KR20090120468A - Composite article having excellent fire resistance - Google Patents

Abstract

A composite article includes a first pane comprising a first window layer formed from a vitreous material and a reinforced silicone layer disposed adjacent to and in contact with the first window layer. The reinforced silicone layer includes a cured silicone composition and a fiber reinforcement. The composite article includes a second pane spaced from the first pane to define a gap therebetween and a frame disposed adjacent to and in contact with the first pane and the second pane to enclose the gap. The composite article may be suitable for load-bearing applications requiring thermal and acoustic insulation.

Description

Composite article having excellent fire resistance {COMPOSITE ARTICLE HAVING EXCELLENT FIRE RESISTANCE}

This patent application claims the priority and all interests of US Provisional Patent Application Nos. 60 / 891,165 and 60 / 955,245, filed February 22, 2007 and August 10, 2007, respectively.

FIELD OF THE INVENTION The present invention generally relates to composite articles having excellent thermal insulation, sound insulation and fire resistance. More specifically, the present invention relates to a composite article wherein at least one of the panes has a novel tempered silicon layer and a plurality of panes having a defined gap between the panes.

Insulated glass panes are known for use in residential and commercial construction to provide insulation and sound insulation. The insulating glass pane often comprises a number of panes, and is often framed to enclose the gap between the panes. The gap contains a gas such as air, argon, helium or nitrogen gas to provide insulation and sound insulation. The gap is alternatively vacuumed to create a vacuum to enhance insulation and sound insulation. However, such insulating glass windows are typically not fire resistant and often fail to maintain sufficient structural integrity after failure of the insulating glass window due to the applied heat, ie the formation of gaps in the pane during combustion. The ability to not maintain sufficient structural integrity can lead to the collapse of the panes after the formation of gaps, which is undesirable.

Refractory glass windows are known for use in residential, commercial and industrial construction as well as in consumer equipment and the automotive industry to prevent the spread of fire, smoke or heat waves through buildings or to include heat or fire in spaces such as in ovens. It is. The fire resistant windows are typically graded as 30, 60, 90, or 120 minutes fire resistant windows, which are at a temperature of 843 ° C. after 30 minutes of starting, 926 ° C. after 60 minutes, 1010 ° C. after 120 minutes, and 1093 ° C. after 240 minutes. When a refractory glass window is exposed to a given combustion condition to be exposed it depends on how long it takes for a gap to form in the refractory glass window. For example, in a 30 minute grade fire resistant glass window, a gap is formed when the window is exposed to the predetermined combustion conditions for a period of at least 30 minutes but less than 60 minutes. The particular fire resistance grade required for the fire resistant glass pane depends on the use and cost considerations, because fire resistant glass panes with longer fire resistance grades are typically more expensive than fire resistant glass panes having shorter fire resistance grades.

Much effort has been put into developing fire-resistant glass windows with sufficient fire resistance ratings. The refractory glass pane is typically formed from a series of layers including conventional glass layers and a layer that provides fire resistance to the refractory glass pane. Although many different materials have been used to form layers that provide fire resistance, many of the materials used to form layers that provide fire resistance have disadvantages. For example, when a carbon-based material, in particular a carbon-based material having at least 50 parts by weight of carbon based on the total weight of all molecules in the material, is used to form a layer that provides fire resistance, the material may result in an excessive amount of It will release smoke and toxic gases.

Other non-carbonaceous materials that will not release much smoke and toxic gases as compared to the case where primarily carbonaceous materials are used have also been used for layers that provide fire resistance. For example, inorganic silicon-based materials have been used in layers that provide fire resistance in the refractory glass panes. Specific examples of inorganic silicone-based materials that have been used to form fire resistant layers in such refractory panes are described in U. S. Patent Nos. 5,716, 424 to Alkali metal polysilicates, Mennig et al. A composition obtained through hydrolysis and condensation of silicates of < RTI ID = 0.0 > and < / RTI > Although the inorganic silicon-based material burns black, the inorganic silicon-based material mainly produces less smoke and toxic gases than carbon-based materials. However, existing fire resistant glass windows, including layers formed from silicon-based materials, can be extremely labor intensive to manufacture, heavy, and sometimes insufficient to maintain structural integrity with fatigue under heating. More specifically, once a gap is formed in the fire resistant glass window due to heat, the fire resistant glass window is likely to be mechanically fatigued. Similar deficiencies exist for other uses where fireproof or fireproof transparent articles are used. Examples include fire rated doors and curtain walls.

Due to the lack of existing windows, including fire resistant windows, they have good thermal insulation and sound insulation and fire resistance, are lighter in weight, and have good structural integrity after formation of the composite article under fatigue, i.e. after a gap is formed in the composite article. It would be advantageous to provide a composite article that either maintains or will not release as much smoke and toxic gas as a composite article that primarily contains carbon-based materials.

The present invention provides a composite article comprising a first pane comprising a glassy material and a first window layer formed of a layer of reinforced silicon. The silicon layer is disposed adjacent to and in contact with the first window layer. The reinforcing silicone layer comprises a cured silicone composition and a fiber reinforcing agent. The second pane is spaced to define a gap between the first pane. The frame is disposed adjacent to and in contact with the first pane and the second pane. The frame surrounds the gap between the first pane and the second pane.

Due to the presence of the gap between the first pane and the second pane, the composite article exhibits good insulation and sound insulation. In addition, due to the presence of the cured silicone composition in the reinforcing silicone layer, the composite article exhibits excellent fire resistance and will not release as much smoke and toxic gas as the composite article mainly comprising carbon-based materials. The gap may also assist in good fire resistance of the composite article by retarding the propagation of heat through the panes of the composite article. In addition, due to the presence of the fiber reinforcing agent in the reinforcing silicon layer, the composite article maintains good structural integrity, and the panes resist collapse even after gaps are formed through the panes due to heat. As such, the composite articles of the present invention may be suitable for load-bearing applications requiring thermal insulation and sound insulation in addition to good fire resistance not possible with prior art composite articles.

Other advantages of the present invention will be readily appreciated and will be better understood with reference to the following detailed description when considered in connection with the accompanying drawings.

1 is a side view of a composite article of the present invention.

1A is a cross-sectional side view of a central bore of the composite article of the present invention.

2 is a cross-sectional side view of the first pane of the composite article of the present invention.

3 is a cross-sectional side view of yet another embodiment of the present invention.

4 is a cross-sectional side view of yet another embodiment of the present invention.

5 is a cross-sectional side view of yet another embodiment of the present invention.

6 is a cross-sectional side view of yet another embodiment of the present invention.

7 is a cross-sectional side view of yet another embodiment of the present invention.

8 is a cross-sectional side view of yet another embodiment of the present invention.

9 is a cross-sectional side view of yet another embodiment of the present invention.

10 is a cross-sectional side view of yet another embodiment of the present invention.

Detailed description of the invention

Referring to the drawings, like numerals indicate corresponding parts throughout the several views, and composite articles are generally represented by 10 in FIG. 1. The composite article 10 has good insulation and sound insulation and good fire resistance, and is intended to prevent fire, smoke or heat waves from propagating through buildings or to include heat or fire in spaces such as in ovens. It is useful not only for industry but also for residential, commercial and industrial construction. The composite article 10 of the present invention may be suitable for rod-bearing applications requiring thermal insulation and sound insulation, as will be appreciated with reference to the more detailed description of the composite article 10 below.

The composite article 10 includes a first pane 12 that includes a first window layer 14 formed from a first glassy material. Although the first window layer 14 typically has a high transparency of at least 80%, it should be appreciated that a window layer having a transparency of less than 80% may be suitable for the purposes of the present invention. The first window layer 14 provides typical wear and scratch resistance to conventional windows.

The first glassy material forming the first window layer 14 is further defined as any material commonly used to form windows. Specific examples of suitable first glassy materials that can be used to form the first window layer 14 include conventional silica-based glass or carbon-based polymers. One particular example of conventional silica-based glass is soda-lime-silica glass. Specific examples of carbon-based polymers suitable for forming the first window layer 14 include, but are not limited to, polymethyl methacrylate (PMMA), polycarbonates, and polysulfonates.

The first window layer 14 may be formed by any method known in the art to form a window layer. Typically, the first window layer 14 is float glass, which is formed through a float process. The glass may be annealed, thermally strengthened, or chemically or thermally tempered by methods known in the art. It should be appreciated that any type of glass formed through any known process may be suitable for the purposes of the present invention.

The first window layer 14 typically has a thickness of about 0.002 to about 1 inch, typically about 0.125 inch. The specific thickness of the first window layer 14 depends on the specific use intended for the composite article 10. For example, for rod bearing applications or for applications in which the composite article 10 may preferably tolerate significant blunt forces, the first window layer 14 may be larger than it may have for decoration. It may have a thickness. However, it should be appreciated that the composite article 10 of the present invention is not limited to use in rod bearing applications.

The first pane 12 further comprises a reinforced silicon layer 16. The reinforced silicon layer 16 is disposed adjacent to and in contact with the first window layer 14. The reinforced silicon layer 16 provides excellent fire resistance to the composite article 10 as described in more detail below. The reinforcement silicon layer 16 includes a cured silicone composition and a fiber reinforcement agent. Typically, the fiber reinforcement is impregnated with the cured silicone composition, that is, the reinforcement silicone layer 16 is a single layer comprising the fiber reinforcement and the cured silicone composition. The reinforced silicon layer 16 is typically 50 weights based on the total weight of the reinforced silicon layer 16 to ensure that the reinforced silicon layer 16 does not emit sufficiently low levels of smoke and toxic gases during combustion. Less than parts carbon, more typically less than 35 parts by weight carbon. The reinforced silicon layer 16 is disposed adjacent to and in contact with the first window layer 14. The method of adhering the reinforced silicon layer 16 and the first window layer 14 is described in more detail below.

In one embodiment, the cured silicone composition is further defined as a hydrosilylation-cured silicone composition. The hydrosilylation-cured silicone composition comprises (C) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule in an amount sufficient to cure the silicone resin and (B) the silicone resin. Reaction products in the presence of a catalytic amount of hydrosilylation catalyst. While any hydrosilylation-cured silicone composition known in the art may be suitable for the purposes of the present invention, some hydrosilylation-cured silicone compositions may be more suitable than others. More specifically, some silicone resins (A) may be more suitable than others.

The silicone resin (A) typically has a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom. The silicone resin (A) is usually from R _² SiO ^_3/2 units, i.e., T units, and / or SiO _4/2 units, that is, the Q unit ^{_{R 1 R 2 2 SiO 1/}} 2 units, that is, M unit, and / or R ^{₂ 2} SiO _^2/2 units, i.e., D units and formulation including by, wherein R ¹ is C ₁ to C ₁₀ hydrocarbyl group or a C ₁ to C ₁₀ halogen-substituted hydrocarbyl group And are all free of aliphatic unsaturated groups and R ² is a copolymer that is R ¹ , alkenyl group, or hydrogen. For example, the silicone resin (A) may be DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin, or MDQ resin. As used herein, the term "without aliphatic unsaturated groups" means that the hydrocarbyl or halogen-substituted hydrocarbyl groups do not contain aliphatic carbon-carbon double bonds or carbon-carbon triple bonds.

The represented by R ^1, C ₁ to C ₁₀ hydrocarbyl group Q and C ₁ to C ₁₀ Q halogen-substituted hydrocarbyl group has more typically from 1 to 6 carbon atoms. Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl groups represented by R ¹ are methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1- Alkyl groups such as ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, and methylcyclohexyl; Aryl groups such as phenyl and naphthyl; Aralkyl groups such as tolyl and xylyl; And aralkyl groups such as benzyl and phenethyl. Examples of halogen-substituted hydrocarbyl groups represented by R ¹ are 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2 , 3,3-tetrafluoropropyl, and 2,2,3,3,4,4,5,5-octafluoropentyl, but are not limited to these.

The alkenyl group as R ² may be the same or different in the silicone resin (A), typically having 2 to about 10 carbon atoms, alternatively 2 to 6 carbon atoms, vinyl, allyl, But exemplified by butenyl, hexenyl, and octenyl. In one embodiment, R ² is predominantly an alkenyl group. In this embodiment, at least 50 mol%, alternatively at least 65 mol%, alternatively at least 80 mol% of the groups represented by R ² in the silicone resin are typically alkenyl groups. As used herein, R ² The mole percent of alkenyl groups in is defined as the ratio of the number of moles of silicon-bonded alkenyl groups in the silicone resin multiplied by 100 to the total moles of R ² groups in the resin. In another embodiment, R ² is predominantly hydrogen. In this embodiment, typically at least 50 mol%, alternatively at least 65 mol%, alternatively at least 80 mol% of the group represented by R ² in the silicone resin is hydrogen. R ² The mole% of hydrogen in is defined as the ratio of the number of moles of silicon-bonded hydrogen in the silicone resin multiplied by 100 to the total moles of R ² groups in the resin.

According to the first embodiment, the silicone resin (A) has the following formula:

In the above formula (I), R ¹ and R ² are as described and exemplified above, w, x, y, and z are mole fractions. The silicone resin (A) represented by formula (I) has on average at least two silicon-bonded alkenyl groups per molecule. More specifically, the subscript w typically has a value between 0 and 0.9, alternatively between 0.02 and 0.75, alternatively between 0.05 and 0.3. The subscript x typically has a value between 0 and 0.9, alternatively between 0 and 0.45, alternatively between 0 and 0.25. The subscript y typically has a value of 0 to 0.99, alternatively 0.25 to 0.8, alternatively 0.5 to 0.8. The subscript z typically has a value of 0 to 0.85, alternatively 0 to 0.25, alternatively 0 to 0.15. In addition, the ratio y + z / (w + x + y + z) is typically 0.1 to 0.99, alternatively 0.5 to 0.95, alternatively 0.65 to 0.9. Further, the ratio w + x / (w + x + y + z) is typically 0.01 to 0.90, alternatively 0.05 to 0.5, alternatively 0.1 to 0.35.

When R ² is predominantly an alkenyl group, specific examples of the silicone resin (A) represented by formula (I) above include, but are not limited to, resins having the following formulas:

_{(Vi 2 MeSiO 1/2)} 0.25 (PhSiO 3/2) 0.75, (ViMe 2 SiO 1/2) 0.25 (PhSiO 3/2) 0.75,

_{(ViMe 2 Si0 1/2)} 0.25 (MeSiO 3/2) 0.25 (PhSiO 3/2) 0.50,

_{(ViMe 2 SiO 1/2)} 0.15 (PhSiO 3/2) 0.75 (SiO 4/2) 0.1, and

_{(Vi 2 MeSiO 1/2)} 0.15 (ViMe 2 SiO 1/2) 0.1 (PhSiO 3/2) 0.75,

In the above formulas, Me is methyl, Vi is vinyl, Ph is phenyl, and the numerical subscripts outside the parentheses represent the mole fractions corresponding to w, x, y, or z as described above for Formula (I). The order of units in the preceding equations should not be considered in any way limiting the scope of the invention.

When R ² is predominantly hydrogen, certain examples of silicone resin (A) represented by formula (I) above include, but are not limited to, resins having the following formulas:

_{(HMe 2 SiO 1/2)} 0.25 (PhSiO 3/2) 0.75, (HMeSiO 2/2) 0.3 (PhSiO 3/2) 0.6 (MeSiO 3/2) 0.1, and _{(Me 3 Si0 1/2)} 0.1 ( _{H 2 Si0 2/2) 0.1} (MeSi0 3/2) 0.4 (PhSi0 3/2) 0.4,

In the above formulas, Me is methyl, Ph is phenyl, and the numerical subscripts outside the parentheses represent the mole fraction. The order of units in the preceding equations should not be considered in any way limiting the scope of the invention.

The silicone resin (A) represented by formula (I) typically has a number average molecular weight (Mn) of 500 to 50,000, alternatively 500 to 10,000, alternatively 1,000 to 3,000, wherein the molecular weight is a low angle laser light It is determined by scattering detector, or gel permeation chromatography using a refractive index detector and a silicone resin (MQ) standard.

The viscosity of the silicone resin (A) represented by formula (I) is typically 0.01 to 100,000 Pa.s, alternatively 0.1 to 10,000 Pa.s, alternatively 1 to 100 Pa.s at 25 ° C.

The silicone resin (A) represented by formula (I) is typically measured by ²⁹ Si NMR, typically less than 10% (w / w), alternatively less than 5% (w / w), alternatively 2% and silicon-bonded hydroxy groups of less than (w / w).

Methods of preparing silicone resin (A) represented by formula (I) are well known in the art; Many of these resins are commercially available. Silicone resins (A) represented by formula (I) are typically prepared by simultaneous hydrolysis of a suitable mixture of chlorosilane precursors in an organic solvent such as toluene. For example, R ¹ R ² ₂ SiO _1/2 units and R ² SiO _{3 /} silicone resin comprising _two units (A) a first compound and a formula R ² SiCl ₃ having the formula R ¹ R ² SiCl ₂ Co-hydrolyzing a second compound having in toluene (wherein R ¹ and R ² are as defined and exemplified above) to form aqueous hydrochloric acid and a silicone resin (A) which is a hydrolysis product of the first and second compounds. It can be manufactured by. The aqueous hydrochloric acid and the silicone resin (A) are separated, the silicone resin (A) is washed with water to remove residual acid, and the silicone resin (A) is to obtain the desired viscosity as known in the art. Heated in the presence of a mild condensation catalyst to "body" the silicone resin (A).

If desired, the silicone resin (A) may be further treated with a condensation catalyst in an organic solvent to reduce the content of silicon-bonded hydroxy groups. Alternatively, in addition to chloro, a first containing hydrolyzable groups such as -Br, -I, -OCH ₃ , -OC (O) CH ₃ , -N (CH ₃ ) ₂ , NHCOCH ₃ , and -SCH ₃ Alternatively, the second compound may be co-hydrolyzed to form the silicone resin (A). The properties of the silicone resin (A) depend on the type of first and second compounds, the molar ratio of the first and second compounds, the degree of condensation, and the processing state.

The organosilicon compound (B) has on average at least two silicon-bonded hydrogen atoms per molecule, alternatively at least three silicon-bonded hydrogen atoms per molecule. It is generally understood that a crosslinking reaction occurs when the sum of the average number of alkenyl groups per molecule in the silicone resin (A) and the average number of silicon-bonded hydrogen atoms per molecule in the organosilicon compound (B) is 4 or more. . Before curing, the organosilicon compound (B) is present in an amount sufficient to cure the silicone resin (A).

The organosilicon compound (B) may be further defined as organohydrogensilane, organohydrogensiloxane, or combinations thereof. The structure of the organosilicon compound (B) may be linear, branched, cyclic or dendritic. In acyclic polysilanes and polysiloxanes, the silicon-bonded hydrogen atoms may be located at the terminal, pendant position or at both the terminal and pendant position. Cyclosilanes and cyclosiloxanes typically have 3 to 12 silicon atoms, alternatively 3 to 10 silicon atoms, alternatively 3 to 4 silicon atoms.

The organohydrogensilane may be monosilane, disilane, trisilane, or polysilane. When R ² is predominantly an alkenyl group, specific examples of organohydrogensilanes suitable for the purposes of the present invention include diphenylsilane, 2-chloroethylsilane, bis [(p-dimethylsilyl) phenyl] ether, 1,4- Dimethyldisilylethane, 1,3,5-tris (dimethylsilyl) benzene, l, 3,5-trimethyl-l, 3,5-trisilane, poly (methylsilylene) phenylene, and poly (methylsilyl Ethylene) methylene, but is not limited thereto. When R ² is predominantly hydrogen, certain examples of organohydrogensilanes suitable for the purposes of the present invention include, but are not limited to, silanes having the following formulas:

Vi ₄ Si, PhSiVi ₃ , MeSiVi ₃ , PhMeSiVi ₂ , Ph ₂ SiVi ₂ , and PhSi (CH ₂ CH = CH ₂ ) ₃ ,

In the above formulas, Me is methyl, Ph is phenyl, and Vi is vinyl.

The organohydrogensilane may also have the following formula:

In formula (II), R ¹ is as defined and exemplified above, R ³ is a hydrocarbylene group free from aliphatic unsaturated groups and having a formula selected from the following structural formulas:

G is 1 to 6 in the above formulas.

Specific examples of organohydrogensilanes having formula (II), wherein R ¹ and R ³ are as defined and exemplified above, include, but are not limited to, organohydrogensilanes having a formula selected from the following structural formulas: :

Methods of preparing the organohydrogensilanes are known in the art. For example, organohydrogensilanes can be prepared by the reaction of Grignard reagents with alkyl or aryl halides. In particular, organohydrogensilanes having the formula HR ¹ ₂ Si—R ³ —SiR ¹ ₂ H treat the aryl dihalide having the formula R ³ X ₂ with magnesium in ether to produce the corresponding Grignard reagent, and The Nyar reagent can be prepared by treating with chlorosilanes having the formula HR ¹ ₂ SiCl, wherein R ¹ and R ³ are as defined and exemplified above.

The organohydrogensiloxane may be disiloxane, trisiloxane, or polysiloxane. Examples of organosiloxanes suitable for use as organosilicon compound (B) when R ₂ is predominantly hydrogen include, but are not limited to: siloxanes having the following formulas:

PhSi (OSiMe ₂ H) ₃ , Si (OSiMe ₂ H) ₄ , MeSi (OSiMe ₂ H) ₃ , and Ph ₂ Si (OSiMe ₂ H) ₂ ,

In formulas, Me is methyl and Ph is phenyl.

Specific examples of organohydrogensiloxanes suitable for the purposes of the present invention when R ₂ is the predominantly alkenyl group include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyl Tris (dimethylsiloxy) silane, 1,3,5-trimethylcyclotrisiloxane, trimethylsiloxy-terminated poly (methylhydrogensiloxane), trimethylsiloxy-terminated poly (dimethylsiloxane / methylhydrogensiloxane), dimethylhydrogensiloxy -terminated poly (methyl hydrogen siloxane), and HMe ₂ SiO _1/2 units, Me ₃ SiO _1/2 units, and SiO _4/2 units containing a resin including a (wherein Me is methyl Im), but is not limited to these Do not.

The organohydrogensiloxane can also be an organohydrogenpolysiloxane resin. The organic hydrogen polysiloxane resins are typically R ⁴ SiO _3/2 units, i.e., T units, and / or SiO _4/2 units, i.e., a Q unit, R ¹ R ₂ Si0 ⁴ _1/2 units, that is, M a copolymer comprising in combination with the unit, and / or R ⁴ ₂ SiO _2/2 units, i.e., D units (wherein, R is as described and exemplified above). For example, the organohydrogenpolysiloxane resin may be DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin, or MDQ resin.

The group represented by R ⁴ is R ¹ or an organosilylalkyl group having at least one silicon-bonded hydrogen atom. Examples of organosilylalkyl groups represented by R ⁴ include, but are not limited to, groups having a formula selected from the following structural formulas:

-CH ₂ CH ₂ SiMe ₂ H, -CH ₂ CH ₂ SiMe ₂ C _n H _2n SiMe ₂ H, -CH ₂ CH ₂ SiMe ₂ C _n H _2n SiMePhH, -CH ₂ CH ₂ SiMePhH,

-CH ₂ CH ₂ SiPh ₂ H, -CH ₂ CH ₂ SiMePhC _n H _2n SiPh ₂ H,

-CH ₂ CH ₂ SiMePhC _n H _2n SiMe ₂ H, -CH ₂ CH ₂ SiMePhOSiMePhH, and

-CH ₂ CH ₂ SiMePhOSiPh (OSiMePhH) ₂ )

In the above formulas, Me is methyl, Ph is phenyl, and the subscript n has a value from 2 to 10. Typically, at least 50 mol%, alternatively at least 65 mol%, alternatively at least 80 mol% of the groups represented by R ⁴ in the organohydrogenpolysiloxane resin have organosilylalkyls having at least one silicon-bonded hydrogen atom Group. As used herein, R ⁴ The mole% of organosilylalkyl group in is defined as the ratio of the mole number of silicon-bonded organosilylalkyl group in the silicone resin (A) multiplied by 100 to the total mole number of R ² groups in the resin.

The organohydrogenpolysiloxane resins typically have the following formula:

In the above formula (III), R ¹ , R ⁴ , w, x, y, and z are as defined and exemplified above, respectively.

Specific examples of the organohydrogenpolysiloxane resin represented by the above formula (III) include, but are not limited to, resins having the following formulas:

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.12 (PhSi0 3/2) 0.88,

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.17 (PhSiO 3/2) 0.83,

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.17 (MeSiO 3/2) 0.17 (PhSi0 3/2) 0.66,

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.15 (PhSi0 3/2) 0.75 (Si0 4/2) 0.10, and

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.08 ((HMe 2 SiC 6 H 4 SiMe 2 CH 2 CH 2)

_{Me 2 SiO 1/2) 0.06} (PhSiO 3/2) 0.86,

In the above formulas Me is methyl, Ph is phenyl, C ₆ H ₄ represents a para-phenylene group and the numerical subscripts outside the parentheses represent the mole fraction. The order of units in the preceding equations should not be considered in any way limiting the scope of the invention.

Specific examples of organohydrogenpolysiloxane resins include, but are not limited to, resins having the following formulas:

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.12 (PhSi0 3/2) 0.88,

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.17 (PhSiO 3/2) 0.83,

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.17 (MeSiO 3/2) 0.17 (PhSi0 3/2) 0.66,

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.15 (PhSi0 3/2) 0.75 (Si0 4/2) 0.10, and

_{((HMe 2 SiC 6 H 4} SiMe 2 CH 2 CH 2) 2 MeSiO 1/2) 0.08 ((HMe 2 SiC 6 H 4 SiMe 2 CH 2 CH 2)

_{Me 2 SiO 1/2) 0.06} (PhSiO 3/2) 0.86,

In the above formulas Me is methyl, Ph is phenyl, C ₆ H ₄ represents a para-phenylene group and the numerical subscripts outside the parentheses represent the mole fraction. The order of units in the preceding equations should not be considered in any way limiting the scope of the invention.

The organic hydrogen polysiloxane resins having the general formula (III) is a formula represented by the above formula ^{(I) (R 1 R 2} 2 SiO 1/2) w (R 2 2 SiO 2/2) x (R 2 SiO 3/2) _{y (SiO 4/2) (} a) a silicone resin and a molecule an average of two to four silicon per having a z - has a bonded hydrogen atom, the reaction mixture containing the organic silicon compound (b) having less than 1000 molecular weight (c) a hydrosilylation catalyst and, optionally, (d) in the presence of an organic solvent, wherein R ¹ , R ² , w, x, y, and z are each defined and exemplified above. Provided that the silicone resin (a) has an average of at least two silicon-bonded alkenyl groups per molecule, and the molar ratio of silicon-bonded hydrogen atoms in (b) to alkenyl groups in (a) is 1.5 to 5. The silicone resin (a) may be the same or different from the particular silicone resin used as component (A) to form the hydrosilylation-cured silicone composition.

As indicated above, the organosilicon compound (b) has an average of 2 to 4 silicon-bonded hydrogen atoms per molecule. Alternatively, the organosilicon compound (b) has an average of 2 to 3 silicon-bonded hydrogen atoms per molecule. As also indicated above, the organosilicon compound (b) typically has a molecular weight of less than 1,000, alternatively less than 750, alternatively less than 500. The organosilicon compound (b) may be selected from the group of hydrocarbyl groups and halogen-substituted hydrocarbyl groups, both free of aliphatic unsaturated groups and silicon-bonded as described and exemplified above for R ¹ . Further comprises an organic group.

The organosilicon compounds (b) may be organohydrogensilanes or organohydrogensiloxanes, each of which is defined and illustrated in detail above. The organosilicon compound (b) may be a single organosilicon compound or a mixture of two or more different organosilicon compounds, each as described above. For example, the organosilicon compound (B) may be a single organohydrogensilane, a mixture of two different organohydrogensilanes, a single organohydrogensiloxane, a mixture of two different organohydrogensiloxanes, or a mixture of organohydrogensilanes and organohydrogensiloxanes. Can be. The molar ratio of silicon-bonded hydrogen atoms in the organosilicon compound (B) to the alkenyl groups in the silicone resin (A) is usually 1.5 to 5, alternatively 1.75 to 3, alternatively 2 to 2.5.

The hydrosilylation catalyst (c) may be any of well-known hydrosilylation catalysts containing platinum group metals (ie, platinum, rhodium, ruthenium, palladium, osmium and iridium) or compounds containing platinum group metals. Typically, the platinum group metal is platinum based on its high activity in hydrosilylation reactions.

Suitable hydrosilylation catalysts for (c) include complexes of chloroplatinic acid with certain vinyl-containing organosiloxanes described by Willing in US Pat. No. 3,419,593, which is incorporated herein by reference. A catalyst of this type is the reaction product of chloroplatinic acid with l, 3-diethenyl-l, l, 3,3-tetramethyldisiloxane.

The hydrosilylation catalyst (c) may also be a supported hydrosilylation catalyst comprising a solid support having a platinum group metal on its surface. The supported catalyst can be conveniently separated from the organohydrogenpolysiloxane resin represented by the formula (III), for example by filtering the reaction mixture. Examples of supported catalysts include, but are not limited to, platinum on carbon, palladium on carbon, ruthenium on carbon, rhodium on carbon, platinum on silica, palladium on silica, platinum on alumina, palladium on alumina, and ruthenium on alumina. Do not.

The concentration of the hydrosilylation catalyst (c) is sufficient to catalyze the addition reaction of the silicone resin (A) and the organosilicon compound (B). Typically, the concentration of hydrosilylation catalyst (c) is 0.1 to 1000 ppm platinum group metal, alternatively 1 to 500 ppm platinum group metal, alternatively based on the combined weight of silicone resin (A) and organosilicon compound (B) Sufficient to provide 5 to 150 ppm of the platinum group metal. The reaction rate is very slow for platinum group metals of less than 0.1 ppm. The use of more than 1000 ppm platinum group metals did not result in any appreciable increase in reaction rate, which is therefore uneconomical.

The organic solvent (d) is at least one organic solvent. The organic solvent (d) does not react with the silicone resin (a), the organosilicon compound (b), or the resulting organohydrogenpolysiloxane resin under the conditions of the method of the present application, and the components (a), (b), and organohydrogen It can be any aprotic or dipolar aprotic organic solvent that is miscible with the polysiloxane resin.

Examples of organic solvents (d) suitable for the purposes of the present invention include saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; Cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Cyclic ethers such as tetrahydrofuran (THF) and dioxane; Ketones such as methyl isobutyl ketone (MIBK); Halogenated alkanes such as trichloroethane; And halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene. The organic solvent (d) may be a single organic solvent or a mixture of two or more different organic solvents, each as described above. The concentration of the organic solvent (d) is typically 0 to 99% (w / w), alternatively 30 to 80% (w / w), alternatively 45 to 60% (w) based on the total weight of the reaction mixture / w).

The reaction for forming the organohydrogenpolysiloxane resin represented by formula (III) may be carried out in any standard reactor suitable for hydrosilylation reactions. Suitable reactors include glass and Teflon-lined glass reactors. Typically, the reactor is equipped with agitation means such as agitation. Also, typically, the reaction is carried out in an inert atmosphere such as nitrogen or argon in the absence of moisture.

Silicone resin (a), organosilicon compound (b), hydrosilylation catalyst (c), and optionally, organic solvent (d) may be combined in any order. Typically, the organosilicon compound (b) and the hydrosilylation catalyst (c) are combined before introducing the silicone resin (a) and, optionally, the organic solvent (d). The reaction is usually carried out at a temperature of 0 to 150 ° C., alternatively at room temperature (˜23 ± 2 ° C.) to 115 ° C. If the temperature is below 0 ° C., the reaction rate is usually very slow. The reaction time depends on various factors such as the structure of the silicone resin (a) and the organosilicon compound (b), and the temperature. The reaction time is usually 1 to 24 hours at room temperature (˜23 ± 2 ° C.) to 150 ° C. Optimum reaction time can be measured by routine experiments.

The organohydrogenpolysiloxane resin represented by formula (III) can be used without isolation or purification of the organohydrogenpolysiloxane resin can be separated from most organic solvents (d) by conventional evaporation methods. For example, the reaction mixture can be heated under reduced pressure. In addition, when the hydrosilylation catalyst (c) is the supported catalyst as described above, the organohydrogenpolysiloxane resin can be easily separated by filtering the reaction mixture from the hydrosilylation catalyst (c). However, the hydrosilylation catalyst (c) can be left mixed with the organohydrogenpolysiloxane resin, and can be used as the hydrosilylation catalyst (C).

The organosilicon compound (B) may be a single organosilicon compound or a mixture comprising two or more different organosilicon compounds, each as described above. For example, the organosilicon compound (B) may comprise a single organohydrogensilane, a mixture of two different organohydrogensilanes, a single organohydrogensiloxane, a mixture of two different organohydrogensiloxanes, or a mixture of organohydrogensilanes and organohydrogensiloxanes. In particular, the organosilicon compound (B) comprises at least 0.5% (w / w), alternatively at least 50, of an organohydrogenpolysiloxane resin having formula (III) based on the total weight of the organosilicon compound (B) % (w / w), alternatively a mixture comprising with organosilicon compounds (B) further comprising organohydrogensilanes and / or organohydrogensiloxanes in an amount of at least 75% (w / w), the latter Is different from the organohydrogenpolysiloxane resin.

The concentration of the organosilicon compound (B) is sufficient to cure (crosslink) the silicone resin (A). The exact amount of organosilicon compound (B) depends on the degree of curing desired. The concentration of the organosilicon compound (B) is typically 0.4 to 2 moles of silicon-bonded hydrogen atoms, alternatively 0.8 to 1.5 moles of silicon-bonded hydrogen atoms, alternatively per mole of alkenyl group in the silicone resin (A) Enough to provide 0.9 to 1.1 moles of silicon-bonded hydrogen atoms.

The hydrosilylation catalyst (C) comprises at least one hydrosilylation catalyst which promotes the reaction between the silicone resin (A) and the organosilicon compound (B). In one embodiment, the hydrosilylation catalyst (C) may be the same as the hydrosilylation catalyst (c) described above to produce an organohydrogenpolysiloxane resin. In addition, the hydrosilylation catalyst (C) may be a microencapsulated platinum group metal-containing catalyst comprising a platinum group metal encapsulated in a thermoplastic resin. Microencapsulated hydrosilylation catalysts and methods for their preparation are well known in the art as illustrated in US Pat. No. 4,766,176 and references cited therein, and US Pat. No. 5,017,654. The hydrosilylation catalyst (C) may be a single catalyst or a mixture comprising two or more different catalysts having different at least one property, such as structure, form, platinum group metal, complexing ligand, and thermoplastic resin.

In another embodiment, the hydrosilylation catalyst (C) may be at least one photoactivated hydrosilylation catalyst. The photoactivated hydrosilylation catalyst may be any hydrosilylation catalyst capable of catalyzing the hydrosilylation of the silicone resin (A) and the organosilicon compound (B) upon exposure to radiation having a wavelength of 150 to 800 nm. Can be. The photoactivated hydrosilylation catalyst can be any of well-known hydrosilylation catalysts including a platinum group metal or a compound containing a platinum group metal. Platinum group metals include platinum, rhodium, ruthenium, palladium, osmium and iridium. Typically, the platinum group metal is platinum based on its high activity in hydrosilylation reactions. The suitability of certain photoactivated hydrosilylation catalysts for use in the silicone compositions of the present invention can be readily determined by routine experimentation.

Specific examples of photoactivated hydrosilylation catalysts suitable for the purposes of the present invention include platinum (II) bis (2,4-pentanedioate), platinum (II) bis (2,4-hexanedioate), platinum ( II) bis (2,4-heptanedioate), platinum (II) bis (l-phenyl-1,3-butanedioate, platinum (II) bis (l, 3-diphenyl-1,3-propanedio Eight), platinum (II) β-diketonate complexes such as platinum (II) bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedioate); (Cp) trimethyl (Η-cyclo, such as platinum, (Cp) ethyldimethyl platinum, (Cp) triethyl platinum, (chloro-Cp) trimethyl platinum, and (trimethylsilyl-Cp) trimethyl platinum, where Cp represents cyclopentadienyl Pentadienyl) trialkylplatinum complexes; Pt [C ₆ H ₅ NNNOCH ₃ ] ₄ , Pt [p-CN-C ₆ H ₄ NNNOC ₆ H ₁₁ ] ₄ , Pt [pH ₃ COC ₆ H ₄ NNNOC ₆ H ₁₁ ] ₄ , Pt [p-CH ₃ (CH ₂ ) _x -C ₆ H ₄ NNNOCH ₃ ] ₄ , l, 5-cyclooctadiene. Pt [p-CN-C ₆ H ₄ NNNOC ₆ H ₁₁ ] ₂ , 1, 5-cyclooctadiene. Pt [p-CH ₃ OC ₆ H ₄ NNNOCH ₃ ] ₂ , [(C ₆ H ₅ ) ₃ P] ₃ Rh [p-CN-C ₆ H ₄ NNNOC ₆ H ₁₁ ], and Pd [p-CH ₃ (CH ₂ ) _x − Triagen oxide-transition metal complexes such as C ₆ H ₄ NNNOCH ₃ ] ₂ , where x is 1, 3, 5, 11, or 17; (η ⁴ -l, 5-cyclooctadienyl) diphenylplatinum , η ⁴ -1,3,5,7-cyclooctatetraenyl) diphenyl platinum, (η ⁴ -2,5-norboradienyl) diphenyl platinum, (η ⁴ -1,5-cyclooctadie Nil) bis- (4-dimethylaminophenyl) platinum, (η ⁴ -1,5-cyclooctadienyl) bis- (4-acetylphenyl) platinum, and (η ⁴ -l, 5-cyclooctadienyl) (Η-diolefin) (σ-aryl) platinum complexes such as bis- (4-trifluoromethylphenyl) platinum, but are not limited to these. Typically, the photoactivated hydrosilylation catalyst is a Pt (II) β-diketonate complex and more typically the catalyst is platinum (II) bis (2,4-pentanedioate). The hydrosilylation catalyst (C) may be a single photoactivated hydrosilylation catalyst or a mixture comprising two or more different photoactivated hydrosilylation catalysts.

Methods of making photoactivated hydrosilylation catalysts are well known in the art. For example, a method for preparing platinum (II) β-diketonate has been reported by Guo et al. (Chemistry of Materials, 1998, 10, 531-536). Methods for preparing (η-cyclopentadienyl) -trialkylplatinum complexes are described in US Pat. No. 4,510,094. Methods of making triazane oxide-transition metal complexes are described in US Pat. No. 5,496,961. In addition, methods for preparing (η-diolefin) (σ-aryl) platinum complexes are taught in US Pat. No. 4,530,879.

The concentration of the hydrosilylation catalyst (C) is sufficient to catalyze the addition reaction of the silicone resin (A) and the organosilicon compound (B). The concentration of the hydrosilylation catalyst (C) is typically 0.1 to 1000 ppm platinum group metal, alternatively 0.5 to 100 ppm platinum group metal, alternatively based on the combined weight of the silicone resin (A) and the organosilicon compound (B) It is sufficient to provide 1 to 25 ppm of platinum group metal.

Optionally, said hydrosilylation-cured silicone composition further comprises (D) silicone rubber having formulas selected from the following group:

(i) R ¹ R ² ₂ SiO (R ² ₂ SiO) _a SiR ² ₂ R ¹ ; And

(ii) R ⁵ R ¹ ₂ SiO (R ¹ R ⁵ SiO) _b SiR ¹ ₂ R ⁵ ;

Wherein R ¹ and R ² are as defined and exemplified above, R ₅ is R ¹ or —H, and the subscripts a and b each have a value of 1 to 4, 2 to 4 or 2 to 3, w , x, y, and z are also as defined and exemplified above, provided that each of the silicone resin and silicone rubber (D) (i) has at least two silicon-bonded alkenyl groups on average per molecule, the silicone Rubber (D) (ii) has an average of at least two silicon-bonded hydrogen atoms per molecule, and silicon-bonded eggs in silicone rubber (D) to silicon-bonded alkenyl groups in silicone resin (A) The molar ratio of the kenyl group or silicon-bonded hydrogen atoms is 0.01 to 0.5.

Specific examples of silicone rubbers suitable for use as component (D) (i) include, but are not limited to, silicone rubbers having the following formulas:

ViMe ₂ SiO (Me ₂ SiO) aSiMe ₂ Vi, ViMe ₂ SiO (Ph ₂ SiO) aSiMe ₂ Vi, and

ViMe ₂ SiO (PhMeSiO) aSiMe ₂ Vi,

In the above formulas Me is methyl, Ph is phenyl, Vi is vinyl and the subscript a has a value of 1-4. The silicone rubber (D) (i) may be a single silicone rubber or a mixture comprising two or more silicone rubbers each satisfying the formula for (D) (i).

Specific examples of silicone rubbers suitable for use as silicone rubber (D) (H) include, but are not limited to, silicone rubber having the following formulas:

HMe ₂ SiO (Me ₂ SiO) bSiMe ₂ H, HMe ₂ SiO (Ph ₂ SiO) bSiMe ₂ H, HMe ₂ SiO (PhMeSiO) b,

SiMe ₂ H, and HMe ₂ SiO (Ph ₂ SiO) ₂ (Me ₂ SiO) ₂ SiMe ₂ H,

In the above formulas Me is methyl, Ph is phenyl and the subscript b has a value from 1 to 4. Component (D) (ii) may be a single silicone rubber or a mixture comprising two or more different silicone rubbers each satisfying the formula for (D) (ii).

The molar ratio of silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the silicone rubber (D) to silicon-bonded alkenyl groups in the silicone resin (A) is typically 0.01 to 0.5, alternatively 0.05 to 0.4 Alternatively 0.1 to 0.3.

When the silicone rubber (D) is (D) (i), the concentration of the organosilicon compound (B) is determined by the number of moles of silicon-bonded alkenyl groups in the silicone resin (A) and the silicone rubber (D) (i). The ratio of the number of moles of silicon-bonded hydrogen atoms in the organosilicon compound (B) to the sum is usually between 0.4 and 2, alternatively between 0.8 and 1.5, alternatively between 0.9 and 1.1. In addition, when the silicone rubber (D) is (D) (II), the concentration of the organosilicon compound (B) is based on the number of moles of the silicon-bonded alkenyl group in the silicone resin (A). And the ratio of the sum of the moles of silicon-bonded hydrogen atoms in the silicone rubber (D) (ii) is typically 0.4 to 2, alternatively 0.8 to 1.5, alternatively 0.9 to 1.1.

Methods of preparing silicone rubber containing silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms are well known in the art; Many of these compounds are commercially available.

In another embodiment of the invention, the hydrosilylation-cured silicone composition comprises (A ') rubber-modified silicone resin and reaction product in the presence of (C) catalytic amount of hydrosilylation catalyst of organosilicon compound (B). . The rubber-modified silicone resin (A ') is a silicone resin (A) and a silicone rubber (D) (iii) having the following formulas:

R ⁵ R ¹ ₂ SiO (R ¹ R ⁵ SiO) 0SiR ¹ ₂ R ⁵ , R ¹ R ² ₂ SiO (R ² ₂ SiO) dSiR ² ₂ R ¹ ,

(Wherein R ¹ and R ⁵ are as defined and exemplified above, c and d each have a value of 4 to 1000, alternatively 10 to 500, alternatively 10 to 50), hydrosilylation catalyst (c) and, optionally, in the presence of an organic solvent, provided that said silicone resin (A) has on average at least two silicon-bonded alkenyl groups per molecule, said silicone rubber (D) ( iii) has on average at least two silicon-bonded hydrogen atoms per molecule, and of silicon-bonded hydrogen atoms in silicone rubber (D) (iii) to silicon-bonded alkenyl groups in silicone resin (A) The molar ratio is 0.01 to 0.5. When an organic solvent is present, the rubber-modified silicone resin (A ') is miscible in the organic solvent and does not form fine particles or suspensions.

The silicone resin (A), silicone rubber (D) (iii), hydrosilylation catalyst (c), and organic solvent can be combined in any order. Typically, the silicone resin (A), silicone rubber (D) (iii), and organic solvent are combined before the introduction of the hydrosilylation catalyst (c).

The reaction is usually carried out at room temperature (˜23 ± 2 ° C.) to 150 ° C., alternatively at room temperature to 100 ° C. The reaction time depends on various factors including the structure and temperature of the silicone resin (A) and the silicone rubber (D) (iii). The components are typically allowed to react for a time sufficient to complete the hydrosilylation reaction. It is determined by FTIR spectrometer that at least 95 mol%, alternatively at least 98 mol%, alternatively at least 99 mol% of the silicon-bonded hydrogen atoms originally present in the silicone rubber (D) (iii) are hydrosilyl It means that the components are allowed to react normally until consumed in the reaction. The reaction time is usually from 0.5 to 24 hours at room temperature (~ 23 ± 2 ℃) to 100 ℃. The optimal reaction time can be determined by routine experimentation.

The molar ratio of silicon-bonded hydrogen atoms in the silicone rubber (D) (iii) to the silicon-bonded alkenyl groups in the silicone resin (A) is typically 0.01 to 0.5, alternatively 0.05 to 0.4, alternatively 0.1 To 0.3.

The concentration of the hydrosilylation catalyst (c) is sufficient to catalyze the addition reaction of the silicone resin (A) and the silicone rubber (D) (iii). Typically, the concentration of hydrosilylation catalyst (c) is sufficient to provide 0.1 to 1000 ppm of platinum group metal based on the combined weight of resin and rubber.

The concentration of the organic solvent is typically from 0 to 95% (w / w), alternatively from 10 to 75% (w / w), alternatively from 40 to 60% (w / w) based on the total weight of the reaction mixture. to be.

The rubber-modified silicone resin (A ') can be used without isolation or purification or the rubber-modified silicone resin (A') can be separated from most solvents by conventional evaporation methods. For example, the reaction mixture can be heated under reduced pressure. In addition, when the hydrosilylation catalyst (c) is a supported catalyst as described above, the rubber-modified silicone resin (A ') can be easily separated by filtering the reaction mixture from the hydrosilylation catalyst (c). . However, when the rubber-modified silicone resin (A ') is not separated from the hydrosilylation catalyst (c) used to prepare the rubber-modified silicone resin (A'), the hydrosilylation catalyst (c) is hydrolyzed. It can be used as the silylation catalyst (C).

The hydrosilylation-cured silicone composition of the present invention may comprise additional components as known in the art. Examples of additional components include 3-methyl-3-penten-l-phosphorus, 3,5-dimethyl-3-hexene-l-phosphorus, 3,5-dimethyl-l-hexyn-3-ol, 1-ethynyl Hydrosilylation catalyst inhibitors such as -1-cyclohexanol, 2-phenyl-3-butyn-2-ol, vinylcyclosiloxane, and triphenylphosphine; Adhesion promoters, such as the adhesion promoters taught in US Pat. No. 4,087,585 and US Pat. No. 5,194,649; dyes; Pigments; Antioxidants; Heat stabilizers; UV stabilizers; Flame retardant; Flow control additives; And diluents such as organic solvents and reactive diluents.

As an alternative to the hydrosilylation-cured silicone composition, condensation-cured silicone compositions are also suitable for the silicone compositions of the present invention.

The condensation-cured silicone composition typically comprises a silicone resin (A ″) having a silicon-bonded hydroxy or hydrolyzable group and optionally a crosslinking agent (B ′) having a silicon-bonded hydrolyzable group, and optionally condensation The reaction product of the catalyst (C). The silicone resin (A ″) is typically a copolymer containing T and / or Q siloxane units in combination with M and / or D siloxane units.

The condensation-cured silicone composition can be any condensation-cured silicone composition as known in the art. However, certain condensation-cured silicone compositions are particularly suitable for the purposes of the present invention. According to one embodiment, the silicone resin (A ") has the formula:

Wherein R ¹ is as defined and exemplified above, R ⁶ is R ¹ , —H, —OH, or a hydrolyzable group, w ′ is 0 to 0.8, alternatively 0.02 to 0.75, alternatively 0.05 To 0.3, x 'is 0 to 0.95, alternatively 0.05 to 0.8, alternatively 0.1 to 0.3, y' is 0 to 1, alternatively 0.25 to 0.8, alternatively 0.5 to 0.8, z ' Is 0 to 0.99, alternatively 0.2 to 0.8, alternatively 0.4 to 0.6, and the silicone resin (A ″) has at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolyzable groups on average per molecule. As used herein, the term “hydrolyzable group” means that the silicon-bonded group is several minutes at room temperature (˜23 ± 2 ° C.) to 100 ° C. in the absence of a catalyst, for example 30 It reacts with the water for a minute is meant to form a silanol (Si-OH) group. mantissa represented by R ⁶ Examples of the water-decomposable ^{groups, -Cl, -Br, -OR 7,} -OCH 2 CH 2 OR 7, CH 3 C (= O) O-, Et (Me) C = NO-, CH 3 C (= O) N (CH ₃ ) —, and —ONH ₂ , including but not limited to, wherein R ⁷ is C ₁ to C ₈ hydrocarbyl or C ₁ to C ₈ Halogen-substituted hydrocarbyl.

The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R ⁷ typically have 1 to 8 carbon atoms, alternatively 3 to 6 carbon atoms. Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least three carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl groups represented by R ⁷ are methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1- Unbranched and branched alkyl such as ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, and octyl; Cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; Phenyl; Alkalis such as tolyl and xylyl; Aralkyl such as benzyl and phenethyl; Alkenyl such as vinyl, allyl, and propenyl; Arylalkenyl such as styryl; And alkynyl such as ethynyl and propynyl. Examples of halogen-substituted hydrocarbyl groups represented by R ⁷ include, but are not limited to, 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, and dichlorophenyl.

Typically, at least 5 mol%, alternatively at least 15 mol%, alternatively at least 30 mol% of the groups R ⁶ in the silicone resin are hydrogen, hydroxy, or hydrolyzable groups. As used herein, the mole percent of groups in R ⁶ is the ratio of the total moles of R ⁶ groups in the silicone resin (A ″) multiplied by 100 by the number of moles of silicon-bonded groups in the silicone resin (A ″). It is defined as

Specific examples of the cured silicone resin formed from the silicone resin (A ″) include but are not limited to cured silicone resins having the following formulas:

_{(MeSiO 3/2) n,} (PhSiO 3/2) n, (Me3SiO 1/2) 0.8 (Si0 4/2) 0.2,

_{(MeSi0 3/2) 0.67 (} PhSi0 3/2) 0.33,

_{(MeSiO 3/2) 0.45 (} PhSiO 3/2) 0.40 (Ph 2 SiO 2/2) 0.1 (PhMeSiO 2/2) 0.05,

_{(PhSi0 3/2) 0.4 (} MeSi0 3/2) o.45 (PhSi0 3/2) 0.1 (PhMeSi0 2/2) 0.05, and

_{(PhSiO 3/2) 0.4 (} MeSiO 3/2) 0.1 (PhMeSiO 2/2) 0.5,

In the above formulas, Me is methyl, Ph is phenyl, the numerical subscripts outside the parentheses represent the mole fraction, and the subscript n has a value such that the silicone resin has a number average molecular weight of 500 to 50,000. The order of units in the preceding equations should not be considered in any way limiting the scope of the invention.

As noted above, the silicone resin (A ″) represented by formula (IV) typically has a number average molecular weight (Mn) of 500 to 50,000. Alternatively, the silicone resin (A ″) is at least 300, alternatively Mn from 1,000 to 3,000, wherein the molecular weight is determined by gel permeation chromatography using a low angle laser light scattering detector, or a refractive index detector and a silicone resin (MQ) standard.

The viscosity of the silicone resin (A ″) at 25 ° C. is typically 0.01 Pa · s to solid, alternatively 0.1 to 100,000 Pa · s, alternatively 1 to 1,000 Pa · s.

Methods of preparing silicone resin (A ″) represented by formula (IV) are well known in the art; many of these resins are commercially available. Silicone resin (A ″) represented by formula (IV) is conventional By co-hydrolysis of an appropriate mixture of chlorosilane precursors in an organic solvent such as toluene. For example, R ¹ R ⁶ ₂ SiO _1/2 units and R ⁶ SiO _3/2 units silicone resin containing the second compound having the first compound and R ⁶ SiCl ₃ having the formula R ¹ R ⁶ ₂ SiCl Can be prepared by simultaneous hydrolysis in toluene, where R ¹ And R ⁶ is as defined and exemplified above. The co-hydrolysis process is defined above in terms of hydrosilylation-cured silicone composition. The co-hydrolyzed reactant may be further "implemented" to the desired degree for controlling the amount and viscosity of the crosslinkable groups.

The Q unit in formula (IV) may be present in the form of discrete particles in the silicone resin (A ″). The particle size is typically between 1 nm and 20 μm. Examples of these particles are 15 nm diameter silica (SiO). _4/2) as particle, but is not limited to this.

The condensation cured silicone composition may further contain inorganic fillers such as silica, alumina, calcium carbonate, and mica.

In another embodiment, the condensation-cured silicone composition comprises the reaction product of a rubber-modified silicone resin (A ′ ″) and other optional components. The rubber-modified silicone resin (A ′ ″) is represented by the formula (i) ^{_{(R 1 R 6 2 SiO 1}} /2) w (R 6 2 SiO 2/2) x (R 6 SiO 3/2) y (SiO 4/2) a silicone resin and (ii) (i) having z of Organosilicon compounds selected from hydrolyzable precursors, and (iii) a silicone rubber having the formula R ⁸ ₃ SiO (R ¹ R ⁸ SiO) _m SiR ⁸ ₃ in the presence of water, (iv) a condensation catalyst, and (v) an organic solvent. Can be prepared by reaction, wherein R ¹ And R ⁶ is as defined and exemplified above, R ⁸ is R ¹ or a hydrolyzable group, m is 2 to 1,000, alternatively 4 to 500, alternatively 8 to 400, w, x, y, And z is as defined and exemplified above, wherein silicone resin (i) has at least two silicon-bonded hydroxy or hydrolyzable groups on average per molecule, and the silicone rubber (iii) is at least 2 on average per molecule Molar ratios of silicon-bonded hydrolyzable groups in the silicone rubber (iii) to silicon-bonded hydroxy or hydrolyzable groups in the silicone resin (i), from 0.01 to 1.5 Alternatively 0.05 to 0.8, alternatively 0.2 to 0.5.

Typically at least 5 mol%, alternatively at least 15 mol%, alternatively at least 30 mol% of the groups R ⁶ in the silicone resin (i) are hydroxy or hydrolyzable groups.

The silicone resin (i) typically has a number average molecular weight (Mn) of at least 300, alternatively 500 to 10,000, alternatively 1,000 to 3,000, wherein the molecular weight is a low angle laser light scattering detector, or refractive index detector. And gel permeation chromatography using a silicone resin (MQ) standard.

Specific examples of the cured silicone resin formed from the silicone resin (i) include, but are not limited to, cured silicone resins having the following formulas:

_{(MeSiO 3/2) n,} (PhSiO 3/2) n,

_{(PhSiO 3/2) 0.4 (} MeSiO 3/2) 0.45 (PhSiO 3/2) 0.1 (phMeSiO 2/2) 0.05, and

_{(PhSiO 3/2) 0.3 (} SiO 4/2) 0.1 (Me 2 SiO 2/2) 0.2 (Ph 2 SiO 2/2) 0.4,

In the above formulas, Me is methyl, Ph is phenyl, the numerical subscripts outside the parentheses represent the mole fraction, and the subscript n has a value such that the silicone resin has a number average molecular weight of 500 to 50,000. The order of units in the preceding equations should not be considered in any way limiting the scope of the invention. The silicone resin (i) may be a single silicone resin or a mixture comprising two or more different silicone resins each having a particular formula.

As used herein, the term “hydrolyzable precursor” means a silane having a hydrolyzable group suitable for use as starting material (precursor) for preparing the silicone resin (i). The hydrolyzable precursor (ii) can be represented by the following formulas R ¹ R ⁸ ₂ SiX, R ⁸ ₂ SiX ₂ , R ⁸ SiX ₃ , and SiX ₄ , wherein R ^{1 ,} R ⁸ and X are defined and exemplified above. As it is.

Particular examples of hydrolyzable precursor (ii) include, but are not limited to, silanes having the following formulas:

Me ₂ ViSiCl, Me ₃ SiCl, MeSi (OEt) ₃ , PhSiCl ₃ , MeSiCl ₃ , Me ₂ SiCl ₂ , PhMeSiCl ₂ ,

SiCl ₄ , Ph ₂ SiCl ₂ , PhSi (OMe) ₃ , MeSi (OMe) ₃ , PhMeSi (OMe) ₂ , and Si (OEt) ₄ ,

In the above formulas Me is methyl, Et is ethyl and Ph is phenyl.

Specific examples of silicone rubber (iii) include, but are not limited to, silicone rubber having the following formulas:

(EtO) ₃ SiO (Me ₂ SiO) ₅₅ Si (OEt) ₃ , (EtO) ₃ SiO (Me ₂ SiO) ₁₆ Si (OEt) ₃ ,

(EtO) ₃ SiO (Me ₂ SiO) ₃₈₆ Si (OEt) ₃ , and (EtO) ₂ MeSiO (PhMeSiO) ₁₀ SiMe (OEt) ₂ ,

In the above formulas Me is methyl and Et is ethyl.

The reaction is usually carried out at room temperature (˜23 ± 2 ° C.) to 180 ° C., alternatively at room temperature to 100 ° C.

The reaction time depends on several factors including the structure of the silicone resin (i) and the silicone rubber (iii), and the temperature. The components are typically allowed to react for a time sufficient to complete the condensation reaction. It is condensation reaction of at least 95 mole percent, alternatively at least 98 mole percent, alternatively at least 99 mole percent of the silicon-bonded hydrolyzable groups originally present in the silicone rubber (iii) as measured by a ²⁹ Si NMR spectrometer. Means that the components are allowed to react until consumed in The reaction time is typically at a temperature of room temperature (˜23 ± 2 ° C.) to 100 ° C. for 1-30 hours. Optimum reaction time can be measured by routine experiments.

Suitable condensation catalysts (iv) are described in more detail below and suitable organic solvents (v) are described above in the context of the rubber-modified silicone resin (A ′). The concentration of the condensation catalyst (iv) is sufficient to catalyze the condensation reaction of the silicone resin (i) and the silicone rubber (iii). Typically, the concentration of the condensation catalyst (iv) is 0.01 to 2% (w / w), alternatively 0.01 to 1% (w / w), alternatively 0.05 to 0.2, based on the weight of the silicone resin (i) % (w / w). The concentration of organic solvent (v) is typically 10 to 95% (w / w), alternatively 20 to 85% (w / w), alternatively 50 to 80% (w) based on the total weight of the reaction mixture. / w).

The concentration of water in the reaction mixture depends on the properties of the group R ^{8 in} the organosilicon compound and the properties of the silicon-bonded hydrolyzable groups in the silicone rubber. When the silicone resin (i) contains hydrolyzable groups, the concentration of water is sufficient to effect hydrolysis of the hydrolyzable groups in the silicone resin (i) and silicone rubber (iii). For example, the concentration of water is typically 0.01 to 3 moles, alternatively 0.05 to 1 mole, per mole of hydrolyzable groups in the silicone resin (i) and the combined silicone rubber (iii). If the silicone resin (i) does not contain hydrolyzable groups, only trace amounts, eg 100 ppm of water, are required in the reaction mixture. Trace amounts of water are commonly present in the reactants and / or solvents.

As noted above, the condensation-cured silicone composition may further comprise a reaction product of the crosslinking agent (B ′). The crosslinker (B ′) may have the formula R ⁷ _q SiX _{4- q} , wherein R ⁷ is C ₁ to C ₈ hydrocarbyl or C ₁ to C ₈ halogen-substituted hydrocarbyl, X is a valence Is a degradable group, q is 0 or 1; The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R ⁷ and the hydrolyzable groups represented by X are as described and exemplified above.

Specific examples of the crosslinking agent (B ′) include MeSi (OCH ₃ ) ₃ , CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ Si (OCH ₂ CH ₂ CH ₃ ) ₃ , and CH ₃ Si [O (CH ₂ ) ₃ CH ₃ ] ₃ , CH ₃ CH ₂ Si (OCH2CH ₃ ) ₃ , C ₆ H ₅ Si (OCH ₃ ) ₃ , C ₆ H ₅ CH ₂ Si (OCH ₃ ) ₃ , C ₆ H ₅ Si (OCH ₂ CH ₃ ) ₃ , CH ₂ = CHSi (OCH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CH ₃ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ , CH ₂ = CHSi (OCH ₂ CH ₂ OCH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ , C ₆ H Alkoxy silanes such as ₅ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , and Si (OC ₃ H ₇ ) ₄ ; Organoacetoxysilanes such as CH ₃ Si (OCOCH ₃ ) ₃ , CH ₃ CH ₂ Si (OCOCH ₃ ) ₃ , and CH ₂ = CHSi (OCOCH ₃ ) ₃ ; CH ₃ Si [ON = C (CH ₃ ) CH ₂ CH ₃ ] ₃ , Si [ON = C (CH ₃ ) CH 2 CH ₃ ] ₄ , and CH ₂ = CHSi [ON = C (CH ₃ ) CH ₂ CH ₃ ] Organoiminooxysilanes such as ₃ ; Organoacetamidosilanes such as CH ₃ Si [NHC (═O) CH ₃ ] ₃ and C ₆ H ₅ Si [NHC (═O) CH ₃ ] ₃ ; Amino silanes such as CH ₃ Si [NH (sC ₄ H ₉ )] ₃ and CH ₃ Si (NHC ₆ H ₁₁ ) ₃ ; And organoaminooxysilanes, but are not limited to these.

The crosslinker (B ′) may be a single silane or a mixture of two or more different silanes, each as described above. In addition, methods for preparing tri- and tetra-functional silanes are well known in the art; Many of these silanes are commercially available.

When used, the concentration of the crosslinking agent (B ′) prior to the formation of the condensation-curable silicone composition is sufficient to cure (crosslink) the condensation-curable silicone resin. The exact amount of crosslinker (B ') depends on the degree of cure desired and the silicone in the crosslinker (B') relative to the number of moles of silicon-bonded hydrogen atoms, hydroxy groups, or hydrolyzable groups in the silicone resin (A "). -Generally increases as the proportion of moles of bonded hydrolyzable groups increases. Typically, the concentration of the crosslinker (B ') is a silicon-bonded hydrogen atom, hydroxy group in the silicone resin (A "). Or 0.2-4 moles of silicon-bonded hydrolyzable groups per mole of hydrolyzable groups. The optimum amount of the crosslinking agent (B ′) can be easily measured by routine experiments.

The condensation catalyst (C) can be any condensation catalyst commonly used to inspire condensation of silicon-bonded hydroxy (silanol) groups to form Si-O-Si linkages. Examples of condensation catalysts include amines; And complexes of lead, tin, zinc and iron with carboxylic acid. In particular, the condensation catalyst (C) comprises tin (II) and tin (IV) compounds such as tin dilaurate, tin dioctoate, and tetrabutyl tin; And titanium compounds such as titanium tetrabutoxide.

When present, the concentration of the condensation catalyst (C) is typically 0.1 to 10% (w / w), alternatively 0.5 to 5% (w / w), based on the total weight of the silicone resin (A ″), Alternatively 1 to 3% (w / w).

When the condensation-cured silicone composition is formed in the presence of the condensation catalyst (C), the condensation-cured silicone composition is typically a 2- wherein the silicone resin (A ″) and the condensation catalyst (C) are present in separate portions. It is formed from a partial composition.

The condensation-cured silicone composition of the present invention is as known in the art and may comprise additional components as described above for the hydrosilylation-cured silicone composition.

In another embodiment, the silicone composition may be a free radical-curable silicone composition. Examples of free radical-cured silicone compositions include peroxide-cured silicone compositions, radiation-cured silicone compositions containing free radical photoinitiators, and high energy radiation-cured silicone compositions. Typically, the free radical-cured silicone composition is a reaction of a silicone resin (A ″ ″) and, optionally, a crosslinking agent (B ″) and / or a free radical initiator (C ″) (eg free radical photoinitiator or organic peroxide). Product.

The silicone resin (A ″ ″) is (i) a method of exposing the silicone resin to radiation having a wavelength of 150 to 800 nm in the presence of a free radical photoinitiator, (ii) the silicone resin (A ″ ″) in the presence of an organic peroxide Under heating, and (iii) any silicone resin that can be cured (ie, crosslinked) by at least one method selected from the method of exposing the silicone resin (A ″ ″) to an electron beam. The silicone resin (A ″ ″) is typically a copolymer containing a T siloxane unit and / or a Q siloxane unit in combination with an M and / or D siloxane unit.

For example, the silicone resin A ″ ″ may have the following formula:

^{_{(R 1 R 9 2 SiO 1}} /2) w "(R 9 2 SiO 2/2) x" (R 9 SiO 3/2) y "(SiO 4/2) z",

Wherein R ¹ is as defined and exemplified above, R ⁹ is R ¹ , alkenyl, or alkynyl, w ″ is 0 to 0.99, x ″ is 0 to 0.99, y ″ is 0 to 0.99, and z "Is 0 to 0.85 and w" + x "+ y" + z "= 1.

The alkenyl groups represented by R ⁹ may be the same or different and as defined and illustrated in the description of R ² above.

The alkynyl groups represented by R ⁹ may be the same or different and typically have 2 to about 10 carbon atoms, alternatively 2 to 6 carbon atoms, ethynyl, propynyl, butynyl, hexynyl, And octynyl, but not limited thereto.

The silicone resin (A ″ ″) typically has a number average molecular weight (Mn) of at least 300, alternatively 500 to 10,000, alternatively 1,000 to 3,000, wherein the molecular weight is a refractive index detector and a silicone resin (MQ). Determined by gel permeation chromatography using a standard.

The silicone resin (A ″ ″), as measured by ²⁹ Si NMR, is less than 10% (w / w), alternatively less than 5% (w / w), alternatively less than 2% (w / w) Silicon-bonded hydroxy groups.

Specific examples of silicone resins (A "") suitable for the purposes of the present invention include, but are not limited to, silicone resins having the following formulas:

_{(Vi 2 MeSi0 1/2)} 0.25 (PhSi0 3/2) 0.75, (ViMe 2 Si0 1/2) 0.25 (PhSi0 3/2) 0.75,

_{(ViMe 2 SiO 1/2)} 0.25 (MeSiO 3/2) 0.25 (PhSiO 3/2) 0.50,

_{(ViMe 2 SiO 1/2)} 0.15 (PhSi0 3/2) 0.75 (Si0 4/2) 0.1 and

_{(Vi 2 MeSiO 1/2)} 0.15 (ViMe 2 SiO 1/2) 0.1 (PhSiO 3/2) 0.75,

In the above formulas, Me is methyl, Vi is vinyl, Ph is phenyl, and the numerical subscripts outside the parentheses represent the mole fraction. The order of units in the preceding equations should not be considered in any way limiting the scope of the invention.

The free radical-cured silicone composition of the method of the invention comprises silicone rubber; Unsaturated compounds; Free radical initiators; Organic solvents; UV stabilizers; Sensitizers; dyes; Flame retardant; Antioxidants; Fillers such as reinforcing fillers, expansion fillers, and conductive fillers; And additional components including, but not limited to, adhesion promoters.

The free radical-cured silicone composition comprises (i) at least one organosilicon compound having at least one silicon-bonded alkenyl group per molecule, (ii) at least one having at least one aliphatic carbon-carbon double bond per molecule And (iii) a reaction product of an unsaturated compound selected from the mixture comprising (i) and (ii), said unsaturated compound having a molecular weight of less than 500. Alternatively, the unsaturated compound has a molecular weight of less than 400 or less than 300. In addition, the unsaturated compound may have a linear, branched, or cyclic structure.

The organosilicon compound (i) may be an organosilane or an organosiloxane. The organosilane may be monosilane, disilane, trisilane, or polysilane. Likewise, the organosiloxane can be disiloxane, trisiloxane, or polysiloxane. Cyclosilanes and cyclosiloxanes typically have 3 to 12 silicon atoms, alternatively 3 to 10 silicon atoms, alternatively 3 to 4 silicon atoms. In acyclic polysilanes and polysiloxanes, the silicon-bonded alkenyl group (s) can be located at the terminal, pendant or at both the terminal and pendant positions.

Specific examples of organosilanes include, but are not limited to, silanes having the following formulas:

Vi ₄ Si, PhSiVi ₃ , MeSiVi ₃ , PhMeSiVi ₂ , Ph ₂ SiVi ₂ , and PhSi (CH ₂ CH = CH ₂ ) ₃ ,

Wherein Me is methyl, Ph is phenyl, and Vi is vinyl.

Specific examples of organosiloxanes include, but are not limited to, siloxanes having the following formulas:

PhSi (OSiMe ₂ Vi) ₃ , Si (OSiMe ₂ Vi) ₄ , MeSi (OSiMe ₂ Vi) ₃ , and Ph ₂ Si (OSiMe ₂ Vi) ₂ ,

In which Me is methyl, Vi is vinyl, and Ph is phenyl.

The organic compound may be any organic compound having at least one aliphatic carbon-carbon double bond per molecule, provided that the compound does not prevent the silicone resin (A "") from curing to form a silicone resin film. Do not. The organic compound may be an alkene, diene, triene, or polyene. In addition, in the acyclic organic compound, the carbon-carbon double bond (s) may be located at the terminal, pendant position or at both the terminal and pendant position.

The organic compound may contain one or more functional groups in addition to aliphatic carbon-carbon double bonds. Examples of suitable functional groups are -O-,> C = O, -CHO, -CO _2- , -C≡N, -NO ₂ ,> C = C <, -C≡C-, -F, -Cl,- Br, and -I, but not limited thereto. Suitability of certain unsaturated organic compounds for use in the free-radical cured silicone compositions of the present invention can be readily determined by routine experimentation.

The organic compound may have a liquid or solid state at room temperature. In addition, the organic compound may be dissolved, partially dissolved or insoluble in the free-radical cured silicone composition prior to curing. The base boiling point of the organic compound, which depends on the molecular weight, structure and number and characteristics of the functional groups in the compound, can vary over a wide range. Typically, the organic compound has a reference boiling point higher than the curing temperature of the composition. Otherwise, significant amounts of organic compounds may be removed by volatilization during curing.

Examples of organic compounds containing aliphatic carbon-carbon double bonds include, but are not limited to, 1,4-divinylbenzene, 1,3-hexadienylbenzene, and 1,2-diethenylcyclobutane.

The unsaturated compound may be a monounsaturated compound or a mixture comprising two or more different unsaturated compounds, each as described above. For example, the unsaturated compound may be a single organosilane, a mixture of two or more different organosilanes, a single organosiloxane, a mixture of two or more different organosiloxanes, a mixture of organosilanes and organosiloxanes, a single organic compound, two or more Mixtures of different organic compounds, mixtures of organosilanes and organic compounds, or mixtures of organosiloxanes and organic compounds.

The concentration of the unsaturated compound is typically 0 to 70% (w / w), alternatively 10 to 50% (w / w), alternatively 20 based on the total weight of the free radical-cured silicone composition prior to curing. To 40% (w / w).

Methods of preparing organosilanes and organosiloxanes containing silicon-bonded alkenyl groups and organic compounds containing aliphatic carbon-carbon double bonds are well known in the art; Many of these compounds are commercially available.

The free radical initiator is typically a free radical photoinitiator or an organic peroxide. In addition, the free radical photoinitiator may be any free radical photoinitiator capable of initiating curing (crosslinking) of the silicone resin upon exposure to radiation having a wavelength of 200 to 800 nm.

Examples of free radical photoinitiators include benzophenones; 4,4'-bis (dimethylamino) benzophenone; Halogenated benzophenones; Acetophenone; α-hydroxyacetophenone; Chloro acetophenones such as dichloroacetophenone and trichloroacetophenone; Dialkoxyacetophenones such as 2,2-diethoxyacetophenone; Α-hydroxyalkylphenones such as 2-hydroxy-2-methyl-1-phenyl-1-propaneone and 1-hydroxycyclohexyl phenyl ketone; Α-aminoalkylphenones such as 2-methyl-4 '-(methylthio) -2-morpholinopropiophenone; Benzoin; Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isobutyl ether; Benzyl ketals such as 2,2-dimethoxy-2-phenylacetophenone; Acylphosphine oxides such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; Xanthone derivatives; Thioxanthone derivatives; Fluorenone derivatives; Methyl phenyl glyoxylate; Acetonaphtone; Anthraquinone derivatives; Sulfonyl chlorides of aromatic compounds; And O-acyl α-oxyminoketones such as 1-phenyl-l, 2-propanedione-2- (0-ethoxycarbonyl) oxime.

Such free radical photoinitiators include phenylmethylpolysilanes as defined by West in U.S. Pat. Aminated methylpolysilanes as defined by Baney et al. In US Pat. No. 4,314,956, the disclosure of which is hereby incorporated by reference as a reference to aminated methylpolysilanes; Methylpolysilanes of Peterson et al. In US Pat. No. 4,276,424, the disclosure of which is hereby incorporated by reference as it relates to methylpolysilanes; And polysilanes such as polysilastyrene as defined by West et al. In US Pat. No. 4,324,901, the disclosure of which is hereby incorporated by reference.

The free radical photoinitiator can be a single free radical photoinitiator or a mixture comprising two or more different free radical photoinitiators. The concentration of the free radical photoinitiator is typically 0.1 to 6% (w / w), alternatively 1 to 3% (w / w), based on the weight of the silicone resin (A "").

The free radical initiator may be an organic peroxide. Examples of organic peroxides include diroyl peroxides such as dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, and bis-2,4-dichlorobenzoyl peroxide; Dialkyl peroxides such as di-t-butyl peroxide and 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane; Dialkyl peroxides such as dicumyl peroxide; alkyl aralkyl peroxides such as t-butyl cumyl peroxide and l, 4-bis (t-butylperoxyisopropyl) benzene; And alkyl aroyl peroxides such as t-butyl perbenzoate, t-butyl peracetate, and t-butyl peroctoate.

The organic peroxide may be a single peroxide or a mixture comprising two or more different organic peroxides. The concentration of the organic peroxide is typically 0.1 to 5% (w / w), alternatively 0.2 to 2% (w / w), based on the weight of the silicone resin (A ″ ″).

The free radical-cured silicone composition can be further formed in the presence of at least one organic solvent. The organic solvent may be any aprotic or dipolar aprotic organic solvent that does not react with the silicone resin (A ″ ″) or additional component (s) and is miscible with the silicone resin (A ″ ″). . Examples of organic solvents include saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; Cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Cyclic ethers such as tetrahydrofuran (THF) and dioxane; Ketones such as methyl isobutyl ketone (MIBK); Halogenated alkanes such as trichloroethane; And halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene. The organic solvent may be a single organic solvent or a mixture comprising two or more different organic solvents, each as described above.

The concentration of the organic solvent is typically from 0 to 99% (w / w), alternatively from 30 to 80% (w / w), alternatively from 45 to 60, based on the total weight of the free radical-cured silicone composition before curing. % (w / w).

When the free-radical cured silicone composition as described above is formed from one or more additional components, such as free radical initiators, the free-radical cured silicone composition is selected from the silicone resin (A ″ ″) and optionally in a single portion. It may be formed from a one-part composition comprising component (s) or a multi-part composition comprising components in two or more portions.

In addition to the silicone compositions as described above, other cured silicone compositions are also suitable for the purposes of the present invention. For example, suitable silicone compositions are described in PCT application JP2006 / 315901 for the purposes of the present invention, the contents of which are hereby incorporated by reference as to a silicone composition. In addition, polysilsesquioxanes may also be suitable for the purposes of the present invention.

As described above, the reinforcement silicon layer 16 includes a fiber reinforcement agent. The fiber reinforcement can be any reinforcement comprising fibers. The fiber reinforcement typically has a Young's modulus of at least 3 GPa at 25 ° C. For example, the reinforcing agent typically has a Young's modulus of 3 to 1,000 GPa, alternatively 3 to 200 GPa, alternatively 10 to 100 GPa at 25 ° C. In addition, the reinforcing agents typically have a tensile strength of at least 50 MPa at 25 ° C. For example, the reinforcing agent typically has a tensile strength of 50 to 10,000 MPa, alternatively 50 to 1,000 MPa, alternatively 50 to 500 MPa at 25 ° C.

The fiber reinforcing agent is a fabric, such as cloth; Nonwovens, eg mats or rovings; Or loose (individual) fibers. The fibers in the reinforcement are typically cylindrical in shape and have a diameter of 1 to 100 μm, alternatively 1 to 20 μm, alternatively 1 to 10 μm. Loose fibers are typically continuous, meaning that the fibers extend through the reinforcing silicon layer 16 in a generally continuous manner.

The fiber reinforcement is typically heat-treated before use to remove organic contaminants. For example, the fiber reinforcement is typically heated at an elevated temperature, for example at 575 ° C. for a suitable time, for example 2 hours.

Specific examples of fiber reinforcements suitable for the purposes of the present invention include glass fibers; Quartz fiber; Graphite fibers; Nylon fibers; Polyester fibers; Aramid fibers such as Kevlar® and Nomex®; Polyethylene fibers; Polypropylene fibers; Silicon carbide fibers; Alumina fibers; Silicon oxycarbide fibers; Metal wires such as steel wires; And reinforcing agents including combinations thereof, but is not limited thereto.

As noted above, the fiber reinforcement is typically impregnated with the silicone composition. The fiber reinforcement is impregnated with the silicone composition using various methods. For example, the silicone composition as described above may be applied to a release liner to form a silicone film. The silicone composition may be applied to the release liner using conventional coating techniques such as spin coating, dipping, spraying, brushing, or screen-printing. The silicone composition is applied in an amount sufficient to impregnate the fiber reinforcement. The release liner may be any rigid or flexible material having a surface from which the reinforced silicon layer 16 can be removed without damage by lamination removal after the silicone resin has cured. Examples of release liners include, but are not limited to, nylon, polyethylene terephthalate, and polyimide.

The fiber reinforcement is then embedded in the silicone film to form an embedded fiber reinforcement. The fiber reinforcement may be embedded in the silicone film by simply placing the reinforcement on the silicone film and allowing the silicone composition to impregnate the reinforcement. However, it should be appreciated that the fiber reinforcement may be first deposited onto the release liner, followed by application of the silicone composition onto the fiber reinforcement. In another embodiment, where the fiber reinforcement is a woven or nonwoven fabric, the reinforcement may be impregnated with the silicone composition by passing it through the silicone composition without the use of a release liner. The fabric is typically passed through the silicone composition at a rate of 1 to 1,000 cm / s at room temperature (˜23 ± 2 ° C.).

The embedded fiber reinforcement is then optionally degassed. The embedded fiber reinforcement may be degassed by application to vacuum at a temperature between room temperature (˜23 ± 2 ° C.) and 60 ° C. for a time sufficient to remove trapped air in the embedded reinforcement. For example, the embedded fiber reinforcement can be degassed by applying it at a pressure of 1,000 to 20,000 Pa, typically for 5 to 60 minutes at room temperature.

After degassing, additional silicone composition is applied to the embedded fiber reinforcement to form the impregnated fiber reinforcement. The silicone composition may be applied to the degassed fiber reinforcement using conventional methods as described above. Additional degassing and application cycles of the silicone composition may occur.

The impregnated fiber reinforcement may be compressed to remove excess silicone composition and / or trapped air and to reduce the thickness of the impregnated fiber reinforcement. The impregnated fiber reinforcement may be compressed using conventional equipment such as stainless steel rollers, hydraulic presses, rubber rollers, or laminating roll sets. The impregnated fiber reinforcement is typically compressed at a pressure of 1,000 Pa to 10 MPa and at room temperature (˜23 ± 2 ° C.) to 50 ° C.

The impregnated fiber reinforcement is heated at a temperature sufficient to cure the silicone composition and form the reinforcement silicone layer 16. The impregnated fiber reinforcement may be heated at atmospheric pressure, sub-atmospheric or atmospheric-excess pressure. The impregnated fiber reinforcement is typically heated at ambient temperature from room temperature (˜23 ± 2 ° C.) to 250 ° C., alternatively from room temperature to 200 ° C., alternatively from room temperature to 150 ° C. The impregnated fiber reinforcement is heated for a time sufficient to cure (crosslink) the silicone composition. For example, the impregnated fiber reinforcement is typically heated at a temperature of 150-200 ° C. for 0.1-3 hours.

Alternatively, the impregnated fiber reinforcement may be heated in a vacuum at a temperature of 100 to 200 ° C. and a pressure of 1,000 to 20,000 Pa for 0.5 to 3 hours to form the reinforced silicon layer 16. The impregnated fiber reinforcement may be heated in vacuo using conventional vacuum bagging processes. In a typical process, a bleeder (e.g. polyester) is applied over the impregnated fiber reinforcement, a breather (e.g. nylon, polyester) is applied over the bleeder and a vacuum bagging film (e.g., mounted with a vacuum nozzle) , Nylon) is applied over the breather, the assembly is sealed by tape, a vacuum (eg 1,000 Pa) is applied to the sealed assembly, and the vacuumed bag is heated as described above.

The thickness of the reinforced silicon layer 16 depends on the intended use of the composite article 10. Typically, the reinforced silicon layer 16 has a thickness of at least 1 mil, more typically 2-100 mils, most typically about 5 mils.

The reinforced silicon layer 16 is disposed adjacent to and in contact with the first window layer 14. More specifically, the reinforced silicon layer 16 is bonded to the first window layer 14. In one embodiment, as shown in FIG. 2, the reinforced silicon layer 16 may be formed directly onto the first window layer 14. In this embodiment, the silicone composition comprises a cured silicone composition and at least one functional group prior to the curing step to bond the reinforced silicone layer 16 to the first window layer 14. The at least one functional group can be selected from, but is not limited to, a group of silanol groups, alkoxy groups, epoxy groups, silicon hydride groups, acetoxy groups, and combinations thereof.

As indicated above, in order to form the reinforcement silicon layer 16 directly onto the first window layer 14, the impregnated fiber reinforcement is formed as described above. The impregnated fiber reinforcement is then placed over the first window layer 14 prior to fully curing the impregnated fiber reinforcement. Once the impregnated fiber reinforcement is disposed over the first window layer 14, the impregnated fiber reinforcement is heated to cure the silicone composition, to form the reinforcement silicon layer 16 and to form the reinforcement silicon layer 16 first. It is bonded onto the window layer 14. When the reinforced silicon layer 16 is formed directly onto the first window layer 14, the first glassy material used to form the first window layer 14 may be used to cure the silicone composition without degradation or deformation. It is important to ensure that it can withstand the temperatures used for this purpose. This may especially be the case when the first glassy material carbonaceous polymer is included.

In another embodiment, as shown in FIG. 3, the first pane 12 may further include an adhesive layer 26 disposed between the reinforced silicon layer 16 and the first window layer 14. . More specifically, the reinforced silicon layer 16 is adhered to the first window layer 14 by an adhesive layer 26. The adhesive layer 26 typically comprises a silicone-based adhesive; It should be appreciated that any adhesive suitable for bonding silicone to glass may be suitable for the purposes of the present invention. Such silicone-based adhesives may provide additional fire resistance to the composite article 10 which may not be possible by using primarily carbon-based adhesives. The silicone-based adhesive typically includes at least one functional group for adhering the adhesive layer 26 to the reinforced silicon layer 16 and for adhering the adhesive layer 26 to the first window layer 14. The at least one functional group can be selected from, but is not limited to, a group of silanol groups, alkoxy groups, epoxy groups, silicon hydride groups, acetoxy groups, and combinations thereof. Such silicone-based adhesives are known in the art. The silicone-based adhesive may be provided as a one part or multi-part system. In one embodiment, the adhesive may be formed from the same silicone composition used to form the reinforcement silicone layer 16.

Typically, as shown in FIG. 4, the first pane 12 is formed from additional glassy material and is disposed adjacent to and in contact with the reinforced silicon layer 16 opposite the first window layer 14. It further comprises a window layer 28. That is, the reinforced silicon layer 16 is typically sandwiched between the first window layer 14 and the additional window layer 28 to protect the reinforced silicon layer 16 from being scratched or otherwise damaged. The additional window layer 28 may be the same or different than the first window layer 14, and the additional glassy material may be the same or different from the first glassy material. For example, the first window layer 14 and the additional window layer 28 may have different thicknesses and may be formed from the different glassy materials described above.

As shown in FIG. 5, the first pane 12 may include an additional adhesive layer 26 disposed between the reinforced silicon layer 16 and the additional window layer 28. The adhesive layer 26 is as described above.

The composite article 10 further comprises a second pane 18. Typically, as shown in FIG. 6, the second pane 18 includes a second window layer 22 formed from a second glassy material. The second window layer 22 may be the same as or different from the first window layer 14 and the additional window layer 28, and the second glassy material is the same as the first glassy material and the additional glassy material. Or may be different. For example, first window layer 14 and second window layer 22 and additional window layer 28 may have different thicknesses and may be formed from different glassy materials as described above.

The second pane may further include a second silicon layer 32. The second silicon layer 32 is typically disposed adjacent to and in contact with the second window layer 22. The second silicon layer 32 is bonded to the second window layer 22 in the same manner as the reinforced silicon layer 16. More specifically, as shown in FIG. 6, the second silicon layer 32 may be directly formed on the second window layer 22. Alternatively, as shown in FIG. 7, the composite article 10 may further include an adhesive layer 26 disposed between the second silicon layer 32 and the second window layer 22. The adhesive layer 26 is as described above. The second silicon layer 32 may further include a fiber reinforcement, and the second silicon layer 32 including the fiber reinforcement may be manufactured in the same manner as the reinforcement silicon layer 16 described above. . Alternatively, the second silicon layer 32 can be formed in the absence of fiber reinforcement. The second silicone layer 32 may be the same as or different from the reinforced silicone layer 16 in terms of thickness, type of fiber reinforcement, and type of cured silicone composition.

As shown in FIG. 8, the second pane 18 is formed from an additional glassy material and is disposed adjacent to and in contact with the second silicon layer 32 opposite the second window layer 22. The window layer 28 may be further included. That is, the second silicon layer 32 may be sandwiched between the second window layer 22 and the additional window layer 28 to protect the second silicon layer 32 from being scratched or otherwise damaged. have. Another adhesive layer 26 may be disposed between the second silicon layer 32 and the additional window layer 28 to bond the second silicon layer 32 and the additional window layer 28.

Referring to FIGS. 1 and 1A, the second pane 18 leaves space from the first pane 12 to define a gap 20 between the first pane 12 and the second pane 18. The composite article 10 further includes a frame 24 disposed adjacent to and in contact with the first pane 12 and the second pane 18. The frame 24 surrounds the gap 20 between the first pane 12 and the second pane 18 and maintains the first pane 12 and the second pane 18 in a spaced relationship. . The frame 24 is typically disposed adjacent the peripheral edges of the first pane 12 and the second pane 18, and the frame 24 is the first pane 12 and the second pane 18. It may comprise a continuous strip of material extending unimpeded adjacent to the peripheral edges of the. Although the frame 24 appears to stay in the gap 20 in the figures, the frames 24 all hold the first pane 12 with space from the second pane 18 and the gap 20 It should be appreciated that other arrangements of the frame 24 are also possible, as long as they enclose it. In addition, the gap 20 may be in fluid communication with an ambient atmosphere, and by enclosing the gap 20, the frame 24 does not necessarily seal the gap 20 from the surrounding environment. You have to be aware. As such, by "enclosing" the gap 20, partial envelopment is expected in addition to the complete envelop. Thus, the frame 24 may be discontinuous. However, in one embodiment, the frame 24 may seal the gap 20.

In one embodiment, the frame 24 is formed from an adhesive. As such, the frame 24 may be directly bonded to the first pane 12 and the second pane 18. The adhesive may comprise a silicone based adhesive as described above for the adhesive layer 26; It should be appreciated that any adhesive suitable for adhering to glass may be suitable for the purposes of the present invention. The use of a silicone based adhesive for the frame 24 may further improve the fire resistance of the composite article 10 as compared to the use of other materials for the frame 24.

The frame 24 may be formed by providing an adhesive of at least one strip and adhering the strip to the first pane 12 and / or the second pane 18. That is, the adhesive is typically provided in a strip having a width of about 0.5 cm to 10 cm and a length corresponding to the length of the edge of the first pane 12 or the second pane 18. It should be understood that the width of the strip depends on the overall size of the first pane 12 and the second pane 18. That is, larger first pane 12 and larger second pane 18 may require a wider strip than is required for smaller first pane 12 and smaller second pane 18. It should be appreciated that the frame 24 may be formed from one continuous strip of adhesive or a plurality of strips of adhesive. The thickness of the frame 24 depends on the intended use of the composite article 10. The frame 24 typically has a thickness of about 0.1 mm to about 5 mm, alternatively about 1 mm to about 3 mm.

Alternatively, the frame 24 may be formed from any non-adhesive material suitable for separating the first pane 12 and the second pane 18. Suitable materials for separating the first pane 12 and the second pane 18 include, but are not limited to, plastics, wood, paper, metals, foaming agents, adhesives, and combinations thereof, in this embodiment. The frame 24 is typically adhered to the first pane 12 and the second pane 18 by the silicone adhesive as described above. However, it should be appreciated that any adhesive may be used. In addition, the frame 24 may be shaped to mechanically connect the first pane 12 and the second pane 18. Such arrangements are known in the art.

Due to the presence of the gap 20 between the first pane 12 and the second pane 18, the composite article 10 exhibits good thermal insulation and sound insulation. The width of the gap 20 depends on the intended use for the composite article 10. The gap 20 typically has a width of about 1 mm to about 30 mm, alternatively about 5 mm to about 25 mm, alternatively about 10 mm to about 20 mm. In one embodiment, the pressure inside the gap 20 may be less than about 0.1 atm to effectively create a vacuum in the gap 20. In another embodiment, an insulator is disposed inside the gap 20. Any suitable insulator known in the art to provide insulation and sound insulation can be disposed within the gap 20. For example, the insulator can be selected from the group of air, argon, helium, nitrogen gas, and combinations thereof.

In another embodiment, as shown in FIG. 9, the composite article 10 may include a third pane 30. The third pane 30 typically includes a third window layer 36 formed from a third glassy material and a third silicon layer 34. The third window layer 36 may be the same as or different from the first window layer 14, the additional window layer 28, and the second window layer 22. Likewise, the third glassy material may be the same or different than the first glassy material, the additional glassy material, and / or the second glassy material. As described above, the third pane 30 may be independently configured in the same manner as the first pane 12 and the second pane 18. The third silicon layer 34 may further include a fiber reinforcement, and the third silicon layer 34 including the fiber reinforcement may be manufactured in the same manner as the reinforcement silicon layer 16 described above. Alternatively, the third silicon layer 34 can be formed in the absence of a fiber reinforcement. The third silicon layer 34 may be the same or different from the reinforcement silicon layer 16 and / or the second silicon layer 32 in terms of thickness, type of fiber reinforcement, or type of cured silicone composition.

As shown in FIG. 9, the third pane 30 is disposed adjacent and in contact with the first window layer 14 to provide additional structural stiffness and fire resistance to the composite article 10. It should be appreciated that the composite article 10 of the present invention may include additional panes 12, 18, 30 to provide additional structural stiffness and fire resistance to the composite article 10.

In another embodiment, as shown in FIG. 10, the third pane 30 may leave a space from the first pane 12 and the second pane 18, with at least one gap 20 therebetween. It can be defined. That is, the composite article 10 may include a plurality of gaps 20. Additional frame 24 may be used to maintain gap 20 as needed. The number of gaps 20 depends on the desired insulation and sound insulation, structural stiffness, fire resistance performance ratings, and mechanical / thermal shock resistance requirements of the composite article 10. In general, multiple gaps 20 in the composite article 10 provide greater thermal insulation and sound insulation to the composite article 10.

The low E coating can be disposed on or within at least one of said panes. More specifically, a low E coating can be disposed on the outer surface of the at least one pane. Alternatively, a low E coating may be disposed in at least one pane, such as between the window layer and the reinforced silicon layer.

The composite article 10 of the present invention has excellent heat insulation and sound insulation. More specifically, the composite article 10 of the present invention typically has a soundproof rating of at least STC 31 in accordance with ASTM E90. The composite article 10 of the present invention typically has an insulation rating (measured as "U value") of at least 0.55 in accordance with ASTM E2188.

The composite article 10 of the present invention has excellent fire resistance. More specifically, the composite article 10 of the present invention is typically at least 30 according to at least one of ASTM E 119-05a, ASTM E 2010-01, and ASTM E 2074-00 without hose stream impact. Has a fire resistance rating of min. The fire rating is an indicator of the fire resistance of the composite article 10 and is a measure of how long it will take to form a gap in the composite article 10 when exposed to heat provided by the furnace. In order to establish a fire rating according to ASTM E 119-05a, the composite article 10 is mounted onto one opening of the furnace, the flame starts in the furnace to raise the temperature inside the furnace from room temperature to about 200 ° F, The supply of fuel to the flame is gradually increased to generate the desired temperature profile, reaching a temperature of about 1950 ° F. at the end of the 190 minute period. Although the gap is formed in the composite article 10 during exposure to heat, the glassy material used to form the window layer of the composite article 10 is typically melted and the reinforced silicon layer 16 is typically It burns black.

Even when a gap is formed in the composite article 10 of the present invention, the composite article 10 can maintain substantial structural integrity due to the presence of the fiber reinforcing agent in the reinforcing silicone layer 16. More specifically, the composite article 10 will typically not collapse to its own weight regardless of the degree of charring due to the presence of the fiber reinforcement.

The following examples are intended to illustrate the invention and should not be considered in any way limiting the scope of the invention.

Example 1

The composite article is formed by providing a first pane, a second pane with a space to define a gap therebetween, and a frame disposed adjacent to and in contact with the first pane and the second pane. . The first pane, the second pane, and the frame surround a gap between the first pane and the second pane.

More specifically, the first window layer, the second window layer, and the additional window layer are formed from annealed float glass having a thickness of about 0.125 inches. Each of the first window layer, the second window layer, and the additional window layer has a width of about 6 inches, a length of about 6 inches, and four edges. The first window layer, the second window layer, and the additional window layer are washed with soapy water, rinsed with deionized water and dried before use.

The adhesive layer is formed from an adhesive. The adhesive comprises 60% by weight of vinyl-terminated polydimethylsiloxane fluid and 40% by weight of trimethylsiloxy surface treated fumed silica, an equivalent molar amount of SiH equal to the molar amount of vinyl in the polydimethyl-methylhydrogen-siloxane and polydimethylsiloxane fluid, and Prepared by mixing 10 ppm Pt (O) and divinyltetramethyldisiloxane as complexes. The adhesive is commercially available from Dow Corning Corporation, Midland, Michigan. The adhesive is extruded onto the polysulfonate film and partially cured to form an adhesive layer. The adhesive layer is peeled off from the polysulfonate film and adhered to the first window layer.

The reinforcing silicone layer comprises a cured silicone composition and a fiber reinforcing agent. The cured silicone composition is formed from a liquid silicone resin comprising a vinyl-terminated phenyl silsesquioxane resin and a liquid SiH-functional crosslinker commercially available from Dow Corning Corporation, Midland, Michigan. The fiber reinforcement includes Style 106 glass fabrics commercially available from BGF Industries, Greensboro, North Carolina, and has a thickness of about 1.5 mils. The reinforced silicone layer is prepared by saturating the fiber reinforcement with a mixture of silicone resin and crosslinking agent and curing in an oven. The reinforced silicon layer is bonded to the adhesive layer opposite the first window layer.

To form the first pane, an additional adhesive layer is bonded to the reinforced silicon layer and the additional window layer is bonded to an additional adhesive layer opposite the reinforced silicon layer. The first pane is enclosed in a vacuum bag and placed in an oven to cure under vacuum. The oven temperature rises from the ambient temperature at a rate of about 1 ° C./minute until the oven temperature reaches 130 ° C. The oven temperature is maintained at 130 ° C. for 30 hours. After 30 hours, the oven is switched off and cooled. After cooling, the first pane is removed from the vacuum bag, washed and dried. The first pane can be represented as: G ₁ / AFA / G _A , where G ₁ = first window layer, A = adhesive layer (or additional adhesive layer), and F = reinforced silicon layer, G _A = addition Window layer.

To form the frame, an adhesive is prepared according to the method described above for producing the adhesive layer. The adhesive is formed into a layer having a thickness of about 2 mm and each strip is cut into four strips having a width of 1 cm. The four strips are arranged adjacent to and in contact with the edge of the first pane.

To form the composite article, the second pane comprising a second window layer is disposed adjacent to and in contact with the frame to define a gap. The composite article is annealed at 150 ° C. for 30 minutes under pressure applied in parts by weight on the composite article to seal the gap. The resulting composite article can be represented by the following formula:

G ₁ / AFA / G _A / B / G ₂

Wherein G ₁ = first window layer, A = adhesive layer, and F = silicone resin layer, G _A = additional window layer, B = frame, and G ₂ = second window layer.

The composite article of Example 1 provides sound insulation graded at least as STC 31 according to ASTM E90. The composite article of Example 1 has a fire rating of at least 30 minutes according to ASTM E 119-05a without a hose stream impact. To test the fire resistance of the composite article of Example 1, the composite article is mounted onto the opening of the furnace with one side of the composite article exposed to the ambient atmosphere. The furnace is heated at the rate indicated in ASTM E 119.

Example 2

The composite article is formed by providing two panes made in the same manner as the first pane of Example 1, and a frame of Example 1. To form the composite article of Example 2, the two panes are spaced from each other to define a gap between them. The frame is disposed between and bonded to the two panes to enclose the gap between the two panes. The composite article is annealed at 150 ° C. for 30 minutes under pressure applied in parts by weight on the composite article to seal the gap. The resulting composite article of Example 2 can be represented by the following formula:

G ₁ / AFA / G _A / B / G _A / AF ₂ A / G ₂

Wherein G ₁ = first window layer of Example 1, A = adhesive layer of Example 1, and F = reinforced silicon layer of Example 1, G _A = additional window layer of Example 1, B = frame of Example 1, F ₂ = Reinforced silicon layer of Example 1, and G ₂ = second window layer of Example 1.

The composite article of Example 2 provides sound insulation graded at least as STC 31 according to ASTM E90. The composite article of Example 2 has a fire rating of at least 30 minutes in accordance with ASTM E 119-05a without hose stream impact. Fire resistance is tested in the same manner as outlined in Example 1.

Example 3

The composite article is formed by providing the composite article of Example 1, an additional reinforced silicon layer, and an additional window layer.

To form the composite article of Example 3, the additional window layer is formed in the same manner as the window layer of Example 1. Laminates comprising an additional window layer and an additional silicon layer are prepared by adhering the additional silicon layer to the additional window layer through an adhesive layer, and then adhering another adhesive layer to the additional silicon layer opposite the additional window layer. do. That is, the additional silicon layer is disposed between two adhesive layers, and the additional window layer is bonded to one of the adhesive layers. The laminate can be represented by the following formula:

G _A / AF ₂ A

Wherein G _A = additional window layer, A = adhesive layer, and F ₂ = additional silicon layer.

To form the composite article of Example 3, the laminate is bonded to the composite article of Example 1 through an adhesive layer freely left in the laminate. The composite article of Example 3 can be represented by the following formula:

G _A / AF ₂ A / G ₁ / AFA / G _A / B / G ₂

Wherein G _A = additional window layer, A = adhesive layer, F ₂ = additional silicon layer, G ₁ = first window layer, and F = reinforced silicon layer, B = frame, and G ₂ = second window layer.

The composite article of Example 3 provides sound insulation graded at least as STC 31 according to ASTM E90. The composite article of Example 3 has a fire rating of at least 30 minutes in accordance with ASTM E 119-05a without hose stream impact. Fire resistance is tested in the same manner as outlined in Example 1.

Apparently, many modifications and variations of the present invention are possible in light of the above teachings, and the invention may be practiced otherwise than as set forth in the appended claims.

As mentioned above, the present invention is used to provide a composite article comprising a first pane comprising a first window layer formed of a glassy material and a reinforced silicon layer.

Claims (28)

As a composite article, A first window layer formed from the first glassy material, A reinforcing silicone layer disposed adjacent and in contact with the first window layer and comprising a cured silicone composition and a fiber reinforcement; A first pane comprising: A second pane that is spaced apart from the first pane and that defines a gap therebetween; A frame disposed adjacent to and in contact with the first pane and the second pane, and surrounding a gap between the first pane and the second pane; Comprising a composite article. The composite article of claim 1, wherein the fiber reinforcing agent is further defined by at least one of a woven fabric, a nonwoven fabric, and loose fibers. The fiber reinforcing agent according to claim 1 or 2, wherein the fiber reinforcing agent is glass fiber, quartz fiber, graphite fiber, nylon fiber, polyester fiber, aramid fiber, polyethylene fiber, polypropylene fiber, silicon carbide fiber, alumina fiber, silicone oxy. A composite article comprising a fiber selected from the group consisting of carbide fibers, metal wires, and combinations thereof. The composite article of claim 1, wherein the fiber reinforcing agent is impregnated with the cured silicone composition. The composite article of claim 1, wherein the cured silicone composition is further defined as a hydrosilylation-cured silicone composition. The method of claim 5, wherein the hydrosilylation-cured silicone composition is (A) silicone resin, (B) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule in an amount sufficient to cure the silicone resin; (C) in the presence of a catalytic amount of hydrosilylation catalyst A composite article comprising a reaction product. The composite article of claim 1, wherein the cured silicone composition is further defined as a condensation-cured silicone composition. The method of claim 7, wherein the condensation-cured silicone composition is (A ″) a silicone resin having at least two of a silicon-bonded hydroxy group or a hydrolyzable group, Optionally, a (B ') crosslinker having a silicon-bonded hydrolyzable group, Optionally, (C) the catalytic amount in the presence of a condensation catalyst A composite article comprising a reaction product. The composite article of claim 7 or 8, wherein the condensation-cured silicone composition further comprises an inorganic filler in particulate form. The composite article of claim 1, wherein the cured silicone composition is further defined as a free radical-cured silicone composition. The composite article of claim 1, wherein the silicone composition comprises at least one functional group prior to a curing step to adhere the cured silicone composition to the first window layer. The composite article of claim 11, wherein the at least one functional group is selected from silanol groups, alkoxy groups, epoxy groups, silicon hydride groups, acetoxy groups, and combinations thereof. The composite article of claim 1, further comprising an adhesive layer disposed between the reinforced silicon layer and the first window layer. The composite article of claim 13, wherein the adhesive layer comprises a silicone based adhesive. The composite article of claim 1, wherein the gap has a width of about 1 mm to about 30 mm. The composite article of claim 1, wherein the pressure in the gap is less than about 0.1 atm. The composite article of claim 1, wherein one insulator is disposed in the gap. 18. The composite article of claim 17, wherein the insulator is selected from the group of air, argon, helium, nitrogen gas, and combinations thereof. 19. The composite article of claim 1, wherein the frame is formed of one adhesive. The composite article of claim 1, wherein the frame is adhered to the first pane and the second pane. 21. The composite article of any one of the preceding claims, wherein the first pane further comprises an additional window layer in contact with the reinforcement silicon layer and disposed opposite the first window layer. 22. The method of claim 1, wherein the second pane comprises a second window layer formed of a second glassy material and a second silicon layer disposed adjacent to and in contact with the second window layer. , Composite articles. 23. The glass pane of claim 1 further comprising a third pane comprising a third window layer formed from a third glassy material and a third silicon layer and disposed adjacent to and in contact with the first window layer. Comprising a composite article. 23. The method of any one of claims 1 to 22, wherein the third is formed from the third glassy material and the third silicon layer and is spaced apart from the first pane and the second pane and defines at least one gap therebetween. The composite article further comprising a third pane comprising a window layer. The composite article of claim 1, wherein the first glassy material is selected from the group of polymethyl methacrylate, polycarbonate, and polysulfonate. 26. The fire rating of any of claims 1-25, having a fire rating of at least 30 minutes according to at least one of ASTM E 119-05a, ASTM E 2010-01, and ASTM E 2074-00. Composite articles. 27. The composite article of any one of the preceding claims, further comprising a low E coating disposed over at least one of the panes. 28. The composite article of any one of the preceding claims, further comprising a low E coating disposed within at least one of the panes.

Images