TWI722552B - 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 SiO_4/2 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 SiO_4/2 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.

With the advent of the recent information age, image display devices such as liquid crystal displays (LCD), organic light emitting diodes (OLED), and tablet terminals (smart phones, PDA terminals, etc.) are forming large-scale markets and applied to various product groups.

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

As the polymer of this optical adhesive material, acrylic polymers that have excellent transparency, easy design, fast UV curing, and economic benefits are mainly used. However, because acrylic polymers have many problems in weather resistance, heat resistance, cold resistance, dimensional stability, etc., the use of silicone-based polymers has been increasing recently.

Japanese Patent Early Publication No. 1900-126317 discloses the use of alkenyl-containing silicones with photosensitizers such as benzophenone and photopolymerization initiators such as tert-hexyl peroxybenzoate The crosslinking reaction. However, the problem with the crosslinking reaction is that the curing speed is not high enough, and there is a risk of discoloration due to residual initiator, resulting in low weather resistance and low processability.

Japanese Patent No. 3912525 discloses a silicone rubber composition. The silicone rubber composition is composed of a combination of silicone resin for imparting viscosity and silicone resin for imparting rubber strength. The prepared addition-curable composition (addition-curable composition) and the silicone rubber composition have certain rubber hardness and rubber strength, and the silicone rubber composition has adhesiveness that can be bonded and fixed with the substrate or various parts. So it can be used as OCA. However, since the OCA film is formed in the form of a solid having a transparent sheet appearance, it is likely to bind air bubbles in the process of attaching the protective part having the light-transmitting property to the substrate part including the image display part of the image display device, Even after attachment, there is a high possibility of delamination or further introduction of bubbles at high temperature, which results in low visibility. In addition, Japanese Patent No. 5010762 discloses a heat-curable polyorganosiloxane composition, which contains a linear polyorganosiloxane having alkenyl groups at both ends, and a linear polyorganosiloxane having hydrosilyl groups at both ends. A mixture of oxanes, specific cyclic polyorganohydrosiloxanes, and adhesion-imparting agents. Although the curing of the composition at a temperature of 50 to 80°C only takes 0.1 to 3 hours, since the cured product itself has no adhesiveness, it is necessary to perform prolonged thermal curing at a high temperature to impart adhesiveness to the adhesive imparting agent to ensure non-stickiness. Adequate bonding of the adhesive body.

In particular, in the silicone-based polymers used as materials for OCA and OCR, UV curing properties that can shorten the working time and enable non-heating processes are required, and it is important to develop addition-curable silicones. Even if it contains a small amount of platinum catalyst, it can ensure useful curability and the most important transparency in optical adhesive materials, and it can be thermally cured in a short time even at a low temperature of 70°C or lower and has excellent The workability (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 excellent curing speed while maintaining transparency, and provides enhanced work convenience by having an improved pot life at room temperature.

[Technical means]

In the present invention, there is provided a silicone composition comprising an organopolysiloxane mixture and a platinum catalyst, wherein the organopolysiloxane mixture includes a first organopolysiloxane (a) and a second organopolysiloxane (a) Polysiloxane (b) and an organohydrogen polysiloxane (c). The first organopolysiloxane (a) includes a unit _{having at least one alkenyl group and at least one SiO 4/2 unit in its molecule,} The second organopolysiloxane (b) contains at least two alkenyl groups in its molecule, wherein the organohydrogenpolysiloxane (c) contains a highly reactive organohydrogenpolysiloxane and a linear organohydrogen Polysiloxane, wherein the highly reactive organohydrogenpolysiloxane comprises a first organohydrogenpolysiloxane (c-1) or a second organohydrogenpolysiloxane (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 organohydrogen 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 the silicon adjacent to the above-mentioned silicone group with an oxygen atom in between The halogenated alkyl group on the atom and the linear organohydrogenpolysiloxane include a third organohydrogenpolysiloxane (c-3) and a third organohydrogenpolysiloxane (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 even if the cured product is exposed to ultraviolet rays for a long time, it will not fade or crack. In addition, it can be cured in a short time, after curing, it can achieve ^{a glass-to-glass adhesive strength of 0.1 MPa/cm 2} or more, and it can ensure effective curability even if it contains a 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 it can achieve a temperature of 0.1M Pa/cm ² or more after curing. The adhesive strength of glass to glass can form a cured product with excellent adhesion to the substrate, without producing by-products, and thus exhibiting excellent dimensional stability against curing shrinkage (dimensional stability), and having excellent usability Time (pot life) and thus show excellent storage stability (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 the effect of providing excellent workability, it is suitable for For example, in an image display device such as LCD or OLED, it is applied to an adhesive (OCA or OCR) between the substrate portion including the image display portion and the light-transmitting protective portion.

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 found that by including an organopolysiloxane having an alkenyl group and a specific organohydrogenpolysiloxane having high addition reactivity, the silicone 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 includes an organopolysiloxane mixture and a platinum catalyst.

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

1. Organopolysiloxane mixture (organopolysiloxane mixture)

The organopolysiloxane mixture contained in the silicone composition of the present invention includes a first organopolysiloxane (a), a second organopolysiloxane (b), and an organohydrogenpolysiloxane Alkane (c).

First organopolysiloxane (a) (first organopolysiloxane)

The first organopolysiloxane (a) used in the present invention is used to improve the mechanical properties of the cured product (such as the adhesive strength of the adhesive) by affecting the initial viscosity of the silicone composition.

The first organopolysiloxane (a) includes 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 that 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, wherein R ¹ and R ² are 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 from 0.05 to 0.25, and "b" is a number from 0.1 to 0.5 Number, and the number whose "c" is 0.4~0.6, and satisfies a + b + c = 1.

^{R 1} and R ² that 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.

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 in the above list, but the present invention is not limited to these.

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

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

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 crosslink density may change with time, and therefore cracks may occur 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 result in a low crosslink density, it is possible to obtain low adhesiveness with respect to glass.

When "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 so that the silicone composition has a high viscosity, it may result in low flowability and low workability.

The first organopolysiloxane (a) can be an MQ resin and especially a silicate resin with two ends of vinyldimethyl and trimethyl respectively, or two The ends are divinylmethyl and trimethyl silicate resins. Silicate resins with divinylmethyl and trimethyl at the ends, which can be (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 present invention is not limited to this.

The content of the first organopolysiloxane (a) in the organopolysiloxane mixture can be 5-50 parts by weight. When the content of the first organopolysiloxane (a) is less than 5 parts by weight so that the adhesive strength with respect to glass is low, it may result in low workability. When the content of the first organopolysiloxane (a) is greater than 50 parts by weight to cause a high crosslink density, cracks may be generated in the silicone cured product due to external impact.

The first organopolysiloxane (a) may contain 0.3-10 mmol/g, especially 0.5-5 mmol/g of vinyl groups (SiVi groups). When the first organopolysiloxane (a) contains a vinyl group of less than 0.3 mmol/g, the first organopolysiloxane (a) may exhibit low reactivity. When the first organopolysiloxane (a) contains a vinyl group greater than 10 mmol/g so that the silicone cured product has a high density, cracks may occur therein due to changes over time.

The weight average molecular weight (Mw) of the first organopolysiloxane (a) can 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 are cases where the effect of imparting viscosity to the cured product or enhancing its strength cannot be sufficiently exerted. When the weight average molecular weight of the first organopolysiloxane (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 organopolysiloxane (b) used in the present invention is used to impart flowability to the silicone composition by controlling the viscosity of the silicone composition, and to cure the product by controlling the silicone composition Modulus to improve the physical properties of silicone cured products.

The second organopolysiloxane (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 that 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 that are the same or different from each other 7 is} 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 (aryl group), 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 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 that 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 The methyl group, ethyl group, and propyl group in, but the present invention is not limited to these.

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

The aryl group of R ⁶ and R ⁷ may specifically be a phenyl group, a tolyl group, a xylyl group, a naphthyl group, or a biphenyl group. group), and preferably the phenyl group listed above, but the present invention is not limited to this.

When d + e of Chemical Formula 2 is less than 10, voids may be generated due to evaporation during the curing process of the silicone composition, resulting in low mold workability. 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 with low curing reactivity and high density is obtained, and therefore cracks may be generated in the cured product due to changes over time.

Specifically, the second organopolysiloxane (b) can be a vinyldimethyl dimethylsiloxane polymer, which can 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 ); methyl vinyl siloxane-dimethyl siloxane block polymer with vinyl dimethylsiloxy group at the end (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 with trimethylsiloxy group at the end, 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} ); methylphenylsiloxane-dimethylsiloxane block polymer with vinyldimethylsiloxy group (vinyldimethylsiloxy group) at the end, which can be represented by the general formula ( 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 vinyl dimethyl at the end Vinyldimethylsiloxy group diphenylsiloxane-dimethylsiloxane block polymer (diphenylsiloxane-dimethylsiloxane block polymer), 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 organopolysiloxane (b) in the organopolysiloxane mixture can be 33 to 92 parts by weight, especially 39 to 91 parts by weight. When the content of the second organopolysiloxane (b) is less than 33 parts by weight, resulting in a high crosslink density, cracks may easily occur due to thermal shock. When the content of the second organopolysiloxane (b) is greater than 92 parts by weight, insufficient adhesion to glass may be obtained.

The first organopolysiloxane (a) and the second organopolysiloxane (b) can be used in a weight ratio of 5:95 to 60:40. When the weight ratio of the first organopolysiloxane (a) to 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) to the second organopolysiloxane (b) is greater than 60:40, since the uncured organosilicon composition has low fluidity, the cured product may It has low flexibility and therefore may be susceptible to external impact, and the possibility of cracks increases.

The viscosity of the second organopolysiloxane (b) at 25°C can be 10~500,000 mPa•s, especially 100~250,000 mPa•s. When the viscosity of the second organopolysiloxane (b) is less than 10 mPa•s, excellent mechanical properties or viscosity cannot be imparted to the cured product. When the viscosity of the second organopolysiloxane (b) is greater than 500,000 mPa•s, it may cause low workability due to low fluidity in the uncured state.

The second organopolysiloxane (b) may contain 0.01 to 5 mmol/g, especially 0.02 to 3 mmol/g of vinyl groups (SiVi groups). When the second organopolysiloxane (b) contains a vinyl group of less than 0.01 mmol/g, the second organopolysiloxane (b) may exhibit low reactivity. When the second organopolysiloxane (b) contains a vinyl group greater than 5mmol/g so that the silicone cured product has a high crosslink density, it may exhibit low viscosity, and may also be due to Changes may cause cracks.

The second organopolysiloxane (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 organopolysiloxane (b) is less than 600 g/mol, the cured product cannot be imparted with excellent mechanical properties or viscosity. When the weight average molecular weight of the second organopolysiloxane (b) is greater than 180,000 g/mol, it may result in low processability due to low fluidity in the uncured state.

Organohydrogenpolysiloxane (c) (organohydrogenpolysiloxane)

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

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

In particular, for the gel-type composition used in OCA or OCR in the cured form in the case of the silicone composition of the present invention, a typical gel-type composition does not contain, for example, a high-viscosity hydrogen polymer having a Q unit. Silicone (such as the above-mentioned first organohydrogenpolysiloxane (c-1)) highly reactive organohydrogenpolysiloxane, and the above-mentioned second organohydrogenpolysiloxane having high crosslinking ability or high reactivity Oxyane (c-2), because the inclusion of this compound will increase the hardness or viscosity of the composition, or make it difficult to maintain a gel state.

However, in the case of the silicone composition of the present invention, the first organopolysiloxane (a ) Or the addition reactivity of the second organopolysiloxane (b) can not only improve the curing speed, but also the composition can maintain a gel state even after its curing is completed.

For example, the organohydrogenpolysiloxane (c) can be a mixture of the first organohydrogenpolysiloxane (c-1) and the third organohydrogenpolysiloxane (c-3), or the second organohydrogenpolysiloxane (c-3) A mixture of polysiloxane (c-2) and third organohydrogen polysiloxane (c-3).

The first organohydrogenpolysiloxane (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 that 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 The methyl group, ethyl group, and propyl group in, but the present invention is not limited to these.

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

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

When the "h" of Chemical Formula 3 is less than 0.3, the first organohydrogenpolysiloxane (c-1) may exhibit low reactivity. When "h" is greater than 0.6 so that the silicone composition has high viscosity and thus low fluidity, low processability may result.

Specifically, the first organohydrogen 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) 0.42 _1/2 ) _0.58 (SiO _4/2 ) _0.42 , or (HMe ₂ SiO _1/2 ) _0.64 (SiO _4/2 ) _0.36 , but the present invention is not limited thereto.

The viscosity of the first organohydrogenpolysiloxane (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 are cases where the effect of increasing the curing speed or enhancing the cured product cannot be fully exerted. When the viscosity of the first organohydrogenpolysiloxane (c-1) is greater than 500 mPa•s, the molecular weight is too large, so it may be difficult to stably prepare the silicone composition.

The first organohydrogenpolysiloxane (c-1) may contain 0.5 to 10 mmol/g, especially 1 to 10 mmol/g of hydrogen groups (SiH groups). When the amount of hydrogen groups contained in the first organohydrogenpolysiloxane (c-1) is less than 0.5mmol/g, the first organohydrogenpolysiloxane (c-1) may exhibit low reactivity. When the first organohydrogenpolysiloxane (c-1) contains hydrogen groups greater than 10 mmol/g so that the silicone cured product has a high crosslink density, it may exhibit low viscosity, and may also be due to The change of time causes cracks.

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

The polymerization degree of the first organohydrogenpolysiloxane (c-1) can be 1.5~75, especially 6~28.

The second organohydrogenpolysiloxane (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 a hydrogen group with an oxygen atom in between. The halogenated alkyl group on the silicon atom adjacent to the silicone 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 the 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 be an aryl group having 1 to 6 carbon atoms. Alkyl group of 6 carbon atoms.

The aryl group of R ¹¹ may be a substituted or unsubstituted phenyl group, such as phenyl group, p-methylphenyl group, or 2,4-dinitrophenyl group. , And preferably are the phenyl groups listed above, but the present invention is not limited to this.

The halogenated alkyl group of R ¹¹ may be specifically trifluoromethyl 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 the methyl group listed above. Group, ethyl group, propyl group, but the present 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 organohydrogenpolysiloxane (c-2) can exhibit low addition reactivity. When "i" is greater than 2, the second organohydrogenpolysiloxane (c-2) cannot be used as a crosslinking agent, and therefore may result in significantly low addition reactivity.

Specifically, the second organohydrogen 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 organohydrogenpolysiloxane in the organopolysiloxane mixture can be 0.1 to 5 parts by weight. When the content of the highly reactive organohydrogenpolysiloxane 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 organohydrogenpolysiloxane is greater than 5 parts by weight, the hardness of the silicone cured product during curing may increase and may not be able to maintain the gel state, or the silicone cured relative to the adherend The product may exhibit very low adhesive strength, which may greatly reduce the applicability of the silicone cured product to OCA or OCR.

The third organohydrogenpolysiloxane (c-3) is a linear organohydrogenpolysiloxane, containing 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 from 0.001 to 2, and "k" The number is 0.7~2, and the number of j + k is 0.8~3.

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

The third organohydrogenpolysiloxane (c-3) is different from the above-mentioned first organohydrogenpolysiloxane (c-1) and the above-mentioned second organohydrogenpolysiloxane (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 the methyl group listed above. Group, ethyl group, propyl group, but the present invention is not limited thereto.

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

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

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

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 silicone cured product may exhibit low hardness or low reactivity. When "j" is greater than 2, due to the high crosslink density of the third organohydrogenpolysiloxane (c-3), cracks may occur in the cured product, and hydrogen may be generated during the curing process, resulting in the formation of voids and It further leads to a decrease in visibility or reliability.

When the "k" of Chemical Formula 5 is less than 0.7, due to the high crosslink density, cracks may be generated in the cured product, and hydrogen may be generated during curing, resulting in the formation of voids and further a decrease in visibility. When "k" is greater than 2 so that the third organohydrogenpolysiloxane (c-3) has a low crosslink density, it may result in low hardness or low reactivity, resulting in prolonged curing time, and possible low molecular weight components. Evaporation causes voids to be formed 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 prolonged due to the low hardness or low reactivity of the third organohydrogenpolysiloxane (c-3), and low molecular weight components may evaporate, resulting in the formation of voids during the curing process And further lead to reduced visibility (visibility) or reliability (reliability).

Specifically, the third organohydrogenpolysiloxane (c-3) can be a dimethylsiloxane polymer with a hydrogendimethylsiloxy group at the end, 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 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 with trimethylsiloxy group at the end ), 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 present invention is not limited to this.

The content of the linear organohydrogenpolysiloxane in the organopolysiloxane mixture can be 0.1-10 parts by weight.

Specifically, the molar ratio of the amount of hydrogen groups contained in the highly reactive organohydrogenpolysiloxane (SiH group) to the amount of hydrogen groups contained in the linear organohydrogenpolysiloxane (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 organohydrogenpolysiloxane (SiH group) to the amount of hydrogen groups contained in the linear organohydrogenpolysiloxane (SiH group) is less than 0.4:1 At this time, it appears that a cured product with a sufficient crosslinking density cannot be obtained, and the curing time can be extended. When the molar ratio is greater than 50:1, the increase in hardness may result in low adhesive strength, and the increase in crosslinking density may result in a hard cured product, which may cause cracks and maintain during long-term storage. The difficulty of the gel state may increase, and hydrogen may be generated during the curing process, leading to the formation of voids and further reducing reliability.

In addition, the total amount of alkenyl groups (SiVi groups) contained in the first organopolysiloxane (a) and the second organopolysiloxane (b) is the same as the organohydrogenpolysiloxane (c) (SiVi group) The molar ratio of the total amount of hydrogen groups contained in 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 organopolysiloxane (a) and the second organopolysiloxane (b) and the organohydrogenpolysiloxane (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 crosslinking density. When the molar ratio is greater than 1:1, because the organohydrogenpolysiloxane has a high crosslinking density, the possibility of cracks in the cured product increases, 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 groups in the first organopolysiloxane (a) and the second organopolysiloxane (b) and directly bond to the silicon The addition reaction between the hydrogen groups of the atomic organohydrogenpolysiloxane (c). Depending on the curing method (light curing or thermal curing), the platinum catalyst may be a photoactive platinum catalyst or a thermal curing platinum catalyst.

Photoactive platinum catalyst

The above-mentioned photoactive platinum catalyst is activated when exposed to 200-500 nm ultraviolet (UV) rays. Therefore, when the catalyst is used for curing, by amplifying the amount of light radiation corresponding to the effective wavelength range of curing, it is still possible to ensure the curability of the organosilicon composition 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(2,4-pentanedionate) platinum complex (trimethyl(2,4 -pentanedionate) platinum complex), trimethyl(3,5-heptanedionate) platinum complex, trimethyl(methyl acetylacetate) platinum complex (trimethyl(3,5-heptanedionate) platinum complex), trimethyl(3,5-heptanedionate) platinum complex) (methyl acetoacetate) platinum complex), bis(2,4-pentanedionate) platinum complex (bis(2,4-pentanedionate) platinum complex), bis(2,4-hexanedione acid) platinum complex ( bis(2,4-hexanedionate) platinum complex), bis(2,4-heptanedionate) platinum complex, bis(3,5-heptanedionate) platinum complex物(bis(3,5-heptanedionate) platinum complex), bis(1-phenyl-1,3-butanedionate) platinum complex (bis(1-phenyl-1,3-butanedionate) platinum complex), Or bis(1,3-diphenyl-1,3-propanedionate) platinum complex (bis(1,3-diphenyl-1,3-propanedionate) platinum complex); the cyclic diene compound is, for example, (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) two ((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), (methylcyclopentadienyl) 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) ) ethyldimethyl 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, or (cyclopentadienyl) dimethyl trimethyl (Cyclopentadienyl) dimethyltrimethylsilylmethyl platinum complex.

Based on 100 parts by weight of the organopolysiloxane 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 organopolysiloxane mixture, the curing of the silicone composition may be significantly delayed, resulting in incomplete curing or processability of the composition The degradation. When the content of the photoactive platinum catalyst is such that the content of platinum atoms is greater than 200 ppm, in the case of having been prepared into a 1-part type (1-part type) silicone composition, 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 thermal curing platinum catalyst is used to accelerate the curing of the addition curable silicone composition. The inclusion of this catalyst allows the composition to be cured in a short time even at a low temperature of 70°C or lower, thereby shortening the working time and thus reducing the influence on the adherend.

Considering reactivity, stability after compounding, and economic aspects, the heat-curing platinum catalyst can be a platinum-vinylsiloxane complex compound and particularly a 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-alcoholate complex, platinum-ether complex, platinum-aldehyde complex, platinum -Ketone complex (platinum-ketone complex), platinum-vinylsiloxane complex (platinum-vinylsiloxane complex) (such as platinum-1,3-divinyl-1,1,3,3-tetramethyl two 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, double( (Alkynyl) (cyclooctadiene) platinum complex (bis(alkynyl) (cyclooctadiene) platinum complex), or the like.

Based on 100 parts by weight of the organopolysiloxane mixture, the content of the thermal curing platinum catalyst can be such that the content of platinum atoms is 0.1-30 ppm, more specifically 0.5-25 ppm.

When the content of the thermal curing platinum catalyst is such that the content of platinum atoms is less than 0.1 ppm based on 100 parts by weight of the organopolysiloxane mixture, curing of the silicone composition may be delayed, resulting in deterioration of workability. When the content of the heat-curing 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 the result is that it has been 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 organic silicon cured products, in addition to the above components, the silicone composition of the present invention may also contain additives, such as ultraviolet fluorescence 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 diluents, pigments, dyes, or curing retarders (e.g. polymethylvinylsiloxane cyclic compound, acetylene compound, or organophosphorus compound) (organic phosphorus compound)).

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

Since two or more types are used in the highly reactive organohydrogenpolysiloxane and the linear organohydrogenpolysiloxane with high addition reactivity as described above to prepare the silicone composition of the present invention, Thereby, the curing speed can be increased, and even a small amount of platinum catalyst can be used to obtain improved curing efficiency. The composition can be cured under ultraviolet radiation, so it has excellent processability and can maintain a gel state even after curing. Thereby achieving excellent adhesion of 0.1 MPa/cm ² or higher relative to the glass adherend.

In addition, the silicone composition of the present invention has the following advantages in terms of thermal curing: shortening the curing time at low temperature (70° or lower) so that the adherend will not be adversely affected, thereby achieving Excellent adhesion above 0.1 MPa/cm ^2.

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. This excellent storage stability lies in: After mixing, the viscosity doubles for at least 14 days at a high temperature of 45°C, and doubles for at least 1 hour at 25°C.

Therefore, due to the above characteristics, the organosilicon composition of the present invention can form a cured product that has excellent adhesion to the adherend substrate (glass) and can still be cured at a high speed, and exhibits excellent dimensional stability by the following methods: It maintains a stable gel state even after curing, and has excellent weather resistance and excellent heat resistance, and will not fade or crack even when exposed to ultraviolet rays or high temperatures for a long time. In particular, since the silicone composition of the present invention has the most important transparency in the OCA or OCR of image display devices such as LCD or OLED, it is suitable for ensuring large-size displays requiring excellent reliability. The 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 1-10 and Comparative Examples 1-10 were evaluated as follows, and the results are shown in Table 6 and Table 7 below.

1) Storage stability: After preparation, the silicone composition is stored in a 45°C oven in a light-shielded state, and the time it takes for the viscosity to double the initial viscosity is reported as the 45°C storage time.

2) Curing time: Apply 16 mg (weighed) of the above silicone composition to the center of a glass sample with a size of 20 mm × 60 mm × 2 mm (thickness) and a weight of 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) for UV irradiation to a cumulative dose of ^{3,000 mJ/cm 2.} Immediately after UV irradiation, another glass sample was placed so that it was superimposed on another sample in a crosswise manner, in which the silicone composition was inserted at the center of the cross between the samples to have a diameter of 10 mm and a thickness of 0.2 mm . After the sample is kept at 25°C for a predetermined time, the upper sample is lifted, and the point in time when the lower sample is lifted instead of falling due to its own weight is reported as the curing time.

3) Adhesive bond strength: After keeping the above sample for curing time measurement at 25°C for 24 hours, use a tensile testing machine to pull the two glass samples apart in the vertical direction, and measure the separation of the sample Strength is reported as bonding strength.

4) Permeability: Inject 50 g of the above silicone composition into a 60-mL polypropylene container, use a UV irradiation device to irradiate UV ^{from above with a cumulative dose of 3000 mJ/cm 2} , and then keep it 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 a load of 47.5 g was applied to measure the degree of penetration.

[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, and the results are shown in Table 8 and Table 9 below.

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

2) Curing time: 16 mg (weighed) of the curable silicone composition added above was applied to the center of a glass sample with a size of 20 mm × 60 mm × 2 mm (thickness) and a weight of 5.2 g. Immediately, another glass sample was placed so that it was superimposed on another sample in a crosswise manner, in which the silicone composition was inserted at the center of the cross between the samples to have a diameter of 10 mm and a thickness of 0.2 mm, and the samples were joined together Together. After the sample is kept in an oven at 50°C for a predetermined time, the upper sample is lifted, and the point in time when 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 to measure the curing time, and then kept at 25°C for 30 minutes, then the two glass samples were placed in the vertical direction with each other using a tensile testing machine. Pull apart, and measure the strength of the separation of the sample and report it as the bonding strength.

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

[Table 7]

Compare the experimental example and the comparative example. In the case of Comparative Examples 1 to 3 and Comparative Examples 11 to 13 where the first organohydrogenpolysiloxane (c-1) and the second organohydrogenpolysiloxane (c-2) are not used, the curing speed is low As a result, the curing time is quite long, and because it is difficult to store for a long time, there are problems in storage stability.

Similarly, in the case of Comparative Examples 4 and 14, wherein the amount of the first organohydrogenpolysiloxane (c-1) and the second organohydrogenpolysiloxane (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, where the amount of the first organohydrogenpolysiloxane (c-1) and the second organohydrogenpolysiloxane (c-2) is greater than 5 parts by weight, showing extremely low bonding strength.

At the same time, in the case of Comparative Example 6 in which the amount of the photoactive platinum catalyst was greater than 200 ppm, it was difficult to store for a long time, and in the case of Comparative Example 16, in which the amount of the thermosetting platinum catalyst was greater than 30 ppm, it showed a short usability. Time (pot life) thus represents low processability.

In the case of the photocured product of Comparative Example 7, in which the amount of the first organopolysiloxane (a) is less than 5 parts by weight, it exhibits low adhesive strength and is difficult to store for a long time. In the case of a cured product, 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, which means that it is difficult to apply the gel-type composition to OCA as expected by the present invention. Or OCR.

Meanwhile, in the case of Comparative Examples 9 and 19, the highly reactive organohydrogenpolysiloxane (ie, the first organohydrogenpolysiloxane (c-1) or the second organohydrogenpolysiloxane (c-1) -2a or c-2b) the molar ratio of the hydrogen group contained in) and the hydrogen group contained in the linear organohydrogenpolysiloxane (that is, the third organohydrogenpolysiloxane (c-3)) The amount of is less than 0.4:1, the curing time is prolonged due to the low curing speed, and in the case of Comparative Examples 10 and 20 with a molar ratio greater than 50:1, it exhibits high hardness as shown by low penetration, and Exhibits low bonding 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 without departing from the spirit and scope of the present invention, as well as these changes and modifications. It is included in the scope of the attached patent application.

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Claims (4)

A silicone composition comprising an organopolysiloxane mixture and a platinum catalyst, wherein the organopolysiloxane mixture includes a first organopolysiloxane (a) and a second organopolysiloxane ( b) and an organohydrogenpolysiloxane (c), the first organopolysiloxane (a) contains a unit _{having at least one alkenyl group and at least one SiO 4/2 unit in its molecule, and the second organic polysiloxane (a)} Polysiloxane (b) contains at least two alkenyl groups in its molecule, wherein the organohydrogenpolysiloxane (c) contains a highly reactive organohydrogenpolysiloxane and a linear organohydrogenpolysiloxane Oxanes, wherein the highly reactive organohydrogenpolysiloxane comprises a first organohydrogenpolysiloxane (c-1) or a second organohydrogenpolysiloxane (c-2), and 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, and the second organohydrogen polysiloxane (c- 2) In its molecule, it 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 with an oxygen atom in between. The halogenated alkyl group on the silicon atom, and the linear organohydrogenpolysiloxane comprises a third organohydrogenpolysiloxane (c-3), and the third organohydrogenpolysiloxane (c -3) Containing a hydrogen group directly bonded to at least one silicon atom in its molecule, wherein the first organopolysiloxane (a) is represented by the following chemical formula 1, and the second organopolysiloxane (b) As represented by the following chemical formula 2, the first organohydrogenpolysiloxane (c-1) is represented by the following chemical formula 3, and the second organohydrogenpolysiloxane (c-2) is represented by the following chemical formula 4, and The third organohydrogenpolysiloxane (c-3) is represented by the following chemical formula 5, wherein the viscosity of the first organohydrogenpolysiloxane (c-1) at 25°C is 1 to 500mPa‧s, where The total amount of alkenyl groups contained in the first organopolysiloxane (a) and the second organopolysiloxane (b) and the hydrogen group contained in the organohydrogenpolysiloxane (c) The molar ratio of the total amount is 1:0.4~1:0.9, [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 that 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, wherein at least ^{one of R 1} and R ² One is an alkenyl group with 2 to 10 carbon atoms, R ^{3 is} each independently an alkyl group with 1 to 10 carbon atoms, "a" is a number from 0.05 to 0.25, and "b" is a number from 0.1 to 0.5 , And "c" is a number from 0.4 to 0.6, and satisfies 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 ^{wherein in the 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 have Alkenyl groups of 2 to 10 carbon atoms, 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 6 to An aryl group of 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 aryl group having 2 to 10 carbon atoms Alkenyl, "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; [Chemical formula 3](HR ⁹ ₂ SiO _1/2 ) _f (R ¹⁰ ₃ SiO _1/2 ) _g (SiO ₂ ) _h ^{wherein in the chemical formula 3, R 9} and R ¹⁰ , which are the same or different from each other, are each independently having 1~ For an alkyl group with 10 carbon atoms, "f" is a number from 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 wherein in Chemical formula 4, R ^{11 is} each independently an aryl group having 6 to 15 carbon atoms or having 1 to 10 carbon atoms In the halogenated alkyl group (halogenated alkyl group), R ^{12 is} each independently an alkyl group having 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 the 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, and "j" is from 0.001 to The number of 2, "k" is the number of 0.7~2, and the number of j+k is 0.8~3. The silicone composition described in item 1 of the scope of patent application, wherein the hydrogen groups of the highly reactive organohydrogenpolysiloxane (SiH) and the hydrogen groups of the linear organohydrogenpolysiloxane (SiH) The mol ratio is 0.4:1~50:1. The silicone composition according to the first item of the patent application, wherein the platinum catalyst comprises any one selected from the group consisting of a photoactive platinum catalyst and a thermal curing platinum catalyst. The silicone composition according to claim 1, wherein the organopolysiloxane mixture comprises: 5 parts by weight to 50 parts by weight of the first organopolysiloxane; 33 parts by weight to 92 parts by weight The second organopolysiloxane; 0.1 to 5 parts by weight of the highly reactive organohydrogenpolysiloxane; and 0.1 to 10 parts by weight of the linear organohydrogenpolysiloxane.