TW202012543A - Silicone composition - Google Patents

Abstract

The present invention relates to a silicone composition containing an organopolysiloxane mixture and a platinum catalyst, wherein the organopolysiloxane mixture contains a first organopolysiloxane (a) including a unit having at least one alkenyl group and at least one SiO4/2 unit in a molecule thereof, a second organopolysiloxane (b) having at least two alkenyl groups in a molecule thereof, and an organohydrogenpolysiloxane (c), wherein the organohydrogenpolysiloxane (c) comprises a highly reactive organohydrogenpolysiloxane and a linear organohydrogenpolysiloxane, wherein the highly reactive organohydrogenpolysiloxane comprises a first organohydrogenpolysiloxane (c-1) including a unit having hydrogen group directly bonded to at least one silicon and at least one SiO4/2 unit in a molecule thereof or a second organohydrogenpolysiloxane (c-2) including, in a molecule thereof, hydrogen groups directly bonded to at least two silicon and at least one aryl group or halogenated alkyl group directly bonded to a silicon atom which is adjacent to the above-described silicon group with an oxygen atom therebetween, and the linear organohydrogenpolysiloxane comprises a third organohydrogenpolysiloxane (c-3) including hydrogen group directly bonded to at least one silicon in a molecule thereof.

Description

Silicone composition

The present invention relates to a silicone composition.

Due to the advent of the recent information age, image display devices such as liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs), tablet terminals (smartphones, PDA terminals, etc.) are forming a large-scale market and are used in various product groups.

In addition, in order to improve the visibility or impact resistance of such an image display device, a touch screen panel (TSP) for a window glass as a protective part of the image display device and a substrate including the image display part Adhesive materials used between sensor glasses have increasing interests and demands. Regarding the manufacture of such TSP, optical bonding materials have been actively researched and developed, and in such optical bonding materials, for example, optically transparent adhesives (OCA) or optically transparent resins (OCR) have been used. There are transparent materials to improve the visibility of capacitive touch panels or displays.

As the polymer of this optical bonding material, acrylic polymers that have excellent transparency, are easy to design, can be quickly UV cured, and also provide economic benefits are mainly used. However, since acrylic polymers have many problems in weather resistance, heat resistance, cold resistance, dimensional stability, etc., the use of silicone-based polymers has gradually increased recently.

Japanese Patent Early Publication No. 1900-126317 discloses alkenyl group-containing siloxanes by a photosensitizer such as benzophenone and a photopolymerization initiator such as tert-hexyl peroxybenzoate Cross-linking reaction. However, the problem of the cross-linking reaction is that the curing speed is not high enough, and there is a risk that discoloration may occur due to the residual initiator, resulting in low weather resistance and low processability.

Japanese Patent No. 3912525 discloses a silicone rubber composition composed of a combination of a silicone resin for imparting viscosity and a silicone resin for imparting rubber strength The prepared addition-curable composition (addition-curable composition) and the silicone rubber composition have a certain rubber hardness and rubber strength, and the silicone rubber composition has a viscosity that can be bonded and fixed to the substrate or various parts Sex is used as an OCA. However, since the OCA film is formed in the form of a solid with a transparent sheet appearance, in the process of attaching the protective portion having light-transmitting properties to the substrate portion including the image display portion of the image display device, bubbles are likely to be incorporated Even after attachment, it is likely that delamination at high temperature or further introduction of bubbles will result, which results in low visibility. In addition, Japanese Patent No. 5010762 discloses a heat-curable polyorganosiloxane composition containing a linear polyorganosiloxane having alkenyl groups at both ends and a linear polyorganohydrogensilicon having hydrogenated silane groups at both ends A mixture of oxane, specific cyclic polyorganohydrogensiloxane, and adhesion-imparting agent. Although the curing of the composition takes only 0.1 to 3 hours at a temperature of 50 to 80° C., since the cured product itself has no adhesiveness, it is necessary to perform an extended thermal curing at a high temperature to impart adhesion to the adhesion-imparting agent to ensure the adhesion Full adhesion of the adhesive body.

In particular, among the siloxane alkyl polymers used as materials for OCA and OCR, UV curing properties that can shorten working time and enable non-heating processes are needed, and it is important to develop addition-curable siloxanes, Even if it contains a small amount of platinum catalyst, it can ensure useful curability and ensure the most important transparency in optical bonding materials, and make it thermally curable in a short time even at a low temperature of 70°C or lower and has excellent Workability.

[Prior Art Literature]

(Patent Document 1) Japanese Early Publication No. 1989-126317

(Patent Document 2) Japanese Patent No. 3912525

(Patent Document 3) Japanese Patent No. 5010762

[technical problem]

The present invention aims to provide a silicone composition that has an excellent curing speed while maintaining transparency and provides enhanced work convenience by having improved pot life at room temperature.

[Technical means]

In the present invention, there is provided a silicone composition comprising an organic polysiloxane mixture and a platinum catalyst, wherein the organic polysiloxane mixture comprises a first organic polysiloxane (a), a second organic Polysiloxane (b) and an organic hydrogen polysiloxane (c), the first organic polysiloxane (a) contains a unit having at least one alkenyl group and at least one SiO _4/2 unit in its molecule, The second organic polysiloxane (b) contains at least two alkenyl groups in its molecule, wherein the organic hydrogen polysiloxane (c) contains a highly reactive organic hydrogen polysiloxane and a linear organic hydrogen Polysiloxane, wherein the highly reactive organic hydrogen polysiloxane contains a first organic hydrogen polysiloxane (c-1) or a second organic hydrogen polysiloxane (c-2), the first organic Hydrogen polysiloxane (c-1) Contains a unit having a hydrogen group directly bonded to at least one silicon atom and at least one SiO _4/2 unit in its molecule, second organic hydrogen polysiloxane (c-2) ) The molecule contains a hydrogen group directly bonded to at least two silicon atoms and at least one aryl group, or a silicon adjacent to the above silicon group (oxygen group) having an oxygen atom in between Atomically halogenated alkyl group (halogenated alkyl group), and linear organic hydrogen polysiloxane contains a third organic hydrogen polysiloxane (c-3), the third organic hydrogen polysiloxane (c-3) Contains a hydrogen group directly bonded to at least one silicon atom in its molecule.

[Beneficial effect]

The silicone composition of the present invention can provide the following effects in terms of UV curing: it has excellent weather resistance and does not fade or crack even if the cured product is exposed to ultraviolet light for a long time. In addition, it can be cured in a short time, and can achieve a glass-to-glass adhesive strength of 0.1 MPa/cm ² or more after curing, and can ensure effective curability despite the small amount of platinum catalyst.

The silicone composition of the present invention can also provide the following effects in terms of thermal curing: it can be cured in a short time even at a temperature as low as 70°C or lower, and after curing can achieve a value of 0.1 M Pa/cm ² or more Glass-glass adhesive strength, can form a cured product with excellent adhesion to the substrate, does not produce by-products and thus exhibits excellent dimensional stability (dimensional stability) against curing shrinkage, and has excellent usable Pot life and thus exhibit excellent storage stability.

Since the silicone composition of the present invention has high flowability in a light-shielding state and exhibits excellent storage stability, and thus has an effect of providing excellent workability, it is applicable to An image display device such as an LCD or OLED is applied to an adhesive (OCA or OCR) between a substrate portion including an image display portion and a protective portion having light transmittance.

Hereinafter, the present invention will be described in detail.

The curing of a typical UV-curable silicone composition requires a large amount of UV radiation, or a high UV curing temperature or a long curing time after UV radiation. The inventors of the present invention have found that by containing an organopolysiloxane having an alkenyl group and a specific organohydrogenpolysiloxane having high addition reactivity, the siloxane composition of the present invention ( The silicone composition) has an improved curing speed, and the present invention has been completed based on this finding.

In the present invention, a silicone composition is provided.

The silicone composition of the present invention comprises an organic polysiloxane mixture and a platinum catalyst.

In addition, the silicone composition of the present invention can provide a gel-type cured product (instead of a typical hard-type cured product) for OCA or OCR in an image display device.

1. Organic polysiloxane mixture (organopolysiloxane mixture)

The organic polysiloxane mixture contained in the silicone composition of the present invention comprises a first organic polysiloxane (a), a second organic polysiloxane (b), and an organic hydrogen polysiloxane Alkanes (c).

First organopolysiloxane (a) (first organopolysiloxane)

The first organic polysiloxane (a) used in the present invention is used to improve the mechanical properties (eg, adhesive strength) of the cured product by affecting the initial viscosity of the silicone composition.

The first organic polysiloxane (a) contains a unit having at least one alkenyl group and at least one SiO _4/2 unit in its molecule, and can be represented by the following Chemical Formula 1: [Chemical Formula 1] (R ¹ ₁ R ² ₂ SiO _1/2 ) _a (R ³ ₃ SiO _1/2 ) _b (SiO _4/2 ) _c

In Chemical Formula 1, R ¹ and R ² which are the same or different from each other are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which R ¹ and R ² At least one is an alkenyl group having 2 to 10 carbon atoms, R ^{3 is} each independently an alkyl group having 1 to 10 carbon atoms, "a" is a number of 0.05 to 0.25, and "b" is 0.1 to 0.5 Number, and "c" is a number between 0.4 and 0.6, and satisfies a + b + c = 1.

R ¹ and R ² which are the same as or different from each other may each independently be an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.

Specifically, the alkyl group of R ¹ and R ² may specifically be methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl group, or cyclohexyl group, and is preferably The methyl, ethyl and propyl listed above, but the invention is not limited thereto.

The alkenyl group of R ¹ and R ² may specifically be a vinyl group, an allyl group, a butenyl group, a pentenyl group, or a hexenyl group And is preferably the vinyl group or butenyl group listed above, but the invention is not limited thereto.

R ³ may each independently be an alkyl group having 1 to 6 carbon atoms. The alkyl group may specifically be methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl group, or cyclohexyl group, and is preferably the methyl or ethyl group listed above Base, propyl, but the invention is not limited to this.

When "a" of Chemical Formula 1 is less than 0.05, the silicone curing reaction may be delayed. When "a" is greater than 0.25 so that the silicone composition has a high density, the cross-linking density may change with time, so cracks may be generated in the silicone cured product.

When the "b" of Chemical Formula 1 is less than 0.1 so that the silicone composition has low fluidity and high viscosity, it may result in low workability. When "b" is greater than 0.5 to cause a low crosslink density, it is possible to obtain low adhesion to glass.

When the "c" of Chemical Formula 1 is less than 0.4, it may be difficult to ensure the curability of the silicone cured product. When "c" is greater than 0.6 to make the silicone composition have a high viscosity, it may therefore result in low flowability and low workability.

The first organic polysiloxane (a) can be MQ resin and especially silicate resin with vinyldimethyl and trimethyl at both ends, or two Silicate resins with divinylmethyl and trimethyl ends. The silicate resins with divinylmethyl and trimethyl ends are (ViMe ₂ SiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.35 (SiO _4/2 ) _0.50 , Or (Vi ₂ MeSiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.35 (SiO _4/2 ) _0.50 , or (ViMe ₂ SiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _0.40 (SiO _{4/ 2} ) _0.50 , or (Vi ₂ MeSiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _0.40 (SiO _4/2 ) _0.50 , or (ViMe ₂ SiO _1/2 ) _0.20 (Me ₃ SiO _1/2 ) _0.30 (SiO _4/2 ) _0.50 , or (Vi ₂ MeSiO _1/2 ) _0.20 (Me ₃ SiO _1/2 ) _0.30 (SiO _4/2 ) _0.50 , or (ViMe ₂ SiO _1/2 ) _0.15 (Me ₃ SiO _{1 /2} ) _0.45 (SiO _4/2 ) _0.40 , or (Vi ₂ MeSiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.40 , or (ViMe ₂ SiO _1/2 ) _0.10 ( Me ₃ SiO _1/2 ) _0.50 (SiO _4/2 ) _0.40 , or (Vi ₂ MeSiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _0.50 (SiO _4/2 ) _0.40 , or (ViMe ₂ SiO _{1/ 2} ) _0.20 (Me ₃ SiO _1/2 ) _0.40 (SiO _4/2 ) _0.40 , or (Vi ₂ MeSiO _1/2 ) _0.20 (Me ₃ SiO _1/2 ) _0.40 (SiO _4/2 ) _0.40 , or (ViMe ₂ SiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.25 (SiO _4/2 ) _0.60 , or (Vi ₂ MeSiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.25 (SiO _4/2 ) _0.60 , Or (ViMe ₂ SiO _1/2 ) _0.10 (Me ₃ SiO _1/2 ) _0.30 (SiO _4/2 ) _0.60 , or (Vi ₂ MeSiO _1/2 ) _{0. 10} (Me ₃ SiO _1/2 ) _0.30 (SiO _4/2 ) _0.60 , or (ViMe ₂ SiO _1/2 ) _0.20 (Me ₃ SiO _1/2 ) _0.20 (SiO _4/2 ) _0.60 , or (ViMe ₂ SiO _1/2 ) _0.125 (Me ₃ SiO _1/2 ) _0.375 (SiO _4/2 ) _0.50 , or (Vi ₂ MeSiO _1/2 ) _0.20 (Me ₃ SiO _1/2 ) _0.20 (SiO _4/2 ) _0.60 , but The invention is not limited to this.

The content of the first organic polysiloxane (a) in the organic polysiloxane mixture may be 5-50 parts by weight. When the content of the first organic polysiloxane (a) is less than 5 parts by weight so that the adhesion strength to the glass is low, it may result in low workability. When the content of the first organic polysiloxane (a) is greater than 50 parts by weight to cause a high cross-linking density, cracks may occur in the cured product of silicone due to external impact.

The first organic polysiloxane (a) may contain 0.3 to 10 mmol/g, especially 0.5 to 5 mmol/g of vinyl (SiVi group). When the first organopolysiloxane (a) contains less than 0.3 mmol/g of vinyl, the first organopolysiloxane (a) may exhibit low reactivity. When the first organopolysiloxane (a) contains more than 10 mmol/g of vinyl to give the silicone cured product a high density, cracks may occur in it due to changes over time.

The weight average molecular weight (Mw) of the first organic polysiloxane (a) may be 400-100,000 g/mol, especially 500-30,000 g/mol. When the weight-average molecular weight of the first organopolysiloxane (a) is less than 400 g/mol, there may be cases where the effect of imparting viscosity to the cured product or increasing its strength cannot be fully exerted. When the weight average molecular weight of the first organic polysiloxane (a) is greater than 100,000 g/mol, it may be difficult to stably prepare a cured product.

Second organopolysiloxane (b) (second organopolysiloxane)

The second organic polysiloxane (b) used in the present invention is used to impart fluidity to the silicone composition by controlling the viscosity of the silicone composition, and to control the cured product of the silicone Modulus to improve the physical properties of silicone cured products.

The second organic polysiloxane (b) contains at least two alkenyl groups in its molecule and can be represented by the following chemical formula 2: [Chemical formula 2] (R ⁴ ₁ R ⁵ ₂ SiO _1/2 ) ₂ (R ⁶ R ⁷ SiO) _d (R ⁸ ₂ SiO) _e

In Chemical Formula 2, R ⁴ and R ⁵ which are the same or different from each other are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and R ⁶ and R which are the same or different from each other ⁷ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R ^{8 is} each independently An alkyl group having 1 to 10 carbon atoms, wherein at least one of R ⁴ to R ⁷ is an alkenyl group having 2 to 10 carbon atoms, and “d” and “e” are each independently 0 or 1 or more A large integer, d + e is an integer from 10 to 10,000, and d / (d + e) is a number from 0 to 0.1.

R ⁴ and R ⁵ which are the same or different from each other may each independently be an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.

R ⁶ and R ⁷ which are the same or different from each other may each independently be an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms (aryl group).

R ⁸ may each independently be an alkyl group having 1 to 6 carbon atoms.

The alkyl group of R ⁴ to R ⁸ may specifically be methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl group, or cyclohexyl group, and is preferably listed above Methyl, ethyl, propyl, but the invention is not limited to this.

The alkenyl group of R ⁴ to R ⁷ may be specifically a vinyl group, an allyl group, a butenyl group, a pentenyl group, or a hexenyl group And is preferably the vinyl group or butenyl group listed above, but the invention is not limited thereto.

The aryl group of R ⁶ and R ⁷ may be specifically phenyl group, tolyl group, xylyl group, naphthyl group, or biphenylyl group), and preferably the phenyl group (phenyl group) listed above, but the invention is not limited thereto.

When d + e of Chemical Formula 2 is less than 10, voids may be generated due to evaporation during curing of the silicone composition, resulting in low moldability. When d + e is greater than 10,000, the silicone composition has low fluidity, and therefore, it is difficult to introduce a sufficient amount of the composition, which may result in low processability.

When d / (d + e) of Chemical Formula 2 is greater than 0.1, a silicone composition having low curing reactivity and high density is obtained, and thus cracks may be generated in the cured product due to changes over time.

Specifically, the second organic polysiloxane (b) may be a dimethylsiloxane polymer terminated with vinyldimethyl, which may be represented by the general formula (ViMe ₂ SiO _1/2 )(Me ₂ SiO) _n (ViMe ₂ SiO _1/2 ) (n=10 ~ 10,000) means, for example (ViMe ₂ SiO _1/2 )(Me ₂ SiO) ₆₀ (ViMe ₂ SiO _1/2 ), or ( ViMe ₂ SiO _1/2 )(Me ₂ SiO) ₁₂₀ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(Me ₂ SiO) ₁₅₀ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(Me ₂ SiO) ₂₂₂ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(Me ₂ SiO) ₂₂₅ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _{1 /2} )(Me ₂ SiO) ₅₀₀ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(Me ₂ SiO) ₁₀₀₀ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(Me ₂ SiO) ₁₂₅₀ (ViMe ₂ SiO _1/2 ); methylvinylsiloxane-dimethylsiloxane block polymer with vinyldimethylsiloxy group ends (methylvinylsiloxane-dimethylsiloxane block polymer), which can be represented by the general formula (ViMe ₂ SiO _1/2 )(ViMeSiO) _n (Me ₂ SiO) _m (ViMe ₂ SiO _1/2 ) (n+m=10 ~ 10,000), for example (ViMe ₂ SiO _1/2 )(ViMeSiO)(Me ₂ SiO) ₅₉ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(ViMeSiO) ₂₀ (Me ₂ SiO) ₁₉₅ (ViMe ₂ SiO _{1 /2} ), or (ViMe ₂ SiO _1/2 ) (ViMeSiO) ₃₀ (Me ₂ SiO) ₄₀₀ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 ) (ViMeSiO) ₅₀ (Me ₂ SiO) _{100 0} (ViMe ₂ SiO _1/2 ); methylvinylsiloxane-dimethylsiloxane block polymer terminated with trimethylsiloxy group (trimethylsiloxy group), It can be represented by the general formula (Me ₃ SiO _1/2 )(ViMeSiO) _n (Me ₂ SiO) _m (Me ₃ SiO _1/2 ) (n+m=10 ~ 10,000), for example (Me ₃ SiO _1/2 ) (ViMeSiO) ₃₀ (Me ₂ SiO) ₄₀₀ (Me ₃ SiO _1/2 ), or (Me ₃ SiO _1/2 ) (ViMeSiO) ₅ (Me ₂ SiO) ₅₄₀ (Me ₃ SiO _1/2 ), or (Me ₃ SiO _1/2 )(ViMeSiO) ₅₀ (Me ₂ SiO) ₁₀₀₀ (Me ₃ SiO _1/2 ), or (Me ₃ SiO _1/2 )(ViMeSiO) ₆ (Me ₂ SiO) ₆₀ (Me ₃ SiO _{1/ 2} ); a methylphenylsiloxane-dimethylsiloxane block polymer with a vinyldimethylsiloxy group at the end and a general formula (methylphenylsiloxane-dimethylsiloxane block polymer) ViMe ₂ SiO _1/2 )(MePhSiO) _n (Me ₂ SiO) _m (ViMe ₂ SiO _1/2 ) (n+m=10 ~ 10,000) means, for example (ViMe ₂ SiO _1/2 )(MePhSiO) ₂ ( Me ₂ SiO) ₂₀ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(MePhSiO) ₁₀ (Me ₂ SiO) ₁₂₅ (ViMe ₂ SiO _1/2 ); or the terminal is vinyl dimethyl Diphenylsiloxane-dimethylsiloxane block polymer of vinyldimethylsiloxy group, which can be represented by the general formula (ViMe ₂ SiO _1/2 ) (Ph ₂ SiO ) _n (Me ₂ SiO) _m (ViMe ₂ SiO _1/2 ) (n+m=10 ~ 10,000) means, for example (ViMe ₂ SiO _1/2 )( Ph ₂ SiO) ₂ (Me ₂ SiO) ₄₀ (ViMe ₂ SiO _1/2 ), or (ViMe ₂ SiO _1/2 )(Ph ₂ SiO) ₁₀ (Me ₂ SiO) ₂₂₅ (ViMe ₂ SiO _1/2 ), However, the present invention is not limited to this.

The content of the second organic polysiloxane (b) in the organic polysiloxane mixture may be 33 to 92 parts by weight, especially 39 to 91 parts by weight. When the content of the second organic polysiloxane (b) is less than 33 parts by weight, resulting in high crosslink density, cracks may easily occur due to thermal shock. When the content of the second organic polysiloxane (b) is greater than 92 parts by weight, insufficient adhesion to glass may be obtained.

The first organic polysiloxane (a) and the second organic polysiloxane (b) can be used in a weight ratio of 5:95~60:40. When the weight ratio of the first organopolysiloxane (a) and the second organopolysiloxane (b) is less than 5:95, the cured product of the silicone cannot be given sufficient mechanical strength, so it may exhibit low modulus the amount. When the weight ratio of the first organopolysiloxane (a) and the second organopolysiloxane (b) is greater than 60:40, the cured product may be due to the low fluidity of the uncured organosilicon composition It has low flexibility and therefore may be susceptible to external impact, and the possibility of cracks increases.

The viscosity of the second organic polysiloxane (b) at 25°C can be 10 to 500,000 mPa·s, especially 100 to 250,000 mPa·s. When the viscosity of the second organic polysiloxane (b) is less than 10 mPa·s, the cured product cannot be given excellent mechanical properties or viscosity. When the viscosity of the second organic polysiloxane (b) is greater than 500,000 mPa·s, low processability may result due to low fluidity in the uncured state.

The second organic polysiloxane (b) may contain 0.01 to 5 mmol/g, especially 0.02 to 3 mmol/g of vinyl (SiVi group). When the second organic polysiloxane (b) contains less than 0.01 mmol/g of vinyl, the second organic polysiloxane (b) may exhibit low reactivity. When the second organic polysiloxane (b) contains more than 5 mmol/g of vinyl to make the cured silicone product have a high cross-link density, it may show low viscosity, and may also occur due to Changes may cause cracks.

The second organic polysiloxane (b) may have a weight average molecular weight (Mw) of 600 to 180,000 g/mol, and may have a degree of polymerization of 9 to 2,400 and particularly 65 to 1,900. When the weight average molecular weight of the second organic polysiloxane (b) is less than 600 g/mol, the cured product cannot be given excellent mechanical properties or viscosity. When the weight average molecular weight of the second organic polysiloxane (b) is greater than 180,000 g/mol, low processability may result due to low fluidity in the uncured state.

Organohydrogenpolysiloxane (c) (organohydrogenpolysiloxane)

The organic hydrogen polysiloxane (c) used in the present invention is used as a crosslinking agent for the first organic polysiloxane (a) and the second organic polysiloxane (b).

Organic hydrogen polysiloxane (c) may contain highly reactive organic hydrogen polysiloxane and linear organic hydrogen polysiloxane, wherein the highly reactive organic hydrogen polysiloxane may contain the first organic hydrogen polysiloxane The oxane (c-1) or the second organohydrogen polysiloxane (c-2), and the linear organohydrogen polysiloxane may include a third organohydrogen polysiloxane (c-3).

In particular, for the gel-type composition for OCA or OCR in the cured form in the case of the siloxane composition of the present invention, a typical gel-type composition does not contain, for example, a high viscosity hydrogen polymer having a Q unit Highly reactive organohydrogen polysiloxanes such as the first organohydrogen polysiloxane (c-1) described above, and the second organohydrogen polysilicon having high cross-linking ability or high reactivity Oxane (c-2), because the inclusion of such a compound causes the hardness or viscosity of the composition to increase, or makes it difficult to maintain the gel state.

However, in the case of the silicone composition of the present invention, by controlling the content or hydrogen group of the highly reactive organic hydrogen polysiloxane (SiH group), the first organic polysiloxane (a ) Or the addition reactivity of the second organic polysiloxane (b), not only improves the curing speed, but also maintains the gel state of the composition even after its curing is completed.

For example, the organic hydrogen polysiloxane (c) may be a mixture of the first organic hydrogen polysiloxane (c-1) and the third organic hydrogen polysiloxane (c-3), or the second organic hydrogen Mixture of polysiloxane (c-2) and third organic hydrogen polysiloxane (c-3).

The first organic hydrogen polysiloxane (c-1) contains a unit, which has a hydrogen group directly bonded to at least one silicon atom and at least one SiO _4/2 unit in its molecule, and can be represented by the following chemical formula 3 ： [Chemical Formula 3] (HR ⁹ ₂ SiO _1/2 ) _f (R ¹⁰ ₃ SiO _1/2 ) _g (SiO _4/2 ) _h

In Chemical Formula 3, R ⁹ and R ¹⁰ which are the same or different from each other are each independently an alkyl group having 1 to 10 carbon atoms, “f” is a number from 0.05 to 0.75, and “g” is a number from 0 to 0.5, And "h" is a number from 0.3 to 0.6, and satisfies f + g + h = 1.

R ⁹ and R ¹⁰ which are the same or different from each other may each independently be an alkyl group having 1 to 6 carbon atoms.

The alkyl groups of R ⁹ and R ¹⁰ may specifically be methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl group, or cyclohexyl group, and are preferably listed above Methyl, ethyl, propyl, but the invention is not limited to this.

When "f" of Chemical Formula 3 is less than 0.05, the first organic hydrogen polysiloxane (c-1) may exhibit low reactivity. When "f" is greater than 0.75 so that the silicone composition has a high density, the cross-linking density may change with time, so cracks may occur.

When the "g" of Chemical Formula 3 is greater than 0.5, the first organic hydrogen polysiloxane (c-1) may exhibit low reactivity.

When the "h" of Chemical Formula 3 is less than 0.3, the first organic hydrogen polysiloxane (c-1) may exhibit low reactivity. When "h" is greater than 0.6 to make the silicone composition have a high viscosity and thus low flowability, it may result in low processability.

Specifically, the first organic hydrogen polysiloxane (c-1) can be expressed as (HMe ₂ SiO _1/2 ) _0.17 (Me ₃ SiO _1/2 ) _0.41 (SiO _4/2 ) _0.42 or (HMe ₂ SiO _1/2 ) _0.58 (SiO _4/2 ) _0.42 , or (HMe ₂ SiO _1/2 ) _0.64 (SiO _4/2 ) _0.36 , but the invention is not limited thereto.

The viscosity of the first organic hydrogen polysiloxane (c-1) at 25°C can be 1 to 500 mPa·s, especially 1 to 200 mPa·s. When the viscosity of the first organohydrogenpolysiloxane (c-1) is less than 1 mPa·s, the molecular weight is too small, so there may be cases where the effect of increasing the curing speed or enhancing the cured product cannot be fully exerted. When the viscosity of the first organic hydrogen polysiloxane (c-1) is greater than 500 mPa·s, the molecular weight is too large, so it may be difficult to prepare the silicone composition stably.

The first organic hydrogen polysiloxane (c-1) may be a hydrogen group (SiH group) containing 0.5 to 10 mmol/g, especially 1 to 10 mmol/g. When the amount of hydrogen groups contained in the first organohydrogen polysiloxane (c-1) is less than 0.5 mmol/g, the first organohydrogen polysiloxane (c-1) may exhibit low reactivity. When the first organohydrogenpolysiloxane (c-1) contains more than 10 mmol/g of hydrogen groups so that the cured product of silicone has a high cross-link density, it may exhibit low viscosity, and may also Changes in time have caused cracks.

The weight average molecular weight (Mw) of the first organic hydrogen polysiloxane (c-1) may be 100 to 5,000 g/mol, especially 500 to 2,000 g/mol. When the weight average molecular weight of the first organic hydrogen polysiloxane (c-1) is less than 100 g/mol, there may be cases where the effect of increasing the curing speed or enhancing the cured product cannot be sufficiently exerted. When the weight average molecular weight of the first organic hydrogen polysiloxane (c-1) is greater than 5,000 g/mol, it may be difficult to prepare the silicone composition stably.

The polymerization degree of the first organic hydrogen polysiloxane (c-1) may be 1.5-75, especially 6-28.

The second organic hydrogen polysiloxane (c-2) contains a hydrogen group directly bonded to at least two silicon atoms and at least one aryl group in its molecule, or directly bonded to an oxygen atom in between The halogenated alkyl group on the silicon atom adjacent to the aforementioned silicon group can be represented by the following chemical formula 4: [Chemical formula 4] R ¹¹ _i Si(OSiR ¹² ₂ H) _4-i

In Chemical Formula 4, R ^{11 is} each independently an aryl group having 6 to 15 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms, and R ^{12 is} each independently having An alkyl group of 1 to 10 carbon atoms, and "i" is a number of 1 or 2.

R ¹¹ may each independently be an aryl group having 6 to 15 carbon atoms or a halogenated alkyl group having 1 to 6 carbon atoms, and R ¹² may each independently have 1 to 6 carbon atom alkyl.

The aryl group of R ¹¹ may specifically be a substituted or unsubstituted phenyl group, such as phenyl, p-methylphenyl group (p-methylphenyl group), or 2,4-dinitrophenyl (2,4-dinitrophenyl group) And is preferably the phenyl group listed above, but the invention is not limited thereto.

The halogenated alkyl group of R ¹¹ may specifically be trifluoromethyl group, 2,2,2-trifluoroethyl group (2,2,2-trifluoroethyl group), 3,3,3- Trifluoropropyl (3,3,3-trifluoropropyl group), 2,2,2-tribromoethyl group (2,2,2-tribromoethyl group), or the like, but the present invention is not limited thereto.

The alkyl group of R ¹² may specifically be methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl group, or cyclohexyl group, and is preferably a Group, ethyl group, propyl group, but the invention is not limited thereto.

In Chemical Formula 4, "i" is an integer of 1 or 2. When "i" is less than 1, the second organic hydrogen polysiloxane (c-2) may exhibit low addition reactivity. When "i" is greater than 2, the second organohydrogenpolysiloxane (c-2) cannot be used as a cross-linking agent, and thus may result in significantly lower addition reactivity.

Specifically, the second organic hydrogen polysiloxane (c-2) can be expressed as PhSi(OSiMe ₂ H) ₃ , Ph ₂ Si(OSiMe ₂ H) ₂ , or CF ₃ CH ₂ CH ₂ Si(OSiMeH) ₃ , However, the present invention is not limited to this.

The content of the highly reactive organic hydrogen polysiloxane in the organic polysiloxane mixture may be 0.1 to 5 parts by weight. When the content of the highly reactive organic hydrogen polysiloxane is less than 0.1 parts by weight, the effect of increasing the curing speed of the silicone composition cannot be exhibited. When the content of the highly reactive organic hydrogen polysiloxane is greater than 5 parts by weight, the hardness of the cured product of the silicone during curing may increase and cannot maintain the gel state, or the silicone may be cured relative to the adherend The product may exhibit a very low adhesive strength, which may greatly reduce the suitability of the cured silicone product for OCA or OCR.

The third organic hydrogen polysiloxane (c-3) is a linear organic hydrogen polysiloxane, which contains at least one hydrogen group directly bonded to a silicon atom in one molecule, and can be represented by the following chemical formula 5: [ Chemical formula 5] H _j R ¹³ _k SiO _{( 4-jk)/2}

In Chemical Formula 5, R ^{13 is} each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, "j" is a number of 0.001 to 2, "k" Is a number of 0.7~2, and j + k is a number of 0.8~3.

Specifically, the third organic hydrogen polysiloxane (c-3) contains a hydrogen group directly bonded to at least two silicon atoms in its molecule, and may contain a repeating unit represented by Chemical Formula 5.

The third organic hydrogen polysiloxane (c-3) is different from the first organic hydrogen polysiloxane (c-1) and the second organic hydrogen polysiloxane (c-2).

R ¹³ may each independently be an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

The alkyl group of R ¹³ may specifically be methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl group, or cyclohexyl group, and is preferably a Group, ethyl group, propyl group, but the invention is not limited thereto.

The aryl group of R ¹³ may be specifically phenyl group, tolyl group, xylyl group, naphthyl group, or biphenylyl group, It is preferably the phenyl group listed above, but the invention is not limited thereto.

In Chemical Formula 5, "j" may be 0.01~1, and "k" may be 1.2~2.

In Chemical Formula 5, j + k may be 1 to 2.7, more specifically 1.8 to 2.4.

When the "j" of Chemical Formula 5 is less than 0.001, due to the low crosslinking density of the third organohydrogenpolysiloxane (c-3), the cured product of siloxane may exhibit low hardness or low reactivity. When "j" is greater than 2, due to the high crosslinking density of the third organic hydrogen polysiloxane (c-3), cracks may be generated in the cured product, and hydrogen gas may be generated during the curing process, resulting in the formation of voids and This further leads to a decrease in visibility or reliability.

When the "k" of Chemical Formula 5 is less than 0.7, cracks may be generated in the cured product due to the high crosslink density, and hydrogen gas may be generated during curing, resulting in the formation of voids and further leading to a decrease in visibility. When "k" is greater than 2 to make the third organohydrogenpolysiloxane (c-3) have a low cross-linking density, it may result in low hardness or low reactivity, resulting in prolonged curing time, and the possibility of low molecular weight components Evaporation leads to the formation of voids during the curing process and further leads to a decrease in visibility or reliability.

When j + k of Chemical Formula 5 is less than 0.8, the silicone composition may have high viscosity, low fluidity, and thus low processability. When j + k is greater than 3, the curing time may be extended due to the low hardness or low reactivity of the third organohydrogenpolysiloxane (c-3), and low molecular weight components may be evaporated, resulting in the formation of voids during the curing process And further leads to a decrease in visibility or reliability.

Specifically, the third organohydrogenpolysiloxane (c-3) may be a dimethylsiloxane polymer terminated with a hydrogendimethylsiloxy group, which can be represented by the general formula (HMe ₂ SiO _1/2 )(Me ₂ SiO) _n (HMe ₂ SiO _1/2 ) (n=1 ~ 1,000 or n=5 ~ 500) means, for example (HMe ₂ SiO _1/2 )(Me ₂ SiO ) ₂₅ (HMe ₂ SiO _1/2 ), or (HMe ₂ SiO _1/2 )(Me ₂ SiO) ₄₅ (HMe ₂ SiO _1/2 ), or (HMe ₂ SiO _1/2 )(Me ₂ SiO) ₁₂₅ (HMe ₂ SiO _1/2 ); a methylhydrogensiloxane polymer with a trimethylsiloxy group (trimethylsiloxy group) at the end, which can be represented by the general formula (Me ₃ SiO _1/2 ) (HMeSiO ) _n (Me ₃ SiO _1/2 ) (n=1 ~ 1,000 or n=5 ~ 500) means, for example (Me ₃ SiO _1/2 )(HMeSiO) ₂₀ (Me ₃ SiO _1/2 ) or (Me ₃ SiO _1/2 )(HMeSiO) ₄₀ (Me ₃ SiO _1/2 ); or methylhydrogensiloxane-dimethylsiloxane terminated with trimethylsiloxy group (trimethylsiloxy group) ), which can be represented by the general formula (Me ₃ SiO _1/2 )(Me ₂ SiO) _n (HMeSiO) _m (Me ₃ SiO _1/2 ) (n+m=1 ~ 1,000 or n+m=5 ~ 500) , Such as (Me ₃ SiO _1/2 )(Me ₂ SiO) ₂₀ (HMeSiO) ₂₀ (Me ₃ SiO _1/2 ), or (Me ₃ SiO _1/2 )(Me ₂ SiO) ₂₅ (HMeSiO) ₁₂ (Me ₃ SiO _1/2 ), or (Me ₃ SiO _1/2 )(Me ₂ SiO) ₄₆ (HMeSiO) ₂₀ (Me ₃ SiO _1/2 ), or (Me ₃ SiO _1/2 )(Me ₂ SiO) ₁₀₀ (HMeSiO) ₁₀ (Me ₃ SiO _1/2 ), or (Me ₃ SiO _1/2 )(Me ₂ SiO) ₇ (HMeSiO) ₃ (Me ₃ SiO _1/2 ), but the invention is not limited thereto.

The content of linear organic hydrogen polysiloxane in the organic polysiloxane mixture may be 0.1 to 10 parts by weight.

Specifically, the molar ratio of the amount of hydrogen groups contained in the highly reactive organic hydrogen polysiloxane (SiH group) to the amount of hydrogen groups contained in the linear organic hydrogen polysiloxane (SiH group) may be 0.4:1~50:1, especially 0.4:1~46:1. When the molar ratio of the amount of hydrogen groups contained in the highly reactive organic hydrogen polysiloxane (SiH group) to the amount of hydrogen groups contained in the linear organic hydrogen polysiloxane (SiH group) is less than 0.4:1 At this time, it was shown that a cured product with a sufficient crosslink density could not be obtained, and the curing time could be extended. When the molar ratio is greater than 50:1, the low adhesive strength may be caused due to the increase in hardness, the hard-type cured product may be obtained due to the increase in crosslink density, the possibility of cracking and long-term storage The difficulty of the gel state may increase, and hydrogen gas may be generated during the curing process, resulting in the formation of voids and further reducing the reliability.

In addition, the total amount of alkenyl groups (SiVi groups) contained in the first organic polysiloxane (a) and the second organic polysiloxane (b) is the same as the organic hydrogen polysiloxane (c) (SiVi group) The molar ratio of the total amount of hydrogen groups contained in the hydride group may be 1:0.3 to 1:1, especially 1:0.4 to 1:0.9. When the total amount of alkenyl groups (SiVi groups) contained in the first organic polysiloxane (a) and the second organic polysiloxane (b) is the same as that in the organic hydrogen polysiloxane (c) (SiH group) When the molar ratio of the total amount of contained hydrogen groups is less than 1:0.3, it is not impossible to obtain a cured product having a sufficient crosslink density. When the molar ratio is greater than 1:1, since the organic hydrogen polysiloxane has a high cross-linking density, the possibility of cracking in the cured product is increased, and hydrogen gas may be generated during the curing process, resulting in the formation of voids and further Reliability is reduced.

2. platinum catalyst

The platinum catalyst contained in the silicone composition of the present invention is used to accelerate the alkenyl group in the first organic polysiloxane (a) and the second organic polysiloxane (b) and bond directly to the silicon The addition reaction between the hydrogen groups of the organic hydrogen polysiloxane (c) on the atom. According to the curing method (photocuring or thermal curing), the platinum catalyst may be a photoactive platinum catalyst or a thermal curing platinum catalyst.

Photoactive platinum catalyst

The above photoactive platinum catalyst is activated when exposed to ultraviolet (UV) rays of 200 to 500 nm. Therefore, when the catalyst is used for curing, by amplifying the amount of light radiation corresponding to the effective wavelength range of curing, the curability of the silicone composition can be ensured while using a small amount of platinum catalyst.

Specifically, the photoactive platinum catalyst may be a β-diketone platinum complex, a cyclic diene compound, or the like, but the present invention is not limited thereto. The β-diketone platinum complex is, for example, trimethyl (acetylacetonate) platinum complex (trimethyl (acetylacetonate) platinum complex), trimethyl (2,4-pentanedione) platinum complex (trimethyl (2,4 -pentanedionate) platinum complex), trimethyl (3,5-heptanedionate) platinum complex (trimethyl(3,5-heptanedionate) platinum complex), trimethyl (methyl acetoacetate) platinum complex (trimethyl (methyl acetoacetate) platinum complex), bis(2,4-pentanedionate) platinum complex (bis(2,4-pentanedionate) platinum complex), bis(2,4-pentanedione acid) platinum complex ( bis(2,4-hexanedionate) platinum complex), bis(2,4-heptanedionate) platinum complex, bis(3,5-heptanedionate) platinum complex (Bis(3,5-heptanedionate) platinum complex), bis(1-phenyl-1,3-)butanedione) platinum complex (bis(1-phenyl-1,3-butanedionate) platinum complex), Or bis(1,3-diphenyl-1,3-propanedione) platinum complex (bis(1,3-diphenyl-1,3-propanedionate) platinum complex); cyclic diene compounds such as (1 , 5-cyclooctadienyl) dimethyl platinum complex ((1,5-cyclooctadienyl) dimethyl platinum complex), (1,5-cyclooctadienyl) diphenyl platinum complex ((1,5 -cyclooctadienyl)diphenyl platinum complex), (1,5-cyclooctadienyl)dipropyl platinum complex ((1,5-cyclooctadienyl)dipropyl platinum complex), (2,5-dicycloheptadiene) di Methyl platinum complex ((2,5-norbornadiene) dimethyl platinum complex), (2,5-dicycloheptadiene) diphenyl platinum complex ((2,5-norbornadiene) diphenyl platinum complex) , (Cyclopentadienyl) dimethyl platinum complex ((cyclopentadienyl) dimethyl platinum complex), (methyl cyclopentadienyl) diethyl platinum complex ((methylcyclopentadienyl) diethyl platinum complex), (trimethyl (Trimethylsilylcyclopentadienyl) diphenyl platinum complex ((trimethylsilylcyclopentadienyl) diphenyl platinum complex), (methylcyclooctyl-1,5-dienyl) diethyl platinum complex ((methylcycloocta-1 ,5-dienyl)diethyl platinum complex),(cyclopentadienyl)trimethyl platinum complex ((cyclopentadienyl)trimethyl platinum complex),(cyclopentadienyl)ethyl dimethyl platinum complex ((cyclopentadienyl)trimethyl platinum complex) )ethyldimethyl platinum complex), (cyclopentadienyl) acetyldimethyl platinum complex ((cyclopentadienyl) acetyldimethyl platinum complex), (methylcyclopentadienyl) trimethyl platinum complex ((methylcyclopentadienyl) trimethyl platinum complex), (methylcyclopentadienyl) trihexyl platinum complex ((methylcyclopentadienyl) trihexyl platinum complex), (trimethylsilyl cyclopentadienyl) trimethyl platinum complex ((trimethylsilylcyclopentadienyl ) trimethyl platinum complex), (dimethylphenylsilylcyclopentadienyl) triphenyl platinum complex ((dimethylphenylsilylcyclopentadienyl) triphenyl platinum complex), or (cyclopentadienyl) dimethyltrimethyl (Cyclopentadienyl) dimethyltrimethylsilylmethyl platinum complex.

Based on 100 parts by weight of the organic polysiloxane mixture, the content of the photoactive platinum catalyst can make the content of platinum atoms 0.01 to 200 ppm, especially 1 to 150 ppm.

When the content of the photoactive platinum catalyst is such that the content of platinum atoms is less than 0.01 ppm based on 100 parts by weight of the organic polysiloxane mixture, the curing of the silicone composition may be significantly delayed, resulting in incomplete curing or processability of the composition Of deterioration. When the content of the photoactive platinum catalyst is such that the content of platinum atoms is greater than 200 ppm, in the case where a 1-part type siloxane composition has been prepared, no additional curing retarder is added. It is difficult to store it for a long time, which is economically disadvantageous.

Heat-curing platinum catalyst

The thermosetting platinum catalyst is used to accelerate the curing of the addition-curable silicone composition. The inclusion of such a catalyst allows the composition to be cured in a short time even at a low temperature of 70°C or lower, so that the working time can be shortened and thus the influence on the adherend can be reduced.

In consideration of reactivity, stability after compounding, and economic aspects, the heat-curable platinum catalyst may be a platinum-vinylsiloxane complex compound (platinum-vinylsiloxane complex compound) and especially a platinum halide (platinum halide) (such as PtCl ₄ H ₂ , which is the reaction product between cyclohexane and PtCl ₄ 6H ₂ O, Na ₂ PtCl ₄ 4H ₂ O, or H ₂ PtCl ₄ 6H ₂ O), platinum-olefin complex, Platinum-alcohol complex (platinum-alcohol complex), platinum-alcoholate complex (platinum-alcoholate complex), platinum-ether complex (platinum-ether complex), platinum-aldehyde complex (platinum-aldehyde complex), platinum -Ketone complex (platinum-ketone complex), platinum-vinylsiloxane complex (platinum-vinylsiloxane complex) (e.g. platinum-1,3-divinyl-1,1,3,3-tetramethylbis Silicone complex (platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), bis-(γ-picoline)-platinum dichloride (bis-(γ-picoline)- platinum dichloride), trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride platinum dichloride), cyclopentadiene-platinum dichloride, bis (alkynyl) bis (triphenylphosphine) platinum complex (bis (alkynyl) bis (triphenylphosphine) platinum complex, bis ( (Alkynyl) (cyclooctadiene)) platinum complex (bis (alkynyl) (cyclooctadiene) platinum complex), or the like.

Based on 100 parts by weight of the organic polysiloxane mixture, the content of the heat-curable platinum catalyst may make the content of platinum atoms 0.1 to 30 ppm, more specifically 0.5 to 25 ppm.

When the content of the heat-curable platinum catalyst is such that the content of platinum atoms is less than 0.1 ppm based on 100 parts by weight of the organic polysiloxane mixture, the curing of the silicone composition may be delayed, resulting in deterioration of workability. When the content of the heat-curable platinum catalyst is such that the content of platinum atoms is greater than 30 ppm, it may be economically disadvantageous: the pot life is shortened to the result of low workability, and after being prepared into a single group In the case of a 1-part type silicone composition, it is difficult to store it for a long time without adding an additional curing retarder.

3. Other additives

In order to improve processability or storage stability or enhance the mechanical properties of silicone cured products, in addition to the above components, the silicone composition of the present invention may also contain additives, such as ultraviolet fluorescent enhancers, adhesion promoters, inorganic Fillers (e.g. fumed silica, Aerosil®, precipitated silica, pulverized silica, diatomite, iron oxide, zinc oxide, titanium oxide, (Calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, hydrotalcite, carbon black, or the like), silicone rubber powder, resin powder, heat resistance enhancer, antioxidant, free radical scavenger, light stabilizer , Flame retardant additives, siloxane-based thinners, pigments, dyes, or curing retarders (such as polymethylvinylsiloxane cyclic compounds (polymethylvinylsiloxane cyclic compounds), acetylene compounds (acetylene compounds), or organophosphorus compounds (organic phosphorus compound)).

In addition, in order to improve the adhesion to the substrate to be adhered, in the silicone composition of the present invention, an adhesion enhancer may be added, such as methyltrimethoxysilane (methyltrimethoxysilane), ethyltrimethoxysilane (ethyltrimethoxysilane) , Vinyltrimethoxysilane (allyltrimethoxysilane), 3-methacryloxypropyltrimethoxysilane (3-methacryloxypropyltrimethoxysilane), 3-epoxypropyloxypropyl 3-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane , Methyl cellosolve orthosilicate, a siloxane oligomer with an epoxy group-containing organic group and a silicon atom-bonded alkoxy group in the molecule, in The molecule has an epoxy group-containing organic group, a silicon atom-bonded alkoxy group and an alkenyl group siloxane oligomer (siloxane oligomer), the molecule has an epoxy group-containing organic group, a silicon atom Silicone oligomers of bonded alkoxy groups and hydrogen atoms bonded to silicon atoms, and if necessary, in addition to the above-mentioned adhesion enhancers, aluminum chelate compounds (aluminum chelate compound) can also be added ) Or titanium compounds.

Since two or more types are used to prepare the silicone composition of the present invention in the highly reactive organic hydrogen polysiloxane and the linear organic hydrogen polysiloxane having high addition reactivity as described above, As a result, the curing speed is improved, and even a small amount of platinum catalyst can be used to obtain improved curing efficiency. This composition can be cured under ultraviolet irradiation, so it has excellent processability and can maintain a gel state even after curing. Thus, an excellent adhesiveness of 0.1 MPa/cm ² or higher with respect to the glass adherend is achieved.

In addition, the silicone composition of the present invention has the following advantages in terms of thermal curing: shortens the curing time at low temperature (70° or lower) so that the adherend is not adversely affected, thereby achieving a relative to the glass adherend Excellent adhesion of 0.1 MPa/cm ² or more.

In addition, since the content of the platinum catalyst is controlled, the silicone composition of the present invention has excellent storage stability as a 1-part type composition (1-part type composition). This excellent storage stability lies in: in all groups After partial mixing, the viscosity doubles at least 14 days even in the shaded state and at a high temperature of 45°C, and at least 1 hour at 25°C.

Therefore, due to the above characteristics, the silicone composition of the present invention can form a cured product having excellent adhesion to the adherend substrate (glass) and still being cured at a high speed, showing excellent dimensional stability in the following manner: Even after curing, it maintains a stable gel state, has excellent weather resistance and excellent heat resistance, and does not discolor or crack even when exposed to ultraviolet rays or high temperatures for a long time. In particular, since the siloxane composition of the present invention has the most important transparency in OCA or OCR of image display devices such as LCDs or OLEDs, it can be applied to ensure a large-size display requiring excellent reliability Visibility of the panel.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are provided only to increase the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

> example 1~20>

The silicone composition was prepared by combining the components shown in Table 1 and Table 2 below.

Here, the organosilicon compositions of Examples 1-10 were photocured using a UV irradiation device, and the organosilicon compositions of Examples 11-20 were thermally cured using an oven with an average temperature of 50°C.

[Table 1]

[Table 2]

> Comparative example 1~20>

The silicone composition was prepared by combining the components shown in Table 3 and Table 4 below.

Here, the silicone compositions of Comparative Examples 1 to 10 were photocured using a UV irradiation device, and the silicone compositions of Comparative Examples 11 to 20 were thermally cured using an oven with an average temperature of 50°C.

[table 3]

[Table 4]

The components used in the examples and comparative examples are shown in Table 5.

[table 5]

> Experimental example 1>

The physical properties of the silicon compositions prepared according to Examples 1 to 10 and Comparative Examples 1 to 10 were evaluated as follows, and the results are shown in Tables 6 and 7 below.

1) Storage stability: The time it takes to store the silicone composition in a light-shielded 45°C oven after preparation and to change the viscosity to twice the initial viscosity is reported as the 45°C storage time.

2) Curing time: apply 16 mg (weight) of the above-mentioned silicone composition to the center of a glass sample measuring 20 mm × 60 mm × 2 mm (thickness) and weighing 5.2 g, and use a UV irradiation device ( Panasonic Aicure UJ35 controller, UV-LED lamp (365nm, high-output head ANUJ6170), 150mW/cm ² at 365 nm, UV irradiation to a cumulative dose of 3,000 mJ/cm ² . Immediately after the UV irradiation, another glass sample was placed so that it was superimposed on the other sample in a cross manner, in which the silicone composition was inserted at the cross center between the samples to have a diameter of 10 mm and a thickness of 0.2 mm . After holding the sample at 25°C for a predetermined time, the time point at which the upper sample was lifted and the lower sample was lifted instead of falling due to its own weight was reported as the curing time.

3) Adhesive bond strength: After holding the above sample for curing time measurement at 25°C for 24 hours, use a tensile tester to pull the two glass samples apart from each other in the vertical direction, and measure the separation of the sample Strength and reported as adhesive strength.

4) Permeability: Inject 50 g of the above-mentioned silicone composition into a 60-mL polypropylene container, use a UV irradiation device to perform UV irradiation from above with a cumulative dose of 3000 mJ/cm ² , and then keep at 25°C for 24 Hours to complete curing. Subsequently, a needle weighing 2.51 g was put into the cured composition and held for 5 seconds while applying a load of 47.5 g to measure the permeability.

[Table 6]

[Table 7]

> Experimental example 2>

The physical properties of the silicon compositions prepared according to Examples 11-20 and Comparative Examples 11-20 are evaluated as follows. The results are shown in Tables 8 and 9 below.

1) Storage stability: After all components are mixed at 25°C, the time it takes for the viscosity to become twice the initial viscosity immediately is reported as pot life.

2) Curing time: 16 mg (weighing) of the above added curable silicone composition is applied to the center of a glass sample measuring 20 mm × 60 mm × 2 mm (thickness) and weighing 5.2 g. Immediately, another glass sample was placed so that it was superimposed on the other sample in a cross manner, in which the silicone composition was inserted at the cross center between the samples to have a diameter of 10 mm and a thickness of 0.2 mm and connect the samples Together. After the sample is held in a 50°C oven for a predetermined time, the time point at which the upper sample is lifted and the lower sample is lifted instead of falling due to its own weight is reported as the curing time.

3) Adhesive bond strength: The above samples were heat-treated at 50°C for 1 hour for curing time measurement, and then held at 25°C for 30 minutes, using a tensile tester to vertically place the two glass samples against each other Pull apart, and measure the strength of the sample separation and report as the adhesive strength.

4) Permeability: 50g of silicone composition was poured into a 60-mL polypropylene container, heat-treated in an oven at 50°C for 3 hours, and kept at 25°C for 30 minutes. Subsequently, a needle weighing 2.51 g was put into the composition and held for 5 seconds while applying a load of 47.5 g to measure the permeability.

[Table 7]

Compare experimental examples and comparative examples. In the case of Comparative Examples 1 to 3 and Comparative Examples 11 to 13 without using the first organic hydrogen polysiloxane (c-1) and the second organic hydrogen polysiloxane (c-2), the curing speed is low Therefore, the curing time is quite long, and there is a problem in storage stability because it is difficult to store for a long time.

Similarly, in the case of Comparative Examples 4 and 14, the amount of the first organic hydrogen polysiloxane (c-1) and the second organic hydrogen polysiloxane (c-2) is less than 0.1 parts by weight due to curing The speed is low to prolong the curing time, and in the case of Comparative Examples 5 and 15, the amount of the first organic hydrogen polysiloxane (c-1) and the second organic hydrogen polysiloxane (c-2) is greater than 5 parts by weight, showing extremely low bonding strength.

Meanwhile, in the case of Comparative Example 6 in which the amount of the photoactive platinum catalyst is greater than 200 ppm, it is difficult to store for a long period of time, and in the case of Comparative Example 16, in which the amount of the thermosetting platinum catalyst is greater than 30 ppm, showing a short usable Pot life thus represents low processability.

In the case of the photocurable product of Comparative Example 7, in which the amount of the first organic polysiloxane (a) is less than 5 parts by weight, it exhibits low adhesive strength, and is difficult to store for a long time, and the heat of Comparative Example 17 In the case of cured products, the curing time is extended.

In the case of Comparative Examples 8 and 18, where the amount of the first organopolysiloxane (a) is greater than 50 parts by weight, it exhibits a very high viscosity and thus represents a difficulty in applying the gel composition to OCA as expected in the present invention Or OCR.

Meanwhile, in the case of Comparative Examples 9 and 19, wherein the highly reactive organic hydrogen polysiloxane (that is, the first organic hydrogen polysiloxane (c-1) or the second organic hydrogen polysiloxane (c -2a or c-2b) the molar ratio of the hydrogen groups contained in) and the linear organic hydrogen polysiloxane (ie, the third organic hydrogen polysiloxane (c-3)) The amount of is less than 0.4:1, the curing time is extended due to the low curing speed, and in the case of Comparative Examples 10 and 20 where the molar ratio is greater than 50:1, the low permeability as shown shows high hardness, and Shows low bond strength.

Although the present invention has been described above in detail with certain preferred exemplary embodiments, those skilled in the art will understand that various changes and modifications can be made and those changes and modifications without departing from the spirit and scope of the present invention It is included in the scope of the attached patent application.

no

no

no

Claims (6)

A silicone composition comprising an organic polysiloxane mixture and a platinum catalyst, wherein the organic polysiloxane mixture comprises a first organic polysiloxane (a) and a second organic polysiloxane ( b) and an organic hydrogen polysiloxane (c), the first organic polysiloxane (a) contains a unit having at least one alkenyl group and at least one SiO _4/2 unit in its molecule, the second organic Polysiloxane (b) contains at least two alkenyl groups in its molecule, wherein the organohydrogen polysiloxane (c) contains a highly reactive organohydrogen polysiloxane and a linear organohydrogen polysilicon Oxane, wherein the highly reactive organohydrogen polysiloxane contains a first organohydrogen polysiloxane (c-1) or a second organohydrogen polysiloxane (c-2), the first organic Hydrogen polysiloxane (c-1) contains a unit having a hydrogen group directly bonded to at least one silicon atom and at least one SiO _4/2 unit in its molecule, the second organic hydrogen polysiloxane (c- 2) The molecule contains a hydrogen group directly bonded to at least two silicon atoms and at least one aryl group, or directly bonded to the adjacent silicon group (oxygen group) having an oxygen atom in between The halogenated alkyl group on the silicon atom, and the linear organic hydrogen polysiloxane contains a third organic hydrogen polysiloxane (c-3), the third organic hydrogen polysiloxane (c-3) -3) Contains a hydrogen group directly bonded to at least one silicon atom in its molecule. The silicone composition as described in item 1 of the patent application scope, wherein the first organic polysiloxane (a) is represented by the following chemical formula 1, and the second organic polysiloxane (b) is represented by the following chemical formula Represented by 2: [Chemical formula 1] (R ¹ ₁ R ² ₂ SiO _1/2 ) _a (R ³ ₃ SiO _1/2 ) _b (SiO _4/2 ) _c where R in the chemical formula 1 is the same as or different from each other ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, wherein at least one of R ¹ and R ² is a group having 2 to 10 carbon atoms Alkenyl, R ³ are each independently an alkyl group having 1 to 10 carbon atoms, "a" is a number of 0.05 to 0.25, "b" is a number of 0.1 to 0.5, and "c" is a number of 0.4 to 0.6 And satisfy a + b + c = 1; and [Chemical Formula 2] (R ⁴ ₁ R ⁵ ₂ SiO _1/2 ) ₂ (R ⁶ R ⁷ SiO) _d (R ⁸ ₂ SiO) _e where in Chemical Formula 2, R ⁴ and R ^{5 which} are the same or different from each other are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and R ⁶ and R ⁷ which are the same or different from each other are each independently An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and each R ⁸ independently has 1 to 10 carbon atoms Carbon atom alkyl group, wherein at least one of R ⁴ to R ⁷ is an alkenyl group having 2 to 10 carbon atoms, “d” and “e” are each independently an integer of 0 or 1 or greater, d + e is an integer from 10 to 10,000, and d / (d + e) is a number from 0 to 0.1. The silicone composition as described in item 1 of the patent application scope, wherein the first organohydrogen polysiloxane (c-1) is represented by the following chemical formula 3, and the second organohydrogen polysiloxane (c-) 2) It is represented by the following chemical formula 4, and the third organic hydrogen polysiloxane (c-3) is represented by the following chemical formula 5: [Chemical formula 3] (HR ⁹ ₂ SiO _1/2 ) _f (R ¹⁰ ₃ SiO _1/2 ) _g (SiO ₂ ) _h where in formula 3, R ⁹ and R ¹⁰ which are the same or different from each other are each independently an alkyl group having 1 to 10 carbon atoms, and “f” is a number of 0.05 to 0.75 , “G” is a number from 0 to 0.5, and “h” is a number from 0.3 to 0.6, and satisfies f + g + h = 1; [Chemical Formula 4] R ¹¹ _i Si(OSiR ¹² ₂ H) _4-i where In Chemical Formula 4, R ^{11 is} each independently an aryl group having 6 to 15 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms, and R ^{12 is} each independently having An alkyl group of 1 to 10 carbon atoms, and "i" is a number of 1 or 2; and [Chemical Formula 5] H _j R ¹³ _k SiO _{( 4-jk)/2} where in Chemical Formula 5, R ^{13 is} independently Is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, "j" is a number of 0.001 to 2, "k" is a number of 0.7 to 2, and j + k is a number of 0.8~3. The silicone composition as described in item 1 of the patent application scope, wherein the hydrogen group of the highly reactive organohydrogen polysiloxane (SiH) and the hydrogen group of the linear organohydrogen polysiloxane (SiH) The molar ratio is 0.4:1 ~ 50:1. The siloxane composition as described in item 1 of the patent application range, wherein the platinum catalyst comprises any one selected from the group consisting of a photoactive platinum catalyst and a thermosetting platinum catalyst. The silicone composition as described in item 1 of the patent application scope, wherein the organic polysiloxane mixture comprises: 5 parts by weight to 50 parts by weight of the first organic polysiloxane; 33 parts by weight to 92 parts by weight of the second organic polysiloxane; 0.1 parts by weight to 5 parts by weight of the highly reactive organic hydrogen polysiloxane; and 0.1 to 10 parts by weight of the linear organic hydrogen polysiloxane.