KR20220022577A - Polysiloxane composition for optical use and reflective materials for optical semiconductor comprising the same - Google Patents

Abstract

The present invention relates to an optical polysiloxane composition which comprises: organopolysiloxane; organohydrogenpolysiloxane; a white pigment; and a reaction catalyst, wherein the organopolysiloxane comprises at least three alkenyl groups in one molecule, and has a viscosity at 25℃ of 20 Pa·s or less, wherein the ratio of the total number of moles of a first divalent repeating unit and a trivalent second repeating unit to the number of moles of a monovalent third repeating unit is 1 : 0.3 to 3.0 and the organohydrogenpolysiloxane comprises at least three hydrogen groups (SiH) bonded to silicon in one molecule and has a viscosity at 25℃ of 20 Pa·s or less.

Description

Optical polysiloxane composition and reflective material for optical semiconductor comprising the same

The present invention relates to an optical polysiloxane composition having excellent dispensing workability in a liquid form at room temperature, and a reflective material for an optical semiconductor comprising the same having high visible light reflectance and hardness and excellent heat resistance.

Conventional surface mount technology (SMT) type optical semiconductor (LED) package (package, PKG) is generally composed of a method of bonding an electrode at the top of a chip and an electrode at the bottom of the PKG with a wire, and protects it In order to do this, the case and frame were made of a material with high reflectivity to act as a reflector. Polyphtalamide resin (PPA resin), condensed resin, etc. are used as materials for the optical semiconductor package of this SMT method, but these are discoloration, burr generation when cutting, void generation, and high temperature. There was a problem such as crack generation during use.

In addition, in response to the recent demand for miniaturization and thinning of optical semiconductor PKG, flip-chip having a structure with electrodes only at the bottom of the chip has been commercialized. Therefore, the frame is omitted or the gap between chips is narrow and the demand for a chip scale package (CSP) capable of high density is increasing. is increasing Accordingly, a method of manufacturing a PKG by curing the gap between the chips by dispensing or molding with silicon (silicone) having high reflectance and cutting the gap into a single chip has been proposed. Accordingly, various liquid silicones for use in the CSP process have been developed, but the cured products formed using them have insufficient hardness, short pot life of the composition, and poor moldability, and the phenyl group contained in the silicone composition under high temperature conditions. There was a problem in that the reflectance was lowered due to discoloration.

On the other hand, the conventional silicone composition for a semiconductor package contains a white pigment and an inorganic filler, and is suitable for injection molding because it is solid at room temperature or has a high viscosity. However, in order to constitute a reflective material of a thin film through dispensing or molding as described above, the viscosity of the composition must be low. However, when the content of solids, such as white pigment, is lowered in order to lower the viscosity of the composition, the content of the white pigment is not sufficient, so there is a problem in that the reflectance of visible light of the prepared cured product is insufficient.

Therefore, there is a need for research on an optical silicone composition that can be applied to dispensing or molding in a liquid phase at room temperature, can be precisely molded, and has high visible light reflectance and excellent heat resistance in a thin film state.

Japanese Patent Publication No. 2,656,336 (published on July 25, 1990)

The present invention is applicable to dispensing or molding molding in liquid form at room temperature, precise molding processing is possible, high reflectance of visible light in a thin film state, and excellent hardness of the cured product. An object is to provide an optical polysiloxane composition.

In order to solve the above problems, the present invention comprises an organopolysiloxane, an organohydrogenpolysiloxane, a white pigment and a reaction catalyst,

The organopolysiloxane contains at least three alkenyl groups in one molecule, has a viscosity at 25°C of 20 Pa·s or less, the total number of moles of the first divalent repeating unit and the trivalent second repeating unit, and the monovalent agent The ratio of moles of 3 repeating units is 1:0.3 to 3.0,

The organohydrogenpolysiloxane includes at least three hydrogen groups (SiH) bonded to silicon in one molecule, and has a viscosity at 25°C of 20 Pa·s or less, providing an optical polysiloxane composition.

In addition, the present invention provides a reflective material for an optical semiconductor comprising a cured product prepared by curing the optical polysiloxane composition.

The optical polysiloxane composition of the present invention is a low-viscosity liquid at room temperature, applicable to dispensing or molding, and sophisticated molding processing is possible. In addition, the cured product has a high visible light reflectance and excellent hardness of the cured product, which causes less burr during cutting and is excellent in heat resistance, so it is very suitable as a reflective material for optical semiconductors.

Hereinafter, the present invention will be described in detail.

The relationship between the structure of a general polysiloxane and its common name is as follows.

(R ₃ SiO _1/2 ) _a unit: M unit

(R ₂ SiO _2/2 ) _b unit: D unit

(RSiO _3/2 ) _c unit: T unit

(SiO _4/2 ) _d units: Q units

In the present specification, M unit, D unit, T unit, and Q unit which are conventionally used in the technical field are used in combination.

Optical polysiloxane composition

The optical polysiloxane composition of the present invention includes an organopolysiloxane, an organohydrogenpolysiloxane, a white pigment, and a reaction catalyst.

In this case, the organopolysiloxane and the organohydrogenpolysiloxane have high reactivity and low viscosity at 25° C., so that the dispersibility of the white pigment is excellent.

Organopolysiloxane

The organopolysiloxane serves to form a main skeleton of the cured product to be prepared.

The organopolysiloxane contains at least three alkenyl groups in one molecule, has a viscosity at 25°C of 20 Pa·s or less, the total number of moles of the first divalent repeating unit and the trivalent second repeating unit, and the monovalent agent The ratio of the number of moles of 3 repeating units is 1:0.3 to 3.0. Specifically, the organopolysiloxane may be represented by the following Chemical Formula 1 and include at least one aryl group.

[Formula 1]

[R ¹ ₃ SiO _1/2 ] _a [R ² (R ³ O)SiO] _b [R ⁴ SiO _3/2 ] _c

In Formula 1,

A plurality of R ¹ is each independently a substituted or unsubstituted C _2-10 alkenyl group, or a C _1-10 alkyl group, at least one R ¹ is an alkenyl group,

R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C _1-10 alkyl group, C _6-14 aryl group, or hydrogen, and at least one of R ² , R ³ and R ⁴ is an aryl group,

a/(b+c) is 0.3 to 3.0,

a+b+c equals 1.

In this case, the alkyl group and the alkenyl group may be linear, branched or cyclic.

For example, a plurality of R ¹ is each independently a substituted or unsubstituted C _2-6 alkenyl group, or a C _1-6 alkyl group, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, vinyl, allyl, butenyl, pentenyl or hexenyl. More specifically, a plurality of R ¹ may each independently be a methyl group or a vinyl group.

In addition, R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C _1-6 alkyl group, C _6-10 aryl group, or hydrogen, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl , cyclopentyl, cyclohexyl, or phenyl. More specifically, R ² , R ³ , and R ⁴ may each independently be phenyl or methyl.

In Formula 1, [R ¹ ₃ SiO _1/2 ] is a monovalent third repeating unit (M unit-1), and [R ² (R ³ O)SiO] is a divalent first repeating unit (D unit- 1), and [R ⁴ SiO _3/2 ] is a trivalent second repeating unit (T unit-1). That is, a/(b+c) may be 0.3 to 3.0, specifically, 0.33 to 3.0. When a/(b+c) exceeds the above range, the molecular weight of the organopolysiloxane is low, and the crosslinking density of the cured product is low, making it difficult to secure sufficient hardness. lower it In addition, when a/(b+c) exceeds the above range, low molecular weight unreactive components that do not participate in the reaction during curing are volatilized and voids are generated on the surface and inside the cured product, thereby adversely affecting reliability. When a/(b+c) is less than the above range, the degree of branching of the organopolysiloxane is high, the molecular weight is high, and it has a structurally steric hindrance effect, which facilitates interaction with the inorganic filler component, thereby increasing the viscosity or thixometry of the composition at room temperature. In this case, the flowability of the composition is lowered, so that the dispensing and dispensing operation is difficult, or curing shrinkage occurs under high temperature conditions, and cracks easily occur in the prepared cured product, thereby reducing reliability.

The organopolysiloxane may include less than 40 mol%, or 39 mol% or less of an aryl group based on the total number of moles of R ¹ to R ⁴ . In this case, the aryl group may be a phenyl group. When the content of the aryl group as described above exceeds the above range, there is a difference in the refractive index between the white pigment and the interface, and the transmittance increases in the prepared cured product having a thickness of 35 μm or less, thereby lowering the visible light reflectance, and storing it for a long time at high temperature There may be a problem in that the reflectance of visible light is greatly reduced due to the time discoloration.

For example, the organopolysiloxane is (ViMe ₂ SiO _0.5 ) _0.35 (PhSiO _1.5 ) _0.65 , (ViMe ₂ SiO _0.5 ) _0.6 (PhSiO _1.5 ) _0.4 , (ViMe ₂ SiO _0.5 ) _0.75 (PhSiO _1.5 ) _0.25 , (ViMe ₂ SiO _0.5 ) _0.35 (MeSiO _1.5 ) _0.65 , (ViMe ₂ SiO _0.5 ) _0.6 (MeSiO _1.5 ) _0.4 , (ViMe ₂ SiO _0.5 ) _0.75 (MeSiO _1.5 ) _0.25 , (ViMe ₂ SiO _0.5 ) _0.2 (Me ₃ SiO _0.5 ) _0.15 (PhSiO _1.5 ) _0.65 , (ViMe ₂ SiO _0.5 ) _0.2 (Me ₃ SiO _0.5 ) _0.15 (MeSiO _1.5 ) _0.65 , (ViMe ₂ SiO _0.5 ) _0.175 (Me ₃ SiO _0.5 ) _0.175 (PhSiO _1.5 ) _0.65 , (ViMe ₂ SiO _0.5 ) _0.175 (Me ₃ SiO _0.5 ) _0.175 (MeSiO _1.5 ) _0.65 , (ViMe ₂ SiO _0.5 ) _0.3 (Me ₃ SiO _0.5 ) _0.1 (PhMeOS0) _0.2 (PhSiO _1.5 ) _0.4 , (ViMe ₂ SiO _0.5 ) _0.25 (Me ₃ SiO _0.5 ) _0.1 (PhMeOS0) _0.2 (PhSiO _1.5 ) _0.1 (MeSiO _1.5 ) _0.35 , (ViMe ₂ SiO _0.5 ) _0.25 (Me ₃ SiO _0.5 ) _0.1 (PhSiO _1.5 ) _0.3 (MeSiO _1.5 ) _0.35 , (ViMe ₂ SiO _0.5 ) ) _0.35 (PhMeOS0) _0.1 (PhSiO _1.5 ) _0.55 , (ViMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.1 (PhSiO _1.5 ) _0.3 (MeSiO _1.5 ) _0.35 and the like. In this case, Vi is a vinyl group, Me is a methyl group, and Ph is a phenyl group.

In addition, the organopolysiloxane may contain an alkenyl group of 1.5 mmol/g or more, or 1.6 to 9.0 mmol/g. When the alkenyl group content is less than the above range, a hard cured product cannot be formed due to low reactivity of the composition, and cracks may easily occur on the surface of the prepared cured product.

The organopolysiloxane may have a viscosity at 25°C of 20 Pa·s or less, or 18 Pa·s or less. When the viscosity at 25° C. of the organopolysiloxane exceeds the above range, the dispersion of the white pigment is non-uniform, so that the thixotropic composition of the composition is increased, which may cause a problem in that the discharge stability is deteriorated.

Organohydrogenpolysiloxane

The organohydrogenpolysiloxane reacts with the organopolysiloxane to form a cured product by crosslinking.

The organohydrogenpolysiloxane includes at least three hydrogen groups (SiH) bonded to silicon in one molecule, and has a viscosity at 25°C of 20 Pa·s or less. For example, the organohydrogenpolysiloxane may be represented by the following Chemical Formula 2 and include at least one aryl group.

[Formula 2]

[HR ¹⁰ ₂ SiO _1/2 ] _l [R ¹¹ (R ¹² O)SiO] _m [R ¹³ SiO _3/2 ] _n

In Formula 2,

R ¹⁰ and R ¹² are each independently a substituted or unsubstituted C _1-10 alkyl group, or hydrogen,

R ¹¹ is a substituted or unsubstituted C _6-14 aryl group,

R ¹³ is each independently a substituted or unsubstituted C _1-10 alkyl group, or a C _6-14 aryl group,

l/(m+n) is 0.3 to 3,

l+m+n is 1.

In this case, the alkyl group may be linear, branched or cyclic.

For example, R ¹⁰ and R ¹² are each independently a substituted or unsubstituted C _1-6 alkyl group, and specifically, may be methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl or cyclohexyl. More specifically, R ¹⁰ and R ¹² may be methyl.

In addition, R ¹¹ and R ¹³ are each independently a substituted or unsubstituted C _6-10 aryl group, and specifically, may be phenyl, naphthyl, biphenyl, or the like. More specifically, R ¹¹ and R ¹³ may be phenyl.

In Formula 2, [HR ¹⁰ ₂ SiO _1/2 ] is a monovalent repeating unit (M unit-2), [R ¹¹ (R ¹² O)SiO] is a divalent repeating unit (D unit-2), [R ¹³ SiO _3/2 ] is a trivalent repeating unit (T unit-2).

In addition, l/(m+n) may be 0.3 to 3.0, specifically, 0.33 to 3.0. When l/(m+n) is less than the above range, the flowability at room temperature is lowered due to high thixotropy of the composition, which makes dispensing and dispensing difficult, or curing shrinkage occurs under high temperature conditions to cause cracks in the prepared cured product. This easily occurs, which may cause a problem of reduced reliability.

The organohydrogenpolysiloxane may include less than 40 mol%, or 39 mol% or less of an aryl group based on the total number of moles of R ¹⁰ to R ¹³ . In this case, the aryl group may be a phenyl group. When the content of the aryl group as described above exceeds the above range, there is a difference in the refractive index between the white pigment and the interface, and the transmittance increases in the prepared cured product having a thickness of 35 μm or less, thereby lowering the visible light reflectance, and storing it for a long time at high temperature There may be a problem in that the reflectance of visible light is greatly reduced due to the time discoloration.

For example, the organohydrogenpolysiloxane is (HMe ₂ SiO _0.5 ) _0.35 (PhSiO _1.5 ) _0.65 , (HMe ₂ SiO _0.5 ) _0.6 (PhSiO _1.5 ) _0.4 , (HMe ₂ SiO _0.5 ) _0.75 (PhSiO _1.5 ) _0.25 , (HMe ₂ SiO _0.5 ) _0.35 (MeSiO _1.5 ) _0.65 , (HMe ₂ SiO _0.5 ) _0.6 (MeSiO _1.5 ) _0.4 , (HMe ₂ SiO _0.5 ) _0.75 (MeSiO _1.5 ) _0.25 , (HMe ₂ SiO _0.5 ) _0.35 (PhMeOSiO) _0.1 (PhSiO _1.5 ) _0.55 , (HMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.1 (PhSiO _1.5 ) _0.3 (MeSiO _1.5 ) _0.35 and the like. In this case, Me is a methyl group, and Ph is a phenyl group.

In addition, the organohydrogenpolysiloxane may include a hydrogen group (SiH) bonded to silicon at 1.5 mmol/g or more, or 1.8 to 10.0 mmol/g. When the SiH content is less than the above range, the reactivity of the composition is low, so that a hard cured product cannot be formed, and cracks may easily occur on the surface of the prepared cured product.

The organohydrogenpolysiloxane may have a viscosity at 25°C of 20 Pa·s or less, or 15 Pa·s or less. When the viscosity at 25° C. of the organohydrogenpolysiloxane exceeds the above range, the dispersion of the white pigment is non-uniform, so that thixotropy of the composition is increased, which may cause a problem in that discharge stability is deteriorated.

A molar ratio of the alkenyl group of the organopolysiloxane and the hydrogen group (SiH) bonded to silicon of the organohydrogenpolysiloxane may be 1:0.5 to 1:2.0, or 1:0.8 to 1:1.5. In this case, the alkenyl group may be a vinyl group. In addition, when the molar ratio of the alkenyl group and SiH as described above is less than the above range, there is a problem in that a large amount of unreacted organopolysiloxane remains and stickiness of the surface of the cured product occurs. The hardness of the cured product prepared by the residual genpolysiloxane is lowered, and shrinkage due to heat easily occurs, which may cause cracks.

white pigment

The white pigment is a component that improves the reflectance in the visible light region by lowering the transmittance of the cured product and implementing white color.

For example, the white pigment may be at least one selected from the group consisting of titanium dioxide, alumina, zinc oxide, zirconium oxide, magnesium oxide, barium sulfate and zinc sulfate, and specifically, may include titanium dioxide.

In addition, the white pigment may have an average particle diameter of 0.05 to 10 μm, or 0.1 to 1.0 μm. When the average particle diameter of the white pigment is less than the above range, the dispersibility of the pigment deteriorates and the viscosity of the composition easily increases. This may cause a decrease in the workability of the composition.

The white pigment may be surface-treated using a silane coupling agent, a surface treatment agent such as silica, alumina, or zirconium, in order to improve compatibility with polysiloxane and dispersibility in the composition.

In addition, the white pigment may be included in the composition in an amount of 60 to 170 parts by weight, or 65 to 165 parts by weight based on 100 parts by weight of the total amount of the organopolysiloxane and the organohydrogenpolysiloxane. If the content of the white pigment is less than the above range, the light transmittance may be lowered in a thin film of less than 35 μm and the visible light reflectance may be lowered. This could get worse.

hydrosilylation catalyst

The optical polysiloxane composition according to the present invention may further include a hydrosilylation catalyst. In this case, the hydrosilylation catalyst is a component that promotes the hydrosilylation reaction of an alkenyl group in the organopolysiloxane and a hydrogen group (SiH) bonded to silicon in the organohydrogenpolysiloxane.

The hydrosilylation catalyst may include, for example, at least one selected from the group consisting of a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Specifically, a platinum-based catalyst may be used as the hydrosilylation catalyst. The platinum-based catalyst may include finely divided powder of platinum, chloroplatinic acid, a platinum-alkenyl siloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex, for example, a platinum-alkenyl siloxane complex. may include

In addition, when a platinum-based catalyst is used as the hydrosilylation catalyst, the platinum-based catalyst is 0.01 to 100 ppm, or 0.1 to 50 ppm, based on 100 parts by weight of the total weight of the organopolysiloxane and the organohydrogenpolysiloxane It may be included in the composition in an amount including platinum atoms. If the content of the hydrosilylation catalyst is less than the above range, it is difficult to form a cured product because the curing reaction of the composition does not occur. .

additive

The optical polysiloxane composition of the present invention may further include additives typically included in the polysiloxane composition within a range that does not impair the object of the present invention. For example, the additive may include an adhesion promoter, an inorganic filler, a silicone powder, a resin powder, a heat resistance agent, an antioxidant, a radical scavenger, a light stabilizer, a flame retardant additive, a silicone-based diluent, and a reaction delay agent.

In this case, the adhesion promoter may include, for example, an unsaturated or epoxy-functional alkoxy silane, specifically, 3-glycidoxypropyltrimethoxy silane, 3-glycidoxypropyltriethoxy silane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, etc. are mentioned.

In addition, the reaction retardant is, for example, an alkynyl (alkynyl) containing alcohol compound, specifically, 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 3,5 -Dimethyl-1-hexyne-3-ol, 2-phenyl-3-butyn-2-ol, etc. are mentioned.

As described above, the optical polysiloxane composition according to the present invention is liquid at room temperature, for example, 20 to 30° C., and has the advantage of being applicable to molding such as dispensing and injection molding, and capable of sophisticated molding processing.

In addition, the optical polysiloxane composition may have a viscosity at 25° C. of 10 Pa·s or less, 1 to 8 Pa·s, or 2 to 6 Pa·s. If the viscosity at 25° C. of the composition exceeds the above range, it is difficult to discharge a very small amount of quantitatively, and the gap between electrodes between chips cannot be easily filled, so that voids may occur on the cured surface during curing. In addition, when the viscosity at 25° C. of the composition is less than the above range, the initial adhesion between the chips and the electrodes may be lowered to cause contamination of the chip surface.

The optical polysiloxane composition has a viscosity at 25°C measured at a shear rate of 1s ^-1 and a viscosity at 25°C measured at a shear rate of 10s ^-1 of 1:1 to 2:1, or 1.3:1.0 to 1.9:1.0 can be

Reflective materials for optical semiconductors

In addition, the present invention provides a reflective material for an optical semiconductor comprising a cured product prepared by curing the optical polysiloxane composition as described above.

The shape of the cured product is not particularly limited, and for example, may be in the form of a sheet, film, convex lens, concave lens, Fresnel lens, truncated cone, or quadrangular pyramid platform.

In addition, the cured product may be handled alone, or it may be handled in a state in which it covers, seals, or adheres to an optical semiconductor element or the like.

The cured product may have a hardness of 85 ShoreA or more, and if the cured product has a hardness of less than 85 ShoreA, burs are likely to occur when cutting the molded material, thereby reducing workability.

In addition, the cured product may have an average thickness of 35 to 50 μm. When the average thickness of the cured product is within the above range, the transmittance for visible light of 450 nm is 3% or less, and thus excellent reflectance of visible light may be exhibited.

The cured product has a high visible light reflectance, excellent hardness, less burr during cutting, and excellent heat resistance, so it is very suitable as a reflective material for optical semiconductors.

The use of the reflective material for the optical semiconductor is not particularly limited, and may be, for example, a backlight module for a liquid crystal display, a flash module for a mobile phone, and a lighting module for a vehicle.

[Example]

Hereinafter, examples and the like will be described in detail to help the understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art to which the present invention pertains.

Examples 1 to 6 and Comparative Examples 1 to 10. Preparation of optical polysiloxane composition

By mixing the components in the composition shown in Tables 1 and 2, an optical polysiloxane composition was prepared.

Ingredients (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 A-1 70 15 A-2 30 15 10 15 A-3 70 60 15 A-4 A-5 A-6 A-7 B-1 20 15 70 B-2 10 10 15 30 B-3 60 70 B-4 B-5 B-6 B-7 A+B 100 100 100 100 100 100 C 0.015 0.015 0.015 0.015 0.015 0.015 D 75 165 65 75 165 65 E-1 2 2 2 2 2 2 E-2 0.1 0.1 0.1 0.1 0.1 0.1

Ingredients (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 A-1 15 15 15 15 70 70 A-2 15 15 15 15 A-3 A-4 70 A-5 70 A-6 70 A-7 70 B-1 20 20 20 20 20 20 B-2 10 10 10 10 10 10 B-3 B-4 70 B-5 70 B-6 70 B-7 70 A+B 100 100 100 100 100 100 100 100 100 100 C 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 D 75 65 65 65 75 65 65 65 55 180 E-1 2 2 2 2 2 2 2 2 2 2 E-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Manufacturers and product names, or material names, etc. of each component used in Comparative Examples and Examples are shown in Table 3. In this case, Vi is a vinyl group, Me is a methyl group, and Ph is a phenyl group.

ingredient note A-1 (ViMe ₂ SiO _0.5 ) _0.25 (Me ₃ SiO _0.5 ) _0.1 (PhMeOS0) _0.2 (PhSiO _1.5 ) _0.45
(Viscosity at 25°C: 2,500 mPa s, vinyl group content: 2.08 mmol/g, phenyl group content: 34.21 mol%) A-2 3-[(Dimethylvinylsilyl)oxy]-1,1,5,5,-tetramethyl-3-phenyltrisiloxane
(Viscosity at 25°C: 10 mPa s, vinyl group content: 7.34 mmol/g, phenyl group content: 10.0 mol%) A-3 (ViMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.1 (PhSiO _1.5 ) _0.35 (MeSiO _1.5 ) _0.3
(Viscosity at 25°C: 15,500 mPa s, vinyl group content: 2.41 mmol/g, phenyl group content: 28.13 mol%) A-4 (ViMe ₂ SiO _0.5 ) _0.1 (Me ₃ SiO _0.5 ) _0.25 (PhMeOS0) _0.2 (PhSiO _1.5 ) _0.45
(Viscosity at 25°C: 1,800 mPa s, vinyl group content: 0.85 mmol/g, phenyl group content: 34.21 mol%) A-5 (ViMe ₂ SiO _0.5 ) _0.2 (PhMeOS0) _0.3 (PhSiO _1.5 ) _0.2 (MeSiO _1.5 ) _0.3
(Viscosity at 25°C: 7,300 mPa s, vinyl group content: 1.81 mmol/g, phenyl group content: 29.41 mol%) A-6 (ViMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.05 (PhSiO _1.5 ) _0.5 (MeSiO _1.5 ) _0.2
(Viscosity at 25°C: 35,500 mPa s, vinyl group content: 2.30 mmol/g, phenyl group content: 35.48 mol%) A-7 (ViMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.25 (PhSiO _1.5 ) _0.5
(Viscosity at 25°C: 6,500 mPa s, vinyl group content: 1.98 mmol/g, phenyl group content: 42.86 mol%) B-1 (HMe ₂ SiO _0.5 ) _0.3 (PhMeOS0) _0.22 (PhSiO _1.5 ) _0.48
(Viscosity at 25°C: 5,000 mPa s, SiH content: 2.59 mmol/g, phenyl group content: 38.46 mol%) B-2 3-[(Dimethylsilyl)oxy]-1,1,5,5,-tetramethyl-3-phenyltrisiloxane
(Viscosity at 25°C: 10 mPa s, SiH content: 9.07 mmol/g, phenyl group content: 10.0 mol%) B-3 (HMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.4 (PhSiO _1.5 ) _0.35
(Viscosity at 25°C: 13,500 mPa s, SiH content: 2.03 mmol/g, phenyl group content: 39.47 mol%) B-4 (HMe ₂ SiO _0.5 ) _0.1 (Me ₃ SiO _0.5 ) _0.25 (PhMeOS0) _0.2 (PhSiO _1.5 ) _0.45
(Viscosity at 25°C: 4,800 mPa·s, SiH content: 0.87 mmol/g, phenyl group content: 34.21 mol%) B-5 (HMe ₂ SiO _0.5 ) _0.2 (PhMeOS0) _0.3 (PhSiO _1.5 ) _0.2 (MeSiO _1.5 ) _0.3
(Viscosity at 25°C: 7,400 mPa s, SiH content: 1.90 mmol/g, phenyl group content: 29.41 mol%) B-6 (HMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.15 (PhSiO _1.5 ) _0.4 (MeSiO _1.5 ) _0.2
(Viscosity at 25°C: 22,000 mPa s, SiH content: 2.39 mmol/g, phenyl group content: 33.33 mol%) B-7 (ViMe ₂ SiO _0.5 ) _0.25 (PhMeOS0) _0.25 (PhSiO _1.5 ) _0.5
(Viscosity at 25°C: 5,800 mPa·s, SiH content: 1.98 mmol/g, phenyl group content: 42.86 mol%) C Platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (platinum content: 1% by weight) D A catalyst surface-treated with TiO ₂ having an average particle diameter of 0.25 μm with Al ₂ O ₃ , ZrO ₂ and trimethylolpropane (TMP) E-1 (3-Glycidoxypropyl) trimethoxy silane E-2 1-ethynyl-1-cyclohexanol

Experimental Example: Characteristic Evaluation

The optical polysiloxane compositions of Examples and Comparative Examples and the physical properties of the cured product prepared therefrom were measured in the following manner, and the results are shown in Table 4.

(1) Viscosity and Thixotoxin Index

Anton Paar's rheometer (Rheometer, model name: MCR301) was used to measure the viscosity of the composition at a shear rate of 1/s at 25°C, or at 10/s. Thereafter, the Chixo index was calculated by the following formula.

Thixox index = (viscosity at shear rate 1/s)/(viscosity at shear rate 10/s)

(2) Hardness (Shore A)

The composition was put into a mold and cured at 150° C. for 2 hours to prepare a 6 mm-thick specimen, and then the hardness at 25° C. was measured with a Shore A-type durometer.

(3) Reflectance (%)

After degassing the composition, a coating film having a thickness of 250 μm was formed using a square applicator, and cured at 150° C. for 2 hours to prepare a cured product.

Thereafter, the reflectance of the cured product with respect to visible light was measured using a UV-Vis Spectrometer (model name: Lambda 950) manufactured by Perkin Elmer. As a base, a barium sulfate standard specimen provided by a measurement equipment manufacturer was used.

(4) Dispensing workability

After setting the composition to 0.3 mg using a piezoelectric 200 μm Nozzle robot dispenser of Vermes, the coefficient of variation (coef.var) for 100 sets of values is 0.5 or less with the cumulative amount of 20 discharges as one set. If it was more than 0.5, it was evaluated as PASS, and if it was more than 0.5, it was evaluated as FAIL.

(5) thermal shock

After coating the composition to be 50mmX50mX0.1mm (width x length x height) using an applicator on a glass specimen having a thickness of 6 mm, curing at 150 ° C. for 2 hours is evaluated for each composition (coating layer thickness: 100 μm) were prepared in 24 pieces.

Heating the prepared evaluation specimen from -25°C to 125°C or cooling from 125°C to -25°C using a thermal shock tester was set as 1 cycle, and 1000 cycles were treated at intervals of 30 minutes with a residence time. Afterwards, evaluation was evaluated as PASS if there was no peeling or cracking on the surface of the evaluation specimen, and FAIL if peeling or cracking occurred in one or more specimens.

(6) Heat-resistant reflectance (%)

The specimen used for measuring the reflectance of item (3) was stored in an oven at 200° C. for 1 week, cooled to room temperature, and the reflectance (heat resistance) to visible light using Perkin Elmer’s UV-Vis Spectrometer (model name: Lambda 950) reflectance) was measured. As a base, a barium sulfate standard specimen provided by a measurement equipment manufacturer was used.

(7) Heat-resistant crack

By observing the appearance of the specimen of item (6), the occurrence of cracks was visually confirmed. If there were no cracks, it was indicated as good, and if cracks occurred, it was indicated as crack.

Viscosity at 25°C (mPa·s) thixo index Hardness
(Shore A) reflectivity
(%) Dispensing workability thermal shock Heat-resistant reflectance (%) heat-resistant crack Example 1 3,000 1.5 90 98.7 PASS PASS 91.3 Good Example 2 2,200 1.8 93 99.2 PASS PASS 92.1 Good Example 3 5,800 1.4 95 97.8 PASS PASS 94.5 Good Example 4 3,100 1.6 88 98.3 PASS PASS 92.1 Good Example 5 4,500 1.8 90 98.8 PASS PASS 90.5 Good Example 6 2,800 1.7 95 98.1 PASS PASS 92.6 Good Comparative Example 1 2,400 1.2 64 98.4 PASS Fail 90.9 Good Comparative Example 2 3,200 1.3 97 97.7 PASS PASS 90.7 crack Comparative Example 3 5,500 3.8 93 97.3 Fail PASS 91.5 Good Comparative Example 4 4,200 1.6 91 95.3 PASS PASS 85.3 Good Comparative Example 5 4,300 1.5 43 98.7 PASS Fail 92.1 Good Comparative Example 6 3,300 1.4 88 97.5 PASS PASS 91.4 crack Comparative Example 7 5,300 4.2 92 97.2 Fail PASS 90.8 Good Comparative Example 8 3,300 1.6 91 96.6 PASS PASS 83.1 Good Comparative Example 9 1,800 1.2 88 93.2 PASS PASS 84.8 Good Comparative Example 10 28,400 2.3 93 98.9 Fail PASS 92.2 Good

As shown in Table 4, it can be seen that the polysiloxane compositions of Examples 1 to 6 are liquids with a low viscosity of 10,000 mPa·s or less at 25° C., a thixotropic index of 2.0 or less, and excellent dispensing workability. there was. In addition, the cured products prepared from the polysiloxane compositions of Examples 1 to 6 were excellent in hardness, visible light reflectance, thermal shock property, and heat resistance (heat reflectance and heat crack resistance).

On the other hand, the cured products of Comparative Example 1 containing a small amount of A-4 containing an alkenyl group and Comparative Example 5 containing a small amount of B-4 containing SiH lacked hardness and thermal shock properties.

In addition, the cured product of Comparative Example 2 containing A-5 having a/(b+c) of 0.25 and Comparative Example 6 containing B-5 having l/(m+n) of 0.25 lacked heat resistance and thus heat resistance. A crack has occurred.

The composition of Comparative Example 3 comprising A-6 having a viscosity of 35,000 mPa·s at 25° C. and Comparative Example 7 comprising B-6 having a viscosity of 22,000 mPa·s at 25° C. has a large thixotropic index, so dispensing workability was lacking.

In addition, the cured product of Comparative Example 4 containing A-7 having a phenyl group content of 42.86 mol% and Comparative Example 8 containing B-7 having a phenyl group content of 42.86 mol% had a reflectance of less than 97% for visible light. and the heat resistance reflectance was also insufficient at 89% or less.

The cured product of Comparative Example 9 containing a small amount of titanium dioxide, which is a white pigment, lacked a reflectance of 93.2% for visible light, and also lacked a reflectance of heat resistance of 84.8%.

In addition, the composition of Comparative Example 10 containing an excessive amount of titanium dioxide as a white pigment had a high viscosity at 25°C of 28,400 mPa·s and a high thixotropic index of 2.3, so dispensing workability was very insufficient.

Claims (6)

an organopolysiloxane, an organohydrogenpolysiloxane, a white pigment and a reaction catalyst;
The organopolysiloxane contains at least three alkenyl groups in one molecule, has a viscosity at 25°C of 20 Pa·s or less, the total number of moles of the first divalent repeating unit and the trivalent second repeating unit, and the monovalent agent 3 The ratio of moles of repeating units is 1:0.3 to 3.0,
The organohydrogenpolysiloxane contains at least three hydrogen groups (SiH) bonded to silicon in one molecule, and the viscosity at 25°C is 20 Pa·s or less, an optical polysiloxane composition. The method according to claim 1,
The organopolysiloxane is an optical polysiloxane composition represented by the following Chemical Formula 1:
[Formula 1]
[R ¹ ₃ SiO _1/2 ] _a [R ² (R ³ O)SiO] _b [R ⁴ SiO _3/2 ] _c
In Formula 1,
A plurality of R ¹ is each independently a substituted or unsubstituted C _2-10 alkenyl group, or a C _1-10 alkyl group, at least one R ¹ is an alkenyl group,
R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C _1-10 alkyl group, C _6-14 aryl group, or hydrogen, and at least one of R ² , R ³ and R ⁴ is an aryl group,
a/(b+c) is 0.3 to 3.0,
a+b+c equals 1. The method according to claim 1,
The organohydrogenpolysiloxane is an optical polysiloxane composition represented by the following Chemical Formula 2:
[Formula 2]
[HR ¹⁰ ₂ SiO _1/2 ] _l [R ¹¹ (R ¹² O)SiO] _m [R ¹³ SiO _3/2 ] _n
In Formula 2,
R ¹⁰ and R ¹² are each independently a substituted or unsubstituted C _1-10 alkyl group, or hydrogen,
R ¹¹ is a substituted or unsubstituted C _6-14 aryl group,
R ¹³ is each independently a substituted or unsubstituted C _1-10 alkyl group, or a C _6-14 aryl group,
l/(m+n) is 0.3 to 3,
l+m+n is 1. The method according to claim 1,
The organopolysiloxane contains 1.5 mmol/g or more of an alkenyl group,
The organohydrogenpolysiloxane has a content of hydrogen groups bonded to silicon of 1.5 mmol/g or more , an optical polysiloxane composition. The method according to claim 1,
The organopolysiloxane comprises an aryl group in an amount of 40 mol% or less based on the total organic groups, an optical polysiloxane composition. A reflective material for an optical semiconductor comprising a cured product prepared by curing the optical polysiloxane composition of any one of claims 1 to 5.