JP7359523B2 - Hydrosilylation reaction curable compositions to form silicone pressure sensitive adhesives that adhere to optical silicone elastomers and methods of preparation and use in flexible display devices - Google Patents

Description

(Cross reference to related applications)
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(Field of invention)
SILICONE PRESSURE SENSITIVE ADHESIVES FIELD OF THE INVENTION This invention relates to silicone pressure sensitive adhesives and methods of their preparation and use. In particular, the present invention relates to hydrosilylation curable compositions that cure to form silicone pressure sensitive adhesives suitable for use in flexible display devices.

Introduction Flexible displays have been developed that can be deformed, for example by bending, folding, rolling, rolling, or stretching. Flexible display devices can be modified depending on consumer needs or usage conditions of the flexible display device. Typically, the various parts of the display are made of multiple layers, and when the flexible display is deformed, the layers adhere to each other and do not suffer damage that would cause component failure. is important.

Optical silicone elastomers can be useful for forming light-transmissive (eg, transparent or translucent) layers in flexible displays. Optical silicone elastomers are known in the art and are commercially available. For example, SILASTIC™ MS-1001, MS-1002, MS-1003, MS-4001, MS-4002, and MS-4007 are moldable optical silicone elastomers, and SYLGARD™ 182, 184, and 186 are also optical silicone elastomers, all of which are commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

However, optical silicone elastomers such as those described above can have the disadvantage that they are difficult to adhere to other layers in flexible displays. Therefore, there is an industrial need for silicone pressure sensitive adhesives that can adhere to optical silicone elastomers and do not cause failure in flexible displays.

Hydrosilylation reaction curable compositions can form silicone pressure sensitive adhesives. Methods of manufacturing compositions and methods of manufacturing articles using the compositions are provided. The article may include parts of a flexible display device.

FIG. 1 shows a partial cross-sectional view of a component 100 of a flexible display device.

Reference Number 100 Portion of flexible display component 101 Substrate 101b Surface of substrate 101 102 Silicone pressure sensitive adhesive 102a Surface of silicone pressure sensitive adhesive 102 102b Opposite surface of silicone pressure sensitive adhesive 102 103 Optical silicone elastomer 103a Surface of optical silicone elastomer 103

Hydrosilylation reaction curable compositions for forming silicone pressure sensitive adhesives are
(A) a polydiorganosiloxane gum component,
Based on the total weight of starting materials (A) to (F), 32.2% to 44.6% by weight of (A-1) unit formula (R ^M ₂ R ^U SiO _1/2 ) ₂ (R ^M ₂ SiO _2/2 ) _a aliphatically unsaturated polydiorganosiloxane gum, where each R ^M is an independently selected monovalent group of 1 to 30 carbon atoms containing no aliphatic unsaturation. is a hydrocarbon group, each R ^U is an independently selected monovalent aliphatic unsaturated hydrocarbon group of 2 to 30 carbon atoms, and the subscript a represents 50 to 200 carbon atoms in the polydiorganosiloxane gum. (A-1) aliphatic unsaturated polydiorganosiloxane gum having a value sufficient to provide plasticity of;
0 to <1.2% by weight of (A-2) hydroxyl-terminated polydiorganosiloxane gum of the unit formula ((HO)R ^M ₂ SiO _1/2 ) ₂ (R ^M ₂ SiO _2/2 ) _a', , where each R ^M is an independently selected monovalent hydrocarbon group of 1 to 30 carbon atoms containing no aliphatic unsaturation, and each subscript a' refers to the polydiorganosiloxane gum. (A-2) a hydroxyl-terminated polydiorganosiloxane gum having a value sufficient to provide a plasticity of 20 mils (0.51 mm) to 80 mils (2.03 mm);
However, the weight ratio of (A-1) aliphatic unsaturated polydiorganosiloxane gum to (A-2) hydroxyl-terminated polydiorganosiloxane gum {(A-1):(A-2) ratio}≧37.4:1 (A) a polydiorganosiloxane gum component,
(B) a polyorganosilicate resin component,
Based on the total weight of starting materials (A) to (F), 44.8% to 58.9% by weight of (B-1) unit formula: (R ^M ₃ SiO _1/2 ) _z (SiO _{4/ 2} ) _o Z _p capped resins, where Z is a hydrolyzable group and the subscript p represents a hydrolyzable group content of 0 to 2% maximum in the capped resin. and the subscripts z and o have values such that z>4, o>1, and the quantity (z+o) is between 500 g/mol and 2,700 g in the capped resin. (B-1) a capped resin having a value sufficient to provide a number average molecular weight of /mol;
Based on the total weight of starting materials (A) to (F), 0 to 7% by weight of (B-2) unit formula (R ^M ₃ SiO _1/2 ) _z' (SiO _4/2 ) _o' Z _{p '} , where the subscript p' has a value sufficient to give the uncapped resin a hydrolyzable group content of >3% to 10%. , the subscripts z' and o' have values where z'>4, o'>1, and the quantity (z'+o') is between 500 g/mol and 5,000 g/mol for the uncapped resin. (B-2) an uncapped resin having a value sufficient to give a number average molecular weight of mol, (B-1) a capped resin and (B-2) an uncapped resin. are present in a total amount of 44.8% to 65.8% by weight based on the total weight of starting materials (A) to (F), with the exception of (B-2) uncapped resin: (B -1) The weight ratio of the capped resin {(B-2):(B-1) ratio} is 0.032:1 to 0.125:1,
(A) the polydiorganosiloxane gum component and (B) the polyorganosilicate resin component are present in a weight ratio of (B):(A) (resin:gum ratio)≦2.0:1; a silicate resin component,
0.01% to 5% by weight of (C) hydrosilylation reaction catalyst, based on the total weight of starting materials (A) to (F);
(D) Unit formula: ( ^RM ₂ SiO _2/2 ) _e (HR ^M SiO _2/2 ) _f ( ^RM ₂ HSiO _1/2 ) _g ( ^RM ₃ SiO _1/2 ) _h polyorganohydrogen siloxane, where subscript e≧0, subscript f≧0, quantity (e+f) is from 4 to 500, subscript g is 0, 1, or 2, and subscript h is 0, 1, or 2, the quantity (g+h)=2, and the quantity (f+g)≧3, and (D) the polyorganohydrogensiloxane is aliphatic unsaturation of the (A) polydiorganosiloxane gum (D) polyorganohydro, present in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms to hydrocarbon groups {(D):(A) ratio} of 20.8:1 to 57.7:1; Gensiloxane and
0.05% to 4.64% by weight of (E) trialkyl borate, based on the total weight of starting materials (A) to (F);
0 to 5% by weight of (F) a hydrosilylation reaction inhibitor, based on the total weight of starting materials (A) to (F);
>0% to 90% by weight of (G) solvent, based on the total weight of all starting materials in the composition;
(H) fixing additive in an amount of 0 to 5% by weight, based on the total weight of starting materials (A) to (F).

(A) Polydiorganosiloxane gum component The hydrosilylation reaction curable composition contains (A) a polydiorganosiloxane gum component. The polydiorganosiloxane gum component includes (A-1) an aliphatic unsaturated polydiorganosiloxane gum and (A-2) a hydroxyl-terminated polydiorganosiloxane gum.

The starting material (A-1), aliphatic unsaturated polydiorganosiloxane gum, has the unit formula: (R ^M ₂ R ^U SiO _1/2 ) ₂ (R ^M ₂ SiO _2/2 ) _a , where , each R ^M is an independently selected monovalent hydrocarbon radical of 1 to 30 carbon atoms containing no aliphatic unsaturation, and each R ^U is an independently selected monovalent hydrocarbon group of 2 to 30 carbon atoms, free of aliphatic unsaturation. subscript a is 20 mils (0.51 mm) to 80 mils (0.203 mm) in (A-1) aliphatic unsaturated polydiorganosiloxane gum; or a value sufficient to provide a plasticity of between 30 mils (0.76 mm) and 70 mils (1.78 mm), or alternatively between 55 mils (1.40 mm) and 65 mils (1.65 mm); Measured according to ASTM D926 by applying a load of 1 kg to a spherical sample weighing 4.2 g for 3 minutes at 25°C, results are measured in 1/1000th of an inch (mil), procedure is based on ASTM D926.

In unit formula (A-1), each R ^M is an independently selected monovalent hydrocarbon group of 1 to 30 carbon atoms containing no aliphatic unsaturation. Alternatively, each R ^M can have 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms. Suitable monovalent hydrocarbon groups for R ^M are exemplified by alkyl groups and aromatic groups such as aryl and aralkyl groups. "Alkyl" means a cyclic, branched or unbranched saturated monovalent hydrocarbon group. Alkyl is methyl, ethyl, propyl (e.g. isopropyl and/or n-propyl), butyl (e.g. isobutyl, n-butyl, tert-butyl and/or sec-butyl), pentyl (e.g. isopentyl, neopentyl and/or or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, and branched alkyl groups of 6 or more carbon atoms, and cyclic alkyl groups such as cyclopentyl and cyclohexyl. . "Aryl" means a fully unsaturated cyclic hydrocarbon group. Aryl is exemplified by, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups can have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, alternatively 5 to 6 carbon atoms. Polycyclic aryl groups can have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, alternatively 12 to 14 carbon atoms. "Aralkyl" means an alkyl group having pendant and/or terminal aryl groups, or an aryl group having pendant alkyl groups. Exemplary aralkyl groups include tolyl, xylyl, benzyl, phenylethyl, phenylpropyl and phenylbutyl. Alternatively, each R ^M may be independently selected from the group consisting of alkyl and aryl. Alternatively, each R ^M may be independently selected from methyl and phenyl. Alternatively, each R ^M may be alkyl. Alternatively, each R ^M may be methyl.

In unit formula (A-1), each R ^U is an independently selected monovalent aliphatic unsaturated hydrocarbon group of 2 to 30 carbon atoms. Alternatively, each R ^U can have 2 to 12 carbon atoms, alternatively 2 to 6 carbon atoms. Suitable monovalent aliphatic unsaturated hydrocarbon groups include alkenyl and alkynyl groups. "Alkenyl" means a branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Suitable alkenyl groups are exemplified by vinyl, allyl, butenyl, pentenyl, hexenyl, and heptenyl (including branched and linear isomers of 3 to 7 carbon atoms); and cyclohexenyl. "Alkynyl" means a branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Suitable alkynyl groups are exemplified by ethynyl, propynyl, and butynyl (including branched and linear isomers of 2 to 4 carbon atoms). Alternatively, each R ^U may be vinyl, allyl, or alkenyl such as hexenyl.

Polydiorganosiloxane gums are known in the art and can be prepared by methods such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes. Examples of polydiorganosiloxane gums suitable for use in hydrosilylation reaction curable compositions include:
i) dimethylvinylsiloxy-terminated polydimethylsiloxane,
ii) dimethylvinylsiloxy terminated poly(dimethylsiloxane/methylphenyl)siloxane,
iii) dimethylvinylsiloxy terminated poly(dimethylsiloxane/diphenyl)siloxane,
iv) phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxane,
v) dimethylhexenylsiloxy-terminated polydimethylsiloxane,
vi) dimethylhexenyl-siloxy terminated poly(dimethylsiloxane/methylphenyl)siloxane,
vii) dimethylvinylsiloxy terminated poly(dimethylsiloxane/diphenyl)siloxane,
viii) is exemplified by a combination of two or more of i) to vii). Alternatively, the polydiorganosiloxane gum comprises: i) dimethylvinylsiloxy terminated polydimethylsiloxane;
v) dimethylhexenylsiloxy terminated polydimethylsiloxane, and combinations of i) and v).

Starting material (A-1), aliphatic unsaturated polydiorganosiloxane gum, is present in the hydrosilylation reaction curable composition in an amount of at least 32.2% by weight, based on the total weight of starting materials (A) to (F). %, alternatively at least 34%, alternatively at least 34.2%, at the same time this amount is at most 44.62%, alternatively at most 35%, alternatively at most 34.4% by weight. Good too. Alternatively, the amount of (A-1) aliphatic unsaturated polydiorganosiloxane gum is 32.2% to 44.6% by weight, or 34% by weight, based on the total weight of starting materials (A) to (F). % to 35% by weight.

In addition to the (A-1) aliphatic unsaturated polydiorganosiloxane gum, the starting material (A) polydiorganosiloxane component has the unit formula: (R ^M ₂ R ^U SiO _1/2 ) ₂ (R ^M ₂ SiO _{2/ 2} ) _a ' (A-2) may optionally further include a hydroxyl-terminated polydiorganosiloxane gum, where R ^M and R ^U are as described above, and the subscript a' is ( A-2) Hydroxyl-terminated polydiorganosiloxane gum with 20 mils (0.51 mm) to 80 mils (2.03 mm), alternatively 30 mils (0.76 mm) to 70 mils (1.78 mm), or alternatively 45 mils (1. 14 mm) to 65 mils (1.65 mm), which plasticity is determined by applying a 1 kg load to a spherical sample weighing 4.2 g for 3 minutes at 25° C. according to ASTM D926. The results are measured in 1/1000th of an inch (mil) and the procedure is based on ASTM D926.

Hydroxyl-terminated polydiorganosiloxane gums suitable for use as starting material (A-2) are known in the art and include hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes. It can be prepared by a method. Examples of hydroxyl-terminated polydiorganosiloxane gums suitable for use as starting material (A-2) in hydrosilylation reaction curable compositions include:
i) bis-hydroxyl terminated polydimethylsiloxane,
ii) bis-hydroxyl terminated poly(dimethylsiloxane/methylphenylsiloxane),
iii) bis-hydroxyl terminated poly(dimethylsiloxane/diphenylsiloxane),
iv) phenyl, methyl, hydroxyl-siloxy terminated polydimethylsiloxane,
v) A combination of two or more of i) to iv). Alternatively, starting material (A-2) comprises a bis-hydroxyl terminated polydimethylsiloxane.

Starting material (A-2) hydroxyl-terminated polydiorganosiloxane gum is present in the hydrosilylation reaction curable composition in amounts ranging from 0% to <1.2% by weight based on the total weight of starting materials (A) to (F). Present in an amount of %. Alternatively, (A-2) the hydroxyl-terminated polydiorganosiloxane gum may be present in an amount of at least 0.1% by weight, alternatively at least 0.13% by weight, while this amount, on the same basis, is at most 1% by weight. .19%, or even up to 0.5%.

The starting materials (A-1) aliphatic unsaturated polydiorganosiloxane gum and (A-2) bis-hydroxyl terminated polydiorganosiloxane have a weight ratio (A-1):(A-2) of ≧37.4:1. may be present in such amounts as may be present. Alternatively, the weight ratio (A-1):(A-2) is at least 37.4:1, alternatively at least 50:1, alternatively at least 100:1, alternatively at least 150:1, alternatively at least 200:1, alternatively at least 250:1, or at least 270:1, while the weight ratio (A-1):(A-2) is up to 350:1 when (A-2) hydroxyl-terminated polydiorganosiloxane gum is present. :1, or up to 340:1, or up to 325:1, or up to 300:1, or up to 275:1.

(B) Polyorganosilicate resin component The hydrosilylation reaction curable composition further contains a polyorganosilicate resin component which is the starting material (B), and the polyorganosilicate resin component comprises (B-1) the capped resin and (B-2) Contains uncapped resin. Monofunctional units (“M” units) of formula R ^M ₃ SiO _1/2 (where R ^M is as defined above), and tetrafunctional silicate units (“Q” units) of formula SiO _4/2 ), polyorganosilicate resins. Alternatively, at least 1/3, or alternatively at least 2/3, of the R ^M groups are alkyl groups (eg, methyl groups). Alternatively, the M unit may be exemplified by (Me ₃ SiO _1/2 ) and (Me ₂ PhSiO _1/2 ). Polyorganosilicate resins can be prepared in solvents such as those exemplified by liquid hydrocarbons such as benzene, toluene, xylene, and heptane, or in liquid organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes. Soluble.

When prepared, the polyorganosilicate resin comprises the M and Q units described above, and the polyorganosiloxane further comprises units having silicon-bonded hydroxyl groups, having the formula Si(OSiR ^M ₃ ) ₄ [wherein R ^M is as described above], for example, the neopentamer may be tetrakis(trimethylsiloxy)silane. ²⁹ Si NMR spectroscopy can be used to measure the hydroxyl content and molar ratio of the M and Q units, which is calculated by removing the M and Q units from the neopentamer {M(resin)}/{Q (resin)}. The M:Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M units) in the resinous part of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous part. The M:Q ratio may be between 0.5:1 and 1.5:1.

The Mn of the polyorganosilicate resin varies depending on various factors such as the type of hydrocarbon group represented by R ^M present. Mn of a polyorganosilicate resin refers to the number average molecular weight measured using GPC when the peak representing neopentamer is excluded from the measurement. Mn of the polyorganosilicate resin is 500 g/mol to 5,000 g/mol, or 2,500 g/mol to 5,000 g/mol, or 2,700 g/mol to 4,900 g/mol, or 2,700 g/mol. ~4,700g/mol. A suitable GPC test method for measuring Mn is disclosed in Reference Example 1 at column 31 of US Pat. No. 9,593,209.

U.S. Patent No. 8,580,073 (column 3, line 5 to column 4, line 31) and U.S. Patent Application Publication No. 2016/0376482 (paragraphs [0023] to [0026]) disclose MQ resin. Incorporated herein by reference for disclosure, this MQ resin is a polyorganosilicate resin suitable for use in the hydrosilylation reaction curable compositions described herein. The polyorganosilicate resin can be prepared by any suitable method, such as co-hydrolysis of the corresponding silane or silica hydrosol capping method. Polyorganosilicate resins are disclosed in U.S. Pat. No. 2,676,182 to Daudt et al., U.S. Pat. No. 4,611,042 to Rivers-Farrell et al., and U.S. Pat. No. 4,774,310 to Butler et al. It can be prepared by a silica hydrosol capping process such as that described above. The method of Daudt et al. described above involves reacting a silica hydrosol with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a mixture thereof under acidic conditions, and forming M units and Q units. and recovering a copolymer having. The resulting copolymers generally contain 2-5% by weight of hydroxyl groups.

The intermediates used to prepare polyorganosilicate resins can be triorganosilanes and silanes containing four hydrolyzable substituents or alkali metal silicates. Triorganosilanes have the formula R ^M ₃ SiX ¹ (where R ^M is as described above and X ¹ is a hydrolyzable substituent such as halogen, alkoxy, acyloxy, hydroxyl, oximo, or ketoximo, or halogen , alkoxy, or hydroxyl). A silane with four hydrolyzable substituents may have the formula SiX ² ₄ , where each X ² is halogen, alkoxy, or hydroxyl. Suitable alkali metal silicates include sodium silicates.

The polyorganosilicate resin prepared as described above is an uncapped resin, which typically contains silicon-bonded hydroxyl groups, i.e. of the formula HOSi _3/2 and/or ^HORM ₂ SiO _1/2 . Contain something. The polyorganosilicate resin may contain >3% to 10% silicon-bonded hydroxyl groups as determined by NMR spectroscopy. For certain applications, the amount of silicon-bonded hydroxyl groups may be ≦2%, alternatively ≦0.89%, alternatively <0.7%, alternatively less than 0.3%, alternatively less than 1%, alternatively 0.3% to 2%. % may be desirable. The silicon-bonded hydroxyl groups formed during the preparation of polyorganosilicate resins are converted to trihydrocarbon siloxane groups by reacting the silicone resin with a silane, disiloxane, or disilazane containing an appropriate end group in a process called capping. Or it can be converted into a different hydrolyzable group. The silane containing hydrolyzable groups may be added in molar excess over the amount needed to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

When the polyorganosilicate resin is a capped resin, the capped resin has the formula HOSiO _3/2 and/or ^HORM ₂ SiO _1/2 where R ^M is as defined above. It may contain 2% or less, or 0.7% or less, or 0.3% or less, or 0.3% to 0.8%. The concentration of silanol groups present in a polyorganosiloxane can be determined using NMR spectroscopy as described above.

Therefore, the polyorganosilicate resin component includes (B-1) a capped resin as described above, and (B-2) an uncapped resin as described above. The capped resin may have the unit formula: (R ^M ₃ SiO _1/2 ) _z (SiO _4/2 ) _o Z _p , where R ^M is as described above and The subscripts z and o have values such that o>1, subscript z>4, and the quantity (o+z) indicates that the capped resin contains the above Mn (e.g., 500 g/mol to 5,000 g/mol , or from 1,000 g/mol to 4,700 g/mol, or from 2,900 g/mol to 4,700 g/mol, or from 2,900 g/mol to 4,100 g/mol). , the subscript p is used to provide the capped resin with a hydrolyzable group content as described above (e.g., 0-2%, alternatively 0-0.7%, alternatively 0-0.3%). Has sufficient value. The uncapped resin starting material (B-2) may have the unit formula (R ^M ₃ SiO _1/2 ) _z' (SiO _4/2 ) _o' Z _p' , where , R ^M are as above, subscripts z' and o' have values where o'>1, subscript z'>4, and the quantity (o'+z') is the cap The above Mn (for example, 500 g/mol to 5,000 g/mol, or 1,000 g/mol to 4,700 g/mol, or 2,700 g/mol to 4,700 g/mol, or 2,700 g /mol to 4,300 g/mol), and the subscript p' indicates that the capped resin has a hydrolyzable group content as described above (e.g., >3% to 10 %).

The hydrosilylation curable composition is based on the total weight of starting materials (A) to (F) (e.g., based on the total weight of all starting materials excluding solvent in the hydrosilylation curable composition). (B) polyorganosilicate resin in an amount of 44.8% to 65.8%, alternatively 46.2% to 65.8%, alternatively 61.5% to 62.6%. The amount of capped and uncapped resin in starting material (B) is determined by the weight ratio of uncapped resin:capped resin {i.e., (B-2):(B-1) ratio} may be sufficient to give 0.032:1 to 0.125:1, alternatively 0.118:1 to 0.124:1, or alternatively 0.123:1 to 0.124:1. Alternatively, the (B-2):(B-1) ratio may be at least 0.032, alternatively at least 0.11, alternatively at least 0.118, while at the same time (B-2):(B-1 ) ratio may be up to 0.125, alternatively up to 0.124, alternatively up to 0.12.

The starting material (A) polydiorganosiloxane gum component and the starting material (B) polyorganosilicate resin component are contained in a hydrosilylation reaction curable composition, (B) polyorganosilicate resin component: (A) polydiorganosiloxane gum component {i.e., (B):(A) ratio} ≦2.0:1. Alternatively, the (B):(A) ratio may be at least 1.5:1, or <1.8:1, while the (B):(A) ratio is at most 2.0:1. , or up to 1.8:1. Alternatively, the (B):(A) ratio may be 1.0:1 to 2.0:1, or 1.8:1 to 1.9:1.

(C) Hydrosilylation reaction catalyst The starting material (C) in the hydrosilylation reaction curable composition is a hydrosilylation reaction catalyst. Hydrosilylation reaction catalysts are known in the art and are commercially available. Examples of hydrosilylation reaction catalysts include platinum group metal catalysts. Such a hydrosilylation reaction catalyst can be (C-1) a metal selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium; alternatively, it can be platinum, ruthenium, and iridium; It can be platinum. Alternatively, the hydrosilylation reaction catalyst is (C-2) a compound of such a metal, such as chloridotris(triphenylphosphane)rhodium(I) (Wilkinson's catalyst), [1,2-bis(diphenylphosphino) ) ethane]dichlorodirhodium or rhodium diphosphine chelates such as [1,2-bis(diethylphospino)ethane]dichlorodirhodium, chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, or It may also be platinum dichloride. Alternatively, the hydrosilylation reaction catalyst is (C-3) a complex of a platinum group metal compound and an alkenyl-functional organopolysiloxane oligomer, or (C-4) a platinum group metal microencapsulated in a matrix or core-shell type structure. It may also be a compound. Complexes of platinum alkenyl functional organopolysiloxane oligomers include platinum complexes of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane (Karstedt catalyst). Alternatively, the hydrosilylation catalyst may include a (C-5) complex microencapsulated in a resin matrix. Exemplary hydrosilylation reaction catalysts include Speier, U.S. Pat. No. 2,823,218, Ashby, U.S. Pat. No. 3,159,601, Lamoreaux, U.S. Pat. No. 296,291, Willing No. 3,419,593, Modic No. 3,516,946, Karstedt No. 3,715,334, Karstedt No. 3,814,730, Chandra No. 3,928,629 of Lee et al. No. 3,989,668 of Lee et al. No. 4,766,176 of Lee et al. No. 4,784,879 of Lee et al. No. 4,784,879 of Lee et al. No. 5,017,654, Chung et al. No. 5,036,117, and Brown No. 5,175,325, and Togashi et al. European Patent No. 0347895(A). Hydrosilylation reaction catalysts are commercially available, for example, SYL-OFF™ 4000 Catalyst and SYL-OFF™ 2700 are available from Dow Silicones Corporation.

The amount of hydrosilylation reaction catalyst used herein is determined by the selection of the starting materials (D) polyorganohydrogensiloxane and (A) polydiorganosiloxane gum components, and their respective silicon-bonded hydrogen atoms (SiH) and fatty acids. Depending on various factors, such as the content of group unsaturation as well as the content of platinum group metal in the selected catalyst, the amount of hydrosilylation reaction catalyst is important for the hydrosilylation reaction between SiH and aliphatic unsaturation. or the amount of catalyst is from 1 ppm to 6,000 ppm of platinum group metals, based on the total weight of the starting materials containing silicon-bonded hydrogen atoms and aliphatic unsaturated hydrocarbon groups. It is sufficient to provide 1 ppm to 1,000 ppm of metal, or 1 ppm to 100 ppm of platinum group metal under the same criteria. Alternatively, when the hydrosilylation reaction catalyst comprises a platinum-organosiloxane complex, the amount of hydrosilylation reaction catalyst is based on the total weight of starting materials (A) through (F) (e.g., in the hydrosilylation reaction curable composition). (based on the total weight of all starting materials excluding solvent) from 0.01% to 5%.

(D) Polyorganohydrogensiloxane The starting material (D) in the hydrosilylation reaction curable composition has the unit formula: ( ^RM ₂ SiO _2/2 ) _e (HR ^M SiO _2/2 ) _f ( ^RM ₂ HSiO _1/2 ) _g (R ^M ₃ SiO _1/2 ) _h is a polyorganohydrogensiloxane, where R ^M is as above, subscript e≧0, subscript f≧0 , the quantity (e+f) is between 4 and 500, the subscript g is 0, 1, or 2, the subscript h is 0, 1, or 2, the quantity (g+h)=2, and the quantity ( f+g)≧3. Alternatively, the quantity (f+g) may be sufficient to give the polyorganohydrogensiloxane a silicon-bonded hydrogen content of 0.5% to 2%, alternatively 0.6% to 1.5%, and The silicon-bonded hydrogen (Si-H) content of organohydrogensiloxanes can be determined using quantitative infrared analysis according to ASTM E168.

Suitable polyorganohydrogensiloxanes are:
(D-1) bis-dimethylhydrogensiloxy-terminated poly(dimethyl/methylhydrogen)siloxane,
(D-2) bis-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane,
(D-3) bis-trimethylsiloxy-terminated poly(dimethyl/methylhydrogen)siloxane,
(D-4) bis-trimethylsiloxy-terminated polymethylhydrogensiloxane, and (D-5) two of (D-1), (D-2), (D-3), and (D-4) Examples include combinations of two or more. Methods for preparing polyorganohydrogensiloxanes, such as hydrolysis and condensation of organohydridohalosilanes, are known in the art and are described, for example, in U.S. Pat. No. 3,957,713 to Jeram et al. and U.S. Pat. No. 4,329,273. Polyorganohydrogensiloxanes can also be prepared, for example, as described in Speier et al., US Pat. No. 2,823,218, which uses organohydrogensiloxane oligomers and linear polymers, such as 1,1,1,3,3-pentamethyldisiloxane, bis-trimethylsiloxy-terminated polymethylhydrogensiloxane homopolymer, bis-trimethylsiloxy-terminated poly(dimethyl/methylhydrogen)siloxane copolymer, and cyclic polymethylhydrogen Discloses siloxanes. Polyorganohydrogensiloxanes are also commercially available, for example from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as HMS-H271, HMS-071, HMS-993, HMS-301, HMS-301 R, HMS-031, HMS-991, HMS-992, HMS -993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301, HPM-502, and HMS-HM271.

The amount of polyorganohydrogensiloxane in the hydrosilylation reaction curable composition is from 0.1% to 5% based on the total weight of starting materials (A) to (F). Alternatively, the amount of polyorganohydrogensiloxane in the hydrosilylation reaction curable composition may be at least 0.1%, alternatively at least 0.25%, alternatively at least 0.3%; , the same criteria may be up to 5%, or up to 2.5%, or up to 1.5%, or up to 1%.

The ratio of silicon-bonded hydrogen to aliphatic unsaturated groups is important when relying on the hydrosilylation curing process. Generally, this is determined by calculating the total weight percent of aliphatic unsaturated groups (e.g., vinyl [V]) in the composition and the total weight percent of silicon-bonded hydrogen [H] in the composition. , where the molecular weight of hydrogen is 1 and the molecular weight of vinyl is 27, the molar ratio of silicon-bonded hydrogen to vinyl is 27 [H]/[V]. The starting materials (A) the polydiorganosiloxane gum component and (D) the polyorganohydrogensiloxane are present in the hydrosilylation reaction curable composition at a molar ratio of silicon-bonded hydrogen atoms to aliphatic unsaturated hydrocarbon groups {(D) :(A) ratio} may be present in an amount sufficient to provide a ratio of at least 20.8:1, alternatively at least 28.7:1, while the ratio is at most 57.7:1, or It may be up to 54.7:1. Alternatively, the (D):(A) ratio is 20.8:1 to 57.7:1, or 28.7:1 to 54.7:1, or 20.8:1 to 28.8:1, Alternatively, it may be 28.7:1 to 57.7:1.

(E) Trialkyl Borate The starting material (E) in the hydrosilylation reaction curable composition is a trialkyl borate of the formula B(OR ^A ) ₃ , where each R ^A is a carbon atom of 1 to independently selected alkyl groups of 30, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms. Alkyl groups include methyl, ethyl, propyl (e.g., isopropyl or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, or sec-butyl), pentyl (e.g., isopentyl, neopentyl, or tert-butyl), pentyl), hexyl, a branched alkyl group of 6 carbon atoms, or a cyclic alkyl group such as cyclopentyl or cyclohexyl. Examples of suitable trialkyl borates include trimethyl borate, triethyl borate, tributyl borate, and combinations of two or more thereof. Alternatively, the trialkyl borate may be triethyl borate.

Trialkyl borates are known in the art and can be made by known methods such as those described in Stange, US Pat. No. 3,020,308. Trialkyl borates are also commercially available; for example, triethyl borate is available from Meryer (Shanghai) Chemical Technology Co. , Ltd. Trialkyl borate additives for silicone compositions are also known in the art, such as DOWSIL™ 7429 PSA Additive, available from Dow Silicones Corporation.

The amount of (E) trialkyl borate added to the hydrosilylation curable composition is from 0.05% to 4.64% by weight, based on the total weight of starting materials (A) to (F). . Alternatively, the amount of (E) trialkyl borate may be at least 0.05%, alternatively at least 0.5%, alternatively at least 0.8%, at the same time on the same basis, It may be up to 4.64%, alternatively up to 4%, alternatively up to 2%, alternatively up to 1.5%, alternatively up to 1.0%. Alternatively, the amount of (E) trialkyl borate may be from 0.5% to 4.64% by weight, alternatively from 0.8% to 4.64% by weight, on the same basis.

(F) Hydrosilylation Reaction Inhibitor Starting material (F) is an optional hydrosilylation reaction inhibitor (inhibitor), which, compared to a composition containing the same starting materials except for the inhibitor, It can be used to change the rate of hydrosilylation reactions. The starting materials (F) are (F-1) acetylenic alcohol, (F-2) silylated acetylenic alcohol, (F-3) en-yne compound, (F-4) triazole, (F-5) phosphine. , (F-6) mercaptan, (F-7) hydrazine, (F-8) amine, (F-9) fumarate, (F-10) maleate, (F-11) ether, (F- 12) may be selected from the group consisting of carbon monoxide, (F-13) alkenyl functional siloxane oligomers, and (F-14) combinations of two or more thereof. Alternatively, the hydrosilylation reaction inhibitor may include (F-1) acetylenic alcohol, (F-2) silylated acetylenic alcohol, (F-9) fumarate, (F-10) maleate, (F- 13) Carbon monoxide, (F-14) may be selected from the group consisting of combinations of two or more thereof.

Acetylenic alcohols include 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl -1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, 3,5-dimethyl -1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol, and combinations thereof. Acetylenic alcohols are known in the art and are commercially available from a variety of sources, see, for example, Kookootsedes et al., US Pat. No. 3,445,420. Alternatively, the inhibitor may be a silylated acetylenic compound. Without wishing to be bound by theory, it is believed that the addition of a silylated acetylenic compound increases the hydrosilylation of a starting material that does not contain a silylated acetylenic compound or that contains an organic acetylenic alcohol inhibitor such as those described above. It is believed that the yellowing of the reaction product prepared from the hydrosilylation reaction is reduced compared to the reaction product of the hydrosilylation reaction. The silylated acetylene compounds include (3-methyl-1-butyne-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyne- 3-oxy)dimethylsilane, bis(3-methyl-1-butyne-3-oxy)silane methylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1 -dimethyl-2-propynyloxy)) silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3- Methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, bis(3-methyl-1-butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyne-3-oxy)trimethylsilane, (3-phenyl-1-butyne-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyne-3-oxy)dimethylphenyl Silane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, Exemplified by (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Ru. The silylated acetylenic compounds useful as inhibitors herein can be prepared by methods known in the art, for example, U.S. Patent No. 6,677,407 to Bilgrien et al. The silylation of the acetylenic alcohols described above by reaction with chlorosilanes in the presence of chlorosilanes is disclosed.

Alternatively, the inhibitor may be an en-yne compound, such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and combinations thereof. Alternatively, the inhibitor may include a triazole, exemplified by benzotriazole. Alternatively, the inhibitor may include phosphine. Alternatively, the inhibitor may include a mercaptan. Alternatively, the inhibitor may include hydrazine. Alternatively, the inhibitor may include an amine. Amines are exemplified by tetramethylethylenediamine, 3-dimethylamino-1-propyne, n-methylpropargylamine, propargylamine, 1-ethynylcyclohexylamine, or combinations thereof. Alternatively, the inhibitor may include a fumarate salt. Examples of fumarate salts include dialkyl fumarates such as diethyl fumarate, dialkenyl fumarates such as diallyl fumarate, and dialkoxyalkyl fumarates such as bis-(methoxymethyl)ethyl fumarate. Alternatively, the inhibitor may include a maleate salt. Maleates include dialkyl maleates such as diethyl maleate, dialkenyl maleates such as diallyl maleate, and dialkoxyalkyl maleates such as bis-(methoxymethyl)ethyl maleate. Alternatively, the inhibitor may include an ether.

Alternatively, the inhibitor may include carbon monoxide. Alternatively, the inhibitor may include alkenyl-functional siloxane oligomers, such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5, 7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-divinyl-1,1,3 , 3-tetramethyldisiloxane, and combinations of two or more thereof. Compounds useful as inhibitors as described above are available from, for example, Sigma-Aldrich Inc. or Gelest, Inc. and are known in the art, see, eg, US Pat. No. 3,989,667 to Lee et al. Suitable inhibitors for use herein are exemplified by those described as Stabilizer E in paragraphs [0148]-[0165] of US Patent Application Publication No. 20007/0099007.

The amount of inhibitor will depend on the desired pot life, whether the composition is a one-part or multi-part composition, the particular inhibitor used, and (C) the choice of hydrosilylation reaction catalyst and Depends on various factors such as quantity. However, when present, the amount of (F) inhibitor may range from 0% to 5%, alternatively from 0% to 5%, based on the total weight of starting materials (A) through (F) in the hydrosilylation reaction curable composition. It may be in the range of 1%, or 0.001% to 1%, or 0.01% to 0.5%, or 0.0025% to 0.025%.

(G) Solvent The hydrosilylation reaction curable composition further contains a solvent, which is the starting material (G). The solvent may be an organic solvent such as a hydrocarbon, a ketone, an acetate, an ether, and/or a cyclic siloxane having an average degree of polymerization of 3 to 10. Hydrocarbons suitable for the solvent include (G-1) aromatic hydrocarbons such as benzene, benzene, toluene, or xylene; (G-2) aliphatic hydrocarbons such as hexane, heptane, octane, or isoparaffin; G-3) Can be a combination of these. Alternatively, the solvent may be a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether. Suitable ketones include acetone, methyl ethyl ketone, or methyl isobutyl ketone. Suitable acetate esters include ethyl acetate or isobutyl acetate. Suitable ethers include diisopropyl ether or 1,4-dioxane. Suitable cyclic siloxanes having a degree of polymerization of 3 to 10, or 3 to 6 include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and/or decamethylcyclopentasiloxane. Alternatively, the solvent may be selected from the group consisting of benzene, toluene, xylene, heptane, ethylbenzene, ethyl acetate, and combinations of two or more thereof.

The amount of solvent will vary depending on various factors, such as the type of solvent selected and the amounts and types of other starting materials selected for the hydrosilylation reaction curable composition. However, the amount of solvent may be >0% to 90%, alternatively 0% to 60%, alternatively 20% to 60%, alternatively 45%, based on the total weight of all starting materials in the hydrosilylation reaction curable composition. 65%, or 50% to 60%. Solvents can be added during the preparation of the hydrosilylation reaction curable composition, for example, to aid in the mixing and delivery of one or more of the starting materials described above. All or a portion of the solvent may be added along with one or more of the other starting materials. For example, the polyorganosilicate resin and/or hydrosilylation catalyst may be dissolved in a solvent prior to combination with other starting materials in the hydrosilylation curable composition. All or a portion of the solvent may optionally be removed after preparation of the hydrosilylation curable composition.

(H) Fixing Additive The starting material (H) in the hydrosilylation reaction curable composition is a fixing additive. Without wishing to be bound by theory, anchoring additives facilitate bonding to substrates by silicone pressure sensitive adhesives prepared by curing the hydrosilylation reaction curable compositions described herein. It is thought that then.

Suitable fixing additives for starting material (H) include methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2 -aminoethyl)-3-aminopropyltrimethoxysilane, bis(trimethoxysilyl)propane, and bis(trimethoxysilylhexane), and mixtures or reaction mixtures of such silane coupling agents. Alternatively, the fixing additive may include tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, It may be allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, or 3-methacryloxypropyltrimethoxysilane.

Other suitable fixing additives are reaction products of vinylalkoxysilanes and epoxy-functional alkoxysilanes; reaction products of vinylalkoxysilanes and epoxy-functional alkoxysilanes; and at least one aliphatic monomer per molecule. Combinations (e.g., physical blends and/or reaction products) of polyorganosiloxanes having saturated hydrocarbon groups and at least one hydrolyzable group with epoxy-functional alkoxysilanes (e.g., hydroxy-terminated vinyl-functional polydimethyl A combination of siloxane and glycidoxypropyltrimethoxysilane) is an example.

Exemplary fixing additives are known in the art, and include, for example, U.S. Patent No. 9,562,149; Disclosed in Application Publication No. 2005/0038188, paragraph [0091] of US Patent Application Publication No. 2012/0328863, and paragraph [0041] of US Patent Application Publication No. 2017/0233612, and European Patent Application No. 0 556 023. ing. Fixing additives are commercially available. For example, SYL-OFF(TM) 9250, SYL-OFF(TM) 9176, SYL-OFF(TM) 297, and SYL-OFF(TM) 397 are available from Dow Silicones Corporation (Midland, Michigan, USA). be. Other exemplary fixing additives include (G-1) vinyltriacetoxysilane, (G-2) glycidoxypropyltrimethoxysilane, and (G-3) (G-1) and (G-2 ). This combination (G-3) may be a mixture and/or a reaction product.

The amount of fixing additive will vary depending on various factors, such as the type of substrate to which the silicone pressure sensitive adhesive is attached. However, when present, the amount of fixing additive may range from 0.5% to 5%, alternatively from 0.5% to 3%, based on the total weight of all starting materials excluding solvent in the hydrosilylation reaction curable composition. , or 0.5% to 2.5%.

Method of Preparing Hydrosilylation Curable Compositions Hydrosilylation curable compositions may be prepared by a method comprising combining all of the starting materials described above in any convenient manner, such as by mixing at ambient or elevated temperatures. can. The hydrosilylation reaction inhibitor may be used before the hydrosilylation reaction catalyst, for example, when the hydrosilylation curable composition is prepared at an elevated temperature and/or when the hydrosilylation curable composition is prepared as a one-part composition. May be added.

The method may further include delivering one or more starting materials (e.g., a hydrosilylation reaction catalyst and/or a polyorganosilicate resin) in a solvent, wherein the starting materials are present in the hydrosilylation reaction curable composition. may be dissolved in a solvent when combined with one or more other starting materials. Those skilled in the art will appreciate that if it is desired that the resulting hydrosilylation reaction curable composition be solvent-free (i.e., free of solvent or may contain trace amounts of residual solvent from delivery of the starting material) It will be appreciated that the solvent may be removed after mixing two or more of the starting materials, in which case no solvent is intentionally added to the hydrosilylation reaction curable composition.

Alternatively, the hydrosilylation curable composition may be used, e.g., for an extended period of time before use, e.g., before applying the hydrosilylation curable composition to an optical silicone elastomer or other substrate. It can be prepared as a multi-part composition if stored for up to 6 hours. In a multi-part composition, the hydrosilylation reaction catalyst is stored in a separate part from any starting materials having silicon-bonded hydrogen atoms, such as polyorganohydrogensiloxane, and these parts are The composition is combined immediately before use.

For example, a multi-part composition may include a polydiorganosiloxane gum component, a polyorganohydrogensiloxane, and optionally one or more other of the above starting materials (hydrosilylation reaction reaction) by any convenient technique such as mixing. (other than a catalyst) may be prepared by combining starting materials to form a base. The curing agent is combined with at least one of the polydiorganosiloxane gum, the hydrosilylation reaction catalyst, and optionally one or more other starting materials (other than the polyorganohydrogensiloxane) by any convenient technique such as mixing. It may also be prepared by combining several starting materials. The starting materials may be mixed at ambient or elevated temperature. The hydrosilylation reaction inhibitor may be included in one or more of the base, the curing agent part, or a separate additional part. The polyorganosilicate resin can be added to the base, to the curing agent part, or to a separate additional part. Alternatively, a polyorganosiloxane resin may be added to the base. A solvent may be added to the base. Alternatively, the starting materials, including the polyorganosilicate resin, and some or all of the solvent may be added in separate additions. When a two-part composition is used, the weight ratio of the amount of base to the hardener part can range from 1:1 to 10:1. The hydrosilylation reaction curable composition is cured by a hydrosilylation reaction to form a silicone pressure sensitive adhesive.

Methods of Use The methods described above may further include one or more additional steps. The hydrosilylation curable composition prepared as described above is used to apply an adhesive article, such as a silicone pressure sensitive adhesive, onto a substrate (prepared by curing the hydrosilylation curable composition described above). ) may be formed. Accordingly, the method may further include applying the hydrosilylation reaction curable composition to the substrate.

Applying the hydrosilylation reaction curable composition to the substrate can be carried out by any convenient means. For example, the hydrosilylation reaction curable composition can be applied to the substrate by a gravure coater, comma coater, offset coater, offset gravure coater, roller coater, reverse roller coater, air knife coater, curtain coater, or slot die.

The substrate can be any material that can withstand the curing conditions (described below) used to cure the hydrosilylation reaction curable composition to form a silicone pressure sensitive adhesive on the substrate. For example, any substrate that can withstand heat treatment at temperatures of 120° C. or higher, or 150° C. or higher is suitable. Examples of materials suitable for such substrates include polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide (PAI), polyether sulfide (PES). , polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), thermoplastic polyurethane (TPU), polyethylene (PE), or polypropylene (PP). Alternatively, the substrate can be glass. Alternatively, the substrate may be a release liner, for example when a silicone pressure sensitive adhesive is used in a dry casting process. Although the thickness of the substrate is not critical, the thickness may be between 5 μm and 300 μm, or alternatively between 10 μm and 200 μm. Alternatively, the substrate may be selected from the group consisting of PI, PET, TPU, PMMA, and optical silicone elastomers.

Optical silicone elastomers are known in the art and are described, for example, in Hasegawa et al., US Pat. No. 8,859,693 and Akitomo et al., US Pat. No. 8,853,332. Optical silicone elastomers are commercially available. For example, the optical silicone elastomers SILASTIC™ MS-1001, MS-1002, MS-1003, MS-4002, and MS-4007 are moldable optical silicone elastomers, and SYLGARD™ 182, 184, and 186 are other optical silicone elastomers, all of which are commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

To improve bonding of the silicone pressure sensitive adhesive to the substrate, the method of forming an adhesive article optionally further comprises treating the substrate prior to applying the hydrosilylation reaction curable composition. But that's fine. Treatment of the substrate may include any convenient treatment such as applying a primer or subjecting the substrate to corona discharge treatment, etching, or plasma treatment prior to applying the hydrosilylation reaction curable composition to the substrate. It may be implemented using any suitable method.

The methods described herein optionally include removable silicone pressure sensitive adhesives on opposite sides of the substrate, e.g., to protect the silicone pressure sensitive adhesive prior to use in the adhesive article. Applying a release liner. The release liner can be applied before, during, or after curing of the hydrosilylation reaction curable composition, or after curing. The adhesive article may be a component for use in a flexible display device, such as an optical component.

Use of Silicone Pressure Sensitive Adhesives in Flexible Display Components FIG. 1 shows a partial cross-sectional view of a flexible display component (100). Part (100) includes a silicone pressure sensitive adhesive (102) having a surface (102a) and an opposing surface (102b). The opposite surface (102b) of the silicone pressure sensitive adhesive (102) is applied to the surface (103a) of the optical silicone elastomer (103) at >500 g/in as measured by the test method described in the Examples below. Adhesive with peel adhesive strength. The silicone pressure sensitive adhesive (102) may have a thickness of 10 μm to 200 μm. A silicone pressure sensitive adhesive (102) is adhered to a substrate (101) having a surface (101a) and an opposite surface (101b). The surface (102a) of the silicone pressure sensitive adhesive (102) is in contact with the opposite surface (101b) of the substrate (101). The substrate (101) may be selected from the group consisting of PI, PET, TPU, PMMA, and optical silicone rubber (which may be the same or different from the optical silicone rubber (103)) and has a thickness of 10 μm to 200 μm. It can have some characteristics.

The hydrosilylation reaction curable composition and method described above can be used to manufacture flexible display components (100) by wet casting. For example, a hydrosilylation reaction curable composition may be applied to the opposite surface (101b) of the substrate (101) and cured to form the silicone pressure sensitive adhesive (102). Alternatively, the hydrosilylation reaction curable composition described herein may be applied to the surface (103a) of the optical silicone elastomer (103) and cured to form the silicone pressure sensitive adhesive (102). . Alternatively, a hydrosilylation reaction curable composition may be applied to the surface of the release liner and cured to form the silicone pressure sensitive adhesive (102). The optical silicone rubber (103) may then be brought into contact with the opposite surface (102b) of the silicone pressure sensitive adhesive (102), and the substrate (101) may be brought into contact with the surface (102a) of the silicone pressure sensitive adhesive (102). ).

The following examples are provided to illustrate the invention to those skilled in the art and should not be construed as limiting the invention as claimed. The starting materials used herein are listed in Table 1.

In Table 1, DOWSIL™, SILASTIC™, and SYL-OFF™ brand starting materials were commercially available from Dow Silicones Corporation.

In this Reference Example 1, samples of hydrosilylation reaction curable compositions were prepared as follows using the starting materials and amounts shown in Table 2 below. Amounts are parts by weight unless otherwise specified. Starting material (A) polydiorganosiloxane gum component and starting material (B) polyorganosilicate resin component were dissolved in (G) solvent with mixing until the resulting mixture was homogeneous. The starting material (F) hydrosilylation reaction inhibitor was then thoroughly blended into the above mixture. The starting material (E) trialkyl borate was then thoroughly blended into the above mixture. The starting material (D) polyorganohydrogensiloxane was then thoroughly blended into the above mixture. Optionally, starting material (H) fixing additive (if used) was then thoroughly blended into the above mixture. Finally, starting material (C) hydrosilylation reaction catalyst was added and mixed until homogeneous. All starting materials were mixed at RT. The starting materials and their amounts (by weight) are shown in Table 2 below.

The hydrosilylation reaction curable compositions of Table 2 contained a small amount of residual solvent 1 incorporated with the starting material.

Prior to coating the hydrosilylation reaction curable composition onto the substrate, the DOWSIL™ 7499 PSA Primer was applied in an amount sufficient to give a dry coat weight of 0.20 gsm after heating in an oven at 120° C. for 0.5 minutes. thickness and coated onto the substrate. The primer layer on the substrate provided a good bond between the substrate and the cured silicone pressure sensitive adhesive. In this reference example 2, a hydrosilylation reaction-curable composition was coated on a substrate and cured according to the following procedure. Each sample prepared as above was applied onto a 50 μm thick PET film at a thickness sufficient to give a dry coat weight of 50 μm after heating in an oven at 140° C. for 2 minutes. After curing, tape samples were cut into 1 inch widths for peel adhesion testing in the following step.

The resulting tape sample was applied to a substrate with the silicone pressure sensitive adhesive in contact with the substrate. The substrates were SUS and Si Rubber B, and after contacting the silicone pressure sensitive adhesive with the substrates, the samples were held at RT for 20 minutes before testing. This test was repeated, but the samples were held at 70°C for one day before testing.

In this Reference Example 3, a sample prepared as described in Reference Example 2 was tested as follows. Each tape sample prepared as described above was tested by peeling each tape from the substrate and checking to see if there was any silicone pressure sensitive adhesive that had migrated from the PET film onto the substrate. The adhesion to the B substrate was tested. An adhesion/peel tester AR-1500 was used. The width of each PET sheet was 1 inch. The peel speed and peel angle were 0.3 m/min and 180°, respectively. The unit was grams/in. The results are shown in Table 4 below.

For the test method of adhesion to SUS, refer to the test standard ASTM D3330. Clean the stainless steel plate with solvent. A tape sample (1 inch wide) is applied to a stainless steel plate. A standard 2 kg test roller is used to rotate twice in each direction at a speed of 10 mm/sec. After a resting time of 20 minutes, the sample is peeled from the steel plate using AR-1500 at a peeling angle of 180° and a speed of 300 mm/min.

The test method for adhesion to silicone rubber B refers to test standard ASTM D3330. Clean the silicone rubber sheet with a solvent. A tape sample (1 inch wide, 25.4 mm) is applied to a silicone rubber sheet. A standard 2 kg test roller is used to rotate twice in each direction at a speed of 10 mm/sec. After a rest time of 20 minutes, the sample is peeled from the silicone rubber sheet using an AR-1500 at a peel angle of 180° and a speed of 300 mm/min.

The test method for adhesion to silicone rubber (70°C - 1 day) refers to test standard ASTM D3330. Clean the silicone rubber sheet with a solvent. A tape sample (1 inch wide, 25.4 mm) is applied to a silicone rubber sheet. A standard 2 kg test roller is used to rotate twice in each direction at a speed of 10 mm/sec. After aging the sample at 70° C. for one day (24 hours), the sample is peeled from the silicone rubber sheet using an AR-1500 at a peel angle of 180° and a speed of 300 mm/min.

Test methods for rheology data (Tg, G' at -20°C, 25°C and 100°C) refer to test standard ASTM D4440-15.

Cured pure silicone pressure sensitive adhesive films (without substrate) each having a thickness of 0.5 mm to 1.5 mm were placed on a rheometer (either TA DHR-2 or ARES-G2) for rheological property testing. was prepared on parallel plates with a diameter of 8 mm. Loss modulus G'' and storage modulus G' at different temperatures (i.e. from 200 °C to -80 °C) using a temperature ramp using vibration mode at a cooling rate of 3 °C/min at 1 Hz and 0.25% strain. Measured by program. Tan δ was calculated by G''/G'. The glass transition temperature was defined as the temperature at the peak point of tan δ. The results are shown in Table 4 below.

Industrial Applicability The above examples demonstrate adhesion to stainless steel >500 g/in, optical silicone elastomer adhesion >500 g/in at RT, and silicone pressure sensitive adhesives to optical silicone rubber at 70 g/in. It is possible to prepare a hydrosilylation reaction curable composition that cures to form a silicone pressure sensitive adhesive having a desirable adhesion to optical silicone elastomers of >800 g/in after aging for one day at °C. Show what you can do. Due to the high adhesion strength, the interface between the silicone pressure sensitive adhesive and the substrate (adherend) resists delamination over repeated deformation tests (e.g., by folding, bending, rolling, or stretching tests) on flexible display devices. be strong enough to The silicone pressure sensitive adhesive may also have a Tg≦0°C, a G'<1 MPa at -20°C, a G'<50 kPa at 25°C, and a G'<50 kPa at 100°C. Due to their low Tg and low G' over a wide temperature range, silicone pressure sensitive adhesives exhibit low stress on other layers during cyclic deformation tests (e.g., by folding, bending, rolling, and stretching tests) and can be used over a wide temperature range. Suitable for use within a range. This combination of properties makes silicone pressure sensitive adhesives suitable for use in flexible display devices, particularly in the optical components of flexible display devices. Because of the superior properties of silicone elastomers to withstand repeated folding, bending, rolling, and stretching, the combination of silicone pressure-sensitive adhesives and optical silicone elastomers prepared as described herein is suitable for repeated deformation tests. The present invention provides an article for use in flexible displays that has excellent reliability tests when subjected to (e.g., folding, bending, rolling, and stretching tests).

Definitions and Use of Terms All amounts, proportions, and percentages are by weight unless otherwise indicated. The Summary of the Invention and the Abstract are incorporated herein by reference. Unless the context of the specification dictates otherwise, the articles "a,""an," and "the" each refer to one or more. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are defined in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 Section §2111.03 I. , II. , and III. The use of "for example,""eg,""suchas," and "including" to list examples is not limited to only the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as as, but not limited to) and includes other similar or equivalent examples. Abbreviations used herein have definitions in Table 5.

The invention has been described in an illustrative manner and it is to be understood that the terminology used is intended to be in the nature of description rather than limitation. With respect to any Markush group on which the description of an individual feature or aspect is relied upon herein, different, special and/or unforeseen consequences may arise for each Markush group independently of all other Markush group members. may be obtained from each element of the group. Each member of the Markush family may be relied upon individually or in combination to provide appropriate basis for particular embodiments within the scope of the appended claims.

Moreover, any ranges and subranges relied upon in describing the invention, independently and inclusively, fall within the scope of the appended claims and are hereby incorporated by reference herein in whole and/or in part. It is understood that even if a value is not specified, the entire range is intended to include all and/or partial values therein. Those skilled in the art will appreciate that the recited ranges and subranges fully describe and enable the various embodiments of the invention, and that such ranges and subranges further include the relevant subranges, It will be readily appreciated that one-third, one-fourth, one-fifth, and any other sub-ranges contained within the range may be further delineated. By way of example only, a range of "0.05-4.64" for the amount of trialkyl borate may be lower third, or "0.05-1.58", and middle third, or "1 .59 to 3.11'', and may be further delineated into the upper third, ie, ``3.12 to 4.64,'' or the range ``0.05 to 4.64'' may be delineated by the subrange ``0.05 to 4.64.''0.05-0.98","0.78-0.98", and "0.98-4.64", and the individual values 0.05, 0.78, 0.98, and 4.64 each of which is individually and collectively within the scope of the appended claims and may be relied upon individually and/or collectively as appropriate to a particular embodiment within the scope of the appended claims. can provide evidence. Furthermore, with respect to words that define or modify ranges, such as "at least,""morethan,""lessthan,""lessthan," etc., such words should be understood to include subranges and/or upper or lower limits. It is.

Claims (14)

A hydrosilylation reaction curable composition for forming a silicone pressure sensitive adhesive, the composition comprising:
(A) a polydiorganosiloxane gum component,
Based on the total weight of starting materials (A) to (F), 32.2% to 44.6% by weight of (A-1) unit formula (R ^M ₂ R ^U SiO _1/2 ) ₂ (R ^M ₂ SiO _2/2 ) _a aliphatically unsaturated polydiorganosiloxane gum, in which each R ^M is an independently selected monovalent group of from 1 to 30 carbon atoms containing no aliphatic unsaturation. a hydrocarbon group, each R ^U is an independently selected monovalent aliphatic unsaturated hydrocarbon group of 2 to 30 carbon atoms, and the subscript a represents a 20 mil in the polydiorganosiloxane gum. (0.51 mm) to 80 mils (2.03 mm); an aliphatic unsaturated polydiorganosiloxane gum, with the results measured in 1/1000 of an inch (mil) and the procedure based on ASTM D926;
0 to <1.2% by weight of (A-2) hydroxyl-terminated polydiorganosiloxane gum of the unit formula ((HO)R ^M ₂ SiO _1/2 ) ₂ (R ^M ₂ SiO _2/2 ) _a', , where each R ^M is an independently selected monovalent hydrocarbon group of 1 to 30 carbon atoms containing no aliphatic unsaturation, and each subscript a' is 20 mils (0. hydroxyl-terminated polydiorganosiloxane gum having a value sufficient to provide the polydiorganosiloxane gum with a plasticity of between 51 mm and 80 mils (2.03 mm);
However, the weight ratio of (A-1) the aliphatic unsaturated polydiorganosiloxane gum to (A-2) the hydroxyl-terminated polydiorganosiloxane gum {(A-1):(A-2) ratio}≧37.4 :1, a polydiorganosiloxane gum component;
(B) a polyorganosilicate resin component,
Based on the total weight of starting materials (A) to (F), 44.8% to 58.9% by weight of (B-1) unit formula: (R ^M ₃ SiO _1/2 ) _z (SiO _{4/ 2} ) _o Z _p capped resin, where Z is a hydrolyzable group, and the subscript p is 0 to a maximum of 2% of the hydrolyzable group contained in the capped resin the subscripts z and o have values such that z>4, o>1, and the quantity (z+o) is between 500 g/mol and 2 , a capped resin having a value sufficient to give a number average molecular weight of , 700 g/mol;
Based on the total weight of starting materials (A) to (F), 0 to 7% by weight of (B-2) unit formula (R ^M ₃ SiO _1/2 ) _z' (SiO _4/2 ) _o' Z _{p '} , wherein the subscript p' has a value sufficient to give the uncapped resin a hydrolyzable group content of >3% to 10%. and the subscripts z' and o' have values such that z'>4, o'>1, and the quantity (z'+o') is from 500 g/mol to the uncapped resin. an uncapped resin having a value sufficient to provide a number average molecular weight of 5,000 g/mol, (B-1) said capped resin and (B-2) said uncapped resin. The resin is present in a total amount of 44.8% to 65.8% by weight based on the total weight of starting materials (A) to (F), with the proviso that (B-2) said uncapped resin: (B-1) the weight ratio of the capped resin {(B-2):(B-1) ratio} is 0.032:1 to 0.125:1;
(A) the polydiorganosiloxane gum component and (B) the polyorganosilicate resin component are present in a weight ratio of (B):(A) (resin:gum ratio)≦2.0:1; resin component,
0.01% to 5% by weight of (C) hydrosilylation reaction catalyst, based on the total weight of starting materials (A) to (F);
(D) Unit formula: ( ^RM ₂ SiO _2/2 ) _e (HR ^M SiO _2/2 ) _f ( ^RM ₂ HSiO _1/2 ) _g ( ^RM ₃ SiO _1/2 ) _h polyorganohydrogen siloxane, where the subscript e≧0, the subscript f≧0, the quantity (e+f) is 4 to 500, the subscript g is 0, 1, or 2, and the subscript h is 0, 1, or 2, the quantity (g+h)=2, and the quantity (f+g)≧3, and (D) the polyorganohydrogensiloxane has a silicon-bonded hydrogen atom (A) the polydiorgano polyorganohydro, present in an amount sufficient to provide a molar ratio of siloxane gum component to aliphatic unsaturated hydrocarbon groups {(D):(A) ratio} of 20.8:1 to 57.7:1; Gensiloxane and
0.05% to 4.64% by weight of (E) trialkyl borate, based on the total weight of starting materials (A) to (F);
0% to 5% by weight of (F) a hydrosilylation reaction inhibitor, based on the total weight of starting materials (A) to (F);
>0% to 90% by weight of (G) solvent, based on the total weight of all starting materials in the composition;
0 to 5% by weight, based on the total weight of starting materials (A) to (F), of (H) a fixing additive. (A) In the polydiorganosiloxane gum component, each R ^M is an independently selected alkyl group of 1 to 6 carbon atoms, and each R ^U is independently selected from the group consisting of vinyl, allyl, and hexenyl. The composition of claim 1, wherein the subscript a is sufficient to provide a plasticity value of 30 mils (0.76 mm) to 70 mils (1.778 mm). (B) in the polyorganosilicate resin component, each R ^M is an independently selected alkyl group of 1 to 6 carbon atoms, each Z is OH, and the quantity (z+o) is 2. The composition of claim 1, having a value sufficient to provide the capped resin with a number average molecular weight of ≦2,700 g/mol. (C) The composition according to claim 1, wherein the hydrosilylation reaction catalyst comprises a Karstedt catalyst. (D) in the polyorganohydrogensiloxane, each R ^M is an independently selected alkyl group of 1 to 6 carbon atoms, subscript g=0, and subscript h=2. , the composition of claim 1. (E) The composition according to claim 1, wherein the trialkyl borate comprises triethyl borate. said composition is a multi-part composition comprising a base and a hardener part, said base comprising starting materials A) and C), said hardener part comprising starting materials A) and D); Any one of claims 1 to 6, wherein the composition further comprises starting materials B), E), and F) in one or more of the base, the curing agent part, or a separate additional part. The composition described in . 1) applying the composition according to any one of claims 1 to 6 to a substrate;
2) curing the composition to form a silicone pressure sensitive adhesive on the substrate. 1) applying the composition according to any one of claims 1 to 6 to a release liner;
2) curing the composition to form a silicone pressure sensitive adhesive on the release liner;
3) applying the silicone pressure sensitive adhesive to a substrate. 10. The method according to claim 8 or 9, wherein the substrate is an optical silicone elastomer. A method according to any one of claims 8 to 10, wherein the silicone pressure sensitive adhesive is optically transparent. An article prepared by the method according to any one of claims 8 to 11. 13. The article of claim 12, wherein the article is part of a flexible display. A part of a flexible display device,
I) an optical silicone elastomer layer;
II) a silicone pressure sensitive adhesive layer adhered to said optical silicone elastomer layer, said silicone pressure sensitive adhesive layer being the product of a composition according to any one of claims 1 to 5. , a silicone pressure sensitive adhesive layer, and a component.