Hydrosilylated reaction-curing silicone pressure-sensitive adhesive, composition, method for preparing the same, and method for use in flexible display devices.

Abstract

Silicone pressure sensitive adhesives prepared by curing a hydrosilylation reaction curable composition are disclosed. The silicone pressure sensitive adhesives are useful in preparing components of flexible displays.

Description

[Technical Field]

[0001] Cross-reference of related applications none

[0002] The present invention relates to a silicone pressure-sensitive adhesive and a method for preparing and using the same. In particular, the present invention relates to a hydrosilylated curable composition that cures to form a silicone pressure-sensitive adhesive suitable for use in flexible display devices.

[0003] Introduction For example, flexible display devices have been developed that can be deformed by bending, folding, winding, reeling, or stretching. Flexible display devices can be deformed according to consumer needs or usage conditions. Typically, the various components of a display device are made of multiple layers, and it is important that when the flexible display device is deformed, the layers adhere to each other and do not suffer damage that would cause component failure. Silicone pressure-sensitive adhesives play an important role in bonding different layers to each other and releasing stress on the various layers of the display device during repeated deformation, such as bending, folding, winding, reeling, or stretching. To have good durability in a flexible display device, silicone pressure-sensitive adhesives should have a low storage modulus (G') and a low glass transition temperature (Tg). However, the peel force of cured silicone pressure-sensitive adhesives with low Tg and low G', especially the peel force of cured silicone pressure-sensitive adhesives with low Tg and low G' on the wet-cast side, is very high, which can hinder the process of manufacturing flexible display devices.

[0004] The industry requires a silicone pressure-sensitive adhesive that possesses one or more of the following characteristics: high temperature resistance, good durability, low peeling force, especially on the wet casting side, and good optical performance that does not cause failure in flexible display devices. [Overview of the project]

[0005] A hydrosilylated reaction-curable composition can cure to form a silicone pressure-sensitive adhesive. A method for producing the composition and a method for producing an article using the composition are provided. The article may include components for a flexible display device. [Brief explanation of the drawing]

[0006] [Figure 1] This is a partial cross-sectional view of the laminated article 100.

[0007] Reference number 100 Part of a laminated article 101 Second release liner 101b Surface of the second release liner 101 102 Silicone pressure-sensitive adhesive 102a Surface of silicone pressure-sensitive adhesive 102 102b Opposite surface of silicone pressure-sensitive adhesive 102 103 First release liner 103a Surface of the first release liner 103 [Modes for carrying out the invention]

[0008] A hydrosilylated reaction curable composition for forming a silicone pressure-sensitive adhesive is, Based on the total weight of the starting materials (A) to (F) in the composition, the (A) polydiorganosiloxane gum component is present in an amount of 35.15% to 43.63% by weight, Based on the total weight of the starting materials (A) to (F), the (A-1) unit formula (R) is used in amounts ranging from 28.03% by weight to 43.5% by weight. M 2R U SiO 1 / 2 )2(R M 2SiO 2 / 2 ) a an aliphatic unsaturated polydiorganosiloxane gum, wherein each R M However, each R is a monovalent hydrocarbon group of 1 to 30 carbon atoms that is independently selected and does not contain aliphatic unsaturated atoms. Uis a monovalent aliphatic unsaturated hydrocarbon group independently selected from 2 to 30 carbon atoms, and the subscript a has a value sufficient to impart plasticity of 20 mils (0.51 mm) to 80 mils (2.03 mm) to the aliphatic unsaturated polydiorganosiloxane gum, (A-1) aliphatic unsaturated polydiorganosiloxane gum, and 0 to <0.3 wt% of (A-2) unit formula ((HO)R M 2SiO 1 / 2 )2(R M 2SiO 2 / 2 ) a’ of a hydroxyl-terminated polydiorganosiloxane gum, wherein each R M is a monovalent hydrocarbon group independently selected from 1 to 30 carbon atoms without aliphatic unsaturation, and each subscript a' has a value sufficient to impart plasticity of 20 mils (0.51 mm) to 80 mils (2.03 mm) to the polydiorganosiloxane gum, (A-2) hydroxyl-terminated polydiorganosiloxane gum, and 0 to 7 wt% of (A-3) unit formula (R M 3SiO 1 / 2 )2(R M 2SiO 2 / 2 ) a” of a non-functional polydiorganosiloxane gum, wherein each R M is a monovalent hydrocarbon group independently selected from 1 to 30 carbon atoms without aliphatic unsaturation, and the subscript a” has a value sufficient to impart plasticity of 20 mils (0.51 mm) to 80 mils (2.03 mm) to the non-functional polydiorganosiloxane gum, (A-3) non-functional polydiorganosiloxane gum, and including, (A) a polydiorganosiloxane gum component, Based on the total weight of starting materials (A) to (F) in the composition, 52.69 wt% to 63.26 wt% of (B) a polyorganosilicate resin component, Based on the total weight of starting materials (A) to (F), 52.39 wt% to 63.11 wt% of (B-1) unit formula: (R M 3SiO 1 / 2 ) z (SiO 4 / 2 ) o Z pA capped resin, wherein Z is a hydrolyzable group, the subscript p ranges from 0 to a value sufficient to give the capped resin a maximum hydrolyzable group content of 2%, the subscripts z and o have values ​​such that z>4 and o>1, and the quantity (z+o) is sufficient to give the capped resin a number-average molecular weight of 500 g / mol to 5,000 g / mol, (B-1) capped resin, Based on the total weight of the starting materials (A) to (F), the (B-2) unit formula (R) is used in units of 0 to 0.37% by weight. M 3SiO 1 / 2 ) z’ (SiO 4 / 2 ) o’ Z p’ (B) a polyorganosilicate resin component comprising: (B-2) an uncapped resin, wherein 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 ​​such that z'>4 and o'>1, and the quantity (z'+o') has a value sufficient to give the uncapped resin a number average molecular weight of 500 g / mol to 5,000 g / mol; and (B-1) a capped resin and (B-2) an uncapped resin, which are present in a total amount of 52.6% to 64.0% by weight based on the total weight of the starting materials (A) to (F); Here, (A) polydiorganosiloxane gum component and (B) polyorganosilicate resin component are present in a weight ratio of (B):(A) (resin:gum ratio) ≤ 1.8. Based on the total weight of the starting materials (A) to (F), 0.01% to 5% by weight of (C) hydrosilylation catalyst and (D) Unit formula: (R M 2SiO 2 / 2 ) e (HR M SiO 2 / 2 ) f (R M 2HSiO 1 / 2 ) g (R M 3SiO 1 / 2 ) hA polyorganohydrogensiloxane in which, in the formula, the subscript e≧0, the subscript f>0, the quantity (e+f) is 4~500, 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, and (D) polyorganohydrogensiloxane is present in an amount sufficient to make the molar ratio {(D):(A) ratio} of silicon-bonded hydrogen atoms to aliphatic unsaturated hydrocarbon groups of (A) polydiorganosiloxane gum 30:1~66:1, and Based on the total weight of the starting materials (A) to (F), >0% to <2.43% by weight of (E) trialkyl borate, Based on the total weight of the starting materials (A) to (F), 0% to 5% by weight of (F) hydrosilylation reaction inhibitor, Based on the total weight of all starting materials in the composition, >0% to 90% by weight of (G) solvent, Based on the total weight of the starting materials (A) to (F), it contains 0 to 5% by weight of (H) fixing additive.

[0009] (A) Polydiorganosiloxane gum component The hydrosilylated reaction curable composition contains (A) a polydiorganosiloxane gum component. The polydiorganosiloxane gum component contains (A-1) aliphatic unsaturated polydiorganosiloxane gum. The polydiorganosiloxane gum component may optionally further contain one or both of (A-2) hydroxyl-terminated polydiorganosiloxane gum and (A-3) non-functional polydiorganosiloxane gum.

[0010] The starting material (A-1), aliphatic unsaturated polydiorganosiloxane gum, has the unit formula: (R M 2R U SiO 1 / 2 )2(R M 2SiO 2 / 2 ) a It has, in the formula, each R M This is a monovalent hydrocarbon group consisting of 1 to 30 carbon atoms, which is not aliphatic unsaturated, and each R UA is an independently selected monovalent aliphatic unsaturated hydrocarbon group with 2 to 30 carbon atoms, where the subscript a has a value sufficient to impart plasticity to (A-1) aliphatic unsaturated polydiorganosiloxane gum of 20 mil (0.51 mm) to 80 mil (0.203 mm), or 30 mil (0.76 mm) to 70 mil (1.78 mm), or 55 mil (1.40 mm) to 65 mil (1.65 mm), the plasticity of which was measured by applying a 1 kg load to a 4.2 g spherical sample at 25°C for 3 minutes according to ASTM D926, the result measured in 1 / 1000 inch (mil), and the procedure according to ASTM D926.

[0011] In the unit formula (A-1), each R M This is a monovalent hydrocarbon group consisting of 1 to 30 carbon atoms, independently selected, that does not contain aliphatic unsaturated carbon atoms. Alternatively, each R M It may have 1 to 12 carbon atoms, or 1 to 6 carbon atoms. MSuitable monovalent hydrocarbon groups 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. Examples of alkyl groups include, but are not limited to, 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 tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as branched alkyl groups with six or more carbon atoms, and cyclic alkyl groups such as cyclopentyl and cyclohexyl. "Aryl" means a completely unsaturated cyclic hydrocarbon group. Examples of aryl groups include, but are not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, or 6 to 7 carbon atoms, or 5 to 6 carbon atoms. Polycyclic aryl groups may have 10 to 17 carbon atoms, 10 to 14 carbon atoms, or 12 to 14 carbon atoms. "Aralkyl" means an alkyl group having a pendant and / or terminal aryl group, or an aryl group having a pendant alkyl group. Exemplary aralkyl groups include tolyl, xylyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl. Alternatively, each R M R may be independently selected from the group consisting of alkyl and aryl. Alternatively, each R M R may be independently selected from methyl and phenyl. Alternatively, each R M It may be an alkyl group. Alternatively, each R M It may also be methyl.

[0012] In the unit formula (A-1), each R U R is an independently selected monovalent aliphatic unsaturated hydrocarbon group with 2 to 30 carbon atoms. Alternatively, each R UThese may have 2 to 12 carbon atoms, or 2 to 6 carbon atoms. Suitable monovalent aliphatic unsaturated hydrocarbon groups include alkenyl groups 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 with 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 with 2 to 4 carbon atoms). Alternatively, each R U This may be an alkenyl such as vinyl, allyl, or hexenyl.

[0013] Polydiorganosiloxane gums are known in the art and can be prepared by methods such as hydrolysis and condensation of the corresponding organohalosilane, or equilibration of cyclic polydiorganosiloxanes. Examples of polydiorganosiloxane gums suitable for use in hydrosilylated reaction curable compositions are: 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) exemplifies a combination of two or more of i) to vii). Alternatively, polydiorganosiloxane gum is i) dimethylvinylsiloxy-terminated polydimethylsiloxane, v) Dimethylhexenylsiloxy-terminated polydimethylsiloxanes may be selected from the group consisting of i) and v).

[0014] The aliphatic unsaturated polydiorganosiloxane gum, which is the starting material (A-1), is present in the hydrosilylation reaction curable composition in an amount of at least 28.0% by weight, or at least 30% by weight, or at least 35% by weight, or at least 35.5% by weight, based on the total weight of the starting materials (A) to (F), and at the same time, this amount may be up to 43.5% by weight, or up to 43.1% by weight, or up to 40% by weight, or up to 35.9% by weight. Alternatively, the amount of (A-1) aliphatic unsaturated polydiorganosiloxane gum may be 28% to 43.5% by weight, or 35.8% to 43.5% by weight, and / or 43.0% to 43.5% by weight, based on the total weight of the starting materials (A) to (F).

[0015] The starting material (A) polydiorganosiloxane component is optionally (A-2) unit formula: {(HO)R M 2SiO 1 / 2}2(R M 2SiO 2 / 2 ) a The formula may further contain a hydroxyl-terminated polydiorganosiloxane gum of ', where R M As stated above, the subscript a' is a value sufficient to give the (A-2) hydroxyl-terminated polydiorganosiloxane gum a plasticity of 20 mil (0.51 mm) to 80 mil (2.03 mm), or 30 mil (0.76 mm) to 70 mil (1.78 mm), or 45 mil (1.14 mm) to 65 mil (1.65 mm), and the plasticity was measured by applying a 1 kg load to a spherical sample weighing 4.2 g for 3 minutes at 25°C, based on ASTM D926, the result measured in 1 / 1000 inch (mil), and the procedure was based on ASTM D926.

[0016] Hydroxyl-terminated polydiorganosiloxane gums suitable for use as starting materials (A-2) are known in the art and can be prepared by methods such as hydrolysis and condensation of the corresponding organohalosilane or equilibration of cyclic polydiorganosiloxanes. Examples of hydroxyl-terminated polydiorganosiloxane gums suitable for use as starting materials (A-2) in hydrosilylation reaction curable compositions are: i) Bis-hydroxyl-terminated polydimethylsiloxane, ii) Bis-hydroxyl-terminated poly(dimethylsiloxane / methylphenylsiloxane), iii) Bis-hydroxyl-terminated poly(dimethylsiloxane / diphenylsiloxane), iv) Phenylen, methyl, hydroxyl-siloxy-terminated polydimethylsiloxane, This is exemplified by a combination of two or more of v)i)~iv). Alternatively, the starting material (A-2) contains a bis-hydroxyl-terminated polydimethylsiloxane.

[0017] The starting material (A-2) hydroxyl-terminated polydiorganosiloxane gum may optionally be present in the hydrosilylated reaction curable composition in an amount of 0% to 0.3% by weight based on the total weight of the starting materials (A) to (F). Alternatively, if present, the (A-2) hydroxyl-terminated polydiorganosiloxane gum may be present in an amount of at least 0.1% by weight, or at least 0.13% by weight, and at the same time, this amount may be a maximum of 0.26% by weight, or a maximum of 0.13% by weight, based on the same criteria.

[0018] Starting material (A) Polydiorganosiloxane component is optionally (A-3) Unit formula: (R M 3SiO 1 / 2 )2(R M 2SiO 2 / 2 ) a” The formula may further contain a non-functionalized polydiorganosiloxane gum, where R MAs stated above, the subscript a' is a value sufficient to give (A-3) non-functional polydiorganosiloxane gum a plasticity of 20 mil (0.51 mm) to 80 mil (2.03 mm), or 30 mil (0.76 mm) to 80 mil (2.03 mm), or 45 mil (1.14 mm) to 75 mil (1.91 mm), and or 60 mil (1.52 mm) to 70 mil (1.78 mm), and the plasticity was measured by applying a 1 kg load to a spherical sample weighing 4.2 g for 3 minutes at 25°C, based on ASTM D926, and the result was measured in 1 / 1000 inch (mil), and the procedure was based on ASTM D926.

[0019] Non-functional polydiorganosiloxane gums suitable for use as starting materials (A-3) are known in the art and can be prepared by methods such as hydrolysis and condensation of the corresponding organohalosilane or equilibration of cyclic polydiorganosiloxanes. Examples of non-functional polydiorganosiloxane gums suitable for use as starting materials (A-3) in hydrosilylation reaction curable compositions are: i) Bis-trimethylsiloxy-terminated polydimethylsiloxane, ii) Bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), iii) Bis-trimethylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), iv) Phenyl, dimethyl-siloxy-terminated polydimethylsiloxane, This is exemplified by a combination of two or more of v)i)~iv). Alternatively, the starting material (A-3) contains a bis-trimethylsiloxy-terminated polydimethylsiloxane.

[0020] The starting material (A-3) non-functional polydiorganosiloxane gum may optionally be present in the hydrosilylated reaction curable composition in an amount of 0% to 7% by weight based on the total weight of the starting materials (A) to (F). Alternatively, if present, the (A-3) non-functional polydiorganosiloxane gum may be present in an amount of at least 1% by weight or at least 2% by weight, and at the same time, this amount may be a maximum of 7% by weight or a maximum of 5% by weight, based on the same criteria. Alternatively, the (A-3) functional polydiorganosiloxane gum may be omitted.

[0021] (B) Polyorganosilicate resin component The hydrosilylated reaction curable composition further comprises a polyorganosilicate resin component, which is the starting material (B), and the polyorganosilicate resin component includes (B-1) a capped resin and (B-2) an uncapped resin. Formula R M 3SiO 1 / 2 [In the formula, R M The above is true for the single functional unit ("M" unit) and the formula SiO 4 / 2 A polyorganosilicate resin containing tetrafunctional silicate units ("Q" units). Alternatively, R M At least 1 / 3, or at least 2 / 3, of the groups are alkyl groups (e.g., methyl groups). Alternatively, the M unit is (Me3SiO 1 / 2 ) and (Me2PhSiO 1 / 2 Polyorganosilicate resins are soluble in solvents such as liquid hydrocarbons, exemplified by benzene, toluene, xylene, and heptane, or in liquid organosilicon compounds such as low-viscosity linear and cyclic polydiorganosiloxanes.

[0022] When prepared, the polyorganosilicate resin contains the above-mentioned M and Q units, and the polyorganosiloxane further contains units having silicon-bonded hydroxyl groups, with the formula Si(OSiR M 3)4[wherein, R MThe above is true, but it may also contain a neopentamer, for example, the neopentamer may be a tetrakis(trimethylsiloxy)silane. 29 Using SiNMR spectroscopy, the hydroxyl content and molar ratio of M-units and Q-units can be measured. This ratio is expressed as {M(resin)} / {Q(resin)}, where the M-units and Q-units are removed from the neopentamer. The M:Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M-units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q-units) in the resinous portion. The M:Q ratio may be between 0.5:1 and 1.5:1.

[0023] The Mn in polyorganosilicate resin is present in the R M It varies depending on various factors, such as the type of hydrocarbon group represented. For polyorganosilicate resins, Mn refers to the number-average molecular weight measured using GPC when peaks representing neopentamers are excluded from the measurement. The Mn of polyorganosilicate resins ranges from 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 to 4,700 g / mol. A suitable GPC test method for measuring Mn is disclosed in Reference Example 1, column 31, U.S. Patent No. 9,593,209.

[0024] 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] ) are hereby incorporated by reference herein for the purpose of disclosing MQ resins, which are polyorganosilicate resins suitable for use in the hydrosilylation reaction curable compositions described herein. The polyorganosilicate resins can be prepared by any suitable method such as co-hydrolysis of the corresponding silanes or silica hydrosol capping method. The polyorganosilicate resins can be prepared by a silica hydrosol capping process such as those disclosed in U.S. Patent No. 2,676,182 to Daudt et al., U.S. Patent No. 4,611,042 to Rivers-Farrell et al., and U.S. Patent No. 4,774,310 to Butler et al. The above method of Daudt et al. 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 recovering a copolymer having M units and Q units. The resulting copolymer generally contains 2 to 5 weight percent of hydroxyl groups.

[0025] The intermediates used to prepare the polyorganosilicate resins can be triorganosilanes and silanes or alkali metal silicates containing four hydrolyzable substituents. The triorganosilane has the formula R M 3SiX 1 [wherein, R M is as described above, and X 1 is a hydrolyzable substituent such as halogen, alkoxy, acyloxy, hydroxyl, oximo, or ketoximo, or represents a hydrolyzable substituent such as halogen, alkoxy, or hydroxyl]. The silane having four hydrolyzable substituents has the formula SiX 2 4 [wherein each X 2 is halogen, alkoxy, or hydroxyl]. Suitable alkali metal silicates include sodium silicate.

[0026] The polyorganosilicate resin prepared as described above is an uncapped resin, and this resin typically contains silicon-bonded hydroxyl groups, such as those of the formula HOSi 3 / 2 and / or HOR M 2SiO 1 / 2 . The polyorganosilicate resin may contain silicon-bonded hydroxyl groups that are > 3% to 10% by measurement using NMR spectroscopy. For certain applications, the amount of silicon-bonded hydroxyl groups may desirably be ≦ 2%, or < 0.7%, or < 0.3%, or < 1%, or 0.3% to 2%. The silicon-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin can be converted to trihydrocarbon siloxane groups or different hydrolyzable groups by reacting the silicone resin with a silane, disiloxane or disilazane containing appropriate end groups in a process called capping. The silane containing a hydrolyzable group may be added in a molar excess over the amount necessary to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

[0027] When the polyorganosilicate resin is a capped resin, the capped resin may contain 2% or less, or 0.7% or less, or 0.3% or less, or 0.3% to 0.8% of units represented by the formula HOSiO 3 / 2 and / or HOR M 2SiO 1 / 2 [where R M is as defined above]. The concentration of silanol groups present in the polyorganosiloxane can be determined using NMR spectroscopy as described above.

[0028] Thus, 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 3SiO 1 / 2 ) z (SiO 4 / 2 ) o Z p , where RM As described above, the subscripts z and o have values ​​such that o > 1 and subscript z > 4, the quantity (o + z) is sufficient to give the capped resin the above Mn (e.g., 500 g / mol to 5,000 g / mol, or 1,000 g / mol to 4,700 g / mol, or 2,900 g / mol to 4,700 g / mol, or 2,900 g / mol to 4,100 g / mol), and the subscript p is sufficient to give the capped resin the above hydrolyzable group content (e.g., 0 to 2%, or 0 to 0.7%, or 0 to 0.3%). The capped resin of the starting material (B-1) may be present in an amount of 52.3% to 63.11% by weight based on the total weight of the starting materials (A) to (F). Alternatively, the capped resin (B-1) may be present in an amount of 52.3% to 62.7% by weight, or 52.3% to 52.9% by weight, or 62.2% to 63.2% by weight, according to the same criteria. Alternatively, the amount of the capped resin (B-1) may be at least 52.3%, or at least 53%, or at least 54%, while at the same time, the amount may be up to 62.7%, or up to 62%, or up to 60%, or up to 55%, or up to 54%, according to the same criteria.

[0029] The starting material (B-2), uncapped resin, has the unit formula (R M 3SiO 1 / 2 ) z’ (SiO 4 / 2 ) o’ Z p’ It may have R MAs described above, the subscripts z' and o' have values ​​such that o'>1 and z'>4, the quantity (o'+z') is sufficient to give the uncapped resin the above Mn (e.g., 500g / mol~5,000g / mol, or 1,000g / mol~4,700g / mol, or 2,700g / mol~4,700g / mol, or 2,900g / mol~3,800g / mol), and the subscript p' is sufficient to give the uncapped resin the above hydrolyzable group content (e.g., >3%~10%). The starting material (B-2), the uncapped resin, is arbitrary and its amount may be 0. Alternatively, if used, (B-2) the uncapped resin may be present in amounts of >0% to 0.3% by weight, or 0.1% to 0.3% by weight, and / or 0.1% to 0.2% by weight, based on the total weight of the starting materials (A) to (F).

[0030] The hydrosilylated curable composition contains (B) a polyorganosilicate resin component in amounts of 52.6% to 63.3% by weight, or 52.6% to 62.7% by weight, or 53.0% to 62.4% by weight, and / or 52.6% to 53.1% by weight, based on the total weight of the starting materials (A) to (F) (for example, the total weight of (B-1) capped resin and (B-2) uncapped resin, based on the total weight of all starting materials in the hydrosilylated curable composition, excluding the solvent). If (B-2) uncapped resin is present, the amounts of capped and uncapped resin in the starting material (B) may be sufficient to ensure that the weight ratio of uncapped resin to capped resin {i.e., the (B-2):(B-1) ratio} is <0.12:1; or <0.006:1; or 0.001:1 to 0.12:1.

[0031] The starting material (A) polydiorganosiloxane gum component and the starting material (B) polyorganosilicate resin component may be present in the hydrosilylation reaction curable composition in an amount sufficient to ensure that the weight ratio of (B) polyorganosilicate resin component to (A) polydiorganosiloxane gum component {i.e., the (B):(A) ratio} is ≤ 1.8:1. Alternatively, the (B):(A) ratio may be at least 1.2:1, or at least 0.1.5:1, while at the same time the (B):(A) ratio may be up to 1.8:1, or up to 1.75:1. Alternatively, the (B):(A) ratio may be between 1.2:1 and 1.8:1, or between 1.2:1 and 1.25:1.

[0032] (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 hydrosilylation reaction catalysts may be (C-1) platinum, rhodium, ruthenium, palladium, osmium, and iridium; or they may be platinum, ruthenium, and iridium; or the metal may be platinum. Alternatively, the hydrosilylation catalyst may be (C-2) a compound of such a metal, for example, a rhodium diphosphine chelate such as chloride tris(triphenylphosphine)rhodium(I) (Wilkinson's catalyst), [1,2-bis(diphenylphosphin)ethane]dichlorodirhodium or [1,2-bis(diethylphospino))ethane]dichlorodirhodium, chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, or platinum dichloride. Alternatively, the hydrosilylation catalyst may be (C-3) a complex of a platinum group metal compound with an alkenyl-functional organopolysiloxane oligomer, or (C-4) a platinum group metal compound microencapsulated in a matrix or core-shell structure. Examples of platinum alkenyl-functionalized organopolysiloxane oligomer complexes include platinum complexes of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane (Karstedt catalyst). Alternatively, the hydrosilylation catalyst may include a complex microencapsulated in a (C-5) resin matrix.Exemplary hydrosilylation catalysts include Speier's U.S. Patent No. 2,823,218, Ashby's No. 3,159,601, Lamoreaux's No. 3,220,972, Chalk et al.'s No. 3,296,291, Willing's No. 3,419,593, Modic's No. 3,516,946, Karstedt's No. 3,715,334, and Karstedt's No. 3,814. This is described in Patent No. 730, Chandra's Patent No. 3,928,629, Lee et al.'s Patent No. 3,989,668, Lee et al.'s Patent No. 4,766,176, Lee et al.'s Patent No. 4,784,879, Togashi's Patent No. 5,017,654, Chung et al.'s Patent No. 5,036,117, and Brown's Patent No. 5,175,325, as well as European Patent No. 0347895(A) by Togashi et al. Hydrosilylation catalysts are commercially available, for example, SYL-OFF® 4000 Catalyst and SYL-OFF® 2700 are available from Dow Silicones Corporation.

[0033] The amount of hydrosilylation catalyst used herein varies depending on various factors such as the selection of the starting materials (D) polyorganohydrogensiloxane and (A) polydiorganosiloxane gum components, the content of silicon-bonded hydrogen atoms (SiH) and aliphatic unsaturated groups in each of them, and the content of platinum group metals in the selected catalyst. However, the amount of hydrosilylation catalyst is sufficient to catalytically act on the hydrosilylation reaction between SiH and aliphatic unsaturated groups, or the amount of catalyst is sufficient to give 1 ppm to 6,000 ppm of platinum group metals, or 1 ppm to 1,000 ppm, or 1 ppm to 100 ppm of platinum group metals, based on the total weight of the starting materials containing silicon-bonded hydrogen atoms and aliphatic unsaturated hydrocarbon groups. Alternatively, if the hydrosilylation catalyst contains a platinum-organosiloxane complex, the amount of the hydrosilylation catalyst may be 0.01% to 5% based on the total weight of the starting materials (A) to (F).

[0034] (D) Polyorganohydrogensiloxane The starting material (D) in the hydrosilylation reaction curable composition is given by the unit formula: (R M 2SiO 2 / 2 ) e (HR M SiO 2 / 2 ) f ,(R M 2HSiO 1 / 2 ) g (R M 3SiO 1 / 2 ) h It is a polyorganohydrogensiloxane, in which R M As described above, the subscript e ≥ 0, the subscript f ≥ 0, the quantity (e + f) is 4 to 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%, or 0.6% to 1.5%, and the silicon-bonded hydrogen (Si-H) content of the polyorganohydrogensiloxane can be determined using quantitative infrared analysis according to ASTM E168.

[0035] 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) is exemplified by combinations of two or more of (D-1), (D-2), (D-3), and (D-4). Methods for preparing polyorganohydrogensiloxanes, such as hydrolysis and condensation of organohydridohalosilanes, are known in the art; see, for example, U.S. Patent No. 3,957,713 by Jeram et al. and U.S. Patent No. 4,329,273 by Hardman et al. Polyorganohydrogensiloxanes can also be prepared, for example, as described in U.S. Patent No. 2,823,218 by Speier et al., which discloses 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 polymethylhydrogensiloxane. Polyorganohydrogensiloxanes are also commercially available, such as those from Gelest, Inc. (Morrisville, Pennsylvania, USA), including 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.

[0036] The amount of polyorganohydrogensiloxane in the hydrosilylated reaction curable composition is 0.1% to 5% based on the total weight of the starting materials (A) to (F). Alternatively, the amount of polyorganohydrogensiloxane in the hydrosilylated reaction curable composition may be at least 0.1%, or at least 0.25%, or at least 0.3%, and at the same time, this amount may be up to 5%, or up to 2.5%, or up to 1.5%, or up to 1%, based on the same criteria.

[0037] The ratio of silicon-bonded hydrogen to aliphatic unsaturated groups is important when the hydrosilylation curing process is dependent. Generally, this is determined by calculating the total weight % of aliphatic unsaturated groups (e.g., vinyl [V]) and the total weight % of silicon-bonded hydrogen [H] in the composition, where, if 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) polydiorganosiloxane gum component and (D) polyorganohydrogensiloxane may be present in the hydrosilylation reaction curable composition in amounts sufficient to result in a molar ratio of silicon-bonded hydrogen atoms to aliphatic unsaturated hydrocarbon groups {(D):(A) ratio} of at least 30:1, or at least 31:1, or at least 45:1, while at the same time, this ratio may be up to 66:1, or up to 60:1, or up to 59:1. Alternatively, the (D):(A) ratio may be 30:1 to 66:1, or 35:1 to 560:1, or 40:1 to 55:1, or 45:1 to 60:1.

[0038] (E) Trialkyl borate The starting material (E) in the hydrosilylation reaction curable composition is of formula B(OR A )3 is a trialkyl borate, in the formula, each R A The alkyl group is an independently selected alkyl group having 1 to 30 carbon atoms, 1 to 12 carbon atoms, or 1 to 6 carbon atoms. The alkyl group may be 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-pentyl), hexyl, a branched alkyl group with 6 carbon atoms, or a cyclic alkyl group such as cyclopentyl or cyclohexyl. Suitable examples of trialkyl borate include trimethyl borate, triethyl borate, tributyl borate, and combinations of two or more of these. Alternatively, the trialkyl borate may be triethyl borate.

[0039] Trialkyl borates are known in the art and can be produced by known methods, such as those described in Stange's U.S. Patent 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.

[0040] The amount of (E) trialkyl borate added to the hydrosilylated curable composition is >0% to <2.43% by weight, based on the total weight of the starting materials (A) to (F). Alternatively, the amount of (E) trialkyl borate may be at least 0.05% by weight, or at least 0.1% by weight, or at least 0.2%, and at the same time, this amount may be up to 2.42% by weight, or up to 2% by weight, or up to 1% by weight, or up to 0.5% by weight, based on the same criteria. Alternatively, the amount of (E) trialkyl borate may be 0.05% to 1% by weight, or 0.4% to 1% by weight, based on the same criteria.

[0041] (F) Hydrosilylation reaction inhibitor The starting material (F) is an optional hydrosilylation inhibitor (inhibitor) which can be used to alter the rate of the hydrosilylation reaction compared to a composition containing the same starting material except for the inhibitor. The starting material (F) may be selected from the group consisting of (F-1) acetylene alcohols, (F-2) silylated acetylene alcohols, (F-3) en-yne compounds, (F-4) triazoles, (F-5) phosphines, (F-6) mercaptans, (F-7) hydrazines, (F-8) amines, (F-9) fumarates, (F-10) maleates, (F-11) ethers, (F-12) carbon monoxide, (F-13) alkenyl-functionalized siloxane oligomers, and (F-14) combinations of two or more of these. Alternatively, the hydrosilylation reaction inhibitor may be selected from the group consisting of (F-1) acetylene alcohols, (F-2) silylated acetylene alcohols, (F-9) fumarates, (F-10) maleates, (F-13) carbon monoxide, and (F-14) combinations of two or more of these.

[0042] Acetylene alcohols are exemplified by 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyne-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-octin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol, and combinations thereof. Acetylene alcohols are known in the art and are commercially available from various suppliers; see, for example, U.S. Patent No. 3,445,420 by Kookootsedes et al. Alternatively, the inhibitor may be a silylated acetylene compound. Although not bound by theory, it is thought that the addition of a silylated acetylene compound reduces the yellowing of the reaction product prepared from the hydrosilylation reaction compared to the reaction product obtained by hydrosilylation of a starting material that does not contain a silylated acetylene compound or contains an organic acetylene alcohol inhibitor such as the one mentioned above.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)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyne-3-oxy))silane, (3-methyl-1-butyne-3-oxy)dimethylphenylsilane, (3-methyl-1-butyne-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyne-3-oxy)triethylsilane, bis(3-methyl-1- These are exemplified by butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Silylated acetylene compounds useful as inhibitors in this specification can be prepared by methods known in the art. For example, U.S. Patent No. 6,677,407 by Bilgrien et al. discloses the silylation of the above-mentioned acetylene alcohol by reaction with chlorosilane in the presence of an acid acceptor.

[0043] Alternatively, the inhibitor may be an en-yne compound, such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, or a combination thereof. Alternatively, the inhibitor may contain a triazole, exemplified by benzotriazole. Alternatively, the inhibitor may contain a phosphine. Alternatively, the inhibitor may contain a mercaptan. Alternatively, the inhibitor may contain a hydrazine. Alternatively, the inhibitor may contain an amine. Examples of amines include tetramethylethylenediamine, 3-dimethylamino-1-propyne, n-methylpropargylamine, propargylamine, 1-ethynylcyclohexylamine, or a combination thereof. Alternatively, the inhibitor may contain a fumarate. Examples of fumarates 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 contain a maleate. Examples of 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.

[0044] Alternatively, the inhibitor may contain carbon monoxide. Alternatively, the inhibitor may contain an alkenyl-functionalized siloxane oligomer, which may be cyclic or linear, such as methyl vinylcyclosiloxane, exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and combinations thereof. Compounds useful as the above inhibitors are commercially available, for example, from Sigma-Aldrich Inc. or Gelest, Inc., and are known in the art; see, for example, U.S. Patent No. 3,989,667 by Lee et al. Suitable inhibitors for use in this specification are exemplified by those described as stabilizer E in paragraphs

[0148] to

[0165] of U.S. Patent Application Publication No. 20007 / 0099007.

[0045] The amount of inhibitor varies depending on various factors such as the desired pot life, whether the composition is partial or multipart, the specific inhibitor used, and the selection and amount of (C) hydrosilylation reaction catalyst. However, if present, the amount of (F) inhibitor may be in the range of 0% to 5%, or 0% to 1%, or 0.001% to 1%, or 0.01% to 0.5%, or 0.01% to 0.4%, based on the total weight of the starting materials (A) to (F) in the hydrosilylation reaction curable composition.

[0046] (G) Solvent The hydrosilylation reaction curable composition further comprises a solvent, which is the starting material (G). The solvent may be an organic solvent such as a hydrocarbon, ketone, acetate ester, ether, and / or a cyclic siloxane with an average degree of polymerization of 3 to 10. Suitable hydrocarbons for the solvent may be (G-1) aromatic hydrocarbons such as benzene, benzene, toluene, or xylene, (G-2) aliphatic hydrocarbons such as hexane, heptane, octane, or isoparaffin, or (G-3) a combination thereof. Alternatively, the solvent may be a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, or 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 two or more combinations thereof.

[0047] The amount of solvent varies depending on various factors, such as the type of solvent selected and the amount and type of other starting materials selected for the hydrosilylation reaction curable composition. However, the amount of solvent may be in the range of >0% to 90%, or 0% to 60%, or 20% to 60%, or 45% to 65%, or 50% to 60%, based on the total weight of all starting materials in the hydrosilylation reaction curable composition. The solvent can be added during the preparation of the hydrosilylation reaction curable composition, for example, to assist in the mixing and delivery of one or more of the above-mentioned starting materials. All or part of the solvent may be added together with one or more of the other starting materials. For example, the polyorganosilicate resin and / or hydrosilylation reaction catalyst may be dissolved in the solvent before being combined with the other starting materials in the hydrosilylation reaction curable composition. All or part of the solvent may optionally be removed after the preparation of the hydrosilylation reaction curable composition.

[0048] (H) Fixing additive The starting material (H) in the hydrosilylated reaction curable composition is a fixing additive. Although not theoretically bound, the fixing additive is thought to facilitate bonding to the substrate by the silicone pressure-sensitive adhesive prepared by curing the hydrosilylated reaction curable composition described herein.

[0049] Suitable fixing additives for the starting material (H) include silane coupling agents such as methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacrylateoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, bis(trimethoxysilyl)propane, and bis(trimethoxysilylhexane), as well as mixtures or reaction mixtures of said silane coupling agents. Alternatively, the fixing additive may be tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, or 3-methacrylateoxypropyltrimethoxysilane.

[0050] Other suitable fixing additives are exemplified by reaction products of vinyl alkoxysilanes and epoxy-functionalized alkoxysilanes; reaction products of vinyl acetoxysilanes and epoxy-functionalized alkoxysilanes; and combinations of polyorganosiloxanes having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolyzable group per molecule with epoxy-functionalized alkoxysilanes (e.g., physical blends and / or reaction products) (e.g., combinations of hydroxy-terminated vinyl-functionalized polydimethylsiloxanes and glycidoxypropyltrimethoxysilanes).

[0051] Exemplary fixing additives are known in the art and are disclosed, for example, in U.S. Patent No. 9,562,149, U.S. Patent Publication No. 2003 / 0088042, U.S. Patent Publication No. 2004 / 0254274, U.S. Patent Publication No. 2005 / 0038188, paragraph

[0091] of U.S. Patent Publication No. 2012 / 0328863, and paragraph

[0041] of U.S. Patent Publication No. 2017 / 0233612, as well as in European Patent No. 0556023. Fixing additives are commercially available. For example, SYL-OFF® 9250, SYL-OFF® 9176, SYL-OFF® 297, and SYL-OFF® 397 are available from Dow Silicones Corporation (Midland, Michigan, USA). Other exemplary fixing additives include (G-1) vinyltriacetoxysilane, (G-2) glycidoxypropyltrimethoxysilane, and (G-3) combinations of (G-1) and (G-2). This combination (G-3) may be a mixture and / or a reaction product.

[0052] The amount of fixing additive varies depending on various factors, such as the type of substrate to which the silicone pressure-sensitive adhesive is bonded. However, if present, the amount of fixing additive may be 0.5-5%, 0.5-3%, or 0.5-2.5%, based on the total weight of all starting materials excluding the solvent in the hydrosilylated reaction curable composition.

[0053] Method for producing a hydrosilylated reaction curable composition Hydrosilylation reaction curable compositions can be prepared by a method that includes combining all of the above starting materials by any convenient method, such as mixing at ambient temperature or at high temperature. Hydrosilylation reaction inhibitors may be added before the hydrosilylation reaction catalyst, for example, when preparing the hydrosilylation reaction curable composition at high temperature, and / or when preparing the hydrosilylation reaction curable composition as a partial composition.

[0054] The method may further include delivering one or more starting materials (e.g., hydrosilylation catalysts and / or polyorganosilicate resins) into a solvent, which may be dissolved in the solvent when combined with one or more other starting materials in the hydrosilylation curable composition. Those skilled in the art will understand that if it is desirable that the resulting hydrosilylation curable composition be solvent-free (i.e., solvent-free or containing trace amounts of residual solvent derived from the delivery of the starting materials), the solvent may be removed after mixing two or more of the starting materials, in which case the solvent is not intentionally added to the hydrosilylation curable composition.

[0055] Alternatively, the hydrosilylation reaction curable composition may be prepared as a multipart composition if, for example, the hydrosilylation reaction curable composition is stored for a long period before use, for example, up to 6 hours before applying the hydrosilylation reaction curable composition to an optical silicone elastomer or other substrate. In a multipart composition, the hydrosilylation reaction catalyst is stored in a portion separate from any starting material having silicon-bonded hydrogen atoms, such as polyorganohydrogensiloxane, and these portions are combined immediately before use of the hydrosilylation reaction curable composition.

[0056] For example, a multipart composition may be prepared by combining a polydiorganosiloxane gum component, a polyorganohydrogensiloxane, and optionally at least several of the above-mentioned starting materials (other than hydrosilylation reaction catalysts) by any convenient method such as mixing to form a base. The curing agent may be prepared by combining a polydiorganosiloxane gum, a hydrosilylation reaction catalyst, and optionally at least several of the above-mentioned starting materials (other than polyorganohydrogensiloxane) by any convenient method such as mixing. The starting materials may be mixed at ambient temperature or high temperature. A hydrosilylation reaction inhibitor may be included in one or more of the base, curing agent portion, or separate additional portions. A polyorganosilicate resin may be added to the base, curing agent portion, or separate additional portion. Alternatively, a polyorganosiloxane resin may be added to the base. A solvent may be added to the base. Alternatively, some or all of the starting material containing the polyorganosilicate resin and the solvent may be added to a separate additional portion. Alternatively, an inhibitor may be added to the base or to a separate additional portion. When using a two-part composition, the weight ratio of the amount of base to the amount of curing agent may be in the range of 1:1 to 10:1. The hydrosilylation reaction curable composition cures by a hydrosilylation reaction to form a silicone pressure-sensitive adhesive.

[0057] How to use The method described above may further include one or more additional steps. An adhesive article, such as a silicone pressure-sensitive adhesive (prepared by curing the hydrosilylated reaction-curable composition described above), may be formed on a substrate using the hydrosilylated reaction-curable composition prepared as described above. Therefore, the method may further include applying the hydrosilylated reaction-curable composition to a substrate.

[0058] The application of a hydrosilylated reaction-curable composition to a substrate can be carried out by any convenient means. For example, a hydrosilylated reaction-curable composition can be applied to a substrate by a gravure coater, comma coater, offset coater, offset gravure coater, roller coater, reverse roller coater, air knife coater, slot die, or curtain coater.

[0059] The substrate can be any material capable of withstanding the curing conditions (described later) used to cure the hydrosilylated reaction-curable composition to form a silicone pressure-sensitive adhesive on the substrate. For example, any substrate capable of withstanding heat treatment at temperatures of 120°C or higher, or 150°C, is preferred. An example of a suitable material for such a substrate may be a release liner used in a wet casting method in which the above-mentioned silicone pressure-sensitive adhesive composition is used. The release liner has a fluorosilicone release coating thereon. Suitable fluorosilicone release coatings include commercially available fluorosilicone release coatings, such as SYL-OFF® 7555 coating, SYL-OFF® 7792 fluorosilicone release coating, SYL-OFF® 7795 fluorosilicone release coating, SYL-OFF® 7785 fluorosilicone release coating, SYL-OFF® 7786 fluorosilicone release coating, and mixtures of the above fluorosilicone release coatings, all of which are commercially available from Dow Silicones Corporation (Midland, Michigan, USA). The base material may further include polymer films and / or foams, which may 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 base material may be glass.The thickness of the substrate is not important, but it may be between 5 μm and 300 μm, or between 10 μm and 200 μm.

[0060] To improve the bonding of the silicone pressure-sensitive adhesive to the substrate, the method for forming the adhesive article may optionally further include treating the substrate before applying the hydrosilylated reaction-curable composition. The substrate treatment may be carried out by any convenient method, such as applying a primer before applying the hydrosilylated reaction-curable composition to the substrate, or subjecting the substrate to corona discharge treatment, etching, or plasma treatment.

[0061] The methods described herein may optionally further include, for example, applying a removable release liner to the silicone pressure-sensitive adhesive on the opposite side of the substrate to protect the silicone pressure-sensitive adhesive before use of the adhesive article. The release liner may be applied before, during, or after curing of the hydrosilylated reaction-curable composition. Alternatively, the hydrosilylated reaction-curable composition may be applied on a first release liner and subsequently cured (wet casting) to form a silicone pressure-sensitive adhesive layer having a first surface that adheres to the first release liner. Optionally, a second release liner may be applied to the opposite surface of the silicone pressure-sensitive adhesive (e.g., the surface of the silicone pressure-sensitive adhesive layer on the opposite side of the first substrate (dry casting)). The adhesive article may be a laminate useful for manufacturing parts for use in flexible display devices, such as optical components. For example, the silicone pressure-sensitive adhesive may be an optically transparent, self-supporting adhesive that can be used when the first release liner (and the second release liner, if present) is removed. Alternatively, one release liner may be removed, bringing the exposed surface of the silicone pressure-sensitive adhesive into contact with the substrate, and then the second release liner may be removed, bringing the second exposed surface of the silicone pressure-sensitive adhesive into contact with the second substrate. The substrate and / or the second substrate may be layers within a component of a flexible display device, such as a polarizing layer or an attenuation layer.

[0062] Use of silicone pressure-sensitive adhesive in components of flexible display devices Figure 1 shows a partial cross-sectional view of the laminated article (100). The laminated article (100) includes a silicone pressure-sensitive adhesive (102) having a surface (102a) and an opposite surface (102b). The silicone pressure-sensitive adhesive (102) is formed by a wet casting process which includes applying the hydrosilylated reaction-curable composition prepared as described above to the surface (103a) of a first release liner (103), and curing the composition to form the silicone pressure-sensitive adhesive (102). The opposite surface (102b) of the silicone pressure-sensitive adhesive (102) adheres to the surface (103a) of the first release liner. The second release liner (101) is applied to the silicone pressure-sensitive adhesive (102) such that the surface (101b) of the second release liner adheres to the surface (102) of the silicone pressure-sensitive adhesive (102). The silicone pressure-sensitive adhesive (102) may have a thickness of 10 μm to 200 μm.

[0063] The silicone pressure-sensitive adhesive described above may be used in the manufacture of flexible display device components (not shown). The first release liner (103) can be removed, leaving the opposite surface (102b) of the silicone pressure-sensitive adhesive (102) exposed. The opposite surface (102b) of the silicone pressure-sensitive adhesive (102) can then be brought into contact with another layer in the flexible display device component, such as an attenuation layer or a polarizing layer (not shown), using the pressure required to bond the silicone pressure-sensitive adhesive (102) thereto. [Examples]

[0064] The following examples are provided to those skilled in the art to illustrate the present invention and should not be construed as limiting the claims of the present invention. The starting materials used herein are listed in Table 1.

[0065] [Table 1]

[0066] In Table 1, the starting materials for the DOWSIL (trademark) and SYL-OFF (trademark) brands were commercially available from Dow Silicones Corporation.

[0067] In this Reference Example 1, a sample of a hydrosilylated reaction curable composition was prepared as follows, using the starting materials and amounts shown in Table 2 below. Unless otherwise specified, amounts are in parts by weight. Starting material (A) polydiorganosiloxane gum component and starting material (B) polyorganosilicate resin component were dissolved in solvent (G) while mixing until the resulting mixture was homogeneous. Next, starting material (F) hydrosilylation reaction inhibitor was completely blended into the above mixture. Next, starting material (E) trialkyl borate was completely blended into the above mixture. Next, starting material (D) polyorganohydrogensiloxane was completely blended into the above mixture. Next, optionally, starting material (H) fixing additive (if used) was completely blended into the above mixture. Finally, starting material (C) hydrosilylation reaction catalyst was added and mixed until homogeneous. All starting materials were mixed at room temperature. The starting materials and their amounts (by weight) are shown in Table 2 below.

[0068] [Table 2]

[0069] [Table 3]

[0070] [Table 4]

[0071] The hydrosilylated reaction curable compositions in Table 2 contained a small amount of residual solvent 1 incorporated along with the starting material.

[0072] In this Reference Example 2, a hydrosilylated reaction-curable composition was coated onto a substrate and cured according to the following procedure. Each sample prepared as described above was applied to a 50 μm thick PET film to a thickness sufficient to provide a 50 μm thick dry coating weight after heating in an oven at 150°C for 3 minutes for adhesion and probe tack tests. Each sample prepared as described above was applied to a release liner to a thickness sufficient to provide a 50 μm thick dry coating weight after heating in an oven at 150°C for 3 minutes for wet peel strength tests. Before testing the peel strength, the 50 μm thick PET film was covered over the (cured) silicone pressure-sensitive adhesive layer to protect the silicone pressure-sensitive adhesive layer before testing.

[0073] The obtained tape sample was applied to the substrate so that the silicone pressure-sensitive adhesive was in contact with the substrate. The substrate was stainless steel (SUS), and after the silicone pressure-sensitive adhesive was brought into contact with the substrate before the test, the sample was held in RT for 20 minutes.

[0074] [Table 5]

[0075] [Table 6]

[0076] [Table 7]

[0077] In this Reference Example 3, the samples prepared as described in Reference Example 2 were tested as follows. Each tape sample prepared as described above was peeled from the substrate, and the adhesion strength to SUS was tested by checking whether any silicone pressure-sensitive adhesive had transferred from the PET film onto the substrate. An adhesive strength / peel tester AR-1500 was used. The width of each PET sheet was 1 inch. The peeling speed and peeling angle were 0.3 m / min and 180°, respectively. The unit was grams / in. The results are shown in Table 4 below.

[0078] The test method for adhesion strength to SUS is as specified in test standard ASTM D3330. The stainless steel sheet is cleaned with a solvent. A tape sample (1 inch wide) is applied to the stainless steel sheet. A standard 2 kg test roller is used to rotate the sheet twice in each direction at a speed of 10 mm / second. After a 20-minute resting period, the sample is peeled off the sheet using an AR-1500 at a peeling angle of 180° and a speed of 300 mm / min.

[0079] For the test method of rheological data (Tg, G' at 25°C), refer to the test standard ASTM D4440-15.

[0080] Cured pure silicone pressure-sensitive adhesive films (without substrate) with thicknesses ranging from 0.5 mm to 1.5 mm were prepared on an 8 mm diameter parallel plate of a rheometer (either TA DHR-2 or ARES-G2) for rheological property testing. The loss modulus G'' and storage modulus G' at different temperatures (i.e., 200°C to -80°C) were measured using a temperature ramp program with vibration modes at 1 Hz and a cooling rate of 3°C / min with a strain of 0.25%. Tanδ was calculated from G'' / G'. The glass transition temperature was defined as the temperature at the peak point of tanδ. The results are shown in Table 4 below.

[0081] [Table 8]

[0082] [Table 9]

[0083] The percentage change for Examples 1-5 relative to Comparative Example 1 was calculated. For example, the percentage change in adhesive strength for Example 1 was calculated as (Adhesion strength to SUS of Example 1 - Adhesion strength to SUS of Comparative Example 1) / (Adhesion strength to SUS of Comparative Example 1) × 100%. The percentage change for Example 6 relative to Comparative Example 2 was calculated. The percentage change for Comparative Example 4 relative to Comparative Example 3 was calculated.

[0084] [Table 10]

[0085] The percentage change of Examples 7, 8, and Comparative Example 6 relative to Comparative Example 5 was calculated. The percentage change of Comparative Example 8 relative to Comparative Example 7 was also calculated.

[0086] The percentage change in adhesion / probe tack / G' at 25°C was calculated by comparing each example with a relative comparative example. The change in Tg was calculated by comparing the difference in each example with a relative comparative example. If the difference in Tg was less than ±6.5°C, it was an example showing good results. If the percentage change in adhesion was less than ±20%, it was an example showing good results. If the percentage change in probe tack was less than ±20%, it was an example showing good results. If the percentage change in G' at 25°C was less than ±50%, it was an example showing good results. If the percentage change in peel force was less than 0, it meant that the peel force had decreased, and this was an example showing good results. In Tables 5a, 6a, 7a, and 8a below, the percentage change in peel force was calculated by comparing each example with Comparative Example 1. In Tables 5b, 6b, and 7b, the percentage change in peel force for Example 6 was calculated by comparing Example 6 with Comparative Example 2. In Tables 5b, 6b, and 7b, the percentage change in peel force for Comparative Example 4 was calculated by comparing it with Comparative Example 3. In Tables 5c, 6c, and 7c, the rate of change in peeling force for Examples 7 and 8 was calculated by comparison with Comparative Example 5. In Tables 5c, 6c, and 7c, the rate of change in peeling force for Comparative Example 8 was calculated by comparison with Comparative Example 7. "Comparative Example (Comp.)" refers to the comparative example.

[0087] In this Reference Example 4, a sample of the hydrosilylated reaction-curable composition prepared as described in Reference Example 1 was directly coated onto a coated release liner and cured. Then, a 50 μm PET sheet was laminated onto the surface of the cured silicone pressure-sensitive adhesive on the opposite side of the release liner, the surface was protected before use, and then cut into 1-inch widths. A weight of 20 g / cm² was applied to the laminated sample and left at room temperature for 20 hours or in an oven at 70°C for 3 days. After 20 hours at room temperature or 3 days at 70°C, the load was removed and the sample was left at room temperature for at least 30 minutes. The release liner was on top in this test. The release force on the liner side was then tested using a ChemInstruments AR-1500. Refer to FINAT Test Method No. 10 (FINAT Technical Handbook 7th edition, 2005). The results are shown in Tables 5-9 below.

[0088] [Table 11]

[0089] [Table 12]

[0090] [Table 13]

[0091] [Table 14]

[0092] [Table 15]

[0093] [Table 16]

[0094] [Table 17]

[0095] [Table 18]

[0096] [Table 19]

[0097] [Table 20]

[0098] [Table 21]

[0099] [Table 22]

[0100] Industrial applicability The above examples demonstrate that a hydrosilylated reaction-curable composition can be prepared, which cures to form a silicone pressure-sensitive adhesive with desirable adhesion properties of >1000 g / inch to stainless steel at room temperature, low peel strength, G' <0.1 MPa at 25°C, and Tg < 0°C. The silicone pressure-sensitive adhesive may also have a Tg ≤ -10°C or ≤ -20°C, and a G' < 50 kPa at 25°C. While not bound by theory, the low Tg and low G' are considered to make the silicone pressure-sensitive adhesive suitable for use over a wide temperature range, as it results in lower stress on other layers during repeated deformation tests (e.g., folding, bending, rolling, and stretching tests). The lower peel strength during wet casting benefits the process of manufacturing flexible display devices. This combination of properties makes silicone pressure-sensitive adhesives suitable for use in the manufacture of multilayer components of flexible display devices, particularly when used to manufacture films that can be used to bond various layers within flexible display devices, such as self-supporting films, or attenuation layers or polarizing layers.

[0101] Definitions and Use of Terms All quantities, ratios, and percentages herein are based on weight unless otherwise specified. The “Summary of the Invention” and the “Abstract” are incorporated herein by reference. Unless otherwise specified in the context of the specification, singular nouns include plural nouns, and the articles “a,” “an,” and “the” refer to one or more nouns. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in sections §2111.03 I, II, and III of the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018. The use of “for example,” “eg,” “such as,” and “including” to list examples is not limited to the examples listed. Therefore, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to,” and includes other similar or equivalent examples. Abbreviations used herein have their definitions in Table 9.

[0102] [Table 23]

[0103] The present invention is described in an exemplary manner, and it should be understood that the terms used are intended to be descriptive rather than restrictive. With respect to any group of Markush on which the description of individual features or embodiments herein relies, different, specific, and / or unforeseen results may be obtained from each element of that Markush group independently of all other elements of the Markush groups. Each element of a Markush group may be relied upon individually and / or in combination in particular embodiments within the scope of the appended claims, providing sufficient support.

[0104] Furthermore, any scopes and subscopes on which the present invention is based, independently and comprehensively, fall within the scope of the appended claims, and are understood to describe and conceive of the entire scope encompassing all and / or partial values ​​therein, even if those values ​​are not explicitly stated herein. Those skilled in the art will readily recognize that the listed scopes and subscopes adequately describe and enable various embodiments of the present invention, and that such scopes and subscopes may be further demarcated into more relevant half-, one-third, one-quarter, one-fifth, and any other subscopes included within the scope. As merely one example, the range "0.05 to 1.00" can be further defined as the bottom third, i.e., "0.05 to 0.36", the middle third, i.e., "0.37 to 0.0.68", and the top third, i.e., "0.69 to 1.00". Alternatively, the range "0.05 to 1.00" includes the subranges "0.05 to 0.30", "0.05 to 0.20", "0.30 to 0.50", and "0.51 to 1.00", each individually and collectively within the scope of the appended claims, which may individually and / or collectively rely on specific embodiments within the appended claims and may provide appropriate grounds for them. In addition, with respect to words defining or modifying ranges, such as "at least", "greater than", "less than", "less than or equal to", such words should be understood to include subranges and / or upper or lower limits. The present invention may provide the following embodiments. [1] A hydrosilylated reaction curable composition for forming a silicone pressure-sensitive adhesive, wherein the composition is Based on the total weight of the starting materials (A) to (F), the (A) polydiorganosiloxane gum component is present in an amount of 35.15% to 43.63% by weight, Based on the total weight of the starting materials (A) to (F), the (A-1) unit formula (R) is used in amounts ranging from 28.03% by weight to 43.50% by weight. M 2 R U SiO 1 / 2 ) 2 (R M 2 SiO 2 / 2 ) a an aliphatic unsaturated polydiorganosiloxane gum, wherein each R M However, each R is a monovalent hydrocarbon group of 1 to 30 carbon atoms that is independently selected and does not contain aliphatic unsaturated atoms. U However, the subscript a is a monovalent aliphatic unsaturated hydrocarbon group consisting of 2 to 30 independently selected carbon atoms, and the subscript a has a value sufficient to give the polydiorganosiloxane gum a plasticity of 20 mil (0.51 mm) to 80 mil (2.03 mm), and the plasticity was measured by applying a 1 kg load to a spherical sample weighing 4.2 g at 25°C for 3 minutes, according to ASTM D926, and the result was measured in 1 / 1000 inch (mil), and the procedure was according to ASTM D926, (A-1) aliphatic unsaturated polydiorganosiloxane gum, (A-2) Unit formula ((HO)R for 0-0.26% by weight M 2 SiO 1 / 2 ) 2 (R M 2 SiO 2 / 2 ) a’ A hydroxyl-terminated polydiorganosiloxane gum, wherein each R M However, the (A-2) hydroxyl-terminated polydiorganosiloxane gum is an independently selected monovalent hydrocarbon group of 1 to 30 carbon atoms that does not contain aliphatic unsaturated atoms, and each subscript a' has a value sufficient to give the polydiorganosiloxane gum 20 mil (0.51 mm) to 80 mil (2.03 mm), (A-3) Unit formula (R) 0-7% by weight M 3 SiO 1 / 2 ) 2 (R M 2 SiO 2 / 2 ) a” an unfunctionalized polydiorganosiloxane gum, wherein each R M (A-3) non-functional polydiorganosiloxane gum, comprising (A) polydiorganosiloxane gum component, which is a monovalent hydrocarbon group consisting of 1 to 30 independently selected carbon atoms that does not contain aliphatic unsaturated carbon atoms, and the subscript a'' has a value sufficient to give the non-functional polydiorganosiloxane gum a plasticity of 20 mil (0.51 mm) to 80 mil (2.03 mm), (B) Polyorganosilicate resin component in an amount of 52.69% to 63.26% by weight, Based on the total weight of the starting materials (A) to (F), the (B-1) unit formula is 52.39% to 63.11% by weight: (R M 3 SiO 1 / 2 ) z (SiO 4 / 2 ) o Z p A capped resin, wherein Z is a hydrolyzable group, the subscript p ranges from 0 to a value sufficient to give the capped resin a maximum hydrolyzable group content of 2%, the subscripts z and o have values ​​such that z>4 and o>1, and the quantity (z+o) is sufficient to give the capped resin a number-average molecular weight of 500 g / mol to 5,000 g / mol, (B-1) capped resin, Based on the total weight of the starting materials (A) to (F), the (B-2) unit formula (R) is used in units of 0 to 0.37% by weight. M 3 SiO 1 / 2 ) z’ (SiO4 / 2 ) o’ Z p’ (B) a polyorganosilicate resin component comprising: (B-1) an uncapped resin, wherein 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 ​​such that z'>4 and o'>1, and the quantity (z'+o') has a value sufficient to give the uncapped resin a number average molecular weight of 500 g / mol to 5,000 g / mol; and (B) a polyorganosilicate resin component comprising: (B-1) an uncapped resin and (B-2) an uncapped resin, wherein the total amount of the capped resin and (B-2) an uncapped resin is 42.4% to 52.4% by weight based on the total weight of the starting materials (A) to (F). Here, (A) the polydiorganosiloxane gum component and (B) the polyorganosilicate resin component are present in a weight ratio (resin:gum ratio) of (B):(A) ≤ 1.8:1. Based on the total weight of the starting materials (A) to (F), 0.01% to 5% by weight of (C) hydrosilylation catalyst and (D) Unit formula: (R M 2 SiO 2 / 2 ) e (HR M SiO 2 / 2 ) f (R M 2 HSiO 1 / 2 ) g (R M 3 SiO 1 / 2 ) h A polyorganohydrogensiloxane wherein the formula is such that (D) the polyorganohydrogensiloxane is present in an amount sufficient to make the molar ratio {(D):(A)} of silicon-bonded hydrogen atoms to aliphatic unsaturated hydrocarbon groups of (A) the polydiorganosiloxane gum component 31.37:1 to 59.04:1, and (D) polyorganohydrogensiloxane, Based on the total weight of the starting materials (A) to (F), 0.05% to 1.00% by weight of (E) trialkyl borate and Based on the total weight of the starting materials (A) to (F), 0% to 5% by weight of (F) hydrosilylation reaction inhibitor, Based on the total weight of all starting materials in the composition, >0% to 90% by weight of solvent (G) and A composition comprising 0 to 5% by weight of a fixing additive (H) based on the total weight of the starting materials (A) to (F). [2] (A) In the polydiorganosiloxane gum component, each R M However, each R is an independently selected alkyl group with 1 to 6 carbon atoms. U The composition according to [1] above, wherein a is independently selected from the group consisting of vinyl, allyl, and hexenyl, and the subscript a is sufficient to give (A-1) the aliphatic unsaturated polydiorganosiloxane gum a plasticity value of 30 mil (0.76 mm) to 70 mil (1.778 mm), the subscript a' is sufficient to give (A-2) the hydroxyl-terminated polydiorganosiloxane gum a plasticity of 30 mil (0.76 mm) to 70 mil (1.778 mm), and the subscript a'' is sufficient to give (A-3) the non-functional polydiorganosiloxane gum a plasticity of 30 mil (0.76 mm) to 70 mil (1.778 mm). [3] (B) In the polyorganosilicate resin component, each R M The composition according to [1] above, wherein the alkyl group is independently selected from 1 to 6 carbon atoms, each Z is OH, and the quantity (z+o) is a value sufficient to give the capped resin having a number average molecular weight of 2,900 g / mol to 4,100 g / mol (B-1). [4] (C) The composition according to [1] above, wherein the hydrosilylation reaction catalyst comprises a Karstedt catalyst. [5] (D) In ​​the polyorganohydrogensiloxane, each R M The composition according to [1] above, wherein the alkyl group is an independently selected alkyl group comprising 1 to 6 carbon atoms, the subscript g=0, and the subscript h=2. [6] (E) The composition according to [1] above, wherein the trialkyl borate comprises triethyl borate. [7] The composition according to any one of the above [1] to [6], wherein the composition is a multipart composition comprising a base and a curing agent portion, the base comprising starting materials (A) and (C), the curing agent portion comprising starting materials (A) and (D), and the composition further comprising starting materials (B), (E), and (F) in one or more of the base, the curing agent portion, or a separate additional portion. [8] A wet casting method, 1) Applying the composition described in any one of the above items [1] to [6] to a substrate, 2) A wet casting method comprising curing the composition to form a silicone pressure-sensitive adhesive on the substrate. [9] A dry casting method, 1) Applying the composition described in any one of the above items [1] to [6] to a release liner, 2) Curing the composition to form a silicone pressure-sensitive adhesive on the release liner, 3) A dry casting method comprising applying the silicone pressure-sensitive adhesive to a substrate.

[10] The method according to [9] above, further comprising removing the release liner and bringing the silicone pressure-sensitive adhesive into contact with the components of the flexible display device.

[11] The method according to [9] or

[10] above, wherein the substrate is a second release liner.

[12] The method according to

[11] , further comprising removing the second release liner and bringing the silicone pressure-sensitive adhesive into contact with the second component of the flexible display device.

[13] Articles prepared by the method described in

[10] or

[12] above.

[14] The article according to

[13] above, wherein the component of the flexible display device substrate comprises a polarizing layer or an attenuation layer.

[15] A component of a foldable display device, I) Optical substrate layer, II) A component comprising a silicone pressure-sensitive adhesive layer bonded to the optical substrate layer, wherein the silicone pressure-sensitive adhesive layer is a product of the composition described in any one of the above [1] to [6].

Claims

1. A hydrosilylated reaction curable composition for forming a silicone pressure-sensitive adhesive, wherein the composition is Based on the total weight of the starting materials (A) to (F), the (A) polydiorganosiloxane gum component is present in an amount of 35.15% to 43.63% by weight, Based on the total weight of starting materials (A) to (F), 28.03% to 43.50% by weight of the (A-1) unit formula (R Ｍ ２ R Ｕ SiO １／２ ) ２ (R Ｍ ２ SiO ２／２ ) ａ an aliphatic unsaturated polydiorganosiloxane gum, wherein each R Ｍ is an independently selected monovalent hydrocarbon group having 1 to 30 carbon atoms and containing no aliphatic unsaturation, and each R Ｕ is an independently selected monovalent aliphatic unsaturated hydrocarbon group having 2 to 30 carbon atoms, and the subscript a has a value sufficient to impart 20 mils (0.51 mm) to 80 mils (2.03 mm) of plasticity to the polydiorganosiloxane gum, and the plasticity is measured by applying a load of 1 kg to a spherical sample weighing 4.2 g at 25°C for 3 minutes based on ASTM D926, the result is measured in 1 / 1,000 inches (mils), and the procedure is based on ASTM D926, (A-1) aliphatic unsaturated polydiorganosiloxane gum, and (A-2) Unit formula ((HO)R) 0 to 0.26% by weight Ｍ ２ SiO １／２ ) ２ (R Ｍ ２ SiO ２／２ ) ａ’ A hydroxyl-terminated polydiorganosiloxane gum, wherein each R Ｍ However, the (A-2) hydroxyl-terminated polydiorganosiloxane gum is an independently selected monovalent hydrocarbon group of 1 to 30 carbon atoms that does not contain aliphatic unsaturated carbon atoms, and each subscript a' has a value sufficient to give the polydiorganosiloxane gum 20 mil (0.51 mm) to 80 mil (2.03 mm), (A-3) Unit formula (R) 0-7% by weight Ｍ ３ SiO １／２ ) ２ (R Ｍ ２ SiO ２／２ ) ａ” an unfunctionalized polydiorganosiloxane gum, wherein each R Ｍ (A) Polydiorganosiloxane Gum Component, which comprises (A-3) non-functional polydiorganosiloxane gum, (A) polydiorganosiloxane gum component (B) Polyorganosilicate resin component in an amount of 52.69% to 63.26% by weight, Based on the total weight of the starting materials (A) to (F), the (B-1) unit formula is 52.39% by weight to 63.11% by weight: (R Ｍ ３ SiO １／２ ) ｚ (SiO ４／２ ) ｏ Z ｐ A capped resin, wherein Z is a hydrolyzable group, the subscript p ranges from 0 to a value sufficient to give the capped resin a maximum hydrolyzable group content of 2%, the subscripts z and o have values ​​such that z > 4 and o > 1, and the quantity (z + o) is sufficient to give the capped resin a number-average molecular weight of 500 g / mol to 5,000 g / mol, (B-1) capped resin, Based on the total weight of the starting materials (A) to (F), 0 to 0.37% by weight of the (B-2) unit formula (R Ｍ ３ SiO １／２ ) ｚ’ (SiO ４／２ ) ｏ’ Z ｐ’ (B) a polyorganosilicate resin component comprising: (B-1) an uncapped resin, wherein 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 ​​such that z' > 4 and o' > 1, and the quantity (z' + o') has a value sufficient to give the uncapped resin a number average molecular weight of 500 g / mol to 5,000 g / mol; and (B) a polyorganosilicate resin component comprising: (B-1) an uncapped resin and (B-2) an uncapped resin, wherein the total amount of the capped resin and (B-2) an uncapped resin is 42.4% to 52.4% by weight based on the total weight of the starting materials (A) to (F). Here, (A) the polydiorganosiloxane gum component and (B) the polyorganosilicate resin component are present in a weight ratio (resin:gum ratio) of (B):(A) ≤ 1.8:

1. Based on the total weight of the starting materials (A) to (F), 0.01% to 5% by weight of (C) hydrosilylation catalyst and Based on the total weight of the starting materials (A) to (F), the unit formula for (D) greater than 0% by weight and less than or equal to 2.5% by weight is: (R Ｍ ２ SiO ２／２ ) ｅ (HR Ｍ SiO ２／２ ) ｆ (R Ｍ ２ HSiO １／２ ) ｇ (R Ｍ ３ SiO １／２ ) ｈ A polyorganohydrogensiloxane wherein the formula is such that (D) the polyorganohydrogensiloxane is present in an amount sufficient to make the molar ratio of silicon-bonded hydrogen atoms to the aliphatic unsaturated hydrocarbon groups of the polydiorganosiloxane gum component {(D):(A) ratio} 31.37:1 to 59.04:1, and (D) polyorganohydrogensiloxane, Based on the total weight of the starting materials (A) to (F), 0.05% to 1.00% by weight of (E) trialkyl borate and Based on the total weight of the starting materials (A) to (F), 0% to 5% by weight of (F) hydrosilylation reaction inhibitor, Based on the total weight of all starting materials in the composition, >0% to 90% by weight of solvent (G) and Based on the total weight of the starting materials (A) to (F), it includes 0 to 5% by weight of (H) fixing additive, The silicone pressure-sensitive adhesive formed from the hydrosilylated curable composition has an adhesive strength of more than 1000 g / inch to stainless steel at room temperature, as measured by the following test method. (Test method) The adhesive strength test method is as specified in the ASTM D3330 standard. The stainless steel sheet is cleaned with a solvent. A tape sample (1 inch wide) of silicone pressure-sensitive adhesive is applied to the stainless steel sheet. A standard 2 kg test roller is used to rotate the sheet twice in each direction at a speed of 10 mm / second. After a 20-minute resting period at room temperature, the sample is peeled off the stainless steel sheet using a peel tester at a peel angle of 180° and a speed of 300 mm / min.

2. (A) In the polydiorganosiloxane gum component, each R Ｍ However, each R is an independently selected alkyl group with 1 to 6 carbon atoms. Ｕ The composition according to claim 1, wherein a is independently selected from the group consisting of vinyl, allyl, and hexenyl, and the subscript a is sufficient to give the aliphatic unsaturated polydiorganosiloxane gum a plasticity value of 30 mil (0.76 mm) to 70 mil (1.778 mm), the subscript a' is sufficient to give the hydroxyl-terminated polydiorganosiloxane gum a plasticity of 30 mil (0.76 mm) to 70 mil (1.778 mm), and the subscript a'' is sufficient to give the non-functional polydiorganosiloxane gum a plasticity of 30 mil (0.76 mm) to 70 mil (1.778 mm).

3. (B) In the polyorganosilicate resin component, each R Ｍ The composition according to claim 1, wherein the alkyl group is an independently selected alkyl group comprising 1 to 6 carbon atoms, each Z being an OH group, and the quantity (z+o) is sufficient to give the capped resin having a number average molecular weight of 2,900 g / mol to 4,100 g / mol (B-1).

4. (C) The composition according to claim 1, wherein the hydrosilylation reaction catalyst comprises a Karstedt catalyst.

5. (D) In ​​the polyorganohydrogensiloxane, each R Ｍ The composition according to claim 1, wherein the alkyl group is independently selected from 1 to 6 carbon atoms.

6. (E) The composition according to claim 1, wherein the trialkyl borate comprises triethyl borate.

7. The composition according to any one of claims 1 to 6, wherein the composition is a multipart composition comprising a base and a curing agent portion, the base comprising starting materials (A) and (C), the curing agent portion comprising starting materials (A) and (D), and the composition further comprising starting materials (B), (E), and (F) in one or more of the base, the curing agent portion, or a separate additional portion.

8. A wet casting method, 1) Applying the composition described in any one of claims 1 to 6 to a substrate, 2) A wet casting method comprising curing the composition to form a silicone pressure-sensitive adhesive on the substrate.

9. A dry casting method, 1) Applying the composition described in claim 6 to a release liner, 2) Curing the composition to form a silicone pressure-sensitive adhesive on the release liner, 3) A dry casting method comprising applying the silicone pressure-sensitive adhesive to a substrate.

10. The method according to claim 9, further comprising removing the release liner and bringing the silicone pressure-sensitive adhesive into contact with the components of the flexible display device.

11. The method according to claim 10, wherein the substrate is a second release liner.

12. The method according to claim 11, further comprising removing the second release liner and bringing the silicone pressure-sensitive adhesive into contact with the second component of the flexible display device.

13. An article prepared by the method described in claim 10 or 12.

14. The article according to claim 13, wherein the flexible display device substrate comprises a polarizing layer or an attenuation layer.

15. A component of a foldable display device, I) Optical substrate layer, II) A component comprising a silicone pressure-sensitive adhesive layer bonded to the optical substrate layer, wherein the silicone pressure-sensitive adhesive layer is a product of the composition described in any one of claims 1 to 6.

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