CN115551909A - Thermosetting silicone composition, sheet, and silicone cured product - Google Patents
Thermosetting silicone composition, sheet, and silicone cured product Download PDFInfo
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- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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Abstract
The present invention is a thermosetting silicone composition comprising: (A) An organopolysiloxane of the 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 (A) is methyl and 0.1 to 50% is alkenyl, X 1 Is a hydrogen atom or an alkyl group; (B) An organopolysiloxane of the 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 having no alkenyl group, X 1 Is a hydrogen atom or an alkyl group; (C) An organopolysiloxane of the average formula (3), (R) 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)R 3 More than 20% of the total amount of the compounds are methyl groups and 0.0001-25% of the total amount of the compounds are alkenyl groups; (D) an organic peroxide; and (E) a solvent. Thus, a thermosetting silicone composition is provided which has excellent stability when uncured without adding a reaction control agent and which provides a cured product having high hardness.
Description
Technical Field
The present invention relates to a thermosetting silicone composition cured by an organic peroxide.
Background
Background of the inventionlight emitting diodes (LEDs) have advantages such as low power consumption, long life, and design, on the background of significantly improving their light emitting efficiency, and have rapidly expanded market share not only in the backlight of Liquid Crystal Displays (LCDs) and in the vehicle-mounted fields such as headlights of vehicles, but also in general illumination.
Since the emission spectrum of the LED depends on the semiconductor material forming the LED chip, the 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 respective chips on the LED chips and convert emission wavelengths. Specifically, a method of providing a yellow phosphor on an LED chip emitting blue light, a method of providing red and green phosphors on an LED chip emitting blue light, a method of providing red, green, and blue phosphors on an LED chip emitting ultraviolet light, and the like have been proposed. Among them, in terms of light emission efficiency and cost of the LED chip, 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.
As one of specific methods for providing a phosphor on an LED chip, a method of attaching a sheet, in which a phosphor is dispersed in an addition curing type silicone composition that causes a hydrogen organopolysiloxane to react with an alkenyl group-containing organopolysiloxane, to an LED chip has been proposed. However, in this method, the sheet must be stored at a low temperature so that the addition reaction does not proceed when producing the phosphor sheet, and a large amount of an addition reaction control agent must be added to the composition (patent documents 1 to 5).
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-001791
Patent document 2: japanese laid-open patent publication No. 2013-001792
Patent document 3: japanese patent laid-open publication No. 2013-138216
Patent document 4: japanese patent laid-open No. 2014-114446
Patent document 5: japanese patent laid-open 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 without adding a reaction control agent and which provides a cured product having high hardness.
Means for solving the 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),
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
in the formula (1), R 1 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 1 50 to 99.9% of the total number of (A) are methyl groups and 0.1 to 50% 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, and a1+ b1+ c1=1;
(B) An organopolysiloxane represented by the following average unit formula (2),
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
in the formula (2), R 2 Is an optionally identical or different, substituted or unsubstituted, alkenyl-free, monovalent hydrocarbon radical, 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 average unit formula (3),
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
in the formula (3), R 3 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 3 20% or more of the total number of (a) is methyl and 0.0001 to 25% is alkenyl, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+ b3=1;
(D) An organic peroxide; and
(E) A solvent.
The thermosetting silicone composition of the present invention has excellent stability in an uncured state without adding a reaction control agent, and can provide a cured product having high hardness.
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).
The amount of the component (C) added is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the component (a).
In this way, a cured product having more excellent mechanical properties can be provided.
The phosphor (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 manner, the wavelength of light emitted from the optical semiconductor element can be efficiently converted into light of a target wavelength.
Further, the present invention provides a sheet formed from the above 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 for surface coating of optical semiconductor devices such as LED elements.
Further, the present invention provides a cured silicone product which is a cured product of the thermosetting silicone composition.
Such a silicone cured product has excellent mechanical properties. Further, since the cured product of the thermosetting silicone composition has excellent stability in an uncured state, the cured product can be applied to a wide range of applications, and is particularly useful for 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 if a reaction control agent is not necessarily added thereto, and provides a cured product having high hardness, and therefore can be applied to a wide range of applications, and is useful for 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 and provides a cured product having high hardness without adding a large amount of a reaction control agent.
The present inventors have made intensive studies with respect to the above-mentioned technical problems, and as a result, have found that the above-mentioned technical problems can be solved by a specific thermosetting silicone composition containing an organic peroxide, and have completed the present invention.
Namely, the present invention is a thermosetting silicone composition comprising:
(A) An organopolysiloxane represented by the following average unit formula (1),
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
in the formula (1), R 1 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 1 50 to 99.9 percent of the total amount ofMethyl and 0.1 to 50% alkenyl, 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, and a1+ b1+ c1=1;
(B) An organopolysiloxane represented by the following average unit formula (2),
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
in the formula (2), R 2 Is an optionally identical or different substituted or unsubstituted alkenyl-free monovalent hydrocarbon radical, 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 average unit formula (3),
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
in the formula (3), R 3 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 3 20% or more of the total number of (a) is methyl and 0.0001 to 25% is alkenyl, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+ b3=1;
(D) An organic peroxide; and
(E) 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 components (a), (B), (C), (D), and (E) described later, and if necessary, the component (F).
< component (A) >
(A) The component (A) is an organopolysiloxane represented by the following average unit formula (1).
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
In the formula (1), R 1 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 1 50 to 99.9% of the total of (A) are methyl groupsAnd 0.1 to 50% of an alkenyl group, X 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.
R 1 Is a monovalent hydrocarbon group which may be substituted or unsubstituted, as R 1 Examples of the alkenyl group in (1) include a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group, and a vinyl group is particularly preferable.
R 1 The ratio of the number of alkenyl groups in the total number of (A) is 0.1 to 50%, preferably 0.1 to 30%, particularly preferably 0.3 to 20%. If the amount is less than 0.1%, the curability of the composition is insufficient, and if the amount is more than 50%, the cured product becomes brittle.
Further, as R 1 Examples of the organic group bonded to a silicon atom other than the alkenyl group in (1) include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenethyl; a substituted or unsubstituted monovalent hydrocarbon group such as a halogenated alkyl group such as chloromethyl, 3-chloropropyl, 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.
R 1 The ratio of the number of methyl groups in the total number of (A) 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 those represented by the formula 1 The same organic groups as those exemplified in (1) above are particularly preferably methyl groups or ethyl groups.
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 resulting cured product will be 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 (c) 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.
(A) The components can be used singly or in combination.
< ingredient (B) >
(B) The component (C) is an organopolysiloxane represented by the following average unit formula (2).
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
In the formula (2), R 2 Is an optionally identical or different, substituted or unsubstituted, alkenyl-free, monovalent hydrocarbon radical, 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.
As R 2 The monovalent hydrocarbon group having no alkenyl group in (A) includes the monovalent hydrocarbon group having no alkenyl group in (A) and R in the component (A) 1 Among them, the same groups as the silicon atom-bonded organic groups except the alkenyl group 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 group represented by R in the component (A) 1 The organic groups represented by the same groups are particularly preferably methyl groups or ethyl groups.
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 resulting cured product will be 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 preferably 0 to 0.05.
(B) The molecular weight of the component (a) is not limited, but is preferably 500 to 20,000, more preferably 700 to 15,000, and particularly preferably 1,000 to 10,000 in weight average molecular weight (Mw) measured by GPC measurement using a toluene solvent (in terms of standard polystyrene).
(B) The components can be used singly or in combination.
The blending amount of the component (B) is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 7 to 50 parts by mass, based on 100 parts by mass of the component (A), from the viewpoint of the hardness of the cured product.
< ingredient (C) >
(C) The component (B) is an organopolysiloxane represented by the following average unit formula (3).
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
In the formula (3), R 3 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 3 20% or more of the total number of (A) is methyl and 0.0001 to 25% is alkenyl, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+ b3=1.
R 3 Examples thereof include the compounds represented by the formula (A) and R in the component (A) 1 The same radicals as R 3 The alkenyl group in (1) is preferably a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group, and particularly preferably a vinyl group.
R 3 The ratio of the number of alkenyl groups in the total number of (A) is 0.0001 to 25%, preferably 0.1 to 20%, particularly preferably 0.3 to 20%. If the amount is less than 0.0001%, the curability of the composition is insufficient, and if the amount is more than 25%, the cured product becomes brittle.
Further, as R 3 Examples of the organic group bonded to a silicon atom other than the alkenyl group in (1) include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenethyl; substituted or unsubstituted monovalent hydrocarbon groups such as a halogenated alkyl group such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc., and among them, methyl is most preferable from the viewpoint of heat resistance. If at all R 3 Among these, the content of the monovalent hydrocarbon group is preferably not less than 20mol% because stable heat resistance can be imparted, and more preferably not less than 40 mol%.
R 3 The ratio of the number of methyl groups in the total number of (A) is 20 to 99.9999%, preferably 40 to 99.9%. When the amount is less than 20mol%, 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. Further, a3+ b3=1.
(C) The components can be used singly or in combination.
The blending amount of the component (C) is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 30 to 60 parts by mass, based on 100 parts by mass of the component (a), from the viewpoint of the hardness of the cured product.
< ingredient (D) >
(D) The component (b) is an organic peroxide, and decomposes by heat to generate radicals, thereby curing the thermosetting silicone composition of the present invention.
Specific examples of the organic peroxide include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxydicarbonates, peroxyketals, hydroperoxides, silyl peroxides (silylperoxides).
Examples of diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, octanoyl peroxide, lauroyl peroxide, distearyl peroxide, succinic peroxide, benzoylperoxy toluene and benzoyl peroxide.
Examples of the peroxyester include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxide) hexane, 1-cyclohexyl-1-methylethyl peroxy2-ethylhexanoate, t-hexyl peroxy2-ethylhexanoate, t-butyl peroxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluate) hexane, t-butylperoxyisopropyl monocarbonate, t-butyl peroxybutyl monocarbonate, t-butyl peroxyhexa, and t-butyl peroxyacetate (tertbutyloxycarbonate).
Examples of the dialkyl peroxide include di-tert-butylperoxydiisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, and tert-butylcumyl peroxide.
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 bis (3-methyl-3-methoxybutyl) peroxydicarbonate.
Examples of the peroxyketal include 1,6-bis (t-butylperoxy-carbonyloxy) hexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane and 2,2-bis (t-butylperoxy) decane.
Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
Examples of the silyl peroxide include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, tri (t-butyl) vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide and tri (t-butyl) allylsilyl peroxide.
From the viewpoint of stability in the uncured state, the component (D) is preferably an organic peroxide having a half-life of 1 hour or more at 100 ℃.
(D) The components can be used singly or in combination.
(D) The amount of the component (A) to be blended may be an effective amount (i.e., a 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).
< ingredient (E) >
(E) The solvent for component (b) is not particularly limited as long as the above-mentioned components (a) to (D) constituting the composition are dissolved, 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; ligroin (ligroin), cyclohexanone, diethyl ether, rubber volatile oil, silicone solvent, etc. Among them, toluene, heptane and ethyl acetate are suitably used.
(E) The components may be used singly or in combination of two or more in the form of a mixed solvent, depending on the evaporation rate in the coating operation of the thermosetting silicone composition of the present invention.
(E) The amount of the component (c) 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 in coating operation.
< ingredient (F) >
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.
The phosphor absorbs blue light, violet light, and ultraviolet light emitted from the optical semiconductor element, converts the wavelength of the light, and emits light having wavelengths in red, orange, yellow, green, and blue regions different from the light emitted from the optical semiconductor element. Thus, part of the light emitted from the optical semiconductor element is mixed with part of the light emitted from the phosphor, and a multicolor optical semiconductor element including white is obtained.
The phosphors described above include various phosphors such as a phosphor emitting green light, a phosphor emitting blue light, a phosphor emitting yellow light, and a phosphor emitting 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 phosphor include an allylsulfonamide-melamine formaldehyde cocondensed dye and a perylene (perylene) based phosphor, and the perylene based phosphor is preferably used from the viewpoint of long-term usability. As the fluorescent substance particularly preferably used in the present invention, an inorganic fluorescent substance can be mentioned. The inorganic phosphor used in the present invention is described below, but is not limited thereto.
Examples of the phosphor emitting green light include SrAl 2 O 4 :Eu、Y 2 SiO 5 :Ce,Tb、MgAl 11 O 19 :Ce,Tb、Sr 7 Al1 2 O 25 Eu, at least 1 of (Mg, ca, sr, ba) Ga 2 S 4 Eu, etc.
Examples of the phosphor emitting blue light include Sr 5 (PO 4 ) 3 Cl:Eu、(SrCaBa) 5 (PO 4 ) 3 Cl:Eu、(BaCa) 5 (PO 4 ) 3 Eu, at least 1 of (Mg, ca, sr, ba) 2 B 5 O 9 Cl is at least 1 of Eu, mn, (Mg, ca, sr, ba) (PO) 4 ) 6 C l2 Eu, mn, etc.
Examples of the phosphor emitting light from green to yellow include an yttrium aluminum oxide phosphor activated at least with cerium, an yttrium gadolinium aluminum oxide phosphor activated at least with cerium, an yttrium aluminum garnet oxide phosphor activated at least with cerium, an yttrium gallium aluminum oxide phosphor activated at least with cerium, and the like (so-called YAG-based phosphor). Specifically, ln can be used 3 M 5 O 12 A (Ln is at least one selected from Y, gd and La; M comprises at least one selected from Al and Ca; A is lanthanide), (Y) 1-x Ga x ) 3 (Al 1-y Ga y ) 5 O 12 A is at least one selected from Ce, tb, pr, sm, eu, dy and Ho, x is more than 0 and less than 0.5, and y is more than 0 and less than 0.5.
Examples of the phosphor emitting red light include Y 2 O 2 S:Eu、La 2 O 2 S:Eu、Y 2 O 3 :Eu、Gd 2 O 2 And S is Eu, etc.
Further, Y is an example of a phosphor that emits light corresponding to a blue LED 3 (Al,Ga) 5 O 12 :Ce、(Y,Gd) 3 Al 5 O 12 :Ce、Lu 3 Al 5 O 12 :Ce、Y 3 Al 5 O 12 YAG-based phosphor such as Ce; tb 3 Al 5 O 12 A TAG-based phosphor such as Ce; (Ba, sr) 2 SiO 4 Eu-based phosphor and Ca 3 Sc 2 Si 3 O 12 Ce-based phosphor, (Sr, ba, mg) 2 SiO 4 A silicate phosphor such as Eu; (Ca, sr) 2 Si 5 N 8 :Eu、(Ca,Sr)AlSiN 3 :Eu、CaSiAlN 3 A nitride phosphor such as Eu; cax (Si, al) 12 (O,N) 16 An oxynitride-based phosphor such as Eu; and (Ba, sr, ca) Si 2 O 2 N 2 Eu-based phosphor and Ca 8 MgSi 4 O 16 Cl 2 Eu-based phosphor; srAl 2 O 4 :Eu、Sr 4 Al 14 O 25 Eu, etc.
Among them, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferably used from the viewpoint of light emission efficiency, luminance, and the like.
In addition to the above-mentioned phosphors, known phosphors can be used according to the application and the target luminescent color.
The particle size of the phosphor is not particularly limited, and D is preferred 50 Is 0.05 μm or more, and more preferably 3 μm or more. Furthermore, D is preferred 50 Is 30 μm or less, more preferably 20 μm or less. Here, D 50 Means a volume-based particle size distribution measured by a laser diffraction scattering particle size distribution measurement method, from the small particle size sideThe particle size at which the excessive components are accumulated to 50%. If D is 50 Within the above range, the dispersion of the phosphor in the thermosetting silicone composition of the invention (for example, a resin composition for a wafer level optical semiconductor device) is good, and stable light emission can be obtained.
One or a mixture of two or more of the above phosphors may be used.
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 used particularly preferably in the form of a phosphor sheet for surface coating of LEDs because it contains a phosphor. In this case, by setting the content of the phosphor in the phosphor sheet within the above range, an LED light emitting device exhibiting excellent performance can be obtained.
< any component >
The thermosetting silicone composition of the present invention may contain, in addition to the components (a) to (F), adhesion improving agents exemplified below.
As the adhesion improver, preferred are: 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 site.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a methoxyethoxy group, and a methoxy group is particularly preferable. Further, as the groups other than the alkoxy group bonded to the silicon atom of the organosilicon compound, there can be exemplified: in the above-mentioned R 1 Etc., the above-mentioned alkyl group, the above-mentioned alkenyl group, the above-mentioned aryl group, the above-mentioned aralkyl group, the above-mentioned haloalkyl group and the like which may be substituted or unsubstituted; a monovalent organic group containing an acryloyl group such as 3-methacryloxypropyl group; a hydrogen atom. Specifically, silane coupling agents such as (meth) acryloyl group-containing silane coupling agents can be exemplifiedAnd a partially hydrolyzed condensate thereof (oligomer of a silane coupling agent). More specifically, it can be exemplified that: silane compounds such as 3-methacryloxypropyltrimethoxysilane; a silicone compound having in one molecule 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, a silane compound having at least one alkoxy group bonded to a silicon atom or a mixture of a silicone compound and a silicone compound having in one molecule at least one hydroxyl group bonded to a silicon atom and an alkenyl group bonded to a silicon atom, respectively, a methyl polysilicate, an ethyl polysilicate containing an epoxy group.
Examples of the group having an epoxy group site include glycidyloxyalkyl groups such as 3-glycidyloxypropyl group and 4-glycidyloxybutyl group; epoxycyclohexylalkyl groups such as 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group and the like; an epoxy group-containing monovalent organic group such as an oxirane group such as a 4-oxirane butyl group or an 8-oxirane octyl group.
The viscosity-improving agent is preferably a low-viscosity liquid, and the viscosity thereof is not limited, but is preferably in the range of 1 to 500 mPas at 23 ℃.
The content of the adhesion improver is not limited, but is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the component (a).
The thermosetting silicone composition of the present invention may contain inorganic fillers other than the component (F), such as fumed silica, fused silica glass, alumina, and zinc oxide; organic resin fine powders such as polymethacrylate resin; heat-resistant agents, dyes, pigments, flame retardancy-imparting agents, and the like.
When an inorganic filler other than the component (F) is used, the 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 composition of the present invention is more excellent in fluidity.
The viscosity of the thermosetting silicone composition of the present invention at 25 ℃ is preferably 10 to 5,000mpa · s, more preferably 20 to 2,000mpa · s. When the amount is within such a range, the obtained composition is easy to be excellent in handling and handleability, and air bubbles and air are not easily entrained during molding and curing. In the present invention, the viscosity can be a value measured by a rotational viscometer.
The viscosity of the thermosetting silicone composition of the present invention can be adjusted by the blending amount and viscosity of the components (a) to (E) and other components, and the blending amount and average particle diameter of the component (F).
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 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 the components (a) to (E).
[ sheet ]
The present invention provides a sheet formed from the above thermosetting silicone composition. The sheet may be 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 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 lower than the temperature at which the composition cures to volatilize (E) the solvent, 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 injection molding (injection molding method) and transfer molding (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 (dispensing) method, a potting (potting) method, and various coating methods.
The thermosetting silicone composition of the present invention is cured by heating, and heating at a high temperature is preferable for rapid curing. The curing conditions vary depending on the shape of the molded product, the curing method, and the like, 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, and more preferably 5 minutes to 5 hours.
The hardness of the silicone cured product of the present invention is preferably 20 or more, and particularly preferably 30 to 70 on the shore D scale.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.
[ example 1]
Mixing 100 parts by mass of constituent Unit ratio (SiO) 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.05 Component (A) shown, a constituent Unit ratio (SiO) of 40 parts by mass 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.45 Component (B) shown, and a constituent unit ratio of 50 parts by mass ((CH) 3 ) 2 SiO) 0.9996 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.0004 A thermosetting silicone composition was prepared from the component (C) shown above, 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).
[ example 2]
A YAG phosphor was mixed by 150 parts by mass with respect to 100 parts by mass of the thermosetting silicone composition obtained in example 1 to prepare a phosphor-containing thermosetting silicone composition.
[ example 3]
Mixing 100 parts by mass of constituent Unit ratio (SiO) 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.05 Component (A) shown, a constituent Unit ratio (SiO) of 25 parts by mass 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.45 Component (B) shown, a constituent Unit ratio of 40 parts by mass ((CH) 3 ) 2 SiO) 0.9996 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.0004 A thermosetting silicone composition was prepared from the component (C) shown above, 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).
[ example 4]
A YAG phosphor was mixed in an amount of 150 parts by mass with respect to 100 parts by mass of the thermosetting silicone composition obtained in example 3 to prepare a phosphor-containing thermosetting silicone composition.
Comparative example 1
Mixing 100 parts by mass of constituent Unit ratio (SiO) 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.05 Component (A) shown, a constituent Unit ratio (SiO) of 40 parts by mass 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.45 Component (B) shown, and a constituent unit ratio of 50 parts by mass ((CH) 3 ) 2 SiO) 0.9996 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.0004 A thermosetting silicone composition was prepared from the component (C) shown below, a platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (the amount of platinum metal in the complex was 10ppm 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).
[ chemical formula 1]
Comparative example 2
Mixing 100 parts by mass of constituent unitsRatio (SiO) 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.45 Component (B) shown, and a constituent unit ratio of 50 parts by mass ((CH) 3 ) 2 SiO) 0.9996 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.0004 A thermosetting silicone composition was prepared from the component (C) shown above, 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).
Comparative example 3
Mixing 100 parts by mass of constituent Unit ratio (SiO) 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.05 Component (A) shown, and a constituent unit ratio of 50 parts by mass ((CH) 3 ) 2 SiO) 0.9996 ((CH 2 ＝CH)(CH 3 ) 2 SiO 1/2 ) 0.0004 A thermosetting silicone composition was prepared from the component (C) shown above, 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).
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 at 60 ℃ for 1 hour, 80 ℃ for 1 hour, and 100 ℃ for 1 hour in this order to volatilize the solvent, thereby producing a sheet. The following tests (1) and (2) were carried out on the obtained sheet to confirm physical properties. The results are shown in table 1.
Test (1): after the sheet was exposed to 120 ℃ for 10 minutes, it was confirmed whether it was soluble in toluene.
Test (2): the sheet was cured at 150 ℃ for 3 hours, and the appearance of the resulting cured product was observed to measure the hardness.
Appearance: the presence or absence of cracks was visually observed.
No cracking (O) and cracking (X)
Hardness: the measurement was performed using a durometer type D durometer manufactured by Ueshima sesakasuho co.
[ 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 having high hardness was provided.
On the other hand, in comparative example 1, which is a curable composition obtained by hydrosilylation, even if the reaction control agent is present, the curable composition is cured by heating at 120 ℃ for 10 minutes, and the uncured state cannot be maintained. 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.
The present invention is not limited to the above embodiments. The above embodiments are merely illustrative, and any embodiment having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operation and effect is included in the scope of the present invention.
Claims (6)
1. A thermosetting silicone composition characterized by comprising:
(A) An organopolysiloxane represented by the following average unit formula (1),
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
in the formula (1), R 1 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 1 50 to 99.9% of the total number of (A) are methyl groups and 0.1 to 50% 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, and a1+ b1+ c1=1;
(B) An organopolysiloxane represented by the following average unit formula (2),
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
in the formula (2), R 2 Is an optionally identical or different, substituted or unsubstituted, alkenyl-free, monovalent hydrocarbon radical, 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 average unit formula (3),
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
in the formula (3), R 3 Is an optionally identical or different, substituted or unsubstituted, monovalent hydrocarbon radical, R 3 20% or more of the total number of (a) is methyl and 0.0001 to 25% is alkenyl, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3+ b3=1;
(D) An organic peroxide; and
(E) A solvent.
2. The heat-curable silicone composition according to claim 1, wherein the amount of component (B) added is 1 to 100 parts by mass relative to 100 parts by mass of component (a).
3. The heat-curable silicone composition according to claim 1 or 2, characterized in that the amount of component (C) added is 5 to 100 parts by mass relative to 100 parts by mass of component (a).
4. The thermosetting silicone composition according to any one of claims 1 to 3, characterized by comprising 20 to 500 parts by mass of (F) a phosphor per 100 parts by mass of the total of the components (A) to (E).
5. A sheet formed from the heat-curable silicone composition according to any one of claims 1 to 4.
6. A cured silicone product which is a cured product of the thermosetting silicone composition according to any one of claims 1 to 4.
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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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| JPH06306294A (en) * | 1993-04-09 | 1994-11-01 | General Electric Co <Ge> | Improved thermosetting elastomer composition based on vinyl-functional resin, polymer chain-terminated with single vinyl and polymer having vinyl in chain |
| US6342324B1 (en) * | 2000-02-16 | 2002-01-29 | Imation Corp. | Release layers and compositions for forming the same |
| 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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| JP6383651B2 (en) * | 2014-12-03 | 2018-08-29 | 富士フイルム株式会社 | Composition for acoustic wave probe, silicone resin for acoustic wave probe using the same, acoustic wave probe and ultrasonic probe, acoustic wave measuring device, ultrasonic diagnostic device, photoacoustic wave measuring device, ultrasonic endoscope and acoustic wave Manufacturing method of silicone resin for probe |
| JP6586555B2 (en) * | 2014-12-26 | 2019-10-09 | ダウ・東レ株式会社 | Curable silicone composition, semiconductor sealant and semiconductor device comprising the same |
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