KR20240008134A - Crosslinking composition and crosslinker composition for olefin based copolymer, encapsulant composition for optical elements and encapsulant film for optical elements comprising the same - Google Patents

Abstract

The present invention relates to a crosslinking agent composition for an olefinic copolymer, an encapsulating material composition for an optical device, an encapsulating material film for an optical device, and an optoelectronic device, wherein the compound of Formula 1 is added to a crosslinking agent composition for an olefinic copolymer or an optical device containing an olefinic copolymer. By applying it as a crosslinking aid for the self-use encapsulant composition, an encapsulant composition for optical devices and an encapsulant film for optical devices with high volume resistivity and light transmittance while exhibiting excellent productivity can be manufactured.

Description

Crosslinking agent composition for olefin-based copolymers, encapsulating material composition for optical devices containing the same, and encapsulating material film for optical devices

The present invention relates to a crosslinking agent composition for an olefin-based copolymer, an encapsulating material composition for an optical device containing the same, and an encapsulating material film for an optical device. A cross-linking agent composition for an olefin-based copolymer used in an encapsulating material composition for an optical device containing the same, It relates to an encapsulant composition for optical devices containing the crosslinking agent, an encapsulant film for optical devices manufactured using the same, and an optical device module including the encapsulant film for optical devices.

As global environmental and energy problems become increasingly serious, solar cells are attracting attention as a means of generating clean, non-depletable energy. When solar cells are used outdoors, such as on the roof of a building, they are generally used in module form. When manufacturing solar cell modules, a protective sheet for solar cell modules (transparent protection member on the surface)/solar cell is used to obtain a crystalline solar cell module. It is manufactured by laminating in the following order: battery encapsulation material/crystalline solar cell device/crystalline solar cell device/solar cell encapsulation material/protective sheet for solar cell module (back side protection member). Meanwhile, in order to obtain a thin film solar cell module, it is manufactured by stacking thin film solar cell element/solar cell encapsulation material/protective sheet for solar cell module (back side protection member) in that order.

As the solar cell encapsulation material described above, ethylene/vinyl acetate copolymer, ethylene/alpha-olefin copolymer, etc. are generally used. In addition, since long-term weather resistance is required in solar cell encapsulation materials, a light stabilizer is usually included as an additive. In addition, in consideration of the adhesion between the front transparent protective member represented by glass and the back side protective member, the solar cell encapsulating material usually also contains a silane coupling agent.

Specifically, ethylene/vinyl acetate copolymer (EVA) sheets have been widely used due to their excellent transparency, flexibility, and adhesiveness. Ethylene/vinyl acetate copolymer (EVA) films are widely used because of their excellent transparency, flexibility, and adhesiveness. However, when using an EVA composition as a component of a solar cell encapsulation material, there was concern that components such as acetic acid gas generated when EVA decomposes may affect the solar cell device.

Since the ethylene/alpha-olefin copolymer does not have the problem of hydrolysis of the resin, it was able to solve the problems of reduced lifespan and reliability. However, since the ethylene/alpha-olefin copolymer does not contain a polar group in the resin, its miscibility with the polar crosslinking aid included as a component of existing solar cell encapsulation materials is poor, and impregnation takes a very long time, causing a problem in productivity. There was.

In this way, the development of a cross-linking aid that can improve the productivity of solar cell encapsulants containing ethylene/alpha-olefin copolymers, which have excellent volume resistivity and can be useful as materials requiring high insulation properties such as solar cell encapsulants, has been developed. It is necessary.

Korean open patent 2018-0063669

The problem to be solved by the present invention is to provide a cross-linking agent composition for olefin-based copolymers used for cross-linking olefin-based copolymers containing a cross-linking aid that has excellent miscibility with the olefin-based copolymer.

Another problem to be solved by the present invention is to provide an encapsulant composition for optical devices that includes an olefin-based copolymer and a crosslinking aid with excellent miscibility, and exhibits high volume resistivity and excellent insulation properties through the same.

Another problem to be solved by the present invention is to provide an encapsulant film for optical devices manufactured using the above encapsulant composition for optical devices.

Another problem to be solved by the present invention is to provide an optoelectronic device including the encapsulant film for optical devices.

In order to solve the above problems, the present invention provides a crosslinking agent composition for olefin-based copolymers, an encapsulant composition for optical devices, an encapsulant film for optical devices, and an optoelectronic device.

[1] The present invention provides a crosslinking agent composition for olefin-based copolymers containing a compound of the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₆ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, where two or more of R ₁ to R ₃ and two or more of R ₄ to R ₆ are each Independently, it is alkenyl having 2 to 20 carbon atoms.

[2] In the present invention, in [1] above, R ₁ , R ₃ , R ₄ and R ₆ are each independently alkenyl having 2 to 20 carbon atoms, and R ₂ and R ₅ are each independently alkenyl having 1 carbon atom. Provided is a crosslinking agent composition for an olefin-based copolymer that is an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms.

[3] The present invention according to the above [1] or [2], wherein R ₁ , R ₃ , R ₄ and R ₆ are each independently alkenyl having 2 to 12 carbon atoms having a double bond at the terminal, and R ₂ and R ₅ are each independently alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms having a double bond at the terminal, providing a crosslinking agent composition for olefin-based copolymers.

[4] The present invention provides a crosslinking agent composition for olefin-based copolymers according to any one of [1] to [3] above, wherein the crosslinking aid compound of Formula 1 is hexavinyl disiloxane or tetravinyldimethyl disiloxane.

[5] The present invention provides a crosslinking agent composition for an olefin-based copolymer according to any one of [1] to [4] above, wherein the crosslinking agent is one or two or more selected from the group consisting of organic peroxides, hydroperoxides, and azo compounds. to provide.

[6] The present invention according to any one of the above [1] to [5], wherein the crosslinking agent is t-butylcumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl- 2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane, t-butylhydroperoxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o- Methylbenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxy isobutyrate, t-butylperoxy acetate, t-butylperoxy-2-ethylhexyl carbonate (TBEC), t-butylperoxy -2-ethylhexanoate, t-butylperoxy pivarate, t-butylperoxy octoate, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)-3-hexyne, methyl ethyl ketone peroxide, cyclohexanone peroxide Provided is a crosslinking agent composition for olefin-based copolymers, which is at least one selected from the group consisting of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile).

[7] The present invention is according to any one of the above [1] to [6], wherein the silane coupling agent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl )-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane The group consisting of ethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, and p-styryl trimethoxysilane. It provides a crosslinking agent composition for olefin-based copolymers, which is at least one selected from the group consisting of:

[8] In addition, the present invention relates to an olefin-based polymer; and a crosslinking agent composition for an olefin-based copolymer according to any one of [1] to [7] above.

[9] The present invention provides the encapsulant composition for optical devices according to [8] above, wherein the olefin-based copolymer is an ethylene/alpha-olefin copolymer.

[10] Additionally, the present invention provides an encapsulant film for optical devices containing a structure derived from an olefin-based copolymer and a compound of the following formula (1):

[Formula 1]

In Formula 1, R ₁ to R ₆ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, where two or more of R ₁ to R ₃ and two or more of R ₄ to R ₆ are each Independently, it is alkenyl having 2 to 20 carbon atoms.

[11] Additionally, the present invention provides an optoelectronic device including an optical device and the encapsulant film for an optical device according to [10].

The cross-linking agent composition for olefin-based copolymers of the present invention contains a compound with excellent miscibility with olefin-based copolymers as a cross-linking aid, and is quick to impregnate olefin-based copolymers, and the encapsulant composition for optical devices manufactured using it is excellent. Because it exhibits volume resistivity and light transmittance, it can be widely used for various purposes in the electrical and electronic industries.

Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.

Terms or words used in the description and claims of the present invention should not be construed as limited to their usual or dictionary meanings, and the inventor appropriately defines the concept of terms in order to explain his or her invention in the best way. Based on the principle that it can be done, it must be interpreted with a meaning and concept consistent with the technical idea of the present invention.

A detailed description of each substituent defined in this specification is as follows.

As used herein, the term 'alkyl' refers to a straight-chain or branched-chain hydrocarbon residue, unless otherwise specified.

As used herein, the term 'alkenyl' refers to a straight-chain or branched-chain alkenyl group, unless otherwise specified.

The branched chain is alkyl having 1 to 20 carbon atoms; Alternatively, it may be alkenyl having 2 to 20 carbon atoms.

[Crosslinking agent composition for olefin-based copolymer]

The crosslinking agent composition for olefin-based copolymers of the present invention includes a crosslinking agent; Silane coupling agent; and a crosslinking aid compound of the following formula (1).

[Formula 1]

In Formula 1, R ₁ , R ₃ , R ₄ and R ₆ may each independently be alkenyl having 2 to 20 carbon atoms, and R ₂ and R ₅ may each independently be alkyl having 1 to 20 carbon atoms or 2 carbon atoms. It may be an alkenyl of 20 to 20.

In addition, in Formula 1, R ₁ , R ₃ , R ₄ and R ₆ may each independently be alkenyl having 2 to 12 carbon atoms having a double bond at the terminal, and R ₂ and R ₅ may each independently have It may be alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms having a double bond at the terminal.

In addition, the crosslinking agent composition for olefin-based copolymers according to an example of the present invention may specifically include hexavinyl disiloxane represented by Formula 2 below or tetravinyldimethyl disiloxane represented by Formula 3 below as the compound of Formula 1. there is.

[Formula 2]

[Formula 3]

The compound of Chemical Formula 1 included in the crosslinking agent composition for olefinic copolymers of the present invention may be included as a crosslinking aid in the crosslinking agent composition for olefinic copolymers, and the compound of Chemical Formula 1 exhibits excellent miscibility with olefinic copolymers. It can exhibit fast impregnation speed. Through this, the absorption rate of the cross-linking agent, which has the slowest absorption rate for olefin-based copolymers, is improved among the cross-linking agents, silane coupling agents, and cross-linking aids included in the cross-linking agent composition used for conventional olefin-based copolymers. It can have the effect of shortening the impregnation time, and can exhibit excellent crosslinking properties for olefin-based copolymers while achieving a short impregnation time.

When the crosslinking agent composition for olefinic copolymers of the present invention containing the compound of Formula 1 is applied as a crosslinking agent to an encapsulating material composition for optical devices containing an olefinic copolymer, the encapsulating material composition for optical devices has a high crosslinking degree, volume resistivity, and It can indicate light transmittance.

As the crosslinking agent, a variety of crosslinking agents known in the art may be used as long as they are crosslinkable compounds capable of initiating radical polymerization or forming crosslinking bonds, and may be selected from the group consisting of organic peroxides, hydroperoxides, and azo compounds. One or two or more types can be used.

Additionally, in one example of the present invention, the crosslinking agent may specifically be an organic peroxide.

The organic peroxide may be an organic peroxide having a 1-hour half-life temperature of 120 to 135°C, for example, 120 to 130°C, 120 to 125°C, specifically 121°C. The “1 hour half-life temperature” refers to the temperature at which the half-life of the crosslinking agent is 1 hour. Depending on the 1-hour half-life temperature, the temperature at which the radical initiation reaction efficiently occurs varies. Therefore, when an organic peroxide having a 1-hour half-life temperature in the above-mentioned range is used as a crosslinking agent, the lamination process temperature for manufacturing an optoelectronic device A radical-initiated reaction, that is, a cross-linking reaction, can proceed effectively.

The crosslinking agent includes t-butylcumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl dialkyl peroxides such as -2,5-di(t-butylperoxy)-3-hexyne; Hydroperoxides such as cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane, and t-butyl hydroperoxide; diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; t-butylperoxy isobutyrate, t-butylperoxy acetate, t-butylperoxy-2-ethylhexyl carbonate (TBEC), t-butylperoxy-2-ethylhexanoate, t-butylperoxy piva. Latex, t-butylperoxy octoate, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 2,5-dimethyl-2,5-di(benzoyl peroxide) Peroxy esters such as oxy)hexane and 2,5-dimethyl-2,5-di(benzoylperoxy)-3-hexyne; and a group consisting of ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, and azo compounds such as lauryl peroxide, azobisisobutyronitrile, and azobis(2,4-dimethylvaleronitrile). One or more types selected from may be included, but are not limited thereto.

The silane coupling agent is, for example, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane (MEMO), vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyl methyldimethoxysilane , 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, and p-styryl trimethoxysilane.

The crosslinking agent composition for an olefin-based copolymer may include 20 to 80 parts by weight of the crosslinking agent, 5 to 30 parts by weight of the silane coupling agent, and 10 to 60 parts by weight of a crosslinking aid including the crosslinking aid compound of Formula 1. there is. The content of each component may refer to the relative ratio between the weights of each component included in the crosslinking agent composition for olefin-based copolymer.

The crosslinking agent may be included in the crosslinking agent composition for olefin-based copolymer in an amount of 20 to 80 parts by weight, specifically 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more to 80 parts by weight. It may be included in an amount of 75 parts by weight or less, or 70 parts by weight or less. If the content of the cross-linking agent is too small, it is difficult for a cross-linking reaction to occur when using the olefin-based copolymer, and if the content of the cross-linking agent is excessive, the volume resistivity of the encapsulant for optical devices manufactured using the olefin-based copolymer may decrease. When the cross-linking agent is included in the above range in the cross-linking agent composition for olefin-based copolymers, the encapsulant composition for optical devices using this can cause an appropriate cross-linking reaction and be manufactured into an encapsulant for optical devices, and the manufactured encapsulant for optical devices has a high volume resistivity. It can be expressed.

The silane coupling agent may be included in the crosslinking agent composition for olefin-based copolymer in an amount of 5 to 30 parts by weight, specifically 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more to 20 parts by weight or less, 19 It may be included in an amount of less than or equal to 18 parts by weight. If the amount of the silane coupling agent is too small, when the olefin-based copolymer is used, the adhesion of the optical device encapsulant composition to a substrate, for example, the adhesive strength of the optical device encapsulant composition to a glass substrate is low, and it can be used as an optical device encapsulant. It is difficult to achieve appropriate performance, and if the amount of the silane coupling agent is excessive, the volume resistivity of the encapsulating material for optical devices decreases, which is not appropriate. When the silane coupling agent is included in the above range in the crosslinking agent composition for olefin-based copolymers, the encapsulant composition for optical devices using the same exhibits excellent adhesion to the substrate of the optical device or the glass substrate on which the optical device is located, effectively preventing the penetration of moisture, etc. Optical devices can maintain excellent performance over the long term, and encapsulating materials for optical devices can exhibit high volume resistivity.

The crosslinking aid containing the crosslinking aid compound of Formula 1 may be included in the crosslinking agent composition for olefin-based copolymer in an amount of 10 to 60 parts by weight, specifically 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more to 60 parts by weight. It may be included in an amount of 55 parts by weight or less, or 50 parts by weight or less.

The olefin-based copolymer to which the crosslinking agent composition for olefin-based copolymer can be applied may, for example, satisfy a) a density of 0.85 to 0.90 g/cc, and (b) a melt index of 0.1 to 100 g/10 min.

The density (a) of the olefin-based copolymer is specifically 0.850 g/cc or more, 0.855 g/cc or more, 0.860 g/cc or more, 0.865 g/cc or more, or 0.870 g/cc to 0.900 g/cc or less 0.895 g. /cc or less, 0.890 g/cc or less, 0.885 g/cc or less, or 0.880 g/cc or less. If the density of the olefin-based copolymer is too high, the light transmittance of the encapsulant composition for optical devices using the same and the encapsulant for optical devices manufactured using the same may decrease due to the crystalline phase contained in the olefin-based copolymer. When the composite satisfies the above density range, it can exhibit high light transmittance.

(b) The melt index of the olefin-based copolymer is 0.1 g/10min or more, 0.5 g/10min or more, 1.0 g/10min or more, 1.5 g/10min or more, 2.0 g/10min or more, 2.5 g/10min or more, 5.0 g /10 min or more, or 10.0 g/10min or more to 100 g/10min or less, 95 g/10min or less, 90 g/10min or less, 85 g/10min or less, 80 g/10min or less, 75 g/10min or less, 70 g/ It may be less than 10 min, less than 60 g/10 min, or less than 50 g/10 min. If the melt index of the olefin-based copolymer is outside the above range and is too low or high, the moldability of the optical device encapsulant composition may deteriorate, making stable extrusion difficult. However, the olefin-based copolymer may have a melt index of When the range is satisfied, the moldability of the optical device encapsulant composition is excellent, so that the optical device encapsulant and the optical device encapsulant sheet can be stably extruded.

The olefin-based copolymer to which the cross-linking agent composition for olefin-based copolymers according to an example of the present invention is applied may specifically be an ethylene/alpha-olefin copolymer.

Typically, the density of ethylene/alpha-olefin copolymers is affected by the type and content of monomers used during polymerization and degree of polymerization, and in the case of copolymers, it is greatly affected by the content of comonomers. At this time, the larger the comonomer content, the lower density ethylene/alpha-olefin copolymer can be produced, and the amount of comonomer that can be introduced into the copolymer may depend on the inherent copolymerization of the catalyst.

The ethylene/alpha-olefin copolymer to which the crosslinking agent composition for olefin-based copolymers of the present invention is applied may exhibit low density as described above and exhibit excellent processability.

The ethylene/alpha-olefin copolymer is manufactured by copolymerizing ethylene and an alpha-olefin monomer. In this case, the alpha-olefin, which refers to the portion derived from the alpha-olefin monomer in the copolymer, has 3 to 20 carbon atoms. Alpha-olefins, specifically propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, Examples include 1-tetradecene, 1-hexadecene, or 1-eicocene, and these may be one type alone or a mixture of two or more types. Among these, the alpha-olefin may be 1-butene, 1-hexene, or 1-octene, and specifically may be 1-butene, 1-hexene, or a combination thereof.

In addition, the content of alpha-olefin in the ethylene/alpha-olefin copolymer may be appropriately selected within a range that satisfies the above-mentioned physical property requirements, and specifically, more than 0 mol% but not more than 99 mol%, or 10 mol%. It may be from 50 mol%, but is not limited thereto.

In addition, the olefin-based copolymer may be an ethylene/alpha-olefin copolymer having a volume resistivity of 1.0×10 ¹⁵ Ω·cm or more, specifically 3.0×10 ¹⁵ Ω·cm or more, 5.0×10 ¹⁵ Ω·cm, or It may be a copolymer of 7.0×10 ¹⁵ Ω·cm or more. If the volume resistivity of the olefin-based copolymer is too low, the volume resistivity of the encapsulant composition for optical devices may not reach an appropriate level after crosslinking. However, if the volume resistivity of the olefin-based copolymer satisfies the above value, the encapsulant composition for optical devices After this crosslinking, it can exhibit excellent volume resistivity. The upper limit of the volume resistivity of the olefin-based copolymer is not particularly limited, but considering the volume resistivity that olefin-based copolymers usually exhibit and the difficulty in producing olefin-based copolymers with high volume resistivity, 9.9 Those of 10 ¹⁷ Ω·cm or less, 9.0×10 ¹⁷ Ω·cm or less, or 7.0×10 ¹⁷ Ω·cm or less may be used.

[Encapsulating material composition for optical devices]

The crosslinking agent composition for olefin-based copolymers of the present invention can be used together with olefin-based copolymers to form an encapsulant composition for optical devices. The present invention relates to an olefin-based polymer; And it provides an encapsulant composition for optical devices comprising the crosslinking agent composition for olefin-based copolymers.

The description of the olefin-based copolymer and the encapsulating material composition for optical devices is the same as described above.

The olefin-based copolymer may be included in an amount of 80 to 99.5 parts by weight based on 100 parts by weight of the encapsulating material composition for optical devices, and specifically, 80 parts by weight or more, 82 parts by weight or more, 85 parts by weight or more, 86 parts by weight or more, 87 parts by weight or more. It may be included in an amount of more than 88 parts by weight, but less than 99.5 parts by weight, less than 99 parts by weight, or less than 98.5 parts by weight. If the amount of the olefin-based copolymer included in the optical device encapsulant composition is too small, it is difficult to properly demonstrate mechanical properties such as tear resistance and tear strength of the optical device encapsulant, so the olefin-based copolymer is used in the entire optical device encapsulant composition. When included in the above range, it can exhibit appropriate mechanical properties as an encapsulant for optical devices.

The crosslinking agent composition for olefin-based copolymer according to an example of the present invention may be used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the olefin-based copolymer. The crosslinking agent composition for the olefin-based copolymer is specifically 0.5 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, based on 100 parts by weight of the olefin-based copolymer. at least 1.4 parts by weight, or at least 1.5 parts by weight and at most 20 parts by weight, at most 18 parts by weight, at most 15 parts by weight, at most 10 parts by weight, at most 8 parts by weight, at most 6 parts by weight, and at most 5 parts by weight, Alternatively, it may be used in an amount of 3 parts by weight or less. If the amount of the crosslinking agent composition used in the olefin-based copolymer is too small, it is difficult for the crosslinking reaction to occur, and if the amount of the crosslinking agent composition used is excessive, the volume resistivity of the encapsulant for optical devices may decrease. When the crosslinking agent composition is used in the above ratio with respect to the olefin-based copolymer, the encapsulating material for optical devices using the same can cause an appropriate crosslinking reaction and be manufactured into an encapsulating material for optical devices, and the manufactured encapsulating material for optical devices exhibits a high volume resistivity. You can.

In the encapsulating material composition for optical devices according to an example of the present invention, the crosslinking aid compound of Formula 1 may be included in an amount of 0.1 to 9 parts by weight based on 100 parts by weight of the olefin-based copolymer. The crosslinking aid compound of Formula 1 is specifically 0.1 part by weight or more, 0.2 part by weight or more, 0.3 part by weight or more, or 0.4 part by weight or more to 9 parts by weight or less, or less than 8 parts by weight, based on 100 parts by weight of the olefin-based copolymer. , may be included in 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, or 2 parts by weight or less. When the crosslinking aid compound of Formula 1 and the second crosslinking aid compound are used together as a crosslinking aid, the total amount may satisfy the above range. If the amount of crosslinking aid used in the olefin-based copolymer is too small, it is difficult for a crosslinking reaction to occur, and if the amount of crosslinking aid used is excessive, the volume resistivity of the encapsulant for optical devices may decrease. When the crosslinking aid is included in the above ratio with respect to the olefin-based copolymer, the encapsulant composition for optical devices can undergo an appropriate crosslinking reaction to form an encapsulant for optical devices, and the formed encapsulant for optical devices can exhibit a high volume resistivity.

In addition, the encapsulant composition for optical devices may further include various additives known in the field, depending on the purpose to which the resin component is applied, in addition to the above components.

Examples of the additive include one or more additives selected from light stabilizers, UV absorbers, and heat stabilizers.

The light stabilizer may serve to prevent photo-oxidation by capturing active species that initiate photodeterioration of the resin, depending on the application to which the composition is applied. The type of light stabilizer that can be used is not particularly limited, and for example, known compounds such as hindered amine-based compounds or hindered piperidine-based compounds can be used.

Depending on the use of the composition, the UV absorber may absorb ultraviolet rays from sunlight or the like and convert them into harmless heat energy within the molecule, thereby preventing the active species that initiate photodeterioration in the resin composition from being excited. The specific type of UV absorber that can be used is not particularly limited, and for example, inorganic UV absorbers such as benzophenone-based, benzotriazole-based, acrylnitrile-based, metal complex salt-based, hindered amine-based, ultrafine particle titanium oxide or ultrafine particle zinc oxide. One type or a mixture of two or more types of absorbent may be used.

In addition, examples of the heat stabilizer include tris(2,4-di-tert-butylphenyl)phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, and tetrakis. (2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, etc. Phosphorus-based heat stabilizer; Lactone-based heat stabilizers such as the reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene may be used, and one or two or more of the above may be used. there is.

The content of the light stabilizer, UV absorber, and/or heat stabilizer is not particularly limited. That is, the content of the additive can be appropriately selected considering the use of the resin composition, the shape or density of the additive, etc., and is usually within the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the encapsulant composition for optical devices. It can be adjusted appropriately.

In addition, the encapsulating material composition for optical devices can be molded by methods such as injection and extrusion to be used as a variety of molded products, and specifically as an encapsulant for encapsulating devices in various optoelectronic devices, such as solar cells. It can be used, for example, as an industrial material applied to a temperature-elevated lamination process, etc., but its use is not limited thereto.

In addition, the present invention provides an encapsulant film for optical devices manufactured using the above encapsulant composition for optical devices.

The encapsulant film for optical devices according to an embodiment of the present invention may include a structure derived from an olefin-based copolymer and a crosslinking aid compound of the following formula (1).

[Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, where two or more of R ₁ to R ₃ and two or more of R ₄ to R ₆ are each independently 2 to 2 carbon atoms. It is the alkenyl of 20.

The description of the olefin-based copolymer and the crosslinking aid compound of Formula 1 is the same as above.

In addition, the encapsulant film for an optical device according to another embodiment of the present invention may include structures derived from the crosslinking aid compound of Formula 1 and the second crosslinking aid compound, respectively.

The description of the second crosslinking aid compound and the description of when the crosslinking aid compound of Formula 1 and the second crosslinking aid compound are used together as a crosslinking aid are as described above.

Additionally, the present invention provides an optoelectronic device including the encapsulant film for an optical device.

Example

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

Example 1

Tetravinyldimethyl disiloxane (TVDMDS, manufactured by Gelest Inc.) was prepared as a crosslinking aid.

500 g of LUCENE ^TM LF675 from LG Chemical, an ethylene/1-butene copolymer, was dried overnight using a convection oven at 40°C. The density of LUCENE ^TM LF675 measured by ASTM D1505 is 0.877 g/cm ³ , and the melt index (190°C, 2.16 Kg) measured by ASTM D1238 is 14.0 g/10 min. The bowl temperature of the viscometer (Haake Modular Torque Viscometer, manufactured by Thermo Electron (Karsruhe) GmbH) was set to 40°C. After adding the ethylene/alpha olefin copolymer to the bowl, using an electric pipette, a cross-linking agent composition (t-butyl 1-(2-ethylhexyl) monoperoxycarbonate (TBEC, manufactured by Sigma-Aldrich as a cross-linking agent) 1.00 phr (parts per hundred rubber), 0.25 phr of tetravinyldimethyl disiloxane (TVDMDS) prepared above as a crosslinking aid, and 0.20 phr of methacryloxypropyltrimethoxysilane (MEMO, manufactured by Shin-Etsu) as a silane coupling agent. While stirring at 40 rpm at 40°C, the change in torque value over time was observed. Impregnation was terminated when the torque value rapidly increased, and the completion time of impregnation with the crosslinking agent composition was measured.

Afterwards, the impregnated sample was press-molded to an average thickness of 0.5 mm using a micro extruder at a low temperature (extruder barrel temperature of 90 to 100°C) to prevent high-temperature crosslinking, thereby producing a sheet-shaped encapsulant film.

Example 2

An encapsulant film was manufactured in the same manner as in Example 1, except that the amount of tetravinyldimethyl disiloxane (TVDMDS) as a crosslinking aid was changed to 0.50 phr.

Example 3

An encapsulant film was manufactured in the same manner as in Example 1, except that the amount of tetravinyldimethyl disiloxane (TVDMDS) as a crosslinking aid was changed to 1.00 phr.

Example 4

An encapsulant film was manufactured in the same manner as Example 1, except that hexavinyl disiloxane (HVDS) was used instead of tetravinyldimethyl disiloxane (TVDMDS).

Example 5

An encapsulant film was manufactured in the same manner as in Example 1, except that hexavinyl disiloxane (HVDS) was used instead of tetravinyldimethyl disiloxane (TVDMDS) and the dosage was changed to 0.50 phr.

Example 6

An encapsulant film was manufactured in the same manner as in Example 1, except that hexavinyl disiloxane (HVDS) was used instead of tetravinyldimethyl disiloxane (TVDMDS) and the input amount was changed to 1.00 phr.

Comparative Example 1

The encapsulant was prepared in the same manner as in Example 1, except that triallyl isocyanurate (TAIC) was used instead of tetravinyldimethyl disiloxane (TVDMDS) as a crosslinking aid, and the dosage was changed to 0.50 phr. A film was prepared.

Comparative Example 2

As a crosslinking aid, 1,3-divinyltetramethyldisiloxane (DVTMDS) was used instead of tetravinyldimethyldisiloxane (TVDMDS), and the dosage was changed to 0.50 phr, the same as Example 1. An encapsulant film was manufactured using this method.

Table 1 below shows the crosslinking agent compositions used in Examples 1 to 6 and Comparative Examples 1 and 2.

Cross-linking aid crosslinking agent
(phr) Silane coupling agent
(phr) ingredient (phr) Example 1 TVDMDS 0.25 One 0.2 Example 2 TVDMDS 0.50 One 0.2 Example 3 TVDMDS 1.00 One 0.2 Example 4 HVDS 0.25 One 0.2 Example 5 HVDS 0.50 One 0.2 Example 6 HVDS 1.00 One 0.2 Comparative Example 1 TAIC 0.50 One 0.2 Comparative Example 2 DVTMDS 0.50 One 0.2

Experiment example

Put the encapsulant film (15 cm × 15 cm) with a thickness of 0.5 mm prepared above between two release films (thickness: about 100 μm) and laminate in a vacuum laminator at a process temperature of 150°C and a process time of 20 minutes (5 minutes vacuum/1 minute). Cross-linked by lamination for 14 min pressure/pressure duration).

(1) Impregnation speed

The crosslinking agent impregnation completion times measured in Examples 1 to 6 and Comparative Examples 1 and 2 are listed in Table 2 below.

(2) Volume resistivity

Tested at room temperature based on ASTM D257. The prepared sample was placed in the Keithley 8009 Resistivity test fixture, and the volume resistivity was measured after applying a voltage of 1,000 V with a 6517B Electrometer/High Resistance meter connected to it.

(3) Vulcanization characteristics

In accordance with ASTM D5289, vulcanization properties were measured using Alpha Techbologies' premier MDR. The test was run at 150°C for 20 minutes, and a torque curve over time was obtained. At this time, the 150°C condition corresponds to the lamination temperature and 20 minutes corresponds to the lamination time. In addition, the curing properties between samples were compared relative to each other using the difference between the maximum torque (MH) and minimum torque (ML) applied by the MDR during the corresponding time. In addition, T90 (90% vulcanization time) was measured, and T90 refers to the vulcanization speed.

(4) Degree of crosslinking

The crosslinked sheet was cut into a size of 3×3 mm ² using scissors. The sides and bottom of a 7×10 cm ² 200 mesh wire mesh were stapled. The sheet was placed in the wire mesh and the weight of the inserted sheet was measured. The amount of sheet was 0.49 to 0.51 g. Once the sheet was inserted, the top of the wire mesh was closed with staples and the total weight of the sample was measured. A solution of 10 g of BHT (dibutylhydroxytoluene) dissolved in 1,000 g of xylene was poured into a 2 L cylinder reactor, and 3 to 4 of the samples were added. Reflux was terminated 5 hours after the reactor was heated and boiled. The sample in the reactor was taken out with a metal scoop and washed with xylene. It was vacuum dried at 100°C overnight. The degree of crosslinking was calculated by measuring the weight of the dried sample. The degree of crosslinking can be determined as the average value of 3 to 4 samples refluxed in xylene.

Degree of cross-linking (%) = [(Weight of sheet after reflux)/(Weight of sheet before reflux)]×100

(5) Light transmittance

The light transmittance was measured from 200 nm to 1,000 nm using a Shimadzu UV-3600 spectrophotometer to obtain a light transmittance curve, and then the values of 280 to 380 nm and 380 to 1,100 nm were confirmed.

- Measurement mode: transmittance

- Wavelength interval: 1 nm

- Measurement speed: medium

(6) Adhesion strength measurement

40% of the glass substrate area was covered with an encapsulant film and the remaining 60% was covered with a polyimide film, and then a fluorine-based solar backsheet was laminated on top of it. Lamination was performed at a temperature of 150°C for 20 minutes so that the encapsulant film was crosslinked and adhered to the glass substrate. The encapsulant film of the specimen was cut with a width of 1 cm so that the width of the measurement area was 1 cm.

A UTM sample holder and a 1 kN load cell were mounted on a tensile compression tester (LRX Plus Universal Test Machine, manufactured by LLOYD), and the encapsulant film adhered to the glass substrate was checked to ensure that the encapsulant film on the glass substrate was not adhered. The ends of the unused parts were each fixed and then pulled at 60 mm/min to test the adhesive strength.

Impregnation time MDR Cross-linking characteristics (minute) MH-ML
(dNm) T90
(min) volume resistivity
(Ωcm) Crosslinking degree (%) light transmittance
(%T, 380~1100 nm) Adhesive strength
(N/cm) Example 1 5 3.12 12.91 3.9×10 ¹⁶ 70.5 92.2 206 Example 2 7 3.33 12.32 4.1×10 ¹⁶ 72.0 92.3 211 Example 3 8 4.35 11.12 4.3×10 ¹⁶ 76.7 92.3 215 Example 4 7 3.24 12.10 5.6×10 ¹⁶ 71.6 92.4 206 Example 5 7 3.67 11.36 1.0×10 ¹⁷ 72.7 92.4 215 Example 6 9 4.44 10.44 8.8×10 ¹⁶ 77.0 92.3 216 Comparative Example 1 60 3.68 13.00 2.9×10 ¹⁶ 77.5 92.3 212 Comparative Example 2 9 1.69 13.52 3.8×10 ¹⁶ 39.0 92.2 212

As can be seen in Table 2, when using the cross-linking agent composition containing the cross-linking aid compound of Formula 1 of Examples 1 to 6, the cross-linking agent composition compared to the case where triallyl isocyanurate of Comparative Example 1 was used as the cross-linking aid. The impregnation completion time could be shortened. When using a cross-linking agent composition containing the cross-linking aid compound of Chemical Formula 1 of Examples 1 to 6, a significantly superior degree of cross-linking was shown compared to when 1,3-divinyltetramethyldisiloxane of Comparative Example 2 was used as a cross-linking aid. .

Claims (11)

crosslinking agent;
Silane coupling agent; and
Crosslinking agent composition for olefin-based copolymers comprising a crosslinking aid compound of the following formula (1):
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, where two or more of R ₁ to R ₃ and two or more of R ₄ to R ₆ are each independently 2 to 2 carbon atoms. It is the alkenyl of 20.
According to claim 1,
R ₁ , R ₃ , R ₄ and R ₆ are each independently alkenyl having 2 to 20 carbon atoms,
Wherein R ₂ and R ₅ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms.
According to claim 1,
R ₁ , R ₃ , R ₄ and R ₆ are each independently alkenyl having 2 to 12 carbon atoms having a double bond at the terminal,
The crosslinking agent composition for an olefin-based copolymer wherein R ₂ and R ₅ are each independently alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms having a double bond at the terminal.
According to claim 1,
A crosslinking agent composition for an olefin-based copolymer wherein the crosslinking aid compound of Formula 1 is hexavinyl disiloxane or tetravinyldimethyl disiloxane.
According to claim 1,
A cross-linking agent composition for an olefin-based copolymer wherein the cross-linking agent is one or two or more selected from the group consisting of organic peroxides, hydroperoxides, and azo compounds.
According to claim 1,
The crosslinking agent is t-butylcumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl- 2,5-di(t-butylperoxy)-3-hexyne, cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane, t- Butylhydroperoxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, 20,4-dichlorobenzoyl peroxide, t-butylperoxy iso Butyrate, t-butylperoxy acetate, t-butylperoxy-2-ethylhexyl carbonate (TBEC), t-butylperoxy-2-ethylhexanoate, t-butylperoxy pivarate, t-butyl peroxide. Oxy octoate, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2, 5-dimethyl-2,5-di(benzoylperoxy)-3-hexyne, methyl ethyl ketone peroxide, cyclohexanone peroxide azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) A crosslinking agent composition for olefin-based copolymers, which is at least one selected from the group consisting of.
According to claim 1,
The silane coupling agent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane (MEMO), vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 - A crosslinking agent composition for olefin-based copolymers, which is at least one selected from the group consisting of methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, and p-styryl trimethoxysilane.
Olefin-based copolymer; and
An encapsulating material composition for optical devices comprising the crosslinking agent composition for olefin-based copolymers of claim 1.
According to claim 8,
The olefin-based copolymer is an ethylene/alpha-olefin copolymer in an encapsulating material composition for optical devices.
Encapsulant film for optical devices comprising a structure derived from an olefin-based copolymer and a compound of the following formula (1):
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, where two or more of R ₁ to R ₃ and two or more of R ₄ to R ₆ are each independently 2 to 2 carbon atoms. It is the alkenyl of 20.
An optoelectronic device comprising an optical device and an encapsulant film for an optical device according to claim 10.