KR102037838B1 - Ultraviolet curable silicone composition - Google Patents

Abstract

The invention of claim 2, including that of the UV-curable silicone composition, an first organopolysiloxane, at least one alkenyl group in one molecule containing at least one alkenyl group and at least one SiO _4/2 units in one molecule An organopolysiloxane mixture comprising an organopolysiloxane and a third organopolysiloxane having a hydrogen group directly bonded to at least one silicon in one molecule, an ultraviolet curable silicone composition comprising a platinum catalyst and an ultraviolet fluorescence brightener.

Description

UV curable silicone composition {ULTRAVIOLET CURABLE SILICONE COMPOSITION}

The present invention relates to an ultraviolet curable silicone composition.

With the advent of the information age in recent years, liquid crystal displays (LCDs), organic light emitting displays (OLEDs), mobile communication terminals (mobile phones, PDA terminals, etc.) form a large market, and the applied product range is diversified.

Accordingly, there is a growing interest and demand for adhesive materials used between window glass and glass of touch screen panel (TSP) sensors. Conventionally used adhesives are optically adhesive (Optically Clear Adhesive (OCA) film), or as the optically adhesive resin (Optically Clear Resin, OCR) it is common to use a room temperature curable liquid silicone rubber composition.

However, since the OCA film is in the form of a solid transparent sheet, it is not easy to remove when foreign matter or bubbles are introduced during the lamination process, and a number of steps are required in the work process, resulting in a decrease in work efficiency. In addition, the adhesive using a room temperature curing type liquid silicone rubber composition requires a long curing time when used in a large area, there are many limitations in the application range.

As an alternative to this, development of a photocurable adhesive has been made, but such a technique generally uses a high curing temperature or a very high amount of ultraviolet irradiation light.

Therefore, the development of a new photocurable adhesive that can solve this situation is required.

The present invention provides an ultraviolet curable silicone composition excellent in curing rate and storage stability.

2 comprises in order to attain the object of the present invention is the first organopolysiloxane, an at least one alkenyl group in one molecule containing at least one alkenyl group and at least one SiO _4/2 units in one molecule An organopolysiloxane mixture comprising an organopolysiloxane and a third organopolysiloxane having a hydrogen group directly bonded to at least one silicon in one molecule, an ultraviolet curable silicone composition comprising a platinum catalyst and an ultraviolet fluorescence brightener.

Since the ultraviolet curable silicone composition of the present invention includes an ultraviolet fluorescent photosensitizer, the curing time is short at the time of ultraviolet irradiation, and the storage stability is excellent in a light shielding state, and thus it may be usefully used as a photocurable adhesive.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention provides an ultraviolet curable silicone composition.

The ultraviolet curable silicone composition of the present invention comprises an organopolysiloxane mixture, a platinum catalyst and an ultraviolet fluorescent photosensitizer.

The organopolysiloxane mixture comprises a first organopolysiloxane, a second organopolysiloxane, and a third organopolysiloxane.

The first organopolysiloxane as the primary component of the ultraviolet-curable silicone composition, may be represented by, for at least one alkenyl group and includes at least one or more of SiO _4/2 units, for example, formula (1) in one molecule.

[Formula 1]

(R ¹ ₃ SiO _1/2 ) _a (R ² ₃ SiO _1/2 ) _b (SiO _4/2 ) _c

In Formula 1, each R ¹ is independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, but at least one is an alkenyl group having 2 to 10 carbon atoms, and R ² is Each independently may be 1 to 10 alkyl groups.

For example, each R ¹ is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, but at least one is an alkenyl group having 2 to 6 carbon atoms, and R ² is each Independently 1 to 6 alkyl groups.

The alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and the like, and may be, for example, a methyl group, an ethyl group, or a propyl group. The alkenyl group may be a vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, or the like, and may be, for example, a vinyl group or a butenyl group.

In Formula 1, a may be 0.05 to 0.25, for example, 0.1 to 0.2. When a is less than 0.05, the reactivity of the first organopolysiloxane may be lowered. As the density increases, cracks may occur due to changes in the crosslinking density over time.

In Chemical Formula 1, b may be 0.1 to 0.5, for example, 0.25 to 0.45, and when b is less than 0.1, the viscosity of the ultraviolet curable silicone composition may be high, such that flowability may not be easy due to low flowability. When b exceeds 0.5, the density of the ultraviolet curable silicone composition may be lowered, and thus the adhesive force with the glass may be lowered. In Chemical Formula 1, c may be 0.4 to 0.6, for example, 0.45 to 0.55, and when c is less than 0.4, it is impossible to secure sufficient hardness of the cured product of the ultraviolet curable silicone composition, and when c exceeds 0.6, ultraviolet curable The viscosity of the silicone composition may be high and flowability may not be easy.

Meanwhile, the first organopolysiloxane represented by Chemical Formula 1 may be in a powder state or a glass state at 25 ° C., may have a number average molecular weight (Mn) of 1,000 to 100,000, and an alkenyl group content of 0.05 to 100,000. 0.6 mmol / g can be used.

As another example, the first organopolysiloxane may be an MQ resin in which the siloxane chemical structure includes M units (SiO _1/2 ) and Q units (SiO _4/2 ), and at the ends thereof, a vinyldimethylsiloxy group and a trimethyl siloxane. Or silicate resins at the end or divinylmethylsiloxy groups and trimethyl siloxy groups. For example, silicate resins having terminal vinyldimethylsiloxy and trimethyl siloxy groups include (ViMe ₂ SiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.35 (SiO _4/2 ) _0.5 , (ViMe ₂ SiO _{1 / 2) 0.10 (Me 3 SiO 1/2} ) 0 .40 (SiO 4/2) 0.5, (ViMe 2 SiO 1/2) 0.2 (Me 3 SiO 1/2) 0.3 (SiO 4/2) 0.5, (ViMe _{2 SiO 1/2) 0.15 (} Me 3 SiO 1/2) 0 .45 (SiO 4/2) 0.4, (ViMe 2 SiO 1/2) 0.10 (Me 3 SiO 1/2) 0.50 (SiO 4/2) _{0.4, (ViMe 2 SiO 1/} 2) 0.2 (Me 3 SiO 1/2) 0 .4 (SiO 4/2) 0.4, (ViMe 2 SiO 1/2) 0.15 (Me 3 SiO 1/2) 0.35 (SiO _{4/2) 0.6, (ViMe 2 SiO} 1/2) 0.10 (Me 3 SiO 1/2) 0 .30 (SiO 4/2) 0.6, (ViMe 2 SiO 1/2) 0.2 (Me 3 SiO 1/2 ) _0.2 (SiO _4/2 ) _0.6 and the like can be used. In addition, silicate resins having terminal divinylmethylsiloxy and trimethyl siloxy groups include (Vi ₂ MeSiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.35 (SiO _4/2 ) _0.5 , (Vi ₂ MeSiO _{1 / 2) 0.10 (Me 3 SiO 1/2} ) 0 .40 (SiO 4/2) 0.5, (Vi 2 MeSiO 1/2) 0.2 (Me 3 SiO 1/2) 0.3 (SiO 4/2) 0.5, (Vi _{2 MeSiO 1/2) 0.15 (} Me 3 SiO 1/2) 0 .45 (SiO 4/2) 0.4, (Vi 2 MeSiO 1/2) 0.10 (Me 3 SiO 1/2) 0.50 (SiO 4/2) _{0.4, (Vi 2 MeSiO 1/} 2) 0.2 (Me 3 SiO 1/2) 0 .4 (SiO 4/2) 0.4, (Vi 2 MeSiO 1/2) 0.15 (Me 3 SiO 1/2) 0.35 (SiO _{4/2) 0.6, (Vi 2 MeSiO} 1/2) 0.10 (Me 3 SiO 1/2) 0 .30 (SiO 4/2) 0.6, (Vi 2 MeSiO 1/2) 0.2 (Me 3 SiO 1/2 ) _0.2 (SiO _4/2 ) _0.6 and the like can be used.

The second organopolysiloxane is a component that provides flowability by adjusting the viscosity of the ultraviolet curable silicone composition, and modulates the modulus of the cured product of the ultraviolet curable silicone composition, and includes at least one alkenyl group in one molecule. It may be represented by two.

[Formula 2]

(R ³ ₃ SiO _1/2 ) ₂ (R ³ R ⁴ SiO) _d (R ⁴ ₂ SiO) _e

In Formula 2, R ³ is independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, but at least one is an alkenyl group having 2 to 10 carbon atoms, and R ⁴ is each It may be an alkyl group having 1 to 10 carbon atoms independently or an aryl group having 6 to 15 carbon atoms.

For example, each of R ³ is independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, at least one of which is 2 to 6 carbon atoms, and R ⁴ is each independently 1 It may be an alkyl group having from 6 to 6 carbon atoms or an aryl group having from 6 to 15 carbon atoms.

The alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and the like, and may be, for example, a methyl group, an ethyl group, or a propyl group. The alkenyl group may be a vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, or the like, and may be, for example, a vinyl group or a butenyl group. The allyl group may be a phenyl group, tolyl group, xylyl group, naphthyl group, biphenylene group, or the like, and may be, for example, a phenyl group.

In Formula 2, d and e are each independently 0 or an integer of 1 or more, d + e is an integer of 10 to 10,000, for example an integer of 50 to 2,000, d / (d + e) is 0 to 0.1, for example, 0 to 0.05. When d + e is less than an integer of 10, the ultraviolet curable silicone composition may be voided by volatile components during curing, and workability may be lowered. When the d + e is more than 10,000, the flowability of the ultraviolet curable silicone composition may be lowered, resulting in lower workability. have.

On the other hand, when d and e are integers greater than or equal to 1, if d / (d + e) exceeds 0.1, the second organopolysiloxane may have a low reactivity and may have a high density of UV-curable silicone composition, resulting in cracking due to changes in hardness over time. Can be.

As another example, the second organopolysiloxane may be a vinyldimethyl siloxy group terminal dimethyl siloxane polymer, vinyldimethyl siloxy group terminal methylvinyl siloxane-dimethyl siloxane block polymer, trimethyl siloxy group terminal methylvinyl siloxane-dimethyl siloxane block polymer, vinyldimethyl siloxane A timing terminal methylphenyl siloxane- dimethylsiloxane block polymer or a vinyl dimethyl siloxy group terminal diphenyl siloxane- dimethyl siloxane block polymer, etc. are mentioned.

The vinyldimethyl siloxy group terminal dimethyl siloxane polymer may be (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) _e (ViMe ₂ SiO _1/2 ), for example (ViMe ₂ SiO _1/2 ) (Me _{2 SiO) 60 (ViMe 2 SiO 1/2} ), (ViMe 2 SiO 1/2) (Me 2 SiO) 120 (ViMe 2 SiO 1/2), (ViMe 2 SiO 1/2) (Me 2 SiO) 150 ( _{ViMe 2 SiO 1/2), (ViMe} 2 SiO 1/2) (Me 2 SiO) 225 (ViMe 2 SiO 1/2), (ViMe 2 SiO 1/2) (Me 2 SiO) 500 (ViMe 2 SiO 1 _{/ 2), (ViMe 2 SiO} 1/2) (Me 2 SiO) 1000 (ViMe 2 SiO 1/2), (ViMe 2 SiO 1/2) (Me 2 SiO) 1250 (ViMe 2 SiO 1/2) etc. Can be.

The vinyldimethyl siloxy group terminal methyl vinyl siloxane-dimethyl siloxane block polymer may be (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) _e (ViMeSiO) _d (ViMe ₂ SiO _1/2 ), for example (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₅₉ (ViMeSiO) ₁ (ViMe ₂ SiO _1/2 ), (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₉₅ (ViMeSiO) ₂₀ (ViMe ₂ SiO _1/2 ), (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₄₀₀ (ViMeSiO) ₃₀ (ViMe ₂ SiO _1/2 ), (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₁₀₀₀ (ViMeSiO) ₅₀ (ViMe ₂ SiO _1/2 ) and the like.

The trimethyl siloxy group terminal methylvinyl siloxane-dimethyl siloxane block polymer may be (Me ₃ SiO _1/2 ) (Me ₂ SiO) _e (ViMeSiO) _d (Me ₃ SiO _1/2 ), for example (Me ₃ SiO _1/2 ) (Me ₂ SiO) ₄₀₀ (ViMeSiO) ₃₀ (Me ₃ SiO _1/2 ), (Me ₃ SiO _1/2 ) (Me ₂ SiO) ₅₄₀ (ViMeSiO) ₅ (Me ₃ SiO _1/2 ) , (Me ₃ SiO _1/2 ) (Me ₂ SiO) ₁₀₀₀ (ViMeSiO) ₅₀ (Me ₃ SiO _1/2 ), (Me ₃ SiO _1/2 ) (Me ₂ SiO) ₆₀ (ViMeSiO) ₇ (Me ₃ SiO _1/2 ) and so on.

The vinyldimethyl siloxy group terminal methylphenyl siloxane-dimethyl siloxane block polymer may be (ViMe ₂ SiO _1/2) (Me ₂ SiO) _e (Me, PhSiO) _d (ViMe2SiO _1/2 ), for example (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₂₀ (Me, PhSiO) ₂ (ViMe ₂ SiO _1/2 ), (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₁₂₅ (Me, PhSiO) ₁₀ (ViMe ₂ SiO _1/2 ) and the like.

The vinyldimethyl siloxy group terminal diphenyl siloxane-dimethyl siloxane block polymer may be (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) _e (Ph ₂ SiO) _d (ViMe ₂ SiO _1/2 ), for example (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₄₀ (Ph ₂ SiO) ₂ (ViMe ₂ SiO _1/2 ), (ViMe ₂ SiO _1/2 ) (Me ₂ SiO) ₂₂₅ (Ph ₂ SiO) ₁₀ ( ViMe ₂ SiO _1/2 ) and the like.

s일 수 있으며, 경화 전의 높은 유동성과 경화 후의 기계적 특성을 부여하기 위하여 1 내지 250 Pa

s를 사용할 수 있다.The viscosity of the second organopolysiloxane is not particularly limited, but is 0.1 to 500 Pa at 25 ° C.

can be s, 1 to 250 Pa to impart high fluidity before curing and mechanical properties after curing

You can use s.

The third organopolysiloxane is a component that forms a cured product by acting as a bridge between the first organopolysiloxane and the second organopolysiloxane, and includes a hydrogen group directly bonded to at least one silicon in one molecule. 3 may be represented.

[Formula 3]

H _f R ⁵ _g SiO _{(4-fg) / 2}

In Formula 3, R ⁵ may be each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.

The alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and the like, and may be, for example, a methyl group, an ethyl group, or a propyl group. The allyl group may be a phenyl group, tolyl group, xylyl group, naphthyl group, biphenylene group, or the like, and may be, for example, a phenyl group.

In Formula 3, when the number of silicon atoms (Si) contained in the third organopolysiloxane is 1 in an empirical formula, f represents a ratio of hydrogen atoms, and g represents a ratio of R ⁵ .

F is a number from 0.001 to 2, for example, from 0.01 to 1, g is from 0.7 to 2, for example from 1.2 to 2, f + g is from 0.8 to 3, For example, a number from 1.8 to 2.4. When f is less than 0.001, the crosslinking density of the third organopolysiloxane is lowered, so that the hardness and reactivity are lowered. When the f is higher than 2, the crosslinking density of the third organopolysiloxane is increased, and the hardened product easily cracks. May be generated to form voids, which may lower reliability. If the g is less than 0.7, the crosslinking density of the third organopolysiloxane is increased, so that the cured product is easily cracked, hydrogen gas is generated during curing, voids are formed, and reliability is lowered. As crosslinking density is lowered, hardness and reactivity are lowered, and as curing time is increased, voids are formed during curing by volatile components, thereby lowering reliability.

On the other hand, if f + g is less than 0.8, the viscosity of the ultraviolet curable silicone composition is high, the flowability is poor, and workability is lowered. If it is more than 3, the hardness or reactivity of the third organopolysiloxane is decreased, and the curing time is increased. Low molecular weight volatiles may cause voids to form during curing, thereby lowering reliability.

For example, the third organopolysiloxane represented by Chemical Formula 3 is (HMe ₂ SiO _1/2 ) (Me ₂ SiO) _n (HMe ₂ SiO _1/2 ) hydrogen dimethyl siloxy group-terminated dimethyl siloxane polymer, Trimethyl siloxy group terminal methylhydrogen siloxane polymer which is (Me ₃ SiO _1/2 ) (HMeSiO) _n (Me ₃ SiO _1/2 ), (Me ₃ SiO _1/2 ) (Me ₂ SiO) _n (HMeSiO) _m ( Trimethyl siloxy group terminal methylhydrogen siloxane-dimethyl siloxane block polymer, Me ₃ SiO _1/2 ), (HMe ₂ SiO _1/2 ) (Me ₂ SiO) _n (HM ₃ SiO) _m (HMe ₂ SiO _1/2 ) Phosphorus Hydrogendimethyl siloxy group terminal dimethyl siloxane-hydrogenmethyl siloxane block polymer, (HMe ₂ SiO _1/2 ) _n (Me ₃ SiO _1/2 ) _m (SiO ₂ ) ₁ phosphorus dimethylsiloxy group-trimethyl siloxy group Terminal silicate resins (n, m or l is an integer of 1 or more).

The dimethyl hydrogen siloxy terminated dimethyl siloxane polymer is, for example, _{(HMe 2 SiO 1/2) (Me} 2 SiO) 25 (HMe 2 SiO 1/2), (HMe 2 SiO 1/2) (Me 2 SiO ) ₄₅ (HMe ₂ SiO _1/2 ), (HMe ₂ SiO _1/2 ) (Me ₂ SiO) ₁₂₅ (HMe ₂ SiO _1/2 ), and the like.

The trimethyl siloxy group terminal methylhydrogen siloxane polymer is, for example, (Me ₃ SiO _1/2 ) (HMeSiO) ₂₀ (Me ₃ SiO _1/2 ), (Me ₃ SiO _1/2 ) (HMeSiO) ₄₀ (Me ₃ SiO _1/2 ) and the like.

It said trimethyl siloxy terminated methyl hydrogen siloxane-dimethyl siloxane block polymer is, for example, _{(Me 3 SiO 1/2)} (Me 2 SiO) 20 (HMeSiO) 20 (Me 3 SiO 1/2), (Me 3 SiO _{1/2) (Me 2 SiO) 25} (HMeSiO) 12 (Me 3 SiO 1/2), (Me 3 SiO 1/2) (Me 2 SiO) 46 (HMeSiO) 20 (Me 3 SiO 1/2), _{(Me 3 SiO 1/2) (Me} 2 SiO) 100 (HMeSiO) 10 (Me 3 SiO 1/2), (Me 3 SiO 1/2) (Me 2 SiO) 7 (HMeSiO) 3 (Me 3 SiO 1 _{/ 2} ) and the like.

The hydrogen-dimethyl-siloxy terminated dimethylsiloxane-hydrogen siloxane block polymer is, for example, _{(HMe 2 SiO 1/2)} (Me 2 SiO) 8 (HM 3 SiO) 2 (HMe 2 SiO 1/2) days Can be.

The dimethyl hydrogen siloxy-terminated trimethyl siloxy silicate resins are, for example, _{(HMe 2 SiO 1/2)} 0.6 (Me 3 SiO 1/2) 0 .1 (SiO 2) 0.2, (HMe 2 SiO 1 / ₂ ) _0.5 (Me ₃ SiO _1/2 ) _0.2 (SiO ₂ ) _0.3 , and the like.

s일 수 있으며, 경화 전의 높은 유동성과 경화 후의 기계적 특성을 부여하기 위하여 0.02 내지 2 Pa

s를 사용할 수 있다.The viscosity of the third organopolysiloxane is not particularly limited, but is 0.01 to 3 Pa at 25 ° C.

may be s, from 0.02 to 2 Pa to impart high fluidity before curing and mechanical properties after curing

You can use s.

The first organopolysiloxane included in the ultraviolet curable silicone composition of the present invention may be included in an amount of 4 to 44% by weight, for example, 5 to 42% by weight based on 100% by weight of the organopolysiloxane mixture.

When the content of the first organopolysiloxane is less than 4% by weight, hardness, mechanical strength and adhesion with glass are low, so that the reliability is lowered. When the content of the first organopolysiloxane is higher than 44% by weight, the workability is decreased by the fluidity decrease of the ultraviolet curable silicone composition. In addition, the crosslinking density may increase and cracks may occur due to external impact.

The second organopolysiloxane included in the ultraviolet curable silicone composition of the present invention may be included in an amount of 24 to 80 wt%, for example, 25 to 78 wt% based on 100 wt% of the organopolysiloxane mixture.

If the content of the second organopolysiloxane is less than 24% by weight, the crosslinking density of the ultraviolet curable silicone composition may be increased, so that cracks may easily occur due to thermal shock, and when the content of the second organopolysiloxane exceeds 80% by weight, adhesion to glass may be reduced.

The third organopolysiloxane included in the ultraviolet curable silicone composition of the present invention has a mole number of hydrogen of 0.3 to 1, for example, 0.4 to 0.9, relative to the number of moles of alkenyl groups of the first organopolysiloxane and the second organopolysiloxane. It may be included in the amount to be.

If the number of moles of hydrogen of the third organopolysiloxane compared to the number of moles of alkenyl groups of the first organopolysiloxane and the second organopolysiloxane is less than 0.3, it is difficult to form a cured product having a sufficient crosslinking density, thereby making it hard or mechanical. When the strength is lowered, the adhesion to glass decreases, and when it exceeds 1, the crosslinking density of the third organopolysiloxane becomes high, and the hardened product easily cracks, hydrogen gas is generated during hardening, voids are formed, and reliability decreases. Can be.

The ultraviolet curable silicone composition of the present invention may further include a platinum catalyst and an ultraviolet fluorescent photosensitizer.

The platinum catalyst is activated when exposed to ultraviolet rays of 200 to 500 nm, and promotes the addition reaction of alkenyl groups of the first organopolysiloxane and the second organopolysiloxane with hydrogen groups directly connected to the silicon of the third organopolysiloxane. It can be, platinum complex.

For example, the platinum complex may be a β-diketone platinum complex or a platinum complex having a cyclic diene compound as a ligand.

The β-diketone platinum complex is trimethyl (acetylacetonate) platinum complex, trimethyl (2,4-pentanedionate) platinum complex, trimethyl (3,5-heptanedionate) platinum complex, trimethyl (methylacetoacetate) platinum Complex, bis (2,4-pentanedionate) platinum complex, bis (2,4-hexanezionate) platinum complex, bis (2,4-heptanedionate) platinum complex, bis (3,5-heptanedionate ) Platinum complex, bis (1-phenyl-1,3-butanedionate) platinum complex, etc. are mentioned.

Platinum complexes having the above cyclic diene compound as ligands include bis (1,3-diphenyl-1,3-propane dionate) platinum complexes, (1,5-cyclooctadienyl) dimethyl platinum complexes, (1,5 -Cyclooctadienyl) diphenyl platinum complex, (1,5-cyclooctadienyl) dipropyl platinum complex, (2,5-norboraziene) dimethyl platinum complex, (2,5-norboraziene) diphenyl Platinum complex, (cyclopentadienyl) dimethyl platinum complex, (methylcyclopentadienyl) diethyl platinum complex, (trimethyl silyl cyclopentadienyl) diphenyl platinum complex, (methyl cycloocta-1,5-dienyl) Diethyl platinum complex, (cyclopentadienyl) trimethyl platinum complex, (cyclopentadienyl) ethyl dimethyl platinum complex, (cyclopentadienyl) acetyl dimethyl platinum complex, (methylcyclopentadienyl) trimethyl platinum complex, (methyl Cyclopentadienyl) trihexyl platinum complex, (trimethyl silyl Cyclopentadienyl) trimethyl platinum complex, (dimethylphenylsilyl cyclopentadienyl) triphenyl platinum complex, (cyclopentadienyl) dimethyltrimethylsilylmethyl platinum complex, and the like.

The platinum catalyst may be included in an amount of 0.01 to 200 ppm, for example, 1 to 150 ppm of platinum atoms in the organopolysiloxane mixture.

When the content of the platinum atom is less than 0.01 ppm, the curing of the ultraviolet curable silicone composition is not significantly slowed or cured, and when it exceeds 200 ppm, an additive such as a curing retardant should be added to store the liquid component for a long time. This not only increases the cost but may also result in yellowing, in which the cured product is colored yellow.

In addition, the ultraviolet fluorescent photosensitizer promotes the activity of the platinum catalyst through the role of increasing the amount of light in the effective wavelength band by absorbing short wavelength region in the wavelength distribution of ultraviolet rays to a wavelength effective for the optical activity affecting the platinum catalyst. Ingredient.

Thus, by including the ultraviolet fluorescent photosensitizer in the ultraviolet curable silicone composition of the present invention, not only can improve the curing speed, but also excellent storage stability, and no additional additives such as a curing retardant during long-term storage are not required. great.

The ultraviolet fluorescent photosensitizer is a thiophene derivative, a triazine derivative, an acenaphthene derivative, an imidazole derivative, an imidazolone derivative, a triazole derivative, a thiazole derivative, an oxazole derivative, an oxadiazole derivative, a coumarin derivative, a carbostyryl derivative , Thiadiazole derivatives, naphthalimide derivatives, pyrazolone derivatives, aromatic ketone compounds, polycyclic aromatic compounds, and the like, preferably thiophene derivatives, triazine derivatives, acenaphthene derivatives, aromatic ketone compounds, Cyclic aromatic compounds can be used.

For example, the ultraviolet fluorescent photosensitizer is a thiophene derivative, which is 2,5-bis (5-talt-butyl-benzooxazol-2-yl) thiophene, 4,4-bis (4-anilino-6- Morpholino 1,3,5-triazin-2-yl) aminostilben-2,2'-disulfonate sodium may be used, and 2,2 '-[vinylene bis (3-sulfo NATO) as the triazine derivative 4,1-phenylene) imino [6- (diethylamino) -1,3,5-triazine 4,2-diyl] imino] bis (benzene-1,4-disulfonic acid) 6 sodium salt Can be used.

4-methoxy naphthalic acid-N-methyl imide may be used as the acenaphthene derivative, benzimidazoline as the imidazole derivative, and 2- (2'-hydroxy-5'-methylphenyl as the triazole derivative. Benzotriazole can be used. 2-mercapto benzothiazole as the thiazole derivative, 2-phenyl-4- (ethoxymethylene) oxazol-5 (4H) -one as the oxazole derivative, 2-trichloro as the oxadiazole derivative Methyl-5-steel-1,3,4-oxadiazole can be used. 7-diethyl amino coumarin may be used as the coumarin derivative, 5- (2,3-dihydroxy) propoxy carbostyryl as the carbostyryl derivative, and 4,5-di as the thiadiazole derivative. Phenyl-1,2,3-thiadiazole, 4-methoxy-N-methylnaphthalimide may be used as the naphthalimide derivative, and 3-methyl-1-phenyl- is used as the parazolone derivative. 5-piazolone may be used, and examples of the aromatic ketone compound or the polycyclic aromatic compound include thioxanthone, 2-chlorothioxanthone, 2-isopropyl thioxanthone, thioxanthone, anthraquinone, benzophenone, and 1- Chloroanthraquinone, bianthrone, 2,4-diethyl-9H-thioxanthine-9-one, anthracene, 9-vinylanthracene, 9,10-dibromoanthracene, 9,10-dichloroanthracene, 9,10 -Dimethyl anthracene, 9,10-diethyl anthracene, 9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethylan Larsen, may include naphthacene, pentacene, benz [a] anthracene, and 7,12- dimethyl-Benz [a] anthracene, azulene.

The ultraviolet fluorescent photosensitizer included in the ultraviolet curable silicone composition of the present invention may include 0.01 to 1 parts by weight, based on 100 parts by weight of the organopolysiloxane mixture, and preferably may be included in an amount of 0.02 to 0.3 parts by weight.

If the content of the ultraviolet fluorescent photosensitizer is less than 0.01 part by weight, there is no sufficient light-sensing effect, and if it exceeds 1 part by weight, the curability of the ultraviolet curable silicone composition may be reduced, or the adhesiveness with the adherend of the cured product may be reduced.

Additionally, the UV curable silicone composition is selected from the group consisting of conventional adhesion promoters, inorganic fillers, silicone rubber powders, resin powders, heat resistant agents, antioxidants, radical scavengers, light stabilizers, flame retardant additives, silicone diluents and retarders. At least one additive may be further included.

Another aspect of the present invention provides a photocurable adhesive comprising the ultraviolet curable silicone composition.

The photocurable adhesive may be an optically clear adhesive (OCA) film or an optically clear resin (OCR), and may be used as a photocurable adhesive used between a window glass and a touch screen panel (TSP). .

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are intended to specifically illustrate the present invention, the content of the present invention is not limited by the following examples.

[ Example  And Comparative example ]

The UV curable silicone composition was prepared using a mechanical mixer, a hand mixer, and a rotary mixer with co-rotation, which are generally well-known by the composition shown in Table 1 below.

division
(unit) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 (A) 19.5 19.5 19.5 19.5 19.5 4.5 42 19.5 19.5 (B-1) 59 59 59 59 59 77.5 27.3 59 59 (B-2) 1.5 1.5 1.5 1.5 1.5 2 0.7 1.5 1.5 (C-1) 10 10 10 10 10 8 15 10 10 (C-2) 10 10 10 10 10 8 15 10 10 A + B + C = Total
(weight%) 100 100 100 100 100 100 100 100 100 (D)
(ppm) 10 10 10 0.2 200 10 10 10 10 (E-1)
(g) 0.05 0.1 0.02 0.1 0.05 0.05 0.05 - 0.09 (E-2)
(g) - - - - - - - 0.1 -

division
(unit) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 (A) 19.5 19.5 19.5 19.5 19.5 19.5 3.5 46 (B-1) 59 59 59 59 59 59 82 22.4 (B-2) 1.5 1.5 1.5 1.5 1.5 1.5 2 0.6 (C-1) 10 10 10 10 10 10 6.3 15.5 (C-2) 10 10 10 10 10 10 6.2 15.5 A + B + C = Total
(weight%) 100 100 100 100 100 100 100 100 (D)
(ppm) 30 50 5 10 10 250 10 10 (E-1)
(g) - - - 1.2 0.005 0.05 0.05 0.05 (E-2)
(g) - - - - - - - -

- (A) a first organopolysiloxane: a the content of the vinyl group 1.5mmol / g, intramolecular SiO _4/2 units is 50 wt%, and the powder (solid powder) is a vinyl terminated dimethyl siloxane group in the state of 25 ℃ And silicate resins sealed with trimethylsiloxy groups (Cas No. 68083-19-2)

s인 양말단이 디메틸 비닐 실록시기로 봉쇄된 폴리 디메틸 실록산(B-1) Second organopolysiloxane-1: vinyl group content is 0.12 mmol / g, viscosity at 25 ° C. is 1 Pa

polydimethyl siloxane whose sock end being s sealed with dimethyl vinyl siloxy group

s인 양말단이 디메틸 비닐 실록시기로 봉쇄된 폴리 디메틸 실록산(B-2) Second organopolysiloxane-2: vinyl group content is 0.027 mmol / g, viscosity at 25 ° C. is 70 Pa

polydimethyl siloxane whose sock end being s sealed with dimethyl vinyl siloxy group

s인 양말단이 하이드로겐 디메틸 실록시기로 봉쇄된 폴리 디메틸 실록산(C-1) Third organopolysiloxane-1: hydrogen content is 0.9 mmol / g, and viscosity at 25 ° C. is 0.2 Pa

polydimethyl siloxane in which the sock end of s is sealed with hydrogen dimethyl siloxy group

s인 양말단이 하이드로겐 디메틸 실록시기로 봉쇄된 폴리 디메틸 실록산(C-2) Third organopolysiloxane-2: hydrogen content is 0.11 mmol / g, viscosity at 25 ° C. is 1 Pa

polydimethyl siloxane in which the sock end of s is sealed with hydrogen dimethyl siloxy group

(D) Platinum catalyst: trimethyl (methylcyclopentadienyl) platinum (Yumicore Corporation HS-161)

(E-1) ultraviolet fluorescent photosensitizer: 2,5-bis (5-tert-butyl-benzooxazol-2-yl) thiophene (Fluorescent Brightener S-FN)

-(E-2) ultraviolet fluorescent photosensitizer: 9,10-dibutoxyanthracene (Kawasaki Chemical Co., Ltd., ANTHRACURE, UVS-1331)

[ Experimental Example ]

UV irradiation apparatus (DYMAX ECE 5000 modular, Metal Halide lamp, 225mW / cm ² at 365nm, 24sec) to form a cured product by irradiation 3000mJ / cm ² , and confirmed the curing time and storage stability, the results are shown in Table 3 and Table 4.

Penetration after curing: The penetration after curing for 1 hour in a 100 ° C. oven after crude liquid curing was measured according to ASTM D-1403.

-Curing time: After the hardening of the crude liquid, the cured product which was cured in the oven for 1 hour at 100 ° C was measured according to ASTM D-1403 as 100, and after the hardening of the crude liquid, the penetration was measured by time at room temperature. The time taken for the measurement was measured and expressed as the curing time.

-Storage stability: The time taken for the viscosity to double to the initial viscosity for each day during storage in a 45 ℃ oven in the shade state after the crude liquid was expressed as 45 ℃ storage time.

Viscosity: measured at 25 ° C. using a rotary viscometer.

-Appearance after hardening: The hardened | cured material which hardened further 1 hour in 100 degreeC oven after hardening of crude liquid was judged visually.

Classification (unit) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Curing time (hr) 7 5 10 5 3 3 15 6 11 45 ℃ storage time (day) 18 18 18 18 13 10 20 10 18

s]Viscosity before curing
[Pa

s] 0.95 0.95 0.95 0.95 0.95 1.05 12.5 0.95 0.95 Appearance after curing transparent transparent transparent transparent transparent transparent transparent transparent transparent Penetration after hardening
(needle 50g, 1 / 10mm) 81 80 80 82 82 90 65 81 82

Classification (unit) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Curing time (hr) 9 One 34 or more 24 25 2 3 18 45 ℃ storage time (day) 5 One 35 30 25 5 10 25

s]Viscosity before curing
[Pa

s] 0.95 0.95 0.95 0.95 0.95 0.95 1.10 36.5 Appearance after curing transparent transparent transparent transparent transparent Yellow and transparent transparent transparent Penetration after hardening
(needle 50g, 1 / 10mm) 80 80 82 81 81 83 105 5

Referring to Tables 1 to 4, by using a predetermined ultraviolet fluorescent photosensitizer based on 100 parts by weight of the organopolysiloxane mixture as in the present invention, even when a small amount of platinum catalyst is used, the curing speed is fast and the storage safety is improved. can confirm.

s로 흐름성, 작업성 및 성형성이 저하될 뿐만 아니라, 경화 후 침입도가 5로 경화물의 유연성이 저하되어 크랙 발생이 된다.On the other hand, in the case of Comparative Examples 1 to 3 that do not use the ultraviolet fluorescent dye, it can be confirmed that the curing rate and / or storage stability is reduced, in the case of Comparative Example 4 and Comparative Example 5 It can be seen that the content is used outside of the predetermined content to lower the curing rate and / or storage stability. In addition, in the case of Comparative Example 6 using an excess platinum catalyst, it can be confirmed that a yellowing phenomenon occurs in which the cured product is colored yellow. In addition, Comparative Example 7 in which the content of (A) corresponding to the first organopolysiloxane of the present invention is less than that of (B) corresponding to the second polysiloxane, has a mechanical strength lowering to 105 after curing. In the case of Comparative Example 8, in which the content of (A) was excessive compared to the content of (B), the viscosity before curing was 36.5 Pa

Not only the flowability, workability and moldability are deteriorated at s, but also the penetration after curing is reduced to 5, and the flexibility of the cured product is deteriorated, resulting in cracking.

Claims (6)

A first organopolysiloxane comprising at least one alkenyl group and at least one SiO _4/2 unit in one molecule, a second organopolysiloxane comprising at least one alkenyl group in one molecule and at least one silicon in one molecule Organopolysiloxane mixture comprising a third organopolysiloxane having a hydrogen group directly attached to it,
Platinum catalyst and
Contains an ultraviolet fluorescent photosensitizer,
The number of moles of hydrogen of the third organopolysiloxane relative to the number of moles of alkenyl groups of the first organopolysiloxane and the second organopolysiloxane is 0.3 to 0.9. The method according to claim 1,
The first organopolysiloxane is represented by the following formula (1), the second organopolysiloxane is represented by the formula (2), and the third organopolysiloxane is represented by the formula (3).
[Formula 1]
(R ¹ ₃ SiO _1/2 ) _a (R ² ₃ SiO _1/2 ) _b (SiO _4/2 ) _c
In Formula 1, R ¹ is each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, but at least one is an alkenyl group having 2 to 10 carbon atoms, and R ² is each Independently 1 to 10 alkyl groups, a is a number from 0.05 to 0.25, b is a number from 0.1 to 0.5, c is a number from 0.4 to 0.6.
[Formula 2]
(R ³ ₃ SiO _1/2 ) ₂ (R ³ R ⁴ SiO) _d (R ⁴ ₂ SiO) _e
In Formula 2, R ³ is each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, but at least one alkenyl group having 2 to 6 carbon atoms, R ⁴ are each independently An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, d and e are each independently 0 or an integer of 1 or more, d + e is an integer of 10 to 10,000, d / (d + e) is 0 to 0.1.
[Formula 3]
H _f R ⁵ _g SiO _{(4-fg) / 2}
In Formula 3, R ⁵ is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, f is a number of 0.001 to 2, g is a number of 0.7 to 2, f + g is a number from 0.8 to 3. The method according to claim 1,
The ultraviolet fluorescent photosensitizer is a thiophene derivative, a triazine derivative, an acenaphthene derivative, an imidazole derivative, an imidazolone derivative, a triazole derivative, a thiazole derivative, an oxazole derivative, an oxadiazole derivative, a coumarin derivative, a carbostyryl derivative , Thiadiazole derivatives, naphthalimide derivatives, pyrazolone derivatives. An ultraviolet curable silicone composition comprising at least one selected from the group consisting of an aromatic ketone compound and a polycyclic aromatic compound. The method according to claim 3,
The ultraviolet fluorescent photosensitizer is 2,5-bis (5-tert-butyl-benzooxazol-2-yl) thiophene, 4,4-bis- (4-anilino-6-morpholino 1, 3 , 5-triazin-2-yl) aminostilben-2,2'-disulfonic acid sodium, 2,2 '-[vinylene bis (3-sulfo NATO 4,1-phenylene) imino [6- (di Group consisting of ethyl amino) -1,3,5-triazine 4,2-diyl] imino] bis (benzene-1,4-disulfonic acid) 6 sodium salt and 4-methoxy naphthalic acid-N-methyl imide UV curable silicone composition comprising at least one selected from. The method according to claim 1,
The ultraviolet fluorescent photosensitizer is an ultraviolet curable silicone composition is contained in an amount of 0.01 to 1 parts by weight based on 100 parts by weight of the organopolysiloxane mixture. The method according to claim 1,
The organopolysiloxane mixture comprises 4 to 44% by weight of the first organopolysiloxane, 24 to 80% by weight of the second organopolysiloxane and the balance of the third organopolysiloxane, based on 100% by weight of the organopolysiloxane mixture. UV curable silicone composition.