KR20170119505A - Organic-silicon composites containing metal and curable organopolysiloxane composition comprising thereof - Google Patents

Abstract

The present invention provides a metal-containing organic-inorganic complex and a curable organopolysiloxane composition comprising the same.
The metal-containing organosilicon complexes and curable organopolysiloxane compositions comprising them according to the present invention can have excellent heat resistance and low tacky properties and are suitable for use in optical members.

Description

TECHNICAL FIELD The present invention relates to a metal-containing organosiloxane composition and a curable organopolysiloxane composition containing the metal-

The present invention relates to metal-containing organo-silicon composites and curable organopolysiloxane compositions comprising them.

LED (Light Emitting Diode) is a solid-state light source with high efficiency and long life, and it has a trade-off relationship with conventional incandescent lamp, fluorescent lamp, HID lamp (High Intensity Discharge Lamp) OLEDs (organic light emitting diodes) are still widely used.

The LED light emitting device is generally several millimeters or less in size, and a single or a plurality of such devices are mounted on various substrates and used as a light source by using a resin as a sealing material for protection and light control.

In the past, epoxy resin was used as an encapsulating resin in the early stage of LED development. Currently, 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 trend of LED light source package which has recently become a high power output, a larger amount of light and heat are emitted, and therefore problems such as peeling of the lens, discoloration of the adhesive and primer layer Can cause.

In addition, it is easy to generate cracks when used at high temperature for a long period of time. In order to minimize the cracks, low hardness organopolysiloxane hardeners are available. In the case of low hardness organopolysiloxanes, high tacky causes dust dust and so on.

The present invention provides a metal-containing organosilicon composite and a curable organopolysiloxane composition containing the same, which can minimize the change in physical properties and heat resistance.

The metal-containing organosilicon composite according to one aspect of the present invention may include at least one of the following chemical formulas (1) and (2).

[Chemical Formula 1]

^{[(R 1 R 2 R 3} SiO 1/2) a (R 4 R 5 SiO 2/2) b (R 6 SiO 3/2) c (SiO 4/2) d] X M Y

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a halogen atom, An alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group, an oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group or a cyano group, Is a metal atom on the periodic table, 0 ∠ X / Y ≤ 4.

(2)

^{[(R 7 R 8 R 9} Si-N-SiR 10 R 11 R 12) e] x M y

The e is less than greater than ^{0 1, R 7, R 8} , R 9, R 10, R 11, R 12 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group , An oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group, or a cyano group, and M is a metal atom on the periodic table and 0 ∠ x / y ≤ 4.

Yet another aspect of the present invention includes 0.5 to 10 parts by weight of the metal containing organo-silicon composite,

30 to 95 parts by weight of an organopolysiloxane represented by the following formula (3)

(3)

(R ¹³ R ¹⁴ R ¹⁵ SiO _1/2 ) _M (R ¹⁶ R ¹⁷ SiO _2/2 ) _D (R ¹⁸ SiO _3/2 ) _T (SiO _4/2 ) _Q

(Wherein M, D, T, Q are each greater than or equal to 0 and smaller number and M + D + T + Q = 1 greater than 1, the _{^{R 13, R 14, R 15}} , R 16, R 17, R 18 Are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having aliphatic saturated groups which are the same as or different from each other, 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, Or a skeleton on a branch.)

1 to 30 parts by weight of an organohydrogenpolysiloxane represented by the following formula (4), and

[Chemical Formula 4]

(R ¹⁹ R ²⁰ R ²¹ SiO _{1/2) m} (R ²² R ²³ SiO _2/2 ) _d (R ²⁴ SiO _3/2 ) _t (SiO _4/2 ) _q

The m, d, t, q is a number greater than or equal to 0 and smaller than 1 respectively, and m + d + t + q = 1, wherein ^{R 19, R 20, R 21} , R 22, R 23, R 24 is Are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond or the same or different from each other.

And 0.00005 to 0.003 parts by weight of a platinum group metal catalyst, based on the total weight of the curable organopolysiloxane composition.

The metal-containing organo-silicon composites of the present invention and the curable organopolysiloxane compositions containing them can have excellent heat resistance and low tacky characteristics and are suitable for use in optical members.

In order to solve the above problems, one aspect of the present invention is a metal-containing organosilicon composite comprising at least one of the following chemical formulas (1) and (2).

 [Chemical Formula 1]

^{[(R 1 R 2 R 3} SiO 1/2) a (R 4 R 5 SiO 2/2) b (R 6 SiO 3/2) c (SiO 4/2) d] X M Y

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a halogen atom, An alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group, an oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group or a cyano group, Is a metal atom on the periodic table, 0 ∠ X / Y ≤ 4.

(2)

^{[(R 7 R 8 R 9} Si-N-SiR 10 R 11 R 12) e] x M y

The e is less than greater than ^{0 1, R 7, R 8} , R 9, R 10, R 11, R 12 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group , An oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group, or a cyano group, and M is a metal atom on the periodic table and 0 ∠ x / y ≤ 4.

The 'organo-silicon composite' in the 'metal-containing organosilicon complex' according to an aspect of the present invention may be an organopolysiloxane as shown in the above formula (1) or an organopolysilane as shown in the above formula (2).

The fact that the metal is contained in the organic-silicon composite means that the metal is not simply physically and mechanically mixed with the organic-silicon composite and is not precisely defined, but the metal is chemically bonded to the inside of the organic- .

Conventionally, in some cases, a metal additive has been added to ensure the physical properties of the curable organopolysiloxane composition at high temperatures. However, when the metal component is added to the composition, the transmittance (or haze) value of the finally cured cured product is remarkably There was a problem of lowering.

Accordingly, the metal contained in the organic-silicon composite can serve to improve the heat resistance and transmittance of the cured organopolysiloxane composition containing the metal-containing organic-silicon composite.

The metal may be a metal atom on the periodic table to improve physical properties at a high temperature. Specific examples thereof include La, Ce, Pr, Ne, Prommium, (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (TM), ytterbium (Yb), ruthenium Zr), and titanium (Ti).

In the above formula (1), d may be in the range of 0 ∠ d ∠ 0.1. The organopolysiloxane of the above formula (1) in the above range is advantageous in reaction with the metal, so that the yield of the metal-containing composite is increased and high heat resistance can be imparted to the cured organopolysiloxane composition requiring heat resistance at high temperature.

When R ¹ to R ¹² in the formulas (1) and (2) are alkyl groups, they may be alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, isopropyl and butyl groups. An aryl group having 6 to 18 carbon atoms such as a naphthyl group and a beta -anthranyl group.

When R ¹ to R ¹² in the above formulas (1) and (2) are alkenyl groups, they may be alkenyl groups having 2 to 6 carbon atoms such as vinyl group, allyl group,? -Butyl group and? -Butenyl group.

When R ¹ to R ¹² in formulas (1) and (2) have substituents having an epoxy group, an oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group or a cyano group, An alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms. Particularly, it is preferable that the above-mentioned substituent is substituted for an alkyl group having 1 to 3 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 oxetanyl group include (3-ethyloxetan-3-yl) propyl group, and the acryloyloxy group includes an acryloyloxymethyl group, a? -Acryloyloxyethyl group, A n-butyloxypropyl group, a γ-acryloyloxypropyl group, and the like.

Examples of the methacryloyloxy group include a methacryloyloxymethyl group, a? -Methacryloyloxyethyl group, a? -Methacryloyloxypropyl group, and a? -Methacryloyloxypropyl group.

The mercapto group includes a mercaptomethyl group, a? -Mercaptoethyl group, a? -Mercaptopropyl group, a? -Mercaptopropyl group and the like, and the amino group is preferably an aminomethyl group, a? -Aminoethyl group, A cyano group, a? -Cyanoethyl group, a? -Cyanopropyl group, a? -Cyanoethyl group, a? -Cyanoethyl group, Examples of the isocyanato group include an isocyanomethyl group, a? -isocyanatoethyl group, a? -isocyanopropyl group, and a? -isocyanopropyl group.

According to another aspect of the present invention, there is provided a curable organopolysiloxane composition using a metal-containing organosilicon composite containing at least one of the above-mentioned chemical formulas 1 and 2 as a heat resistant additive.

Specifically, the curable organopolysiloxane composition may include from 0.5 to 10 parts by weight of a metal-containing organosilicon composite containing at least one of the above-mentioned formula (I) or (II) as a heat resistant additive. When the amount of the metal-containing organosilicon composite is less than 0.5 parts by weight, there is a problem that heat resistance is not exhibited. When the amount of the metal-containing organosilicon composite is more than 10 parts by weight, have.

The curable organopolysiloxane composition according to one embodiment of the present invention is a silicone composition that forms a skeleton after curing, and may include 30 to 95 parts by weight of an organopolysiloxane represented by the following formula (3). If the amount of the organopolysiloxane is less than 30 parts by weight, there arises a problem that the cured product of the curable composition recedes after being cured, causing scratches or tearing in the cured product. When the organopolysiloxane is more than 95 parts by weight, There is a problem that the property is deteriorated.

(3)

(R ¹³ R ¹⁴ R ¹⁵ SiO _1/2 ) _M (R ¹⁶ R ¹⁷ SiO _2/2 ) _D (R ¹⁸ SiO _3/2 ) _T (SiO _4/2 ) _Q

Wherein M, D, T, Q are each greater than or equal to 0 and smaller number and M + D + T + Q = 1 greater than 1, the _{^{R 13, R 14, R 15}} , R 16, R 17, R 18 is A substituted or unsubstituted monovalent hydrocarbon group having a hydrogen atom or an aliphatic saturated group which is the same as or different from each other, at least one of the hydrocarbon groups having one or two or more unsaturated groups at the terminal or side chain of the molecule, You can have a skeleton on a branch.

The M value of Formula 3 is 0.01 to 0.3, the D value is 0.3 to 0.6, the T value is 0 to 0.3, the Q value is 0.4 to 0.8, and Q and D are Q / D = 0.3 to 0.9. By setting the numerical value of the above formula (3) within the above range, it is possible to control the viscosity and hardness of the cured product to a wide range, and the cured product of the composition can have high transparency and adhesion reliability to secure high durability against light and heat can do.

The curable organopolysiloxane composition according to one embodiment of the present invention has a hydrogen atom at the molecular end or side chain and forms a skeleton after curing the silicone composition and is used in combination with the organopolysiloxane to form a curable composition finally cured The organohydrogenpolysiloxane represented by the following general formula (4) may be added in an amount of 1 to 30 parts by weight to improve the mechanical strength and hardness of the cured product.

If the amount of the organohydrogenpolysiloxane is less than 1 part by weight, there is a problem that the cured composition of the curable composition tends to be torn off after curing. If the organopolysiloxane is more than 30 parts by weight, the tackiness of the cured composition .

[Chemical Formula 4]

(R ¹⁹ R ²⁰ R ²¹ SiO _{1/2) m} (R ²² R ²³ SiO _2/2 ) _d (R ²⁴ SiO _3/2 ) _t (SiO _4/2 ) _q

The m, d, t, q is a number greater than or equal to 0 and smaller than 1 respectively, and m + d + t + q = 1, wherein ^{R 19, R 20, R 21} , R 22, R 23, R 24 is Each independently, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, which are the same as or different from each other.

The hydrocarbon group of the functional groups R ¹³ to R ²⁴ of the above-described general formula (3) or (4) may be an alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, isopropyl or butyl, An aryl group having 6 to 18 carbon atoms such as a phenyl group, a β-naphthyl group and a β-anthranyl group, and the aryl group may be 45 mol% or less based on the total number of moles of all organic groups contained in the above formula (3) If the aryl group is at least 45 mol%, the yellowing becomes severe due to pyrolysis and oxidation of the aryl group in the high-temperature heat resistance test, so that the transmittance is remarkably lowered and it is not applicable to optical instruments.

When the hydrocarbon group is an alkenyl group, it may be an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, an allyl group, a? -Butyl group, and a? -Butenyl group.

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 in the above chemical formula 3 or 4, an alkyl group having 1 to 6 carbon atoms, Cycloalkyl groups of 3 to 12 are suitable. Particularly, it is very suitable that the above-mentioned substituent is substituted in the alkyl group having 1 to 3 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, -Acryloyloxypropyl group,? -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, ,? - aminopropyl group,? -aminopropyl group, N- (? - (aminoethyl),? -aminopropyl group and the like. As the substituent having cyano group, cyanomethyl group,? -cyanoethyl group ,? -cyanopropyl group,? -cyanopropyl group and the like. Examples of the substituent having an isocyanato group include an isocyanomethyl group, a? -isocyanatoethyl group, a? -isocyanopropyl group, a? And an isocyanopropyl group.

The curable organopolysiloxane composition is a hydrosilylation catalyst that promotes curing and may comprise from 0.00005 to 0.003 parts by weight of a platinum group metal catalyst. If the content of the platinum group catalyst is less than 0.00005 parts by weight, the crosslinking reaction is delayed and the curing is not completed. If the content of the platinum group catalyst is more than 0.003 parts by weight, the curing rate becomes too fast and workability is poor. And problems such as coloring may occur, resulting in functional problems.

The platinum group metal catalyst may be at least one selected from platinum fine powder, platinum black, chloroplatinic acid, alcohol modified product of chloroplatinic acid, chloroplatinic acid / diolefin complex, platinum / olefin complex, platinum bis (acetoacetate) A platinum / divinyltetramethyldisiloxane complex, a chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complex, and a platinum / divinyltetrasiloxane complex as a platinum / alkenylsiloxane complex, as a bis (acetylacetonate), a chloroplatinic acid / Methyldisiloxane complexes, platinum / tetravinyltetramethylcyclotetrasiloxane complexes, and complexes of chloroplatinic acid and acetylenic alcohol.

The curable organopolysiloxane composition may contain, if necessary, a small amount of a reaction retarder. For example, 2-Phenyl-3-butyn-2-ol may be used as the reaction retarder. The content of the reaction retarding agent is preferably (0.0080) parts by weight or less based on the total weight of the composition. The lower limit of the reaction retarder may be, for example, (0.00010) parts by weight. In particular, when the reaction retarder is contained too much, the curing rate may be slowed down.

The composition of the present invention may also 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.

In addition, the curable organopolysiloxane composition according to the present invention can be prepared by applying various methods known in the art. For example, the composition of the composition of the present invention is divided into a solution A and a solution B, And mixing the two to form the final composition.

The curable organopolysiloxane composition according to one embodiment of the present invention has a transmittance of less than 45% at a wavelength of 260 nm and a transmittance of at least 80% at a wavelength of 450 nm in a ultraviolet-visible ray spectroscopy when cured to form a cured product . By having the cured product of the present curable organopolysiloxane composition have the above physical properties, it is possible to improve the heat resistance at a high temperature while having high transparency.

According to another aspect of the present invention there is provided an optical material comprising a curable organopolysiloxane composition, wherein the optical material is selected from the group consisting of light emitting diodes, optical semiconductors, adhesives, optical coatings, optical potting agents, optical sealants, , And an optical film, for example.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples.

Preparation of metal-containing organic-inorganic composites

Synthetic example  One

120 g of mineral oil containing 22% of cerium octoate was added to 50 g of xylene and mixed. 120 g of hexamethyldisilazane was added thereto, stirred at 80 DEG C for 12 hours, 20 g of a vinyl group-containing organopolysiloxane (ViMe ₂ SiO (Me ₂ SiO) ₇₀ SiMe ₂ Vi) was added and sufficiently stirred.

Thereafter, the pressure was reduced to 5 Torr at 150 DEG C to distill off the low-boiling substance, and the resulting precipitate was filtered to obtain a fluid yellow metal-containing organopolysiloxane complex (SYN-1).

Synthetic example  2

120 g of mineral oil containing 22% of cerium octoate was added to 50 g of xylene and mixed. 180 g of hexamethyldisilazane was added thereto, stirred at 80 DEG C for 12 hours, 20 g of a vinyl group-containing organopolysiloxane (ViMe ₂ SiO (Me ₂ SiO) ₇₀ SiMe ₂ Vi) was added and sufficiently stirred.

Thereafter, the pressure was reduced to 5 torr at 150 DEG C to distill off the low-boiling substance, and the resulting precipitate was filtered to obtain a fluid brown organic metal-containing organopolysiloxane complex (SYN-2).

Synthetic example  3

100 g of mineral oil containing 22% of cerium octoate was added to 50 g of xylene and mixed. Then, 107 g of glycidoxypropyltrimethoxysilane was added and stirred at 70 캜 for 9 hours, and then 40 g of a vinyl group-containing organopolysiloxane (ViMe ₂ SiO (Me ₂ SiO) ₇₀ SiMe ₂ Vi) was added and sufficiently stirred.

Thereafter, the pressure was reduced to 5 Torr at 150 DEG C to distill off the low-boiling substance, and the resulting precipitate was filtered to obtain a flowable brown metal-containing organopolysiloxane complex (SYN-3).

Synthetic example  4

100 g of mineral oil containing 22% of cerium octoate was added to 50 g of xylene and mixed. 125 g of phenyltrimethoxysilane was added thereto, and the mixture was stirred at 105 DEG C for 12 hours.

Thereafter, the pressure was reduced to 5 torr at 150 DEG C to distill off the low-boiling substance, and the resulting precipitate was filtered to obtain a flowable dark yellow metal-containing organopolysiloxane complex (SYN-4).

Synthetic example  5

15 g of cerium butoxide was added to 50 g of xylene and mixed. To this was added 550 g of?,? - hydroxypolysiloxane (HOMe ₂ SiO (Me ₂ SiO) ₄₀ SiMe ₂ OH) and the mixture was stirred at 80 ° C. for 9 hours.

Thereafter, the pressure was reduced to 5 torr at 150 DEG C to distill off the low-boiling substance, and the resulting precipitate was filtered to obtain a fluid pale yellow metal-containing organopolysiloxane complex (SYN-5).

Synthetic example  6

18 g of cerium isopropoxide was mixed with 50 g of xylene. 550 g of?,? - hydroxypolysiloxane (HOMe ₂ SiO (Me ₂ SiO) ₄₀ SiMe ₂ OH) was added thereto and stirred at 65 ° C for 12 hours.

Thereafter, the pressure was reduced to 5 torr at 150 DEG C to distill off the low-boiling substance, and the generated precipitate was filtered to obtain a fluid pale yellow metal-containing organopolysiloxane complex (SYN-6).

Example  1-8 and Comparative Example  1-6

Example  One

100 g of a vinyl group-containing MQ resin (vinyl content: 0.74 mmol / g) and 100 g of linear dimethylpolyorganosiloxane (ViMe ₂ SiO (Me ₂ SiO) ₁₃₀₀ SiMe ₂ Vi, hereinafter referred to as VP) Were mixed using a planetary mixer to prepare a master batch (hereinafter referred to as MB1).

 (1) Preparation of composition A

 25 g of the previously prepared MB1, 28 g of VP, 0.03 g of platinum complex and 1.2 g of SYN-1 of Synthesis Example 1 were mixed at room temperature for 1 hour in an oil mixer to obtain a curable organopolysiloxane composition A (hereinafter referred to as "PTA" .

 (2) Preparation of composition B

5.4 g of organohydrogenpolysiloxane (H content 7.3 mmol / g) and 8.7 g of VP, 0.01 g of 1-ethylnyl-1-cyclohexanol and 0.7 g of glycidoxypropyltrimethoxysilane were mixed in a glass vessel for 1 hour in an oil-in-water mixer, To obtain a polysiloxane composition B (hereinafter, referred to as 'PTB').

(3) Mixing of the compositions A and B

30 parts by weight of the composition A and 10 parts by weight of the composition 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 produce a cured sheet.

Example  2

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1, except that SYN-1 of Synthesis Example 1 was changed to SYN-2 of Synthesis Example 2. The curable organopolysiloxane composition was thermally cured to prepare a cured sheet.

Example  3

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1, except that 'SYN-1' in Synthesis Example 3 was changed to 'SYN-3' in Synthesis Example 3. The curable organopolysiloxane composition was thermally cured to prepare a cured sheet.

Example  4

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1, except that 'SYN-1' in Synthesis Example 4 was changed to 'SYN-4' in Synthesis Example 4, and the cured organopolysiloxane composition was thermally cured to prepare a cured sheet.

Example  5

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1, except that 'SYN-1' in Synthesis Example 5 was changed to 'SYN-5' in Synthesis Example 5. The curable organopolysiloxane composition was thermally cured to prepare a cured sheet.

Example  6

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1, except that 'SYN-1' in Synthesis Example 6 was changed to 'SYN-6' in Synthesis Example 6, and the composition was thermally cured to prepare a cured sheet.

Example  7

A curable organopolysiloxane composition was obtained in the same manner as in Example 1, except that the amount of SYN-1 added in Synthesis Example 1 was changed to 3.0 g, and the curable organopolysiloxane composition was thermally cured to prepare a cured sheet.

Example  8

The curable organopolysiloxane composition was obtained in the same manner as in Example 1, except that the amount of SYN-1 added in Synthesis Example 1 was changed to 7.2 g, and the cured organopolysiloxane composition was thermally cured to prepare a cured sheet.

Comparative Example  One

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1 except that 'SYN-1' was not added, and the cured organopolysiloxane composition was thermally cured to prepare a cured sheet.

Comparative Example  2

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1 except that 'SYN-1' was changed to 0.5% of a mineral oil containing 22% of cerium octoate, and the mixture was thermally cured to obtain a cured sheet Respectively.

Comparative Example  3

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1 except that SYN-1 in Synthesis Example 1 was replaced by 0.11% of cerium octoate having a purity of 99.8%, and the resulting curable organopolysiloxane composition was thermally cured to prepare a cured sheet Respectively.

Comparative Example  4

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1, except that SYN-1 in Synthesis Example 1 was replaced by 0.01% purity of cerium butoxide having a purity of 99.8%. The curable organopolysiloxane composition was thermally cured to prepare a cured sheet Respectively.

Comparative Example  5

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1, except that "SYN-1" in Synthesis Example 1 was changed to 0.07% purity cerium isopropoxide of 99.8% Respectively.

Comparative Example  6

A curable organopolysiloxane composition was obtained in the same manner as in Synthesis Example 1 except that 'SYN-1' in Synthesis Example 1 was not added, and the curable organopolysiloxane composition was thermally cured to prepare a cured sheet.

Test Example

[Test Methods]

Cured sheet production

The curable organopolysiloxane composition was prepared by first curing the mold at 120 DEG C for 30 minutes in a mold capable of forming a sheet having a thickness of 2 mm and then curing the cured secondarily in an oven at 150 DEG C for 2 hours.

1) Initial hardness

Three layers of the prepared cured sheet were stacked and measured at 25 캜 using a Shore A type or Shore D type hardness meter.

2) Hardness change

The sheet prepared in the measurement of the initial hardness was placed in an oven at 250 ° C. and measured in the same manner as in the initial hardness measurement by elapsed time.

3) Transmittance

The organosiloxane cured sheet (thickness: 2 mm) according to the present invention was measured using an ultraviolet-visible light spectral spectrum (model name: Lambda 950, manufactured by PERKIN ELMER).

4) Remaining weight ratio

The organopolysiloxane cured product was allowed to stand in an oven at 250 캜 for 168 hours, and the weight before and after storage was measured to calculate the remaining weight ratio. The higher the remaining weight percentage, the better the heat resistance.

5) Coefficient of Thermal Expansion (CTE) Rate of Change (%)

The organopolysiloxane cured product was stored in an oven at 250 ° C for 168 hours, and the thermal expansion coefficient before and after storage was measured using a dynamic thermal analyzer (model: DMA8000, manufactured by PERKIN ELMER) and calculated according to the following formula. A lower value of the coefficient of change of the thermal expansion coefficient is excellent in heat resistance.

Change in thermal expansion coefficient (%) = {(CTE before storage) - (CTE after storage)} / (CTE before storage) * 100 (%

Example One 2 3 4 5 6 7 8 Initial transmittance
(@ 260 nm),% 10.3 18.9 21.4 23.8 32.7 35.7 7.5 8.9 Change in coefficient of thermal expansion (%) -1.02 -0.68 -0.34 0.34 0.34 0.68 0.34 0.21 Before and after storage at 250 ℃
Hardness (Shore A) 0hr 50 52 52 50 50 50 50 52 168hr 50 51 51 52 51 51 49 51 250 ℃ storage
Before / after transmittance
(@ 450 nm),% 0hr 94.2 93.5 93.4 93.1 92.9 92.1 92.6 93.4 168hr 91.3 91.3 91.2 90.7 90.9 90.9 92.1 92.6 After 168 hours at 168 ° C
Remaining weight percentage (%) 96.5 96.1 96.2 96.1 95.6 95.3 97.3 97.1 250 ℃ Curing Specimen
Crack occurrence time
(Up to 2,000 hours) crack
none crack
none crack
none crack
none crack
none crack
none crack
none crack
none

Comparative Example One 2 3 4 5 6 7 8 Initial transmittance
(@ 260 nm),% 76.6 61.2 65.2 63.6 62.1 79.7 58.6 3.2 Change in coefficient of thermal expansion (%) 44.67 30.61 31.16 33.90 37.41 48.76 25.7 0.21 Before and after storage at 250 ℃
Hardness (Shore A) 0hr 52 50 51 50 51 51 53 50 168hr 88 59 62 61 63 93 82 53 250 ℃ storage
Before / after transmittance
(@ 450 nm),% 0hr 94.1 87.2 87.5 85.4 81.6 93.8 93.8 76.4 168hr 91.2 80.4 81.2 80.9 80.4 91.1 91.4 71.2 After 168 hours at 168 ° C
Weight remaining ratio (%) 91.3 93.1 92.0 92.4 92.8 90.2 91.1 97.4 250 ℃ Curing Specimen
Crack occurrence time
(Up to 2,000 hours) 216 672 648 456 408 168 193 No crack

As shown in Tables 1 and 2, in the case of the highly reliable curable organopolysiloxane composition (Examples 1 to 8) according to the present invention, transmittance at 260 nm is 50% or less when measured by ultraviolet-visible ray spectroscopic kramatography , But the transmittance of Comparative Examples 1 to 6, which had poor heat resistance, was 60% or more as measured by the same method.

As a result of closely observing the above Examples 1 to 8 and Comparative Examples 1 to 6, it was found that the initial transmittance at 260 nm of the organopolysiloxane cured product measured by ultraviolet-visible ray spectroscopic kramatography was excellent in heat resistance (weight remaining ratio) The results are shown to be proportional to the results.

The present inventors have found that the same initial hardness (250 DEG C, 0 hr) is comparable to that of the specimens (Examples 1 to 6 and Comparative Examples 1 to 3 and Comparative Examples 1 to 6), and the coefficient of thermal expansion is different according to the hardness of the organopolysiloxane cured product. Comparative Example 5), it was confirmed that the lower the initial transmittance, the smaller the change rate of the thermal expansion coefficient before and after the 168 hours heat resistance test at 250 占 폚.

In Examples 1 to 4, the hardness was not increased for 168 hours at 250 ° C even in the case of low hardness (Examples 1 to 6) as well as high hardness (Examples 7 to 8) The cured sheet was less pyrolyzed, the weight retention was high, and the sheet was not cracked for up to 2,000 hours.

In the case of the hard shore 50A composition (Examples 1 to 6) though not shown in the above table, cracks did not occur until 2,000 hours.

In contrast, Comparative Example 1 and Comparative Example 6 which did not contain the heat resistant additive, which is a metal-containing organic-inorganic composite according to an embodiment of the present invention, show a small change in transmittance but a marked increase in hardness due to thermal decomposition and weight loss I could.

Further, in the case of Comparative Examples 2 to 5 including a heat resistant additive having a composition different from that of the heat resistant additive which is a metal-containing organic-inorganic composite according to one embodiment of the present invention, the change in hardness, And the transmittance was markedly poor. In contrast to Examples 1 to 8, all of the measured physical properties were markedly lowered, and in particular, cracks were generated within 700 hours at 250 DEG C, Respectively.

Accordingly, it was confirmed that the curable organopolysiloxane composition including the heat-resistant additive, which is a metal-containing organic-inorganic complex according to an embodiment of the present invention, has better physical properties than the other compositions.

Claims (12)

A metal-containing organo-silicon composite comprising at least one of the following chemical formulas (1) and (2):
[Chemical Formula 1]
^{[(R 1 R 2 R 3} SiO 1/2) a (R 4 R 5 SiO 2/2) b (R 6 SiO 3/2) c (SiO 4/2) d] X M Y
(Wherein a, b, c, d is greater than or equal to 0, each smaller than 1, a + b + c + a ^{d = 1, R 1, R} 2, each ^{R 3, R 4, R 5} , R 6 An alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group, an oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group or a cyano group, Is a metal atom on the periodic table and is 0 ∠ X / Y ≤ 4.
(2)
^{[(R 7 R 8 R 9} Si-N-SiR 10 R 11 R 12) e] x M y
(Wherein e is less than greater than ^{0 1, R 7, R 8} , R 9, R 10, R 11, R 12 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy An acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group, or a cyano group, and M is a metal atom on the periodic table and 0 ∠ x / y ≤ 4. The method according to claim 1,
M is at least one selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium At least one selected from the group consisting of Dy, Ho, Er, Thulium, Yb, Ru, Zr, and Ti. Lt; RTI ID = 0.0 > organo-silicon < / RTI > The method according to claim 1,
Wherein d in the above formula (1) is 0 ∠ d ∠ 0.1. 0.5 to 10 parts by weight of the metal-containing organo-silicon composite of claim 1;
30 to 95 parts by weight of an organopolysiloxane represented by the following formula (3);
(3)
(R ¹³ R ¹⁴ R ¹⁵ SiO _1/2 ) _M (R ¹⁶ R ¹⁷ SiO _2/2 ) _D (R ¹⁸ SiO _3/2 ) _T (SiO _4/2 ) _Q
(Wherein M, D, T, Q are each greater than or equal to 0 and smaller number and M + D + T + Q = 1 greater than 1, the _{^{R 13, R 14, R 15}} , R 16, R 17, R 18 Are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having aliphatic saturated groups which are the same as or different from each other, 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, Or a skeleton on a branch.)
1 to 30 parts by weight of an organohydrogenpolysiloxane represented by the following formula (4); And
[Chemical Formula 4]
(R ¹⁹ R ²⁰ R ²¹ SiO _{1/2) m} (R ²² R ²³ SiO _2/2 ) _d (R ²⁴ SiO _3/2 ) _t (SiO _4/2 ) _q
(Wherein m, d, t, q is a number greater than or equal to 0 and smaller than 1 respectively, and m + d + t + q = 1, wherein ^{R 19, R 20, R 21} , R 22, R 23, R 24 Is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond or the same or different from each other.
0.00005 to 0.003 parts by weight of a platinum group metal-based catalyst. The method of claim 4,
Wherein the M value in the formula (3) is 0.01 to 0.3, the D value is 0.3 to 0.6, the T value is 0 to 0.3, the Q value is 0.4 to 0.8, and Q and D are Q / D = 0.3 to 0.9. ≪ / RTI > The method of claim 4,
Wherein the m value of the formula (4) is 0.01 to 0.2, the d value is 0.3 to 0.9, the t value is 0 to 0.3, and the q value is 0.1 to 0.8. The method of claim 4,
The platinum group metal catalyst may be at least one selected from platinum fine powder, platinum black, chloroplatinic acid, alcohol modified product of chloroplatinic acid, chloroplatinic acid / diolefin complex, platinum / olefin complex, platinum bis (acetoacetate) A platinum / divinyltetramethyldisiloxane complex, a chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complex, and a platinum / divinyltetrasiloxane complex as a platinum / alkenylsiloxane complex, as a bis (acetylacetonate), a chloroplatinic acid / Methyldisiloxane complex, a platinum / tetravinyltetramethylcyclotetrasiloxane complex, and a complex of chloroplatinic acid and acetylenic alcohol. The curable organopolysiloxane composition of claim 1, The method of claim 4,
Wherein the organylpolysiloxane and the organohydrogenpolysiloxane comprise allyl groups in an amount of up to 45 mole percent based on the total number of moles of organic groups bonded to the organopolysiloxane. The method of claim 4,
A curable organopolysiloxane composition wherein the ultraviolet-visible spectral spectrum has a transmittance at 260 nm wavelength of 45% or less and a transmittance at 450 nm wavelength of 80% or more. The method of claim 4,
Curing organopolysiloxane composition having a heating loss of less than 8% after 168 hours at 250 占 폚. An optical material comprising the curable organopolysiloxane composition of claim 4. The method of claim 11,
Wherein the optical material comprises at least one selected from the group consisting of a light emitting diode, an optical semiconductor, an adhesive, an optical coating agent, an optical potting agent, an optical sealant, an optical coating agent, and an optical film.