Silicone hybrid pressure-sensitive adhesive and method for its preparation and use in protective films for (opto)electronic device manufacturing

Abstract

The present invention provides a silicone hybrid pressure-sensitive adhesive composition, which is cured to form a silicone hybrid pressure-sensitive adhesive and contains a polydiorganosiloxane having reactive groups. These reactive groups include silicon-bonded (meth)acryloxyalkyl functional groups in the side chain position and optionally silicon-bonded aliphatic unsaturated hydrocarbon groups in the terminal position. The silicone hybrid pressure-sensitive adhesive composition can be cured on the surface of a substrate via a hydrosilylation reaction to form a protective film. The protective film can be used to protect a passivation layer during the manufacturing process of (opto)electronic devices such as flexible organic light-emitting diode displays. The protective film can be exposed to radiation to reduce viscosity and facilitate the separation of the protective film from the passivation layer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 021,186, filed on May 7, 2020, under 35 USC §119(e). U.S. Provisional Patent Application No. 63 / 021,186 is hereby incorporated herein by reference. Technical Field

[0003] The present invention relates to a silicone hybrid pressure-sensitive adhesive composition, which is cured to form a silicone hybrid pressure-sensitive adhesive. The silicone hybrid pressure-sensitive adhesive can be used in the process of manufacturing (opto)electronic devices such as flexible organic light-emitting diode (OLED) displays. Background Art

[0004] In a typical process for manufacturing flexible OLED displays, an OLED is formed on a relatively rigid substrate (e.g., a thin film metal (oxide) or a metal (oxide) coated with a polyimide varnish), and a passivation layer is formed on the surface of the OLED opposite the substrate. The weak or brittle layer needs to be protected from damage (e.g., scratches or other impacts) during further processing.

[0005] In order to protect these layers during the manufacturing process, a protective film with low adhesion is required to prevent the layers (e.g., passivation layer) from being delaminated on the surface of the OLED module during the release of the protective film after use. If the adhesion control fails (or is too low), the protective film may be delaminated prematurely. If the adhesion is a little high so as to tightly hold the layers of the OLED module, the layers may be damaged when the protective film is removed. Therefore, there is a need in the industry to provide a protective film with appropriate adhesion to protect the layers during processing, but also to remove the layers without damaging them.

[0006] It is also important that the surface of the layer remains clean so that additional films or layers can be laminated thereto after the protective film is removed. Therefore, there is a need in the industry to provide a protective film with low migration so that after the protective film is removed, no adhesive from the protective film or minimal adhesive from the protective film remains on the surface of the layer in the flexible OLED device. Summary of the invention

[0007] Provided are an organosilicon hybrid pressure-sensitive adhesive composition and a method for preparing the same. Also provided is a method for preparing a protective film from an organosilicon hybrid pressure-sensitive adhesive film. Also provided is a method for using the protective film in a method for manufacturing an (opto)electronic device. DETAILED DESCRIPTION

[0008] The silicone hybrid pressure-sensitive adhesive composition comprises: (A) a linear or substantially linear polydiorganosiloxane having reactive groups including silicon-bonded (meth)acryloxyalkyl functional groups in pendant positions and optionally silicon-bonded aliphatic unsaturated hydrocarbon groups in terminal positions; (B) a polyorganosilicate resin; (C) a polyorganohydrogensiloxane; (D) a hydrosilylation reaction catalyst, (E) a photoradical initiator; (F) a hydrosilylation reaction inhibitor; and (G) a radical scavenger. The silicone hybrid pressure-sensitive adhesive composition may also optionally comprise (H) a solvent and (I) one or more additives selected from sensitizers and synergists.

[0009] (A) Polydiorganosiloxane having reactive groups

[0010] The silicone hybrid pressure-sensitive adhesive composition comprises 100 parts by weight of a starting material (A) linear or substantially linear polydiorganosiloxane having reactive groups including silicon-bonded (meth)acryloxyalkyl functional groups in pendant positions and optionally silicon-bonded aliphatic unsaturated hydrocarbon groups in terminal positions. The starting material (A) comprises units of formula M p M” q D m D' n D” o T'' r Q s , where M represents the formula (R 1 3SiO 1 / 2 ) unit, M" represents the formula (R 1 2R 3 SiO 1 / 2 ) unit, D represents the formula (R 1 2SiO 2 / 2 ) unit, D' represents the formula (R 1 R 2 SiO 2 / 2 ) unit, D" represents the formula (R 1 R 3 SiO 2 / 2 ) unit, T"' represents the formula (R 5 SiO 3 / 2 ) and Q represents the formula (SiO 4 / 2 ) units. In these units, each R 1 is a monovalent hydrocarbon group without aliphatic unsaturated groups, each R 2 is a (meth)acryloyloxyalkyl functional group, each R 3 is an aliphatic unsaturated monovalent hydrocarbon group, each R 5 Independently selected from R 1 , R2 and R 3 . And the values of the subscripts p, q, m, n, r, and s are such that 0 ≤ p, 0 ≤ q, the quantity (p + q) ≥ 2, 0 < m < 10,000, 2 < n ≤ 10,000, o ≥ 0, the quantity (m + n + o) is from 100 to 10,000, the ratio (m + o) / n is from 1 / 1 to 500 / 1, the ratio (q + o) / (m + n) is from 0 to ≤ 1 / 5, 0 ≤ r ≤ 100 and 0 ≤ s ≤ 100; if 0 < r or if 0 < s, then the ratio (m + n + o) / (r + s) is from 50 / 1 to 10,000 / 1. The polydiorganosiloxane may optionally also contain a small amount of units of the formula M OH , where M OH has the formula [R 1 2(HO)SiO 1 / 2 , where R 1 is as described above. Without wishing to be bound by theory, it is believed that a small amount of terminal M OH residues may be present as impurities in the starting material (A), but M OH is not intended to be incorporated during synthesis, and it is not expected that the hydroxyl groups will significantly affect the present application.

[0011] The monovalent hydrocarbon groups (excluding aliphatic unsaturated groups) suitable for R 1 in the above unit formulas include alkyl groups and aryl groups. The alkyl groups can be straight-chain, branched-chain, or cyclic. Examples of alkyl groups include methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (including isopentyl, neopentyl, and / or tert-pentyl); and hexyl, heptyl, octyl, nonyl, and decyl, and branched-chain saturated monovalent hydrocarbon groups having 6 or more carbon atoms; and cycloalkyl groups such as cyclopentyl or cyclohexyl. The alkyl groups can have at least one carbon atom. Alternatively, the alkyl groups can have 1 to 12 carbon atoms, alternatively 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms, and alternatively 1 carbon atom. The aryl groups include, alternatively, hydrocarbon groups derived from aromatic hydrocarbons by removing a hydrogen atom from a ring carbon atom. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, benzyl, tolyl, xylyl, phenethyl, phenylpropyl, and phenylbutyl. The aryl groups have at least 5 carbon atoms. The monocyclic aryl groups can have 5 to 12 carbon atoms, alternatively 6 to 9 carbon atoms, and alternatively 6 carbon atoms. The polycyclic aryl groups can have 9 to 17 carbon atoms, alternatively 9 to 14 carbon atoms, and alternatively 9 to 12 carbon atoms. Alternatively, for R 1 , the alkyl group can be methyl, and the aryl group can be phenyl. Alternatively, each R 1 can be an alkyl group, as described above. Based on R 1, R 2 and R 3 The starting material (A) may contain 70 mol % or more, alternatively 80 mol % or more of R 1 . And each R 1 It may be a methyl group. Without wishing to be bound by theory, it is believed that the methyl group is non-reactive and may provide wettability to the surface of the adherend and stability (e.g., no or minimal heat shrinkage, degradation) after heat treatment of the silicone hybrid pressure-sensitive adhesive (e.g., after exposure to temperatures as high as 200° C. during the (opto)electronic device manufacturing process).

[0012] R in the unit formula applicable to this article 2 The (meth)acryloxyalkyl functional groups are each independently selected from acryloxypropyl and methacryloxypropyl. 1 , R 2 and R 3 The combined meter, R 2 It may be present in a mole % range of 0.1% to 25%. Alternatively, R 2 It may be present in a mole % range of 0.8% to 12%. Alternatively, R 2 It may be present in a mole % range of 1.5% to 6%. Alternatively, based on R 1 , R 2 and R 3 The starting material (A) may contain 0.1 mol % to 25 mol %, alternatively 0.2 mol % to 3 mol % of R 2 .

[0013] Applicable to R 3 The aliphatic unsaturated monovalent hydrocarbon group includes alkenyl groups and alkynyl groups. The alkenyl group has a double bond and can be branched or unbranched. The alkenyl group has at least 2 carbon atoms. Alternatively, the alkenyl group may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, and alternatively 2 carbon atoms. Suitable alkenyl groups include but are not limited to vinyl, allyl and hexenyl; or vinyl and hexenyl. The alkynyl group has a triple bond and can be branched or unbranched. The alkynyl group has at least 2 carbon atoms. Alternatively, the alkynyl group may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, and alternatively 2 carbon atoms. The alkynyl group includes ethynyl and propynyl.

[0014] Alternatively, for R 3 Each aliphatic unsaturated monovalent hydrocarbon group is an independently selected alkenyl group, which can be selected from vinyl and hexenyl. 1 , R 2and R 3 The starting material (A) may contain 0 mol% to 6 mol%, alternatively 0.001 mol% to 3 mol%, and alternatively 0.005 mol% to 0.2 mol% of R 3 .

[0015] When the starting material (A) has a subscript p=2 and a subscript o=q=r=s=0, the starting material (A) may include a unit formula M2D m D' n , wherein the amount (m+n) is 100 to 10,000 and the ratio m / n is 1 / 1 to 500 / 1. Alternatively, the amount (m+n) may be 200 to 9,900. Alternatively, the amount (m+n) may be 300 to 7,000; and alternatively 400 to 6,000. Alternatively, the amount (m+n) may be 1,000 to 5,000. Alternatively, the ratio m / n may be 10 / 1 to 400 / 1; and alternatively 20 / 1 to 300 / 1.

[0016] The starting material (A) can be prepared by a condensation reaction or an equilibrium reaction using a (meth)acryloyl functional silane reagent with reference to "Chemistry and Technology of Silicone", Noll, Academic Press, 1968, Chapter 5, pp. 190-245. Hereinafter, the actual method for preparing polydiorganosiloxane (A) is described as follows, but is not limited to these methods. For example, polydiorganosiloxane (A) can be prepared by a one-pot synthesis method using silanol fluid, (meth)acryloyl functional dialkoxysilane and a capping agent in the presence of a trifluoromethanesulfonic acid catalyst. Heptane or toluene is used to promote the removal of methanol by azeotropic distillation. Water is also added to the reaction to ensure the complete hydrolysis of 3-methacryloyloxypropylmethyldimethoxysilane. After the reaction is completed, a neutralizing agent (such as calcium carbonate) is used to neutralize trifluoromethanesulfonic acid and filtered out after treatment. Another method can be prepared by pre-hydrolysis of (meth)acryloyl functional dialkoxysilane and subsequent condensation / disproportionation reaction involving silanol fluid and end-capping agent in the presence of phosphazene catalyst (described in U.S. Pat. No. 9,051,428 to Davio et al.). Toluene is used to reduce viscosity and facilitate removal of water / methanol by azeotropic distillation. After the reaction is completed, a neutralizing agent (such as trialkylamine and disilazane derivatives) is used to neutralize the acidic catalyst and filtered out after treatment.

[0017] Depending on the choice of the intermediate, various structures of the polydiorganosiloxane (A) can be obtained. The (meth)acryloyl functional dialkoxysilane can be selected from 3-[dimethoxy(methyl)silyl]propyl methacrylate (CAS#14513-34-9) and 3-[dimethoxy(methyl)silyl]propyl acrylate (CAS#13732-00-8). The silanol fluid can be selected from hydroxyl-terminated polydimethylsiloxane (CAS#70131-67-8), hydroxyl-terminated vinylmethylsiloxane-dimethylsiloxane copolymer (CAS#67923-19-7), hydroxyl-terminated polyvinylmethylsiloxane (CAS#68083-20-5), hydroxyl-terminated polyphenylmethylsiloxane (CAS#80801-30-5), and diphenylsilanediol (CAS#947-42-2). The end-capping agent may be selected from hexamethyldisiloxane (CAS#107-46-0), 1,3-divinyltetramethyldisiloxane (CAS#2626-95-4) and dimethylvinylsiloxy-terminated polydimethylsiloxane (CAS#68083-19-2). In addition, dialkoxysilanes or dichlorosilanes such as dimethoxydiphenylsilane (CAS#6843-66-9), dimethoxymethylvinylsilane (CAS#16753-62-1), dichlorodiphenylsilane (CAS#80-10-4), 3-mercaptopropylmethyldimethoxysilane (CAS#31001-77-1), dimethoxy(methyl)(3,3,3-trifluoropropyl)silane (CAS#358-67-8), diethoxy(methyl)phenylsilane (CAS#775-56-4), diethoxymethylsilane (CAS#2031-62-1), and dimethoxymethylsilane (CAS#16881-77-9) may be added as co-reactants. In addition, a small amount of trialkoxysilane and tetraalkoxysilane such as trimethoxy(methyl)silane (CAS#1185-55-3), 3-(trimethoxysilyl)propyl methacrylate (CAS#2530-85-0), 3-(triethoxysilyl)propyl methacrylate (CAS#21142-29-0), tetramethyl orthosilicate (CAS#681-84-5) can be added to obtain a branched structure. Typical catalysts for condensation reactions are summarized in U.S. Pat. No. 8,076,411 to Maton et al.

[0018] Examples of polydiorganosiloxanes suitable for use as the starting material (A) include one or more of the following average composition formulas: The following average formulas Ai) to Axiv). In the average composition formula, the subscript after each unit represents the average number of the unit per molecule. In the average formula, the subscript after each unit represents the mole fraction of the unit. In the following formula, 'R' represents the above R 1 , R 2 and R3 combination.

[0019] Ai)(ViMe2SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 10 (Me2SiO 2 / 2 ) 1000

[0020] Aii)(ViMe2SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 50 (Me2SiO 2 / 2 ) 2000

[0021] Aiii)(Me3SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 500 (Me2SiO 2 / 2 ) 6000

[0022] Aiv)(ViMe2SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 1000 (Me2SiO 2 / 2 ) 6000

[0023] Av)(ViMe2SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 50 (Me2SiO 2 / 2 ) 1990 (ViMeSiO 2 / 2 ) 200

[0024] Avi)(Me3SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 50 (Me2SiO 2 / 2 ) 1990 (ViMeSiO 2 / 2 ) 200

[0025] Avii)(Me3SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 50 (Me2SiO 2 / 2 ) 1990 (HexMeSiO 2 / 2 ) 50

[0026] Aviii)(Me3SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 50 (Me2SiO 2 / 2 ) 1990 (HexMeSiO 2 / 2 ) 50

[0027] Aix)(ViMe2SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 1000 (Me2SiO 2 / 2 ) 6000 (PhMeSiO 2 / 2 ) 100

[0028] Ax)(ViMe2SiO 1 / 2 )3(MaMeSiO 2 / 2 ) 100 (Me2SiO 2 / 2 ) 1900 (MeSiO 3 / 2 )

[0029] Axi)(Me3SiO 1 / 2 )4(MaMeSiO 2 / 2 ) 50 (Me2SiO 2 / 2 ) 3960 (SiO 4 / 2 )

[0030] Axii)(Me3SiO 1 / 2 )3(MaMeSiO 2 / 2 ) 20 (Me2SiO 2 / 2 ) 1979 (ViMeSiO 2 / 2 ) 100 (MeSiO 3 / 2 )

[0031] Axiii)(ViMe2SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 1000 (Me2SiO 2 / 2 ) 6000 (PhPhSiO 2 / 2 ) 100

[0032] Axiv)(ViMe2SiO 1 / 2 )2(MaMeSiO 2 / 2 ) 16(Me2SiO 2 / 2 ) 265

[0033] (B) Polyorganosilicate resin

[0034] The starting material (B) is a polyorganosilicate resin. The polyorganosilicate resin is used in the silicone hybrid pressure-sensitive adhesive composition in an amount sufficient to provide a weight ratio (resin / polymer ratio) of (B) polyorganosilicate resin to (A) polydiorganosiloxane of 0.15 / 1 to 1.9 / 1. Alternatively, the resin / polymer ratio may be 0.2 / 1 to 1.5 / 1. Alternatively, the resin / polymer ratio may be 0.25 / 1 to 1.2 / 1.

[0035] The polyorganosilicate resin comprises a unit formula M a M” b M"' c D d D' e T'' f Q h X i , wherein M, M", D, D', T"' and Q are as described above, M"' represents the formula (R 1 2R 2 SiO 1 / 2 ), X represents a hydroxyl group and / or an alkoxy group, and the values ​​of the subscripts a, b, c, d, e, f, h, and i are such that a ≥ 0, b ≥ 0, c ≥ 0, and the amount (a + b + c) > 10 mole %; d ≥ 0, e ≥ 0, and the amount (d + e) ​​is from 0 to a value sufficient to provide up to 30 mole % of the combined D units and D' units to the resin; f ≥ 0, provided that the subscript f has a maximum value sufficient to provide 40 mole %, alternatively 30 mole % of T"' units to the resin; h > 0, provided that the subscript h has a maximum value sufficient to provide 30 mole % to 70 mole %, alternatively 30 mole % of T"' units to the resin 0 mol % to 60 mol % of Q units; (a+b+c+d+e+f+h)=100 mol %; i≥0 is not included in the molar ratio, provided that subscript i has a maximum value sufficient to provide 5 mol % of hydroxyl groups to the resin. Alternatively, the amount (d+e) is 0 to a value sufficient to provide up to 20 mol % of the combined D units and D' units to the resin. Alternatively, the amount (d+e) is 0 to a value sufficient to provide up to 10 mol % of the combined D units and D' units to the resin. Alternatively, the subscript h is 0 to a value sufficient to provide up to 15 mol % of T"' units to the resin. Alternatively, the subscript h is 0 to a value sufficient to provide up to 8 mol % of T"' units to the resin. Alternatively, the values ​​of subscripts c, e and f may be such that if b>0, then 0≤(c+e+f)<20 mol %; and if b=0, then (c+e+f)=0;

[0036] Alternatively, the polyorganosilicate resin may comprise a unit formula selected from the following: M a Q h 、M a M” b Q h 、M a M” b M"' c Q h 、M a M"' c Q h 、M a D d Q h 、M a D' e Q h 、M a M” b D' e Q h 、M a M” b T'' f Q h 、M a M” b T'' f Q h , wherein subscripts a, b and c are 20 mol % to 70 mol %, subscripts d and e are 1 mol % to 20 mol %, subscript f is 1 mol % to 25 mol %, and subscript h is 35 mol % to 65 mol %. Alternatively, the polyorganosilicate resin may include a unit formula selected from the following: M a Q h 、M a M” b Q h 、M a M” b M"' c Q h 、M a D d Q h , M” b D' e Q h 、M a M” b M"' c D d Q h 、M a M” b M"' c D' e Q h 、M a M” b D' e Q h 、Ma M” b M"' c D' e Q h 、M a M” b T'' f Q h 、M a M” b M"' c T'' f Q h , wherein subscript a is 20 mol % to 65 mol %, subscripts b and c are 1 mol % to 30 mol %, subscripts d and e are 1 mol % to 20 mol %, subscript f is 1 mol % to 25 mol %, and subscript h is 35 mol % to 55 mol %.

[0037] Based on the resin R 1 , R 2 and R 3 The polyorganosilicate resin may contain 0 mol % to 20 mol % of R 2 , where R 1 , R 2 and R 3 As described above, the polyorganosilicate resin may contain at least 70 mol % of R 1 (Based on the R 1 , R 2 and R 3 Alternatively, based on the combined amount of R 1 , R 2 and R 3 The polyorganosilicate resin may contain 0 mol % to 15 mol % of R 2 Alternatively, the polyorganosilicate resin may contain at least 80 mol % of R 1 (Based on the R 1 , R 2 and R 3 (measured by the combined amount of the groups).

[0038] Examples of the polyorganosilicate resin suitable for use as the starting material (B) include one or more of the following Bi) to Bxi).

[0039] Bi)(Me3SiO 1 / 2 ) 0.45 (SiO 4 / 2 ) 0.55

[0040] Bii)(Me3SiO 1 / 2 ) 0.50 (SiO 4 / 2 )0.50

[0041] Biii)(Me3SiO 1 / 2 ) 0.42 (ViMe2SiO 1 / 2 ) 0.05 (SiO 4 / 2 ) 0.53 (OH) 0.02

[0042] Biv)(Me3SiO 1 / 2 ) 0.40 (ViMe2SiO 1 / 2 ) 0.10 (SiO 4 / 2 ) 0.50

[0043] Bv)(Me3SiO 1 / 2 ) 0.42 (MaMe2SiO 2 / 2 ) 0.05 (SiO 4 / 2 ) 0.53 (OH) 0.02

[0044] Bvi)(Me3SiO 1 / 2 ) 0.4 (MaMe2SiO 2 / 2 ) 0.2 (SiO 4 / 2 ) 0.40

[0045] Bvii)(Me3SiO 1 / 2 ) 0.42 (MaMe2SiO 3 / 2 ) 0.05 (SiO 4 / 2 ) 0.53

[0046] Bviii)(Me3SiO 1 / 2 ) 0.4 (MaMe2SiO 3 / 2 ) 0.2 (SiO 4 / 2 ) 0.40

[0047] Bix)(Me3SiO 1 / 2 ) 0.40 (ViMe2SiO 1 / 2 ) 0.04 (TheMessio 2 / 2 ) 0.02 (SiO 4 / 2 ) 0.54

[0048] Bx)(Me3SiO 1 / 2 ) 0.40 (MaSiO 1 / 2 ) 0.04 (SiO 4 / 2 ) 0.56

[0049] Bxi)(Me3SiO 1 / 2 ) 0.40 (ViMe2SiO 1 / 2 ) 0.02 (MaSiO 1 / 2 ) 0.02 (SiO 4 / 2 ) 0.56

[0050] Bxii)(Me3SiO 1 / 2 ) 0.42 (MaMe2SiO 1 / 2 ) 0.05 (SiO 4 / 2 ) 0.53

[0051] The polyorganosilicate resins can be prepared by any suitable method, such as co-hydrolysis of the corresponding silanes or by a silica hydrosol end-capping method. The polyorganosilicate resins can be prepared by a silica hydrosol end-capping method, such as those 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. The above-mentioned 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 typically contains 2 to 5 weight percent hydroxyl groups.

[0052] The intermediates used to prepare the polyorganosilicate resin may have two, three or four hydrolyzable substituents per molecule, for example, they may be diorganoalkoxysilanes, triorganoalkoxysilanes and silanes or alkali metal silicates having four hydrolyzable substituents. The intermediates may have the formula R M 2SiX 1 2 and R M SiX 1 3, where R M Selected from the above R 1 , R 2 and R 3 , and X 1= represents a hydrolyzable substituent. A silane having four hydrolyzable substituents may have the formula SiX 2 4, where each X 2 is halogen, alkoxy or hydroxy. Suitable alkali metal silicates include sodium silicate.

[0053] The polyorganosilicate resins prepared as described above typically contain silicon-bonded hydroxyl groups, i.e., of the formula HOSi 3 / 2 , HOR M SiO 2 / 2 and / or HOR M 2SiO 1 / 2 The polyorganosilicate resin may contain up to 5% silicon-bonded hydroxyl groups. The concentration of silicon-bonded hydroxyl groups present in the polyorganosilicate resin may be determined using Fourier transform infrared (FTIR) spectroscopy according to ASTM standard E-168-16. For certain applications, it may be desirable that the amount of silicon-bonded hydroxyl groups be 2% or less, alternatively less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, and alternatively 0.3% to 0.8%. The silicon-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin may be converted to triorgano (e.g., trihydrocarbyl) siloxane groups or different hydrolyzable groups by reacting the organosilicate resin with a silane, disiloxane, or disilazane containing appropriate terminal groups. The silane containing the hydrolyzable group may be added in an excess molar amount of the amount required to react with the silicon-bonded hydroxyl groups on the polyorganosilicate resin.

[0054] Alternatively, the polyorganosilicate resin may further comprise 2% or less, alternatively 0.7% or less, and alternatively 0.3% or less, and alternatively 0.3% to 0.8% of the compound represented by formula X 2 SiO 3 / 2 , X 2 R M SiO 2 / 2 and / or X 2 R M 2SiO 1 / 2 Represents a unit, where R M and X 2 As mentioned above.

[0055] Alternatively, the polyorganosilicate resin may have a terminal aliphatic unsaturated group (R 3). A polyorganosilicate resin having terminal aliphatic unsaturated groups can be prepared by reacting the product of Daudt et al. with an end-capping agent containing unsaturated organic groups and (optionally) an end-capping agent free of aliphatic unsaturated groups in an amount sufficient to provide 3 to 30 mole percent of unsaturated organic groups in the final product. Examples of end-capping agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable end-capping agents are known in the art and are exemplified in U.S. Patents 4,584,355; 4,591,622; and 4,585,836. A single end-capping agent or a mixture of such agents can be used to prepare such resins.

[0056] When prepared, the polyorganosilicate resin comprises the above units, and the polyorganosiloxane further comprises units having silanol (silicon-bonded hydroxyl) groups and may comprise a polyorganosiloxane of the formula Si(OSiR M 3)4 neopentamers, where R M As described above. As described in Reference Example 2 of U.S. Pat. No. 9,593,209, column 32, Si 29 Nuclear magnetic resonance (NMR) spectroscopy can be used to measure the molar ratio of M units and Q units, where the ratio is expressed as {M(resin)+(M(neopentamer)} / {Q(resin)+Q(neopentamer)} and represents the molar ratio of the total number of triorganosiloxy groups of the resin portion and the neopentamer portion of the polyorganosilicate resin to the total number of silicate groups (Q units) of the resin portion and the neopentamer portion.

[0057] The Mn of a polyorganosilicate resin depends on various factors, including the presence of M The Mn of the polyorganosilicate resin refers to the number average molecular weight measured using gel permeation chromatography (GPC) according to the procedure in Reference Example 1 of column 31 of U.S. Patent 9,593,209 when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resin may be 1,500 g / mol to 5,000 g / mol.

[0058] Methods for preparing the above (meth)acryloyloxy-functional polyorganosilicate resins containing D' and T' units suitable for use as component (B), such as hydrolysis or non-hydrolysis condensation or equilibration reaction of polyorganosilicate resins with (meth)acryloyloxy-functional alkoxysilanes or halosilanes under acidic or basic conditions; and similar methods for preparing organofunctional polyorganosilicates known to those skilled in the art, such as co-hydrolysis of typical organohalosilanes or organoalkoxysilanes with (meth)acryloyloxy-functional alkoxysilanes or halosilanes followed by condensation or equilibration reactions, will be described in U.S. Pat. No. 8,377,634 to Albaugh, U.S. Pat. No. 5,516,858 to Morita et al., U.S. Pat. No. 9,023,433 to Fu et al., U.S. Pat. No. 6,281,285 to Becker et al., and U.S. Pat. No. 5,010,159 to Bank et al. The (meth)acryloyloxy functional alkoxysilane or halosilane may be selected from 3-(chlorodimethylsilyl)propyl methacrylate (CAS#24636-31-5), 3-[dimethoxy(methyl)silyl]propyl methacrylate (CAS#14513-34-9), methacryloxypropylmethyldichlorosilane (CAS#18301-56-9), (3-acryloyloxypropyl)methyldichlorosilane (CAS#71550-63-5), 3-[dimethoxy(methyl)silyl]propyl acrylate (CAS#13732-00-8), 3-(Trimethoxysilyl)propyl acrylate (CAS#4369-14-6), 3-[diethoxy(methyl)silyl]propyl methacrylate (CAS#65100-04-1), 3-(trimethoxysilyl)propyl methacrylate (CAS#2530-85-0), 3-(triethoxysilyl)propyl methacrylate (CAS#21142-29-0), methacryloxypropyltrichlorosilane (CAS#7351-61-3), (3-acryloxypropyl)trichlorosilane (CAS#38595-89-0).

[0059] Another method for preparing a (meth)acryloyloxy-functional polyorganosilicate resin containing M'' suitable for use as starting material (B) is the hydrosilylation reaction between a hydrosilyl (-SiH)-functional polyorganosilicate and a (meth)acryloyl-functional olefin or alkynyl; or the hydrosilylation reaction between an alkenyl-functional polyorganosilicate and a (meth)acryloyl-functional hydrosilane as described in U.S. Pat. No. 4,503,208, "Macromolecular Materials and Engineering", Hung-Wen et al., Vol. 292, No. 5, pp. 666-673 (2007). The (meth)acryloyl-functional olefin or alkyne can be selected from allyl methacrylate (CAS#96-05-9) and propargyl acrylate (CAS#10477-47-1). The (meth)acryloyl-functional hydrosilane can be selected from methacryloxypropyl tris(dimethylsiloxy)silane (CAS#17096-08-1) and 2-acrylic acid, 2-methyl-3-(1,1,3,3-tetramethyldisiloxanyl)propyl ester (CAS#96474-12-3).

[0060] (C) Polyorganohydrogensiloxane

[0061] The starting material (C) in the silicone hybrid pressure-sensitive adhesive composition is a polyorganohydrogensiloxane in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms in the starting material (C) to reactive groups in the combined starting materials (A) and (B) (SiH / reactive group ratio) of 0.3 / 1 to 2 / 1, wherein the reactive groups are the combined R 2 and R 3 , wherein the polyorganohydrogensiloxane comprises a unit formula M t M H u D v D H w T x T H y Q z , wherein M, D, T and Q represent units in the formula shown above, and M H Expression (HR 1 2SiO 1 / 2 ) unit, D H Expression (HR 1 SiO 2 / 2 ) unit, T H Expression (HSiO 3 / 2), and the values ​​of the subscripts t, u, v, w, x, y, and z are such that t≥0, u≥0, v≥0, w≥0, x≥0, y≥0, z≥0, the amount (u+w+y)≥3, and the amount (t+u+v+w+x+y+z) is sufficient to give the polyorganohydrogensiloxane a viscosity of 3 mPa·s to 1,000 mPa·s at 25°C, alternatively a viscosity of 5 mPa·s to 500 mPa·s at 25°C; and wherein R 1 As described above. Alternatively, the amount (t+u+v+w+x+y+z) may be 3 to 2,000; alternatively 3 to 1,000; and alternatively 3 to 500. Alternatively, when the subscript x=y=z=0, the polyorganohydrogensiloxane may include a unit formula M t M H u D v D H w , wherein the amount (t+u)=2, and the amount (u+w)≥3. Alternatively, the SiH / reactive group ratio may be from 0.4 / 1 to <1 / 1 and alternatively from 0.5 / 1 to 0.9 / 1.

[0062] Examples of the polyorganohydrogensiloxane used as the starting material (C) are: Ci) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), Cii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, Ciii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), Civ) trimethylsiloxy-terminated polymethylhydrogensiloxane, and Cv) a combination of two or more of Ci) to Civ).

[0063] Methods for preparing polyorganohydrogensiloxanes suitable for use as starting material (C) such as hydrolysis and condensation reactions of organohalosilanes are well known in the art. In addition, polyorganohydrogensiloxanes are known in the art and are commercially available, for example, from Dow Silicones Corporation (Midland, Michigan, USA).

[0064] (D) Hydrosilylation Reaction Catalyst

[0065] The starting material (D) in the silicone hybrid pressure-sensitive adhesive composition is a hydrosilylation catalyst. The hydrosilylation catalyst includes a platinum group metal catalyst. For example, the hydrosilylation catalyst may be Di) a metal selected from platinum, rhodium, ruthenium, palladium, osmium and iridium. Alternatively, the hydrosilylation catalyst may be Dii) a compound of such a metal, such as tris(triphenylphosphine)rhodium(I) chloride (Wilkinson catalyst), a rhodium diphosphine chelate such as [1,2-bis(diphenylphosphine)ethane]dichlororhodium or [1,2-bis(diethylphosphine)ethane]dichlororhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride; or Diii) a complex of such a compound with a low molecular weight organopolysiloxane. Alternatively, the hydrosilylation catalyst may be Div) a compound microencapsulated in a matrix or core / shell structure. For example, complexes of platinum with low molecular weight organopolysiloxanes include complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum (Karstedt catalyst). Alternatively, the hydrosilylation catalyst may be a complex of Dv) microencapsulated in a resin matrix. Exemplary hydrosilylation catalysts are described in U.S. Patents 3,159,601; 3,220,972; 3,296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,766,176; 4,784,879; 5,017,654; 5,036,117; and 5,175,325; and EP 0 347 895B. Suitable hydrosilylation catalysts are known in the art and are commercially available. For example, SYL-OFF TM 4000 Catalyst and SYL-OFF TM 2700 is commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[0066] The amount of catalyst used herein will depend on various factors, including the selection of starting materials A), B) and C) and their respective contents of aliphatic unsaturated monovalent hydrocarbon groups and silicon-bonded hydrogen atoms, and the presence or absence of inhibitors, however, the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and aliphatic unsaturated monovalent hydrocarbon groups, alternatively, the amount of catalyst is sufficient to provide 1 ppm to 1000 ppm of platinum group metal based on the combined weight of all starting materials in the silicone hybrid pressure-sensitive adhesive composition; alternatively, 2 ppm to 500 ppm and alternatively 10 ppm to 100 ppm of platinum group metal based on the same basis.

[0067] (E) Photoradical initiator

[0068] The starting material (E) in the silicone hybrid pressure-sensitive adhesive composition is a photoradical initiator. Suitable photoradical initiators include UV initiators such as benzophenone derivatives, acetophenone derivatives (α-hydroxy ketones), benzoin and its alkyl esters, phosphine oxide derivatives, xanthone derivatives, oxime ester derivatives and camphorquinone. Photoradical initiators are commercially available. For example, photoradical initiators suitable for use herein include 2,6-bis(4-azidobenzylidene)cyclohexanone, 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone, 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE TM 184), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (IRGACURE TM 907); 2-Hydroxy-2-methyl-1-phenyl-propane-1-one (DAROCUR TM 1173); 50% IRGACURE TM 184C and 50% benzophenone mixed initiator (IRGACURE TM 500); 20% IRGACURE TM 184C and 80% DAROCUR TM 1173 mixed initiator (IRGACURE TM 1000); 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (IRGACURE TM 2959); methylbenzoyl formate (DAROCUR TM MBF); α,α-dimethoxy-α-phenylacetophenone (IRGACURE TM 651); 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (IRGACURE TM 369); 30% IRGACURE TM 369 and 70% IRGACURE TM 651 mixed initiator (IRGACURE TM 1300); diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (IRGACURE TM TPO), (2,4,6-trimethylbenzoyl)phenylphosphinate (IRGACURE TMTPO-L), proprietary oxime ester compounds (N-1919, NCI-831, NCI-930, NCI-730 and NCI-100 supplied from Adeka Corporation), thioxanthen-9-one; 10-methylphenothiazine; isopropyl-9H-thioxanthen-9-one; 2,4-diethyl-9H-thioxanthen-9-one; 2-chlorothioxanthen-9-one; 1-chloro-4-propoxy-9H-thioxanthen-9-one; or a combination of two or more thereof. DAROCUR TM IRGACURE TM The brand of photoradical initiators is commercially available from BASF SE (Ludwigshafen, Germany). Alternatively, the photoradical initiator may be selected from: Ei) benzophenone, Eii) substituted benzophenone compounds, Eiii) acetophenone, Eiv) substituted acetophenone compounds, Ev) benzoin, Evi) alkyl esters of benzoin, Evii) substituted phosphine oxide compounds, Eviii) xanthone and Eix) substituted xanthone; and Ex) a combination of two or more of Ei) to Eviii). Alternatively, the photoradical initiator may be a substituted acetophenone, such as 1-hydroxycyclohexyl phenyl ketone. The type of photoradical initiator is not particularly limited, however, some photoradical initiators, especially those containing a thioether group, a phosphinate group or a phosphine oxide group, may inhibit the hydrosilylation reaction catalyst, and therefore, when such a photoradical initiator is included, it may be necessary to control the appropriate amounts of (D) the hydrosilylation reaction catalyst and (I) the additive and / or the curing temperature / time may be adjusted.

[0069] The amount of photoinitiator in the silicone hybrid pressure-sensitive adhesive composition will depend on various factors, including the desired reaction rate, the photoinitiator used, and the selection and amount of the starting materials (A) and (B) and their corresponding (meth)acryloyloxyalkyl group content, however, the amount may be 1 to 20 parts by weight per 100 parts by weight of the starting material (A). Alternatively, the amount of photoinitiator may be 0.1 to 10% by weight, alternatively 0.5 to 5% by weight, based on the combined weight of the starting materials (A), (B) and (C) in the composition.

[0070] (F) Hydrosilylation Reaction Inhibitor

[0071] The starting material (F) in the silicone hybrid pressure-sensitive adhesive composition is a hydrosilylation reaction inhibitor (inhibitor) which can optionally be used to alter the rate of reaction of the silicon-bonded hydrogen atoms of the starting materials (A), (B) and (C) with the aliphatic unsaturated hydrocarbon groups compared to the reaction rate of the same starting materials but omitting the inhibitor. Examples of inhibitors are acetylenic alcohols such as dimethyl hexynol and 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 (ETCH), and combinations thereof; cycloalkenyl siloxanes such as methylvinylcyclosiloxanes, exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and combinations thereof; ene-yne ​​compounds such as 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne and combinations thereof; triazoles such as benzotriazole; phosphines; thiols; hydrazines; amines such as tetramethylethylenediamine, 3-dimethylamino-1-propyne, n-methylpropargylamine, propargylamine and 1-ethynylcyclohexylamine; fumarate esters including fumarate dialkyl esters such as fumarate diethyl ester and / or fumarate dienyl esters such as fumarate diallyl ester and / or fumarate diallyloxyalkyl esters; maleates such as maleate diallyl ester and maleate diethyl ester; nitriles; ethers; carbon monoxide; olefins such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols such as benzyl alcohol; and combinations thereof.

[0072] 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 reduces the yellowing of the reaction product prepared by the hydrosilylation reaction compared to the reaction product obtained by the hydrosilylation of the starting materials that do not contain a silylated acetylenic compound or contain an organic acetylenic alcohol inhibitor such as those described above.

[0073] Examples of silylated acetylenic compounds are (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, 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)tris((1,1-dimethyl-2-propynyl)oxy)silane) Ethylsilane, bis(3-methyl-1-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. Alternatively, silylated acetylenic compounds are exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or combinations thereof. Silylated acetylenic compounds useful as inhibitors herein may be prepared by methods known in the art, for example, U.S. Pat. No. 6,677,740 discloses silylation of the above acetylenic alcohols by reacting the above acetylenic alcohols with chlorosilanes in the presence of an acid acceptor. Alternatively, the hydrosilylation inhibitor may be selected from: acetylenic alcohols, cycloalkenylsiloxanes, enyne compounds, triazoles, phosphines, thiols, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated acetylenic alcohols. Alternatively, the hydrosilylation inhibitor may be an acetylenic alcohol, such as ETCH.

[0074] The amount of inhibitor used herein will depend on various factors, including the desired reaction rate, the specific inhibitor used, and the selection and amount of starting materials (A), (B), and (C). However, when present, the amount of inhibitor may be 0.1 to 4 parts by weight per 100 parts by weight of starting materials (A). Alternatively, the amount of inhibitor may be 0.0001 to 1% by weight based on the combined weight of starting materials (A), (B), and (C) in the composition.

[0075] (G) Free radical scavengers

[0076] Starting material (G) is a radical scavenger (scavenger) that can be used to control or suppress the radical reaction of the organosilicon hybrid pressure-sensitive adhesive composition. Because the organosilicon hybrid pressure-sensitive adhesive composition includes reactive (meth) acrylate groups, there can be effective radical scavengers to prevent premature reactions, such as in storage and during the use of the protective film prepared using the organosilicon hybrid pressure-sensitive adhesive composition. The scavenger comprising phenolic compounds is a class of such substances that can be used in the present invention, and these substances include, for example, 4-methoxyphenol (MEHQ, methyl ether of hydroquinone), hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, tert-butylcatechol, butylated hydroxytoluene and butylated hydroxyanisole, a combination of two or more of them. Other scavengers that can be used include phenothiazine and anaerobic inhibitors, such as NPAL type inhibitors (tri-(N-nitroso-N-phenylhydroxylamine) aluminum salts) from Albemarle Corporation (Baton Rouge, La.). Alternatively, the radical scavenger can be selected from phenolic compounds, phenothiazine and anaerobic inhibitors.

[0077] Free radical scavengers are known, for example, in U.S. Pat. No. 9,475,968 and are commercially available. The amount of scavenger in the silicone hybrid pressure-sensitive adhesive composition will depend on various factors, including the type and amount of (meth)acryloxyalkyl groups in the starting materials (A) and (B), however, the scavenger may be present in an amount of 0.001 to 1 part by weight per 100 parts by weight of the starting materials (A). Alternatively, the amount of the scavenger may be 0.001 to 0.5 parts by weight, alternatively 0.01 to 0.1 parts by weight, based on the combined weight of all starting materials in the composition.

[0078] (H) Solvent

[0079] The starting material (H) in the organosilicon hybrid pressure-sensitive adhesive composition is a solvent. A solvent may be added during the preparation of the organosilicon hybrid pressure-sensitive adhesive composition, for example, to help mix and deliver one or more starting materials when preparing the organosilicon hybrid pressure-sensitive adhesive composition and / or to promote the coating of the organosilicon hybrid pressure-sensitive adhesive composition on a substrate, as described below. When preparing the organosilicon hybrid pressure-sensitive adhesive composition, some starting materials such as polyorganosilicate resins and / or hydrosilylation catalysts may be delivered in a solvent. Suitable solvents include organic liquids, examples of which include but are not limited to aromatic hydrocarbons, aliphatic hydrocarbons, ketones, esters, ethers, glycols and glycol ethers. Hydrocarbons include benzene, toluene, xylene, naphtha, hexane, cyclohexane, methylcyclohexane, heptane, octane, decane, hexadecane, isoparaffins (such as Isopar L (C11-C13), Isopar H (C11-C12)), hydrogenated polydecene. Suitable ketones include, but are not limited to, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, and cyclohexanone. Esters include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate. Ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane. Solvents having both ester and ether moieties include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; ethers and esters also include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dioctyl carbonate, diethylhexyl carbonate, propylene glycol n-propyl ether, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dipropylene glycol methyl ether, or ethylene glycol n-butyl ether, octyl dodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dioctanoate / dicaprate, octyl ether, and octyl palmitate. Alternatively, the solvent may be selected from polyalkylsiloxanes, ketones, glycol ethers, tetrahydrofuran, mineral oil, naphtha, or a combination thereof. Polyalkylsiloxanes having a suitable vapor pressure can be used as the solvent, and these polyalkylsiloxanes include hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, tetrakis(trimethylsiloxy)silane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane, hexamethyl-3,3-bis{(trimethylsilyl)oxy}trisiloxane, pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, and combinations thereof.Low molecular weight polyalkylsiloxanes such as 0.5 cSt to 1.5 cSt polydimethylsiloxane are known in the art and are available under the trade name DOWSIL. TM 200 Fluid and DOWSIL TM OS fluids are commercially available and are commercially available from Dow Silicones Corporation. Alternatively, the solvent may be selected from: aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters, and solvents having both ether and ester moieties.

[0080] The amount of solvent will depend on a variety of factors, including the type of solvent selected, and the amount and type of other starting materials selected. However, when present, the amount of solvent may be 20 to 300 parts by weight per 100 parts by weight of starting materials (A). Alternatively, the amount of solvent may be 10 to 80 weight percent based on the combined weight of starting materials (A), (B) and (C) in the composition.

[0081] (I) Additives

[0082] The silicone hybrid pressure-sensitive adhesive composition may also optionally include additives such as ii) synergists, iii) chain transfer agents (hydrogen donors), iii) sensitizers, combinations of two or more of additives ii) to iv). The above additives may help improve UV sensitivity and reduce one or more of oxygen inhibition and adhesion of the silicone hybrid pressure-sensitive adhesive when exposed to UV radiation. Suitable types of additives are summarized in "The formulator's guide to anti-oxygen inhibition additives", Progress in Organic Coatings, Vol. 77, No. 11 (2014): pp. 1789-1798, Husár, Branislav et al. and PCT Publication WO2017182638A1. The type of additive is not particularly limited, however, some additives, especially additives containing mercapto groups, phosphine or phosphine oxide groups, can inhibit the hydrosilylation reaction catalyst, therefore, when such additives are included, it is necessary to control the appropriate amount of (D) hydrosilylation reaction catalyst and (I) additive and / or adjust the curing temperature / time. The amount of the additive may be 0 to 5 parts by weight per 100 parts by weight of the starting material (A). Alternatively, based on the combined weight of the starting materials (A), (B) and (C) in the composition, the amount of the additive may be 0 to 5 weight %, alternatively 0 to 2 weight %. Examples of commercially available additives are as follows.

[0083] The synergist may be selected from the following amine-containing compounds: tertiary amines, glycine, oximes, aminobenzoates, acrylated amines, amine-modified acrylates, and combinations of at least two of these synergists. Examples of tertiary amines and aminobenzoates are commercially available and include, but are not limited to, N-methyldiethanolamine (CAS#105-59-9; Sigma-Aldrich), p-tolyldiethanolamine (CAS#3077-12-1), N-ethyldiisopropylamine (CAS#7087-68-5, Sigma-Aldrich), 2-(diisopropylamino)ethanol (CAS#96-80-0, Sigma-Aldrich), N-phenylglycine (CAS#103-01-5, TCI), Speedcure PDO (Lambson), ethyl 4-(dimethylamino)benzoate (CAS#10287-53-3, TCI), 2-ethylhexyl 4-(dimethylamino)benzoate (CAS#21245-2-3), Speedcure EDB (Lamson), Speedcure DMB (Lamson), Speedcure EHA (Lamson), Speedcure BDMB (Lamson), Speedcure XFLM01 (Lamson), Speedcure XFLM02 (Lamson), Speedcure EMD (Lamson), Speedcure BEDB (Lamson), Speedcure 7040 (Lamson), Speedcure EPD (Lamson), dimethylamine borane (CAS#74-94-2, Sigma-Aldrich), N-vinyl pyrrolidone (BASF).Examples of amine-modified acrylates and acrylated amines are also commercially available and include, but are not limited to, 2-(dimethylamino)ethyl methacrylate (CAS#2867-47-2, TCI), 2-(dimethylamino)ethyl acrylate (CAS#2439-35-2, TCI), N-[3-(dimethylamino)propyl]acrylamide (CAS#3845-76-9, TCI), Ebecryl P115 (Allnex), Ebecryl 7100 (Allnex), Ebecryl 80 (Allnex), Ebecryl 81 (Allnex), Ebecryl 83 (Allnex), Ebecryl 85 (Allnex), Ebecryl 880 (Allnex), Ebecryl LEO10551 (Allnex), Ebecryl LEO10552 (Allnex), Ebecryl LEO10553 (Allnex), Ebecryl 3600 (Allnex), Ebecryl 3703 (Allnex), DEAEMA (BASF), DMAEMA (BASF), TBAEMA (BASF), Genomer 5271 (Rahn), Genomer 5142 (Rahn), Genomer 5161 (Rahn), Genomer 5275 (Rahn), CN UVA 421 (Sartomer), CN3702 (Sartomer), CN3715 (Sartomer), CN3715 LM (Sartomer), CN3755 (Sartomer), CN381 (Sartomer), CN 386 (Sartomer), CN501 (Sartomer). The amount of the synergist may be 0.01 to 10 parts by weight, alternatively 0.1 to 2.0 parts by weight per 1 part by weight of the photoinitiator (E).

[0084] The chain transfer agent may be selected from mercapto-containing compounds and any other hydrogen donors. Examples are pentaerythritol tetrakis (3-mercaptopropionate) (CAS#7575-23-7; Sigma-Aldrich), trimethylolpropane tris (3-mercaptopropionate) (CAS#33007-83-9; Sigma-Aldrich), tris (trimethylsilyl) silane (CAS#1873-77-4, Alfa Aesar), 3-mercaptopropyl (dimethoxy) methyl silane (CAS#31001-77-1; TCI), (3-mercaptopropyl) trimethoxy silane (CAS#4420-74-0; TCI), mercaptosiloxane (CAS 102783-03-9; Gelest) and 1-hexanethiol (CAS#111-31-9, Sigma-Aldrich). The amount of the chain transfer agent may be 0.01 to 10 parts by weight, alternatively 0.1 to 2.0 parts by weight, per 1 part by weight of the photoinitiator (E).

[0085] Alternatively, the synergist may be a sensitizer, such as those disclosed in PCT Publication WO2015194654A1 and U.S. Patent No. 4,250,053. Available sensitizers include 2-isopropylthioxanthone, 1,3-diphenyl-2-pyrazoline, and 1,3-diphenylisobenzofuran. Other examples of sensitizers include anthracene compounds, 4-methoxy-1-naphthol, fluorene, pyrene, and diphenylethylene. Examples of anthracene compounds include anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 4'-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and 4'-nitrobenzyl-9,10-dipropoxyanthracene-2-sulfonate. Sensitizers are commercially available, for example, under the trade names Anthracure UVS-1331, 1221, 1101, and ET-2111 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.). The amount of the sensitizer may be 0.01 to 10 parts by weight, alternatively 0.1 to 2.0 parts by weight, per 1 part by weight of the photoinitiator (E).

[0086] (J) Bis-SiH-terminated polydiorganosiloxane

[0087] Optionally, in addition to the starting material (C) in the silicone hybrid pressure-sensitive adhesive composition, a bis-SiH-terminated polydiorganosiloxane may be used. The polydiorganosiloxane may have a unit formula M H 2D k , where M Hand D units are as described above, and the subscript k ≥ 1, alternatively 1 ≤ k ≤ 500. Suitable polydiorganosiloxanes for starting material (J) include dimethylhydrogensiloxy-terminated polydimethylsiloxane and dimethylhydrogensiloxy-terminated polydiphenylsiloxane. When present, the weight ratio of starting material (J) to starting material (C) [(J) / (C) ratio] may be 0.25 / 1 to 4 / 1.

[0088] When selecting starting materials for the above-described silicone hybrid pressure-sensitive adhesive composition, there may be overlap between the types of starting materials because some of the starting materials described herein may have more than one function. For example, some reducing agents may also function as hydrosilylation reaction inhibitors (e.g., phosphines such as triphenylphosphine). When additional starting materials are added to the silicone hybrid pressure-sensitive adhesive composition, the additional starting materials are different from each other and from the desired starting materials in the silicone hybrid pressure-sensitive adhesive composition.

[0089] Method for preparing silicone hybrid pressure-sensitive adhesive composition

[0090] The silicone hybrid pressure-sensitive adhesive composition can be prepared by a method comprising the steps of combining all starting materials by any convenient means, such as mixing at ambient temperature or elevated temperature. For example, when the silicone hybrid pressure-sensitive adhesive composition is prepared at elevated temperature and / or the silicone hybrid pressure-sensitive adhesive composition is prepared as a one-part composition, a hydrosilylation reaction inhibitor can be added before the hydrosilylation reaction catalyst.

[0091] Alternatively, the organosilicon hybrid pressure-sensitive adhesive composition can be prepared as a multi-part composition, for example, when the organosilicon hybrid pressure-sensitive adhesive composition will be stored for a long period of time before use. In the multi-part composition, the hydrosilylation reaction catalyst is stored in a separate part from any starting material having silicon-bonded hydrogen atoms (e.g., polyorganohydrogensiloxane), and the parts are combined just before the organosilicon hybrid pressure-sensitive adhesive composition is used. For example, a two-part composition can be prepared by combining starting materials in any convenient manner (such as mixing) to form a base part, and these starting materials include starting material (C) polyorganohydrogensiloxane, all or part of starting materials (A) and (B) and optionally all or part of (H) solvent and optionally one or more other additional starting materials mentioned above. The curing agent can be prepared by combining starting materials in any convenient manner (such as mixing), and these starting materials include: starting material (D) hydrosilylation reaction catalyst and all or part of starting materials (A) and (H) and optionally one or more other additional starting materials mentioned above. The starting materials can be mixed at ambient temperature or at elevated temperature. The starting material (F) hydrosilylation reaction inhibitor may be included in one or more of the base part, the curing agent part or a separate additional part. The starting material (B) polyorganosilicate resin may be added to the base part, the curing agent part or a separate additional part. The starting material (E), the photoradical initiator and the starting material (G), the radical scavenger may be added to the base part or a separate additional part. When a two-part composition is used, the weight ratio of the amount of the base part to the amount of the curing agent part may be in the range of 1:1 to 10:1. The silicone hybrid pressure-sensitive adhesive composition will be cured via a hydrosilylation reaction to form a pressure-sensitive adhesive.

[0092] Preparation of adhesive products

[0093] The above method may also include one or more additional steps. The organosilicon hybrid pressure-sensitive adhesive composition prepared as described above can be used to form an adhesive article, for example, a pressure-sensitive adhesive (prepared by thermally curing the above organosilicon hybrid pressure-sensitive adhesive composition) on the surface of a substrate. Therefore, the above method may also include applying the organosilicon hybrid pressure-sensitive adhesive composition to a substrate.

[0094] The pressure-sensitive adhesive curable composition can be applied to the substrate by any convenient means. For example, the pressure-sensitive adhesive curable composition can be applied to the substrate by a spin coater, a gravure coater, a photographic coater, a photo-gravure coater, a roll coater, a reverse roll coater, an air knife coater, or a curtain coater.

[0095] Substrate can be any material that can withstand the curing conditions (described below) for curing the pressure-sensitive adhesive curable composition to form a pressure-sensitive adhesive on a substrate. For example, any substrate that can withstand the heat treatment of a temperature equal to or greater than 120°C, alternatively 150°C is suitable. Examples of materials suitable for such substrates include plastic films, such as polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide (PAI), polyether sulfide (PES), or polyethylene terephthalate (PET), or PE (polyethylene), or PP (polypropylene). The thickness of the substrate is not critical, however, the thickness can be in the range of 25 microns to 300 microns. The substrate is preferably transparent, and alternatively, a substrate that allows the silicone hybrid pressure-sensitive adhesive to be exposed to UV radiation can be used.

[0096] In order to improve the bonding of the silicone hybrid pressure-sensitive adhesive to the substrate, the method may also optionally include treating the surface of the substrate before applying the silicone hybrid pressure-sensitive adhesive composition. Treating the substrate may be performed in any convenient manner, such as applying a primer, or subjecting the substrate to corona discharge treatment, etching or plasma treatment before applying the pressure-sensitive adhesive composition to the substrate.

[0097] Adhesive articles (such as protective films) can be prepared by applying the above-mentioned silicone hybrid pressure-sensitive adhesive composition to the surface of the above-mentioned substrate. The method may also optionally include removing all or part of the solvent before and / or during curing. Removal of the solvent can be carried out in any convenient manner, such as heating at a temperature that evaporates the solvent without completely curing the silicone hybrid pressure-sensitive adhesive composition via a hydrosilylation reaction, for example, heating at a temperature of 70°C to 120°C, alternatively 50°C to 100°C, and alternatively 70°C to 80°C for a time sufficient to remove all or part of the solvent (e.g., 30 seconds to 1 hour, alternatively 1 minute to 5 minutes). Therefore, the method also includes curing the silicone hybrid pressure-sensitive adhesive composition (which can remove part or all of the solvent when performing the drying step) via a hydrosilylation reaction at room temperature or by heating at a temperature of 60°C to 220°C, alternatively 70°C to 200°C, alternatively 80°C to 180°C, and alternatively 120°C to 160°C for a time sufficient to form a silicone hybrid pressure-sensitive adhesive on the surface of the substrate (e.g., 30 seconds to one hour, alternatively 1 minute to 5 minutes). Drying and / or hydrosilylation curing can be performed by placing the substrate in an oven. The amount of the silicone hybrid pressure-sensitive adhesive composition to be applied to the substrate depends on the specific application, however, the amount can be sufficient to make the thickness of the silicone hybrid pressure-sensitive adhesive after curing be 5 microns to 200 microns, and for the protective film, after curing via a hydrosilylation reaction, the thickness can be 10 microns to 50 microns, alternatively 20 microns to 40 microns, and alternatively 30 microns.

[0098] Therefore, a method for forming a protective film including a silicone hybrid pressure-sensitive adhesive layer on a surface of a substrate comprises:

[0099] 1) optionally treating the surface of the substrate as described above;

[0100] 2) applying the above organosilicon hybrid pressure-sensitive adhesive composition to the surface of a substrate, and

[0101] 3) The silicone hybrid pressure-sensitive adhesive composition is heated to form a silicone hybrid pressure-sensitive adhesive layer on the surface of the substrate.

[0102] The above method may also optionally include applying a removable release liner to the silicone hybrid pressure-sensitive adhesive layer opposite the substrate, for example, to protect the silicone hybrid pressure-sensitive adhesive prior to use. The release liner (e.g., protective film) may be removed prior to using the adhesive article.

[0103] The adhesive article (eg, protective film) prepared as described above is suitable for use in a (opto)electronic device (eg, flexible OLED display device) manufacturing process as a protective film.

[0104] A method for producing an (opto)electronic device may comprise:

[0105] 4) applying the protective film prepared as described above to the passivation layer in the device so that the silicone hybrid pressure sensitive adhesive contacts the passivation layer;

[0106] 5) using a protective film to protect the passivation layer in the device (e.g., during processing and / or transportation of the device); and thereafter

[0107] 6) exposing the protective film to UV radiation; thereby reducing the tack of the silicone hybrid pressure-sensitive adhesive. The silicone hybrid pressure-sensitive layer of the above cured film obtained contains free (meth)acryloyl groups, which can be analyzed by Fourier transform infrared (FT-IR) spectroscopy, and their relative amount in the cured film and their reaction when exposed to UV radiation can be monitored by the vibration absorption intensity of unsaturated bonds in the FT-IR spectrum, as shown in the following literature: "UV coatings: basics, recent developments and new applications", page 33 (Elsevier; December 21, 2006), Schwalm; Polymer Chemistry., 2013; Vol. 4, No. 8: pp. 2449-2456, Espeel. At about 1296 cm -1 and 938cm 1 Free (meth)acryloyl groups in the silicone hybrid pressure-sensitive adhesive prepared by using the starting material (A) were detected at . Without wishing to be bound by theory, it is believed that exposure to UV radiation results in the formation of (meth)acryloyloxyalkyl groups R 2 Further reaction and further crosslinking reduce the tack of the silicone hybrid pressure sensitive adhesive, which can allow the protective film to be removed from the passivation layer in the device while minimizing damage to the passivation layer and / or minimizing residual silicone hybrid pressure sensitive adhesive remaining on the passivation layer.

[0108] The step of exposing the protective film to UV radiation can be performed using a general ultraviolet irradiation device, for example, a surface type or conveyor type ultraviolet irradiation device, in which a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, an ultraviolet light emitting diode, etc. are used as a light source. The ultraviolet irradiation dose is generally 0.1 W / cm 2 Up to 5W / cm 2 Lasts for 5 to 60 seconds (=0.5 J / cm 2 Up to 300J / cm 2 If the adherend, such as an optoelectronic device, is sensitive and can be damaged by the heat or light generated by the UV lamp, an ultraviolet light emitting diode can be used, and the actual dose can be 0.5 J / cm2 To less than 10J / cm 2 Alternatively, exposure to UV radiation may be performed by any convenient means such as those disclosed in US Patent Application Publication No. 2002 / 0071958A1 and Korean Patent No. 101704548B1. Alternatively, the method described below in Reference Example 8 may be used.

[0109] Example

[0110] These examples are intended to illustrate some embodiments of the invention and should not be construed as limiting the scope of the invention described in the claims.The starting materials used in these examples are described in Table 1.

[0111] Table 1 - Starting materials used in the examples

[0112]

[0113]

[0114]

[0115] DOWSIL TM and SYL-OFF TM The starting materials under the brand name of HYDRA® are commercially available from Dow Silicones Corporation.

[0116] In this Reference Example 1, a bisvinyl-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer shown as starting material A-1 in Table 1 above was synthesized as follows. 3-methacryloxypropylmethyldimethoxysilane (50.78 g, DOWSIL TMZ-6033) and 0.1N HCl (45.45g), and use a magnetic stirring bar to mix at about 23°C. Use a simple distillation glassware device to evacuate to about 20mmHg for 1.5 hours. After 1.5 hours, release the vacuum and add dihydroxy-terminated polydimethylsiloxane (550.00g, OH fluid) together with 0.16g (G-1) MEHQ to the reaction solution. Take out the magnetic stirring bar, and use a Teflon paddle with a glass stirring rod to mix the solution. Evacuate to about 5mmHg, and heat the reaction system to 80°C for 1.5 hours. Remove the simple distillation glassware device, and use the Dean Stark distillation device for the final reaction step. Add (H-1) toluene (300g, Sigma-Aldrich) and dimethylvinylsiloxy-terminated polydimethylsiloxane (2g, end-capping agent) to the reaction solution. The solution was then heated to 111°C-115°C, and 0.4 mL of phosphazene catalyst was added at 90°C. The overhead distillate was collected in a Dean Stark trap, and an additional 0.4 mL of phosphazene catalyst was added. The solution was maintained at toluene reflux for 1 hour. The heat source was removed, and the solution was cooled. At about 60°C, DVTMDZ (1 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. Also, the solution was heated to 120°C with nitrogen / 2% oxygen bubbling for 1 hour, and cooled to RT with gas bubbling. The solid content of the solution (which is the weight measured before and after drying at 150°C for 1 hour) was adjusted to 75% by adding additional toluene. Then, a product dissolved in toluene was obtained. Based on 13 C-NMR and 29 Si-NMR analysis shows that the obtained bis(dimethylvinylsiloxy)-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer contains the following average unit formula: 4 3SiO 1 / 2 ) 0.00091 (R 4 2SiO 2 / 2 ) 0.99909 ; where each R 4 R is independently selected from methyl, methacryloyloxypropyl and vinyl; and the subscript represents the molar fraction. The methacryloyl content is the total R 4 1.325 mol% vinyl content for total R 4 0.015 mol%, and the methyl content is the total R 4The obtained bis(dimethylvinylsiloxy)-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer may have an average unit formula of (ViMe2SiO)2(MaMeSiO) 58 (Me2SiO) 2130 Shown.

[0117] In this Reference Example 2, a bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer shown as starting material A-2 in Table 1 above was synthesized as follows. 3-methacryloxypropylmethyldimethoxysilane (33.3 g, DOWSIL TM Z-6033) and 0.1N HCl (45.45g), and use a magnetic stirring bar to mix at room temperature (about 23°C). Use a simple distillation glassware device to evacuate to about 20mmHg for 1.5 hours. After 1.5 hours, release the vacuum and add dihydroxy-terminated polydimethylsiloxane (600.00g, OH fluid) together with 0.23g (G-1) MEHQ to the reaction solution. Take out the magnetic stirring bar, and use a Teflon paddle with a glass stirring rod to mix the solution. Evacuate to about 5mmHg, and heat the reaction system to 80°C for 1.5 hours. Remove the simple distillation glassware device, and use the Dean Stark distillation device for the final reaction step. Add (H-1) toluene (300g, Sigma-Aldrich) and dimethylvinylsiloxy-terminated polydimethylsiloxane (2.2g, end-capping agent) to the reaction solution. The solution was then heated to 111°C-115°C, and 0.4 mL of phosphazene catalyst was added at 90°C. The overhead distillate was collected in a Dean Stark trap, and an additional 0.4 mL of phosphazene catalyst was added. The solution was maintained at toluene reflux for 1 hour. The heat source was removed, and the solution was cooled. At about 60°C, DVTMDZ (1 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. Also, the solution was heated to 120°C with nitrogen / 2% oxygen bubbling for 1 hour, and cooled to RT with gas bubbling. The solids content of the solution was adjusted to 75% by adding additional toluene. Then, a product dissolved in toluene was obtained. Based on 13 C-NMR and 29Si-NMR analysis shows that the obtained bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer contains the following average unit formula: 4 3 SiO 1 / 2 ) 0.00035 (R 4 2SiO 2 / 2 ) 0.99965 ; where each R 4 R is independently selected from methyl, methacryloyloxypropyl and vinyl; and the subscript represents the molar fraction. The methacryloyl content is the total R 4 The vinyl content of the total R 4 0.006 mol%, and the methyl content is the total R 4 99.1187 mol%. (m+o) / n ratio is 56 / 1. [Methacryloyl content = 0.230 mmol / g, Vi content = 0.005 mmol / g, total reactive groups = 0.235 mmol / g]. Alternatively, the obtained bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer can be represented as: (ViMe2SiO)2(MaMeSiO) 100 (Me2SiO) 5610 .

[0118] In this Reference Example 3, a bisvinyl-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer shown as starting material A-3 in Table 1 above was synthesized as follows. 3-methacryloxypropylmethyldimethoxysilane (13.7 g, DOWSIL TMZ-6033) and 0.1N HCl (24.37g), and use a magnetic stirring bar to mix at about 23°C. Use a simple distillation glassware device to evacuate to about 20mmHg for 1.5 hours. After 1.5 hours, release the vacuum and add dihydroxy-terminated polydimethylsiloxane (1179.49g, OH fluid) together with 0.34g (G-1) MEHQ to the reaction solution. Take out the magnetic stirring bar, and use a Teflon paddle with a glass stirring rod to mix the solution. Evacuate to about 5mmHg, and heat the reaction system to 80°C for 1.5 hours. Remove the simple distillation glassware device, and use the Dean Stark distillation device for the final reaction step. Add (H-1) toluene (550g, Sigma-Aldrich) and dimethylvinylsiloxy-terminated polydimethylsiloxane (2.2g, end-capping agent) to the reaction solution. The solution was then heated to 111°C-115°C, and 0.1 mL of phosphazene catalyst was added at 90°C. The overhead distillate was collected in a Dean Stark trap, and an additional 0.1 mL of phosphazene catalyst was added. The solution was maintained at toluene reflux for 1 hour. The heat source was removed, and the solution was cooled. At about 60°C, DVTMDZ (0.3 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. Also, the solution was heated to 120°C with nitrogen / 2% oxygen bubbling for 1 hour, and cooled to RT. The solids content of the solution was adjusted to 75% by adding additional toluene. Then, a product dissolved in toluene was obtained. Based on 13 C-NMR and 29 Si-NMR analysis shows that the obtained bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer contains the following average unit formula: 4 3SiO 1 / 2 ) 0.00074 (R 4 2SiO 2 / 2 ) 0.99926 ; where each R 4 R is independently selected from methyl, methacryloyloxypropyl and vinyl; and the subscript represents the molar fraction. The methacryloyl content is the total R 4 The vinyl content of the total R 4 0.012 mol%, and the methyl content is the total R 4The obtained bisvinyldimethylsiloxy terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer can be represented as: (ViMe2SiO)2ViMe2SiO(MaMeSiO) 10 (Me2SiO) 2679 .

[0119] In this Reference Example 4, a bisvinyl-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer shown as starting material A-4 in Table 1 above was synthesized as follows. 3-methacryloxypropylmethyldimethoxysilane (120.00 g, DOWSIL TM Z-6033) and 0.1N HCl (128.87g), and use a magnetic stirring bar to mix at about 23°C. Use a simple distillation glassware device to evacuate to about 20mmHg for 1.5 hours. After 1.5 hours, release the vacuum and add dihydroxy-terminated polydimethylsiloxane (786.50g, OH fluid) together with 0.23g (G-1) MEHQ to the reaction solution. Take out the magnetic stirring bar, and use a Teflon paddle with a glass stirring rod to mix the solution. Evacuate to about 5mmHg, and heat the reaction system to 80°C for 1.5 hours. Remove the simple distillation glassware device, and use the Dean Stark distillation device for the final reaction step. Add (H-1) toluene (380g, Sigma-Aldrich) and dimethylvinylsiloxy-terminated polydimethylsiloxane (2.87g, end-capping agent) to the reaction solution. The solution is then heated to 111°C-115°C, and 0.3 mL of phosphazene catalyst is added at 90°C. The overhead distillate is collected in a Dean Stark trap, and an additional 0.3 mL of phosphazene catalyst is added. The solution is maintained at toluene reflux for 1 hour. The heat source is removed, and the solution is cooled. At about 60°C, trihexylamine (0.3 g, Sigma Aldrich) is added to the reaction solution and mixed for 2 hours. And, the solution is heated to 120°C with nitrogen / 2% oxygen bubbling, continues for 1 hour, and cooled to RT. The solid content of the solution is adjusted to 75% by adding additional toluene. Then, a product dissolved in toluene is obtained. Based on 13 C-NMR and 29 Si-NMR analysis shows that the obtained bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer contains the following average unit formula:4 3SiO 1 / 2 ) 0.00071 (R 4 2SiO 2 / 2 ) 0.99929 ; where each R 4 R is independently selected from methyl, methacryloyloxypropyl and vinyl; and the subscript represents the molar fraction. The methacryloyl content is the total R 4 The vinyl content is 2.406 mol% for the total R 4 0.012 mol%, and the methyl content is the total R 4 The obtained bisvinyldimethylsiloxy terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer can also be represented by the unit formula: (ViMe2SiO)2(MaMeSiO) 136 (Me2SiO) 2679 .

[0120] In this Reference Example 5, a bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer shown as starting material A-5 in Table 1 above was synthesized as follows. 3-methacryloxypropylmethyldimethoxysilane (4.5 g, DOWSIL TMZ-6033) and 0.1N HCl (4.55g), and mixed at room temperature (about 23°C) using a magnetic stirring bar. Use a simple distillation glassware device to evacuate to about 20mmHg for 1.5 hours. After 1.5 hours, release the vacuum and add silanol-terminated dimethylsiloxane (786.5g, OH fluid) together with 0.23g (G-1) MEHQ to the reaction solution. Take out the magnetic stirring bar, and use a Teflon paddle with a glass stirring rod to mix the solution. Evacuate to about 5mmHg, and heat the reaction system to 80°C for 1.5 hours. Remove the simple distillation glassware device, and use the Dean Stark distillation device for the final reaction step. Add (H-1) toluene (450g, Sigma-Aldrich) and bis(dimethylvinylsiloxy)-terminated polydimethylsiloxane (5g, end-capping agent) to the reaction solution. The solution was then heated to 111°C-115°C and 0.1 mL of phosphazene catalyst was added at 90°C. The overhead distillate was collected in a Dean Stark trap and an additional 0.1 mL of phosphazene catalyst was added. The solution was kept at toluene reflux for 1 hour. About 80 g of overhead distillate was collected. The heat source was removed and the solution was cooled. At about 60°C, DVTMDZ (0.3 g, Sigma Aldrich) was added to the reaction solution and mixed for 2 hours. The solid content of the solution was adjusted to 75% by adding additional toluene. Then, a product dissolved in toluene was obtained. Based on 13 C-NMR and 29 Si-NMR analysis shows that the obtained bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer contains the following average unit formula: 4 3 SiO 1 / 2 ) 0.00074 (R 4 2SiO 2 / 2 ) 0.99926 , where each R 4 R is independently selected from methyl, methacryloyloxypropyl and vinyl, and the subscript indicates the molar fraction. The methacryloyl content is the total R 4 0.097 mol% vinyl content for total R 4 0.022 mol%, and the methyl content is the total R 4The obtained bisvinyldimethylsiloxy terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer can also be represented by the unit formula: (ViMe2SiO)2(MaMeSiO)3(Me2SiO) 1536 .

[0121] In this Reference Example 6, a bisvinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl)siloxane copolymer shown as starting material A-6 in Table 1 above was synthesized as follows. 3-methacryloxypropylmethyldimethoxysilane (30 g, DOWSIL TM Z-6033), silanol-terminated dimethyl, methylvinylsiloxane (9.5g, ME2 / MeVi diol) and 0.1N HCl (4.55g), and mixed at room temperature (about 23°C) using a magnetic stirring bar. Use a simple distillation glassware device to evacuate to about 20mmHg for 1.5 hours. After 1.5 hours, release the vacuum and add silanol-terminated dimethylsiloxane (300g, OH fluid) together with 0.03g (G-1) MEHQ to the reaction solution. Take out the magnetic stirring bar, and use a Teflon paddle with a glass stirring rod to mix the solution. Evacuate to about 5mmHg, and heat the reaction system to 80°C for 1.5 hours. Remove the simple distillation glassware device, and use the Dean Stark distillation device for the final reaction step. Add (H-1) toluene (200g, Sigma-Aldrich) to the reaction solution. The solution was then heated to 111°C-115°C and 0.1 mL of phosphazene catalyst was added at 90°C. The overhead distillate was collected in a Dean Stark trap and an additional 0.1 mL of phosphazene catalyst was added. The solution was kept at toluene reflux for 1 hour. About 80 g of overhead distillate was collected. The heat source was removed and the solution was cooled. At <50°C, HMDZ (1.31 g, Sigma Aldrich) was added to the reaction solution and mixed for 1 hour. Water was added and mixed for 30 minutes. The temperature was then raised to 110°C to remove water, volatile residues and ammonia for 1 hour. The solids content of the solution was adjusted to 40% by adding additional toluene. Then, a product dissolved in toluene was obtained. Based on 13 C-NMR and 29Si-NMR analysis shows that the obtained bistrimethylsiloxy-terminated poly(dimethyl / methyl, vinyl / methyl, methacryloxypropyl)siloxane copolymer contains the following average unit formula: (R 4 3 SiO 1 / 2 ) 0.00004 (R 4 2SiO 2 / 2 ) 0.99916 , where each R 4 R is independently selected from methyl, methacryloyloxypropyl and vinyl, and the subscript indicates the molar fraction. The methacryloyl content is the total R 4 1.55 mol% vinyl content for total R 4 0.4 mol%, and the methyl content is the total R 4 The obtained bisvinyldimethylsiloxy terminated poly(dimethyl / methyl, vinyl / methyl, methacryloxypropyl)siloxane copolymer can also be represented by the unit formula: (Me3SiO)2(MaMeSiO) 155 (ViMeSiO) 40 (Me2SiO) 4795 .

[0122] In this Reference Example 7, a methacryloxy and vinyl functional polyorganosilicate resin shown as starting material B-3 in Table 4 was synthesized as follows. The following starting materials were charged into a 3-neck 2L flask of Dean Stark equipped with a thermocouple, a mechanical stirrer, a water-cooled condenser and a N2 bubbler: 742.2 g of a 75% xylene solution of (B-2) dimethylvinylated and trimethylated silica (Mn=4830, Mw=5030), 39.5 g of 3-methacryloxypropylmethyldimethoxysilane, 0.20 g of 4-methoxyphenol and 120 g of toluene. Under vigorous stirring, 1.2 g of trifluoromethanesulfonic acid (from Sigma-Aldrich) was slowly added and heated to 60°C. After 1 hour, 9.18 g of water was added and stirred for 2 hours. After 1 hour, the reflux temperature was gradually increased to 90°C to collect methanol. The reflux temperature was gradually increased to 127°C. In the above process, the water / methanol collected in the Dean Stark was discharged. After the anhydrous distillation, the flask contents were refluxed for another 2 hours while maintaining the temperature. Thereafter, the heat source was removed and 22.8 g of calcium carbonate (from Sigma-Aldrich) and 50 g of sodium sulfate (from Sigma-Aldrich) were added to the flask. The flask was cooled to RT. After stirring for 3 hours, the solids were filtered out through a 0.20 μm filter membrane. The resulting methacryloxy and vinyl functional polyorganosilicate resin was a liquid in a solvent (xylene and toluene) (solids content = 68.4%). The methacryloxy and vinyl functional polyorganosilicate resin is represented by the following average formula: (Me3SiO 1 / 2 ) 0.40 (ViMe2SiO 1 / 2 ) 0.039 (MaMeSiO 2 / 2 ) 0.024 (SiO 4 / 2 ) 0.537 (OH) 0.01 , where methacryloyl content = total R 4 1.79 mol %. Vinyl content = 2.86 mol % of total R; methyl content = 95.36 mol % of total R; b = 3.9 mol %, c + e + f = 2.4 mol % [methacryloyl content = 0.332 mmol / g, Vi content = 0.532 mmol / g, total reactive groups = 0.864 mmol / g].

[0123] In this Reference Example 8, a methacryloxy-functional polyorganosilicate resin shown as starting material B-4 in Table 4 was synthesized as follows. In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer and a Dean Stark trap; a mixture of 375.31 g of a solution containing 75% (B-1) MQ resin (Mn=3065, Mw=5664) dissolved in 25% xylene, 1.5 g of 11N KOH aqueous solution and toluene was refluxed to remove water for 2 hours. 46.47 g of Z-6033 and 0.11 g of (G-1) MEHQ were added to the mixture, and the resulting mixture was refluxed for 5 hours. After cooling to below 50° C., toluene, methanol, water were added and refluxed at 73° C. for 1 hour. Methanol and water were removed with toluene. Toluene corresponding to the toluene lost with methanol and water was added to the mixture. The resulting mixture was refluxed for another 3 hours. After cooling to room temperature, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The resulting methacryloxy-functional polyorganosilicate resin was a liquid (solids content = 75%) in solvent (xylene and toluene). The methacryloxy-functional polyorganosilicate resin was represented by the following average formula: (Me3SiO 1 / 2 ) 0.496 (MaMeSiO 2 / 2 ) 0.039 (SiO 4 / 2 ) 0.465 (OH) 0.45 (OCH3) 0.03 , wherein the methacryloyl content = 2.49 mol % of the total R; ; methyl content = 97.51 mol % of the total R; b = 0 mol %, c+e+f = 3.9 mol % [methacryloyl content = 0.518 mmol / g, total reactive groups = 0.518 mmol / g].

[0124] In this reference example 9, the adhesion (initial adhesion) before UV irradiation is measured as follows. The silicone hybrid pressure-sensitive adhesive composition for forming a silicone hybrid pressure-sensitive adhesive layer applied to a polyethylene terephthalate (PET, 75 μm) film has a thickness of 50 μm-100 μm after curing. The silicone hybrid pressure-sensitive adhesive sheet is produced by heating the film for 3 minutes at 150 ° C. The obtained sheet is attached to a removable polyethylene terephthalate film by a laminator, and the resulting laminate is aged for 1 day at RT. The resulting sheet is cut into 2.54 cm (1 inch) wide tape strips, which are placed on a glass plate, and bonded to it by moving a rubber-lined roller with a weight of 2 kg back and forth twice on the strip. The assembly is kept at RT for 1 hour. The adhesive force (g / inch) required for the tape to be peeled off from the glass plate is pulled at a speed of 2,400 mm / min and an angle of 180 °.

[0125] To measure the adhesion after UV irradiation, the assemblies prepared as described above were kept at room temperature for 1 day. Then, the assemblies were irradiated with UV light under the following conditions: 1. TM FJ100) irradiated from the top surface of the substrate film at 1 W / cm 2 UV light under UV illumination. The total dose is 5J / cm 2 of UVA.

[0126] In this Reference Example 10, in order to check the residual adhesion rate in the present invention, the index indicating the migration amount of the migrating component after peeling was studied as follows. As described above in Reference Example 7, an adhesive article was prepared on a PET film. The resulting sheet was placed on a glass plate and bonded to it by moving a 2 kg weight rubber-lined pressure roller back and forth twice on the strip. After keeping the assembly at RT for 1 day, the assembly was irradiated with UV light under the same conditions as described above. Then, the resulting sheet was removed from the glass. In one, TESA TM 7475 (manufactured by TESA) as a reference acrylic tape was placed on the same area of ​​glass adhered to / removed from the resulting sheet of the silicone hybrid pressure-sensitive layer and bonded thereto by moving a 2 kg-weighted rubber-backed pressure roller back and forth twice over the strip. TM 7475 was bonded to new glass in the same manner. The adhesion (g / inch) required to peel the tape from the steel plate by pulling at a speed of 300 mm / min and an angle of 180°. The degree of migration, called residual adhesion (%), was calculated as follows: Residual adhesion (%) = [Adhesion of test sample, gf / inch] / [Adhesion of standard sample, gf / inch].

[0127] In this reference example 11, a silicone hybrid pressure-sensitive adhesive composition and a comparative composition are prepared. The starting materials (A) and (B) are soluble in a solvent. The general procedure is described as follows; for the preparation of Inv.1, a solution is prepared by mixing the following components in a mixer: 133.33 g of 100 g of the starting material (A-1) and 300 ppm (G-1) dissolved in toluene (H-1); 33.28 g of a solution of 24.96 g of the starting material (B-1) dissolved in a solvent; 1.33 g of polyorganohydrogensiloxane (C-1); 5.05 g of a photoradical initiator (E-1); 0.13 g of a hydrosilylation reaction inhibitor (F-1); 50 g of toluene (H-1). After mixing the above components, the obtained solution is further combined with 0.13 g of a hydrosilylation reaction catalyst (D-1). The above components are mixed with the above solution to produce a silicone-based pressure-sensitive adhesive composition. The obtained composition is used to manufacture an adhesive tape. The lamination characteristics and adhesion of the produced adhesive tape were evaluated. Comparative Examples and Inv.2-27 were prepared in the same manner using the starting materials and amounts in the table. Tables 2 and 3 show the starting materials used (described in detail in Table 1) and their amounts [based on solids in grams and (solutions in grams)]. The value (solution in grams) indicates that the starting material is first dissolved in the solvent and represents the weight of the solution in grams. The value based on the solid indicates the amount of the starting material excluding the solvent.

[0128] Table 2 - Comparative Examples 1-10 (Comp. 1-Comp. 10)

[0129]

[0130]

[0131] Table 3 - Comparative Examples 11-13 (Comp.11-Comp.13) and Working Examples 1 to 7 (Inv.1 to 7)

[0132]

[0133]

[0134] Table 4 - Working Examples 8 to 17 (Inv. #8 to Inv. 17)

[0135]

[0136]

[0137] Table 5 - Working Examples 18 to 27 (Inv. #18 to Inv. 27)

[0138]

[0139]

[0140] Table 6 - Comparative Examples 14-15 (Comp.14-Comp.15) and Working Example 28 (Inv.28)

[0141]

[0142] Industrial Applicability

[0143] The silicone hybrid pressure-sensitive adhesive composition described herein can be cured to form a silicone hybrid pressure-sensitive adhesive suitable for a protective film in a manufacturing process of (opto)electronic devices (e.g., flexible OLED display devices or other devices). The above examples show that the silicone hybrid pressure-sensitive adhesive composition can be formulated to be cured via hydrosilylation to form a silicone hybrid pressure-sensitive adhesive having an initial adhesion of 4 gf / inch to 385 gf / inch on glass (before UV irradiation), as tested by the method of Reference Example 7 described herein. Compared to the initial adhesion, after UV irradiation, the adhesion is reduced by at least 40%, alternatively at least 50%, alternatively 44% to 88%.

[0144] Without wishing to be bound by theory, it is believed that the adhesion properties on glass will provide comparable results on substrates (such as passivation layers) used in (optical) electronic device manufacturing processes, and it is expected that the combination of the above characteristics allows the silicone hybrid pressure-sensitive adhesive film to be used as a protective film on these substrates during the manufacture of (optical) electronic devices. The silicone hybrid pressure-sensitive adhesive composition can be heated to cure via a hydrosilylation reaction to produce a silicone hybrid pressure-sensitive adhesive on a substrate (such as PET) to form a protective film. The resulting protective film can be used to protect the layer in the device during processing. Thereafter, the silicone hybrid pressure-sensitive adhesive can be irradiated with UV radiation, which results in a reduction in adhesion. Without wishing to be bound by theory, it is believed that the reduction in adhesion can allow the silicone hybrid pressure-sensitive adhesive to be detached from the passivation layer when the passivation layer in the device is minimally damaged and / or minimal residue is left on the passivation layer in the device. Without wishing to be bound by theory, it is believed that a SiH / reactive group ratio of <2 contributes to the beneficial effect of modifying adhesion by ensuring that sufficient reactive groups are present after hydrosilylation cure to allow further reaction when the silicone hybrid pressure sensitive adhesive is irradiated with UV radiation.

[0145] For example, Comp.9-12 in Table 1 above show that when the SiH / reactive group ratio is higher than 2, the adhesion after UV irradiation is not greatly reduced. Using different amounts of the same starting material so that the SiH / reactive group ratio is 0.46 to 1.12, Inv.1 to Inv.4 and Inv.7 to Inv.9 in Table 2 show that silicone hybrid pressure-sensitive adhesives having an adhesion of 4.6 gf / inch to 11.2 gf / inch before irradiation (protective films suitable for passivation layers in OLED display devices) and an adhesion of 2.3 gf / inch to 4.4 gf / inch after UV irradiation can be prepared. Inv.5 and Inv.10 in Table 2 also show that when the SiH / reactive group ratio is less than 2, the adhesion after UV irradiation is effectively reduced by -52% to -83% at a relatively high resin / polymer (R / P) ratio of 0.99 to 1.94. This parameter can also be confirmed by using different types of polyorganosilicate (B-3) and polyorganohydrogensiloxane (C-3) through Inv. 11 to Inv. 18.

[0146] Furthermore, without wishing to be bound by theory, it is believed that in the unit formula of the polydiorganosiloxane (A), an m / n ratio of <500 / 1 contributes to the beneficial effect of modifying the adhesion by ensuring sufficient reactive groups to allow further sufficient reaction by UV irradiation. For example, Comp.13 shows that when the m / n ratio is 527 (>500 / 1), the adhesion after UV irradiation is not greatly reduced. Using different polydiorganosiloxanes, such that the m / n ratio is 20 / 1 to 260 / 1, Inv.8 (A-1, m / n=37 / 1), Inv.21 (A-2, 56 / 1), Inv.22 (A-3, 260 / 1), Inv.23 (A-4, 20 / 1) show that after UV irradiation, the adhesion is reduced by (at least) more than 40%. Inv.8, Inv.21 and Inv.23 show that when the m / n ratio is <100 / 1, the adhesion after UV irradiation is reduced by more than 50%. Thus, a lower m / n ratio helps to modify the adhesion benefits by ensuring that sufficient reactive groups are present after hydrosilylation cure to allow further reaction when the silicone hybrid pressure sensitive adhesive is irradiated with UV radiation.

[0147] Do not wish to be bound by theory, think that conventional organosilicon pressure sensitive adhesive may suffer from a shortcoming in the following shortcomings.If the adhesion of organosilicon pressure sensitive adhesive is too low, then protective film can easily delaminate or not adhere to passivation layer during the manufacture of (optical) electronic device, therefore provide insufficient protection.But if the adhesion of organosilicon pressure sensitive adhesive to passivation layer is too high, then passivation layer may not be easy to peel off, and may be impaired when protective film is removed.For industrial use, depending on the surface characteristics of adherend, in narrow range (for example, 3gf / inch, 4gf / inch, 5gf / inch, 6gf / inch, 7gf / inch, 8gf / inch, 9gf / inch, 10gf / inch, 11gf / inch, 12gf / inch) each different adhesion level at place should be controlled by some compositions specifically, to meet the requirement of being easy to attach and peel off.Therefore, organosilicon hybrid pressure sensitive adhesive as herein described can provide a kind of integrated solution to meet the requirement of the overall type of the surface characteristics of (optical) electronic device.

[0148] In addition, the residual migration of silicone based pressure-sensitive adhesives at the surface of adherends has become an unsolvable problem in the industrial field, which leads to the pollution of (optical) electronic devices. For example, Comp.1 to Comp.6 are conventional pressure-sensitive adhesives, which show 47% to 72%, mainly less than 70% residual adhesion rate (%), while Inv.1 to Inv.23 show 72% to> 99.9% residual adhesion rate (%). Among them, Inv.23 shows that under the lowest m / n ratio (20 / 1 of (A-4)), the highest residual adhesion rate (%) is> 99.9%, which shows that it may be related to the minimum migration of residual silicone caused by sufficient further reaction after UV irradiation. In addition, it is believed that the addition of additive (I) helps to improve the beneficial effect of residual silicone migration by allowing sufficient and effective further reaction through UV irradiation. For example, using the same starting materials with similar SiH / reactive group ratios, Inv.21 and Inv.24 showed that Inv.24 with the addition of additive (I-1) showed a residual adhesion rate (%) = 92% higher than 73% of Inv.21. When compared to Inv.7 to Inv.8 (97%-98%), Inv.26 to Inv.27 with the addition of additive (I-2) also showed improved residual adhesion rates (%) = > 99.9%.

[0149] Comp.14 and Comp.15 show that under the conditions tested herein, the (meth)acryloyl-functional polyorganosilicate (B-4) without vinyl groups is not as effective as the (meth)acryloyl-functional polyorganosilicate that additionally has vinyl groups in reducing adhesion after UV irradiation. Under the conditions tested herein, the performance of the (meth)acryloyl-functional polyorganosilicate (B-4) is different from that of the polyorganosilicate (B-3) that is both (meth)acryloyl- and vinyl-functional, as shown in Inv.11 to Inv.19. Without wishing to be bound by theory, it may be because the methacryloyl-functional polyorganosilicate (B-3) containing vinyl groups effectively participates in the hydrosilylation reaction promoted by the hydrosilylation catalyst, and therefore, it is uniformly incorporated into the curing matrix with the starting material (A) through the crosslinker (starting material (C)). In contrast, since the (meth)acryloyl group is less reactive than the vinyl group during the hydrosilylation reaction, the (meth)acryloyl-functional polyorganosilicate may not be well incorporated into the cured matrix. In this case, intermolecular reactions between the microphase-separated methacryloyl-functional polyorganosilicates may occur by UV irradiation, rather than reactions with the methacryloyl groups of the starting material A. Therefore, the adhesion reduction characteristics between the starting materials (B-3) and (B-4) are different.

[0150] Problems to be solved

[0151] Organic-based pressure-sensitive adhesives comprising polymers having hydrocarbon backbone polymer chains may have poor wettability to substrates used during the manufacture of (opto)electronic devices. Without wishing to be bound by theory, it is believed that the rigidity of the hydrocarbon backbone contributes to this poor wettability, which may lead to difficulty in lamination and / or the formation of bubbles on the substrate. If pressure or heat is applied, this may cause damage to delicate surfaces such as passivation layers in (opto)electronic devices.

[0152] In the past, adhesives comprising physical mixtures of polyorganosiloxanes and UV-reactive organic molecules have been proposed. However, due to the poor compatibility of polyorganosiloxanes and organic molecules, it is difficult to obtain a uniform pressure-sensitive adhesive composition, which may have the disadvantage of forming a turbid or opaque pressure-sensitive adhesive. Such compositions are not suitable for (opto)electronic device manufacturing processes.

[0153] The silicone hybrid pressure-sensitive adhesive composition of the present invention solves the above-mentioned problems because it can be cured to form a silicone hybrid pressure-sensitive adhesive having suitable adhesion and wetting ability to surfaces such as passivation layers in (opto)electronic devices without trapping bubbles or requiring pressure or harsh conditions for adhesion that may damage the passivation layer. However, the silicone hybrid PSA may also have the ability to release from such surfaces with minimal damage and / or minimal residue after UV irradiation.

[0154] Use of terminology

[0155] Summary of the invention and description abstract are hereby incorporated by reference. Unless otherwise specified in the context of this specification, all amounts, ratios and percentages are by weight. Unless otherwise specified in the context of the specification, the articles "one", "one (a kind of)" and "the (said)" all refer to one (a kind of) or more (multiple). The disclosure of a range includes the range itself and any value and endpoints contained therein. For example, the disclosure of a range>0.3 to 0.8 not only includes a range>0.3 to 0.8, but also includes 0.4, 0.55, 0.6, 0.7, 0.78 and 0.8 and any other number contained in the range individually. In addition, for example>0.3 to 0.8 The disclosure of the range includes, for example, 0.4 to 0.6, 0.35 to 0.78, 0.41 to 0.75, 0.78 to 0.8, 0.32 to 0.41, 0.35 to 0.5 subsets and any other subsets contained in the range. Similarly, the disclosure of a Markush group includes the entire group and also includes any individual members and subgroups contained therein. For example, the disclosure of the Markush group: vinyl, allyl, or hexenyl includes the individual member vinyl; the subgroups vinyl and hexenyl; and any other individual members and subgroups contained therein.

[0156] Abbreviations used in this application are as defined in Table 5 below.

[0157] Table 5

[0158]

[0159]

[0160] Test Method

[0161] [NMR analysis]

[0162] The average molecular formula of the starting materials (A) and (B) (such as those mentioned in Reference Examples 1 to 6) is based on the following 29 Si-NMR and 13 C-NMR analysis to determine:

[0163] NMR equipment: Fourier transform nuclear magnetic resonance spectrometer JEOL (JEOL is a registered trademark of JEOL Ltd., Japan) JNM-EX400 (product of JEOL Ltd.).

[0164] Determination method: Based on the various siloxane units derived from the following29 The average molecular formula is identified by finding the ratio of the integrated signal values ​​obtained for the various siloxane units (M unit, D unit, T unit, and Q unit) and then finding the siloxane unit ratio based on the determined signal ratio. 28 Me2SiO in Si-NMR 2 / 2 Unit and MaMeSiO 2 / 2 The chemical shifts of the units overlap, so 13 C-NMR was used to identify Me2SiO 2 / 2 (D) and MaMeSiO 2 / 2 The content of reactive groups including unsaturated bonds and (meth)acryloyl groups was obtained from the average molecular formula.

[0165] [SiH / Vi ratio and SiH / reactive group ratio]

[0166] The SiH / Vi ratio was calculated according to the following equation.

[0167]

[0168]

[0169] [Gel Permeation Chromatography]

[0170] Molecular weights were measured by gel permeation chromatography according to the following method; samples were prepared in toluene at 0.5% weight / volume concentration, filtered with a 0.45 μm PTFE syringe filter, and analyzed relative to polystyrene standards. The relative calibration (third order fit) for molecular weight determination was based on 16 polystyrene standards ranging from 580 Daltons to 2,610,000 Daltons. The chromatographic equipment consisted of a Waters 2695 separation module equipped with a vacuum degasser, a Waters 2414 differential refractometer, and two (7.8 mm×300 mm) styragel HR columns (molecular weight separation range of 100 to 4,000,000) preceded by a styragel guard column (4.6 mm×30 mm). Separations were performed using toluene programmed to flow at 1.0 mL / min, the injection volume was set to 100 μL, and the column and detector were heated to 45°C. Data were collected for 60 min and processed using Empower software. As used herein, for resins, Mw (weight average molecular weight) and Mn (number average molecular weight) are used. [Adhesion and residual adhesion rate]

[0171] Adhesion and residual adhesion were measured as described above in Reference Examples 7 and 8, respectively.

[0172] Embodiments of the present invention

[0173] In a first embodiment of the present invention, the silicone hybrid pressure-sensitive adhesive composition comprises:

[0174] 100 parts by weight of (A) a linear or substantially linear polydiorganosiloxane having reactive groups including silicon-bonded (meth)acryloxyalkyl functional groups in pendant positions and optionally silicon-bonded aliphatic unsaturated hydrocarbon groups in terminal positions, wherein the starting material (A) comprises units of formula M p M” q D m D' n D” o T'' r Q s ,in

[0175] M expression (R 1 3SiO 1 / 2 ),

[0176] M" expression (R 1 2R 3 SiO 1 / 2 ),

[0177] D expression (R 1 2SiO 2 / 2 ),

[0178] D' expression (R 1 R 2 SiO 2 / 2 ),

[0179] D" expression (R 1 R 3 SiO 2 / 2 ),

[0180] T"' expression (R 5 SiO 3 / 2 ) units, and

[0181] Q expression (SiO 4 / 2 ) units, where

[0182] Each R 1 is a monovalent hydrocarbon group containing no aliphatic unsaturated groups,

[0183] Each R 2 is a (meth)acryloyloxyalkyl functional group,

[0184] Each R 3 is an aliphatic unsaturated monovalent hydrocarbon group,

[0185] Each R5 independently selected from R 1 , R 2 and R 3 , and

[0186] the values of the subscripts p, q, m, n, r and s are such that:

[0187] 0 ≤ p, 0 ≤ q, and the quantity (p + q) ≥ 2,

[0188] 0 < m < 10,000, 2 < n ≤ 10,000, o ≥ 0, the quantity (m + n + o) is from 100 to 10,000, and the ratio (m + o) / n is from 1 / 1 to 500 / 1,

[0189] the ratio (q + o) / (m + n) is from 0 to ≤ 1 / 5,

[0190] 0 ≤ r ≤ 100 and 0 ≤ s ≤ 100, and if 0 < r or if 0 < s, then the ratio (m + n + o) / (r + s) is from 50 / 1 to 10,000 / 1;

[0191] (B) a polyorganosilicate resin in an amount sufficient to provide a weight ratio of polyorganosilicate resin to (A) polydiorganosiloxane of 0.15 / 1 to 1.9 / 1 (resin / polymer ratio), wherein the polyorganosilicate resin comprises the units M a M” b M”' c D d D' e T”' f Q h X i ,

[0192] wherein M, M”, D, D', T and Q are as described above, M”' represents a unit of the formula (R 1 2R 2 SiO 1 / 2 ), T' represents a unit of the formula (R 2 SiO 3 / 2 ), X represents a hydroxyl group and / or an alkoxy group, and the values of the subscripts a, b, c, d, e, f, h and i are such that:

[0193] a ≥ 0, b ≥ 0, c ≥ 0, and the quantity (a + b + c) > 10 mol%;

[0194] d ≥ 0, e ≥ 0, and the quantity (d + e) is from 0 to a value sufficient to provide 30 mol% of the combined D units and D' units to the resin;

[0195] f ≥ 0, provided that the subscript f has a maximum value sufficient to provide 30 mol% of the T”' units to the resin;

[0196] h>0, provided that subscript h has a value sufficient to provide 30 mol % to 60 mol % of Q units to the resin;

[0197] If b>0, then 0≤c+e+f<20 mol%;

[0198] If b=0, then c+e+f=0;

[0199] a+b+c+d+e+f+h=100 mol%;

[0200] i > 0 is not included in the molar ratio, provided that the subscript i has a maximum value sufficient to provide 5 mole % of hydroxyl groups to the resin.

[0201] (C) a polyorganohydrogensiloxane in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms in the starting material (C) to reactive groups in the combined starting materials (A) and (B) (SiH / reactive group ratio) of 0.3 to 2, wherein the reactive groups are the combined R 2 and R 3 , wherein the polyorganohydrogensiloxane comprises a unit formula M t M H u D v D H w T x T H y Q z , wherein M, D, T and Q represent units in the formula shown above, and

[0202] M H Expression (HR 1 2SiO 1 / 2 ),

[0203] D H Expression (HR 1 SiO 2 / 2 ),

[0204] T H Expression (HSiO 3 / 2 ) units, and

[0205] the values ​​of the subscripts t, u, v, w, x, y, and z are such that t ≥ 0, u ≥ 0, v ≥ 0, w ≥ 0, x ≥ 0, y ≥ 0, z ≥ 0, the amount (u + w + y) ≥ 3, and the amount (t + u + v + w + x + y + z) is sufficient to give the polyorganohydrogensiloxane a viscosity of 3 mPa·s to 1,000 mPa·s at 25°C;

[0206] (D) a hydrosilylation catalyst in an amount sufficient to provide from 2 ppm to 500 ppm of platinum based on the combined weight of all starting materials in the composition;

[0207] 0.1 wt % to 10 wt % of (E) a photoradical initiator, based on the combined weight of starting materials (A), (B) and (C);

[0208] 0.0001 wt % to 1 wt % of (F) a hydrosilylation reaction inhibitor, based on the combined weight of the starting materials (A), (B) and (C);

[0209] 0.001 wt % to 0.5 wt % of (G) a free radical scavenger, based on the combined weight of the starting materials (A), (B) and (C);

[0210] 0 to 80 wt % of (H) a solvent, based on the combined weight of the starting materials (A), (B), and (C); and

[0211] 0% to 5% by weight of (I) an additive selected from sensitizers and synergists, based on the combined weight of the starting materials (A), (B) and (C).

[0212] In a second embodiment, a method for producing an (opto)electronic device comprises:

[0213] 1) applying an organosilicon hybrid pressure-sensitive adhesive composition to a surface of a substrate, the organosilicon hybrid pressure-sensitive adhesive composition comprising:

[0214] A silicone hybrid pressure-sensitive adhesive composition comprises:

[0215] 100 parts by weight of (A) a linear or substantially linear polydiorganosiloxane having reactive groups including silicon-bonded (meth)acryloxyalkyl functional groups in pendant positions and optionally silicon-bonded aliphatic unsaturated hydrocarbon groups in terminal positions, wherein the starting material (A) comprises units of formula M p M” q D m D' n D” o T r Q s ,in

[0216] M expression (R 1 3SiO 1 / 2 ),

[0217] M" expression (R 1 2R 3 SiO 1 / 2 ),

[0218] The unit of the formula (R 1 2SiO 2 / 2 ),

[0219] The unit of the formula (R 1 R 2 SiO 2 / 2 ),

[0220] The unit of the formula (R 1 R 3 SiO 2 / 2 ),

[0221] The unit of the formula (R 1 SiO 3 / 2 ), and

[0222] The unit of the formula (SiO 4 / 2 ), where

[0223] each R 1 is a monovalent hydrocarbon group without aliphatic unsaturated groups,

[0224] each R 2 is a (meth)acryloyloxyalkyl functional group,

[0225] each R 3 is an aliphatic unsaturated monovalent hydrocarbon group, and

[0226] the values of the subscripts p, q, m, n, r, and s are such that:

[0227] the quantity (p + q) ≥ 2,

[0228] 0 < m < 10,000, 2 < n ≤ 10,000, 0 < o < 10,000, the quantity (m + n + o) is from 100 to 10,000, the ratio (m + o) / n is from 1 / 1 to 500 / 1,

[0229] if 0 < r or if 0 < s, then the ratio (m + n) / (r + s) is from 100 / 1 to 10,000 / 1;

[0230] (B) a polyorganosilicate resin in an amount sufficient to provide a weight ratio of polyorganosilicate resin to (A) polydiorganosiloxane of 0.15 / 1 to 1.9 / 1 (resin / polymer ratio), where the polyorganosilicate resin contains the units of the formula M a M” b M”' c D d D' e T”' f Q h X i, wherein M, M", D, D', T and Q are as described above, M"' represents the formula (R 1 2R 2 SiO 1 / 2 ) unit, T"' represents the formula (R 2 SiO 3 / 2 ), X represents a hydroxyl group and / or an alkoxy group, and the values ​​of the subscripts a, b, c, d, e, f, h and i are such that:

[0231] a≥0, b≥0, c≥0, and the amount (a+b+c)>10 mol%;

[0232] d≥0, e≥0, and the amount (d+e) is from 0 to a value sufficient to provide 30 mole % of combined D units and D' units to the resin;

[0233] f ≥ 0, provided that subscript f has a maximum value sufficient to provide 30 mol % of T"' units to the resin;

[0234] h>0, provided that subscript h has a value sufficient to provide 30 mol % to 60 mol % of Q units to the resin;

[0235] If b>0, then 0≤c+e+f<20 mol%;

[0236] If b=0, then c+e+f=0;

[0237] a+b+c+d+e+f+h=100 mol%;

[0238] i ≥ 0 is not included in the molar ratio, provided that the subscript i has a maximum value sufficient to provide 5 mol % of hydroxyl groups to the resin;

[0239] (C) a polyorganohydrogensiloxane in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms in the starting material (C) to reactive groups in the combined starting materials (A) and (B) (SiH / reactive group ratio) of 0.3 to 2, wherein the reactive groups are the combined R 2 and R 3 , wherein the polyorganohydrogensiloxane comprises a unit formula M t M H u D v D H w T x T H y Q z , wherein M, D, T and Q represent units in the formula shown above, and

[0240] M H Expression (HR 1 2SiO1 / 2 ),

[0241] D H Expression (HR 1 SiO 2 / 2 ),

[0242] T H Expression (HSiO 3 / 2 ) units, and

[0243] the values ​​of the subscripts t, u, v, w, x, y, and z are such that t ≥ 0, u ≥ 0, v ≥ 0, w ≥ 0, x ≥ 0, y ≥ 0, z ≥ 0, the amount (u + w + y) ≥ 3, and the amount (t + u + v + w + x + y + z) is sufficient to give the polyorganohydrogensiloxane a viscosity of 3 mPa·s to 1,000 mPa·s at 25°C;

[0244] (D) a hydrosilylation catalyst in an amount sufficient to provide from 2 ppm to 500 ppm of platinum based on the combined weight of all starting materials in the composition;

[0245] 0.1 wt % to 10 wt % of (E) a photoradical initiator, based on the combined weight of starting materials (A), (B) and (C);

[0246] 0.0001 wt % to 1 wt % of (F) a hydrosilylation reaction inhibitor, based on the combined weight of the starting materials (A), (B) and (C);

[0247] 0.001 wt % to 0.5 wt % of (G) a free radical scavenger, based on the combined weight of the starting materials (A), (B) and (C);

[0248] 0 to 500 wt % of (H) a solvent, based on the combined weight of the starting materials (A), (B), and (C); and

[0249] 0 to 5 wt % of (I) an additive selected from sensitizers and synergists, based on the combined weight of the starting materials (A), (B) and (C);

[0250] 2) heating the composition to form a hybrid pressure-sensitive adhesive film;

[0251] 3) applying a pressure sensitive adhesive film to the passivation layer in the device;

[0252] 4) using a pressure sensitive adhesive film to protect the passivation layer in the device; and thereafter

[0253] 5) Exposing the pressure-sensitive adhesive film to UV radiation; thereby reducing the tack of the pressure-sensitive adhesive film.

[0254] In a third embodiment, in the composition of the first embodiment or the method of the second embodiment, (A) the polydiorganosiloxane comprises units of formula M2D m D' n , the amount (m+n) is 100 to 9,000, and the ratio m / n is 10 / 1 to 500 / 1.

[0255] In a fourth embodiment, in the composition of the first embodiment or the method of the second embodiment, the amount (m+n) is from 200 to 9,900.

[0256] In a fifth embodiment, in the composition of the first embodiment or the method of the second embodiment, the amount (m+n) is from 300 to 7,000.

[0257] In a sixth embodiment, in the composition of the first embodiment or the method of the second embodiment, the amount (m+n) is from 400 to 6,000.

[0258] In a seventh embodiment, in the composition of the first embodiment or the method of the second embodiment, based on R 1 , R 2 and R 3 The combined meter, R 2 Present in a mole % of 0.1% to 25%.

[0259] In an eighth embodiment, in the composition of the first embodiment or the method of the second embodiment, R 2 Present in a mole % range of 0.8% to 12%.

[0260] In a ninth embodiment, in the composition of the first embodiment or the method of the second embodiment, R 2 Present in a mole % of 1.5% to 6%.

[0261] In a tenth embodiment, in the composition of the first embodiment or the method of the second embodiment, the (B) polyorganosilicate resin comprises a unit formula selected from the group consisting of: M a Q h 、M a M” b Q h 、M a M” b M"' c Q h 、M a D d Q h , M” b D' e Q h 、M a M” b M"' cD d Q h 、M a M” b M"' c D' e Q h 、M a M” b D' e Q h 、M a M” b M"' c D' e Q h 、M a M” b T'' f Q h 、M a M” b M"' c T'' f Q h , wherein subscript a is 20 mol % to 65 mol %, subscripts b and c are 1 mol % to 30 mol %, subscripts d and e are 1 mol % to 20 mol %, subscript f is 1 mol % to 25 mol %, and subscript h is 35 mol % to 55 mol %.

[0262] In an eleventh embodiment, in the composition of the first embodiment or the method of the second embodiment, (C) the polyorganohydrogensiloxane crosslinker comprises units of formula M t M H u D v D H w , where the quantity (t+u)=2, and the quantity (u+w)≥3.

[0263] In a twelfth embodiment, in the composition of the first embodiment or the method of the second embodiment, for R 1 Each monovalent hydrocarbon group of is independently selected from an alkyl group and an aryl group.

[0264] In a thirteenth embodiment, in the twelfth embodiment, the alkyl group is methyl and the aryl group is phenyl.

[0265] In a fourteenth embodiment, in the composition of the first embodiment or the method of the second embodiment, each R 1 An alkyl group.

[0266] In a fifteenth embodiment, in the composition of the first embodiment or the method of the second embodiment, for R 2 Each (meth)acryloxyalkyl functional group of is independently selected from acryloxypropyl and methacryloxypropyl.

[0267] In a sixteenth embodiment, in the composition of the first embodiment or the method of the second embodiment, for R 3 Each aliphatically unsaturated monovalent hydrocarbon group of is an independently selected alkenyl group.

[0268] In a seventeenth embodiment, in a sixteenth embodiment, the alkenyl group is selected from vinyl and hexenyl.

[0269] In an eighteenth embodiment, in the composition of the first embodiment or the method of the second embodiment, the resin / polymer ratio is 0.2 / 1 to 1.5 / 1. (See Inv 1 and 2 and Inv 10, 14)

[0270] In a nineteenth embodiment, in the eighteenth embodiment, the resin / polymer ratio is from 0.25 / 1 to 1.2 / 1.

[0271] In a twentieth embodiment, in the composition of the first embodiment or the method of the second embodiment, the SiH / reactive group ratio is from 0.4 to 0.9.

[0272] In a twenty-first embodiment, in the composition of the first embodiment or the method of the second embodiment, (D) the hydrosilylation reaction catalyst is selected from: i) platinum group metals, ii) compounds of said metals, iii) complexes of said metals or said compounds, v) complexes microencapsulated in a matrix or core-shell structure.

[0273] In a twenty-second embodiment, in the twenty-first embodiment, the (D) hydrosilylation reaction catalyst is present in an amount sufficient to provide 10 ppm to 100 ppm of a platinum group metal based on the combined weight of all starting materials in the composition.

[0274] In the twenty-third embodiment, in the composition of the first embodiment or the method of the second embodiment, (E) the photoradical initiator is selected from the group consisting of benzophenone, substituted benzophenone compounds, acetophenone, substituted acetophenone compounds, benzoin, alkyl esters of benzoin, xanthone, and substituted xanthone.

[0275] In a twenty-fourth embodiment, in the twenty-third embodiment, the photoradical initiator is a substituted acetophenone.

[0276] In a twenty fifth embodiment, in the twenty fourth embodiment, the substituted acetophenone is 1-hydroxycyclohexyl phenyl ketone.

[0277] In a twenty-sixth embodiment, in the composition of the first embodiment or the method of the second embodiment, the starting material (E) is present in an amount of 5 to 12 parts by weight.

[0278] In a twenty-seventh embodiment, in the composition of the first embodiment or the method of the second embodiment, (F) a hydrosilylation reaction inhibitor is present and is selected from the group consisting of alkynols, cycloalkenylsiloxanes, enyne compounds, triazoles, phosphines, thiols, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated alkynols.

[0279] In a twenty-eighth embodiment, in the twenty-seventh embodiment, the alkynyl alcohol is ethynylcyclohexanol.

[0280] In a twenty-ninth embodiment, in the composition of the first embodiment or the method of the second embodiment, (G) the free radical scavenger is selected from the group consisting of phenolic compounds, phenothiazines, and anaerobic inhibitors.

[0281] In a thirtieth embodiment, in the twenty-ninth embodiment, the free radical scavenger is a phenolic compound.

[0282] In a thirty-first embodiment, in the composition of the first embodiment or the method of the second embodiment, (H) a solvent is present and is selected from aliphatic hydrocarbons and aromatic hydrocarbons.

[0283] In a thirty-second embodiment, in the thirty-first embodiment, the solvent is present in an amount of 80 to 120 parts by weight per 100 parts by weight of the starting material (A).

[0284] In a thirty-third embodiment, in the method of the second embodiment, the (opto)electronic device includes a flexible organic light emitting diode.

[0285] In the thirty-fourth embodiment, in the composition of the first embodiment or the method of the second embodiment, the starting material (J) bis-SiH-terminated polydiorganosiloxane is present in a weight ratio of starting material (J) to starting material (C) [(J) / (C) ratio] of 0.25 / 1 to 4 / 1.

Claims

1. An organosilicon hybrid pressure-sensitive adhesive composition, the organosilicon hybrid pressure-sensitive adhesive composition comprising: 100 parts by weight of a starting material (A) having reactive groups comprising silicon-bonded (meth)acryloyloxyalkyl functional groups in pendant positions and optionally silicon-bonded aliphatic unsaturated hydrocarbon groups in terminal positions, wherein the starting material (A) comprises units of formula M p M” q D m D' n D” o T'' r Q s ,in M expression (R 1 3SiO 1 / 2 ), M" expression (R 1 2R 3 SiO 1 / 2 ), D expression (R 1 2SiO 2 / 2 ), D' expression (R 1 R 2 SiO 2 / 2 ), D" expression (R 1 R 3 SiO 2 / 2 ), T"' expression (R 5 SiO 3 / 2 ) units, and Q expression (SiO 4 / 2 ) units, where Each R 1 is a monovalent hydrocarbon group containing no aliphatic unsaturated groups, Each R 2 is the (meth)acryloyloxyalkyl functional group, Each R 3 is the aliphatic unsaturated monovalent hydrocarbon group, Each R 5 Independently selected from R 1 , R 2 and R 3 ,and The values of the subscripts p, q, m, n, r, and s are such that: 0 ≤ p, 0 ≤ q, and the amount (p + q) ≥ 2, 0 < m < 10,000, 2 < n ≤ 10,000, o ≥ 0, the amount (m + n + o) is 100 to 10,000, and the ratio (m + o) / n is 1 / 1 to 500 / 1, The ratio (q + o) / (m + n) is 0 to ≤ 1 / 5, 0 ≤ r ≤ 100 and 0 ≤ s ≤ 100, and if 0 < r or if 0 < s, then the ratio (m + n + o) / (r + s) is 50 / 1 to 10,000 / 1; Starting material (B), in an amount sufficient to provide a weight ratio of the starting material (B) to the starting material (A) of 0.15 / 1 to 1.9 / 1, wherein the starting material (B) comprises units of the formula M a M” b M"' c D d D' e T'' f Q h X i , wherein M, M", D, D', T and Q are as described above, M'' represents the formula (R 1 2R 2 SiO 1 / 2 ) unit, T"' represents the formula (R 2 SiO 3 / 2 ), X represents a hydroxyl group and / or an alkoxy group, and the values ​​of the subscripts a, b, c, d, e, f, h and i are such that: a ≥ 0, b ≥ 0, c ≥ 0, and the amount (a + b + c) > 10 mol%; d ≥ 0, e ≥ 0, and the amount (d + e) is 0 to a value sufficient to provide 30 mol% of the combined D units and D' units to the starting material (B); f ≥ 0, provided that the subscript f has a maximum value sufficient to provide 40 mol% of the T''' units to the starting material (B); h > 0, provided that the subscript h has a value sufficient to provide 30 mol% to 70 mol% of the Q units to the starting material (B); If b > 0, then 0 ≤ c + e + f < 20 mol%; If b = 0, then c + e + f = 0; a + b + c + d + e + f + h = 100 mol%; i ≥ 0 is not included in the molar ratio, provided that the subscript i has a maximum value sufficient to provide 5 mol% of hydroxyl groups to the starting material (B); Starting material (C) in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms in starting material (C) to reactive groups in starting materials (A) and (B) combined of 0.3 to 2, wherein the reactive groups are R 2 and R 3 wherein the starting material (C) comprises a unit formula M t M H u D v D H w T x T H y Q z , wherein M, D, T and Q represent units in the formula shown above, and M H Expression (HR 1 2SiO 1 / 2 ), D H Expression (HR 1 SiO 2 / 2 ), T H Expression (HSiO 3 / 2 ) units, and The values of the subscripts t, u, v, w, x, y, and z are such that t ≥ 0, u ≥ 0, v ≥ 0, w ≥ 0, x ≥ 0, y ≥ 0, z ≥ 0, the amount (u + w + y) ≥ 3, and the amount (t + u + v + w + x + y + z) is sufficient to give the starting material (C) a viscosity of 3 mPa·s to 1,000 mPa·s at 25°C; (D) A hydrosilylation catalyst, in an amount sufficient to provide 2 ppm to 500 ppm of platinum based on the combined weight of all starting materials in the composition; 1 part by weight to 20 parts by weight of (E) a photoinitiator per 100 parts by weight of the starting material (A); 0.1 part by weight to 4 parts by weight of (F) a hydrosilylation inhibitor per 100 parts by weight of the starting material (A); 0.001 part by weight to 0.1 part by weight of (G) a radical scavenger per 100 parts by weight of the starting material (A); 0 parts by weight to 120 parts by weight of (H) a solvent per 100 parts by weight of the starting material (A); and 0 parts by weight to 2 parts by weight of (I) an additive selected from sensitizers and synergists per 100 parts of the starting material (A).

2. The composition according to claim 1, wherein the starting material (A) comprises a unit formula M2D m D' n , the amount (m+n) is 100 to 9,900, and the ratio m / n is 1 / 1 to 500 / 1.

3. The composition according to claim 2, wherein when the m / n ratio is 1 / 1, based on R 1 , R 2 and R 3 The combined meter, R 2 Present in a mole % of 0.1% to 25%.

4. The composition according to claim 1, wherein the starting material (B) comprises a unit formula selected from the group consisting of: M a Q h 、M a M” b Q h 、M a M” b M"' c Q h 、M a M"' c Q h 、M a D d Q h 、M a D' e Q h 、M a M” b D' e Q h 、M a M” b T'' f Q h 、M a M” b T'' f Q h , wherein subscripts a, b and c are 20 mol % to 70 mol %, subscripts d and e are 1 mol % to 20 mol %, subscript f is 1 mol % to 25 mol %, and subscript h is 35 mol % to 65 mol %.

5. The composition according to claim 1, wherein the starting material (C) comprises a unit formula M t M H u D v D H w , where the quantity (t+u)=2, and the quantity (u+w)≥3.

6. The composition according to claim 1, wherein the 1 Each monovalent hydrocarbon group of is independently selected from an alkyl group and an aryl group; for R 2 Each (meth)acryloxyalkyl functional group of is independently selected from acryloxypropyl and methacryloxypropyl; and for R 3 Each aliphatically unsaturated monovalent hydrocarbon group of is an independently selected alkenyl group.

7. The composition according to claim 1, wherein the weight ratio of the starting material (B) to the starting material (A) is 0.2 / 1 to 1.5 / 1.

8. The composition according to claim 1, wherein the molar ratio of the silicon-bonded hydrogen atoms in the starting material (C) to the reactive groups in the combined starting materials (A) and (B) is from 0.5 / 1 to 0.9 / 1.

9. A method for forming a protective film comprising an organosilicon hybrid pressure-sensitive adhesive layer on the surface of a substrate, wherein the method comprises: 1) optionally treating the surface of the substrate; 2) applying the composition according to any one of claims 1 to 8 to the surface of the substrate; 3) heating the composition to form the organosilicon hybrid pressure-sensitive adhesive layer on the surface of the substrate.

10. A method for manufacturing an optoelectronic device, the improvement of the method comprising: 4) applying the protective film formed by the method according to claim 9 to the optoelectronic device such that the organosilicon hybrid pressure-sensitive adhesive layer contacts the passivation layer in the optoelectronic device; 5) using the pressure-sensitive adhesive film to protect the passivation layer in the device; and thereafter 6) exposing the pressure-sensitive adhesive layer to UV radiation; thereby reducing the tack of the pressure-sensitive adhesive layer.

11. An organosilicon hybrid pressure-sensitive adhesive composition, the organosilicon hybrid pressure-sensitive adhesive composition comprising: 100 parts by weight of a starting material (A) having reactive groups comprising silicon-bonded (meth)acryloyloxyalkyl functional groups in pendant positions and optionally silicon-bonded aliphatic unsaturated hydrocarbon groups in terminal positions, wherein the starting material (A) comprises units of formula M p M” q D m D' n D” o T'' r Q s ,in M expression (R 1 3SiO 1 / 2 ), M" expression (R 1 2R 3 SiO 1 / 2 ), D expression (R 1 2SiO 2 / 2 ), D' expression (R 1 R 2 SiO 2 / 2 ), D" expression (R 1 R 3 SiO 2 / 2 ), T"' expression (R 5 SiO 3 / 2 ) units, and Q expression (SiO 4 / 2 ) units, where Each R 1 is a monovalent hydrocarbon group containing no aliphatic unsaturated groups, Each R 2 is the (meth)acryloyloxyalkyl functional group, Each R 3 is the aliphatic unsaturated monovalent hydrocarbon group, Each R 5 Independently selected from R 1 , R 2 and R 3 ,and The values of the subscripts p, q, m, n, r, and s are such that: 0 ≤ p, 0 ≤ q, the amount (p + q) ≥ 2, 0 < m < 10,000, 2 < n ≤ 10,000, o ≥ 0, the amount (m + n + o) is from 100 to 10,000, the ratio (m + o) / n is from 1 / 1 to 500 / 1, the ratio (q + o) / (m + n) is from 0 to ≤ 1 / 5, 0 ≤ r ≤ 100 and 0 ≤ s ≤ 100, if 0 < r or if 0 < s, then the ratio (m + n + o) / (r + s) is from 50 / 1 to 10,000 / 1; A starting material (B) in an amount sufficient to provide a weight ratio of the starting material (B) to the starting material (A) of 0.15 / 1 to 1.9 / 1, wherein the starting material (B) comprises a unit formula M a M” b M"' c D d D' e T'' f Q h X i , wherein M, M", D, D', T and Q are as described above, M'' represents the formula (R 1 2R 2 SiO 1 / 2 ) unit, T"' represents the formula (R 2 SiO 3 / 2 ), X represents a hydroxyl group and / or an alkoxy group, and the values ​​of the subscripts a, b, c, d, e, f, h and i are such that: a ≥ 0, b ≥ 0, c ≥ 0, and the amount (a + b + c) > 10 mol%; d ≥ 0, e ≥ 0, and the amount (d + e) is from 0 to a value sufficient to provide 30 mol% of the combined D units and D' units to the starting material (B); f ≥ 0, provided that the subscript f has a maximum value sufficient to provide 30 mol% of the T''' units to the starting material (B); h > 0, provided that the subscript h has a value sufficient to provide 30 mol% to 60 mol% of the Q units to the starting material (B); if b > 0, then 0 ≤ c + e + f < 20 mol%; if b = 0, then c + e + f = 0; a + b + c + d + e + f + h = 100 mol%; i ≥ 0 is not included in the molar ratio, provided that the subscript i has a maximum value sufficient to provide 5 mol% of hydroxyl groups to the starting material (B); Starting material (C) in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms in starting material (C) to reactive groups in starting materials (A) and (B) combined of 0.3 to 2, wherein the reactive groups are R 2 and R 3 wherein the starting material (C) comprises a unit formula M t M H u D v D H w T x T H y Q z , wherein M, D, T and Q represent units in the formula shown above, and M H Expression (HR 1 2SiO 1 / 2 ), D H Expression (HR 1 SiO 2 / 2 ), T H Expression (HSiO 3 / 2 ) units, and The values of the subscripts t, u, v, w, x, y, and z are such that t ≥ 0, u ≥ 0, v ≥ 0, w ≥ 0, x ≥ 0, y ≥ 0, z ≥ 0, the amount (u + w + y) ≥ 3, and the amount (t + u + v + w + x + y + z) is sufficient to give the starting material (C) a viscosity of 3 mPa·s to 1,000 mPa·s at 25°C; (D) a hydrosilylation catalyst in an amount sufficient to provide 2 ppm to 500 ppm of platinum based on the combined weight of all starting materials in the composition; Based on the combined weight of starting materials (A), (B) and (C), 0.1 wt % to 10 wt % of (E) a photoradical initiator; 0.0001 wt % to 1 wt % of (F) a hydrosilylation reaction inhibitor, based on the combined weight of the starting materials (A), (B) and (C); 0.001 wt % to 0.5 wt % of (G) a free radical scavenger, based on the combined weight of the starting materials (A), (B) and (C); 0 to 500 wt % of (H) a solvent, based on the combined weight of the starting materials (A), (B) and (C); as well as 0% to 5% by weight of (I) an additive selected from sensitizers and synergists, based on the combined weight of the starting materials (A), (B) and (C).

12. The composition according to claim 11, wherein the starting material (B) comprises a unit formula selected from the group consisting of: M a Q h 、M a M” b Q h 、M a M” b M"' c Q h 、M a D d Q h , M” b D' e Q h 、M a M” b M"' c D d Q h 、M a M” b M"' c D' e Q h 、M a M” b D' e Q h 、M a M” b M"' c D' e Q h 、M a M” b T'' f Q h 、M a M” b M"' c T'' f Q h , wherein subscript a is 20 mol % to 65 mol %, subscripts b and c are 1 mol % to 30 mol %, subscripts d and e are 1 mol % to 20 mol %, subscript f is 1 mol % to 25 mol %, and subscript h is 35 mol % to 55 mol %.

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