can be used to distinguish the ratio of each structural unit in the above formula (51).

  The content of the second organopolysiloxane is preferably 10 parts by weight or more and preferably 400 parts by weight or less with respect to 100 parts by weight of the first organopolysiloxane. When the content of the first and second organopolysiloxanes is not less than the above lower limit and not more than the above upper limit, a coating layer more excellent in gas barrier properties can be obtained. From the viewpoint of obtaining a coating layer having further excellent gas barrier properties, the content of the second organopolysiloxane is more preferably 30 parts by weight or more, still more preferably with respect to 100 parts by weight of the first organopolysiloxane. Is 50 parts by weight or more, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less.

(Other properties of the first and second organopolysiloxanes and synthesis methods thereof)
The content of alkoxy groups in the first and second organopolysiloxanes is preferably 0.1 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less. Adhesiveness of a coating layer becomes it high that content of an alkoxy group is more than the said minimum. When the content of the alkoxy group is not more than the above upper limit, the storage stability of the first and second organopolysiloxanes and the coating material is increased, and the heat resistance of the coating layer is further increased.

  The content of the alkoxy group means the amount of the alkoxy group contained in the average composition formula of the first and second organopolysiloxanes.

  The first and second organopolysiloxanes preferably do not contain silanol groups. When the first and second organopolysiloxanes do not contain silanol groups, the storage stability of the first and second organopolysiloxanes and the coating material is increased. The silanol group can be reduced by heating under vacuum. The content of silanol groups can be measured using infrared spectroscopy.

  The number average molecular weight (Mn) of the first and second organopolysiloxanes is preferably 500 or more, more preferably 800 or more, still more preferably 1000 or more, preferably 200000 or less, more preferably 100000 or less. When the number average molecular weight is equal to or more than the above lower limit, the volatile components are reduced at the time of thermosetting, and the thickness of the coating layer is hardly reduced under a high temperature environment. When the number average molecular weight is not more than the above upper limit, viscosity adjustment is easy.

  The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) was measured using two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

  The method for synthesizing the first and second organopolysiloxanes is not particularly limited, and examples thereof include a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction, and a method in which a chlorosilane compound is hydrolyzed and condensed. Especially, the method of hydrolyzing an alkoxysilane compound from a viewpoint of control of reaction is preferable.

  Examples of the method for hydrolyzing and condensing the alkoxysilane compound include a method of reacting the alkoxysilane compound in the presence of water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

  Examples of the organosilicon compound for introducing an aryl group into the first and second organopolysiloxanes include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) dimethoxysilane, And phenyltrimethoxysilane.

  Examples of the organosilicon compound for introducing an alkenyl group into the first organopolysiloxane include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3-divinyl. -1,1,3,3-tetramethyldisiloxane and the like.

  Examples of the organosilicon compound for introducing a hydrogen atom bonded to a silicon atom into the second organopolysiloxane include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3, Examples include 3-tetramethyldisiloxane.

  Examples of other organosilicon compounds that can be used to obtain the first and second organopolysiloxanes include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and isopropyl (methyl) dimethoxy. Examples include silane, cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane.

  Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.

  Examples of the inorganic acid include hydrochloric acid, phosphoric acid, boric acid, and carbonic acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and oleic acid. Is mentioned.

  Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of the alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide.

  Examples of the alkali metal silanol compound include a sodium silanolate compound, a potassium silanolate compound, and a cesium silanolate compound. Of these, a potassium-based catalyst or a cesium-based catalyst is preferable.

(Catalyst for hydrosilylation reaction)
The hydrosilylation reaction catalyst contained in the coating material for an optical semiconductor device according to the present invention includes an alkenyl group in the first organopolysiloxane and a hydrogen bonded to a silicon atom in the second organopolysiloxane. It is a catalyst that causes a hydrosilylation reaction with atoms.

  As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. A platinum-based catalyst is preferable because the transparency of the coating layer can be increased.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  Since the stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  In the coating material, the content of the hydrosilylation reaction catalyst is preferably 0.01 ppm or more, more preferably 1 ppm or more, preferably 1000 ppm or less, more preferably 500 ppm or less in terms of the weight unit of metal atoms. When the content of the catalyst for hydrosilylation reaction is not less than the above lower limit, it is easy to sufficiently cure the coating material, and the gas barrier property of the coating layer can be further enhanced. When the content of the catalyst for hydrosilylation reaction is not more than the above upper limit, the problem of coloring of the coating layer hardly occurs.

(Silicon oxide particles)
The coating material for optical semiconductor devices according to the present invention contains silicon oxide particles. By using the silicon oxide particles, the viscosity of the coating material can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the coating layer. Therefore, the handleability of the coating material can be improved.

  The primary particle diameter of the silicon oxide particles is preferably 5 nm or more, more preferably 8 nm or more, preferably 200 nm or less, more preferably 150 nm or less. When the primary particle diameter of the silicon oxide particles is not less than the above lower limit, the dispersibility of the silicon oxide particles is further enhanced, and the transparency of the coating layer is further enhanced. When the primary particle diameter of the silicon oxide particles is not more than the above upper limit, it is possible to sufficiently obtain the effect of increasing the viscosity at 25 ° C. and to suppress the decrease in the viscosity due to the temperature increase.

  The primary particle diameter of the silicon oxide particles is measured as follows. The coating layer formed of the coating material for optical semiconductor devices is observed using a transmission electron microscope (trade name “JEM-2100”, manufactured by JEOL Ltd.). The size of the primary particles of 100 silicon oxide particles in the visual field is measured, and the average value of the measured values is defined as the primary particle diameter. The primary particle diameter means an average value of the diameters of the silicon oxide particles when the silicon oxide particles are spherical, and an average value of the major diameters of the silicon oxide particles when the silicon oxide particles are non-spherical.

The BET specific surface area of the silicon oxide particles is preferably 30 m ² / g or more, and preferably 400 m ² / g or less. When the BET specific surface area of the silicon oxide particles is 30 m ² / g or more, the viscosity of the coating material at 25 ° C. can be controlled within a suitable range, and a decrease in viscosity due to a temperature rise can be suppressed. When the BET specific surface area of the silicon oxide particles is 400 m ² / g or less, the aggregation of the silicon oxide particles hardly occurs, the dispersibility can be increased, and the transparency of the coating layer can be further increased. it can.

  The silicon oxide particles are not particularly limited, and examples thereof include silica produced by a dry method such as fumed silica and fused silica, and silica produced by a wet method such as colloidal silica, sol-gel silica and precipitated silica. It is done. Among these, fumed silica is preferably used as the silicon oxide particles from the viewpoint of obtaining a coating layer with less volatile components and higher transparency.

Examples of the fumed silica include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 (specific surface area). : 200 m ² / g), Aerosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area: 380 m ² / g) (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

  The silicon oxide particles are preferably surface-treated with an organosilicon compound. By this surface treatment, the dispersibility of the silicon oxide particles becomes very high, and it is possible to further suppress the decrease in the viscosity due to the temperature increase of the coating material before curing.

  The organosilicon compound is not particularly limited. For example, a silane compound having an alkyl group, a silicon compound having a siloxane skeleton such as dimethylsiloxane, a silicon compound having an amino group, and a silicon compound having a (meth) acryloyl group. Examples thereof include a compound and a silicon compound having an epoxy group. The “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.

  From the viewpoint of further enhancing dispersibility of the silicon oxide particles, the organosilicon compound is selected from the group consisting of an organosilicon compound having a dimethylsilyl group, an organosilicon compound having a trimethylsilyl group, and an organosilicon compound having a polydimethylsiloxane group. It is preferable that at least one selected. Further, from the viewpoint of further enhancing dispersibility of the silicon oxide particles, the organosilicon compound used for the surface treatment is at least one of an organosilicon compound having a trimethylsilyl group and an organosilicon compound having a polydimethylsiloxane group. It is preferable that

  As an example of a method for surface treatment with an organosilicon compound, when using an organosilicon compound having a dimethylsilyl group or an organosilicon compound having a trimethylsilyl group, for example, dichlorodimethylsilane, dimethyldimethoxysilane, hexamethyldisilazane, A method of surface-treating silicon oxide particles using trimethylsilyl chloride, trimethylmethoxysilane, or the like can be given. In the case of using an organosilicon compound having a polydimethylsiloxane group, a method of surface-treating silicon oxide particles using a compound having a silanol group at the terminal of the polydimethylsiloxane group, cyclic siloxane, or the like can be mentioned.

Examples of commercially available silicon oxide particles surface-treated with the above organosilicon compound having a dimethylsilyl group include R974 (specific surface area: 170 m ² / g) and R964 (specific surface area: 250 m ² / g) (both Nippon Aerosil Etc.).

Commercially available silicon oxide particles surface-treated with the above organosilicon compound having a trimethylsilyl group include RX200 (specific surface area: 140 m ² / g) and R8200 (specific surface area: 140 m ² / g) (both from Nippon Aerosil Co., Ltd.) Manufactured) and the like.

RY200 (specific surface area: 120 m ² / g) (manufactured by Nippon Aerosil Co., Ltd.) and the like can be mentioned as a commercial product of silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group.

  The method for surface-treating the silicon oxide particles with the organosilicon compound is not particularly limited. As this method, for example, a dry method in which silicon oxide particles are added to a mixer and an organosilicon compound is added while stirring, a slurry method in which an organosilicon compound is added to a slurry of silicon oxide particles, and silicon oxide particles And a direct treatment method such as a spray method in which an organosilicon compound is sprayed after drying. Examples of the mixer used in the dry method include a Henschel mixer and a V-type mixer. In the dry method, the organosilicon compound is added directly or as an alcohol aqueous solution, an organic solvent solution or an aqueous solution.

  When preparing a coating material for an optical semiconductor device in order to obtain silicon oxide particles that are surface-treated with the organosilicon compound, the silicon oxide particles and the matrix resin such as the first and second organopolysiloxane are used. An integral blend method in which an organosilicon compound is directly added during mixing may be used.

  The content of the silicon oxide particles is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight with respect to a total of 100 parts by weight of the first organopolysiloxane and the second organopolysiloxane. Part or more, more preferably 1 part by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less. When the content of the silicon oxide particles is equal to or higher than the lower limit, it is possible to suppress a decrease in viscosity at the time of curing. When the content of the silicon oxide particles is not more than the above upper limit, the viscosity of the coating material can be controlled to a more appropriate range, and the transparency of the coating layer is further enhanced.

(Phosphor)
The coating material for optical semiconductor devices according to the present invention may further contain a phosphor. Moreover, the coating material for optical semiconductor devices according to the present invention may not contain a phosphor. In this case, the coating material can be used with a phosphor added at the time of use. Even if the phosphor is added to the coating material, the added phosphor is unlikely to settle.

  The phosphor absorbs light emitted from an optical semiconductor element (light emitting element) on which a coating material for an optical semiconductor device is disposed, and generates fluorescence to finally obtain light of a desired color. It works to be able to. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color can be obtained by a combination of light emitted from the light emitting element and fluorescence emitted from the phosphor.

  For example, when it is intended to finally obtain white light using an ultraviolet LED chip as a light emitting element, it is preferable to use a combination of a blue phosphor, a red phosphor and a green phosphor. When it is intended to finally obtain white light using a blue LED chip as a light emitting element, it is preferable to use a combination of a green phosphor and a red phosphor, or a yellow phosphor. As for the said fluorescent substance, only 1 type may be used and 2 or more types may be used together.

The blue phosphor is not particularly limited. For example, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu and the like.

It is not particularly restricted but includes the red phosphor, for _{example, (Sr, Ca) S:} Eu, (Ca, Sr) 2 Si 5 N 8: Eu, CaSiN 2: Eu, CaAlSiN 3: Eu, Y 2 O 2 S : Eu, La ₂ O ₂ S: Eu, LiW ₂ O ₈ : (Eu, Sm), (Sr, Ca, Bs, Mg) ₁₀ (PO ₄ ) ₈ Cl ₂ : (Eu, Mn), Ba ₃ MgSi ₂ And O ₈ : (Eu, Mn).

The green phosphor is not particularly limited, and for example, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, SrGa ₂ S ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, SrSiON: Eu, ZnS: (Cu, Al), BaMgAl ₁₀ O ₁₇ (Eu, Mn), SrAl ₂ O ₄ : Eu, and the like.

Is not particularly restricted but includes the yellow phosphor, for _{example, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, Tb 3 Al 5 O 12: Ce, CaGa 2 S 4: Eu , Sr ₂ SiO ₄ : Eu, and the like.

  Furthermore, examples of the phosphor include perylene compounds that are organic phosphors.

  The phosphor has a volume average particle size of preferably 1 μm or more, more preferably 2 μm or more, preferably 30 μm or less, more preferably 25 μm or less.

  The phosphor content can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 200 parts by weight or less with respect to 100 parts by weight of the coating material for optical semiconductor devices according to the present invention. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 200 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the coating material for optical semiconductor devices.

(Organic solvent)
The coating material for an optical semiconductor device according to the present invention preferably contains an organic solvent. By using the organic solvent, the viscosity of the coating material can be optimized, and the coating material can be easily applied on the surface of the optical semiconductor element. For example, a coating material can be sprayed onto the surface of the optical semiconductor element.

  Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol monomethyl. Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene Glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Esters such as propylene carbonate, octane, aliphatic hydrocarbons decane, petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha. As for the said organic solvent, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of facilitating application of the coating material on the surface of the optical semiconductor element, forming a uniform coating layer, and further enhancing the stability of the color of light extracted from the optical semiconductor device, the organic solvent is an aromatic solvent. The organic solvent is preferably an organic hydrocarbon, and more preferably contains toluene or xylene.

  The content of the organic solvent is not particularly limited. The content of the organic solvent is appropriately adjusted in consideration of the viscosity of the coating material and the like. The content of the organic solvent is preferably 1 part by weight or more, more preferably 3 parts by weight or more, preferably 100 parts by weight in total of the first organopolysiloxane and the second organopolysiloxane. 100 parts by weight or less, more preferably 80 parts by weight or less. When the content of the organic solvent is not less than the above lower limit and not more than the above upper limit, it is easy to make the viscosity of the coating material moderate.

(Coupling agent)
The coating material for an optical semiconductor device according to the present invention may further contain a coupling agent in order to impart adhesiveness.

  It does not specifically limit as said coupling agent, For example, a silane coupling agent etc. are mentioned. Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxy. Examples include silane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. As for a coupling agent, only 1 type may be used and 2 or more types may be used together.

(Other ingredients)
The coating material for an optical semiconductor device according to the present invention includes a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, a heat conductive filler, a flame retardant, and the like as necessary. An additive may be further contained.

  The first organopolysiloxane, the second organopolysiloxane, the silicon oxide particles, and the hydrosilylation catalyst are prepared separately in a liquid containing one or more of these. A plurality of liquids may be mixed immediately before use, and the coating material for an optical semiconductor device according to the present invention may be a two-liquid mixed coating material. For example, liquid A containing the first organopolysiloxane and catalyst for hydrosilylation reaction and liquid B containing the second organopolysiloxane are prepared separately, and liquid A and liquid B are mixed immediately before use. May be. Thus, the storage stability of the first organopolysiloxane and the hydrosilylation reaction catalyst and the second organopolysiloxane is separately made into two liquids of the first liquid and the second liquid. Can be improved. The silicon oxide particles, the phosphor and the organic solvent may be blended in the liquid A, the liquid B, or both the liquid A and the liquid B.

(Details and applications of coating materials for optical semiconductor devices)
The viscosity of the coating material for optical semiconductor devices according to the present invention at 5 rpm at 25 ° C. measured using an E-type viscometer is preferably 10 mPa · s or more, and preferably 500 mPa · s or less. When the viscosity is not less than the above lower limit and not more than the above upper limit, the coating property of the coating material becomes high, and it becomes easy to form a uniform coating layer on the surface of the optical semiconductor element. For this reason, the stability of the color of the light emitted from the optical semiconductor device can be further enhanced.

  The curing temperature of the coating material for optical semiconductor devices according to the present invention is not particularly limited. The curing temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When the curing temperature is equal to or higher than the lower limit, the coating material is sufficiently cured. When the curing temperature is not more than the above upper limit, the package is unlikely to be thermally deteriorated.

  The curing method is not particularly limited, but it is preferable to use a step cure method. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the coating material can be suppressed.

  The method for producing a coating material for an optical semiconductor device according to the present invention is not particularly limited. Or the method of mixing the said 1st organopolysiloxane, the said 2nd organopolysiloxane, the said catalyst for hydrosilylation reaction, and the other component mix | blended as needed under heating is mentioned.

  The light emitting element is not particularly limited as long as it is a light emitting element using a semiconductor. For example, when the light emitting element is a light emitting diode, for example, a structure in which a semiconductor material for LED type is stacked on a substrate can be given. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the material for the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

  Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. , Displays, decorations, various lights, switching elements and the like.

  An optical semiconductor device according to the present invention includes an optical semiconductor element and a coating layer disposed on the surface of the optical semiconductor element. The coating layer is formed of the coating material for optical semiconductor devices according to the present invention. Since the coating layer is disposed on the surface of the optical semiconductor element and the coating material for forming the coating layer has a specific composition as described above, the coating layer is unlikely to be cracked and peeled off easily. Light transmittance, heat resistance, weather resistance and gas barrier properties can be improved. The optical semiconductor device according to the present invention preferably further includes a sealant that seals the optical semiconductor element and the coating layer. The sealant is preferably present separately from the coating layer.

(Embodiment of optical semiconductor device)
FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  The optical semiconductor device 1 of this embodiment has a housing 2. An optical semiconductor element 3 made of LEDs is mounted in the housing 2. The optical semiconductor element 3 is surrounded by an inner surface 2 a having light reflectivity of the housing 2. In the present embodiment, the optical semiconductor element 3 is used as a light emitting element formed of an optical semiconductor.

  The inner surface 2a is formed so that the diameter of the inner surface 2a increases toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light that has reached the inner surface 2 a is reflected by the inner surface 2 a and travels forward of the optical semiconductor element 3.

  A coating layer 4 is disposed on the surface 3 a of the optical semiconductor element 3. The coating layer 4 is formed of the above-described coating material for optical semiconductor devices. The coating layer 4 covers the upper surface and the side surface of the optical semiconductor element 3. A sealing agent 5 is filled in a region surrounded by the inner surface 2 a so as to seal the optical semiconductor element 3 and the coating layer 4. The sealant 5 covers the surface 4 a of the coating layer 4. The thickness of the coating layer 4 is preferably 5 μm or more, more preferably 10 μm or more, preferably 200 μm or less, more preferably 150 μm or less.

  Note that the structure shown in FIG. 1 is merely an example of an optical semiconductor device according to the present invention, and the mounting structure of the optical semiconductor device can be modified as appropriate.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(Synthesis Example 1) Synthesis of First Organopolysiloxane A 1000 mL separable flask equipped with a thermometer, a dropping device, and a stirrer was mixed with 63 g of trimethylmethoxysilane, 90 g of dimethyldimethoxysilane, 183 g of diphenyldimethoxysilane, and vinyltrimethoxysilane. 133 g was added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 114 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (A).

The number average molecular weight (Mn) of the obtained polymer (A) was 1700. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (A) had the following average composition formula (A1).

(Me ₃ SiO _1/2 ) _0.19 (Me ₂ SiO _2/2 ) _0.24 (Ph ₂ SiO _2/2 ) _0.26 (ViSiO _3/2 ) _0.31 ... Formula (A1)

  In the above formula (A1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (A) was 37 mol%.

In addition, the molecular weight of each polymer obtained in Synthesis Example 1 and Synthesis Examples 2 to 8 was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved. In GPC measurement, a measuring device manufactured by Waters (column: Shodex GPC manufactured by Showa Denko KK)
LF-804 (length: 300 mm) × 2, measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene) were used.

(Synthesis Example 2) Synthesis of First Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device, and a stirrer, 96 g of dimethyldimethoxysilane, 318 g of diphenyldimethoxysilane, and 119 g of vinylmethyldimethoxysilane were added, and 50 Stir at ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 108 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (B).

The number average molecular weight (Mn) of the obtained polymer (B) was 5300. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(Me ₂ SiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.45 (ViMeSiO _2/2 ) _0.30 ... Formula (B1)

  In the above formula (B1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (B) was 52 mol%.

(Synthesis Example 3) Synthesis of First Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 6.3 g of trimethylmethylmethoxysilane, 89 g of dimethyldimethoxysilane, 318 g of diphenyldimethoxysilane, and vinyl 119 g of methyldimethoxysilane was added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 107 g of water was slowly added dropwise thereto, and after the addition, the mixture was stirred at 50 ° C. for 6 hours to be reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (C).

The number average molecular weight (Mn) of the obtained polymer (C) was 5000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(Me ₃ SiO _1/2 ) _0.01 (Me ₂ SiO _2/2 ) _0.24 (Ph ₂ SiO _2/2 ) _0.45 (ViMeSiO _2/2 ) _0.30 ... Formula (C1)

  In the above formula (C1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (C) was 52 mol%.

(Synthesis Example 4) Synthesis of Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 31 g of trimethylmethoxysilane, 50 g of 1,1,3,3-tetramethyldisiloxane, dimethyl Dimethoxysilane 108 g and phenyltrimethoxysilane 208 g were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 101 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (D) was obtained.

The number average molecular weight (Mn) of the obtained polymer (D) was 1000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (D) had the following average composition formula (D1).

(Me ₃ SiO _1/2 ) _0.09 (HMe ₂ SiO _1/2 ) _0.23 (Me ₂ SiO _2/2 ) _0.27 (PhSiO _3/2 ) _0.41 ... Formula (D1)

  In the above formula (D1), Me represents a methyl group, and Ph represents a phenyl group.

  The content ratio of the phenyl group of the obtained polymer (D) was 33 mol%.

Synthesis Example 5 Synthesis of Second Organopolysiloxane A 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer was charged with 16 g of trimethylmethoxysilane, 50 g of 1,1,3,3-tetramethyldisiloxane, and dimethyl. 36 g of dimethoxysilane, 183 g of diphenyldimethoxysilane, 149 g of phenyltrimethoxysilane, and 45 g of vinyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 104 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (E) was obtained.

The number average molecular weight (Mn) of the obtained polymer (E) was 1000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (E) had the following average composition formula (E1).

(Me ₃ SiO _1/2 ) _0.05 (HMe ₂ SiO _1/2 ) _0.23 (Me ₂ SiO _2/2 ) _0.09 (Ph ₂ SiO _2/2 ) _0.26 (PhSiO _3/2 ) _0.27 (ViSiO _3/2 ) _0.10 Formula (E1)

  In the above formula (E1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (E) was 51 mol%.

Synthesis Example 6 Synthesis of Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 31 g of trimethylmethoxysilane, 40 g of 1,1,3,3-tetramethyldisiloxane, diphenyl 110 g of dimethoxysilane, 268 g of phenyltrimethoxysilane, and 45 g of vinyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 116 g of water was slowly added dropwise, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (F) was obtained.

The number average molecular weight (Mn) of the obtained polymer (F) was 1100. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (F) had the following average composition formula (F1).

(Me ₃ SiO _1/2 ) _0.09 (HMe ₂ SiO _1/2 ) _0.19 (Ph ₂ SiO _2/2 ) _0.16 (PhSiO _3/2 ) _0.46 (ViSiO _3/2 ) _{0. 10} : Formula (F1)

  In the above formula (F1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (F) was 51 mol%.

Synthesis Example 7 Synthesis of First Organopolysiloxane A 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer was added with 94 g of trimethylmethoxysilane, 99 g of dimethyldimethoxysilane, 92 g of diphenyldimethoxysilane, and vinyltrimethoxysilane. 133 g was added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 108 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (G).

The number average molecular weight (Mn) of the obtained polymer (G) was 1800. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (G) had the following average composition formula (G1).

(Me ₃ SiO _1/2 ) _0.29 (Me ₂ SiO _2/2 ) _0.27 (Ph ₂ SiO _2/2 ) _0.13 (ViSiO _3/2 ) _0.31 ... Formula (G1)

  In the above formula (G1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (G) was 21 mol%.

(Synthesis Example 8) Synthesis of Second Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 31 g of trimethylmethoxysilane, 50 g of 1,1,3,3-hexamethyldisiloxane, dimethyl 140 g of dimethoxysilane, 59 g of diphenyldimethoxysilane, 48 g of phenyltrimethoxysilane, and 45 g of vinyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 92 g of water was slowly added dropwise, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, and reduced in pressure to remove volatile components, thereby obtaining a polymer (H).

The number average molecular weight (Mn) of the obtained polymer (H) was 600. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (H) had the following average composition formula (H1).

(Me ₃ SiO _1/2 ) _0.09 (HMe ₂ SiO _1/2 ) _0.24 (Me ₂ SiO _2/2 ) _0.38 (Ph ₂ SiO _2/2 ) _0.08 (PhSiO _3/2 ) _0.10 (ViSiO _3/2 ) _0.10 Formula (H1)

  In the above formula (H1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (H) was 23 mol%.

Example 1
Polymer A (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (amount of platinum element content in the coating material is 10 ppm) 1 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), phosphor powder (volume average particle size 17 μm, A specific gravity of 4.7, “EY4453” (manufactured by Inmatics) 5 g, and 5 g of toluene as an organic solvent were mixed and defoamed to obtain a coating material for an optical semiconductor device.

(Example 2)
Polymer B (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (amount of platinum element content in the coating material is 10 ppm) 1 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), phosphor powder (volume average particle size 17 μm, A specific gravity of 4.7, “EY4453” (manufactured by Inmatics) 5 g, and 5 g of toluene as an organic solvent were mixed and defoamed to obtain a coating material for an optical semiconductor device.

(Example 3)
Polymer C (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (amount of platinum element content in the coating material is 10 ppm) 1 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), phosphor powder (volume average particle size 17 μm, A specific gravity of 4.7, “EY4453” (manufactured by Inmatics) 5 g, and 5 g of toluene as an organic solvent were mixed and defoamed to obtain a coating material for an optical semiconductor device.

Example 4
Polymer C (10 g), Polymer E (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (amount of platinum element content in the coating material is 10 ppm) 1 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), phosphor powder (volume average particle size 17 μm, A specific gravity of 4.7, “EY4453” (manufactured by Inmatics) 5 g, and 5 g of toluene as an organic solvent were mixed and defoamed to obtain a coating material for an optical semiconductor device.

(Example 5)
Polymer C (10 g), Polymer F (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (amount of platinum element content in the coating material is 10 ppm) 1 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), phosphor powder (volume average particle size 17 μm, A specific gravity of 4.7, “EY4453” (manufactured by Inmatics) 5 g, and 5 g of toluene as an organic solvent were mixed and defoamed to obtain a coating material for an optical semiconductor device.

(Example 6)
Polymer G (10 g), Polymer H (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (amount of platinum element content in the coating material is 10 ppm) 1 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), phosphor powder (volume average particle size 17 μm, A specific gravity of 4.7, “EY4453” (manufactured by Inmatics) 5 g, and 5 g of toluene as an organic solvent were mixed and defoamed to obtain a coating material for an optical semiconductor device.

(Comparative Example 1)
Polymer A (10 g), Polymer D (10 g), platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (amount of platinum element content in the coating material is 10 ppm) 5 g of phosphor powder (volume average particle size 17 μm, specific gravity 4.7, “EY4453”, manufactured by Inmatics Co., Ltd.) and 5 g of toluene as an organic solvent are mixed and defoamed to obtain a coating material for an optical semiconductor device. Obtained.

(Preparation of sealant X)
Polymer A (10 g), Polymer D (10 g), and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum element content in the sealant X is 10 ppm) To obtain a sealant X for an optical semiconductor device.

(Preparation of phosphor-containing sealant Y)
Polymer A (10 g), Polymer D (10 g), and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the platinum element content in the sealant Y is 10 ppm) Silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.) 0.4 g, and phosphor powder ( 0.8 g of a volume average particle diameter of 17 μm, a specific gravity of 4.7, “EY4453” (manufactured by Intermatics) was mixed and degassed to obtain a sealing agent Y for an optical semiconductor device containing a phosphor.

(Evaluation)
(Measurement of viscosity at 25 ° C.)
Using an E-type viscometer (TV-22 type, manufactured by Toki Sangyo Co., Ltd.), the viscosity of the obtained coating material for an optical semiconductor device at 25 ° C. at 5 rpm was measured.

(Phosphor stability)
The obtained optical semiconductor coating material was placed in a sample bottle and allowed to stand at 23 ° C. for 1 hour. After 1 hour, the case where the phosphor did not settle was judged as “◯”, and the case where the phosphor settled was judged as “x”.

(Production of optical semiconductor device)
In a structure in which a light emitting element having a main emission peak of 460 nm is mounted on a silver-plated polyphthalamide housing material with a lead electrode by a die bond material, and the light emitting element and the lead electrode are connected by a gold wire. The obtained coating material for an optical semiconductor device is spray-applied on the surface of the element, cured by heating at 80 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 2 hours, and a thickness of 150 μm on the surface of the light emitting element A coating layer was formed. Next, the obtained sealing agent X was injected, and heated at 150 ° C. for 2 hours to be cured, thereby producing an optical semiconductor device X.

  In addition, in a structure in which a light emitting element having a main light emission peak of 460 nm is mounted on a silver-plated polyphthalamide housing material with a lead electrode by a die bond material, and the light emitting element and the lead electrode are connected by a gold wire. Then, without forming a coating layer with a coating material for an optical semiconductor device, the obtained optical semiconductor encapsulant Y containing a phosphor is injected and heated at 150 ° C. for 2 hours to be cured. Prepared (reference example).

  In the obtained optical semiconductor devices X and Y, the color stability and the angle dependency were evaluated. Further, the following thermal shock test was performed using the obtained optical semiconductor device X.

(Evaluation of color stability)
In 20 obtained optical semiconductor devices X and 20 obtained optical semiconductor devices Y, the chromaticity when a current of 60 mA was passed through the light emitting element was measured using a photometric measuring device ("OL770", manufactured by Optronic Laboratories). Measured. When the maximum value and the minimum value of chromaticity were within 5% from the average value of 20 chromaticities (x), it was judged as “◯”, and when it was 5% or more, it was judged as “x”. As shown in FIG. 2, the chromaticity (x) at 0 ° in front of the LED was determined.

(Angle dependence)
In the obtained optical semiconductor device X and the obtained optical semiconductor device Y, the chromaticity at 0 ° and 70 ° when a current of 60 mA was passed through the light emitting element was measured at a temperature of 23 ° C. It measured using the goniometer of "OL770" (made by Optronic Laboratories). As shown in FIG. 2, the front of the LED is 0 °. The rate of change of chromaticity (x) at 70 ° was obtained with 0 ° as a reference. The case where the rate of change was less than 3% was judged as “◯”, and the case where the rate of change was 3% or more was judged as “x”.

(Thermal shock test)
The obtained optical semiconductor device X was held at −50 ° C. for 5 minutes using a liquid tank thermal shock tester (“TSB-51”, manufactured by ESPEC), then heated to 135 ° C. and 135 ° C. Then, a heat cycle test was performed in which the process of holding at 5 minutes and then lowering the temperature to −50 ° C. was 1 cycle. Twenty samples were taken after 500, 1000 and 1500 cycles, respectively.

  The sample was observed with a stereomicroscope (“SMZ-10”, manufactured by Nikon Corporation). The number of samples (NG number) in which cracks or peeling occurred was counted by observing whether or not cracks occurred in the coating layers of 20 samples or whether the coating layer was peeled off from the light emitting element. .

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Housing 2a ... Inner surface 3 ... Optical semiconductor element 3a ... Surface 4 ... Coating layer 4a ... Surface 5 ... Sealing agent

Claims (12)

An optical semiconductor device coating material used to form a coating layer on the surface of an optical semiconductor element,
A first organopolysiloxane having an alkenyl group;
A second organopolysiloxane having a hydrogen atom bonded to a silicon atom;
Silicon oxide particles,
A coating material for an optical semiconductor device, comprising a hydrosilylation reaction catalyst.   The coating material for optical semiconductor devices according to claim 1, further comprising a phosphor.   The coating material for optical semiconductor devices according to claim 1, further comprising an organic solvent.   The coating material for optical semiconductor devices according to claim 3, wherein the organic solvent is an aromatic hydrocarbon organic solvent. The first organopolysiloxane is a first organopolysiloxane having an aryl group and an alkenyl group,
5. The coating material for an optical semiconductor device according to claim 1, wherein the second organopolysiloxane is a second organopolysiloxane having a hydrogen atom bonded to an aryl group and a silicon atom. The first organopolysiloxane is a first organopolysiloxane represented by the following formula (1) and having an aryl group and an alkenyl group,
6. The optical semiconductor device according to claim 5, wherein the second organopolysiloxane is a second organopolysiloxane represented by the following formula (51) and having a hydrogen atom bonded to an aryl group and a silicon atom. Coating material.

In the formula (1), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one aryl group, at least one represents an alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

In the formula (51), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represent at least one aryl group, at least one represents a hydrogen atom bonded to a silicon atom, and R51 to R51 other than an aryl group and a hydrogen atom bonded to a silicon atom R56 represents a hydrocarbon group having 1 to 8 carbon atoms. The content ratio of the aryl group calculated | required from the following formula (X) in said 1st organopolysiloxane and said 2nd organopolysiloxane is 30 mol% or more and 70 mol% or less, respectively. The coating material for optical semiconductor devices of any one.
Aryl group content ratio (mol%) = (average number of aryl groups contained in one molecule of the first organopolysiloxane or the second organopolysiloxane × the molecular weight of the aryl group / the first organopolysiloxane) Number average molecular weight of siloxane or the second organopolysiloxane) × 100 Formula (X)   8. The coating material for an optical semiconductor device according to claim 1, which is used for forming a coating layer on the surface of the optical semiconductor element, and the coating layer is a coating material for an optical semiconductor device sealed with a sealing agent. Coating materials for optical semiconductor devices.   The coating for optical semiconductor devices according to claim 1, which is a coating material for optical semiconductor devices used for forming a coating layer having a thickness of 5 μm or more and 200 μm or less on the surface of the optical semiconductor element. material.   The light according to any one of claims 1 to 9, which is a coating material for an optical semiconductor device that is spray-coated on the surface of an optical semiconductor element and used to form a coating layer on the surface of the optical semiconductor element. Coating material for semiconductor devices. An optical semiconductor element;
A coating layer disposed on the surface of the optical semiconductor element,
The optical semiconductor device in which the said coating layer is formed with the coating material for optical semiconductor devices of any one of Claims 1-10.   The optical semiconductor device according to claim 11, further comprising a sealant that seals the optical semiconductor element and the coating layer.

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