KR101334349B1 - Heat-curable siloxane encapsulant components - Google Patents

Abstract

The present invention relates to a heat-curable siloxane encapsulant composition, and more particularly, 1) a phenylsiloxane core, and a siloxane unit including an additional hardenable functional group (X) at an end thereof to a surface of the core. phenylpolysiloxane resin having a core-shell structure forming a shell), 2) a linear polysiloxane having an addition-curable functional group (X) bonded to both ends thereof, and 3) a polyfunctional polysiloxane having three or more addition-curable functional groups (X) bonded thereto. 4) an alkoxypolysiloxane having an addition-curable functional group (X) bonded to the terminal or the middle of the chain, and 5) a heat curable siloxane encapsulant composition comprising a catalyst for hydrogen siliconization reaction, According to a two-part curing system divided into two containers.

Description

Heat-curable siloxane encapsulant composition {Heat-curable siloxane encapsulant components}

The present invention relates to a heat-curable siloxane encapsulant composition, and more particularly, 1) a phenylsiloxane core, and a siloxane unit including an additional hardenable functional group (X) at an end thereof to a surface of the core. phenylpolysiloxane resin having a core-shell structure forming a shell), 2) a linear polysiloxane having an addition-curable functional group (X) bonded to both ends thereof, and 3) a polyfunctional polysiloxane having three or more addition-curable functional groups (X) bonded thereto. 4) an alkoxypolysiloxane having an addition-curable functional group (X) bonded to the terminal or the middle of the chain, and 5) a heat curable siloxane encapsulant composition comprising a catalyst for hydrogen siliconization reaction, According to a two-part curing system divided into two containers.

The heat curable optical semiconductor encapsulant minimizes the loss of high power light from the optical semiconductor and protects the semiconductor chip and the electrode. The encapsulant material requires a resin having excellent light resistance to light sources, heat resistance to strong heat generation, and excellent sealing properties. Initially, an epoxy compound was mainly used as an encapsulant material, but an epoxy compound had an advantage of excellent adhesiveness, but had weakness of heat resistance and light resistance. In order to improve this, an aromatic epoxy resin incorporating an aromatic group has been developed and applied as an LED optical semiconductor encapsulant. However, the aromatic epoxy resin has a disadvantage in that a yellowing phenomenon occurs. In recent years, silicone resins have emerged as a highly transparent material having excellent heat resistance and light resistance, which secure the disadvantages of epoxy resins. In particular, optical semiconductors are required to have high luminous efficiency and stability to encapsulating materials for protecting semiconductor chips and electrodes. In general, silicone resins satisfy the requirements of the encapsulating materials mentioned above. Silicone resins applied in the field of heat-curable encapsulant are mainly addition-curable silicone resins, which are composed of two components. In general, the thermosetting of the silicone resin is caused by hydrogen-siliconization of a polysiloxane containing an alkenyl group and a polysiloxane containing a hydrogen atom in the presence of a platinum catalyst. Japanese Patent Application Laid-Open No. 2004-186168 discloses a silicone resin having at least two alkenyl groups bonded to a silicon atom in one molecule and an organosilane and / or organohydropolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule. A resin composition composed of polysiloxane) is disclosed. In addition, Japanese Patent Application Laid-Open No. 2008-150437 discloses an organohydropolysiloxane resin composed of an organopolysiloxane having an average of at least 0.2 alkenyl groups in one molecule, a siloxane having a hydrogen atom in the middle of the molecular chain, and a siloxane having hydrogen atoms bonded to both ends of the molecular chain. A composition is disclosed. In the curing composition disclosed in the above-mentioned Japanese Patent Laid-Open, the hydrogen siliconization reaction with other compositions occurs effectively in the curing reaction of the silicone resin having a terminal functional group, and thus the transparency, insulation characteristics and strength by the unreacted functional group inside the silicone resin Can be improved. However, there still remains a problem with respect to the control of the rate of deterioration of the adhesive strength due to the detachment of the encapsulant and the speed control in the curing process.

Platinum complexes are mainly used as catalysts for hydrogen siliconization reactions, and among them, Karstedt catalysts having zero oxidation number are generally used. The general structural formula of the Castestz catalyst is Pt ₂ [(CH ₂ = CH) Me ₂ Si-O-SiMe ₂ (CH = CH ₂ )] ₃ . U. S. Patent No. 3,775, 452 mentions the formation of metallic platinum precipitates and insoluble colloids in the reaction medium due to catalyst instability problems in silicon hydride by the Castes catalyst. This implies that due to the rapid activity of the catalyst it is impossible to control the alteration and internal exotherm of the catalyst generated during the curing process, it is difficult to obtain a stable and uniform cured product. In Japanese Patent Laid-Open No. 6-118254, active inhibitors such as phosphorus, nitrogen, sulfur, and acetylene compounds have been separately added to suppress the catalytic activity, but these activity inhibitors are known to affect the durability of the cured product. In Korean Patent Laid-Open No. 2004-0053395, the reaction rate was controlled by using divinyl tetramethyldisiloxane or 3-butyn-1-ol as an activity inhibitor. In addition, Japanese Patent Application Laid-Open No. 2011-0074464 discloses a method of performing semi-hardening reaction using an addition reactive functional group after forming a semi-cured material through a primary curing reaction using a condensation-reactive functional group as a method of not separately adding a reaction inhibitor. Although disclosed, the method is difficult to see as a fundamental solution as a method of controlling the internal heat generation by using a small amount of addition reactive functional groups and catalysts.

In addition, the encapsulant silicone resin may reinforce advantages such as high light transmittance, light resistance, and heat resistance, compared to the existing epoxy resin, but has a low refractive index of less than 1.5, thereby maximizing luminous efficiency. In particular, the role of silicone resin is important in improving the hardness, refractive index, and stability of encapsulant in an additive curing system.

The present invention has the properties of high refractive index (1.5 or more) with the heat resistance, high transparency and light resistance of the heat-curable siloxane encapsulant composition, improves the storage stability, and gives excellent viscosity and excellent workability, and a curing catalyst. It is an object of the present invention to provide a heat curable siloxane encapsulant composition that enables a stable thermosetting reaction.

Another object of the present invention is to provide a curing system that can stably control a hydrogen siliconization reaction without adding a separate active inhibitor.

In order to solve the above problems, the present invention

1) a phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1 below, in which a phenylsiloxane core (Core) and a siloxane unit including a terminal functional group (X) are bonded to a surface of the core to form a shell;

2) linear polysiloxane represented by the following formula (2) in which functional groups (X) are bonded at both ends;

3) a linear or cyclic polyfunctional polysiloxane represented by the following formula (3a) or a mixture thereof, in which three or more functional groups (X) are bonded;

4) linear or cyclic alkoxypolysiloxanes represented by the following general formula (4a) in which alkenyl and alkoxy functional groups are bonded to terminals, or a mixture thereof; And

5) catalysts for hydrogen siliconization reactions; It is characterized by a heat curable siloxane encapsulant composition comprising a.

[Formula 1]

(In Formula 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same as or different from each other and represent a C _1-20 alkyl group or C _6-20 aryl group, and X is hydrogen. of atoms, or an alkenyl group of c _2~20, the average value of a is a real number of 5-120, a mean value of b is 0.01 to 0.9 and the percentage of a, and the average value of d is 0.0 to 0.8 percentage of a, c Average is a real number from 0 to 4)

(2)

In Formula 2, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are the same as or different from each other, and represent an alkyl group of C _1-20 or an aryl group of C _6-20 , and X represents a hydrogen atom or C _2-20 An alkenyl group, e is an integer of 10 to 1,000, f is an integer of 10 to 1,000, the weight average molecular weight (Mw) of the linear polysiloxane represented by the formula (2) is 1,000 to 150,000 g / mol, and in the molecular chain The molar ratio of the alkyl group and the aryl group bonded is in the range of 1: 9 to 9: 1)

[Chemical Formula 3]

(In Formula 3a, R ¹² , R ¹³ , and R ¹⁴ are the same as or different from each other, and represent an alkyl group of C _1-20 or an aryl group of C _6-20 , and X represents a hydrogen atom or an alkenyl group of C _2-20 . Y represents a hydrogen atom, an alkenyl group of C _2-20 , or an alkoxy group of C _1-20 , and g is an integer of 1 to 10).

(3b)

(In Formula 3b, R ¹⁵ represents an alkyl group of C _1-20 or an aryl group of C _6-20 , X represents a hydrogen atom or an alkenyl group of C _2-20 , and g is an integer of 3 to 10.)

[Chemical Formula 4a]

(In Chemical Formula 4a, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ , which are the same as or different from each other, represent an alkyl group of C _1-20 or an aryl group of C _6-20 , where A is — (CH ₂ ) _p −, wherein p is an integer from 1 to 20 Z represents an alkenyl group of C _2-20 , and i is an integer of 0 to 10).

(4b)

(In Formula 4b, Z represents an alkenyl group of C _2-20 , B represents a bond or-(R ²³ R ²⁴ Si)-(CH ₂ ) _m- , and R ²¹ , R ²² , R ²³ , R ²⁴ , and R ²⁵ , which are the same as or different from each other, represent an alkyl group of C _1-20 or an aryl group of C _6-20 , j is an integer of at least 1 to 18, k is an integer of 2 to 19, and j + k Is an integer of 3 to 20, and m and n are the same or different and are integers of 0 to 10.

The composition of the present invention has a high refractive index of 1.50 or more as well as heat resistance, light resistance, and high transparency, and is excellent in storage stability and optimum viscosity, and thus is useful as a heat-curable siloxane encapsulant composition.

In addition, the composition of the present invention can be carried out stably hydrogen siliconization reaction without using a separate active inhibitor to provide a stable and uniform cured product.

The present invention relates to a heat curable siloxane encapsulant composition.

The heat curable siloxane encapsulant composition of the present invention comprises: 1) 10 to 88% by weight of a phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1; 2) 10 to 50% by weight of the linear polysiloxane represented by Formula 2; 3) 1 to 30% by weight of the multifunctional polysiloxane represented by Chemical Formula 3a or 3b or a mixture thereof; 4) 0.1 to 20% by weight of an alkoxypolysiloxane represented by Formula 4a or 4b or a mixture thereof; And 5) 0.1 to 1000 ppm of the silicon hydride catalyst.

It will be described in more detail with respect to each component constituting the heat-curable siloxane sealing material composition according to the present invention.

1) Phenylpolysiloxane resin of core-shell structure

The silicone resin used in the present invention is not particularly limited, but in view of the interactive aspect of each component, a phenylpolysiloxane resin having a core-shell structure is particularly used.

The phenylpolysiloxane resin of the core-shell structure used in the present invention is a novel phenylpolysiloxane resin developed by the present inventors and has been patented in Korean Patent Application No. 2011-0134471, and the characteristics and manufacturing method of the phenylpolysiloxane resin It is described in detail in the foregoing application specification.

The phenylpolysiloxane resin of the core-shell structure is a reactive terminal group -OSiR ³ R ⁴ X (hereinafter referred to as M unit) to the core of the phenylsiloxane network structure, as represented by the following formula (1) A non-reactive end group -OSiR ⁵ R ⁶ R ⁷ (hereinafter referred to as M 'unit) or [(-OSiR ¹ R ² ) _c -OSiR ³ R ⁴ X] _b (hereinafter referred to as DM unit) is bonded To form a shell.

[Formula 1]

In Formula 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as or different from each other and represent a C _1-20 alkyl group or C _6-20 aryl group, preferably It represents a C _1-10 alkyl group or C _6-10 aryl group, specifically, may be a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group and the like, in terms of high refractive index, light resistance and light transmittance Methyl and phenyl groups are most suitable. In Formula 1, X represents a hydrogen atom or a C _2-20 alkenyl group as an addition-curable functional group bonded to the M unit, preferably a hydrogen atom, or a C _1-10 alkenyl group, specifically, a hydrogen atom , Vinyl group, allyl group, butenyl group and the like are most suitable. In Chemical Formula 1, a represents the content of the phenylsiloxane core unit, and the average value of a is 5 to 120 real number, preferably 6 to 50 real number. In Formula 1, b represents the total content of the M unit or DM unit constituting the shell, the average value of b is 0.01 to 0.9 fraction of a, preferably 0.05 to 0.8 fraction of a. In Formula 1, c represents the content of M units, the average value of c is a real number of 0 to 4, preferably a real number of 0 to 2. In Formula 1, d represents the total content of the M 'unit constituting the shell, the average value of d is 0.0 to 0.8 fraction of a, preferably 0.0 to 0.5 fraction of a.

The structure of the phenylsiloxane (PhSiO _3/2 ) constituting the core of the phenylpolysiloxane resin represented by Formula 1 may be random, ladder or cage type, and may be composed of a single phase or a complex phase. (R ¹ R ² SiO ₁ ) Form D-units serve as a spacer to connect the core and terminal functional groups, or to facilitate the addition reaction of the M unit to the phenylsiloxane core unit. In addition, when the structure of the phenylpolysiloxane resin represented by Formula 1 is examined, the addition-curable functional group (X) bonded to the terminal group protrudes outward from the surface of the core to easily cause a curing reaction. The number of such addition-curable functional groups (X) can be easily controlled by the amount of the monochlorosilane monomer constituting the M unit.

In addition, the phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1 may be capped with M ′ units to remove unreacted silanol (Si—OH). As the number of unreacted silanol (Si-OH) bonded to the phenylpolysiloxane resin increases, the unreacted silanol is a non-reactive end group, -OSiR, because it increases the reactivity of the resin and causes the storage stability or ease of operation. Capping with ⁵ R ⁶ R ⁷ is recommended. As capping agents of unreacted silanol (Si-OH), silazane compound derivatives, monochlorosilane derivatives, or hydrosilane derivatives having R ⁵ , R ⁶ , and R ⁷ substituents can be used. As the capping agent, the silazane compound derivative is a silazane compound derivative substituted with a C _1-20 alkyl group and a C _6-20 aryl group, and preferably a sila substituted with a C _1-10 alkyl group and a C _6-10 aryl group. The residue is a derivative, specifically 1,1,1,3,3,3-hexamethyldisilazane, 1,3-dipentyl-1,1,3,3-tetramethyldisilazane, 1,1 , 3,3-tetraphenyl-1,3-dimethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, 1,1,3,3,5,5,7, 7-octamethylcyclotetrasilazane and the like can be used. In addition, as the capping agent, the monochlorosilane derivative is a C _1-20 alkyl group, C _6-20 aryl group, or a monochlorosilane derivative containing them simultaneously, preferably a C _1-10 alkyl group, C _6-10 It is an aryl group or the monochlorosilane derivative containing them simultaneously, Specifically, trimethylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, triphenylchlorosilane, etc. can be used. In addition, the hydrosilane derivative as a capping agent is a hydrosilane derivative including a C _1-20 alkyl group and a C _6-20 aryl group, and preferably a hydrosilane substituted with a C _1-10 alkyl group and a C _6-10 aryl group. It is a derivative, and specifically, trimethylsilane, triethylsilane, dimethylphenylsilane, methyldiphenylsilane, triphenylsilane and the like can be used. Particularly in the case of hydrosilane derivatives, tin (Sn) complexes such as tin (II) acetate, tin (II) 2-ethylhexanoate (stanus octo) as catalysts to promote reaction with silanol groups (Si-OH) Eight), tin (II) acetylacetonate, tin (II) ionophore, tin (II) oxalate, tin (II) stearate, dibutyltin (IV) dilaurate, dioctyltin (IV) dilaurate Rate and the like can be used. The tin (Sn) complex is preferably used in an amount showing its activity as a catalyst, and 10 to 100,000 ppm is preferably used, preferably 100 to 10,000 ppm.

The phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1 may be used alone or in combination of two or more thereof.

The phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1 may use any compound having a high molecular weight from a low molecular weight compound having a weight average molecular weight (Mw) of 500 to 50,000 g / mol.

In the case of the phenylpolysiloxane resin of the core-shell structure represented by the formula (1), it is preferably contained in the range of 10 to 88% by weight in the siloxane encapsulant composition of the present invention. If the content of the core-shell phenylpolysiloxane resin included in the siloxane encapsulant composition is less than 10 wt%, the hardness is low and the gas permeability is high. If the content is more than 88 wt%, the hardness is high and cracks may occur.

(2) linear polysiloxanes having an addition-curable functional group (X) bound to both ends;

In the present invention, as the organic polysiloxane, a linear polysiloxane having an addition-curable functional group (X) bonded to both terminals is used.

The linear polysiloxane used in the present invention is represented by the following Chemical Formula 2, the main structural unit is a composite structural unit of the form CH ₃ R ¹⁰ SiO- and PhR ¹¹ SiO-, both ends are -O _1/2 SiR ⁸ R ⁹ X type M unit is located, and the addition hardenable functional group (X) is couple | bonded with M unit.

(2)

In Formula 2, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are the same as or different from each other, and represent C _1-20 alkyl group or C _6-20 aryl group, preferably C _1-10 alkyl group or C _{6 to 10} aryl groups, specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, naphthyl group and the like, methyl and phenyl group is most suitable in terms of high refractive index, light resistance and light transmittance. In Formula 2, X represents a hydrogen atom or a C _2-20 alkenyl group as the addition-curable functional group, preferably a hydrogen atom, or a C _1-10 alkenyl group, specifically, a hydrogen atom, a vinyl group, or an allyl Group, butenyl group, and the like are most suitable. In Formula 2, e represents the content of CH ₃ R ¹⁰ SiO- unit, the average value of d is a real number of 10 to 1000, preferably a real number of 10 to 500. In Formula 2, f represents the content of PhR ¹¹ SiO- unit, the average value of e is a real number of 10 to 1000, preferably a real number of 10 to 500. The composition ratio (e / f) of the unit may form various ratios.

 In addition, the linear polysiloxane represented by the formula (2) determines the refractive index and viscosity by controlling the molar ratio of the alkyl group and the aryl group bonded in the molecular chain, the molar ratio of the alkyl group: aryl group is in the range of 1: 9 to 9: 1, Preferably, it is preferable to maintain the range of 3: 1 to 1: 3. In addition, it is preferable that the viscosity of the linear polysiloxane represented by the formula (2) has a viscosity of 10 to 150,000 cSt, and more preferably has a viscosity of 100 to 30,000 cSt in view of handling and workability for curing.

As the linear polysiloxane represented by Formula 2, the linear polysiloxane in which the vinyl group is substituted with the addition-curable functional group (X) is specifically, vinyl dimethyl siloxy-methylphenyl polysiloxane, polyvinyl methylphenyl siloxy-methylphenyl polysiloxane, polysulfone vinyl di Phenylsiloxy-methylphenylpolysiloxane, sock end vinyldimethylsiloxy- [dimethylpolysiloxy-co-methylphenylpolysiloxane], sock end vinylmethylphenylsiloxy- [dimethylpolysiloxy-co-methylphenylpolysiloxane], sock end vinyldiphenylsiloxy -[Dimethylpolysiloxy-co-methylphenylpolysiloxane], sock-end vinyldimethylsiloxy- [diphenylpolysiloxy-co-methylphenylpolysiloxane], sock-end vinylmethylphenylsiloxy- [diphenylpolysiloxy-co-methylphenylpolysiloxane], Socks end vinyldiphenylsiloxy- [diphenylpolysiloxy-co-methylphenylpolysiloxane], sock end vinylmethylsiloxy- [dimethylpolysiloxane Ci-co-diphenylpolysiloxy-co-methylphenylpolysiloxane], sock end vinylmethylphenylsiloxy- [dimethylpolysiloxy-co-diphenylpolysiloxy-co-methylphenylpolysiloxane], sock end vinyldiphenylsiloxy- [dimethyl Polysiloxy-co-diphenylpolysiloxy-co-methylphenylpolysiloxane] and the like. In addition, the linear polysiloxane substituted with the hydrogen atom by the addition-curable functional group (X) is specifically succinyl dimethylsiloxy-methylphenylpolysiloxane, succinyl methylphenylsiloxy-methylphenylpolysiloxane, succinol diphenylsiloxy-methylphenylpolysiloxane, and soxic dimethyl Siloxy- [dimethylpolysiloxy-co-methylphenylpolysiloxane], sock end methylphenylsiloxy- [dimethylpolysiloxy-co-methylphenylpolysiloxane], sock end diphenylsiloxy- [dimethylpolysiloxy-co-methylphenylpolysiloxane], sock Monomethyldimethyloxy- [diphenylpolysiloxy-co-methylphenylpolysiloxane], sock end methylphenylsiloxy- [diphenylpolysiloxy-co-methylphenylpolysiloxane], sock end diphenylsiloxy- [diphenylpolysiloxy-co- Methylphenylpolysiloxane], sock end methylsiloxy- [dimethylpolysiloxy-co-diphenylpolysiloxy-co-methylphenylpolysiloxane], sock end methylphenylsiloxy- [dimethylpoly Hydroxy-co-diphenyl polysiloxane city-co-methylphenyl polysiloxane], both ends of diphenyl siloxy-methylphenyl polysiloxane, etc. may be included; - [dimethyl polysiloxane city-co-diphenyl polysiloxane-upon-nose. Linear polysiloxane represented by the formula (2) can be used alone or in combination of two or more.

The linear polysiloxane represented by Chemical Formula 2 has a weight average molecular weight (Mw) in the range of 1,000 to 150,000 g / mol, and any compound having a high molecular weight can be used from a low molecular weight compound.

In the case of the linear polysiloxane represented by Chemical Formula 2, the siloxane encapsulant composition of the present invention is preferably contained in a range of 10 to 50% by weight. If the content of the linear polysiloxane included in the siloxane encapsulant composition is less than 10% by weight, the hardness may be increased and cracks may occur. If the content of the linear polysiloxane is greater than 50% by weight, the hardness may be low and the gas permeability may be increased.

(3) polyfunctional polysiloxanes having three or more addition-curable functional groups (X) bound thereto;

In the present invention, as the organic polysiloxane, a polyfunctional polysiloxane having three or more addition-curable functional groups (X) bonded thereto is used. The polyfunctional polysiloxane used in the present invention is included in the encapsulant composition to act as a crosslinker, and is used to increase the blending ratio and the degree of crosslinking at a molar ratio of 1: 1 in a two-component curing system. .

As the polyfunctional polysiloxane used in the present invention, a linear polyfunctional polysiloxane may be used as represented by the following general formula (3a).

[Chemical Formula 3]

In Formula 3a, R ¹² , R ¹³ , and R ¹⁴ , which are the same as or different from each other, represent an alkyl group of C _1-20 or an aryl group of C _6-20 , preferably an alkyl group of C _1-10 or C _6-10. It represents an aryl group of, specifically, may be a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group and the like, methyl and phenyl group is most suitable in terms of high refractive index, light resistance and light transmittance. In Chemical Formula 3a, X represents a hydrogen atom or an alkenyl group of C _2-20 as an addition-curable functional group, preferably a hydrogen atom, or an alkenyl group of C _1-10 , and specifically, a hydrogen atom, a vinyl group, allyl Group, butenyl group, and the like are most suitable. In Formula 3a, Y represents a hydrogen atom, an alkenyl group of C _2-20 , or an alkoxy group of C _1-20 , preferably a hydrogen atom, an alkenyl group of C _2-10 , or an alkoxy group of C _1-10 Specifically, hydrogen atom, vinyl group, allyl group, butenyl group, methoxy, ethoxy, propoxy, butoxy and the like are most suitable. In Chemical Formula 3a, g represents the content of a structural unit of -SiR ¹⁴ YO-, and the average value of g is 1 to 10 real number, preferably 1 to 4 real number.

Examples of the linear polyfunctional polysiloxane represented by the general formula (3a) include tri (vinyldimethylsiloxy) cyclopentylsilane and tri (vinyldimethylsiloxy) cycloane as linear polyfunctional polysiloxanes in which a vinyl group is substituted with an addition-curable functional group (X). Hexylsilane, tri (vinyldimethylsiloxy) cycloheptylsilane, tri (vinyldimethylsiloxy) cyclopentenylsilane, tri (vinyldiphenylsiloxy) cyclopentylsilane, tri (vinyldiphenylsiloxy) cyclohexylsilane, Tri (vinyldiphenylsiloxy) cycloheptylsilane, tri (vinyldiphenylsiloxy) cyclopentenylsilane, tri (vinylphenylmethylsiloxy) cyclopentylsilane, tri (vinylphenylmethylsiloxy) cyclohexylsilane, tri (Vinylphenylmethylsiloxy) cycloheptylsilane, tri (vinylphenylmethylsiloxy) cyclopentenylsilane, di (vinyldimethylsiloxy) cyclopentylphenylsilane, di (vinyldimethylsiloxy) cyclohexylphenylsilane, di ( vinyl Methylsiloxy) cycloheptylphenylsilane, di (vinyldimethylsiloxy) cyclopentenylphenylsilane, di (vinyldiphenylsiloxy) cyclopentylphenylsilane, di (vinyldiphenylsiloxy) cyclohexylphenylsilane, di ( Vinyldiphenylsiloxy) cycloheptylphenylsilane, di (vinyldiphenylsiloxy) cyclopentenylphenylsilane, di (vinylphenylmethylsiloxy) cyclopentylphenylsilane, di (vinylphenylmethylsiloxy) cyclohexylphenylsilane , Di (vinylphenylmethylsiloxy) cycloheptylphenylsilane, di (vinylphenylmethylsiloxy) cyclopentenylphenylsilane, and the like. Moreover, as a linear polyfunctional polysiloxane in which the hydrogen atom is substituted by the addition-curable functional group (X), tri (dimethyl siloxy) cyclopentyl silane, tri (dimethyl siloxy) cyclohexyl silane, and tri (dimethyl siloxy) cycloheptyl silane , Tri (dimethylsiloxy) cyclopentenylsilane, tri (diphenylsiloxy) cyclopentylsilane, tri (diphenylsiloxy) cyclohexylsilane, tri (diphenylsiloxy) cycloheptylsilane, tri (diphenylsiloxane Cyclopentenylsilane, tri (phenylmethylsiloxy) cyclopentylsilane, tri (phenylmethylsiloxy) cyclohexylsilane, tri (phenylmethylsiloxy) cycloheptylsilane, tri (phenylmethylsiloxy) cyclopentenyl Silane, di (dimethylsiloxy) cyclopentylphenylsilane, di (dimethylsiloxy) cyclohexylphenylsilane, di (dimethylsiloxy) cycloheptylphenylsilane, di (dimethylsiloxy) cyclopentenylphenylsilane, di (di Phenylsiloxy) cyclopentylphenylsilane, di (di Phenylsiloxy) cyclohexylphenylsilane, di (diphenylsiloxy) cycloheptylphenylsilane, di (diphenylsiloxy) cyclopentenylphenylsilane, di (phenylmethylsiloxy) cyclopentylphenylsilane, di (phenylmethyl Siloxy) cyclohexylphenylsilane, di (phenylmethylsiloxy) cycloheptylphenylsilane, di (phenylmethylsiloxy) cyclopentenylphenylsilane and the like. Linear polyfunctional polysiloxane represented by the formula (3a) can be used alone or in combination of two or more.

In addition, the polyfunctional polysiloxane used by this invention can use the cyclic polyfunctional polysiloxane represented by following General formula (3b).

(3b)

In Formula 3b, R ¹⁵ represents an alkyl group of C _1-20 or an aryl group of C _6-20 , preferably an alkyl group of C _1-10 or an aryl group of C _6-10 , and specifically, a methyl group, an ethyl group, or a propyl group. Group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group and the like, methyl and phenyl group is most suitable in terms of high refractive index, light resistance and light transmittance. In Chemical Formula 3b, X represents a hydrogen atom or an alkenyl group of C _{2 to 20} as an addition-curable functional group, preferably a hydrogen atom or an alkenyl group of C _{1 to 10} , specifically, a hydrogen atom, a vinyl group or an allyl Group, butenyl group, and the like are most suitable. In Chemical Formula 3b, h represents the content of-(SiR ¹⁵ XO)-structural unit, and is 3 to 10 real number, preferably 3 to 6 real number.

As cyclic polyfunctional polysiloxane represented by the said Formula (3b), as a cyclic polyfunctional polysiloxane in which a vinyl group is substituted by the addition-curable functional group (X), trivinyl trimethyl cyclotrisiloxane, tetravinyl tetramethyl cyclo tetrasiloxane, and pentavinyl pentamethyl Cyclopentasiloxane, octavinyloctamethylcyclooctasiloxane, and the like. In addition, the cyclic polyfunctional polysiloxane in which the hydrogen atom is substituted with the addition-curable functional group (X) may include trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, octamethylcyclooctasiloxane, and the like. The cyclic polyfunctional polysiloxane represented by the said Formula (3b) can be used individually or in combination of 2 or more types.

In addition, the polyfunctional polysiloxane represented by the said Formula (3a) or (3b) can be used individually or in combination of 2 or more types.

In the case of the multifunctional polysiloxane represented by Chemical Formula 3a or 3b, the siloxane encapsulant composition of the present invention is preferably contained in the range of 1 to 30% by weight. If the content of the polyfunctional polysiloxane included in the siloxane encapsulant composition is less than 1 wt%, crosslinking may occur, resulting in low hardness. If it exceeds 30 wt%, gas permeability may be increased.

(4) Alkoxypolysiloxanes having alkenyl and alkoxy functional groups bonded to terminals

In the present invention, as the organic polysiloxane, an alkoxypolysiloxane represented by the above formula (4a) or (4b) having an alkenyl and alkoxy functional group bonded to the terminal is used. The alkoxypolysiloxane used in the present invention is included in the encapsulant composition to serve to adjust the adhesion.

As the alkoxypolysiloxane used in the present invention, a linear alkoxypolysiloxane can be used as represented by the following formula (4a).

[Chemical Formula 4a]

In Chemical Formula 4a, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ , which are the same as or different from each other, represent an alkyl group of C _1-20 or an aryl group of C _6-20 , preferably an alkyl group of C _1-10 or an aryl group of C _6-10 , Specifically, it may be a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group and the like, methyl and phenyl group is most suitable in terms of high refractive index, light resistance and light transmittance. In Chemical Formula 4a, A represents-(CH ₂ ) _p- (wherein p is an integer of 1 to 20, preferably an integer of 1 to 10) as a side chain construct. In Formula 4a, Z represents an alkenyl group of C _2-20 as a curing reactive terminal functional group, an alkenyl group of C _2-10 is preferable, and a vinyl group, allyl group, butenyl group, and the like are most suitable. In Formula 4a, i represents the content of a structural unit of the form-(OSiR ¹⁸ R ¹⁹ )-, i is a real number of 0 to 10, preferably a real number of 1 to 10, more preferably 3 to It is a mistake of five.

The linear alkoxypolysiloxane represented by the formula (4a) is specifically 2- (trimethoxysilyl) ethyl-1-vinyl-1,1,3,3-tetramethyldisiloxane, 2- (triethoxysilyl) ethyl- 1-vinyl-1,1,3,3-tetramethyldisiloxane, 3- (trimethoxysilyl) propyl-1-vinyl-1,1,3,3-tetramethyldisiloxane, 3- (triethoxy Silyl) propyl-1-vinyl-1,1,3,3-tetramethyldisiloxane, 1-allyl-2- (trimethoxysilyl) ethyl-1,1,3,3-tetramethyldisiloxane, 1- Allyl-2- (triethoxysilyl) ethyl-1,1,3,3-tetramethyldisiloxane, allyldimethyl (3- (trimethoxysilyl) propyl) silane, allyldimethyl (3- (triethoxysilyl ) Propyl) silane, allyldimethyl (3- (triethoxysilyl) propyl) silane, and the like. Said linear alkoxypolysiloxane can be used individually or in combination of 2 or more types.

As the alkoxypolysiloxane used in the present invention, a cyclic alkoxypolysiloxane represented by the following general formula (4b) can be used.

(4b)

In Chemical Formula 4b, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ , which are the same as or different from each other, represent an alkyl group of C _1-20 or an aryl group of C _6-20 , preferably an alkyl group of C _1-10 or an aryl group of C _6-10 , and specifically, a methyl group. , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group and the like, methyl and phenyl group is most suitable in terms of high refractive index, light resistance and light transmittance. In particular, in view of the adhesive side, R ²⁵ is very preferably a methyl group, an ethyl group or an i-propyl group. In Chemical Formula 4b, Z represents an alkenyl group of C _2-20 as a curing reactive group, an alkenyl group of C _2-10 is preferable, and specifically a vinyl group, allyl group, butenyl group, and the like are most suitable. It is preferable that two or more Z are contained in one molecule. In Formula 4b, j and k represent the content of each structural unit, j is a real number of 1 to 18, k is an integer of 2 to 19, j + k is an integer of 3 to 20. In Formula 4b, m and n represent the contents of each structural unit and are equal to or different from each other, and are 0 to 10 real numbers. In Formula 4b, B may be a bond line or-(R ²³ R ²⁴ Si)-(CH ₂ ) _m- , wherein R ²³ , R ²⁴ , m are as defined above.

The cyclic alkoxypolysiloxane represented by the formula (4b) is specifically 1,3,5-trimethyl-1-trimethoxysilylethyl-3,5-divinylcyclotrisiloxane, 1,3,5-trimethyl-1,3 -Trimethoxysilylethyl-5-vinylcyclotrisiloxane, 1,3,5-trimethyl-1-triethoxysilylethyl-3,5-divinylcyclotrisiloxane, 1,3,5-trimethyl-1, 3-triethoxysilylethyl-5-vinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1-trimethoxysilylethyl-3,5,7-trivinylcyclotetrasiloxane, 1,3, 5,7-tetramethyl-1,3-trimethoxysilylethyl-5,7-divinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,5-trimethoxysilylethyl-3, 7-divinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5-trimethoxysilylethyl-7-vinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1 -Triethoxysilylethyl-3,5,7-trivinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3-triethoxysilylethyl-5,7-divinyl Clotetrasiloxane, 1,3,5,7-tetramethyl-1,5-triethoxysilylethyl-3,7-divinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3, 5-triethoxysilylethyl-7-vinylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1-trimethoxysilylethyl-3,5,7,9-tetravinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3-di-trimethoxysilylethyl-5,7,9-trivinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl- 1,5-di-trimethoxysilylethyl-3,7,9-trivinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3,5-tri-trimethoxysilylethyl -7,9-divinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3,7-tri-trimethoxysilylethyl-5,9-divinylcyclopentasiloxane, 1, 3,5,7,9-pentamethyl-1,3,5,7-tetra-trimethoxysilylethyl-9-vinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1-tri Methoxysilylethyl-3,5,7,9-tetravinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3-di-triethoxysilylethyl-5, 7,9-trivinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,5-di-triethoxysilylethyl-3,7,9-trivinylcyclopentasiloxane, 1,3 , 5,7,9-pentamethyl-1,3,5-tri-triethoxysilylethyl-7,9-divinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3 , 7-tri-triethoxysilylethyl-5,9-divinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7-tetra-triethoxysilylethyl- 9-vinylcyclopentasiloxane and the like. Said linear alkoxypolysiloxane can be used individually or in combination of 2 or more types.

In addition, the alkoxypolysiloxane represented by the said Formula (4a) or (4b) can be used individually or in combination of 2 or more types.

In the case of linear and cyclic alkoxypolysiloxanes represented by the above formulas (4a) or (4b), the siloxane encapsulant composition of the present invention is preferably contained in an amount of 0.1 to 20% by weight. If the content of the linear alkoxypolysiloxane contained in the siloxane encapsulant composition is less than 0.1 wt%, the adhesive strength is insignificant, and if it exceeds 20 wt%, the hardness of the cured product may be lowered.

(5) catalyst for hydrogen siliconization reaction

The catalyst used in the present invention can be used as long as the catalyst used in the hydrogen siliconization reaction. Among the transition metal series, platinum, palladium and rhodium catalysts are particularly useful as catalysts for hydrogen siliconization. Among them, platinum-based catalysts are most widely used in terms of catalyst activity and cost. Platinum-based catalysts are K ₂ PtCl ₆ , H ₂ PtCl _6, n ₂ O (n = 5 ~ 6), H ₂ PtCl ₆ in isopropanol [Speier's Cat.] Platinum chloride compounds such as the same and a platinum compound such as ₃ Pt ₂ [Karstedt's Cat.] Having an oxidation number of zero (DVTMS) are used. These catalysts are further used with inhibitors to control the reaction rate and are known to use as little as 50 times as much as 100 times the inhibitor amount in the amount of catalyst. It is also known that catalyst stability in the air at room temperature is insufficient.

In the encapsulant composition of the present invention, a conventional catalyst is used as the catalyst for the hydrogen siliconization reaction, and the catalysts listed above may also be used, but the platinum represented by the following Chemical Formula 5 can be easily controlled for heat stability and addition reaction rate. Particular preference is given to using complexes.

[Chemical Formula 5]

In Formula 5, R ²⁶ and R ²⁷ are the same as or different from each other, and represent a C _1-20 alkyl group, C _3-20 cycloalkyl group, or C _6-20 aryl group, and the aryl group is selected from C _1-20 alkyl group. It may be substituted or unsubstituted with one to three substituents selected. Specifically, R ²⁶ and R ²⁷ are the same as or different from each other, methyl, ethyl, propyl, i -propyl, n- , i- , t -butyl, pentyl, neopentyl, hexyl, cyclopentyl, Cyclohexyl group, cycloheptyl group, adamantyl group, and the like, and the nature of the present invention, methyl group, ethyl group, propyl group, i -propyl group, t -butyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, Adamantyl is the most suitable. In Formula 5, D represents (-CH ₂ ) _t- (where t is an integer of 1 to 20) or -CH = CH-. In Formula 5, E represents CR ²⁸ R ²⁹ , SiR ³⁰ R ³¹ , or NR ³² , and R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² are The same as or different from each other, an alkyl group of C _1-20 or an aryl group of C _6-20 is represented. In Formula 5, F represents E or O or S.

부분을 좀 더 구체적으로 예시하면 하기와 같다. 포화 상태의 N-헤테로사이클릭카르빈계로서는 1,3-디알킬-이미다졸리딘-2-일리딘 (

), 1,3-디알킬-헥사하이드로피리미딘-2-일리딘(

), 1,3-디알킬-옥타하이드로-1,3-디아제핀-2-일리딘(

)이 사용될 수 있다. 불포화 상태의 N-헤테로사이클릭카르빈계로서는 1,3-디알킬-이미다졸-2-일리딘 (

) 등이 가장 대표적으로 사용될 수 있다. In the platinum complex represented by the formula (5),

More specifically exemplified as follows. As a saturated N-heterocyclic carbinic system, 1,3-dialkyl-imidazolidine-2-ylidine (

), 1,3-dialkyl-hexahydropyrimidin-2-ylidine (

), 1,3-dialkyl-octahydro-1,3-diazepine-2-yridine (

) Can be used. As the N-heterocyclic carbinic system in an unsaturated state, 1,3-dialkyl-imidazol-2-yridine (

) May be most representatively used.

In addition, the content of the catalyst for curing reaction contained in the encapsulant composition of the present invention can be suitably used in an amount having activity as a catalyst. Specifically, in terms of the content of the platinum metal excluding the ligand, it may be used at a concentration of 0.1 to 1000 ppm, preferably at a concentration of 1 to 100 ppm. Pt-carbine ligand catalyst represented by the formula (5) shows a lower reaction activity at room temperature and a higher reaction temperature when the reaction temperature is higher than the general custard or spier platinum catalyst, so that the encapsulant composition is mixed at room temperature. When the curing reaction proceeds slowly, the mixing work stability is excellent.

On the other hand, the present invention may constitute a two-component curing system in which each component constituting the siloxane encapsulant composition described above is stored separately in two containers according to the chemical structural configuration.

Specifically, the first liquid comprising a compound represented by the formula (1), (2), (3a), (3b), (4a) and (4b) in which an alkenyl group is bonded to an addition-curable functional group (X); And a second liquid comprising a compound represented by Chemical Formulas 1, 2, 3a, 3b, 4a, and 4b in which a hydrogen atom or a hydrogen atom and an alkenyl group are simultaneously bonded to the addition-curable functional group (X); It is also possible to configure a two-component curing system that is divided into two containers.

Or, a first liquid comprising a compound represented by the formula (2), 3b, 4a and 4b in which the alkenyl group is bonded to the addition-curable functional group (X), and a catalyst for hydrogen siliconization reaction; And a phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1, a compound represented by Chemical Formula 3a in which an alkenyl group is bonded to an addition-curable functional group (X), and a hydrogen atom bonded to an addition-curable functional group (X). A second liquid containing a polyfunctional polysiloxane represented by 3b; It is also possible to configure a two-component curing system that is divided into two containers.

Or, a first liquid containing a compound represented by the formula (1), (2), (4a) and (4b) in which the alkenyl group is bonded to the addition-curable functional group (X) and a catalyst for hydrogen siliconization reaction; And a second liquid comprising a compound represented by Chemical Formulas 3a and 3b, wherein a hydrogen atom is bonded to an addition-curable functional group (X); It is also possible to configure a two-component curing system that is divided into two containers.

Or, the first liquid containing a compound represented by the formula (2), 4a, and 4b in which the alkenyl group is bonded to the addition-curable functional group (X); And a phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1 in which an alkenyl group is bonded to an addition-curable functional group (X), and a compound represented by Chemical Formulas 3a and 3b in which a hydrogen atom is bonded to the addition-curable functional group (X). 2nd liquid to make; It is also possible to configure a two-component curing system that is divided into two containers.

Or, the first liquid containing a compound represented by the formula (2), 4a, and 4b in which the alkenyl group is bonded to the addition-curable functional group (X); And a second liquid comprising a compound represented by Chemical Formulas 1, 3a, and 3b, wherein a hydrogen atom is bonded to an addition-curable functional group (X); It is also possible to configure a two-component curing system that is divided into two containers.

Moreover, this invention features the hardened | cured material which heat-hardened the said siloxane sealing material composition. The heat curing is made of a temperature of 70 ℃ to 200 ℃ temperature, the heat curing reaction proceeds stably without adding a separate reaction delay agent can form a curing having excellent optical properties. If necessary, it is also included in the scope of the present invention to add and use the conventional reaction retardant used in the usual content range to control the heat curing reaction rate. Conventional reaction delay agents may specifically include 1-ethynyl-1-cyclohexanol or the like, and these reaction delay agents may be used in the range of 1 ppm to 600 ppm based on the total weight of the siloxane encapsulant. The heat curing reaction may be performed using a conventional organic solvent, or may be performed in solvent-free conditions without a separate solvent. The use of the solvent can be appropriately selected at the level of the job.

The present invention will now be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Reference Example: Preparation of Phenylpolysiloxane Resin (Formula 1) Having a Terminal Vinyldimethylsilyl Group

It can be prepared by the method disclosed in Korean Patent Application No. 2011-0134471. In the present invention, a method for producing a phenylpolysiloxane resin having a terminal vinyl dimethylsilyl group is representatively exemplified, but other phenylpolysiloxane resins can be easily produced by the representative production methods illustrated below.

A 2000 mL three-neck reactor was equipped with a thermometer and a dropping funnel, and dried in a nitrogen atmosphere. 220 g of diethyl ether and 132 g of phenyltrichlorosilane were added to the reactor, and the mixture was cooled and maintained at 0 ° C. while stirring. 16.9 g of distilled water was added dropwise through the dropping device for 10 minutes, stirred for 10 minutes, 22.6 g of vinyldimethylchlorosilane was added dropwise for 10 minutes through the dropping device, and 500 g of distilled water was added dropwise through the dropping device for 30 minutes. Was stirred. Thereafter, the organic layer was separated at room temperature, washed three times with 200 mL of distilled water, and then the organic layer was dried over magnesium sulfate and filtered. The filtrate (reaction product) removed solvent and low boiling siloxane compounds under vacuum (0.01 mmHg) at 100 ° C. for 2 hours to give a clear transparent phenylpolysiloxane resin (90 g).

Examples 1 to 17 Formulation of Encapsulant Composition

In this embodiment, a two-component encapsulant was prepared by dividing the pot A (P _A ) and the port B (P _B ) according to the functional group of the polysiloxane used.

P _A is a linear polysiloxane (Formula 2) containing a vinyl group as the addition-curable functional group (X), a cyclic polyfunctional polysiloxane (Formula 3b) containing a vinyl group as the addition-curable functional group (X), and an alkenyl and alkoxy functional group are bonded to the terminal. Prepared linear alkoxypolysiloxane (Chemical Formula 4a), cyclic alkoxypolysiloxane (Chemical Formula 4b) having an alkenyl and alkoxy functional group bonded thereto, and a platinum catalyst (Chemical Formula 5) were mixed, followed by stirring for 1 hour.

On the other hand, P _B is a cyclic polyfunctional resin containing a hydrogen atom as a linear polyfunctional polysiloxane (Chemical Formula 3a) containing a vinyl group as a phenylpolysiloxane resin (Chemical Formula 1) and an addition-curable functional group (X), and an addition-curable functional group (X). Polysiloxane (Formula 3b) was mixed and then prepared by stirring for 1 hour.

The components and the component ratios used in the encapsulation material are summarized in Tables 1 to 3, respectively.

Experimental example. Measurement of Cured Material Properties

Port A (P _A ) and Port B (P _B ) prepared in Examples 1 to 17 were mixed and stirred for 30 minutes, and then bubbles were removed and injected into each mold. And it hardened | cured under the conditions of the following Table 4, and each resin hardened | cured material was obtained. The physical properties of each cured product were measured by the following experimental method, and the results are shown in Table 4 below.

[Measurement of Physical Properties of Hardened Materials]

1) Refractive index: Measured at 633 nm wavelength using Prism Coupler 2010 manufactured by USA Metricon.

2) Transmittance: Using a UV / Vis spectrum analyzer Cary 100 Cornc. Equipped with internal Diffuse Reflectance from Varian, the measurement was carried out at 450 nm wavelength in an area of 1 cm thickness and 1 mm thickness.

3) Hardness: measured by using ASKER Shore hardness tester Durometer Hardness A Type, the result is expressed as Shore A value.

4) Adhesiveness: As a result of hardening on the metal surface to determine the state of adhesion, the state of A is completely bonded between the metal surface and the cured product, B is unevenly bonded, and adhesiveness is inferior to A, C Denotes a state in which no adhesion occurs.

room
city
Yes Phenylpolysiloxane resin (Formula 1) Linear Polysiloxanes (Formula 2) R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ R ⁷ X Molecular Weight
(Mw) ^a usage
(weight%) R ⁸ R ⁹ R ¹⁰ R ¹¹ X Molecular Weight
(Mw) usage
(weight%) One - - CH ₃ CH ₃ - - - vinyl 970 25.5 CH ₃ CH ₃ Ph CH ₃ vinyl 13,000 43.9 2 - - CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 2,530 25.5 CH ₃ CH ₃ CH ₃ Ph vinyl 5,500 ^b 43.5 3 CH ₃ Ph CH ₃ CH ₃ - - - vinyl 1,180 25.5 CH ₃ CH ₃ CH ₃ CH ₃ vinyl 6,200 ^c 43.5 4 - - CH ₃ CH ₃ - - - vinyl 1,780 25.5 CH ₃ CH ₃ Ph CH ₃ vinyl 10,000 43.0 5 - - CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 2,370 48.8 CH ₃ CH ₃ Ph CH ₃ vinyl 2,400 32.0 6 - - CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 1,480 48.8 CH ₃ CH ₃ Ph CH ₃ vinyl 13,000 32.0 7 - - CH ₃ CH ₃ CH ₃ Ph Ph vinyl 1,760 51.3 CH ₃ CH ₃ CH ₃ Ph vinyl 5,500 ^b 33.5 8 CH ₃ CH ₃ CH ₃ Ph - - - vinyl 1,120 63.2 CH ₃ CH ₃ Ph CH ₃ vinyl 10,000 15.8 9 - - CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 2,530 48.8 CH ₃ CH ₃ Ph CH ₃ vinyl 13,000 32.0 10 CH ₃ Ph CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 2,610 48.8 CH ₃ CH ₃ CH ₃ Ph vinyl 5,500 ^b 32.0 11 - - CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 2,370 48.8 CH ₃ CH ₃ Ph CH ₃ vinyl 10,000 32.0 12 - - CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 1,480 48.8 CH ₃ CH ₃ CH ₃ CH ₃ vinyl 6,200 ^c 32.1 13 - - CH ₃ CH ₃ CH ₃ Ph Ph vinyl 1,720 48.8 CH ₃ CH ₃ CH ₃ CH ₃ vinyl 13,000 32.1 14 CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 1,940 48.8 CH ₃ CH ₃ Ph CH ₃ vinyl 2,400 31.6 15 - - CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 1,820 48.8 CH ₃ CH ₃ Ph CH ₃ vinyl 10,000 32.0 16 CH ₃ CH ₃ CH ₃ Ph - - - vinyl 1,120 48.8 CH ₃ CH ₃ CH ₃ Ph vinyl 5,500 ^b 32.5 17 CH ₃ Ph CH ₃ CH ₃ CH ₃ CH ₃ Ph vinyl 2,610 49.3 CH ₃ CH ₃ Ph CH ₃ vinyl 13,000 32.0 ^a Ratio of structural units for each molecular weight Mw in Formula 1 (a: b: c: d)
970 (1.0: 0.27: 0.0: 0.0), 1,120 (1.0: 0.27: 0.27: 0.0), 1,180 (1.0: 0.25: 0.28: 0.0), 1,480 (1.0: 0.27: 0.0: 0.37), 1720 (1.0: 0.26: 0.0: 0.35), 1760 (1.0: 0.27: 0.0: 0.35), 1780 (1.0: 0.25: 0.0: 0.0), 1,820 (1.0: 0.27: 0.0: 0.29), 1940 (1.0: 0.27: 0.26: 0.31), 2,230 (1.0: 0.27: 0.0: 0.28), 2530 (1.0: 0.26: 0.0: 0.26), 2610 (1.0: 0.26: 0.27: 0.27)
^{b The} ratio of structural units in formula (2) is e: f = 1: 1
^{c The} proportion of structural units in formula (2) is e: f = 1: 9

Example Polyfunctional polysiloxanes Formula 3a 3b R ¹² R ¹³ R ¹⁴ Y X g usage
(weight%) R ¹⁵ X h usage
(weight%) One CH ₃ CH ₃ C ₅ H ₉ Ph H One 30.0 CH ₃ vinyl 4 0.1 2 CH ₃ CH ₃ C ₆ H ₁₁ Ph H One 30.0 - - - - 3 Ph CH ₃ C ₅ H ₉ Ph H One 30.0 - - - - 4 CH ₃ CH ₃ C ₅ H ₉ Ph H One 30.0 CH ₃ vinyl 4 0.1 5 CH ₃ CH ₃ C ₆ H ₁₁ Ph H One 18.0 CH ₃ vinyl 3 0.1 6 Ph CH ₃ CH ₃ Ph H One 18.0 - - - - 7 CH ₃ CH ₃ C ₅ H ₉ XR ⁹ R ¹⁰ SiO H One 14.0 CH ₃ vinyl 4 0.2 8 CH ₃ CH ₃ Ph (C ₂ H ₄ ) Ph H One 20.0 - - - - 9 CH ₃ CH ₃ C ₆ H ₁₁ Ph H One 18.0 CH ₃ vinyl 4 0.1 10 Ph CH ₃ CH ₃ Ph H One 18.0 CH ₃ vinyl 4 0.1 11 CH ₃ CH ₃ C ₅ H ₉ Ph H One 18.0 CH ₃ H 4 0.1 ^k 12 CH ₃ CH ₃ Ph (C ₂ H ₄ ) Ph H One 18.0 - - - - 13 CH ₃ CH ₃ Ph Ph H One 18.0 - - - - 14 CH ₃ CH ₃ CH ₃ Ph H One 18.0 - - - - 15 CH ₃ CH ₃ C ₆ H ₁₁ Ph H One 18.0 CH ₃ vinyl 4 0.1 16 Ph CH ₃ C ₅ H ₉ CH ₃ H One 18.0 CH ₃ vinyl 3 0.1 17 CH ₃ CH ₃ C ₅ H ₉ Ph H One 18.0 CH ₃ vinyl 4 0.1

Example Alkoxypolysiloxanes (Formula 4a, 4b) R ¹⁶ ,
R ¹⁷ R ¹⁸ ,
R ¹⁹ R ²¹ ,
R ²² R ²³ ,
R ²⁴ A R ²⁰ or
R ²⁵ i j + k m n B usage
(weight%) One - - CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - CH ₃ - 4 2 2 O 0.5 2 CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - - (CH ₂ ) ₂ C ₂ H ₅ One - - - - 1.0 3 CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - - (CH ₂ ) ₂ CH ₃ One - - - - 1.0 4 - - - - - - - - - - - - 5 - - CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - CH ₃ - 4 2 4 - 1.0 6 CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - - (CH ₂ ) ₂ CH ₃ One - - - - 0.5 7 - - CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - CH ₃ - 4 2 4 - 1.0 8 - - CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - CH ₃ - 4 2 2 O 1.0 9 - - CH ₃ ,
CH ₃ - - CH ₃ - 4 2 - - 1.0 10 Ph
CH ₃ Ph
CH ₃ - - (CH ₂ ) ₂ CH ₃ One - - - - 1.0 11 - - CH ₃ ,
CH ₃ - - CH ₃ - 4 2 - - 1.0 12 - - CH ₃ ,
CH ₃ Ph
CH ₃ - CH ₃ - 4 2 2 O 1.0 13 CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - - (CH ₂ ) ₂ CH ₃ One - - - - 1.0 14 Ph
CH ₃ Ph
CH ₃ - - (CH ₂ ) ₂ CH ₃ One - - - - 1.5 15 - - CH ₃ ,
CH ₃ - - CH ₃ - 4 2 - - 1.0 16 - - CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - CH ₃ - 4 2 2 O 0.5 17 - - CH ₃ ,
CH ₃ CH ₃ ,
CH ₃ - CH ₃ - 4 2 4 - 1.0

Example Primary curing Secondary curing Properties of Cured Products Temperature
(℃) time
(h) Temperature
(℃) time
(h) Refractive index Transmittance Hardness Adhesiveness One 170 2 - - 1.53 99 49 B 2 70 2 150 2 1.53 99 44 B 3 170 2 - - 1.53 98 46 A 4 80 2 150 One 1.53 99 50 C 5 170 2 - - 1.54 98 48 A 6 70 2 150 2 1.54 99 66 B 7 170 2 - - 1.54 99 79 A 8 170 2 - - 1.55 99 81 A 9 170 2 - - 1.54 99 74 A 10 80 2 150 One 1.55 98 67 B 11 170 2 - - 1.54 99 78 A 12 170 2 - - 1.55 98 68 A 13 80 2 150 One 1.55 99 67 A 14 170 2 - - 1.53 98 47 A 15 170 2 - - 1.54 99 71 A 16 70 2 150 2 1.54 99 65 B 17 200 One - - 1.55 98 82 A

Claims (12)

1) a phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1 below, in which a phenylsiloxane core (Core) and a siloxane unit including a terminal functional group (X) are bonded to a surface of the core to form a shell;
2) linear polysiloxane represented by the following formula (2) in which functional groups (X) are bonded at both ends;
3) a linear or cyclic polyfunctional polysiloxane represented by the following formula (3a) or a mixture thereof, in which three or more functional groups (X) are bonded;
4) linear or cyclic alkoxypolysiloxanes represented by the following general formula (4a) in which the alkenyl and alkoxy functional groups are bonded to a terminal thereof, or a mixture thereof; And
5) catalysts for hydrogen siliconization reactions;
Heat curable siloxane encapsulant composition comprising a.
[Formula 1]

(In Formula 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same as or different from each other and represent a C _1-20 alkyl group or C _6-20 aryl group, and X is hydrogen. of atoms, or an alkenyl group of C _2~20, the average value of a is a real number of 5-120, a mean value of b is 0.01 to 0.9 and the percentage of a, and the average value of d is 0.0 to 0.8 percentage of a, c Average is a real number from 0 to 4)
(2)

In Formula 2, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are the same as or different from each other, and represent an alkyl group of C _1-20 or an aryl group of C _6-20 , and X represents a hydrogen atom or C _2-20 An alkenyl group, e is an integer of 10 to 1,000, f is an integer of 10 to 1,000, the weight average molecular weight (Mw) of the linear polysiloxane represented by the formula (2) is 1,000 to 150,000 g / mol, and in the molecular chain The molar ratio of the alkyl group and the aryl group bonded is in the range of 1: 9 to 9: 1)
[Chemical Formula 3]

(In Formula 3a, R ¹² , R ¹³ , and R ¹⁴ are the same as or different from each other, and represent an alkyl group of C _1-20 or an aryl group of C _6-20 , and X represents a hydrogen atom or an alkenyl group of C _2-20 . Y represents a hydrogen atom, an alkenyl group of C _2-20 , or an alkoxy group of C _1-20 , and g is an integer of 1 to 10).
(3b)

(In Formula 3b, R ¹⁵ represents an alkyl group of C _1-20 or an aryl group of C _6-20 , X represents a hydrogen atom or an alkenyl group of C _2-20 , and h is an integer of 3 to 10.)
[Chemical Formula 4a]

(In Chemical Formula 4a, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ , which are the same as or different from each other, represent an alkyl group of C _1-20 or an aryl group of C _6-20 , where A is — (CH ₂ ) _p −, wherein p is an integer from 1 to 20 Z represents an alkenyl group of C _2-20 , and i is an integer of 0 to 10).
(4b)

(In Formula 4b, Z represents an alkenyl group of C _2-20 , B represents a bond or-(R ²³ R ²⁴ Si)-(CH ₂ ) _m- , and R ²¹ , R ²² , R ²³ , R ²⁴ , and R ²⁵ , which are the same as or different from each other, represent an alkyl group of C _1-20 or an aryl group of C _6-20 , j is an integer of at least 1 to 18, k is an integer of 2 to 19, and j + k Is an integer of 3 to 20, and m and n are the same or different and are integers of 0 to 10.
The method of claim 1,
1) 10 to 88% by weight of a phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1;
2) 10 to 50% by weight of the linear polysiloxane represented by Formula 2;
3) 1 to 30% by weight of the multifunctional polysiloxane represented by Chemical Formula 3a or 3b or a mixture thereof;
4) 0.1 to 20% by weight of an alkoxypolysiloxane represented by Formula 4a or 4b or a mixture thereof; And
5) 0.1 to 1000 ppm of the silicon hydride catalyst;
A heat curable siloxane encapsulant composition comprising a.
The method according to claim 1,
Heat-curable siloxane encapsulant composition, characterized in that the hydrogen-silicon reaction catalyst is a platinum complex represented by the following formula (5).
[Chemical Formula 5]

(In Formula 5, R ²⁶ and R ²⁷ are the same or different as an alkyl group of C _1-20, it represents a group of C _3-20 cycloalkyl, or C _6-20 aryl, the aryl group of C _1-20 Substituted or unsubstituted with 1 to 3 substituents selected from the alkyl groups, D represents (-CH ₂ ) _t- (where t is an integer from 1 to 20) or -CH = CH-, and E is CR ²⁸ R ²⁹ , SiR ³⁰ R ³¹ , or NR ³² , and R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , and R ^{32 represent the} same or different alkyl group of C _1-20 or aryl group of C _6-20 , and F Is E or O or S)
The method according to claim 3,
In Chemical Formula 5

The ligand is 1,3-dialkyl-imidazolidine-2-ylidine (

), 1,3-dialkyl-hexahydropyrimidin-2-ylidine (

), 1,3-dialkyl-octahydro-1,3-diazepine-2-yridine (

), And 1,3-dialkyl-imidazol-2-yridine (

Heat-curable siloxane encapsulant composition, characterized in that the N-heterocyclic carbinic ligand (wherein R ²⁶ and R ²⁷ are as defined in claim 3).
The method according to claim 1,
A first liquid comprising a compound represented by the formulas (1), (2), (3a), (3b), (4a) and (4b) in which an alkenyl group is bonded to an addition-curable functional group (X); and a catalyst for hydrogen siliconization reaction; And
A second liquid containing a compound represented by Chemical Formulas 1, 2, 3a, 3b, 4a, and 4b in which a hydrogen atom or a hydrogen atom and an alkenyl group are simultaneously bonded to the addition-curable functional group (X);
A heat curable siloxane encapsulant composition, characterized in that consisting of.
The method according to claim 1,
A first liquid comprising a compound represented by the formulas (2), (3b), (4a) and (4b) in which an alkenyl group is bonded to an addition-curable functional group (X); and a catalyst for hydrogen siliconization reaction; And
A phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1, a compound represented by Chemical Formula 3a in which an alkenyl group is bonded to an addition-curable functional group (X), and the chemical formula 3b in which a hydrogen atom is bonded to an addition-curable functional group (X) A second liquid containing a polyfunctional polysiloxane represented by;
A heat curable siloxane encapsulant composition, characterized in that consisting of.
The method according to claim 1,
A first liquid comprising a compound represented by the formula (1), (2), (4a) and (4b) in which an alkenyl group is bonded to an addition-curable functional group (X) and a catalyst for hydrogen siliconization reaction; And
A second liquid containing a compound represented by Chemical Formulas 3a and 3b having a hydrogen atom bonded to an addition-curable functional group (X);
A heat curable siloxane encapsulant composition, characterized in that consisting of.
The method according to claim 1,
A first liquid containing a compound represented by the formula (2), (4a) and (4b) in which the alkenyl group is bonded to the addition-curable functional group (X); And
A phenylpolysiloxane resin having a core-shell structure represented by Chemical Formula 1 in which an alkenyl group is bonded to the addition-curable functional group (X), and a compound represented by Chemical Formulas 3a and 3b in which a hydrogen atom is bonded to the addition-curable functional group (X). Second liquid;
A heat curable siloxane encapsulant composition, characterized in that consisting of.
The method according to claim 1,
A first liquid containing a compound represented by the formulas (2), (4a) and (4b) in which an alkenyl group is bonded to an addition-curable functional group (X); And
A second liquid containing a compound represented by Chemical Formulas 1, 3a, and 3b having a hydrogen atom bonded to an addition-curable functional group (X);
A heat curable siloxane encapsulant composition, characterized in that consisting of.
Hardened | cured material characterized by heat-hardening the composition of any one of Claims 1-9 by 70 degreeC-200 degreeC temperature conditions.
The cured product of claim 10, wherein the heat curing is performed under conditions in which a reaction retardant is present.
The cured product of claim 10, wherein the heat curing is performed in a solvent-free condition.