Thermosetting silicone composition, sheet and silicone cured product

Abstract

The present invention is a thermosetting silicone composition, which comprises: (A) an organopolysiloxane of average formula (1), (SiO 2 ) a1 (R 1 3 SiO 1 / 2 ) b1 (X 1 O 1 / 2 ) c1 (1)R 1 50 to 99.9% of X is methyl and 0.1 to 50% of X is alkenyl, 1 is a hydrogen atom or an alkyl group; (B) an organopolysiloxane of average formula (2), (SiO 2 ) a2 (R 2 3 SiO 1 / 2 ) b2 (X 1 O 1 / 2 ) c2 (2)R 2 is a hydrocarbon group without an alkenyl group, X 1 is a hydrogen atom or an alkyl group; (C) an organopolysiloxane of average formula (3), (R 3 2 SiO) a3 (R 3 3 SiO 1 / 2 ) b3 (3)R 3 20% or more of the total amount is methyl and 0.0001 to 25% of the total amount is alkenyl; (D) an organic peroxide; and (E) a solvent. Thus, a thermosetting silicone composition is provided, which has excellent stability when not cured without adding a reaction control agent and provides a cured product with high hardness.

Description

Technical Field

[0001] The present invention relates to a thermosetting silicone composition cured by an organic peroxide. Background Art

[0002] Light-emitting diodes (LEDs) have significantly improved their luminous efficiency and have advantages such as low power consumption, long life, and design. Their market share is rapidly expanding not only in the backlight source of liquid crystal displays (LCDs) and automotive headlights, but also in general lighting.

[0003] Since the light spectrum of LED depends on the semiconductor material forming the LED chip, the light color is limited. Therefore, in order to use LED to obtain white light suitable for LCD backlight and general lighting, it is necessary to configure the phosphor suitable for each chip on the LED chip and convert the emission wavelength. Specifically, a method of setting a yellow phosphor on an LED chip that emits blue light, a method of setting red and green phosphors on an LED chip that emits blue light, and a method of setting red, green, and blue phosphors on an LED chip that emits ultraviolet light have been proposed. Among them, from the perspective of the luminous efficiency and cost of the LED chip, the most widely used method is currently to set a yellow phosphor on a blue LED, and a method of setting red and green phosphors on a blue LED.

[0004] As one of the specific methods for providing a phosphor on an LED chip, a method has been proposed in which a sheet is attached to the LED chip, the sheet being formed by dispersing the phosphor in an addition-curable silicone composition in which a hydrogen organopolysiloxane and an alkenyl-containing organopolysiloxane are reacted. However, this method requires the sheet to be stored at a low temperature so that the addition reaction does not proceed when the phosphor sheet is produced, and a large amount of an addition reaction control agent must be added to the composition (Patent Documents 1 to 5).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-001791

[0008] Patent Document 2: Japanese Patent Application Publication No. 2013-001792

[0009] Patent Document 3: Japanese Patent Application Publication No. 2013-138216

[0010] Patent Document 4: Japanese Patent Application Publication No. 2014-114446

[0011] Patent Document 5: Japanese Patent Application Publication No. 2014-116598 Summary of the invention

[0012] Technical Problems to be Solved by the Invention

[0013] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermosetting silicone composition which has excellent stability in an uncured state even without adding a reaction control agent and provides a cured product with high hardness.

[0014] Technical means to solve technical problems

[0015] In order to achieve the above technical problem, the present invention provides a thermosetting silicone composition, which comprises:

[0016] (A) an organopolysiloxane represented by the following average unit formula (1),

[0017] (SiO2) a1 (R 1 3SiO 1 / 2 ) b1 (X 1 O 1 / 2 ) c1 (1)

[0018] In formula (1), R 1 are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 1 50 to 99.9% of the total number of X are methyl groups and 0.1 to 50% are alkenyl groups, 1 is a hydrogen atom or an alkyl group; a1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c1 is 0 to 0.1, a1+b1+c1=1;

[0019] (B) an organopolysiloxane represented by the following average unit formula (2),

[0020] (SiO2) a2 (R 2 3SiO 1 / 2 ) b2 (X 1 O 1 / 2 ) c2 (2)

[0021] In formula (2), R 2 is an optionally identical or different substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, X 1 is a hydrogen atom or an alkyl group; a2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c2 is 0 to 0.1, a2+b2+c2=1;

[0022] (C) an organopolysiloxane represented by the following average unit formula (3),

[0023] (R 3 2SiO) a3 (R 3 3SiO 1 / 2 ) b3 (3)

[0024] In formula (3), R 3 are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 3 20% or more of the total number of are methyl groups and 0.0001 to 25% are alkenyl groups, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+b3=1;

[0025] (D) organic peroxides; and

[0026] (E) Solvent.

[0027] The thermosetting silicone composition of the present invention has excellent stability in an uncured state even without adding a reaction control agent, and can provide a cured product having high hardness.

[0028] Furthermore, the amount of the component (B) added is preferably 1 to 100 parts by mass relative to 100 parts by mass of the component (A).

[0029] Furthermore, the amount of the component (C) added is preferably 5 to 100 parts by mass relative to 100 parts by mass of the component (A).

[0030] This provides a cured product having more excellent mechanical properties.

[0031] Furthermore, it is preferred that 20 to 500 parts by mass of the (F) phosphor is contained based on 100 parts by mass of the total of the components (A) to (E).

[0032] In this manner, the wavelength of light emitted from the optical semiconductor element can be efficiently converted into light of a target wavelength.

[0033] Furthermore, the present invention provides a sheet formed from the above-mentioned thermosetting silicone composition.

[0034] Such a sheet is excellent in stability in an uncured state and can be used in a wide range of applications, and is particularly useful for surface coating of optical semiconductor devices such as LED elements.

[0035] Furthermore, the present invention provides a cured organosilicon material, which is a cured product of the above-mentioned thermosetting organosilicon composition.

[0036] Such a cured silicone product has excellent mechanical properties. In addition, since it is a cured product of a thermosetting silicone composition having excellent stability in an uncured state, it can be used in a wide range of applications and is particularly useful for surface coating of optical semiconductor devices such as LED elements.

[0037] Effects of the Invention

[0038] The thermosetting silicone composition of the present invention has excellent stability in an uncured state even without necessarily adding a reaction control agent, and provides a cured product with high hardness, so it can be used in a wide range of applications and is useful for surface coating of phosphor sheets and LEDs. DETAILED DESCRIPTION

[0039] As described above, there has been a long-standing demand for the development of a thermosetting silicone composition that has excellent stability in an uncured state and provides a cured product with high hardness even without adding a large amount of a reaction control agent.

[0040] The inventors of the present application have conducted intensive studies on the above-mentioned technical problems and have found that a specific thermosetting silicone composition containing an organic peroxide can solve the above-mentioned technical problems, thereby completing the present invention.

[0041] That is, the present invention is a thermosetting silicone composition comprising:

[0042] (A) an organopolysiloxane represented by the following average unit formula (1),

[0043] (SiO2) a1 (R 1 3SiO 1 / 2 ) b1 (X 1 O 1 / 2 ) c1 (1)

[0044] In formula (1), R 1 are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 1 50 to 99.9% of the total number of X are methyl groups and 0.1 to 50% are alkenyl groups, 1 is a hydrogen atom or an alkyl group; a1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c1 is 0 to 0.1, a1+b1+c1=1;

[0045] (B) an organopolysiloxane represented by the following average unit formula (2),

[0046] (SiO2) a2 (R 2 3SiO 1 / 2 ) b2 (X1 O 1 / 2 ) c2 (2)

[0047] In formula (2), R 2 is an optionally identical or different substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, X 1 is a hydrogen atom or an alkyl group; a2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c2 is 0 to 0.1, a2+b2+c2=1;

[0048] (C) an organopolysiloxane represented by the following average unit formula (3),

[0049] (R 3 2SiO) a3 (R 3 3SiO 1 / 2 ) b3 (3)

[0050] In formula (3), R 3 are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 3 20% or more of the total number of are methyl groups and 0.0001 to 25% are alkenyl groups, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+b3=1;

[0051] (D) organic peroxides; and

[0052] (E) Solvent.

[0053] The present invention will be described in detail below, but the present invention is not limited thereto.

[0054] [Thermosetting silicone composition]

[0055] The thermosetting silicone composition of the present invention comprises the components (A), (B), (C), (D), and (E) described below, and the component (F) as required.

[0056] <(A)Component>

[0057] The component (A) is an organopolysiloxane represented by the following average unit formula (1).

[0058] (SiO2) a1 (R 1 3SiO 1 / 2 ) b1 (X 1 O 1 / 2 ) c1 (1)

[0059] In formula (1), R 1are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 1 50 to 99.9% of the total number of X are methyl groups and 0.1 to 50% are alkenyl groups, 1 is a hydrogen atom or an alkyl group. a1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c1 is 0 to 0.1, and a1+b1+c1=1.

[0060] R 1 is a substituted or unsubstituted monovalent hydrocarbon group, as R 1 Examples of the alkenyl group in include vinyl, allyl, butenyl, pentenyl and hexenyl, and vinyl is particularly preferred.

[0061] R 1 The ratio of the number of alkenyl groups to the total number of is 0.1 to 50%, preferably 0.1 to 30%, and particularly preferably 0.3 to 20%. If it is less than 0.1%, the curing property of the composition is insufficient, and if it is more than 50%, the cured product becomes brittle.

[0062] In addition, as R 1 The organic group bonded to the silicon atom other than the alkenyl group in the above-mentioned group may be alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenethyl; substituted or unsubstituted monovalent hydrocarbon groups such as haloalkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, etc., preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group from the viewpoint of heat resistance.

[0063] R 1 The ratio of the number of methyl groups to the total number of methyl groups is 50 to 99.9%, preferably 60 to 97%. When it is less than 50 mol%, the heat resistance of the obtained cured product is insufficient.

[0064] X 1 is a hydrogen atom or an alkyl group, and examples of the alkyl group include 1 The organic groups are the same as those exemplified in , and methyl and ethyl are particularly preferred.

[0065] a1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c1 is 0 to 0.1, and a1+b1+c1=1. If a1, b1 and c1 are outside the above ranges, the hardness and / or strength of the obtained cured product is insufficient.

[0066] a1 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6, b1 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6, and c1 is preferably 0 to 0.05.

[0067] The molecular weight of the component (A) is not limited, but the weight average molecular weight (Mw) measured by GPC measurement using a toluene solvent (in terms of standard polystyrene) is preferably 500 to 20,000, more preferably 700 to 15,000, and particularly preferably 1,000 to 10,000.

[0068] The component (A) may be used alone or in combination of two or more.

[0069] <(B) Ingredient>

[0070] The component (B) is an organopolysiloxane represented by the following average unit formula (2).

[0071] (SiO2) a2 (R 2 3SiO 1 / 2 ) b2 (X 1 O 1 / 2 ) c2 (2)

[0072] In formula (2), R 2 is an optionally identical or different substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, X 1 is a hydrogen atom or an alkyl group. a2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c2 is 0 to 0.1, and a2+b2+c2=1.

[0073] As R 2 The monovalent hydrocarbon group not containing an alkenyl group in the component (A) may be exemplified by the following: 1 The organic group bonded to the silicon atom other than the alkenyl group in the above is the same group, and among them, a methyl group is most preferred from the viewpoint of heat resistance.

[0074] X 1 is a hydrogen atom or an alkyl group, and examples of the alkyl group include the same group as R in component (A). 1 The same organic groups as those exemplified are particularly preferably methyl and ethyl.

[0075] a2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c2 is 0 to 0.1, and a2+b2+c2 = 1. If a2, b2 and c2 are outside the above ranges, the hardness and / or strength of the obtained cured product is insufficient.

[0076] a2 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6, b2 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6, and c2 can be 0.01 to 0.1, but is preferably 0 to 0.05.

[0077] The molecular weight of the component (B) is not limited, but the weight average molecular weight (Mw) measured by GPC measurement using a toluene solvent (in terms of standard polystyrene) is preferably 500 to 20,000, more preferably 700 to 15,000, and particularly preferably 1,000 to 10,000.

[0078] The component (B) may be used alone or in combination of two or more.

[0079] From the viewpoint of hardness of the cured product, the amount of the component (B) is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, and even more preferably 7 to 50 parts by mass per 100 parts by mass of the component (A).

[0080] <(C) Ingredients>

[0081] The component (C) is an organopolysiloxane represented by the following average unit formula (3).

[0082] (R 3 2SiO) a3 (R 3 3SiO 1 / 2 ) b3 (3)

[0083] In formula (3), R 3 are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 3 20% or more of the total number of is methyl group and 0.0001 to 25% is alkenyl group, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+b3=1.

[0084] R 3 Examples include: 1 The same group as R 3 Preferred examples of the alkenyl group in include vinyl, allyl, butenyl, pentenyl and hexenyl, and vinyl is particularly preferred.

[0085] R 3 The ratio of the number of alkenyl groups to the total number of is 0.0001 to 25%, preferably 0.1 to 20%, and particularly preferably 0.3 to 20%. If it is less than 0.0001%, the curing property of the composition is insufficient, and if it is more than 25%, the cured product becomes brittle.

[0086] In addition, as R 3Examples of the organic groups bonded to the silicon atom other than the alkenyl group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenethyl; halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, etc., which are substituted or unsubstituted monovalent hydrocarbon groups. Among them, methyl is the most preferred from the viewpoint of heat resistance. 3 Among them, the content of these monovalent hydrocarbon groups is preferably 20 mol % or more because stable heat resistance can be imparted, and more preferably 40 mol % or more.

[0087] R 3 The ratio of the number of methyl groups to the total number of methyl groups is 20 to 99.9999%, preferably 40 to 99.9%. When it is less than 20 mol%, the heat resistance of the obtained cured product is insufficient.

[0088] a3 is 0.9980 to 0.9999, preferably 0.9985 to 0.9999, and more preferably 0.9987 to 0.9999. b3 is 0.0001 to 0.002, preferably 0.0001 to 0.0015, and more preferably 0.0001 to 0.0013. In addition, a3+b3=1.

[0089] The component (C) may be used alone or in combination of two or more.

[0090] From the viewpoint of hardness of the cured product, the amount of the component (C) is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 30 to 60 parts by mass per 100 parts by mass of the component (A).

[0091] <(D) Ingredient>

[0092] The component (D) is an organic peroxide, which is decomposed by heat to generate free radicals, thereby curing the thermosetting silicone composition of the present invention.

[0093] Specific examples of the organic peroxide include diacyl peroxide, peroxyester, dialkyl peroxide, peroxydicarbonate, peroxyketal, hydroperoxide, and silyl peroxide.

[0094] Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, bis(3,5,5-trimethylhexanoyl)peroxide, octanoyl peroxide, lauroyl peroxide, distearic acid peroxide, succinic acid peroxide, benzoylperoxytoluene, and benzoyl peroxide.

[0095] Examples of the peroxyester include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, and tert-hexyl peroxy-2-ethylhexanoate. tert-Butyl 2-ethylhexanoate, tert-butyl peroxyisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-bis(m-toluic acid peroxy)hexane, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy 2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, tert-butyl peroxyacetate and bis(tert-butylperoxy)hexahydroterephthalate.

[0096] Examples of the dialkyl peroxide include di-tert-butyl diisopropylbenzene peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and tert-butyl isopropylbenzene peroxide.

[0097] Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, bis(2-ethoxymethoxy) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, dimethoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutyl) peroxydicarbonate.

[0098] Examples of the peroxyketal include 1,6-bis(tert-butylperoxy-carbonyloxy)hexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-(tert-butylperoxy)cyclododecane, and 2,2-bis(tert-butylperoxy)decane.

[0099] Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0100] Examples of the silyl peroxide include tert-butyltrimethylsilyl peroxide, bis(tert-butyl)dimethylsilyl peroxide, tert-butyltrivinylsilyl peroxide, bis(tert-butyl)divinylsilyl peroxide, tri(tert-butyl)vinylsilyl peroxide, tert-butyltriallylsilyl peroxide, bis(tert-butyl)diallylsilyl peroxide, and tri(tert-butyl)allylsilyl peroxide.

[0101] From the viewpoint of stability in an uncured state, the component (D) is preferably an organic peroxide having a half-life of 1 hour or more at 100°C.

[0102] The component (D) may be used alone or in combination of two or more.

[0103] The amount of the component (D) may be an effective amount (ie, a so-called catalytic amount), and is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the component (A).

[0104] <(E) Ingredient>

[0105] The solvent of the component (E) is not particularly limited as long as it dissolves the above-mentioned components (A) to (D) constituting the present composition, and a known organic solvent can be used. Examples of the solvent include aromatic hydrocarbon solvents such as xylene, toluene, and benzene; aliphatic hydrocarbon solvents such as heptane and hexane; halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene, and dichloromethane; ester solvents such as ethyl acetate; ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone; alcohol solvents such as ethanol, isopropanol, and butanol; light petroleum (ligroin), cyclohexanone, diethyl ether, rubber volatile oil, silicone solvents, etc. Among them, toluene, heptane, and ethyl acetate are preferably used.

[0106] The component (E) may be used alone or in combination of two or more thereof as a mixed solvent, depending on the evaporation rate of the thermosetting silicone composition of the present invention during coating operation.

[0107] The amount of the component (E) to be added is not particularly limited, but is preferably 50 to 200 parts by mass, more preferably 100 to 150 parts by mass, based on 100 parts by mass of the total of the components (A) to (D), from the viewpoint of workability during coating.

[0108] <(F)Component>

[0109] The thermosetting silicone composition of the present invention may contain (F) a phosphor. By mixing and dispersing the phosphor in the thermosetting silicone composition, the wavelength of light emitted from the optical semiconductor element can be efficiently converted into light of a target wavelength.

[0110] The phosphor absorbs the blue light, purple light, and ultraviolet light emitted from the optical semiconductor element and converts the wavelength to emit light of wavelengths in the red, orange, yellow, green, and blue regions that are different from the light emitted from the optical semiconductor element. As a result, part of the light emitted from the optical semiconductor element is mixed with part of the light emitted from the phosphor, thereby obtaining a multi-color optical semiconductor element including white.

[0111] Among the above-mentioned fluors, there are various fluors such as fluors emitting green light, fluors emitting blue light, fluors emitting yellow light, fluors emitting red light. As the specific fluor used in the present invention, known fluors such as organic fluors, inorganic fluors, fluorescent pigments, fluorescent dyes can be listed. As organic fluors, allylsulfonamide-melamine formaldehyde co-condensation dyeing products and perylene (perylene) system fluors can be listed. From the perspective of being able to use for a long time, perylene system fluors are preferably used. As the fluorescent material particularly preferably used in the present invention, inorganic fluors can be listed. The inorganic fluors used in the present invention are described below, but are not limited to this.

[0112] Examples of green light emitting phosphors include SrAl2O4:Eu, Y2SiO5:Ce,Tb, MgAl 11 O 19 :Ce,Tb,Sr7Al12O 25 :Eu, (at least one of Mg, Ca, Sr, Ba) Ga2S4:Eu, etc.

[0113] Examples of phosphors that emit blue light include Sr5(PO4)3Cl:Eu, (SrCaBa)5(PO4)3Cl:Eu, (BaCa)5(PO4)3Cl:Eu, (at least one of Mg, Ca, Sr, and Ba)2B5O9Cl:Eu,Mn, (at least one of Mg, Ca, Sr, and Ba) (PO4)6C l2 :Eu,Mn,etc.

[0114] Examples of phosphors that emit light ranging from green to yellow include yttrium aluminum oxide phosphors activated by at least cerium, yttrium gadolinium aluminum oxide phosphors activated by at least cerium, yttrium aluminum garnet oxide phosphors activated by at least cerium, and yttrium gallium aluminum oxide phosphors activated by at least cerium (so-called YAG-based phosphors). Specifically, Ln3M5O 12 : A (Ln is at least one selected from Y, Gd, and La; M contains at least one of Al and Ca; A is a lanthanide), (Y 1-x Ga x )3(Al 1-y Ga y )5O 12 :A (A is at least one selected from Ce, Tb, Pr, Sm, Eu, Dy, and Ho; 0<x<0.5, 0<y<0.5).

[0115] Examples of phosphors that emit red light include Y2O2S:Eu, La2O2S:Eu, Y2O3:Eu, and Gd2O2S:Eu.

[0116] In addition, as a phosphor that emits light corresponding to a blue LED, Y3(Al,Ga)5O 12 :Ce、(Y,Gd)3Al5O 12 :Ce、Lu3Al5O 12 :Ce、Y3Al5O 12 : Ce and other YAG phosphors; Tb3Al5O 12 :Ce and other TAG phosphors; (Ba,Sr)2SiO4:Eu phosphors and Ca3Sc2Si3O 12 :Ce-based phosphors, (Sr,Ba,Mg)2SiO4:Eu and other silicate-based phosphors; (Ca,Sr)2Si5N8:Eu, (Ca,Sr)AlSiN3:Eu, CaSiAlN3:Eu and other nitride-based phosphors; Cax(Si,Al) 12 (O,N) 16 :Eu and other nitrogen oxide phosphors; and (Ba, Sr, Ca)Si2O2N2:Eu phosphors, Ca8MgSi4O 16 Cl2:Eu phosphor; SrAl2O4:Eu, Sr4Al 14 O 25 :Eu and other phosphors.

[0117] Among them, from the viewpoint of luminous efficiency and brightness, it is preferable to use YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors.

[0118] In addition to the above-mentioned phosphors, known phosphors can be used according to the application and the target luminescent color.

[0119] The particle size of the phosphor is not particularly limited, but preferably D 50 It is preferably 0.05 μm or more, and more preferably 3 μm or more. 50 is 30 μm or less, more preferably 20 μm or less. 50 It refers to the particle size at which the cumulative passing component from the small particle size side reaches 50% in the volume-based particle size distribution measured by the laser diffraction scattering particle size distribution measurement method. 50 When the content is within the above range, the dispersibility of the phosphor in the thermosetting silicone composition (for example, the resin composition for a wafer-level optical semiconductor device) of the present invention is good, and stable light emission can be obtained.

[0120] The above-mentioned phosphors may be used alone or in combination of two or more.

[0121] The content of component (F) is preferably 20 to 500 parts by mass, more preferably 50 to 400 parts by mass, and even more preferably 80 to 300 parts by mass relative to 100 parts by mass of the total of components (A) to (E). By setting the phosphor content within the above range, light conversion efficiency can be improved.

[0122] Since the thermosetting silicone composition of the present invention contains a phosphor, it can be used particularly preferably in the form of a phosphor sheet for LED surface coating. In this case, by setting the phosphor content in the phosphor sheet within the above range, an LED light-emitting device showing excellent performance can be obtained.

[0123] <Optional ingredients>

[0124] The thermosetting silicone composition of the present invention may contain an adhesion enhancer as exemplified below in addition to the above components (A) to (F).

[0125] As the adhesion improver, preferably, an organopolysiloxane or organosilane compound having at least one, preferably two or more, alkoxy groups bonded to a silicon atom in one molecule; or an organopolysiloxane or organosilane compound containing a group having an epoxy moiety.

[0126] Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy, and a methoxy group is particularly preferred. In addition, examples of groups other than the alkoxy group bonded to the silicon atom of the organosilicon compound include: 1 The substituted or unsubstituted monovalent hydrocarbon groups such as the alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups exemplified in the above examples; monovalent organic groups containing an acryloyl group such as 3-methacryloxypropyl groups; and hydrogen atoms. Specifically, silane coupling agents such as silane coupling agents containing (meth)acryloyl groups and their partial hydrolysis condensates (oligomers of silane coupling agents) can be exemplified. More specifically, silane compounds such as 3-methacryloxypropyltrimethoxysilane can be exemplified; siloxane compounds each having at least one alkenyl group bonded to a silicon atom or a hydrogen atom bonded to a silicon atom and an alkoxy group bonded to a silicon atom in one molecule, silane compounds each having at least one alkoxy group bonded to a silicon atom, or a mixture of a siloxane compound and a siloxane compound each having at least one hydroxyl group bonded to a silicon atom and an alkenyl group bonded to a silicon atom in one molecule, polymethyl silicate, polyethyl silicate, and polyethyl silicate containing an epoxy group can be exemplified.

[0127] Examples of the group having an epoxy moiety include glycidyloxyalkyl groups such as 3-glycidyloxypropyl and 4-glycidyloxybutyl; epoxycyclohexylalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl and 3-(3,4-epoxycyclohexyl)propyl; and epoxyalkyl groups such as 4-oxiranylbutyl and 8-oxiranyloctyl.

[0128] The adhesion improver is preferably in the form of a low-viscosity liquid. The viscosity is not limited, but is preferably in the range of 1 to 500 mPa·s at 23°C.

[0129] The content of the adhesion improver is not limited, but is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the component (A).

[0130] In addition, the thermosetting silicone composition of the present invention may contain inorganic fillers other than component (F) such as fumed silica, fused silica glass, alumina, and zinc oxide; organic resin fine powders such as polymethacrylate resins; heat-resistant agents, dyes, pigments, flame retardants, and the like.

[0131] When an inorganic filler other than the component (F) is used, the amount thereof is preferably 5 to 500 parts by mass, more preferably 10 to 200 parts by mass, relative to 100 parts by mass of the component (A). Within such a range, the composition of the present invention has better fluidity.

[0132] The viscosity of the thermosetting silicone composition of the present invention at 25°C is preferably 10 to 5,000 mPa·s, more preferably 20 to 2,000 mPa·s. Within this range, the operability and handling properties of the obtained composition are easily improved, and bubbles and air are not easily involved during molding and curing. In addition, in the present invention, the viscosity can be set to the value when measured using a rotational viscometer.

[0133] The viscosity of the thermosetting silicone composition of the present invention can be adjusted by adjusting the blending amount and viscosity of the components (A) to (E) and other components, and the blending amount and average particle size of the component (F).

[0134] The thermosetting silicone composition of the present invention has excellent stability in an uncured state even without adding a reaction control agent, and provides a cured product with high hardness, so it can be used in a wide range of applications, and is particularly useful in surface coating applications of optical semiconductor devices such as LED elements. However, the thermosetting silicone composition of the present invention may contain a reaction control agent according to the purpose as long as it contains components (A) to (E).

[0135] [Sheet]

[0136] The present invention provides a sheet formed from the above-mentioned thermosetting silicone composition. The sheet may be a sheet formed by curing the composition or an uncured sheet, but is preferably an uncured sheet. The sheet of the present invention is particularly useful for surface coating of optical semiconductor devices such as LED elements.

[0137] The method for producing the sheet of the present invention is not particularly limited. For example, the sheet (uncured sheet) can be obtained by heating the thermosetting silicone composition of the present invention at a temperature lower than the temperature at which the composition cures to volatilize the (E) solvent.

[0138] [Silicone Cured Product]

[0139] By molding and curing the thermosetting silicone composition of the present invention, a cured product can be obtained. As a molding method, conventional methods such as injection molding method and transfer molding method can be applied. In addition, since the thermosetting silicone composition of the present invention has high fluidity, it can be molded by dispensing method, potting method and various coating methods.

[0140] The thermosetting silicone composition of the present invention is cured by heating, and preferably heated at a high temperature for rapid curing. The curing conditions vary depending on the shape of the molded object and the curing method, but are not particularly limited. The curing temperature is preferably in the range of 130 to 200° C., and the curing time is preferably 1 minute to 24 hours, more preferably 5 minutes to 5 hours.

[0141] The hardness of the silicone cured product of the present invention is preferably 20 or more, particularly preferably 30 to 70 in terms of Shore D.

[0142] Example

[0143] Hereinafter, the present invention will be specifically described using Examples and Comparative Examples, but the present invention is not limited thereto.

[0144] [Example 1]

[0145] Mix 100 parts by mass of constituent unit ratio (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.40 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.05 The constituent unit ratio (A) of 40 parts by mass (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.45The component (B) represented by the formula ((CH3)2SiO) is 50 parts by mass. 0.9996 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.0004 A thermosetting silicone composition was prepared by mixing the component (C) represented by , 3.5 parts by mass of an organic peroxide (Kayaren 6-70 manufactured by KAYAKU AKZO CO., LTD.) as the component (D), and 200 parts by mass of toluene as the component (E).

[0146] [Example 2]

[0147] 150 parts by mass of a YAG phosphor were mixed with 100 parts by mass of the thermosetting silicone composition obtained in Example 1 to prepare a phosphor-containing thermosetting silicone composition.

[0148] [Example 3]

[0149] Mix 100 parts by mass of constituent unit ratio (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.40 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.05 The constituent unit ratio (A) of 25 parts by mass (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.45 The component (B) represented by the formula ((CH3)2SiO) is 40 parts by mass. 0.9996 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.0004 A thermosetting silicone composition was prepared by mixing the component (C) represented by , 3 parts by mass of an organic peroxide (Kayaren 6-70 manufactured by KAYAKU AKZO CO., LTD.) as the component (D) and 170 parts by mass of toluene as the component (E).

[0150] [Example 4]

[0151] 150 parts by mass of a YAG phosphor were mixed with 100 parts by mass of the thermosetting silicone composition obtained in Example 3 to prepare a phosphor-containing thermosetting silicone composition.

[0152] [Comparative Example 1]

[0153] Mix 100 parts by mass of constituent unit ratio (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.40 ((CH2=CH)(CH3)2SiO1 / 2 ) 0.05 The constituent unit ratio (A) of 40 parts by mass (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.45 The component (B) represented by the formula ((CH3)2SiO) is 50 parts by mass. 0.9996 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.0004 A thermosetting silicone composition is prepared by mixing the component (C) represented by the formula (A), a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (the amount of platinum metal in the complex is 10 ppm by mass relative to the total of the components (A) to (C)), 7 parts by mass of an organohydrogenpolysiloxane represented by the following formula (4), 0.2 parts by mass of ethynylcyclohexanol as a reaction control agent, and 200 parts by mass of toluene as the component (E).

[0154] [Chemical formula 1]

[0155]

[0156] [Comparative Example 2]

[0157] Mix 100 parts by mass of constituent unit ratio (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.45 The component (B) represented by the formula ((CH3)2SiO) is 50 parts by mass. 0.9996 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.0004 A thermosetting silicone composition was prepared by mixing the component (C) represented by the formula (A), 3.5 parts by mass of an organic peroxide (Kayaren 6-70 manufactured by KAYAKU AKZO CO., LTD.) as the component (D), and 150 parts by mass of toluene as the component (E).

[0158] [Comparative Example 3]

[0159] Mix 100 parts by mass of constituent unit ratio (SiO2) 0.55 ((CH3)3SiO 1 / 2 ) 0.40 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.05 The constituent unit ratio of the component (A) represented by 50 parts by mass ((CH3)2SiO) 0.9996 ((CH2=CH)(CH3)2SiO 1 / 2 ) 0.0004A thermosetting silicone composition was prepared by mixing the component (C) represented by , 3 parts by mass of an organic peroxide (Kayaren 6-70 manufactured by KAYAKU AKZO CO., LTD.) as the component (D) and 150 parts by mass of toluene as the component (E).

[0160] The compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were poured into a Teflon (registered trademark) frame having a thickness of 2 mm and heated in the order of 60°C for 1 hour, 80°C for 1 hour, and 100°C for 1 hour to volatilize the solvent, thereby preparing a sheet. The following tests (1) and (2) were performed on the obtained sheet to confirm the physical properties. The results are shown in Table 1.

[0161] Test (1): After the sheet was exposed to 120° C. for 10 minutes, whether it was soluble in toluene was confirmed.

[0162] Test (2): The sheet was cured at 150°C for 3 hours, and the appearance of the obtained cured product was observed and the hardness was measured.

[0163] Appearance: Observe with naked eyes for cracks.

[0164] No cracks (○), Cracks (×)

[0165] Hardness: The hardness was measured using a durometer type D hardness meter manufactured by Ueshima Seisakusho Co., Ltd.

[0166] [Table 1]

[0167]

[0168] As shown in Table 1, the sheets obtained in Examples 1 to 4 were soluble in toluene even after heating at 120° C. for 10 minutes, and remained in an uncured state. In addition, heating at 150° C. for 3 hours provided a cured product with high hardness.

[0169] On the other hand, in Comparative Example 1, which is a curable composition obtained by hydrosilylation, even in the presence of a reaction control agent, it was cured by heating at 120° C. for 10 minutes and could not maintain an uncured state. In addition, in Comparative Example 2, which does not contain component (A), the hardness of the cured product was significantly reduced, and in Comparative Example 3, which does not contain component (B), cracks occurred in the cured product.

[0170] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any technical solution having substantially the same structure and having the same function and effect as the technical concept described in the claims of the present invention is included in the protection scope of the present invention.

Claims

1. A thermosetting silicone composition, characterized in that: It contains: (A) an organopolysiloxane represented by the following average unit formula (1), (SiO2) a1 (R 1 3SiO 1 / 2 ) b1 (X 1 THE 1 / 2 ) c1 (1) In formula (1), R 1 are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 1 50 to 99.9% of the total number of X are methyl groups and 0.1 to 50% are alkenyl groups, 1 is a hydrogen atom or an alkyl group; a1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c1 is 0 to 0.1, a1+b1+c1=1; (B) an organopolysiloxane represented by the following average unit formula (2), (SiO2) a2 (R 2 3SiO 1 / 2 ) b2 (X 1 THE 1 / 2 ) c2 (2) In formula (2), R 2 is an optionally identical or different substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, X 1 is a hydrogen atom or an alkyl group; a2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c2 is 0 to 0.1, a2+b2+c2=1; (C) an organopolysiloxane represented by the following average unit formula (3), (R 3 2SiO) a3 (R 3 3SiO 1 / 2 ) b3 (3) In formula (3), R 3 are optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, R 3 20% or more of the total number of are methyl groups and 0.0001 to 25% are alkenyl groups, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+b3=1; (D) organic peroxides; and (E) a solvent, The thermosetting silicone composition is not a curable composition obtained by hydrosilylation.

2. The thermosetting silicone composition according to claim 1, characterized in that: The amount of the component (B) added is 1 to 100 parts by mass based on 100 parts by mass of the component (A).

3. The thermosetting silicone composition according to claim 1, characterized in that: The amount of the component (C) added is 5 to 100 parts by mass based on 100 parts by mass of the component (A).

4. The thermosetting silicone composition according to claim 2, characterized in that: The amount of the component (C) added is 5 to 100 parts by mass based on 100 parts by mass of the component (A).

5. The thermosetting silicone composition according to any one of claims 1 to 4, characterized in that: The (F) phosphor is contained in an amount of 20 to 500 parts by mass based on 100 parts by mass of the total of the components (A) to (E).

6. A sheet material, characterized in that: The thermosetting silicone composition is formed from the thermosetting silicone composition according to any one of claims 1 to 5.

7. A cured organosilicon material, characterized in that: This is a cured product of the thermosetting silicone composition according to any one of claims 1 to 5.

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