KR101695316B1 - Curable organopolysiloxane composition and optical semiconductor device using the same - Google Patents
Curable organopolysiloxane composition and optical semiconductor device using the same Download PDFInfo
- Publication number
- KR101695316B1 KR101695316B1 KR1020150114675A KR20150114675A KR101695316B1 KR 101695316 B1 KR101695316 B1 KR 101695316B1 KR 1020150114675 A KR1020150114675 A KR 1020150114675A KR 20150114675 A KR20150114675 A KR 20150114675A KR 101695316 B1 KR101695316 B1 KR 101695316B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- substituted
- sio
- composition
- alkyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- H01L51/5246—
Abstract
Description
The present invention relates to a curable organopolysiloxane composition and an optical semiconductor device using the curable organopolysiloxane composition. More particularly, the present invention relates to a high heat-resistant organopolysiloxane composition having low hardness and low tackiness and free from cracking even when left at high temperature for a long time, To a semiconductor device.
BACKGROUND ART Light emitting diodes (hereinafter referred to as "LEDs") are characterized by small size, light weight, energy saving, and the like. In recent years, white LEDs, which are a combination of blue LEDs and phosphors, have been used as backlight light sources for PCs, TVs, Many are being adopted.
The LED light emitting device is generally several millimeters or less in size. After mounting a single or a plurality of such devices on various substrates, the LED light emitting device is used as a light source by using resin as an encapsulant for protection and light control.
At the beginning of development of LED in the past, epoxy resin was used as the encapsulating resin. Nowadays, more and more solid silicone resin is dominant as the demand for higher output and reliability of LED is increased.
As a method of forming a lens on an LED, there has been a method of performing only an LED encapsulation process using a resin having a low viscosity by a method such as potting and then bonding a lens made in another process. In this case, However, according to the recent trend of high output LED packages, more amount of light and heat are emitted, which may cause problems such as peeling of the lens, discoloration of the adhesive and primer layer . In addition, cracks tend to occur during high-temperature use for a long time, and organopolysiloxane hardeners having low hardness are advantageous in order to minimize the cracking. However, in the case of organopolysiloxanes having low hardness, there are many problems in the manufacturing process due to high tackiness.
The present invention provides a curable organopolysiloxane composition having low hardness that does not cause cracking even when used at high temperature for a long period of time, but is less tacky due to low hardness.
A curable organopolysiloxane composition according to one aspect of the present invention comprises:
An alkenyl group-containing organopolysiloxane represented by the following formula (1);
A hydrogen-containing organopolysiloxane of the following formula (2);
A compound of Formula 3; And
And a hydrosilylation catalyst.
[Chemical Formula 1]
(R 1 R 2 R 3 SiO 1/2 ) M (R 4 R 5 SiO 2/2 ) D (R 6 SiO 3/2 ) T (SiO 4/2 ) Q
(Where M, D, T, and Q are respectively greater than or equal to 0 and less than 1 and M + D + T + Q = 1 , R 2 , R 3 , R 4 , R 5 , R 6 is a substituted or unsubstituted monovalent hydrocarbon group having the same or different aliphatic saturated groups and at least one of the hydrocarbon groups has one or two or more unsaturated groups at the terminal or side chain of the molecule.
(2)
(R 7 R 8 R 9 SiO 1/2 ) m ( R 10 R 11 SiO 2/2 ) d (R 12 SiO 3/2 ) t (SiO 4/2 ) q
(At this time, m, d, t, q are each greater than or equal to 0 and smaller than 1, and m + d + t + q = 1, R 7, R 8, R 9, R 10, R 11, R 12 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond or the like and at least one of the hydrocarbon groups contains one or more active hydrogen atoms in the terminal or side chain of the molecule .)
(3)
Wherein each of X 1 and X 2 is independently hydrogen, -CH (O), -CN, isocyanate, thioisocyanate, SO 3 H and its salts and esters, NR 13 R 14 , OR 15, -C (O) NR 16 R 17, -CR 18 (O), -C (O) OC (O) R 19, -C (O) NR 20 COR 21, -OC (O) R 22, -OR 23 , substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl and substituted and unsubstituted aryl; R 13 , R 14 , R 15 , R 16, R 17, R 18, R 19, R 20, R 21 and R 22 are each independently selected from hydrogen, alkyl, aryl, the group consisting of substituted alkyl or substituted aryl group and; R 23 is alkyl, aryl, Substituted alkyl and substituted aryl; Y is selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, and substituted and unsubstituted aryl .
In this case, the M may be 0.01-0.3, the D may be 0.3-0.6, the T may be 0-0.3, and the Q may be 0.4-0.8. The Q and D may be Q / D = 0.3-0.9 Lt; / RTI >
The above m may be in the range of 0.01 to 0.2, the d may be in the range of 0.3 to 0.9, the t may be in the range of 0 to 0.3, and the q may be in the range of 0.1 to 0.8.
In addition, the compound of Formula 3 may be? -Methylstyrene (also referred to as isopropenylbenzene), styrene, or divinylbenzene.
The hydrosilylation catalyst may be one or more catalysts selected from the group consisting of platinum catalysts, rhodium catalysts and palladium catalysts, although not limited thereto, And 0.1 to 100 ppm based on the organopolysiloxane composition.
Also, the curable organopolysiloxane composition of the present invention comprises 1 to 80 parts by weight of an alkenyl group-containing organopolysiloxane, 1 to 80 parts by weight of the hydrogen-containing organopolysiloxane, and 1 to 20 parts by weight of the compound of the formula .
Further, the curable organopolysiloxane composition of the present invention may further comprise an adhesion promoter represented by the following formula (4).
[Chemical Formula 4]
R 24 a SiO (4-a) / 2
(At this time, R 24 is C 1 - aryl of C 10 - C 10 alkyl, C 5 of the - C 8 cycloalkyl group, C 6 of the - C 10 aryl group, C 1 - C 6 a C 6 substituted with an alkyl group Group, a C 1 - C 6 alkyl group substituted with 1 to 3 halogens, a C 2 - C 8 alkenyl group, and an epoxy - containing organic group, at least two alkenyl groups in one molecule, Containing organic group, and a is a number satisfying the condition of 1.0? A? 4.0.
In addition, the curable organopolysiloxane composition of the present invention can be obtained from the group consisting of a reaction retarder, an inorganic filler, a silicone rubber powder, a resin powder, an antiseptic, an antioxidant, a radical scavenger, a light stabilizer, a dye, And may further comprise one or more components selected.
Another aspect of the present invention provides an optical semiconductor device in which the curable organopolysiloxane composition according to one aspect of the present invention described above is used as an encapsulant of a light emitting device.
The curable organopolysiloxane composition of the present invention has a low hardness that does not cause cracks even when used at a long time at a high temperature, but has a low stickiness due to low hardness, and is excellent in adhesiveness for optical semiconductor devices and parts, coating agents, sealants, Film or the like.
Hardenability Organopolysiloxane Composition
One. Alkenyl group contain Organopolysiloxane
The structure and common name of general polyorganosiloxane are as follows.
(R 1 3 SiO 1/2 ) a Units: M units
(R 2 2 SiO 2/2 ) b units: D units
(R 1 3 SiO 3/2) c unit: T unit
(SiO 4/2) d units: Q units
In this specification, the names of M units, D units, T units, and Q units used in the related art will be used.
The alkenyl group-containing organopolysiloxane used for preparing the curable organopolysiloxane composition of the present invention has a structure represented by the following formula (1).
[Chemical Formula 1]
(R 1 R 2 R 3 SiO 1/2 ) M (R 4 R 5 SiO 2/2 ) D (R 6 SiO 3/2 ) T (SiO 4/2 ) Q
In this case, M, D, T and Q are respectively greater than or equal to 0 and smaller than 1 and M + D + T + Q = 1. More specifically, the M value is 0.01 to 0.3, the D value is 0.3 to 0.6, The T value may be in the range of 0 to 0.3, and the Q value may be in the range of 0.4 to 0.8.
The R 1 , R 2 , R 3 , R 4 , R 5 , R 6 is a substituted or unsubstituted monovalent hydrocarbon group having the same or different aliphatic saturated groups and at least one of the hydrocarbon groups has one or two or more unsaturated groups at the terminal or side chain of the molecule, It has a skeleton.
At this time, the ratio of the Q value to the D value, that is, the ratio of the Q unit to the D unit, may be in the range of Q / D = 0.3 - 0.9. Within the above range, viscosity and rigidity and hardness of cured material can be controlled in a wide range, and high transparency, adhesion reliability, and high durability to light and heat are obtained.
2. Hydrogen contain Organopolysiloxane Composition
The hydrogen-containing organopolysiloxane used in the preparation of the curable organopolysiloxane composition of the present invention has a structure represented by the following formula (2).
(2)
(R 7 R 8 R 9 SiO 1/2 ) m ( R 10 R 11 SiO 2/2 ) d (R 12 SiO 3/2 ) t (SiO 4/2 ) q
M, d, t and q are respectively greater than or equal to 0 and less than 1 and m + d + t + q = 1, and R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond or different from each other and at least one of the hydrocarbon groups contains one or more active hydrogen atoms at the terminal or side chain of the molecule.
At this time, the hydrogen-containing organopolysiloxane has a preferred m value of 0.01 to 0.2, a d value of 0.3 to 0.9, a t value of 0 to 0.3 and a q value of 0.1 to 0.8. However, the MDTQ resin MT resins, DTQ resins, DTQ resins, MTQ resins and DQ resins, MQ resins, DTQ resins, MTQ resins, MDQ resins, etc., as well as bonds containing one or more active hydrogen atoms in place of alkenyl groups Combinations containing one or more active hydrogens are also possible. Here, M, D, T, and Q are the above-mentioned common name units.
On the other hand, when the hydrocarbon group of the functional groups R 1 to R 12 in the above-mentioned formulas (1) and (2) is an alkyl group, an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable. , Fluorophenyl group,? -Naphthyl group,? -Anthranyl group and the like are suitable. In the case of an alkenyl group, a C2-6 alkenyl group such as vinyl group, aryl group,? -Butenyl group,? -Butenyl group and the like is suitable.
When a substituent having an epoxy group, an oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group or a cyano group is contained, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms Suitable.
It is particularly preferable that the above-mentioned substituent is substituted for an alkyl group having 1 to 6 carbon atoms and having a cycloalkyl group having 3 to 6 carbon atoms.
The epoxy group may be substituted with at least one of a glycidyl group, a glycidoxy ethyl group, an? -Glycidoxypropyl group,? -Glycidoxypropyl group,? -Glycidoxypropyl group,? -Glycidoxybutyl group, (3,4-epoxycyclohexyl) ethyl group,? - (3,4-epoxycyclohexyl) ethyl group,? - 4-epoxycyclohexyl) propyl group, and? - (3,4-epoxycyclohexyl) butyl group.
Examples of the substituent having an oxetanyl group include (3-ethyloxetan-3-yl) propyl group and the like, and examples of the substituent having an acryloyloxy group include an acryloyloxymethyl group, a? -acryloyloxypropyl group, a? -acryloyloxypropyl group, and the like.
Examples of the substituent having a methacryloyloxy group include methacryloyloxymethyl,? -Methacryloyloxyethyl,? -Methacryloyloxypropyl,? -Methacryloyloxypropyl and the like. .
Examples of the substituent having a mercapto group include a mercaptomethyl group, a? -Mercaptoethyl group, a? -Mercaptopropyl group, and a? -Mercaptopropyl group. Examples of the substituent having an amino group include an aminomethyl group, Examples of the substituent having a cyano group include a cyano group, a cyano group, a cyano group, a cyano group, a cyano group, Examples of the substituent having an isocyanato group include an isocyanomethyl group, a? -Isocyanatoethyl group, a? -Isocyanopropyl group, a? -Cyanopropyl group, a? -Cyclopropyl group, -Isocyanopropyl group and the like.
3. Organic compound additives
As the non-silicon organic compound to be added in order to improve heat resistance and to minimize tackiness of the curable organopolysiloxane composition of the present invention, it is possible to use a structure represented by the following formula (3).
(3)
Wherein X 1 and X 2 are each independently selected from the group consisting of hydrogen, -CH (O), -CN, isocyanate, thioisocyanate, SO 3 H and salts and esters thereof, NR 13 R 14 , halogen, -C 15, -C (O) NR 16 R 17, -CR 18 (O), -C (O) OC (O) R 19, -C (O) NR 20 COR 21, -OC (O) R 22, - OR 23 , substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, and substituted and unsubstituted aryl; Wherein each of R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 is independently selected from the group consisting of hydrogen, alkyl, aryl, substituted alkyl or substituted aryl Selected; R < 23 > is selected from the group consisting of alkyl, aryl, substituted alkyl or substituted aryl; Y is selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, and substituted and unsubstituted aryl.
Methylstyrene in which X 1 and X 2 are each hydrogen and Y is a methyl group, or X 1 , X 2 and Y are both hydrogen, one of X 1 and X 2 is a vinyl group, And divinylbenzene in which Y is hydrogen.
4. Hydrosilylation catalyst
The catalyst for hydrosilylation reaction contained in the curable organopolysiloxane composition of the present invention is not particularly limited, and for example, a catalyst in the form of a platinum group element or a platinum group element compound can be used. For example, a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst may be used.
Examples of the platinum-based catalyst include platinum fine powders, platinum black, chloroplatinic acid, alcohol modified products of chloroplatinic acid, chloroplatinic acid / diolefin complexes, platinum / olefin complexes, platinum-carbonyl complexes such as platinum bis (acetoacetate) And platinum / alkenylsiloxane complexes (e.g., chloroplatinic acid / divinyltetramethyldisiloxane complex and chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complex), chloroplatinic acid / alkenylsiloxane complexes (For example, platinum / divinyltetramethyldisiloxane complex and platinum / tetravinyltetramethylcyclotetrasiloxane complex), complexes of chloroplatinic acid and acetylene alcohol, and the like can be used. More specifically, platinum / alkenylsiloxane complexes can be used.
Examples of the alkenylsiloxane for the complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl Cyclotetrasiloxane, an alkenylsiloxane oligomer obtained by replacing the methyl moiety of the foregoing alkenylsiloxane with, for example, ethyl, phenyl, and the like, and vinyl of the foregoing alkenylsiloxane, such as allyl or hexenyl And the like can be used. Among these, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane can be used in view of producing a platinum / alkenylsiloxane complex having excellent stability.
The platinum-siloxane complex may be contained in the composition in a state dissolved in an organic solvent such as xylene.
The catalyst for the hydrosilylation reaction is compounded in such an amount as to accelerate the curing of the composition of the present invention, but the amount thereof is not particularly limited. The catalyst for hydrosilylation reaction may be contained in an amount of 0.1 to 100 ppm, more specifically 0.5 to 30 ppm, in the total composition. If the amount is too small, the curing speed during curing may be slow or may not be hardened at all, and if it is contained too much, problems such as coloring may occur, resulting in functional problems.
5. Adhesion promoter
The adhesion promoter that can be further included in the curable organopolysiloxane composition of the present invention is represented by the following formula (4).
[Chemical Formula 4]
R 24 a SiO (4-a) / 2
R 24 represents an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, decyl group or octadecyl group], C 5 - C 8 cycloalkyl groups [e.g., a cyclopentyl group or cyclohexyl group], C 6 - aryl group of C 10 - for example, a phenyl group, a tolyl group, a xylyl group or a naphthyl group , A C 6 - C 10 aryl group substituted by a C 1 - C 6 alkyl group (for example, a benzyl group, a phenethyl group or a 3 - phenylpropyl group), a C 1 - C 6 group substituted by 1 to 3 halogens alkyl [e. g., 3,3, 3-propyl or 3-chloro-propyl group trifluoromethyl], C 2 - C 8 alkenyl group [for example, vinyl group, allyl group, butenyl group, pentenyl group or hexenyl group; And epoxy-containing organic groups such as 2- glycidoxypropyl, 4-glycidoxybutyl, or similar glycidoxyalkyl groups, 2- (3,4-epoxycyclohexyl) 4-epoxy cycle 4-oxiranylbutyl, 8-oxiranyloctyl or oxiranylalkyl group], at least two alkenyl groups in one molecule and at least one epoxy group in the molecule Containing organic group, and a is a number satisfying the condition of 1.0? A? 4.0.
The curable organopolysiloxane composition containing the adhesion promoter is not particularly limited in its use, but can be particularly useful for sealing semiconductor optical device elements or for optical lenses.
6. Reaction Retarder And other additives
The curable organopolysiloxane composition of the present invention may contain a small amount of a reaction retarder as needed. For example, 2-phenyl-3-butyn-2-ol may be used as the reaction retarder. The content of the reaction retarder may be 0.008% by weight or less based on the total weight of the composition. The lower limit value of the reaction retarder may be, for example, 0.0001% by weight. In particular, when the reaction retarder is contained too much, the curing rate may be slowed down.
In addition, the composition of the present invention may contain inorganic fillers (e.g., silica, glass, alumina, zinc oxide, etc.) as long as they do not impair the object of the present invention; Silicone rubber powder; Resin powder (e.g., silicone resin, polymethacrylate resin, etc.); Heat resisting agent; Antioxidants; Radical scavenger; Light stabilizer; dyes; Pigments; And one or more additional optional components selected from flame retardant additives and the like.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not to be construed as limiting the scope of the present invention. It will be self-evident.
The physical properties before and after curing of the curable organopolysiloxane composition were measured by the method shown below.
[Viscosity of curable organopolysiloxane composition]
The viscosity was measured at 25 DEG C using a Rheometer (model name: MCR301) manufactured by Anton Paar.
[Refractive index]
The refractive index was measured at 259C using an Abbe refractometer at 589nm.
[Hardness]
The curable organopolysiloxane composition was cured in a mold capable of forming a sheet having a thickness of 2 mm at 150 캜 for 3 hours, and then the three layers were stacked and measured with a Shore D type hardness meter.
[Tensile strength and elongation]
The cured product in the form of a dumbell No. 3 test piece according to JIS K 6251 was prepared by compression molding the curable organopolysiloxane composition at 150 캜 for 3 hours. The tensile strength of the obtained cured product was measured according to JIS K 6251.
[Tackiness]
The slip resistance of the organopolysiloxane cured product was compared by hand rubbing.
The case where no stickiness was observed was marked as "? &Quot;, and a case where the finger slid slightly on the sample surface due to little tackiness was evaluated as " ", a case where there was a slight grip feeling as " DELTA ", a case where there was a feeling of sticky sticking Quot; x ".
[APHA growth rate]
The organopolysiloxane cured product was stored in an oven at 200 ° C for 1000 hours, and the degree of discoloration (APHA color) before and after storage was measured to calculate the increase rate. The lower the APHA growth rate value, the better the heat resistance.
Growth rate (%) = (APHA color value after storage) / (APHA color value before storage) × 100 (%)
[Heat loss]
The organopolysiloxane cured product was stored in an oven at 200 ° C for 1000 hours, and the weight was measured before and after storage to calculate the weight reduction rate. The smaller the heating weight loss value, the better the heat resistance.
Heat loss (%) = {(Before storage) - (After storage)} / (Before storage) ⅹ100 (%)
Example
Example 1
100 g of a vinyl group-containing MQ resin (vinyl equivalent: 0.74 mmol / g) and 100 g of straight chain dimethylpolysiloxane (hereinafter referred to as VP) substituted with vinyl at both terminals were mixed using a planetary mixer to obtain a master batch ).
(1) Preparation of composition A
15 g of pre-made MB1, 28 g of VP, 0.03 g of platinum complex, 1 g of organopolysiloxane (hereinafter referred to as VHEO) in which both terminals were substituted with a hydroxyl group and part of the side chain was substituted with vinyl and? ) Was mixed with an oil-based mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
5.4 g of a hydrogen-containing organopolysiloxane (H equivalent 4.3 mmol / g, hereinafter referred to as MHBP43) and 8.7 g of VP, as a retarder, 0.01 g of 1-ethenyl-1-cyclohexanol, Was mixed with an oil-based mixer for 1 hour at room temperature to obtain a curable organopolysiloxane composition B.
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) A polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A of 35.
Example 2
(1) Preparation of composition A
40 g of MB1, 5 g of VP, 0.03 g of platinum complex, 1 g of VHEO and 2 g of? -Methylstyrene were mixed at room temperature for 1 hour in an oil-based mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
7 g of MHBP43 and 4 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 0.7 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A of 65.
Example 3
(1) Preparation of composition A
37 g of MB1 prepared in Example 1, 5 g of VP, 0.03 g of platinum complex, 1 g of VHEO and 1 g of? -Methylstyrene were mixed at room temperature for 1 hour in an oil mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
7 g of MHBP43 and 4 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 0.7 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A of 62.
Example 4
(1) Preparation of composition A
37 g of MB1 prepared in Example 1, 5 g of VP, 0.03 g of platinum complex, 1 g of VHEO and 2 g of styrene were mixed at room temperature for 1 hour in an oil-based mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
7 g of MHBP43 and 4 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 0.7 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A 61.
Example 5
(1) Preparation of composition A
37 g of MB1 prepared in Example 1, 5 g of VP, 0.03 g of platinum complex, 1 g of VHEO and 2 g of divinylbenzene were mixed at room temperature for 1 hour in an oil mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
7 g of MHBP43 and 4 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 0.7 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A 68.
Comparative Example 1
(1) Preparation of composition A
44 g of MB1, 34 g of VP, 0.05 g of platinum complex, and 1 g of VHEO were mixed at room temperature for 1 hour in an oil-based mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
5 g of MHBP73 and 14 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 1.2 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
40 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed with a rotary mixer (ARE-310, Shinki Co., Ltd.) for 1 minute and defoamed under vacuum to obtain a curable organo A polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A of 35.
Comparative Example 2
(1) Preparation of composition A
60 g of MB1 prepared in Example 1, 14 g of VP, 0.05 g of platinum complex and 1 g of VHEO were mixed at room temperature for 1 hour in an oil-based mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
8 g of MHBP73 and 16 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder, and 1.2 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel in an oil-based mixer for 1 hour at room temperature to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A of 65.
Comparative Example 3
(1) Preparation of composition A
55 g of MB1 made in Example 1, 12 g of VP, 0.05 g of platinum complex, 1 g of VHEO and 0.5 g of? -Methylstyrene were mixed at room temperature for 1 hour in an oil mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
6 g of MHBP73 and 16 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 1.2 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A of 62.
Comparative Example 4
(1) Preparation of composition A
55 g of MB1 made in Example 1, 12 g of VP, 0.05 g of platinum complex, 1 g of VHEO and 10 g of? -Methyl styrene were mixed at room temperature for 1 hour in an oil mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
15 g of MHBP73 and 16 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 1.2 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A 52. In the case of Comparative Example 4, a phenomenon that the white turbidity became very deep after curing occurred.
Comparative Example 5
(1) Preparation of composition A
37 g of MB1 prepared in Example 1, 5 g of VP, 0.03 g of platinum complex, 1 g of VHEO and 2 g of? -Methylstyrene dimer were mixed at room temperature for 1 hour in an oil mixer to obtain a curable organopolysiloxane composition A.
(2) Preparation of composition B
7 g of MHBP43 and 4 g of VP, 0.01 g of 1-ethenyl-1-cyclohexanol as a retarder and 0.7 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel with an oil mixer at room temperature for 1 hour to obtain a curable organopolysiloxane composition B .
(3) Mixing of the compositions A and B
30 parts by weight of the resin mixture A and 10 parts by weight of B were weighed into a vessel and spun using a spatula. The mixture was stirred and defoamed for 1 minute by a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.) Polysiloxane composition was obtained and thermally cured to obtain an organopolysiloxane curing composition having a hardness shore A 68.
The tackiness and heat resistance of the example 1-5 and the comparative example 1-5 were measured and the results shown in Table 1 were obtained.
In the above measurement results, in Comparative Example 4, the content of? -Methylstyrene (compound of Formula 3) was too high to cause clouding after curing and was excluded from the APHA color and heat resistance test.
From the above measurement results, it can be seen that the curable organopolysiloxane composition (Examples) of the present invention is less sticky and has excellent heat resistance at lower hardness than conventional compositions (Comparative Examples). In particular, it was confirmed that the content of? -Methylstyrene (compound of Formula 3) exhibits excellent performance in the range of 1-10% of the total amount of the curable organopolysiloxane.
Claims (11)
A hydrogen-containing organopolysiloxane of the following formula (2);
A compound of Formula 3; And
A curable organopolysiloxane composition comprising a hydrosilylation catalyst:
[Chemical Formula 1]
(R 1 R 2 R 3 SiO 1/2 ) M (R 4 R 5 SiO 2/2 ) D (R 6 SiO 3/2 ) T (SiO 4/2 ) Q
(Where M, D, T, and Q are respectively greater than or equal to 0 and less than 1 and M + D + T + Q = 1 , R 2 , R 3 , R 4 , R 5 , R 6 is a substituted or unsubstituted monovalent hydrocarbon group having the same or different aliphatic saturated groups and at least one of the hydrocarbon groups has one or two or more unsaturated groups at the terminal or side chain of the molecule.
(2)
(R 7 R 8 R 9 SiO 1/2 ) m ( R 10 R 11 SiO 2/2 ) d (R 12 SiO 3/2 ) t (SiO 4/2 ) q
(At this time, m, d, t, q are each greater than or equal to 0 and smaller than 1, and m + d + t + q = 1, R 7, R 8, R 9, R 10, R 11, R 12 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond or the like and at least one of the hydrocarbon groups contains one or more active hydrogen atoms in the terminal or side chain of the molecule .)
(3)
Wherein each of X 1 and X 2 is independently hydrogen, -CH (O), -CN, isocyanate, thioisocyanate, SO 3 H and its salts and esters, NR 13 R 14 , OR 15, -C (O) NR 16 R 17, -CR 18 (O), -C (O) OC (O) R 19, -C (O) NR 20 COR 21, -OC (O) R 22, -OR 23 , substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl and substituted and unsubstituted aryl; R 13 , R 14 , R 15 , R 16, R 17, R 18, R 19, R 20, R 21 and R 22 are each independently selected from hydrogen, alkyl, aryl, the group consisting of substituted alkyl or substituted aryl group and; R 23 is alkyl, aryl, Substituted alkyl and substituted aryl; Y is selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, and substituted and unsubstituted aryl .
Wherein the M is 0.01-0.3, the D is 0.3-0.6, the T is 0-0.3, and the Q is 0.4-0.8. The curable organopolysiloxane composition of claim 1,
Wherein Q and D are in the range of Q / D = 0.3 - 0.9.
M is from 0.01 to 0.2, d is from 0.3 to 0.9, t is from 0 to 0.3, and q is from 0.1 to 0.8.
Wherein the compound of Formula 3 is? -Methylstyrene, styrene or divinylbenzene.
Wherein the hydrosilylation catalyst is at least one catalyst selected from the group consisting of platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
Wherein the hydrosilylation catalyst is included at 0.1 to 100 ppm based on the total organopolysiloxane composition.
1 to 80 parts by weight of the alkenyl group-containing organopolysiloxane, 1 to 80 parts by weight of the hydrogen-containing organopolysiloxane, and 1 to 20 parts by weight of the compound of the formula (3).
A curable organopolysiloxane composition, further comprising an adhesion promoter of formula (4): < EMI ID =
[Chemical Formula 4]
R 24 a SiO (4-a) / 2
(At this time, R 24 is C 1 - aryl of C 10 - C 10 alkyl, C 5 of the - C 8 cycloalkyl group, C 6 of the - C 10 aryl group, C 1 - C 6 a C 6 substituted with an alkyl group Group, a C 1 - C 6 alkyl group substituted with 1 to 3 halogens, a C 2 - C 8 alkenyl group, and an epoxy - containing organic group, at least two alkenyl groups in one molecule, Containing organic group, and a is a number satisfying the condition of 1.0? A? 4.0.
Which may further comprise at least one component selected from the group consisting of a thermosetting resin, a colorant, a colorant, a colorant, a colorant, a colorant, a colorant, a colorant, a colorant, Lt; RTI ID = 0.0 > organopolysiloxane composition. ≪ / RTI >
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150114675A KR101695316B1 (en) | 2015-08-13 | 2015-08-13 | Curable organopolysiloxane composition and optical semiconductor device using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150114675A KR101695316B1 (en) | 2015-08-13 | 2015-08-13 | Curable organopolysiloxane composition and optical semiconductor device using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR101695316B1 true KR101695316B1 (en) | 2017-01-11 |
Family
ID=57832737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150114675A KR101695316B1 (en) | 2015-08-13 | 2015-08-13 | Curable organopolysiloxane composition and optical semiconductor device using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101695316B1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200208032A1 (en) * | 2018-12-31 | 2020-07-02 | Samsung Sdi Co., Ltd. | Silicone-based adhesive protective film and optical member comprising the same |
| WO2020149578A1 (en) * | 2019-01-17 | 2020-07-23 | Dow Silicones Corporation | Antistatic silicone rubber composition |
| WO2020218879A1 (en) * | 2019-04-25 | 2020-10-29 | 삼성에스디아이 주식회사 | Silicone-based adhesive protection film and optical member comprising same |
| WO2020226461A1 (en) * | 2019-05-09 | 2020-11-12 | 삼성에스디아이 주식회사 | Silicone-based adhesive protection film and optical member comprising same |
| WO2021102073A1 (en) * | 2019-11-24 | 2021-05-27 | Dow Toray Co., Ltd. | Photocurable silicone composition and cured product thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03174713A (en) | 1989-12-04 | 1991-07-29 | Hitachi Ltd | Clean storage |
| JP2636948B2 (en) * | 1990-06-12 | 1997-08-06 | 信越化学工業株式会社 | Manufacturing method of high hardness silicone rubber |
| JP3924154B2 (en) | 2001-11-12 | 2007-06-06 | 東レ・ダウコーニング株式会社 | Additive for organic resin, curable organic resin composition containing the same, and cured product thereof |
| KR101278456B1 (en) | 2004-07-29 | 2013-07-01 | 다우 코닝 도레이 캄파니 리미티드 | Curable organopolysiloxane composition, method of curing thereof, semiconductor device, and adhesion promoter |
| KR101285145B1 (en) | 2006-05-11 | 2013-07-12 | 다우 코닝 도레이 캄파니 리미티드 | Adhesion-promoting agent, curable organopolysiloxane composition, and semiconductor device |
| KR20140038045A (en) | 2012-09-19 | 2014-03-28 | 주식회사 케이씨씨 | Heat curable silicone composition and the light emitting device using the same |
| JP2014062198A (en) * | 2012-09-21 | 2014-04-10 | Dow Corning Toray Co Ltd | Curable silicone composition, and semiconductor sealing material and optical semiconductor device using the same |
-
2015
- 2015-08-13 KR KR1020150114675A patent/KR101695316B1/en active IP Right Grant
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03174713A (en) | 1989-12-04 | 1991-07-29 | Hitachi Ltd | Clean storage |
| JP2636948B2 (en) * | 1990-06-12 | 1997-08-06 | 信越化学工業株式会社 | Manufacturing method of high hardness silicone rubber |
| JP3924154B2 (en) | 2001-11-12 | 2007-06-06 | 東レ・ダウコーニング株式会社 | Additive for organic resin, curable organic resin composition containing the same, and cured product thereof |
| KR101278456B1 (en) | 2004-07-29 | 2013-07-01 | 다우 코닝 도레이 캄파니 리미티드 | Curable organopolysiloxane composition, method of curing thereof, semiconductor device, and adhesion promoter |
| KR101285145B1 (en) | 2006-05-11 | 2013-07-12 | 다우 코닝 도레이 캄파니 리미티드 | Adhesion-promoting agent, curable organopolysiloxane composition, and semiconductor device |
| KR20140038045A (en) | 2012-09-19 | 2014-03-28 | 주식회사 케이씨씨 | Heat curable silicone composition and the light emitting device using the same |
| JP2014062198A (en) * | 2012-09-21 | 2014-04-10 | Dow Corning Toray Co Ltd | Curable silicone composition, and semiconductor sealing material and optical semiconductor device using the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200208032A1 (en) * | 2018-12-31 | 2020-07-02 | Samsung Sdi Co., Ltd. | Silicone-based adhesive protective film and optical member comprising the same |
| US11767453B2 (en) * | 2018-12-31 | 2023-09-26 | Samsung Sdi Co., Ltd. | Silicone-based adhesive protective film and optical member comprising the same |
| WO2020149578A1 (en) * | 2019-01-17 | 2020-07-23 | Dow Silicones Corporation | Antistatic silicone rubber composition |
| WO2020218879A1 (en) * | 2019-04-25 | 2020-10-29 | 삼성에스디아이 주식회사 | Silicone-based adhesive protection film and optical member comprising same |
| WO2020226461A1 (en) * | 2019-05-09 | 2020-11-12 | 삼성에스디아이 주식회사 | Silicone-based adhesive protection film and optical member comprising same |
| WO2021102073A1 (en) * | 2019-11-24 | 2021-05-27 | Dow Toray Co., Ltd. | Photocurable silicone composition and cured product thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101695316B1 (en) | Curable organopolysiloxane composition and optical semiconductor device using the same | |
| TWI465487B (en) | Resin composition for sealing optical semiconductor | |
| US8895678B2 (en) | Cross-linkable silicone composition and cross-linked product thereof | |
| JP5827834B2 (en) | Silicone resin composition, silicone resin sheet, method for producing silicone resin sheet, and optical semiconductor device | |
| EP3360928A1 (en) | Addition-curable silicone resin composition, method for producing said composition, and optical semiconductor device | |
| TWI577738B (en) | A hardened resin composition, a hardened product, a packaging material, and a semiconductor device | |
| KR20100100662A (en) | Composition for thermosetting silicone resin | |
| TWI491674B (en) | A resin composition for a light-emitting semiconductor element, and a light-emitting device | |
| TWI483995B (en) | Polyorganosiloxane and encapsulation material obtained from the polyorganosiloxane and electronic device including the encapsulation material | |
| TWI534181B (en) | Curable silicone resins for led encapsulation | |
| KR20140015218A (en) | Curable composition | |
| KR20120120005A (en) | Curable composition, cured product, photo-semiconductor device, and polysiloxane | |
| US10927278B2 (en) | Curable organopolysiloxane composition and semiconductor device | |
| JP6974475B2 (en) | Curable silicone composition | |
| KR101980935B1 (en) | adhesion promoter, composition comprising the same and optical device of the composition | |
| JP7158100B2 (en) | Crosslinkable organopolysiloxane composition, cured product thereof, and LED device | |
| CN107001769B (en) | The optical semiconductor device of heat-curing type silicon oxygen composition, the die bond material that the composition is constituted and the solidfied material with the die bond material | |
| KR20190105509A (en) | Curable silicone composition for light reflecting material, silicone resin cured product, reflector, and led device | |
| KR20110085214A (en) | Thermosetting silicone composition for light emitting diode encapsulant | |
| JP2015129274A (en) | Silicone resin composition and use of the same | |
| KR101804047B1 (en) | Organic-silicon composites containing metal and curable organopolysiloxane composition comprising thereof | |
| EP2960295B1 (en) | Curable composition | |
| TW201713708A (en) | Crosslinkable organopolysiloxane composition and cured object obtained therefrom | |
| US10259912B2 (en) | Organopolysiloxane composition | |
| KR101418012B1 (en) | curable silicone compositions and electronic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |