CN115551909B - Thermosetting silicone composition, sheet and silicone cured product - Google Patents
Thermosetting silicone composition, sheet and silicone cured product Download PDFInfo
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Abstract
本发明为一种热固性有机硅组合物，其包含：(A)平均式(1)的有机聚硅氧烷，(SiO2)a1(R1 3SiO1/2)b1(X1O1/2)c1(1)R1的50～99.9％为甲基且0.1～50％为烯基，X1为氢原子或烷基；(B)平均式(2)的有机聚硅氧烷，(SiO2)a2(R2 3SiO1/2)b2(X1O1/2)c2(2)R2为不含烯基的烃基，X1为氢原子或烷基；(C)平均式(3)的有机聚硅氧烷，(R3 2SiO)a3(R3 3SiO1/2)b3(3)R3的20％以上为甲基且0.0001～25％为烯基；(D)有机过氧化物；及(E)溶剂。由此，提供一种热固性有机硅组合物，其在不添加反应控制剂的情况下未固化时的稳定性优异，提供高硬度的固化物。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) 50 to 99.9% of R 1 is a methyl group and 0.1 to 50% is an alkenyl group, and X 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 not containing an alkenyl group, and 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 2 is a hydrocarbon group not containing an alkenyl group, and X 1 is a hydrogen atom or an alkyl group. 20% or more of 3 is methyl and 0.0001-25% 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
The present invention relates to a thermosetting silicone composition cured by an organic peroxide.
Background
Light Emitting Diodes (LEDs) have the advantages of low power consumption, long life, design, and the like, because of their remarkably improved luminous efficiency, and have a rapidly expanding market ratio not only in the field of backlight sources of Liquid Crystal Displays (LCDs) and in the field of vehicle-mounted vehicles such as headlamps of vehicles, but also in general illumination.
Since the light emission spectrum of an LED depends on the semiconductor material forming the LED chip, the light emission color is limited. Therefore, in order to obtain white light suitable for LCD backlights and general illumination using LEDs, it is necessary to dispose phosphors suitable for the respective chips on the LED chips and convert the emission wavelengths. Specifically, a method of providing a yellow phosphor on an LED chip that emits blue light, a method of providing red and green phosphors on an LED chip that emits blue light, a method of providing red, green, and blue phosphors on an LED chip that emits ultraviolet light, and the like have been proposed. Among them, a method of providing a yellow phosphor on a blue LED and a method of providing red and green phosphors on a blue LED are most widely used at present from the viewpoints of light emission efficiency and cost of the LED chip.
As one of specific methods for providing a phosphor on an LED chip, a method of attaching a sheet to an LED chip, the sheet being formed by dispersing a phosphor in an addition curing type silicone composition that reacts a hydrogen organopolysiloxane with an alkenyl group-containing organopolysiloxane, has been proposed. However, this method requires that the sheet is stored at a low temperature so that the addition reaction does not proceed when the phosphor sheet is produced, and that a large amount of addition reaction controlling agent should be added to the composition (patent documents 1 to 5).
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2013-001791
Patent document 2 Japanese patent application laid-open No. 2013-001792
Patent document 3 Japanese patent application laid-open No. 2013-138216
Patent document 4 Japanese patent application laid-open No. 2014-114446
Patent document 5 Japanese patent laid-open publication No. 2014-116598
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermosetting silicone composition which is excellent in stability in an uncured state even without adding a reaction control agent and provides a cured product having high hardness.
Technical means for solving the technical problems
In order to achieve the above technical problem, the present invention provides a thermosetting silicone composition comprising:
(A) An organopolysiloxane represented by the following average unit formula (1),
(SiO2)a1(R1 3SiO1/2)b1(X1O1/2)c1(1)
In the formula (1), R 1 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, 50-99.9% of the total number of R 1 are methyl groups and 0.1-50% of R 1 are alkenyl groups, X 1 is a hydrogen atom or an alkyl group, a1 is 0.2-0.8, b1 is 0.2-0.8, c1 is 0-0.1, a1+b1+c1=1;
(B) An organopolysiloxane represented by the following average unit formula (2),
(SiO2)a2(R2 3SiO1/2)b2(X1O1/2)c2(2)
In the formula (2), R 2 is optionally same or different substituted or unsubstituted monovalent hydrocarbon groups containing no alkenyl, X 1 is a hydrogen atom or an alkyl group, a2 is 0.2-0.8, b2 is 0.2-0.8, c2 is 0-0.1, a2+b2+c2=1;
(C) An organopolysiloxane represented by the following average unit formula (3),
(R3 2SiO)a3(R3 3SiO1/2)b3(3)
In the formula (3), R 3 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, 20% or more of the total number of R 3 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, a3+b3=1;
(D) Organic peroxide; and
(E) And (3) a solvent.
The thermosetting silicone composition of the present invention is excellent in stability in an uncured state even without adding a reaction control agent, and can provide a cured product having high hardness.
The amount of the component (B) to be added is preferably 1 to 100 parts by mass per 100 parts by mass of the component (a).
The amount of the component (C) to be added is preferably 5 to 100 parts by mass per 100 parts by mass of the component (A).
In this way, a cured product having more excellent mechanical properties is provided.
Further, the fluorescent material (F) is preferably 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).
In this way, the wavelength of light emitted from the optical semiconductor element can be efficiently converted into light of the target wavelength.
Further, the present invention provides a sheet formed from the above-described thermosetting silicone composition.
Such a sheet is excellent in stability in an uncured state, and therefore, can be used in a wide range of applications, and is particularly useful in applications for surface coating of optical semiconductor devices such as LED elements.
Further, the present invention provides a cured silicone composition which is a cured product of the above thermosetting silicone composition.
The cured silicone product has excellent mechanical properties. Further, since the cured product of the thermosetting silicone composition is excellent in stability in an uncured state, the cured product 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.
Effects of the invention
The thermosetting silicone composition of the present invention is excellent in stability in an uncured state even without adding a reaction controlling agent, and provides a cured product of high hardness, and therefore can be used in a wide range of applications, and is useful in surface coating applications of a phosphor sheet and an LED.
Detailed Description
As described above, there has been a demand for development of a thermosetting silicone composition which is excellent in stability in an uncured state without adding a large amount of a reaction controlling agent and provides a cured product having high hardness.
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by a specific thermosetting silicone composition containing an organic peroxide, and have completed the present application.
That is, the present invention is a thermosetting silicone composition comprising:
(A) An organopolysiloxane represented by the following average unit formula (1),
(SiO2)a1(R1 3SiO1/2)b1(X1O1/2)c1(1)
In the formula (1), R 1 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, 50-99.9% of the total number of R 1 are methyl groups and 0.1-50% of R 1 are alkenyl groups, X 1 is a hydrogen atom or an alkyl group, a1 is 0.2-0.8, b1 is 0.2-0.8, c1 is 0-0.1, a1+b1+c1=1;
(B) An organopolysiloxane represented by the following average unit formula (2),
(SiO2)a2(R2 3SiO1/2)b2(X1O1/2)c2(2)
In the formula (2), R 2 is optionally same or different substituted or unsubstituted monovalent hydrocarbon groups containing no alkenyl, X 1 is a hydrogen atom or an alkyl group, a2 is 0.2-0.8, b2 is 0.2-0.8, c2 is 0-0.1, a2+b2+c2=1;
(C) An organopolysiloxane represented by the following average unit formula (3),
(R3 2SiO)a3(R3 3SiO1/2)b3(3)
In the formula (3), R 3 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, 20% or more of the total number of R 3 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, a3+b3=1;
(D) Organic peroxide; and
(E) And (3) a solvent.
The present invention will be described in detail below, but the present invention is not limited thereto.
[ Thermosetting Silicone composition ]
The thermosetting silicone composition of the present invention contains the following components (a), (B), (C), (D), (E), and (F) as required.
Component (A)
(A) The component (A) is an organopolysiloxane represented by the following average unit formula (1).
(SiO2)a1(R1 3SiO1/2)b1(X1O1/2)c1(1)
In the formula (1), R 1 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, 50 to 99.9% of the total number of R 1 are methyl groups and 0.1 to 50% are alkenyl groups, and X 1 is a hydrogen atom or an alkyl group. a1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c 10 to 0.1, a1+b1+c1=1.
R 1 is a monovalent hydrocarbon group which may be substituted or unsubstituted, and examples of the alkenyl group in R 1 include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and particularly preferably a vinyl group.
The ratio of the number of alkenyl groups to the total number of R 1 is 0.1 to 50%, preferably 0.1 to 30%, particularly preferably 0.3 to 20%. If the content is less than 0.1%, the curability of the composition is insufficient, and if the content is more than 50%, the cured product becomes brittle.
Examples of the organic group bonded to a silicon atom other than an alkenyl group in R 1 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group, an aryl group such as a phenyl group, a naphthyl group, an aralkyl group such as a benzyl group, or a phenethyl group, a monovalent hydrocarbon group which may be substituted or unsubstituted such as a chloromethyl group, a 3-chloropropyl group, or a3, 3-trifluoropropyl group, and an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is most preferable from the viewpoint of heat resistance.
The ratio of the number of methyl groups in the total number of R 1 is 50 to 99.9%, preferably 60 to 97%. When the amount is less than 50 mol%, the heat resistance of the resulting cured product is insufficient.
X 1 is a hydrogen atom or an alkyl group, and examples of the alkyl group include the same organic groups as those exemplified in R 1, and methyl and ethyl are particularly preferred.
A1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c 10 to 0.1, a1+b1+c1=1. When a1, b1 and c1 are out of the above ranges, the hardness and/or strength of the obtained cured product is insufficient.
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.
(A) The molecular weight of the component (a) is not limited, but the weight average molecular weight (Mw) measured by GPC using a toluene solvent (in terms of standard polystyrene) is preferably 500 to 20,000, more preferably 700 to 15,000, particularly preferably 1,000 to 10,000.
(A) The components may be used singly or in combination of two or more.
Component (B)
(B) The component (A) is an organopolysiloxane represented by the following average unit formula (2).
(SiO2)a2(R2 3SiO1/2)b2(X1O1/2)c2(2)
In formula (2), R 2 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, and X 1 is a hydrogen atom or an alkyl group. a2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c 20 to 0.1, a2+b2+c2=1.
The monovalent hydrocarbon group having no alkenyl group in R 2 includes the same groups as those of the organic groups bonded to silicon atoms other than alkenyl groups in R 1 in component (a), and methyl groups are most preferable from the viewpoint of heat resistance.
X 1 is a hydrogen atom or an alkyl group, and examples of the alkyl group include the same organic groups as those exemplified for R 1 in the component (A), and methyl and ethyl are particularly preferred.
A2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c 20 to 0.1, a2+b2+c2=1. When a2, b2 and c2 are out of the above ranges, the hardness and/or strength of the obtained cured product is insufficient.
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.
(B) The molecular weight of the component (a) is not limited, but the weight average molecular weight (Mw) measured by GPC using a toluene solvent (in terms of standard polystyrene) is preferably 500 to 20,000, more preferably 700 to 15,000, particularly preferably 1,000 to 10,000.
(B) The components may be used singly or in combination of two or more.
The blending 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) in view of the hardness of the cured product.
Component (C)
(C) The component (A) is an organopolysiloxane represented by the following average unit formula (3).
(R3 2SiO)a3(R3 3SiO1/2)b3(3)
In the formula (3), R 3 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon group, 20% or more of the total number of R 3 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, a3+b3=1.
R 3 is the same as R 1 in the component (A), and the alkenyl group in R 3 is preferably vinyl, allyl, butenyl, pentenyl or hexenyl, particularly preferably vinyl.
The ratio of the number of alkenyl groups to the total number of R 3 is 0.0001 to 25%, preferably 0.1 to 20%, particularly preferably 0.3 to 20%. If the content is less than 0.0001%, the curability of the composition is insufficient, and if the content is more than 25%, the cured product becomes brittle.
Examples of the organic group bonded to a silicon atom other than an alkenyl group in R 3 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group, an aryl group such as a phenyl group, a naphthyl group, an aralkyl group such as a benzyl group, or a phenethyl group, and a monovalent hydrocarbon group substituted or unsubstituted by a haloalkyl group such as a chloromethyl group, a 3-chloropropyl group, or a3, 3-trifluoropropyl group, and among these, a methyl group is most preferable from the viewpoint of heat resistance. When the content of these monovalent hydrocarbon groups is 20mol% or more in all of R 3, stable heat resistance can be imparted, and thus, it is preferable that the content is 40mol% or more.
The ratio of the number of methyl groups in the total number of R 3 is 20 to 99.9999%, preferably 40 to 99.9%. When the amount is less than 20 mol%, the heat resistance of the resulting cured product is insufficient.
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, in the case of the optical fiber, a3+b3=1.
(C) The components may be used singly or in combination of two or more.
The blending 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) in view of the hardness of the cured product.
Component (D)
(D) The thermosetting silicone composition of the present invention is cured by decomposition of the component which is an organic peroxide by heat and further generates radicals.
Specific examples of the organic peroxide include diacyl peroxide, peroxyester, dialkyl peroxide, peroxydicarbonate, peroxyketal, hydroperoxide, silyl peroxide (silyl peroxide), and the like.
Examples of diacyl peroxides include isobutyl peroxide, 2, 4-dichlorobenzoyl peroxide, bis (3, 5-trimethylhexanoyl) peroxide, octanoyl peroxide, lauroyl peroxide, distearyl peroxide, succinic acid peroxide, benzoyl-peroxy toluene peroxide and benzoyl peroxide.
As the peroxyester, there is used, examples thereof include cumene peroxyneodecanoate, 1, 3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1, 3-tetramethylbutyl peroxy2-ethylhexanoate, 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxyhexane, 1-cyclohexyl-1-methylethyl peroxy2-ethylhexanoate, t-hexyl peroxy2-ethylhexanoate, t-butyl peroxypivalate tert-butyl peroxyisobutyrate, 1-bis (tert-butylperoxy) cyclohexane, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy 3, 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.
Examples of the dialkyl peroxide include di-t-butyldiisopropylbenzene peroxide, dicumyl peroxide, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, and t-butylcumyl peroxide.
Examples of the peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, bis (2-ethoxymethoxy) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, dimethoxybutyl peroxydicarbonate, and bis (3-methyl-3-methoxybutyl) peroxydicarbonate.
Examples of the peroxyketal include 1, 6-bis (t-butylperoxy-carbonyloxy) hexane, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 1- (t-butylperoxy) cyclododecane and 2, 2-bis (t-butylperoxy) decane.
Examples of the hydroperoxide include dicumyl hydroperoxide and cumene hydroperoxide.
Examples of silyl peroxides include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, tris (t-butyl) vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide and tris (t-butyl) allylsilyl peroxide.
From the viewpoint of stability in an uncured state, an organic peroxide having a half-life of 1 hour or more at 100 ℃ is preferable as the component (D).
(D) The components may be used singly or in combination of two or more.
(D) The blending amount of the component (a) may be an effective amount (i.e., a so-called catalytic amount), and is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (a).
Component (E)
(E) The solvent of the component (a) to (D) 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 methylene chloride, 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 oil (ligroin), cyclohexanone, diethyl ether, rubber volatile oil, and silicone solvents. Among them, toluene, heptane and ethyl acetate are suitably used.
(E) The components may be used singly or in combination of two or more kinds in the form of a mixed solvent according to the evaporation rate at the time of the application operation of the thermosetting silicone composition of the present invention.
(E) The blending amount of the components 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) in terms of operability during the coating operation.
Component (F)
The thermosetting silicone composition of the present invention may contain (F) a fluorescent material. 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.
The phosphor absorbs blue light, violet light, and ultraviolet light emitted from the optical semiconductor element and converts the light into a wavelength, and emits light having wavelengths in red, orange, yellow, green, and blue regions different from the light emitted from the optical semiconductor element. Thus, a part of the light emitted from the optical semiconductor element is mixed with a part of the light emitted from the phosphor, and a multicolor optical semiconductor element including white is obtained.
Examples of the above-mentioned phosphors include various phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Specific examples of the phosphor used in the present invention include known phosphors such as organic phosphors, inorganic phosphors, fluorescent pigments, and fluorescent dyes. Examples of the organic fluorescent material include allylsulfonamide-melamine formaldehyde co-condensed dye and perylene (perylene) fluorescent material, and perylene fluorescent material is preferably used in view of its long-term use. The fluorescent material particularly preferably used in the present invention includes inorganic fluorescent materials. The inorganic phosphor used in the present invention is described below, but is not limited thereto.
Examples of the phosphor emitting green light include at least 1 or more of SrAl2O4:Eu、Y2SiO5:Ce,Tb、MgAl11O19:Ce,Tb、Sr7Al12O25:Eu、(Mg、Ca、Sr、Ba) Ga 2S4:eu.
Examples of the phosphor emitting blue light include at least 1 or more of Sr5(PO4)3Cl:Eu、(SrCaBa)5(PO4)3Cl:Eu、(BaCa)5(PO4)3Cl:Eu、(Mg、Ca、Sr、Ba) 2B5O9 Cl, eu, mn, and at least 1 or more of (Mg, ca, sr, ba) (PO 4)6Cl2: eu, mn, and the like.
Examples of the phosphor that emits light from green to yellow include yttrium aluminum oxide phosphor that has been activated at least by cerium, yttrium gadolinium aluminum oxide phosphor that has been activated at least by cerium, yttrium aluminum garnet oxide phosphor that has been activated at least by cerium, yttrium gallium aluminum oxide phosphor that has been activated at least by cerium, and the like (so-called YAG-based phosphor). Specifically, ln 3M5O12:A (Ln is at least one selected from Y, gd, and La; M contains at least one of Al and Ca; A is a lanthanoid), (Y 1-xGax)3(Al1-yGay)5O12:A (A is at least one selected from Ce, tb, pr, sm, eu, dy, ho; 0< x < 0.5; 0< Y < 0.5) can be used.
Examples of the phosphor that emits red light include Y2O2S:Eu、La2O2S:Eu、Y2O3:Eu、Gd2O2S:Eu.
Examples of the phosphor that emits light corresponding to the blue LED include YAG phosphor such as Y3(Al,Ga)5O12:Ce、(Y,Gd)3Al5O12:Ce、Lu3Al5O12:Ce、Y3Al5O12:Ce, TAG phosphor such as Tb 3Al5O12 and Ce, (Ba, sr) 2SiO4 and Ca 3Sc2Si3O12 and Ce phosphor, (Sr, ba, mg) 2SiO4 and Eu silicate phosphor, (Ca, sr) 2Si5N8:Eu、(Ca,Sr)AlSiN3:Eu、CaSiAlN3 and Eu nitride phosphor, cax (Si, al) 12(O,N)16 and Eu oxynitride phosphor, and (Ba, sr, ca) Si 2O2N2 and Eu phosphor, ca 8MgSi4O16Cl2 and SrAl 2O4:Eu、Sr4Al14O25 and Eu phosphor.
Among them, a YAG-based phosphor, a TAG-based phosphor, and a silicate-based phosphor are preferably used from the viewpoints of luminous efficiency, luminance, and the like.
In addition to the above-described fluorescent materials, known fluorescent materials can be used depending on the application and the intended emission color.
The particle size of the phosphor is not particularly limited, and D 50 is preferably 0.05 μm or more, more preferably 3 μm or more. Further, D 50 is preferably 30 μm or less, more preferably 20 μm or less. Here, D 50 is the particle size at which the passing component from the small particle size side is accumulated to 50% in the volume-based particle size distribution measured by the laser diffraction scattering particle size distribution measurement method. When D 50 is within the above range, the dispersibility of the phosphor in the thermosetting silicone composition of the present invention (for example, the resin composition for wafer level optical semiconductor device) is good, and stable light emission can be obtained.
The above-mentioned phosphors may be used singly or in combination.
The content of the component (F) is preferably 20 to 500 parts by mass, more preferably 50 to 400 parts by mass or more, and still more preferably 80 to 300 parts by mass, based on 100 parts by mass of the total of the components (A) to (E). By setting the phosphor content to the above range, the light conversion efficiency can be improved.
The thermosetting silicone composition of the present invention can be particularly preferably used for surface coating of LEDs in the form of a phosphor sheet since it is blended with a phosphor. At this time, by making the content of the phosphor in the phosphor sheet within the above range, an LED light emitting device exhibiting excellent performance can be obtained.
< Optional ingredients >
In addition to the above components (A) - (F), the thermosetting silicone composition of the present invention may contain the following adhesion improving agents.
The adhesion improver is preferably an organopolysiloxane or an organosilane compound having at least one, preferably two or more alkoxy groups bonded to silicon atoms in one molecule, or an organopolysiloxane or an organosilane compound having a group having an epoxy group site.
Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and methoxyethoxy groups, and methoxy groups are particularly preferred. Examples of the group other than the alkoxy group bonded to the silicon atom of the organosilicon compound include monovalent hydrocarbon groups which may be substituted or unsubstituted, such as the alkyl group, the alkenyl group, the aryl group, the aralkyl group, and the haloalkyl group, which are exemplified by the above-mentioned R 1, etc., monovalent organic groups which may be substituted or unsubstituted, such as 3-methacryloxypropyl group, etc., and a hydrogen atom. Specifically, a silane coupling agent such as a (meth) acryl-containing silane coupling agent, a partially hydrolyzed condensate thereof (oligomer of the silane coupling agent), and the like can be exemplified. More specifically, a silane compound such as 3-methacryloxypropyl trimethoxysilane, a siloxane compound 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, a silane compound having at least one alkoxy group bonded to a silicon atom or a mixture of a siloxane compound and a siloxane compound having at least one hydroxyl group bonded to a silicon atom and an alkenyl group bonded to a silicon atom in one molecule, respectively, methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate can be exemplified.
Examples of the group having an epoxy group moiety include glycidyl ether oxyalkyl groups such as 3-glycidyl ether oxypropyl and 4-glycidyl ether oxybutyl, epoxycyclohexylalkyl groups such as 2- (3, 4-epoxycyclohexyl) ethyl and 3- (3, 4-epoxycyclohexyl) propyl, and monovalent organic groups containing an epoxy group such as oxiranyl groups such as 4-oxiranylbutyl and 8-oxiranyloctyl.
The adhesion improving agent is preferably a low-viscosity liquid, but the viscosity is not limited, and is preferably in the range of 1 to 500mpa·s at 23 ℃.
The content of the adhesion improving agent is not limited, but is preferably 0.01 to 10 parts by mass per 100 parts by mass of the component (a).
The thermosetting silicone composition of the present invention may contain an inorganic filler other than component (F), such as fumed silica, fused silica glass, alumina, and zinc oxide, an organic resin fine powder, such as a polymethacrylate resin, a heat-resistant agent, a dye, a pigment, a flame-retardant agent, and the like.
When an inorganic filler other than the component (F) is used, the blending amount is preferably 5 to 500 parts by mass, more preferably 10 to 200 parts by mass, per 100 parts by mass of the component (A). Within such a range, the fluidity of the composition of the present invention is more excellent.
The viscosity of the thermosetting silicone composition of the present invention is preferably 10 to 5,000mpa·s, more preferably 20 to 2,000mpa·s, at 25 ℃. When the amount is within such a range, the handleability and handling properties of the resulting composition are easily improved, and air bubbles and air are less likely to be trapped during molding and curing. In the present invention, the viscosity can be set to a value at the time of measurement using a rotational viscometer.
The viscosity of the thermosetting silicone composition of the present invention can be adjusted by the blending amounts of the components (a) to (E) and other components, the viscosity, the blending amount of the component (F), the average particle diameter, and the like.
The thermosetting silicone composition of the present invention is excellent in stability in an uncured state without adding a reaction control agent, and provides a cured product having high hardness, and therefore, can be used in a wide range of applications, and is particularly useful in applications for surface coating of optical semiconductor devices such as LED elements. However, the thermosetting silicone composition of the present invention may contain a reaction controlling agent according to the purpose as long as it contains the components (a) to (E).
[ Sheet ]
The present invention provides a sheet formed from the above-described thermosetting silicone composition. The sheet may be any of a sheet obtained 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 applications of optical semiconductor devices such as LED elements.
The method for producing the sheet of the present invention is not particularly limited. For example, the thermosetting silicone composition of the present invention can be heated at a temperature less than the temperature at which the composition cures to volatilize the solvent (E), thereby obtaining a sheet (uncured sheet).
[ Silicone cured product ]
The thermosetting silicone composition of the present invention can be molded and cured to obtain a cured product. As the molding method, conventionally used methods such as an injection molding method (injection molding method) and a transfer molding method (injection molding method) can be applied. Further, since the thermosetting silicone composition of the present invention has high fluidity, it can be molded by a dispensing method, a potting method (potting) method, and various coating methods.
The thermosetting silicone composition of the present invention is cured by heating, and is preferably heated at a high temperature for rapid curing. The curing conditions vary depending on the shape of the molded article, the curing method, etc., but are not particularly limited, and the curing temperature is preferably in the range of 130 to 200 ℃, and the curing time is preferably 1 minute to 24 hours, more preferably 5 minutes to 5 hours.
The hardness of the cured silicone of the present invention is preferably 20 or more, particularly preferably 30 to 70 on the shore D scale.
Examples
Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto.
Example 1
100 Parts by mass of the component (A) represented by the constituent unit ratio (SiO2)0.55((CH3)3SiO1/2)0.40((CH2＝CH)(CH3)2SiO1/2)0.05, 40 parts by mass of the constituent unit ratio (component (B) represented by SiO 2)0.55((CH3)3SiO1/2)0.45), 50 parts by mass of the constituent unit ratio ((component (C) represented by CH 3)2SiO)0.9996((CH2＝CH)(CH3)2SiO1/2)0.0004), 3.5 parts by mass of the 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) were mixed to prepare a thermosetting silicone composition.
Example 2
A phosphor-containing thermosetting silicone composition was prepared by mixing 150 parts by mass of YAG phosphor with respect to 100 parts by mass of the thermosetting silicone composition obtained in example 1.
Example 3
100 Parts by mass of the component (A) represented by the constituent unit ratio (SiO2)0.55((CH3)3SiO1/2)0.40((CH2＝CH)(CH3)2SiO1/2)0.05, 25 parts by mass of the constituent unit ratio (component (B) represented by SiO 2)0.55((CH3)3SiO1/2)0.45), 40 parts by mass of the constituent unit ratio ((component (C) represented by CH 3)2SiO)0.9996((CH2＝CH)(CH3)2SiO1/2)0.0004), 3 parts by mass of the organic peroxide (Kayaren-70 manufactured by KAYAKU AKZO Co., ltd.) as the component (D) and 170 parts by mass of toluene as the component (E) were mixed to prepare a thermosetting silicone composition.
Example 4
A phosphor-containing thermosetting silicone composition was prepared by mixing 150 parts by mass of YAG phosphor with respect to 100 parts by mass of the thermosetting silicone composition obtained in example 3.
Comparative example 1
100 Parts by mass of the component (A) represented by the constituent unit ratio (SiO2)0.55((CH3)3SiO1/2)0.40((CH2＝CH)(CH3)2SiO1/2)0.05, 40 parts by mass of the component (B) represented by SiO 2)0.55((CH3)3SiO1/2)0.45, 50 parts by mass of the constituent unit ratio ((C) represented by CH 3)2SiO)0.9996((CH2＝CH)(CH3)2SiO1/2)0.0004, 1, 3-tetramethyl disiloxane complex of platinum in an amount of 10ppm in terms of mass units relative to the total of the components (A) to (C)), 7 parts by mass of an organohydrogen polysiloxane represented by the following formula (4), 0.2 part by mass of ethynyl cyclohexanol as a reaction controlling agent, and 200 parts by mass of toluene as the component (E) were mixed to prepare a thermosetting silicone composition.
[ Chemical formula 1]
Comparative example 2
100 Parts by mass of a constituent unit ratio (component (B) represented by SiO 2)0.55((CH3)3SiO1/2)0.45, 50 parts by mass of a constituent unit ratio ((component (C) represented by CH 3)2SiO)0.9996((CH2＝CH)(CH3)2SiO1/2)0.0004), 3.5 parts by mass of an organic peroxide (Kayaren-70 manufactured by KAYAKU AKZO Co., ltd.) as component (D) and 150 parts by mass of toluene as component (E) were mixed to prepare a thermosetting silicone composition.
Comparative example 3
A thermosetting silicone composition was prepared by mixing 100 parts by mass of the component (a) represented by the constituent unit ratio (SiO2)0.55((CH3)3SiO1/2)0.40((CH2＝CH)(CH3)2SiO1/2)0.05, 50 parts by mass of the constituent unit ratio ((component (C) represented by CH 3)2SiO)0.9996((CH2＝CH)(CH3)2SiO1/2)0.0004), 3 parts by mass of the organic peroxide (Kayaren-70 manufactured by KAYAKU AKZO corporation) as the component (D), and 150 parts by mass of toluene as the component (E).
The compositions obtained in examples 1 to 4 and comparative examples 1 to 3 were poured into a frame made of Teflon (registered trademark) having a thickness of 2mm, and heated in the order of 60 ℃ for 1 hour, 80 ℃ for 1 hour, and 100 ℃ for 1 hour to volatilize the solvent, thereby producing a sheet. The obtained sheet was subjected to the following tests (1) and (2), and physical properties were confirmed. The results are shown in Table 1.
Test (1) after exposing the sheet to 120℃for 10 minutes, it was confirmed whether or not it was soluble in toluene.
In test (2), the sheet was cured at 150℃for 3 hours, and the appearance of the obtained cured product was observed to measure the hardness.
Appearance, visual observation of the presence or absence of cracks.
No crack (o), crack (x)
Hardness was measured using a durometer type D durometer manufactured by Ueshima Seisakusho co., ltd.
TABLE 1
As shown in Table 1, the sheets obtained in examples 1 to 4 were soluble in toluene even after heating at 120℃for 10 minutes, and remained uncured. Further, by heating at 150 ℃ for 3 hours, a cured product of high hardness was provided.
On the other hand, in comparative example 1, which is a curable composition obtained by hydrosilylation, the curable composition was cured by heating at 120 ℃ for 10 minutes even in the presence of the reaction controlling agent, and failed to remain in an uncured state. In comparative example 2 containing no component (a), the hardness of the cured product was significantly reduced, and in comparative example 3 containing no component (B), cracks were generated in the cured product.
In addition, the present invention is not limited to the above embodiments. The above embodiments are examples, and all embodiments having substantially the same constitution and exhibiting the same effects as the technical idea described in the claims of the present invention are included in the scope of the present invention.
Claims (7)
1. A thermosetting silicone composition characterized in that it comprises:
(A) An organopolysiloxane represented by the following average unit formula (1),
(SiO2)a1(R1 3SiO1/2)b1(X1O1/2)c1(1)
In the formula (1), R 1 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, 50-99.9% of the total number of R 1 are methyl groups and 0.1-50% of R 1 are alkenyl groups, X 1 is a hydrogen atom or an alkyl group, a1 is 0.2-0.8, b1 is 0.2-0.8, c1 is 0-0.1, a1+b1+c1=1;
(B) An organopolysiloxane represented by the following average unit formula (2),
(SiO2)a2(R2 3SiO1/2)b2(X1O1/2)c2(2)
In the formula (2), R 2 is optionally same or different substituted or unsubstituted monovalent hydrocarbon groups containing no alkenyl, X 1 is a hydrogen atom or an alkyl group, a2 is 0.2-0.8, b2 is 0.2-0.8, c2 is 0-0.1, a2+b2+c2=1;
(C) An organopolysiloxane represented by the following average unit formula (3),
(R3 2SiO)a3(R3 3SiO1/2)b3(3)
In the formula (3), R 3 is optionally the same or different substituted or unsubstituted monovalent hydrocarbon groups, 20% or more of the total number of R 3 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, a3+b3=1;
(D) Organic peroxide; and
(E) The solvent is used for the preparation of the aqueous solution,
The thermosetting silicone composition is not a curable composition resulting from hydrosilylation.
2. The thermosetting silicone composition according to claim 1, wherein the amount of the component (B) added is 1 to 100 parts by mass per 100 parts by mass of the component (a).
3. The thermosetting silicone composition according to claim 1, wherein the amount of the component (C) added is 5 to 100 parts by mass per 100 parts by mass of the component (a).
4. The thermosetting silicone composition according to claim 2, wherein the amount of the component (C) added is 5 to 100 parts by mass per 100 parts by mass of the component (a).
5. The thermosetting silicone composition according to any one of claims 1 to 4, comprising 20 to 500 parts by mass of (F) fluorescent material per 100 parts by mass of the total of the components (a) to (E).
6. A sheet formed from the thermosetting silicone composition of any one of claims 1 to 5.
7. A cured silicone composition comprising the thermosetting silicone composition according to any one of claims 1 to 5.
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| JP2020085761A JP7325375B2 (en) | 2020-05-15 | 2020-05-15 | Thermosetting silicone composition, sheet, and silicone cured product |
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| PCT/JP2021/013446 WO2021229940A1 (en) | 2020-05-15 | 2021-03-30 | Thermosetting silicone composition, sheet, and cured silicone product |
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| US6342324B1 (en) * | 2000-02-16 | 2002-01-29 | Imation Corp. | Release layers and compositions for forming the same |
| JP5568240B2 (en) * | 2009-02-02 | 2014-08-06 | 東レ・ダウコーニング株式会社 | Curable silicone rubber composition |
| JP5287935B2 (en) | 2011-06-16 | 2013-09-11 | 東レ株式会社 | Phosphor-containing sheet, LED light-emitting device using the same, and manufacturing method thereof |
| JP5862066B2 (en) | 2011-06-16 | 2016-02-16 | 東レ株式会社 | Phosphor-containing sheet, LED light-emitting device using the same, and manufacturing method thereof |
| JP2014116598A (en) | 2012-11-15 | 2014-06-26 | Toray Ind Inc | Light emitting diode sealing composition, phosphor sheet, led package employing the same and manufacturing method thereof |
| JP2014114446A (en) | 2012-11-16 | 2014-06-26 | Toray Ind Inc | Polyorganosiloxane composition, hardened product of the composition, phosphor sheet, method of producing the phosphor sheet, light-emitting device and method of producing the light-emitting device |
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