KR20230170009A - Pressure-sensitive adhesive composition, method of making it and its use in flexible organic light-emitting diode applications - Google Patents

Abstract

The pressure-sensitive adhesive composition can be cured through hydrosilylation to form a pressure-sensitive adhesive. The pressure-sensitive adhesive composition can be coated on a substrate and cured to form a protective film. Protective films are useful in flexible OLED device fabrication processes, for example, for protecting passivation layers.

Description

Pressure-sensitive adhesive composition, method of making it and its use in flexible organic light-emitting diode applications

Cross-reference to related applications

This application is filed under 35 U.S.C. Claims the benefit of U.S. Provisional Patent Application No. 63/172,737, filed April 9, 2021, under §119(e). U.S. Provisional Patent Application No. 63/172,737 is incorporated herein by reference.

Technology field

The present invention relates to pressure-sensitive adhesive compositions useful in processes for manufacturing flexible organic light-emitting diode (OLED) displays. The pressure-sensitive adhesive composition cures to form a pressure-sensitive adhesive with low initial adhesion, high adhesive stability over time, and low mobility.

In a typical process for manufacturing flexible OLED displays, the OLED is formed on a relatively rigid substrate (e.g., glass or glass coated with polyimide varnish), and a passivation layer is formed on the OLED on the opposite side of the substrate. formed on the surface. During further processing, the rigid substrate is removed. Weak or brittle layers need to be protected from damage (e.g. scratches or other impacts) during further processing.

To protect the layer during the fabrication process, a protective film with low adhesion is preferred to prevent peeling of the layer (e.g., passivation layer) on the surface of the OLED module during release of the protective film after use. If adhesion control fails and the adhesion increases over time (i.e., during the manufacturing process), such layers may peel or be damaged when the protective film is removed. Accordingly, there is an industrial need to provide protective films that have low adhesion and high adhesive stability (where the adhesion does not increase to the extent of causing delamination or damage over the time required for the fabrication process).

It is also important that the surface of the layer is kept clean so that additional films or layers can be laminated thereto after removal of the protective film. Accordingly, there is an industrial need to provide protective films with low mobility (so that no or minimal amount of adhesive from the protective film remains on the layer surface of the flexible OLED device after removal of the protective film).

The pressure sensitive adhesive composition is

Poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer (poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer is a silicon-bonded alkyl group having 1 to 10 carbon atoms and a silicon bonded alkyl group having 2 to 6 carbon atoms. Contains silicone bonded alkenyl groups, the alkenyl groups being present in an amount of 0.14% to 0.3% by weight of the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer),

unit chemical formula

(R ¹ ₂ HSiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (R ¹ HSiO _2/2 ) _y (each R ¹ is an independently selected alkyl group of 1 to 10 carbon atoms, and a polyalkylhydrogensiloxane with a subscript (x) ≥ 0, a subscript (y) ≥ 0, where (xy) is sufficient to provide the polyalkylhydrogensiloxane with a viscosity of <20 mPa·s,

a platinum group metal catalyst, and

Acetylenic alcohol, and

Contains organic solvents.

Also disclosed are methods of making pressure-sensitive adhesive compositions, methods of forming pressure-sensitive adhesive tapes using the pressure-sensitive adhesive compositions, and methods of making flexible organic light-emitting diode devices using the pressure-sensitive adhesive tapes.

The pressure sensitive adhesive composition is

(A) 85 to 100 parts by weight of a poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer (the copolymer has a silicone-bonded alkyl group having 1 to 10 carbon atoms and a silicone-bonded alkyl group having 2 to 6 carbon atoms) containing kenyl groups, wherein the alkenyl groups are present in an amount of 0.14% to 0.3% by weight of the copolymer),

(C) Unit formula (R ¹ ₂ HSiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (R ¹ HSiO _2/2 ) _y (each R ¹ is independently selected from 1 to 10 carbon atoms is an alkyl group, with subscript (x) ≥ 0 and subscript (y) ≥ 0, where (xy) is <20 mPa·s (alternatively 8 mPa·s to 16 mPa·s) in the polyalkylhydrogensiloxane. 0.1 to 5 parts by weight of a polyalkylhydrogensiloxane having a viscosity of (s) sufficient to provide a viscosity of

(F) a platinum group metal catalyst in an amount sufficient to provide a concentration of platinum group metal in the composition of 10 to 5000 ppm, and

(E) 0.01 to 1 part by weight of acetylenic alcohol, and

(G) 10% to 90% by weight of an organic solvent, based on the combined weight of all starting materials in the composition, provided that all starting materials in the combined composition contain 0.5:1 to 2:1 silicon bonded hydrogen atoms/silicon and the molar ratio of bonded alkenyl groups (having the SiH::alkenyl ratio).

Starting material (A) poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer

The starting material (A) in the pressure-sensitive adhesive composition is poly(dialkylsiloxane/alkylalkenylsiloxane containing a silicone-bonded alkyl group having 1 to 10 carbon atoms and a silicone-bonded alkenyl group having 2 to 6 carbon atoms. ) is a copolymer, and the alkenyl group is present in an amount of 0.14% to 0.3% by weight of the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer. Alternatively, the starting material (A) contains at least 0.15%, alternatively > 0.20%, alternatively at least 0.21%, and alternatively at least 0.22% of alkenyl groups; At the same time, the starting material (A) is, on the same basis, not more than 0.29%, alternatively not more than 0.28%, alternatively not more than 0.27%, alternatively not more than 0.26%, alternatively not more than 0.25%, alternatively not more than 0.24%, alternatively Typically, it may contain up to 0.23%, alternatively up to 0.22%, and alternatively up to 0.21% of alkenyl groups. Alternatively, the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer may comprise 0.14% to 0.3%, alternatively 0.20% to 0.26% of alkenyl groups and alternatively 0.202% of alkenyl groups. Without wishing to be bound by theory, if the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer contains >0.3% alkenyl groups, pressure sensitive adhesives made from the composition can be used for the fabrication of electronic devices such as flexible organic light emitting diode devices. When the pressure-sensitive adhesive film is removed, it may cause burrs that cause damage to the passivation layer. And, if the alkenyl content of the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer is too low ( e.g. , <0.14%), migration may increase and subsequent adhesive strength test results may be too low. and/or the adhesive strength may increase too much after aging (adhesion stability may become poor). The starting material (A) may be free of silicon-bonded aromatic hydrocarbon groups. “Free of” in this context means that the starting material (A) does not contain aromatic hydrocarbon groups (such as phenyl, tolyl, xylyl or benzyl) or is determined by resolved gas chromatography mass spectrometry (GCMS) analysis. It means containing an undetectable amount of aromatic hydrocarbon groups.

The starting material (A) has the average unit formula (I) (R ¹ ₂ R ² SiO _1/2 ) _d (R ¹ ₃ SiO _1/2 ) _e (R ¹ R ² SiO _2/2 ) _f (R ¹ ₂ SiO _2/2 ) _g (subscript (d) ≥ 0, subscript (e) ≥ 0, subscript (f) > 0, subscript (g) ≥ 0, where (d+e) = 2, ( d+e+f+g) is from 3 to 10,000, alternatively from 2,000 to 9,500, alternatively from 4,500 to 5,000) of poly(dialkylsiloxane/alkylalkenylsiloxane). Alternatively, the subscripts (d, e, f, and g) have values such that 2 ≥ d ≥ 0, 2 ≥ e ≥ 0, 70 ≥ f ≥ 0, 10,000 ≥ g ≥ 0. Alternatively, the subscript f may have a value such that 50 ≥ f ≥ 0, alternatively 40 ≥ f ≥ 10, and alternatively 37 ≥ f ≥ 20. Alternatively, the subscript (g) can have values such that 9,500 ≥ g ≥ 0, alternatively 5,500 ≥ g ≥ 4,000, alternatively 5,000 ≥ g ≥ 4,500, and alternatively 4,950 ≥ g ≥ 4,450. there is. The subscripts (d, e, f, and g) have values selected such that the poly(dialkylsiloxane/alkylakenylsiloxane) has the alkenyl content described above. Alternatively, the subscripts (d, e, f, and g) indicate that the number average molecular weight (Mn) of starting material (A) is at least 200,000 g/mol; alternatively at least 250,000 g/mol; alternatively at least 300,000 g/mol, and alternatively at least 330,000 g/mol; However, at the same time, Mn, as measured by gel permeation chromatography according to the test method in reference example (1), column 31 of U.S. Patent No. 9,593,209, is 500,000 g/mol or less, alternatively 450,000 g. /mol or less, alternatively 400,000 g/mol or less, and alternatively 370,000 g/mol or less.

In the unit formula (I), each R ¹ is independently an alkyl group of 1 to 10 carbon atoms, and each R ² is independently an alkenyl group of 2 to 6 carbon atoms. Suitable alkyl groups include branched or unbranched saturated monovalent hydrocarbon groups. Alkyl is methyl, ethyl, propyl (e.g. iso-propyl and/or n-propyl), butyl (e.g. isobutyl, n-butyl, tert-butyl and/or sec-butyl), pentyl (e.g. For example, isopentyl, neopentyl and/or tert-pentyl), hexyl, heptyl, octyl, nonyl and decyl, as well as branched, saturated monovalent hydrocarbon groups of 6 to 10 carbon atoms. No. Alternatively, each R ¹ may be selected from methyl, ethyl, and iso-propyl. Alternatively, each R ¹ can be methyl. Suitable alkenyl groups include branched or unbranched monovalent hydrocarbon groups with terminal double bonds. Alkenyl includes vinyl, allyl, butenyl (e.g., isobutenyl, n-butenyl, tert-butenyl, and/or sec-butenyl), and hexenyl (branched and linear groups of 6 carbon atoms) ), but is not limited thereto. Alternatively, each R ² can be alkenyl. Alternatively, each R ² can be vinyl, allyl, or hexenyl. Alternatively, each R ² can be vinyl or hexenyl.

The alkenyl content of the starting material (A) is calculated by calculating the total molecular weight of the poly(dialkylsiloxane/alkylalkenylsiloxane), calculating the molecular weight of each unit containing an alkenyl group, and calculating the molecular weight of each unit containing an alkenyl group. It can be calculated by dividing the combined molecular weight of by the total molecular weight. For example, in the unit formula for starting material (A): (R ¹ ₂ R ² SiO _1/2 ) _d (R ¹ ₃ SiO _1/2 ) _e (R ¹ R ² SiO _2/2 ) _f (R ¹ ₂ SiO _2/2 ) _g (R ¹ is methyl, R ² is vinyl, subscript (d) = 2, subscript (e) = 0, subscript (f) = 25, and subscript (g ) = 4829), then the starting material (A) is a dimethylvinylsiloxy terminated poly(dimethylsiloxane/methylvinylsiloxane) copolymer with number average molecular weight (Mn) and alkenyl (vinyl) content calculated as (M ^Vi ₂ D ^Vi ₂₅ D ₄₈₂₉ ):

공중합체의 수 평균 분자량; 360,429.89 gf/mol

Number average molecular weight of the copolymer; 360,429.89 gf/mol

If Mw of M ^Vi = 93.20 g/mol, then Mw of D = 74.15 g/mol and Mw of D ^Vi = 86.17 g/mol

→ M ^Vi D ₄₈₂₉ D ^Vi ₂₅ M ^Vi of Mn = 2*93.2 + 4829*74.15 + 25*86.17 = 360,429.89 g/mol

Vinyl content = 0.202%

If Mw of M ^Vi = 93.20 g/mol, Mw of D = 74.15 g/mol, Mw of D ^Vi = 86.17 g/mol, and Mw of vinyl = 27,

→ M ^Vi D ₄₈₂₉ D ^Vi ₂₅ M ^Vi of Mn = (27*27)/(2*93.2 + 4829*74.15 + 25*86.17)

Starting material (A) is

i) dimethylvinylsiloxy terminated poly(dimethylsiloxane/methylvinylsiloxane),

ii) dimethylvinylsiloxy terminated polymethylvinylsiloxane,

iii) bis-trimethylsiloxy terminated poly(dimethylsiloxane/methylvinylsiloxane),

iv) trimethylsiloxy terminated polymethylvinylsiloxane,

v) dimethylvinylsiloxy terminated poly(dimethylsiloxane/methylvinylsiloxane),

vi) dimethylhexenylsiloxy terminated poly(dimethylsiloxane/methylhexenylsiloxane),

vii) dimethylhexenylsiloxy terminated polymethylhexenylsiloxane,

viii) trimethylsiloxy terminated poly(dimethylsiloxane/methylhexenylsiloxane),

ix) trimethylhexenylsiloxy terminated polymethylhexenylsiloxane,

x) dimethylvinylsiloxy terminated poly(dimethylsiloxane/methylhexenylsiloxane),

xi) Combination of two or more of i), ii), iii), iv), v), vi), vii), viii), ix), and x)

This is exemplified by:

The starting material (A) is one poly(dialkylsiloxane/alkylalkenylsiloxane) that differs in at least one characteristic such as the choice of alkyl groups, the choice of alkenyl groups, molecular weight, and the number of dialkylsiloxane units and alkylalkenylsiloxane units. ) It may be a combination of two or more of a copolymer or a poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer. Methods for preparing poly(dialkylsiloxanes/alkylalkenylsiloxanes) suitable for use as starting material (A) include hydrolysis and condensation of the corresponding organohalosilanes, or equilibration of cyclic polydiorganosiloxanes. It is well known in the art.

Starting material (B) polyalkylsiloxane resin

The pressure-sensitive adhesive composition may optionally further include starting material (B) polyalkylsiloxane resin. Polyalkylsiloxane resins are MQ resins consisting essentially of R ³ ₃ SiO _1/2 (M) units and SiO _4/2 (Q) units (each R ³ having 1 to 10 units as described for R ¹ independently selected from an alkyl group of carbon atoms and an alkenyl group of 2 to 6 carbon atoms as described above for R ² . The starting material (B) may be free of silicon-bonded aromatic hydrocarbon groups.

When prepared, the polyorganosilicate resin comprises the M and Q units described above, and the polyorganosilicate resin further comprises units bearing silanol (silicon-bonded hydroxyl) groups, having the formula Si(OSiR ³ ₃ ) It may include a neopentamer of ₄ (R ³ is as described above). Si ²⁹ nuclear magnetic resonance (NMR) spectroscopy, as described in U.S. Pat. No. 9,593,209, column 32, reference example (2), is based on the molar ratio of M and Q units, wherein {M(resin)+M(neopentamer) )}/{Q(resin)+Q(neopentamer)}, expressed as the total number of triorganosiloxy groups (M units) of the resinous and neopentamer portions of the polyorganosilicate resin versus the resin and neopentamer. It can be used to determine the molar ratio (M:Q ratio) of the total number of silicate groups (Q units) of the pentamer moiety. The M:Q ratio may be 0.5:1 to 1.5:1, alternatively 0.6:1 to 1.2:1.

The Mn of a polyorganosilicate resin depends on a variety of factors, including the type of hydrocarbon group represented by R ³ present. Mn of the polyorganosilicate resin is measured using gel permeation chromatography (GPC) according to the procedure in Column 31, Reference Example (1) of U.S. Pat. No. 9,593,209, when the peak representing neopentamer is excluded from the measurement value. refers to the number average molecular weight. The Mn of the polyorganosilicate resin may be greater than 2,000 g/mol, alternatively from 2,000 g/mol to 10,000 g/mol, and alternatively from 3,000 g/mol to 8,000 g/mol. Alternatively, the Mn of the polyorganosilicate resin may be 4,000 g/mol to 7,000 g/mol.

U.S. Patent No. 8,580,073, column 3, line 5 to column 4, line 31, is incorporated herein by reference to disclose silicone resins that are polyorganosilicate resins suitable for use herein. Polyorganosilicate resins can be prepared by any suitable method, such as cohydrolysis of the corresponding silanes or silica hydrosol capping methods. Polyorganosilicate resins include those disclosed in US Pat. No. 2,676,182 to Daudt et al.; US Patent No. 4,611,042 to Rivers-Farrell et al.; and U.S. Pat. No. 4,774,310 to Butler et al. The method of Daudt et al., described above, involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane, such as trimethylchlorosilane, a siloxane, such as hexamethyldisiloxane, or a mixture thereof, and and recovering the copolymer. The resulting copolymer typically contains 2 to 5% by weight of silicone-bonded hydroxyl (silanol) groups.

Intermediates used to prepare polyorganosilicate resins can be triorganosilanes, and silanes with four hydrolyzable substituents or alkali metal silicates. Triorganosilanes have ^the formula R ^M ₃ SiX ¹ (R ³ is as previously described and or hydroxyl). Silanes with four hydrolyzable substituents can have the formula SiX ² ₄ (each X ² is halogen, alkoxy or hydroxyl). Suitable alkali metal silicates include sodium silicate.

Polyorganosilicate resins prepared as described above typically contain silicone-linked hydroxyl groups, for example with the unit formula HOSi _3/2 and/or HOR ³ ₂ SiO _1/2 . The polyorganosilicate resin may contain up to 2% silicone bonded hydroxyl groups. The concentration of silicone-bonded hydroxyl groups present in the polyorganosilicate resin can be measured using Fourier transform infrared (FTIR) spectroscopy according to ASTM standard E-168-16. For certain applications, it may be desirable to have less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, alternatively 0.3% to 0.8% of silicone bound hydroxyl groups. The silicone-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin are converted to trihydrocarbyl-siloxy groups or other hydrolyzable groups by reacting the polyorganosilicate resin with a silane, disiloxane or disilazane containing appropriate end groups. It can be. Silane containing hydrolyzable groups can be added in molar excess of the amount necessary to react with the silicon bonded hydroxyl groups on the polyorganosilicate resin.

^{Alternatively , the} polyorganosilicate _resin has _{the formula} It may further include 2% or less, alternatively 0.7% or less, and alternatively 0.3% or less, and alternatively 0.3% to 0.8% of the units represented by.

Alternatively, the polyorganosilicate resin may have terminal aliphatic unsaturated groups. Polyorganosilicate resins having terminal aliphatic unsaturated groups are prepared by reacting the product of Daudt et al. with an end blocker containing an unsaturated organic group and an end blocker without aliphatic unsaturation in an amount sufficient to provide 3 to 30 mol% of unsaturated organic groups in the final product. can be manufactured. Examples of endblockers include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblockers are known in the art and include, but are not limited to, those described in US Pat. No. 4,584,355; No. 4,591,622; and 4,585,836. Single end blocking agents or mixtures of these agents can be used to prepare these resins.

Alternatively, the polyalkylsiloxane resin has the unit formula (II) (R ¹ ₂ R ² SiO _1/2 ) _a (R ¹ ₃ SiO _1/2 ) _b (SiO _4/2 ) _c (R ¹ and R ² are As described above, the subscripts (a, b, and c) represent mole fractions having values such that subscript (a) ≥ 0, subscript (b) ≥ 0, subscript (c) > 0, Here, (a+b) > 0, and the subscripts (a, b, and c) may include values such that 0.9 ≤ (a+b)/c ≤ 1.3.

The amount of starting material (B) in the pressure-sensitive adhesive composition depends on the desired reaction product form of the composition, the quantity and hydrosilylation reactivity of the alkenyl groups of the starting material (A), the type and amount of catalyst, and the silicone bond of the starting material (C). It depends on a variety of factors including the content of hydrogen atoms. However, the amount of starting material (B) may range from 0 to 15 parts by weight per 100 parts by weight of starting material (A) or alternatively from 0 to 15 parts by weight on the same basis.

Starting material (C) polyalkylhydrogensiloxane

The pressure-sensitive adhesive composition further comprises starting material (C) polyalkylhydrogensiloxane. Polyalkylhydrogensiloxane has the formula (III):

(R ¹ ₂ HSiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (R ¹ HSiO _2/2 ) _y (R ¹ is as described above).

In the unit formula (III), subscript (x) ≥ 0, subscript (y) ≥ 0, where (x + y) is <20 mPa, measured at 25°C with a capillary viscometer in polyalkylhydrogensiloxane. s, alternatively sufficient to provide a viscosity of 8 mPa·s to 16 mPa·s. The subscript (x) may be sufficient to provide a SiH content of 0 to 1%, alternatively 0 to 0.75%, based on the weight of the starting material (C), polyalkylhydrogensiloxane, starting material (C). .

The polyalkylhydrogensiloxane of starting material (C) is:

a) dimethylhydrogensiloxy terminated polydimethylsiloxane,

b) dimethylhydrogensiloxy terminated poly(dimethylsiloxane/methylhydrogensiloxane),

c) dimethylhydrogensiloxy terminated polymethylhydrogensiloxane, and

d) Combination of two or more of a), b), and c)

This is exemplified by:

Methods for preparing polyalkylhydrogensiloxanes suitable for use as starting material (C), such as hydrolysis and condensation of alkylhalosilanes, are well known in the art.

The exact amount of starting material (C) in the composition will depend on the reactivity of starting material (A), whether starting material (B) is present, and, if present, any additional starting material (e.g., starting material (D)). It depends on a variety of factors including the type and amount of However, the amount of starting material (C) in the pressure-sensitive adhesive composition may be 0.1% to 5%, alternatively 0.5% to 3%, based on the total weight of all starting materials in the composition.

the alkenyl content of starting material (A) and any other starting material in the composition containing a silicon-bonded alkenyl group (e.g., if alkenyl functional, starting material (B) and starting material (C)), and The SiH content of material (B) and any other SiH-containing material of the pressure-sensitive adhesive composition (e.g., if SiH functional, the starting material (D) adhesion promoter) is determined by the silicon bond hydrogen atom to silicon bond bond in the pressure-sensitive adhesive composition. The molar ratio of alkenyl groups (SiH:alkenyl) is at least 0.5:1, alternatively 2:1 or less, alternatively 0.5:1 to 2:1, alternatively 1:1 to 1.5:1, and alternatively It is sufficient to provide a ratio of 1 to 1.2.

Starting Material (D) Fixative Additive

The starting material (D) is a fixative additive that can optionally be included in the pressure-sensitive additive composition. Without wishing to be bound by theory, it is believed that the fixative additive will facilitate bonding to the substrate by the pressure sensitive adhesive prepared by curing the pressure sensitive adhesive composition described herein. However, the presence of the fixative additive will not adversely affect the desired peel force, allowing the pressure sensitive adhesive to be removed from the electronic device without damaging the device or leaving a significant residue.

Suitable fixative additives are methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl) silane coupling agents such as -3-aminopropyltrimethoxysilane, bis(trimethoxysilyl)propane, and bis(trimethoxysilyl)hexane; and a mixture or reaction mixture of the above silane coupling agents. Alternatively, the fixative additive may be tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Vinyltriethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or It may be 3-methacryloxypropyl trimethoxysilane.

Alternatively, the anchoring additive may be the reaction product of an alkenyl functional alkoxysilane (e.g. vinyl alkoxysilane) and an epoxy functional alkoxysilane; reaction products of alkenyl functional acetoxysilanes (such as vinyl acetoxysilane) and epoxy functional alkoxysilanes; and combinations of epoxy functional alkoxysilanes with polyorganosiloxanes having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolyzable group per molecule (e.g., hydroxy terminated vinyl functional polydimethylsiloxane and glycidoxypropyltri). combinations of methoxysilanes) (e.g., physical blends and/or reaction products). Suitable anchoring additives and methods for their preparation are described, for example, in U.S. Pat. No. 9,562,149; U.S. Patent Application Publication Nos. 2003/0088042, 2004/0254274, 2005/0038188, 2012/0328863 at paragraph [0091], and U.S. Patent Application Publication No. 2017/0233612 at paragraph [0041] like; and European Patent No. 0 556 023.

Fixative additives are commercially available. For example, SYL-OFF™ 297, SYL-OFF™ 397 and SYL-OFF™ 9176 are available from Dow Silicones Corporation, Midland, MI. Other exemplary fixative additives include (D-1) vinyltriacetoxysilane, (D-2) glycidoxypropyltrimethoxysilane, (D-3) 2-(3,4-epoxycyclohexyl)ethyltrimeth Toxysilane, (D-4) a combination of two or more of (D-1), (D-2) and (D-3); and (D-5) a combination of any of (D-1), (D-2), (D-3) and/or (D-4), and terminated with a hydroxyl group, a methoxy group, or It includes polydimethylsiloxane terminated with both hydroxy and methoxy groups. The combination of (D-4) and (D-5) may be a physical blend and/or reaction product.

The amount of fixative additive depends on a variety of factors, including the type of substrate to which the composition will be applied, and whether a primer or other surface treatment agent will be used prior to application of the composition. However, the amount of fixative additive may be 0 to 5%, alternatively 1% to 5%, alternatively 1% to 3%, alternatively 0 to 1%, based on the combined weight of all starting materials in the composition. . The adhesion promoter may be free of silicone bonded aromatic hydrocarbon groups.

Starting material (E) inhibitor

The pressure-sensitive adhesive composition further includes starting material (E) acetylenic alcohol. Acetylenic alcohol may be added as an inhibitor or stabilizer to the pressure-sensitive adhesive composition. Suitable acetylenic alcohols include methyl butynol, ethynyl cyclohexanol (ETCH), dimethyl hexynol, and 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyne. -3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3 -ol, 4-ethyl-1-octin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol, and combinations thereof. Alternatively, the starting material (E) is (E-1) 1-ethynyl-1-cyclohexanol, (E-2) methyl butynol, (E-3) diallyl maleate, and (E-4) ) It may be selected from the group consisting of a combination of two or more of (E-1), (E-2), and (E-3). Alternatively, starting material (E) is exemplified by ETCH.

The amount of acetylenic alcohol added to the composition will depend on the desired pot life of the pressure-sensitive adhesive composition, whether the composition is a one-part composition or a multi-part composition, the specific acetylenic alcohol used, and the selection and amount of starting materials (C). It will depend on a variety of factors including: However, if present, the amount of starting material (E) may range from 0.01 to 0.5 parts by weight.

Starting material (F) Hydrosilylation reaction catalyst

The pressure-sensitive adhesive composition further includes a starting material (F) hydrosilylation reaction catalyst. Suitable hydrosilylation reaction catalysts are known in the art and are commercially available. The hydrosilylation catalyst may be a platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium and iridium. Alternatively, hydrosilylation catalysts may be prepared by compounds of these metals, such as chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of these compounds with low molecular weight organopolysiloxanes, or in matrix or core/shell type structures. It may be a microencapsulated platinum compound. Complexes of platinum and low molecular weight organopolysiloxane include complexes of platinum and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane. These complexes can be microencapsulated within a resin matrix. Exemplary hydrosilylation catalysts are described in US Pat. No. 3,159,601; No. 3,220,972; No. 3,296,291; No. 3,419,593; No. 3,516,946; No. 3,814,730; No. 3,989,668; No. 4,784,879; No. 5,036,117; and 5,175,325, and European Patent No. 0 347 895. Microencapsulated hydrosilylation catalysts and methods for their preparation are known in the art, as exemplified in U.S. Pat. Nos. 4,766,176 and 5,017,654.

The hydrosilylation reaction catalyst is added to the pressure sensitive adhesive composition in an amount sufficient to catalyze the hydrosilylation reaction, typically to provide 10 ppm to 5,000 ppm by weight of platinum group metal.

Starting Material (G) Solvent

The pressure-sensitive adhesive composition further includes a solvent. The solvent may be an organic solvent. Organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, or n-propanol; Ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, or xylene; aliphatic hydrocarbons such as heptane, hexane, or octane; Glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, dichloromethane, 1,1,1-trichloroethane, or halogenated hydrocarbons such as methylene chloride; chloroform; dimethyl sulfoxide; Dimethyl formamide, acetonitrile; tetrahydrofuran; white spirit; mineral spirits; naphtha; n-methyl pyrrolidone; Or it may be a combination thereof. Alternatively, the solvent may be selected from the group consisting of benzene, toluene, heptane, ethylbenzene, xylene, and combinations of two or more thereof.

The amount of solvent will depend on a variety of factors, including the type of solvent selected and the amounts and types of other starting materials selected for the pressure sensitive adhesive composition. However, the amount of solvent may range from 10% to 90%, alternatively from 20% to 60%, based on the combined weight of all starting materials in the pressure sensitive adhesive composition. Solvents may be added during preparation of the pressure sensitive adhesive composition, for example, to aid mixing and transfer. All or part of the solvent may be added along with one of the other starting materials. For example, starting material (A), and if present starting material (B), may be dissolved in a solvent, such as an aromatic hydrocarbon, prior to combination with other starting materials in the composition. All or part of the solvent may be optionally removed after the pressure-sensitive adhesive composition is prepared.

Starting material (H) Additional polyalkylhydrogensiloxane

The pressure sensitive adhesive composition optionally has the unit formula (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ HSiO _2/2 ) _z (R ¹ is as previously described and the subscript (z) is 200 to 250) and, based on the weight of the starting material (C), may further include 20% or less of additional polyalkylhydrogensiloxane as the starting material (H). Without wishing to be bound by theory, it is believed that starting materials (H) can be used to adjust the SiH:alkenyl ratio to the ranges described herein.

Methods for preparing polyalkylhydrogensiloxanes suitable for use as starting materials (H), such as hydrolysis and condensation of alkylhalosilanes, are well known in the art. Examples of suitable additional polyalkylhydrogensiloxanes for the starting material (H) include (H-1) trimethylsiloxy terminated poly(methylhydrogensiloxane);

(H-2) trimethylsiloxy terminated poly(dimethylsiloxane/methylhydrogensiloxane), and (H-3) combinations of both (H-1) and (H-2).

When selecting starting materials for the pressure sensitive adhesive compositions described above, there may be overlap between the types of starting materials as certain starting materials described herein may have more than one function. For example, certain alkoxysilanes may be useful as filler treatments and adhesion promoters. Certain particulates, such as carbon black, can be useful as fillers and pigments, and even as flame retardants. When adding additional starting materials to the composition, the additional starting materials are distinguished from each other and from the starting materials required for the composition.

The pressure sensitive adhesive composition may be prepared by a process comprising combining all starting materials by any convenient means, such as mixing at ambient or elevated temperature. The starting material (E) acetylenic alcohol can be added before the starting material (F) platinum group metal catalyst, for example, when the pressure-sensitive adhesive composition is prepared at elevated temperature and/or the composition is prepared as a partial composition.

Alternatively, the pressure-sensitive adhesive composition may be prepared as a multi-part composition, for example, if the composition is to be stored for an extended period of time before use. In multi-part compositions, the starting material (F) platinum group metal catalyst may be any starting material having a silicon bonded hydrogen atom, such as starting material (C) polyalkylhydrogensiloxane and (if present) starting material (H) and stored separately, the parts are combined immediately prior to use of the pressure-sensitive adhesive composition. For example, the two part composition may include an alkenyl-containing polydialkylsiloxane (A), a polyalkylhydrogensiloxane (C) (if present, the starting material (H)) and an organic solvent (G), and optionally the foregoing. The starting materials may be prepared by combining the starting materials, including one or more other additional starting materials, to form the base portion by any convenient means, such as mixing. The curing agent can be prepared by any convenient means, such as mixing starting materials comprising an alkenyl-containing polydialkylsiloxane (A), a platinum group metal catalyst (F), and an organic solvent (G), and optionally one or more other additional starting materials described above. It can be manufactured by combining. Starting materials can be combined at ambient or elevated temperature. The starting material (E) acetylenic alcohol may be included in one or more of the base part, the hardener part, or a separate additional part. Starting material (D) The adhesion promoter, if used, may be added to the base part or may be added as a separate additional part. The starting material (B) polyalkylsiloxane resin, if used, can be added to the base part, to the hardener part or to a separate additional part. When a two part composition is used, the weight ratio of the amount of base part to hardener part can range from 1:1 to 10:1. The pressure sensitive adhesive composition will cure through a hydrosilylation reaction to form a pressure sensitive adhesive.

The methods described above may further include one or more additional steps. The pressure sensitive adhesive composition prepared as described above can be used to form adhesive articles on substrates, such as pressure sensitive adhesives (made by curing the pressure sensitive adhesive composition described above). Accordingly, the above-described method may further include the step of applying the pressure-sensitive adhesive composition to the substrate.

The step of applying the pressure sensitive adhesive curable composition to the substrate can be performed by any conventional means. For example, the pressure-sensitive adhesive curable composition can be applied by a gravure coater, offset coater, offset-gravure coater, roller coater, reverse roller coater, air-knife coater or curtain coater. It can be applied on a substrate.

The substrate can be any material that can withstand the curing conditions (described below) used to cure the pressure sensitive adhesive curable composition to form a pressure sensitive adhesive on the substrate. For example, any substrate that can withstand heat treatment at temperatures above 120°C, alternatively 150°C, is suitable. Examples of materials suitable for these substrates include polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), liquid crystalline polyarylate, polyamidoimide (PAI), polyether sulfide (PES), or polyethylene. Includes plastic films such as terephthalate (PET), or polyethylene (PE) or polypropylene (PP). Alternatively, the substrate may be a metal foil such as aluminum foil or copper foil. The thickness of the substrate is not critical, but may range from 5 micrometers to 300 micrometers.

To improve the bonding of the pressure-sensitive adhesive to the substrate, the method may optionally further include treating the substrate prior to applying the pressure-sensitive adhesive composition. Treatment of the substrate may be performed by any convenient means, such as applying a primer, or subjecting the substrate to a corona-discharge treatment, etching, or plasma treatment, prior to applying the pressure-sensitive adhesive composition to the substrate. .

Adhesive articles such as protective films can be prepared by applying the pressure-sensitive adhesive composition described above onto the substrate described above. The method may optionally further include removing all or part of the solvent prior to and/or during curing. Removing the solvent may be performed at a temperature that evaporates the solvent without completely curing the pressure sensitive adhesive composition, for example, 70°C to 120°C, alternatively 50°C to 100°C, and alternatively 70°C to 80°C. This can be accomplished by any convenient means, such as heating at a temperature 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). Accordingly, the method involves heating the pressure sensitive adhesive composition (which may have some or all of the solvent removed when a drying step is performed) at room temperature, or between 140° C. and 220° C., alternatively between 150° C. and 220° C., alternatively between 150° C. and 220° C. Heating at a temperature of 160°C to 200°C, and alternatively 165°C to 180°C, for a time sufficient to cure the pressure sensitive adhesive curable composition (e.g., 30 seconds to 1 hour, alternatively 1 minute to 5 minutes). It additionally includes the step of hardening by doing so. This forms a pressure sensitive adhesive on the substrate. Drying and/or curing can be performed by placing the substrate in an oven. The amount of pressure-sensitive adhesive composition applied to the substrate will vary depending on the specific application, but the amount may be sufficient to provide a thickness of the pressure-sensitive adhesive after curing of 5 micrometers to 200 micrometers, and in the case of a protective film, said thickness. may be between 10 microns and 50 microns, alternatively between 20 microns and 40 microns, and alternatively between 30 microns.

The methods described herein may optionally further include applying a removable release liner to the pressure sensitive adhesive opposite the substrate, for example, to protect the pressure sensitive adhesive prior to use of the adhesive article. .

Adhesive articles (e.g., protective films) prepared as described above are suitable for use in flexible OLED device fabrication processes as protective films with low adhesion, high adhesive stability, and/or low mobility.

For example, a method of fabricating a flexible OLED device may include forming an OLED module on the surface of a substrate, forming a passivation layer, e.g., on the surface of the OLED module opposite the substrate, and forming a passivation layer as described herein. It may include applying the protective film prepared as described above to the surface of the passivation layer on the opposite side of the OLED module.

Example

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

[Table 1]

In the table above, 'N/A' means not applicable and 'Me' means methyl. OWSIL™, SILASTIC™, and SYL-OFF™ products are commercially available from Dow Silicones Corporation, Midland, Michigan.

Reference Example 1 - Preparation of pressure sensitive adhesive composition samples

Pressure-sensitive adhesive composition samples were prepared by combining the starting materials shown in Table 1. First, 100 parts by weight of the starting material (A1) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane) copolymer was mixed with the starting material (G1) toluene solvent to prepare a 25% by weight solution. Polyalkylhydrogensiloxanes (one or more of (H1) to (H4) and (C1)) were added to the mixture in the amounts indicated in Tables 2 and 3 below. The amount of polyalkylhydrogensiloxane was sufficient to achieve a SiH/Vi molar ratio of 0.5, 1, or 2 in the mixture. This ratio included the vinyl present in the vinyl-containing siloxane complexed platinum catalyst (F1) added at the end of this procedure. Inhibitor (E1) was added and the resulting combination was mixed well. After homogenizing the mixture, starting material (F1) was added to the mixture. The mixture was immediately mixed again, taking care not to generate heat. Now, the resulting pressure sensitive adhesive composition sample is ready for use. The amount of each starting material (parts by weight) in the samples is shown below in Tables 2 (Comparison) and 3 (Working). Tables 2 and 3 also show the SiH/Vi ratio, total Pt content, and % solids (based on the weight of all starting materials excluding solvent).

Reference Example 2 - Preparation of adhesive sheet

A pressure-sensitive adhesive composition sample was prepared as described in Reference Example (1) and applied on a 50 um polyethylene terephthalate (PET) film to form a pressure-sensitive adhesive layer (having a thickness of 30 um after curing). The coated film was heated at 150°C for 2 minutes to produce a pressure-sensitive adhesive sheet. The substrate film (PET) was commercially available; It was sold under the trade name (trade name SH-86, TAMK) of Toray Advanced Material Korea.

Reference Example 3 - Initial Adhesion Measurement

The sheet obtained according to Reference Example (2) was cut into 1 inch wide strips to form a pressure-sensitive adhesive tape. Adhesion strength to a stainless steel plate (SUS304) was measured according to the 180 degree peel test specified in ASTM D1000. Each tape was peeled from a peelable polyethylene terephthalate film and adhered to an adherend in the form of a mirror-polished stainless steel sheet (SUS304) under 2 kgf pressure generated by a rubber roller. Initial adhesion greater than 2 gf/inch was defined as failure.

Reference Example 4 - Adhesion at 85°C/85% (adhesive stability)

The sheet obtained according to Reference Example (2) was cut into 1 inch wide strips to form a pressure-sensitive adhesive tape. Adhesion strength to a stainless steel plate (SUS304) was measured after aging according to the 180 degree peel test specified in ASTM D1000. Each tape was peeled from a peelable polyethylene terephthalate film and adhered to an adherend in the form of a mirror-polished stainless steel sheet (SUS304) under 2 kgf pressure generated by a rubber roller. The tapes were aged in an oven at 85° C./85% humidity for 1 day (24 hours) and 3 days (72 hours). After the tape was cooled to room temperature, the adhesive force was measured by pulling the pressure-sensitive adhesive tape from the adherend at a 180 angle with respect to the surface of the adherend using a tensile tester at a constant speed of 12 inches/minute. (Test equipment; AR-1000 (Cheminstrument Company)). The results are shown in Tables 2 and 3 below. For some applications, it may be desirable for the adhesion to be <9 gf/in after 24 hours, and <15 gf/in after 72 hours.

Reference Example 5 - Simple scratch test (burr test)

A pressure-sensitive adhesive sheet was prepared according to Reference Example (2). Cuts were made on the pressure-sensitive adhesive surface by a cutter, and the cross-sections were observed visually and under a microscope. If the edges of the cut look clean and no particles are generated, the result is a pass. If particles were generated and observed at the edge, or if burrs were visible at the edge, the result was a failure.

Reference Example 6 - Simple Rub-off test (anchorage test)

A pressure-sensitive adhesive coated on PET was prepared according to Reference Example (2), and the anchorage of the pressure-sensitive adhesive was evaluated as follows. Cuts were cross-marked at 10 cm x 10 cm on the PSA only by a cutter (being careful not to cut the PET underneath). The marked surface was vigorously rubbed with a finger. After 30 seconds of rubbing, the surface was observed to determine whether the PSA had fallen off. When rubbing the PSA, the results were unacceptable.

Reference Example 7 - Residual adhesive remaining properties and silicone migration properties (residual adhesion) after exposure to 85°C/85% conditions

The sheet obtained according to Reference Example (2) was cut into 1 inch wide strips to form a pressure-sensitive adhesive tape. Each tape was peeled from a peelable polyethylene terephthalate film and adhered to an adherend in the form of a mirror-polished stainless steel sheet (SUS304) under 2 kgf pressure generated by a rubber roller. These samples were aged in an oven at 85°C/85% for 1 day (24 hours) and 3 days (72 hours). After cooling to room temperature, the PSA tape was removed from a mirror stainless steel plate. Nitto 31B was adhered to the location where the tape was removed with a 2KG roller. After 30 minutes, adhesion was measured by pulling the pressure-sensitive adhesive tape from the adherend at a 180 angle with respect to the surface of the adherend using a tensile tester at a constant speed of 12 inches/minute. Results for each sample are also shown in Tables 2 and 3 below. “AF” in the table indicates adhesive failure and is undesirable for some applications.

Reference Example 8 - Burr Test

A pressure-sensitive adhesive sheet sample was prepared according to Reference Example (2). Cuts were made on the pressure-sensitive adhesive surface using a cutter, which were visually observed with the naked eye and a microscope. If the edges of the cut look clean and no particles are generated, the result is a pass. If particles or fragments are generated at the edges or burrs, the sample has failed. Results for each sample are also shown in Tables 2 and 3 below.

[Table 2]

[Table 3]

In Tables 2 and 3, "N/D" means not detected due to adhesive transfer, 'AF' means adhesive failure, i.e. transfer of adhesive to the substrate, and 'RF' means rubbing. Fracture, i.e., means that the adhesive rubs under stress, and “RF” means that the result is not applicable to the invention.

Example 9 (Comparative Example)

A sample was prepared according to the procedure of Reference Example (1), except that the composition contained 100 parts by weight of starting material (A2), and a dimethylvinylsiloxy terminated poly(dimethylsiloxane/methylvinylsiloxane) copolymer for comparison. has both pendant and terminal vinyl groups, but vinyl content = 0.41% and DP > 5,000, 300 parts by weight of toluene, 0.748 parts by weight of starting material (H4), 0.15 parts by weight of starting material (E1) and starting material ( F1) has 1.5 parts by weight. A silicone pressure sensitive adhesive prepared by curing this composition failed the burr test when tested according to Reference Example (8). Without wishing to be bound by theory, it is believed that when the vinyl content of the starting material (A) in the pressure-sensitive adhesive composition is too high, the pressure-sensitive adhesive made therefrom fails the burr test.

The pressure sensitive adhesive compositions described herein cure to form pressure sensitive adhesives suitable for use in flexible OLED device fabrication processes. This example shows that a pressure sensitive adhesive prepared by curing the pressure sensitive adhesive composition described above can have an initial adhesion <2 gf/inch on stainless steel (SUS) (as tested according to Reference Example (3)) ); Adhesion <9 gf/in after 24 hours and <15 gf/in after 72 hours, as tested according to Reference Example (4). The pressure sensitive adhesive compositions described herein can also be cured to form a pressure sensitive adhesive having a residual adhesion on SUS of >300 gf/in after 24 hours and >250 g/in after 72 h (tested according to Reference Example (7) ). SUS stands for the industry standard for developing and testing pressure-sensitive adhesives. Therefore, without being bound by theory, it is believed that the adhesion properties to SUS will provide similar results to substrates used in the OLED fabrication process, such as passivation layers, and that the combination of these properties allows the pressure-sensitive adhesive film to be used in flexible OLED devices. It is expected that this will enable it to be used as a protective film on the passivation layer during fabrication.

Moreover, surprisingly, when the pressure-sensitive adhesive composition contained a poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer with an alkenyl content of 0.14% to 0.3%, the resulting pressure-sensitive adhesive passed the burr test (alkenyl It was found that comparative pressure sensitive adhesives containing alternatively functional polydialkylsiloxanes with content > 0.3% failed the burr test as shown in Example (8).

Use of Terms

Unless otherwise indicated in the context of this specification, all amounts, ratios and percentages are by weight. Unless otherwise indicated in the context of the specification, the articles 'a', 'an' and 'the' each refer to one or more. The disclosure of a range includes the range itself and also anything included therein, as well as endpoints. For example, the disclosure of a range from 0.14 to 0.3 includes not only the range 0.14 to 0.3, but also 0.15, 0.20, 0.26, and 0.3 individually, as well as any other numbers falling below that range. Additionally, for example, the disclosure of a range of 0.15 to 3.0 includes subsets of, for example, 0.15 to 0.21, 0.15 to 0.26, 0.202 to 0.26, and 0.202 to 3.0, as well as any other subsets that fall below that range. Also includes. Similarly, disclosure of a Markush group includes the entire group as well as any individual members and subgroups included therein. For example, the disclosure of the Markush group, vinyl, allyl or hexenyl, individually refers to the members vinyl; subgroup vinyl and hexenyl; and any other individual members and subgroups included therein.

Abbreviations used herein have the following meanings: '°C' and 'degree C' each refer to a temperature in degrees Celsius; 'DP' means degree of polymerization. 'ETCH' means ethynyl cyclohexanol; ‘GPC’ stands for gel permeation chromatography and ‘GCMS’ stands for gas chromatography mass spectrometry; 'gf' means gram force; 'Hr' means time; 'KG' or 'kg' means kilogram; 'kgf' means kilogram force; 'min' means minute; 'Me' means methyl, 'mPa·s' means millipascal second, 'OLED' means organic light emitting diode; 'um' means micrometer, and 'Vi' means vinyl.

Embodiments of the present invention

In a first embodiment, a method for manufacturing a flexible organic light emitting diode device includes

1) Applying a pressure-sensitive adhesive composition to the surface of a substrate,

2) curing the pressure-sensitive adhesive composition to form a pressure-sensitive adhesive film, and

3) applying a pressure sensitive adhesive film to the passivation layer within the device;

(The pressure-sensitive adhesive composition is

(A) 85 to 100 parts by weight of a poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer (the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer comprising a silicon-bonded alkyl group having 1 to 10 carbon atoms and Containing silicone bonded alkenyl groups having 2 to 6 carbon atoms, said alkenyl groups being present in an amount of 0.14% to 0.3% by weight of the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer),

(C) Unit formula (R ¹ ₂ HSiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (R ¹ HSiO _2/2 ) _y (each R ¹ is independently selected from 1 to 10 carbon atoms is an alkyl group, with subscript (x) ≥ 0 and subscript (y) ≥ 0, where (xy) is sufficient to provide the polyalkylhydrogensiloxane with a viscosity of <20 mPa·s measured at 25°C. 0.1 to 5% by weight of polyalkylhydrogensiloxane,

(F) a platinum group metal catalyst in an amount sufficient to provide a concentration of platinum group metal in the composition of 10 to 5000 ppm, and

(E) 0.01 to 1 part by weight of acetylenic alcohol, and

(G) 10% to 90% by weight of an organic solvent, based on the combined weight of all starting materials in the composition, provided that all starting materials in the combined composition contain 0.5:1 to 2:1 silicon bonded hydrogen atoms/silicon and the molar ratio of bonded alkenyl groups (having the SiH::alkenyl ratio).

In a second embodiment, in the method of the first embodiment, the starting material (A) has i) a number average molecular weight of 200,000 g/mol to 500,000 g/mol, ii) an alkenyl group content of 0.20% to 0.26%, and iii) i) and ii) both.

In a third embodiment, in the method of the first or second embodiment, the starting material (A) has the average unit formula (R ¹ ₂ R ² SiO _1/2 ) _d (R ¹ ₃ SiO _1/2 ) _e ( R ¹ R ² SiO _2/2 ) _f (R ¹ ₂ SiO _2/2 ) _g (each R ¹ is independently an alkyl group of 1 to 10 carbon atoms; each R ² is R ¹ , OH, and independently selected from alkenyl groups of 2 to 6 carbon atoms; subscript (d) ≥ 0, subscript (e) ≥ 0, subscript (f) > 0, subscript (g) ≥ 0, where , (d+e) = 2, and (d+e+f+g) is 4,500 to 5,000.

In a fourth embodiment, in the process of any one of the first to third embodiments, the starting material (C) has i) a viscosity at 25° C. of 8 mPa·s to 16 mPa·s, ii) 0% to 16 mPa·s. a SiH content of 1%, iii) having properties selected from the group consisting of both i) and ii).

In a fifth embodiment, in the method of any one of the first to fourth embodiments, the starting material (F) is a platinum group metal (F-1) selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium. ; Compounds of platinum group metals (F-2); The compound is selected from the group consisting of complex (F-3) and (F-4) of low molecular weight organopolysiloxane, compound (F-2) microencapsulated in a matrix or core/shell-type structure, or complex (F-3). .

In a sixth embodiment, in the process of any one of the first to fifth embodiments, the starting material (E) is 1-ethynyl-1-cyclohexanol (E-1), methyl butynol (E- 2), diallyl maleate (E-3), and (E-4) is selected from the group consisting of a combination of two or more of (E-1), (E-2), and (E-3). The starting material (E) comprises ethynyl cyclohexanol.

In a seventh embodiment, in the process of any one of the first to sixth embodiments, the starting material (G) is selected from the group consisting of benzene, toluene, heptane, ethylbenzene, xylene, and combinations of two or more thereof. do.

In an eighth embodiment, the method of any one of the first to seventh embodiments, wherein the pressure-sensitive adhesive composition has (H) the unit formula (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ HSiO _2/2 ) _z (the subscript (z) is 200 to 250) and further comprises up to 20% by weight of additional polyalkylhydrogensiloxane, based on the weight of the starting material (C).

In a ninth embodiment, the method of any one of embodiments 1 to 8, wherein the pressure-sensitive adhesive composition has (B) the unit formula (R ¹ ₂ R ³ SiO _1/2 ) _a (R ¹ ₃ SiO _1/2 ) _b (SiO _4/2 ) _c (each R ¹ is independently an alkyl group of 1 to 10 carbon atoms; each R ² is R ¹ , OH, and 2 to 6 carbon atoms) independently selected from an alkenyl group; subscript (a) ≥ 0, subscript (b) ≥ 0, subscript (c) > 0, where (a+b) > 0, and subscript (a, b) , and c) has a value such that 0.9 ≤ (a+b)/c ≤ 1.2), further comprising 15 parts by weight or less of a polyalkylsiloxane resin.

In a tenth embodiment, in the method of any one of the first to ninth embodiments, the pressure-sensitive adhesive composition further comprises (D) 1 part by weight or less of a fixative additive.

In the ninth embodiment, in the method of the tenth embodiment, the starting material (D) is vinyltriacetoxysilane (D-1), glycidoxypropyltrimethoxysilane (D-2), (D-3) ( A combination of D-1) and (D-2), and (D-4) a combination of (D-3) and polydimethylsiloxane terminated with a hydroxyl group, a methoxy group, or both hydroxyl groups and methoxy groups. is selected from the group consisting of

In a twelfth embodiment, the method of any one of the first to eleventh embodiments further comprises removing all or part of the solvent from the pressure-sensitive adhesive composition before step (2).

In a thirteenth embodiment, the method of any one of the first to twelfth embodiments further comprises the step of treating the substrate before step (1).

In a twentieth embodiment, the starting material (A) is free from silicon-bonded aromatic hydrocarbyl groups or, if present, is free from silicon-bonded aromatic hydrocarbyl groups in the starting material (B) according to the nineteenth embodiment. (C) has no silicon-bonded aromatic hydrocarbyl groups, or, if present, starting material (D) has no silicon-bonded aromatic hydrocarbyl groups, or two or more of these.

Claims (15)

A pressure sensitive adhesive composition, comprising:
(A) 85 to 100 parts by weight of a poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer (the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer comprising a silicon-bonded alkyl group having 1 to 10 carbon atoms and Containing silicone bonded alkenyl groups having 2 to 6 carbon atoms, said alkenyl groups being present in an amount of 0.14% to 0.3% by weight of the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer),
(C) Unit formula (R ¹ ₂ HSiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (R ¹ HSiO _2/2 ) _y (each R ¹ is independently selected from 1 to 10 carbon atoms) is an alkyl group, and the subscript (x) ≥ 0 and the subscript (y) ≥ 0, where (xy) gives the polyalkylhydrogensiloxane a viscosity of <20 mPa·s measured at 25°C with a capillary viscometer. 0.1 to 5 parts by weight of polyalkylhydrogensiloxane having (sufficient to:
(F) a platinum group metal catalyst in an amount sufficient to provide a concentration of platinum group metal in the composition from 10 to 5000 ppm, and
(E) 0.01 to 1 part by weight of acetylenic alcohol, and
(G) 10% to 90% by weight of an organic solvent, based on the combined weight of all starting materials in the composition, provided that all starting materials in the combined composition contain 0.5:1 to 2:1 silicon bonded hydrogen atoms/silicon A pressure-sensitive adhesive composition comprising a molar ratio of bonded alkenyl groups (SiH::alkenyl ratio). 2. The composition according to claim 1, wherein the composition has the (H) unit formula (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ HSiO _2/2 ) _z (subscript (z) is 200 to 250) and the starting materials A composition further comprising, based on the weight of (C), up to 20% by weight of additional polyalkylhydrogensiloxane. 3. Composition according to claim 1 or 2, wherein the starting material (C) contains 0 to 1% by weight of silicon bonded hydrogen (SiH). The method according to any one of claims 1 to 3, wherein (B) the unit formula (R ¹ ₂ R ³ SiO _1/2 ) _a (R ¹ ₃ SiO _1/2 ) _b (SiO _4/2 ) _c (each R ¹ is independently an alkyl group of 1 to 10 carbon atoms; each R ³ is independently selected from R ¹ , OH, and an alkenyl group of 2 to 6 carbon atoms; subscript (a) ≥ 0, subscript(b) ≥ 0, subscript(c) > 0, where (a+b) > 0, and subscripts (a, b, and c) are 0.9 ≤ (a+b)/c It has a value such that ≤ 1.2) and further comprises 15 parts by weight or less of a polyalkylsiloxane resin. The composition according to any one of claims 1 to 4, further comprising (D) not more than 1 part by weight of an anchorage additive. The method of claim 5, wherein the starting material (D) is (D-1) vinyltriacetoxysilane, (D-2) glycidoxypropyltrimethoxysilane, (D-3) 2-(3,4-epoxy) Cyclohexyl)ethyltrimethoxysilane, (D-4) a combination of two or more of (D-1), (D-2) and (D-3); and (D-5) a group consisting of a combination of any of (D-1), (D-2), (D-3) and/or (D-4), and terminated with a hydroxyl group or a methoxy group. or is selected from polydimethylsiloxane terminated with both hydroxy and methoxy groups. 7. The composition according to any one of claims 1 to 6, wherein the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer (A) contains 0.2% to 0.26% of alkenyl groups. The method according to any one of claims 1 to 7, wherein the poly(dialkylsiloxane/alkylalkenylsiloxane) copolymer (A) has the unit formula (R ¹ ₂ R ² SiO _1/2 ) _d (R ¹ ₃ SiO _1/2 ) _e (R ¹ R ² SiO _2/2 ) _f (R ¹ ₂ SiO _2/2 ) _g (each R ¹ is independently an alkyl group of 1 to 10 carbon atoms; R ² is independently is an alkenyl group of 2 to 6 carbon atoms; subscript (d) ≥ 0, subscript (e) ≥ 0, subscript (f) > 0, subscript (g) ≥ 0, where (d+ e) = 2 and (d+e+f+g) is 4,500 to 5,000. The method according to any one of claims 1 to 8, wherein the starting material (F) is (F-1) a platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium and iridium; (F-2) Compounds of platinum group metals; (F-3) a complex of the above compound with a low molecular weight organopolysiloxane, (F-4) a compound (F-2) microencapsulated in a matrix or core/shell-type structure, or a complex (F-3) selected from the group consisting of A composition. The method according to any one of claims 1 to 9, wherein the starting material (E) is (E-1) 1-ethynyl-1-cyclohexanol, (E-2) methyl butynol, (E-3) A composition selected from the group consisting of diallyl maleate, and (E-4) a combination of two or more of (E-1), (E-2), and (E-3). 11. The composition according to any one of claims 1 to 10, wherein the starting material (G) is selected from the group consisting of benzene, toluene, heptane, xylene, and combinations of two or more thereof. 12. The method of any one of claims 1 to 11, wherein the composition is a multi-part composition comprising a base part and a curing agent part, wherein the base part comprises starting material (A), starting material (C), and starting material (G). ); wherein the curing agent part comprises starting material (A), starting material (F), and starting material (G); wherein the composition comprises starting material in at least one of the base part or a separate third part; A composition further comprising (E). A method for producing a pressure-sensitive adhesive tape comprising a pressure-sensitive adhesive film on the surface of a substrate, comprising:
Optionally, 1) treating the surface of the substrate,
2) Applying the pressure-sensitive adhesive composition of any one of claims 1 to 12 on the surface of the substrate,
optionally 3) removing all or part of the solvent, and
4) curing the pressure-sensitive adhesive composition to form a pressure-sensitive adhesive film on the surface of the substrate. A method of manufacturing a flexible organic light emitting diode device, comprising performing the method steps of claim 13, thereby producing a pressure-sensitive adhesive tape, and applying the pressure-sensitive adhesive tape to a passivation layer in the device. method. Use of the pressure-sensitive adhesive tape produced by the method of claim 13 for the protection of a passivation layer in a flexible organic light-emitting diode device.