Silicone-based adhesive protective film and optical member comprising the same

Abstract

A polysiloxane adhesive protective film and an optical element comprising the same. The polysiloxane adhesive protective film is formed from a composition comprising an alkenyl-containing organic polysiloxane mixture, an organic polysiloxane resin, a crosslinking agent, and a hydrogenated silanizing catalyst, wherein the organic polysiloxane resin comprises at least one of organic polysiloxane resins containing RaRbRcSiO1 / 2 units and SiO4 / 2 units, and wherein Ra, Rb, and Rc are each independently C1 to C6 alkyl or C2 to C10 alkenyl.

Description

[Technical Field]

[0001] This invention relates to a polysiloxane-based adhesive protective film and an optical element including the same. [Cross Reference to Related Applications]

[0002] This application claims the rights of Korean Patent Application No. 10-2019-0048753, filed on April 25, 2019, with the Korean Intellectual Property Office, and Korean Patent Application No. 10-2019-0049625, filed on April 29, 2019, the entire disclosure of which is incorporated herein by reference. [Previous Technology]

[0003] The environments in which optical displays are used, stored, and manufactured are becoming increasingly demanding. Furthermore, there is growing interest in new optical displays (such as wearable devices, foldable devices, etc.). As a result, adhesive protective films used to protect the panels of optical displays need to possess a variety of properties. In particular, with the development of panels with compact structures and high flexibility, there is a need to develop adhesive protective films that cause less damage to the panel and less change in its properties when the protective film is removed, even under harsh conditions.

[0004] Therefore, acrylate or urethane acrylate-based adhesive protective films have been developed in this technology. However, when the acrylate or urethane acrylate-based adhesive protective film is left on the adherend for a long time, the peel strength of the adhesive protective film to the adherend will increase excessively, resulting in damage and / or deformation of the adherend when the adhesive protective film is removed from the adherend, and at the same time, the handleability will deteriorate due to the difficulty in removing the protective film.

[0005] The background technology of the present invention is disclosed in Korean Patent Publication No. 2012-0050136, etc. [Summary of the Invention]

[0006] One object of the present invention is to provide a polysiloxane adhesive protective film that provides good protection for the adhered material, provides a low peel strength increase rate, good wettability and good step embedding properties.

[0007] Another object of the present invention is to provide a polysiloxane adhesive protective film that can prevent contamination and damage to the adhered material when the polysiloxane adhesive protective film is removed from the adhered material.

[0008] One aspect of the present invention relates to a polysiloxane adhesive protective film.

[0009] The polysiloxane adhesive protective film is formed from a composition comprising an alkenyl-containing organic polysiloxane mixture, an organic polysiloxane resin, a crosslinking agent, and a hydrogenated silanizing catalyst, wherein the alkenyl-containing organic polysiloxane mixture comprises a mixture of component (i) and component (ii), component (i): an organic polysiloxane having at least one silicon bond of a C3 to C10 alkenyl group, and component (ii): an organic polysiloxane having at least one silicon bond of a vinyl group; and the organic polysiloxane resin comprises at least one of organic polysiloxane resins comprising RaRbRcSiO1 / 2 units (Ra, Rb, and Rc are each independently C1 to C6 alkyl or C2 to C10 alkenyl) and SiO4 / 2 units.

[0010] The polysiloxane adhesive protective film may have a peel strength increase rate of 50% or less, calculated by Equation 1: [Equation 1] Peel strength increase rate = (P2 - P1) / P1 × 100, where P1 represents the initial peel strength of the polysiloxane adhesive protective film relative to the adhered object in the sample of the polysiloxane adhesive protective film and the adhered object (unit: grams per inch); and P2 represents the peel strength of the polysiloxane adhesive protective film relative to the adhered object of the sample measured after the sample has been stored at 23°C and 50% relative humidity (RH) for 14 days (unit: grams per inch).

[0011] The polysiloxane adhesive protective film may have a peel strength increase rate of 100% or less than 100% calculated by Equation 1-1: [Equation 1-1] Peel strength increase rate = (P3 - P1) / P1 × 100, where P1 represents the initial peel strength of the polysiloxane adhesive protective film relative to the adhered object in the sample of the polysiloxane adhesive protective film and the adhered object (unit: grams per inch); and P3 represents the peel strength of the polysiloxane adhesive protective film relative to the adhered object of the sample measured after the sample has been placed at 50°C for 7 days (unit: grams per inch).

[0012] The polysiloxane adhesive protective film may have a residual peel strength variation rate of less than 20% calculated by Equation 2: [Equation 2] Residual peel strength variation rate = (1 - (M2 / M1)) × 100, Where M1 represents the peel strength of the adhesive tape relative to the substrate (unit: grams per inch); and M2 represents the peel strength of the adhesive tape relative to the substrate when the adhesive film is removed from the sample (unit: grams per inch), the peel strength being measured after removing the polysiloxane adhesive protective film from the sample and attaching the adhesive tape to the surface of the sample from which the polysiloxane adhesive protective film has been removed, and leaving it at 23°C and 50% relative humidity (RH) for 24 hours, wherein the sample is prepared by attaching the polysiloxane adhesive protective film and release film to the substrate via the polysiloxane adhesive protective film, and leaving it at 50°C for 14 days.

[0013] The polysiloxane adhesive protective film may have a residual peel strength reduction rate of -50% or greater than -50% calculated by Equation 2-1: [Equation 2-1] Residual peel strength reduction rate = (M3 – M4) / M4 × 100, Wherein M3 represents the peel strength of the adhesive tape (in grams per inch) when the adhesive film is removed from the substrate of the sample, the peel strength being measured after the polysiloxane adhesive protective film is removed from the sample and the adhesive tape is attached to the surface of the sample from which the polysiloxane adhesive protective film has been removed, and the sample is left at 25°C for 30 minutes, wherein the sample is prepared by attaching the polysiloxane adhesive protective film and release film to the substrate via a stack of the polysiloxane adhesive protective film, left at 50°C for 7 days, and cooled at 25°C for 30 minutes; and M4 represents the peel strength of the adhesive tape relative to the initial substrate without the polysiloxane adhesive protective film attached (in grams per 25 millimeters).

[0014] The polysiloxane adhesive protective film may have a peel strength of 3 g / inch or less relative to the adherend.

[0015] In component (i), the C3 to C10 alkenyl group may be hexenyl.

[0016] Hexenyl can be 5-hexenyl.

[0017] Component (i) may include an organic polysiloxane represented by Formula 1.

[0018] [Formula 1] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y, In Formula 1, R1 is a C3 to C10 alkenyl group; R2 is a C1 to C10 alkyl group; R3 and R4 are each independently a C1 to C10 alkyl group; and 0>x≤1, 0≤y>1, and x+y=1.

[0019] In Equation 1, x and y can satisfy 0.001≤x≤0.4 and 0.6≤y≤0.999.

[0020] Component (ii) may include at least one of the organopolysiloxanes represented by Formula 2, Formula 3 and Formula 4.

[0021] [Formula 2] R5R6R7SiO(R1R2SiO2 / 2)x(R3R4SiO2 / 2)ySiR8R9R10, In Formula 2, R1, R2, R3 and R4 are each independently C1 to C10 alkyl; R5, R6 and R7 are each independently vinyl or C1 to C10 alkyl, and at least one of R5, R6 and R7 is vinyl; R8, R9 and R10 are each independently vinyl or C1 to C10 alkyl, and at least one of R8, R9 and R10 is vinyl; and 0≤x≤1, 0≤y≤1, and x+y=1.

[0022] [Equation 3] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y(R5R6SiO2 / 2)z, In Equation 3, R1, R2, R3, R4, R5, and R6 are each independently C1 to C10 alkyl, vinyl, or C6 to C10 aryl, and at least one of R1 and R2 is vinyl; and 0>x≤1, 0≤y>1, 0≤z>1, and x+y+z=1.

[0023] [Formula 4] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y, In Formula 4, R1, R2, R3 and R4 are each independently C1 to C10 alkyl, vinyl or C6 to C10 aryl, at least one of R1 and R2 is vinyl; and 0>x≤1, 0≤y>1, and x+y=1.

[0024] The organopolysiloxane of Formula 2 may be Vi(CH3)2SiO-((CH3)2SiO2 / 2)n-Si(CH3)2Vi [Vi is a vinyl group, and n is an integer greater than 0 to 5,000].

[0025] In Formula 3, both R3 and R4 can be C6 to C10 aryl; both R5 and R6 can be C1 to C10 alkyl, and x, y and z satisfy the following relationships: 0>x>1, 0>y>1, 0>z>1, and x+y+z=1.

[0026] In Formula 4, both R3 and R4 can be C1 to C10 alkyl groups, and x, y and z satisfy the following relationships: 0>x>1, 0>y>1, and x+y=1.

[0027] Relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture, component (i) may be present in an amount of 10 parts by weight to 70 parts by weight, and component (ii) may be present in an amount of 30 parts by weight to 90 parts by weight.

[0028] In the organic polysiloxane resin, at least one of Ra, Rb and Rc of the organic polysiloxane resin may be C2 to C10 alkenyl.

[0029] In the organic polysiloxane resin, the RaRbRcSiO1 / 2 unit and the SiO4 / 2 unit may exist in the organic polysiloxane resin in a molar ratio of 0.25:1 to 2.5:1 (RaRbRcSiO1 / 2 unit: SiO4 / 2 unit).

[0030] The organopolysiloxane resin may include a mixture of component (iii) and component (iv): Component (iii): an organopolysiloxane resin comprising RaRbRcSiO1 / 2 units (Ra, Rb and Rc are each independently C1 to C6 alkyl or C2 to C10 alkenyl, at least one of Ra, Rb and Rc is C2 to C10 alkenyl) (M unit) and SiO4 / 2 units (Q unit), and component (iv): an organopolysiloxane resin comprising RdReRfSiO1 / 2 units (Rd, Re and Rf are each independently C1 to C6 alkyl) (M unit) and SiO4 / 2 units (Q unit).

[0031] The organopolysiloxane resin may be present in an amount from 0.01 parts by weight to 20 parts by weight relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture.

[0032] The composition may further include an anchoring agent.

[0033] Another aspect of the present invention relates to an optical element comprising: an optical film and a polysiloxane adhesive protective film according to the present invention formed on a surface of the optical element.

[0034] The present invention provides a polysiloxane adhesive protective film that provides good protection for the adhered material, provides a low peel strength increase rate, good wettability and good step embedding properties.

[0035] The present invention provides a polysiloxane adhesive protective film that can prevent contamination and damage to the adhered material when it is peeled off.

Implementation Method

[0036] Embodiments of the present invention will now be described in detail with reference to the accompanying drawings. However, it should be understood that the present invention is not limited to the following embodiments, but can be implemented in different ways. The following embodiments are provided to give those skilled in the art a thorough understanding of the present invention.

[0037] In this document, "C3 to C10 alkenyl" refers to C3 to C10 monoalkenyl, such as propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.

[0038] In this document, in the “C3 to C10 alkenyl”, the alkenyl group may be bonded to silicon in the organopolysiloxane to be located at its distal end.

[0039] In this document, "hexenyl" (Hex) may be 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. Preferably, the hexenyl is 5-hexenyl (*-(CH2)4-CH=CH2, * is the silicon linkage site).

[0040] In this document, “vinyl” (Vi) means *-CH=CH2 (* is the linking site).

[0041] In this document, "Me" may be methyl and "Ph" may be phenyl.

[0042] In this document, "adhesive" may include a glass plate or a plastic film, such as a polyimide film, an acrylic film, a polyacrylamide film, etc. Preferably, the adhesive is a glass plate or a polyimide film.

[0043] In this document, "peel strength" can be measured using a tensile strength tester according to JIS Z2037 at a peel speed of 2,400 mm / min, a peel angle of 180° and a peel temperature of 25°.

[0044] As used in this document to represent a specific numerical range, the expression "X to Y" means a value that is greater than or equal to X and less than or equal to Y (X ≤ and ≤ Y).

[0045] The inventors of the present invention have developed a polysiloxane adhesive protective film using a composition comprising an alkenyl-containing organic polysiloxane mixture, an organic polysiloxane resin mixture, a crosslinking agent, and a hydrogenated silanizing catalyst.

[0046] According to the present invention, the polysiloxane adhesive protective film has good peel strength relative to the substrate, providing a good effect in protecting the substrate, and the peel strength increases less over time when attached to the substrate, thereby providing good storage stability without deforming and / or damaging the substrate when the polysiloxane adhesive protective film is removed from the substrate. Furthermore, the polysiloxane adhesive protective film has good step-embedding properties and / or wettability relative to the substrate to prevent air bubbles from forming when the polysiloxane adhesive protective film is attached to the substrate, thereby providing good handleability when cutting the stack of the polysiloxane adhesive protective film and the substrate. In addition, the polysiloxane adhesive protective film prevents contamination or damage to the substrate when the polysiloxane adhesive protective film is removed from the substrate, thereby providing good handleability.

[0047] Hereinafter, a polysiloxane adhesive protective film according to an embodiment of the present invention will be described.

[0048] The polysiloxane adhesive protective film is formed from a composition comprising an alkenyl-containing organic polysiloxane mixture, an organic polysiloxane resin, a crosslinking agent, and a hydrogenated silanization catalyst, wherein the alkenyl-containing organic polysiloxane mixture comprises a mixture of component (i) and component (ii), and the organic polysiloxane resin comprises at least one organic polysiloxane resin comprising RaRbRcSiO1 / 2 units (Ra, Rb, and Rc will be described in detail below) and SiO4 / 2 units: Component (i): an organic polysiloxane having at least one silicon bond with a C3 to C10 alkenyl group, and component (ii): an organic polysiloxane having at least one silicon bond with a vinyl group.

[0049] Component (i) and component (ii) are distinguished based on the number of carbon atoms in the alkenyl group of the silicon bond.

[0050] When the alkenyl-containing organopolysiloxane mixture contains only component (i) and not component (ii), the polysiloxane adhesive protective film is brittle and exhibits poor properties in terms of peel strength, wettability, cutability, and step embedding properties. When the alkenyl-containing organopolysiloxane mixture contains only component (ii) and not component (i), the polysiloxane adhesive protective film exhibits an excessive rate of increase in peel strength, which leads to deformation and / or damage to the adhered object upon removal of the polysiloxane adhesive protective film, thereby deteriorating the storage stability of the polysiloxane adhesive protective film. When the composition contains only an alkenyl-containing organopolysiloxane mixture without an organopolysiloxane resin, the polysiloxane adhesive protective film is brittle, exhibiting poor properties in terms of peel strength, wettability, and cutability, and allowing for excessive peel strength gain. This leads to deformation and / or damage to the adhered object upon removal of the polysiloxane adhesive protective film, thereby deteriorating the storage stability of the polysiloxane adhesive protective film. >Alkenyl-containing organopolysiloxane mixture>

[0051] A matrix for forming a polysiloxane adhesive protective film by an alkenyl-containing organic polysiloxane mixture.

[0052] In one embodiment, the alkenyl-containing organopolysiloxane mixture comprises component (i) and component (ii) to form a polysiloxane adhesive protective film with a peel strength of 3 gf / inch or less and a peel strength increase rate of 50% or less calculated by Equation 1, wherein the polysiloxane adhesive protective film has good peel strength relative to the adherend to provide good protection for the adherend and can prevent damage and / or deformation of the adherend by allowing easy removal of the polysiloxane adhesive protective film from the adherend. [Equation 1] Peel strength increase rate = (P2 - P1) / P1 × 100, where P1 represents the initial peel strength of the polysiloxane adhesive protective film relative to the adhered object in the sample of polysiloxane adhesive protective film and adhered object (unit: grams per inch); and P2 represents the peel strength of the polysiloxane adhesive protective film relative to the adhered object measured after the sample was placed at 23°C and 50% relative humidity for 14 days (unit: grams per inch).

[0053] In this document, "initial peel strength" refers to the peel strength of the polysiloxane adhesive protective film relative to the adherend before the sample is stored at 23°C and 50% RH for 14 days.

[0054] In one embodiment, the polysiloxane adhesive protective film may have a peel strength relative to the adherend greater than 0 g / inch to 3 g / inch, for example, 1 g / inch to 3 g / inch. A polysiloxane adhesive protective film with a peel strength of 1 g / inch to 3 g / inch can further improve the protection of the adherend.

[0055] In one embodiment, the polysiloxane adhesive protective film may have a peel strength increase rate of 0% to 40% calculated by Equation 1. For example, the polysiloxane adhesive protective film may have a peel strength increase rate of 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50% calculated by Equation 1.

[0056] In Equation 1, each of P1 and P2 may be 3 g / inch or less than 3 g / inch, preferably greater than 0 g / inch to 3 g / inch, for example, 1 g / inch to 3 g / inch.

[0057] In one embodiment, the polysiloxane adhesive protective film may have a peel strength increase rate of 100% or less, for example 0% to 100%, or for example 5% to 100%, calculated by Equation 1-1. [Equation 1-1] Peel strength increase rate = (P3 - P1) / P1 × 100, where P1 represents the initial peel strength of the polysiloxane adhesive protective film relative to the adhered object in the sample of the polysiloxane adhesive protective film and the adhered object (in grams per inch); and P3 represents the peel strength of the polysiloxane adhesive protective film relative to the adhered object of the sample measured after the sample has been stored at 50°C for 7 days (in grams per inch).

[0058] For example, the polysiloxane-based adhesive protective film may have the following values ​​calculated by Equation 1-1: 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%. Peel strength increase rates of 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100%.

[0059] In Equation 1, each of P1 and P3 may be in the range of greater than 0 g / inch to 3 g / inch, for example, from 1 g / inch to 3 g / inch.

[0060] In one embodiment, the polysiloxane adhesive protective film may have a residual peel strength variation rate of less than 20%, for example, from 0% to 15%, calculated by Equation 2. Within this range, the polysiloxane adhesive protective film can prevent contamination and damage to the adhered object when the polysiloxane adhesive protective film is removed from the adhered object after it has been applied to it. [Equation 2] Residual peel strength change rate = (1 - (M2 / M1)) × 100, where M1 represents the peel strength of the adhesive tape relative to the substrate (unit: grams per inch); and M2 represents the peel strength of the adhesive tape relative to the substrate when the adhesive film is removed from the sample (unit: grams per inch), said peel strength is measured after removing the polysiloxane adhesive protective film from the sample and attaching the adhesive tape to the surface of the sample from which the polysiloxane adhesive protective film has been removed, and leaving it at 23°C and 50% RH for 24 hours, wherein the sample is prepared by attaching the polysiloxane adhesive protective film and release film stacked to the substrate via the polysiloxane adhesive protective film and leaving it at 50°C for 14 days.

[0061] For example, the polysiloxane adhesive protective film may have a residual peel strength variation rate of 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15% calculated by Equation 2.

[0062] The adhesive tape may be a typical adhesive tape with adhesive properties. For example, the adhesive tape may be Nitto 31B adhesive tape. In one embodiment, M1 may be in the range of 800 g / inch to 1,000 g / inch.

[0063] In one embodiment, the polysiloxane adhesive protective film may have a residual peel strength reduction rate of -50% or greater than -50%, preferably -45% to 0%, calculated by Equation 2-1. Within this range, the polysiloxane adhesive protective film can prevent contamination and damage to the substrate when the polysiloxane adhesive protective film is removed from the substrate after it has been applied to it. [Equation 2-1] Residual peel strength reduction rate = (M3 – M4) / M4 × 100, where M3 represents the peel strength of the adhesive tape (in grams per inch) when the adhesive film is removed from the substrate of the sample, the peel strength being measured after the polyoxymethylene adhesive protective film is removed from the sample and the adhesive tape is attached to the surface of the sample from which the polyoxymethylene adhesive protective film has been removed, and the sample is prepared by attaching a stack of polyoxymethylene adhesive protective film and release film to the substrate via the polyoxymethylene adhesive protective film, leaving it at 50°C for 7 days and cooling it at 25°C for 30 minutes; and M4 represents the peel strength of the adhesive tape relative to the initial substrate without the polyoxymethylene adhesive protective film attached (in grams per 25 mm).

[0064] In one embodiment, M4 may be in the range of 650 gf / inch to 1,100 gf / inch.

[0065] For example, the polysiloxane adhesive protective film may have a residual peel strength reduction rate of -45%, -44%, -43%, -42%, -41%, -40%, -39%, -38%, -37%, -36%, -35%, -34%, -33%, -32%, -31%, -30%, -29%, -28%, -27%, -26%, -25%, -24%, -23%, -22%, -21%, -20%, -19%, -18%, -17%, -16%, -15%, -14%, -13%, -12%, -11%, -10%, -9%, -8%, -7%, -6%, -5%, -4%, -3%, -2%, -1%, or 0% calculated by Equation 2-1.

[0066] Alkenyl-containing organopolysiloxane mixtures containing only component (i) but not component (ii) can lead to deterioration of the wettability of polysiloxane adhesive protective films, thereby providing poor handleability. Alkenyl-containing organopolysiloxane mixtures containing only component (ii) but not component (i) can lead to an increase in the rate of increase in peel strength and the rate of change in residual peel strength of polysiloxane adhesive protective films.

[0067] In the polysiloxane adhesive protective film, component (i) is used together with component (ii) to ensure the peel strength, peel strength increase rate and residual peel strength change rate of the polysiloxane adhesive protective film by preventing excessive increase in the peel strength of the polysiloxane adhesive protective film.

[0068] In component (i), the C3 to C10 alkenyl group is preferably hexenyl, more preferably 5-hexenyl. The 5-hexenyl group is bonded to the silicon in the organopolysiloxane and has an alkenyl group at the distal end of the silicon to ensure a rapid curing speed, thereby increasing the curing density, while controlling the change in peel strength over time.

[0069] Component (i) is a linear organopolysiloxane having at least one silicon bond with a C3 to C10 alkenyl group, and may include at least one diorganosiloxane unit having a C3 to C10 alkenyl group.

[0070] For example, component (i) may contain R1R2SiO2 / 2 units, wherein R1 may be a C3 to C10 alkenyl and R2 may be a C1 to C10 alkyl, such as methyl, ethyl or propyl.

[0071] The R1R2SiO2 / 2 units of component (i) may be present in the organopolysiloxane in an amount of 0.01 mmol / g to 0.5 mmol / g, preferably 0.1 mmol / g to 0.3 mmol / g. Within this range, the polysiloxane adhesive protective film may have a suitable curing density.

[0072] In one embodiment, component (i) may be an organic polysiloxane represented by Formula 1.

[0073] [Formula 1] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y, In Formula 1, R1 is a C3 to C10 alkenyl group; R2 is a C1 to C10 alkyl group; R3 and R4 are each independently a C1 to C10 alkyl group; and 0>x≤1, 0≤y>1, and x+y=1.

[0074] Preferably, in the organic polysiloxane mixture, component (i) is a monobasic organic polysiloxane.

[0075] In one embodiment, component (i) may include an organopolysiloxane comprising Hex(CH3)SiO2 / 2 units and (CH3)2SiO2 / 2 units.

[0076] In one embodiment, component (i) may include an organic polysiloxane composed of Hex(CH3)SiO2 / 2 units and (CH3)2SiO2 / 2 units.

[0077] In one embodiment, component (i) may be free of vinyl-bonded siloxanes, such as vinyl-bonded dialkoxysilanes, vinyl-bonded trialkoxysilanes, or vinyl-bonded monoalkoxysilanes.

[0078] In one embodiment, component (i) may not contain SiO4 / 2 units (Q units).

[0079] In one embodiment, component (i) may be an end-capped organic polysiloxane represented by formula 1-1.

[0080] [Formula 1-1] R5R6R7SiO(R1R2SiO2 / 2)x(R3R4SiO2 / 2)ySiR8R9R10, In Formula 1-1, R1 is a C3 to C10 alkenyl group; R2 is a C1 to C10 alkyl group; R3 and R4 are each independently a C1 to C10 alkyl group; R5, R6, R7, R8, R9 and R10 are each independently a C1 to C10 alkyl group; and 0>x≤1, 0≤y>1, and x+y=1.

[0081] In the organopolysiloxane of Formula 1 or Formula 1-1, the R1R2SiO2 / 2 unit may be present in an amount of 0.01 mmol / g to 0.5 mmol / g, preferably 0.1 mmol / g to 0.3 mmol / g. Within this range, the polysiloxane adhesive protective film may have a suitable curing density.

[0082] The organopolysiloxane of Formula 1 or Formula 1-1 or component (i) may have a weight average molecular weight of 50,000 to 200,000, preferably 70,000 to 150,000. Within this range, the polysiloxane adhesive protective film may have suitable curing density and wettability.

[0083] Preferably, in Equation 1 or Equation 1-1, x, y, and z satisfy the following relationships: 0.001 ≤ x ≤ 0.4, 0.6 ≤ y ≤ 0.999, and x + y = 1; more preferably, 0.005 ≤ x ≤ 0.2, 0.8 ≤ y ≤ 0.995, and x + y = 1. Within this range, the polysiloxane adhesive protective film can have a low peel strength increase rate and can suppress contamination of the adhered object when the polysiloxane adhesive protective film is removed from the adhered object.

[0084] The organopolysiloxane of Formula 1 or Formula 1-1 may have a weight average molecular weight of 100,000 to 800,000, preferably 200,000 to 700,000. Within this range, the polysiloxane adhesive protective film may have a low peel strength increase rate and may suppress contamination of the adhered material when the polysiloxane adhesive protective film is removed from the adhered material.

[0085] Preferably, in the organic polysiloxane mixture, component (i) is a monobasic organic polysiloxane.

[0086] Preferably, component (i) may include an organopolysiloxane comprising Hex(CH3)SiO2 / 2 units and (CH3)2SiO2 / 2 units.

[0087] Preferably, component (i) may include an organic polysiloxane composed of Hex(CH3)SiO2 / 2 units and (CH3)2SiO2 / 2 units.

[0088] Component (i) can be (CH3)3SiO-(Hex(CH3)SiO2 / 2)x((CH3)2SiO2 / 2)y-Si(CH3)3 (0>x≤1, 0≤y>1, x+y=1).

[0089] In one embodiment, component (i) may not contain SiO4 / 2 units (Q units).

[0090] Relative to a total of 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii), component (i) may be present in an amount of 10 to 70 parts by weight, preferably 20 to 60 parts by weight. Within this range, the polysiloxane adhesive protective film may have good wettability and suppress changes in peel strength over time.

[0091] Component (i) can be prepared by hydrolysis and condensation of alkoxysilanes providing R1R2SiO2 / 2 units and R3R4SiO2 / 2 units using methods known to those skilled in the art.

[0092] Relative to a total of 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii), component (i) may be present in an amount of 10 parts by weight to 70 parts by weight, preferably 30 parts by weight to 70 parts by weight, and more preferably 40 parts by weight to 60 parts by weight. Within this range, the polysiloxane adhesive protective film can have good wettability and suppress changes in peel strength over time while ensuring good step-in-place properties. For example, component (i) can be 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, or 39 parts by weight. It is present in amounts of 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 parts by weight.

[0093] In the polysiloxane adhesive protective film, component (ii) can work together with component (i) to increase the peel strength of the polysiloxane adhesive protective film, so as to ensure the peel strength of the present invention while improving wettability.

[0094] Component (ii) is a linear organopolysiloxane having a vinyl group, and may include at least one diorganosiloxane unit having a vinyl group.

[0095] In one embodiment, component (ii) may be an organopolysiloxane of vinyl having at least one silicon bond at its side chain or at its two ends.

[0096] For example, component (ii) may contain R5R6R7SiO- at the distal end of the organopolysiloxane, wherein R5, R6, and R7 are each independently vinyl or C1 to C10 alkyl, and at least one of R5, R6, and R7 is vinyl.

[0097] Component (ii) is a linear organopolysiloxane and may include two organosiloxane units.

[0098] In one embodiment, component (ii) may not contain SiO4 / 2 units (Q units).

[0099] In one embodiment, component (ii) may comprise an organopolysiloxane of vinyl groups having at least one silicon bond at both ends thereof. For example, component (ii) may be an organopolysiloxane represented by Formula 2.

[0100] [Formula 2] R5R6R7SiO(R1R2SiO2 / 2)x(R3R4SiO2 / 2)ySiR8R9R10, In Formula 2, R1, R2, R3 and R4 are each independently C1 to C10 alkyl; R5, R6 and R7 are each independently vinyl or C1 to C10 alkyl, at least one of R5, R6 and R7 is vinyl; R8, R9 and R10 are each independently vinyl or C1 to C10 alkyl, at least one of R8, R9 and R10 is vinyl; and 0≤x≤1, 0≤y≤1, and x+y=1.

[0101] Component (ii) or the organopolysiloxane represented by Formula 2 may have a vinyl equivalent weight of 0.01 mmol / g to 0.5 mmol / g, preferably 0.1 mmol / g to 0.3 mmol / g. Within this range, the polysiloxane adhesive protective film may have suitable reaction rate and reactivity.

[0102] Component (ii) represented by Formula 2 or the organopolysiloxane may have a weight average molecular weight of 100,000 to 300,000, preferably 200,000 to 300,000, more preferably 20,000 to 300,000, and even more preferably 30,000 to 50,000. Within this range, the polysiloxane adhesive protective film may have suitable reactivity.

[0103] Preferably, the organopolysiloxane represented by Formula 2 comprises Vi(CH3)2SiO-((CH3)2SiO2 / 2)n-Si(CH3)2Vi (n is an integer greater than 0 to 5,000).

[0104] In another embodiment, component (ii) may be an organopolysiloxane comprising at least silicon-bonded vinyl groups at its side chains. For example, component (ii) may be an organopolysiloxane represented by Formula 3.

[0105] [Equation 3] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y(R5R6SiO2 / 2)z, In Equation 3, R1, R2, R3, R4, R5 and R6 are each independently C1 to C10 alkyl, vinyl or C6 to C10 aryl, at least one of R1 and R2 is vinyl; and 0≤x≤1, 0≤y≤1, 0≤z>1, x+y+z=1.

[0106] In one embodiment, at least one of R3 and R4, preferably both R3 and R4, may be C6 to C10 aryl.

[0107] In one embodiment, at least one of R5 and R6, preferably both R5 and R6, may be C1 to C10 alkyl.

[0108] Preferably, the organopolysiloxane represented by Formula 3 comprises (Vi(CH3)SiO2 / 2)x-((CH3)2SiO2 / 2)y-(Ph2SiO2 / 2)z.

[0109] In one embodiment, the organopolysiloxane represented by Formula 3 may be an end-capped organopolysiloxane represented by Formula 3-1.

[0110] [Formula 3-1] R7R8R9SiO(R1R2SiO2 / 2)x(R3R4SiO2 / 2)y(R5R6SiO2 / 2)zSiR10R11R12, In Formula 3-1, R1, R2, R3, R4, R5 and R6 are each independently C1 to C10 alkyl, vinyl or C6 to C10 aryl, and at least one of R1 and R2 is vinyl; R7, R8, R9, R10, R11 and R12 are each independently C1 to C10 alkyl; and 0>x≤1, 0≤y>1, 0≤z>1, and x+y+z=1.

[0111] Component (ii) or the organopolysiloxane represented by Formula 3 or Formula 3-1 may have a vinyl equivalent weight of 0.01 mmol / g to 0.5 mmol / g, preferably 0.1 mmol / g to 0.3 mmol / g. Within this range, the polysiloxane adhesive protective film may have suitable reaction rate and reactivity.

[0112] Preferably, the organopolysiloxane represented by Formula 3-1 includes organopolysiloxanes comprising (CH3)3SiO-(Vi(CH3)SiO2 / 2)x-((CH3)2SiO2 / 2)y-(Ph2SiO2 / 2)z-Si(CH3)3.

[0113] Component (ii) or the organopolysiloxane represented by Formula 3 or Formula 3-1 may have a weight average molecular weight of 50,000 to 800,000, preferably 100,000 to 700,000, more preferably 200,000 to 700,000, and even more preferably 100,000 to 150,000. Within this range, the polysiloxane adhesive protective film may have suitable reactivity and reduce the rate of increase in peel strength, while inhibiting contamination of the adhered material.

[0114] Preferably, in the organopolysiloxane represented by Formula 3 or Formula 3-1, x, y, and z satisfy the following relationships: 0.005≤x≤0.1, 0.001≤y≤0.2, 0.7≤z≤0.994, and x+y+z=1. Within this range, the polysiloxane adhesive protective film can reduce the rate of increase in peel strength while inhibiting contamination of the adhered material.

[0115] In another embodiment, component (ii) may be an organopolysiloxane of vinyl groups having at least one silicon bond at its side chain. For example, component (ii) may be an organopolysiloxane represented by Formula 4.

[0116] [Equation 4] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y, In Equation 4, R1, R2, R3 and R4 are each independently C1 to C10 alkyl, vinyl or C6 to C10 aryl, at least one of R1 and R2 is vinyl; and 0>x≤1, 0≤y>1, and x+y=1.

[0117] Preferably, the organopolysiloxane represented by Formula 4 includes organopolysiloxanes comprising (Vi(CH3)SiO2 / 2)x-((CH3)2SiO2 / 2)y.

[0118] For example, component (ii) may be an end-capped organic polysiloxane represented by formula 4-1.

[0119] [Formula 4-1] R5R6R7SiO(R1R2SiO2 / 2)x(R3R4SiO2 / 2)ySiR8R9R10, In Formula 4-1, R1, R2, R3 and R4 are each independently C1 to C10 alkyl, vinyl or C6 to C10 aryl, and at least one of R1 and R2 is vinyl; R5, R6, R7, R8, R9 and R10 are each independently C1 to C10 alkyl; 0>x≤1, 0≤y>1, and x+y=1.

[0120] Preferably, in the organopolysiloxane represented by Formula 4 or Formula 4-1, x, y, and z satisfy the following relationships: 0.005 ≤ x ≤ 0.1, 0.9 ≤ y ≤ 0.995, and x + y = 1. Within this range, the polysiloxane adhesive protective film can reduce the rate of increase in peel strength while inhibiting contamination of the adhered material.

[0121] Preferably, the organopolysiloxane represented by Formula 4-1 includes organopolysiloxanes comprising (CH3)3SiO-(Vi(CH3)SiO2 / 2)x-((CH3)2SiO2 / 2)y-Si(CH3)3.

[0122] Component (ii) or the organopolysiloxane represented by Formula 4 or Formula 4-1 may have a vinyl equivalent weight of 0.01 mmol / g to 0.5 mmol / g, preferably 0.1 mmol / g to 0.3 mmol / g. Within this range, the polysiloxane adhesive protective film may have suitable reaction rate and reactivity.

[0123] Component (ii) or the organopolysiloxane represented by Formula 4 or Formula 4-1 may have a weight average molecular weight of 50,000 to 800,000, more preferably 100,000 to 700,000, more preferably 150,000 to 700,000, and even more preferably 200,000 to 700,000. Within this range, the polysiloxane adhesive protective film may have suitable curing density and wettability, and may reduce the rate of increase in peel strength while inhibiting contamination of the adhered material.

[0124] Preferably, in the organic polysiloxane mixture, component (ii) is a monobasic organic polysiloxane.

[0125] Preferably, in the organic polysiloxane mixture, component (ii) consists of an organic polysiloxane represented by formula 2.

[0126] Preferably, in the organic polysiloxane mixture, component (ii) consists of an organic polysiloxane represented by formula 3.

[0127] Preferably, in the organic polysiloxane mixture, component (ii) is a mixture of organic polysiloxane represented by formula 2 and organic polysiloxane represented by formula 4.

[0128] In one embodiment, component (ii) may not contain SiO4 / 2 units (Q units).

[0129] Relative to a total of 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii), component (ii) may be present in an amount of 30 to 90 parts by weight, preferably 40 to 80 parts by weight, and more preferably 40 to 60 parts by weight. Within this range, the polysiloxane adhesive protective film may have suitable initial peel strength and good wettability, and may reduce the peel strength increase rate while inhibiting contamination of the adhered material.

[0130] For example, component (ii) may be 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight. It is present in amounts of 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 parts by weight. >Organopolysiloxane resin>

[0131] In polysiloxane adhesive protective films, organopolysiloxane resins are used to reduce the rate of increase in peel strength over time, while improving reliability and the rate of decrease in residual peel strength. Organopolysiloxane resins are also used to improve the step-intercalation properties of polysiloxane adhesive protective films.

[0132] The organopolysiloxane resin may include at least one of organopolysiloxane resins comprising RaRbRcSiO1 / 2 units (Ra, Rb and Rc are each independently C1 to C6 alkyl or C2 to C10 alkenyl) and SiO4 / 2 units.

[0133] In one embodiment, the organopolysiloxane resin includes an MQ resin comprising M units and Q units. As is known to those skilled in the art, an M unit refers to a trisubstituted SiO1 / 2 unit, and a Q unit refers to a SiO4 / 2 unit.

[0134] In one embodiment, the organopolysiloxane resin may include a mixture of a first MQ resin and a second MQ resin, the first MQ resin comprising M units and Q units having C2 to C10 alkenyl groups, and the second MQ resin comprising M units and Q units not having C2 to C10 alkenyl groups. The presence of the first MQ resin and the second MQ resin further reduces the rate of increase in peel strength of the polysiloxane adhesive protective film.

[0135] In one embodiment, the organopolysiloxane resin may include a mixture of component (iii) as a first MQ resin and component (iv) as a second MQ resin.

[0136] Component (iii): An organopolysiloxane resin containing RbRcSiO1 / 2 units (Ra, Rb and Rc will be described in detail below) (M unit) and SiO4 / 2 units (Q unit).

[0137] Component (iv): Organopolysiloxane resin containing RdReRfSiO1 / 2 units (R4, R5 and R6 will be described in detail below) (M unit) and SiO4 / 2 units (Q unit).

[0138] In the RaRbRcSiO1 / 2 unit of component (iii), Ra, Rb and Rc are each independently C1 to C6 alkyl or C2 to C10 alkenyl, such as methyl, ethyl, propyl (e.g., isopropyl and n-propyl), vinyl or allyl, and at least one of Ra, Rb and Rc may be C2 to C10 alkenyl.

[0139] In the RdReRfSiO1 / 2 unit of component (iv), Rd, Re and Rf are each independently C1 to C6 alkyl, such as methyl, ethyl or propyl (e.g. isopropyl and n-propyl).

[0140] In one embodiment, in the RaRbRcSiO1 / 2 unit of component (iii), at least one of Ra, Rb and Rc may be vinyl.

[0141] In one embodiment, in the RdReRfSiO1 / 2 unit of component (iv), at least two or three of Rd, Re and Rf may be methyl.

[0142] For example, in component (iii), the molar ratio (RaRbRcSiO1 / 2 unit:SiO4 / 2 unit) of the RaRbRcSiO1 / 2 unit and the SiO4 / 2 unit can be present in a molar ratio of 0.5:1 to 1.5:1, preferably 0.8:1 to 1.2:1. Within this range, the polysiloxane adhesive protective film can increase the curing density while ensuring a suitable modulus. Here, the "molar ratio" can be calculated based on, but is not limited to, the area ratio between the SiO1 / 2 unit and the SiO4 / 2 unit obtained by measuring the silicon nuclear magnetic resonance (NMR) of the polysiloxane adhesive protective film.

[0143] In another example, in component (iii), the molar ratio (RaRbRcSiO1 / 2 units:SiO4 / 2 units) of RaRbRcSiO1 / 2 units and SiO4 / 2 units can be present in a molar ratio of 0.25:1 to 2.5:1, preferably 0.45:1 to 2:1. Within this range, the polysiloxane adhesive protective film can reduce the rate of increase in peel strength while inhibiting contamination of the adhered material. Here, the "molar ratio" can be calculated based on, but is not limited to, the area ratio between SiO1 / 2 units and SiO4 / 2 units obtained by measuring silicon nuclear magnetic resonance with respect to the polysiloxane adhesive protective film.

[0144] In component (iii), the C2 to C10 alkenyl groups of Ra, Rb, and Rc, preferably vinyl, may be present in an amount of 0.1 mol% to 30 mol%, preferably 0.5 mol% to 20 mol%. Within this range, the polysiloxane adhesive protective film can substantially suppress the increase in peel strength over time.

[0145] In component (iii), the C2 to C10 alkenyl groups of Ra, Rb, and Rc, preferably vinyl, may be present in an amount of 0.1 mmol / g to 1.5 mmol / g, more preferably 0.5 mmol / g to 1.0 mmol / g. Within this range, the polysiloxane adhesive protective film can substantially suppress the increase in peel strength over time.

[0146] In component (iv), the RdReRfSiO1 / 2 units and SiO4 / 2 units may be present in a molar ratio (RdReRfSiO1 / 2 units:SiO4 / 2 units) of 0.5:1 to 1.5:1, preferably 0.8:1 to 1.2:1. Within this range, the polysiloxane adhesive protective film may have suitable initial peel strength.

[0147] Component (iii) may be present in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 1 to 5 parts by weight, relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii). Within this range, component (iii) may reduce unreacted groups in the alkenyl-containing organopolysiloxane mixture, thereby improving the peel strength increase rate.

[0148] Component (iv) may be present in an amount of 0.01 to 2 parts by weight, more preferably 0.05 to 2 parts by weight, and even more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii). Within this range, the polysiloxane adhesive protective film may have suitable initial peel strength.

[0149] The organopolysiloxane resin may be present in an amount from 0.01 parts by weight to 20 parts by weight, more preferably from 0.5 parts by weight to 15 parts by weight, and even more preferably from 0.5 parts by weight to 10 parts by weight, relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii). Within this range, the polysiloxane adhesive protective film may have suitable initial peel strength, and the change in peel strength over time can be controlled.

[0150] The organopolysiloxane resin may be present in an amount from 0.01 parts by weight to 20 parts by weight, more preferably from 0.1 parts by weight to 15 parts by weight, more preferably from 0.1 parts by weight to 10 parts by weight, even more preferably from 0.1 parts by weight to 7 parts by weight, even more preferably from 1 part by weight to 7 parts by weight, and even more preferably from 2 parts by weight to 7 parts by weight, relative to 100 parts by weight of the mixture of alkenyl-containing organopolysiloxanes or the mixture of components (i) and (ii) by weight. Within this range, the polysiloxane adhesive protective film can reduce the rate of increase in peel strength while inhibiting contamination of the adhered material. For example, organopolysiloxane resins may be present in amounts of 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or 20 parts by weight. >Crosslinking Agent>

[0151] The crosslinking agent may include a hydrogen organopolysiloxane having two or more silicon bonds and a hydrogen (Si-H) group. In one embodiment, the crosslinking agent may be represented by Formula 5: [Formula 5] R4R5R6SiO(R1R2SiO2 / 2)x(HR3SiO2 / 2)ySiR7R8R9, where R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently C1 to C10 alkyl groups, and 0≤x>1, 0>y≤1, and x+y=1.

[0152] The crosslinking agent may be present in an amount of 1 to 5 parts by weight, preferably 1 to 3 parts by weight, relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii). Within this range, the crosslinking agent can reduce the change in peel strength over time.

[0153] Relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii), the crosslinking agent may be present in an amount of 0.1 parts by weight to 5 parts by weight, preferably 1 part by weight to 3 parts by weight. Within this range, the crosslinking agent can reduce the change in peel strength over time. For example, the crosslinking agent may be present in amounts of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, or 5 parts by weight. >Hydrogenated Silanization Catalyst>

[0154] Hydrogenated silanizing catalysts accelerate the reaction between organopolysiloxanes and crosslinking agents. Hydrogenated silanizing catalysts may include platinum catalysts, ruthenium catalysts, or osmium catalysts. Specifically, hydrogenated silanizing catalysts may include typical platinum catalysts known to those skilled in the art. For example, hydrogenated silanizing catalysts may include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, complexes of chloroplatinic acid and olefins, complexes of chloroplatinic acid and alkenyl siloxanes, etc.

[0155] The hydrogenated silanizing catalyst may be present in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture or the mixture of component (i) and component (ii). Within this range, the crosslinking agent can suppress the change in peel strength over time. For example, the hydrogenated silanizing catalyst may be present in amounts of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, or 3 parts by weight. >Anchoring Agent>

[0156] The composition of the polysiloxane adhesive protective film may further include an anchoring agent.

[0157] The anchoring agent is used to further improve the peel strength of the polysiloxane adhesive protective film. The anchoring agent may include typical siloxane compounds known to those skilled in the art. The anchoring agent may include at least one selected from the group consisting of vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-(meth)acryloxypropyltrimethoxysilane.

[0158] The anchoring agent may be present in an amount of less than 1 part by weight, specifically from 0.05 parts by weight to less than 1 part by weight, and preferably from 0.1 parts by weight to 0.5 parts by weight, relative to 100 parts by weight of the alkenyl-containing organic polysiloxane mixture or the mixture of component (i) and component (ii). Within this range, the anchoring agent can improve the adhesion of the polysiloxane adhesive protective film to the base film.

[0159] The composition used for polysiloxane adhesive protective films may further contain organic solvents to form a thin composition layer by improving the coatability of the composition. Organic solvents may include, but are not limited to, toluene, xylene, hexane, heptane, and methyl ethyl ketone.

[0160] The composition for use in polysiloxane adhesive protective films may further include a hydrogenated silanization inhibitor. The hydrogenated silanization inhibitor is used to inhibit the reaction between the alkenyl-containing organic polysiloxane mixture and the crosslinking agent, and / or the reaction between the organic polysiloxane resin mixture and the crosslinking agent, to form a composition having a target viscosity while improving storage stability. The hydrogenated silanization inhibitor may include typical types of hydrogenated silanization inhibitors known to those skilled in the art. For example, the hydrogenated silanization inhibitor may include, but is not limited to, 3-methyl-1-butyn-1-ol and 3,5-dimethyl-1-butyn-1-ol.

[0161] Polysiloxane adhesive protective films may contain more typical additives known to those skilled in the art.

[0162] The polysiloxane adhesive protective film may have a tensile strength of 0.5 MPa to 10 MPa, preferably 0.7 MPa to 7 MPa, and more preferably 1.5 MPa to 7 MPa. Within this range, the polysiloxane adhesive protective film may have good wettability and step-in embedding properties.

[0163] Polysiloxane adhesive protective films may have a haze of 5% or less, for example, 0% to 1%. Within this range, polysiloxane adhesive protective films can be applied to optical displays.

[0164] The polysiloxane adhesive protective film may have a thickness of 100 micrometers or less, for example 75 micrometers or less, or greater than 0 micrometers up to 75 micrometers. Within this thickness range, the polysiloxane adhesive protective film can protect the adhered object, and when the polysiloxane adhesive protective film is attached to the adhered object, it can be easily removed from it.

[0165] The polysiloxane adhesive protective film can be formed from the composition for the polysiloxane adhesive protective film. Each component of the composition for the polysiloxane adhesive protective film according to the present invention can be obtained by means of methods known to those skilled in the art, or can be obtained from commercially available products in the art.

[0166] An optical element according to an embodiment of the present invention includes an optical film and an adhesive protective film formed on at least one surface of the optical film, wherein the adhesive protective film may include a polysiloxane adhesive protective film according to an embodiment of the present invention.

[0167] The optical film is a display panel and may include a polyimide film. In one embodiment, the optical film may include a light-emitting element layer and a polyimide film formed on at least one surface of the light-emitting element layer. An organic insulating layer or an inorganic insulating layer may be further formed between the optical film and the polysiloxane adhesive protective film. The optical element may further include a release film (pad) located on another surface of the polysiloxane adhesive protective film. The release film prevents contamination of the adhesive protective film due to foreign matter, etc. As the release film, an optical film formed of the same material as or different from the above-described optical film may be used. For example, the release film may be formed of at least one resin selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, polyimide resin, poly(meth)acrylate resin, cyclic olefin polymer resin, and acrylic resin. The release film may have a thickness of 10 micrometers to 100 micrometers, preferably 10 micrometers to 50 micrometers. Within this range, the release film may support the adhesive protective film.

[0168] Next, the invention will be described in more detail with reference to some examples. However, it should be noted that these examples are provided for illustration only and should not be considered as limiting the invention in any way. Example 1

[0169] The components listed in Table 1 are mixed in the amounts (unit: parts by weight) listed in Table 1, and 10 parts by weight of toluene is further added to the mixture as a solvent to prepare a composition for a polysiloxane adhesive protective film.

[0170] The prepared composition was deposited onto a release film (polyethylene terephthalate (PET) film, thickness: 75 micrometers) to a predetermined thickness, dried in an oven at 80°C for 2 minutes and at 130°C for 3 minutes, and left at room temperature for 3 days to prepare a stack of a polysiloxane-based adhesive protective film (thickness: 25 micrometers) and a release film. Examples 2 to 13

[0171] Except for changing the type and amount of each component in the composition of the polysiloxane adhesive protective film as listed in Tables 1 and 2, each polysiloxane adhesive protective film was prepared in the same manner as in Example 1. Comparative Examples 1 to 6

[0172] Except for changing the type and amount (in parts by weight) of each component in the composition of the polysiloxane adhesive protective film as listed in Table 2, each polysiloxane adhesive protective film was prepared in the same manner as in Example 1. Example 14

[0173] The components listed in Table 3 are mixed in the amounts (unit: parts by weight) listed in Table 3, and 10 parts by weight of toluene is further added to the mixture as a solvent to prepare a composition for a polysiloxane adhesive protective film.

[0174] The prepared composition was deposited onto a release film (polyethylene terephthalate (PET) film, thickness: 75 micrometers) to a predetermined thickness, dried in an oven at 80°C for 2 minutes and at 130°C for 3 minutes, and left at room temperature for 3 days to prepare a stack of a polysiloxane-based adhesive protective film (thickness: 25 micrometers) and a release film. Examples 15 to 20

[0175] Except for the types and amounts of each component in the composition of the polysiloxane adhesive protective film used in Example 14 as listed in Table 3, each polysiloxane adhesive protective film was prepared in the same manner as in Example 1. Comparative Examples 7 to 9

[0176] Except for the types and amounts of each component in the composition of the polysiloxane adhesive protective film used in Example 14, as listed in Table 3, each polysiloxane adhesive protective film was prepared in the same manner as in Example 1. Property evaluation (1)

[0177] The compositions and / or polysiloxane adhesive protective films prepared in Examples 1 to 13 and Comparative Examples 1 to 6 were evaluated for the following properties, and the results are shown in Tables 1 to 3.

[0178] (1) Initial peel strength (A) (unit: grams per inch): The stack of polysiloxane adhesive protective film and release film (PET film) prepared in each of the examples and comparative examples was cut into 25 mm × 200 mm dimensions, and the polysiloxane adhesive protective film was bonded to a polyimide (PI) film (GF200, SKC Kolon PI) and then compressed using a 2 kg roller to prepare the sample. Then, the peel strength was measured using a texture analyzer (TA) when the polysiloxane adhesive protective film was removed from the polyimide film under the conditions of a peel rate of 2,400 mm / min, a peel angle of 180° and a peel temperature of 25°C. Three samples were prepared, and the peel strength was measured for each sample, and the average value was calculated. This value was defined as the initial peel strength. The initial peel strength was evaluated using the same method, instead of a glass plate, instead of a polyimide film.

[0179] (2) Peel strength over time (A) (unit: grams per inch): Samples were prepared in the same manner as in (1), placed in an oven at 50°C for 7 days, and cooled outside the oven at room temperature for 30 minutes. Peel strength was then measured in the same manner as in (1). A glass plate was used instead of the polyimide film, and peel strength was measured in the same manner.

[0180] (3) Peel strength increase rate (A) (unit: %): Based on the peel strength values ​​obtained in (1) and (2), the peel strength increase rate is calculated according to Equation 1-1.

[0181] (4) Residual peel strength (unit: grams per inch): The stack of polysiloxane adhesive protective film and release film (PET film) prepared in each of the examples and comparative examples was cut into 35 mm × 120 mm sizes and bonded to a polyimide film (GF200, SKC Kolomb PI) by means of the polysiloxane adhesive protective film, and then compressed under 2 kg rollers to prepare a sample. The prepared sample was placed in an oven at 50°C for 7 days and cooled at room temperature outside the oven for 30 minutes, and then the polysiloxane adhesive protective film was removed from the polyimide film. Next, in the same area as the polysiloxane adhesive protective film removed from the polyimide film, an adhesive tape (31B-75PLC, Nitto Denko Co., Ltd.) was attached to the surface of the polyimide film where the polysiloxane adhesive protective film was removed. The adhesive tape attached to the polyimide film was then left at room temperature for 30 minutes. The residual peel strength (M3) was measured at 25°C when the tape was removed from the polyimide film at a peel rate of 300 mm / min and a peel angle of 180°. The peel strength was measured using a texture analyzer (TA). An alkali-free glass plate was used instead of the polyimide film, and the residual peel strength was measured using the same method.

[0182] (5)Residual peel strength reduction rate (unit: %): The adhesive tape (31B-75PLC, Nitto Denko Co., Ltd.) used in (4) was attached to the polyimide film [the initial polyimide film without the attached polysiloxane adhesive protective film] in the same area and left at room temperature for 30 minutes. Then the standard peel strength (M4) was measured in the same manner as the measurement of M3. The standard peel strength (M4) was 970 gf / inch. The residual peel strength reduction rate was calculated by Equation 2-1: [Equation 2-1] Residual peel strength reduction rate = (M3 – M4) / M4 × 100

[0183] The adhesive tape (31B-75PLC, Nitto Denko Co., Ltd.) used in (4) was attached to the glass plate [an initial alkali-free glass plate without a polysiloxane adhesive protective film] in the same area and left at room temperature for 30 minutes. The standard peel strength (M4) was then measured in the same manner as the measurement of M3. The standard peel strength (M4) was 652 gf / inch. The residual peel strength reduction rate was calculated using Equation 2-1.

[0184] (6) Tensile strength (unit: megapascal): The composition prepared in each of the examples and comparative examples was coated to a predetermined thickness on one surface of a fluorinated film (FL-75BML, Dongwon Intech Co., Ltd.), and a PET film was bonded to the coating and cured at 130°C for 5 minutes, thereby preparing a stack in which a 75-micron-thick polysiloxane adhesive protective film was sandwiched between the fluorinated film and the PET film. As shown in Figure 1, the stack was cut into a dog bone shape, and then the fluorinated film and the PET film were removed to prepare a sample for measuring tensile strength.

[0185] Referring to Figure 1, the sample has a dog bone shape, with a total length of 40 mm, a total width of 15 mm, and a thickness of 75 μm. For the sample used for modulus measurement, tensile strength was measured using a tensile strength tester (Instron Co., Ltd.). Specifically, the dog bone-shaped sample shown in Figure 1 was connected to the first clamp of the tester at its left end and to the second clamp of the tester at its right end. Here, the connection portion between the left end and the first clamp has the same area as the connection portion between the right end and the second clamp. The tensile strength was then measured by moving the second clamp at 25°C with the first clamp fixed to the tester, under conditions of a 1 kN pressure element and a tensile speed of 50 mm / min, until a portion of the dog bone-shaped sample shown in Figure 1, indicated by a width of 15 mm and a thickness of 5 mm, broke.

[0186] (7)Step embedding: As shown in FIG2, step embedding was evaluated on a sample having a cross-section. The stack of polysiloxane adhesive protective film and release film prepared in each of the examples and comparative examples was cut to a size of 50 mm × 50 mm, and the release film was removed from the stack to prepare a sample for measuring step embedding. Referring to FIG2, the prepared polysiloxane adhesive protective film 2 was stacked on the patterned film [material: polyimide] 1. Here, in FIG2, the space 3 between the patterned film 1 and the polysiloxane adhesive protective film 2 is an air gap. In FIG2, the height H is 2 μm, the length A is 1 mm, the length B is 3 mm, and the length C is 1 mm. The length A of the air gap (the length of each of A and C in FIG2 without the adhesive protective film attached) was measured using an optical microscope. Air gaps less than or equal to 20 micrometers in length are rated as "○", and air gaps greater than 20 micrometers in length are rated as "x". Property Evaluation (2)

[0187] The compositions and / or polysiloxane adhesive protective films prepared in Examples 14 to 20 and Comparative Examples 7 to 9 were evaluated for the following properties, and the results are shown in Table 3.

[0188] (1) Initial peel strength (B) (unit: grams per inch): The stack of polysiloxane adhesive protective film and release film (PET film) prepared in each of the examples and comparative examples was cut into 25 mm × 100 mm sizes, bonded to a glass plate by the polysiloxane adhesive protective film, compressed by a 2 kg roller, and left at 23°C and 50% RH for 30 minutes to prepare samples. Then, the peel strength was measured using a texture analyzer (TA) when the polysiloxane adhesive protective film was removed from the glass plate at 25°C, a peel rate of 2,400 mm / min, and a peel angle of 180°. Three samples were prepared, and the peel strength was measured for each sample, and the average value was calculated. This value was defined as the initial peel strength.

[0189] (2) Peel strength over time (B) (unit: grams per inch): Samples were prepared in the same manner as in (1) and stored at 23°C and 50% RH for 14 days, and then the peel strength was measured in the same manner as in (1).

[0190] (3) Peel strength increase rate (B) (unit: %): Based on the peel strength values ​​obtained in (1) and (2), the peel strength increase rate is calculated according to Equation 1.

[0191] (4)Initial peel strength (A) (unit: grams per inch), peel strength over time (A) (unit: grams per inch) and peel strength increase rate (A) (unit: %): For the polysiloxane adhesive protective films prepared in each of Examples 14 to 20 and Comparative Examples 7 to 9, the initial peel strength (A) and peel strength over time (A) were measured, and the peel strength increase rate (A) was calculated according to Equation 1-1.

[0192] (5)Residual properties: An adhesive tape (Nitto 31B) with a size of 25 mm × 100 mm was attached to a polyimide film (GF700, SKC Kelon PI), compressed by a 2 kg roller, and left for 24 hours at 23°C and 50% RH. Then, the peel strength (M1) was measured using a texture analyzer (TA) at 25°C with a peel rate of 2,400 mm / min and a peel angle of 180° according to JIS Z0237.

[0193] The adhesive films prepared in each of the Examples and Comparative Examples were cut into samples with dimensions of 25 mm × 100 mm. The samples were placed at 23°C and 50% RH, attached to a polyimide film (GF700, SKC Kolon PI), compressed by a 2 kg roller, and left at 50°C for 14 hours. The adhesive film was then removed from the samples. The adhesive tape (Nitto 31B) used for measuring M1 was attached to the surface of the sample from which the adhesive film had been removed, and left at 23°C and 50% RH for 24 hours. The peel strength (M2) was then measured using a texture analyzer (TA) at 25°C with a peel rate of 2,400 mm / min and a peel angle of 180°, according to JIS Z0237. The residual peel strength change rate was calculated according to Equation 2. [Equation 2] Residual peel strength change rate = (1 - (M2 / M1)) × 100

[0194] ○: The rate of change in residual peel strength is less than 20%, which is excellent.

[0195] △: Residual peel strength variation rate is 20% to less than 50%, usable.

[0196] ×: Residual peel strength change rate is 50% or greater, not available.

[0197] (5) Wettability: The stacks of polysiloxane adhesive protective films and release films prepared in each of the Examples and Comparative Examples were cut into samples with dimensions of 50 mm × 100 mm. The samples were placed at 23°C and 50% RH for 30 minutes, and the release film was removed from the samples to expose the adhesive film. Here, the sample with the adhesive film attached to the PET film will be referred to as the adhesive tape. With both ends of the adhesive tape held by hand, the center of the adhesive tape was brought into contact with the glass plate, and the hand was removed from the glass plate. The wettability was evaluated based on the time until the entire adhesive tape was in close contact with the glass plate due to the contact between the center of the adhesive tape and the glass plate. The shorter the time of close contact with the glass plate, the better the affinity for the glass plate, which means that the polysiloxane adhesive protective film is easier to protect the glass plate in the display and display manufacturing process using the glass plate. ○: 3 seconds or less until close contact (excellent wettability) △: 3 seconds or less than 5 seconds until close contact (good wettability) X: 5 seconds or more until close contact (not usable) Table 1 Example 1 2 3 4 5 6 7 8 9 10 7654 40 40 40 40 40 20 20 20 20 20 7626 60 60 60 60 60 0 0 0 0 0 7664 0 0 0 0 0 0 0 0 0 0 X-40-3306K 0 0 0 0 0 80 80 80 80 80 7210 0.648 1.487 2.35 3.56 6.05 0.26 0.465 0.94 1.425 2.43 7028 1.5 1.5 1.5 1.5 1.5 0 0 0 0 0 4000 1.09 1.09 1.09 1.09 1.09 0 0 0 0 0 CAT-PL-50T 0 0 0 0 0 0.44 0.44 0.44 0.44 0.44 NC-25 0 0 0 0 0 0 0 0 0 0 9250 0.2 0.2 0.2 0.2 0.2 0 0 0 0 0 In the case of PI film Initial peel strength (A) 1.32 1.36 1.47 1.49 1.60 1.45 1.66 1.76 1.89 1.96 Peeling strength over time (A) 2.56 2.35 2.28 2.01 1.89 2.41 2.38 2.38 2.25 2.18 Peel strength increase rate (A) 94 73 55 35 18 66 43 35 19 11 In the case of glass plates Initial peel strength (A) 1.21 1.32 1.44 1.38 1.38 1.12 1.18 1.12 1.22 1.35 Peel strength over time (A) 2.40 2.20 1.97 1.89 1.65 1.85 1.80 1.63 1.56 1.51 Peel strength increase rate (A) 98 67 37 37 20 65 53 46 28 12 In the case of PI film Residual peel strength 769 858 780 747 786 783 798 802 822 862 Residual peel strength reduction rate -twenty one -12 -20 -twenty three -19 -19 -18 -17 -15 -11 In the case of glass plates Residual peel strength 385 410 421 485 534 419 423 454 522 433 Residual peel strength reduction rate -41 -37 -35 -26 -18 -36 -35 -30 -20 -34 Tensile strength 1.9 2.2 3.5 4.1 5.2 5.4 5.6 6.3 6.6 6.9 Step embedding O O O O O O O O O O Table 2 Example Comparative example 11 12 13 1 2 3 4 5 6 7654 29 29 29 40 20 20 100 0 40 7626 30 30 30 60 0 0 0 100 0 7664 41 41 41 0 0 80 0 0 0 X-40-3306K 0 0 0 0 80 0 0 0 0 7210 2 4 6 0 0 0 0.648 0.648 0.648 7028 1.0 1.0 1.0 1.50 0 0.25 1.5 1.5 1.50 4000 0 0 0 1.09 0 0 1.09 1.09 1.09 CAT-PL-50T 0 0 0 0 0.44 0.44 0 0 0 NC-25 0.56 0.56 0.56 0 0 0 0 0 0 9250 0 0 0 0.2 0 0 0.2 0.2 0.2 RJ-201 Polysiloxane Oil (12,500 cst) 0 0 0 0 0 0 0 0 60 In the case of PI film Initial peel strength (A) 1.23 1.39 1.49 1.19 1.17 1.34 1.45 1.11 5.32 Peel strength over time (A) 1.39 1.49 1.59 2.76 2.45 1.41 1.52 3.2 13.53 Peel strength increase rate (A) 13 7 7 132 109 5 5 188 154 In the case of glass plates Initial peel strength (A) 1.34 1.26 1.54 1.15 0.92 1.20 1.21 0.95 4.67 Peel strength over time (A) 2.27 1.77 1.82 2.85 1.95 1.77 1.31 3.1 15.2 Peel strength increase rate (A) 70 40 18 148 112 48 8 226 225 In the case of PI film Residual peel strength 599 677 691 675 711 916 851 821 315 Residual peel strength reduction rate -38 -30 -29 -30 -27 -6 -12 -15 -68 In the case of glass plates Residual peel strength 493 525 541 341 399 531 521 528 153 Residual peel strength reduction rate -twenty four -19 -17 -48 -39 -19 -20 -20 -77 Tensile strength 4.1 4.4 5.3 1.7 5.2 6.1 10.3 0.39 0.86 Step embedding O O O O X X X X O Table 3 Example Comparative example 14 15 16 17 18 19 20 7 8 9 7654 40 40 40 40 40 40 60 40 100 0 7646 60 60 60 60 60 60 40 60 0 100 7028 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 7210 1 3 5 1 3 5 5 0 1 1 7426 0.1 0.1 0.1 0.5 0.5 0.5 0.5 0 0.1 0.1 4000 1 1 1 1 1 1 1 1 1 1 In the case of glass plates Initial peel strength (A) 1.7 1.68 1.64 1.95 1.84 1.66 1.54 1.67 0.9 2.5 Peel strength over time (A) 3.16 3.04 2.79 3.34 3.11 2.85 2.54 6.05 1.61 6.84 Peel strength increase rate (A) 86 81 70 71 69 72 65 262 79 174 In the case of PI film Initial peel strength (A) 2.43 2.21 2.15 2.39 2.27 2.1 2.19 2.52 1.34 3.64 Peel strength over time (A) 4.34 3.83 3.64 4.09 3.80 3.47 3.53 6.40 2.18 8.41 Peel strength increase rate (A) 79 73 70 71 68 65 61 154 63 131 In the case of glass plates Initial peel strength (B) 1.7 1.68 1.64 1.95 1.84 1.66 1.54 1.67 0.9 2.5 Peel strength over time (B) 2.24 2.15 2.09 2.54 2.38 2.28 2.08 3.24 1.1 4.5 Peel strength increase rate (B) 32 28 27 30 29 37 35 94 twenty two 80 Residual properties O O O O O O O O O X Wetting properties O O O O O O O O X O

[0198] *The components listed in Tables 1 to 3 are shown in Table 4. Table 4 Product Name Category (Manufacturer) illustrate 7654 Organic polysiloxane 1 (Dow Corning) Polydimethylsiloxane with 5-hexenyl groups at the side chain, end-capped with trimethylsilyl or trimethylsilyloxy groups. 7626 Organic polysiloxane 2 (Dow Corning) Polydimethylsiloxane with only vinyl groups at both ends 7646 Organic polysiloxane II (Dow Corning) Polydimethylsiloxane with only vinyl groups at both ends XX-03 Organic polysiloxane 3 (Shin-Etsu Corporation) Vinyl polydimethylsiloxanes with only silicic bonds at the side chains, end-capped with trimethylsilyl or trimethylsilyloxy groups. XX-40-3306K Organic polysiloxane 4 (Shin-Etsu Chemical Co., Ltd.) Polydimethylsiloxane (trimethylsilyl, trimethylsilyloxy-terminated) with vinyl groups only having silicon bonds at the side chains and phenyl groups having silicon bonds at the side chains, with some crosslinking agents. 7210 Organopolysiloxane resin (Dow Corning) MQ resins containing only (vinyl)(CH3)2SiO1 / 2 units as M units and SiO4 / 2 units 7426 Organopolysiloxane resin (Dow Corning) MQ resins containing only (vinyl)(CH3)2SiO1 / 2 units as M units and SiO4 / 2 units 7028 Crosslinking agent (Dow Corning) Polydimethylsiloxane with Si-H groups 4000 Hydrogenated silanized catalyst 1 (Dow Corning) Platinum Catalyst CAT-PL-50T Hydrogenated silanized catalyst 2 (Dow Corning) Platinum Catalyst NC-25 Hydrogenated silanized catalyst 3 (Dow Corning) Platinum Catalyst 9250 Anchoring agent (Dow Corning) - RJ-201 Polysiloxane Oil 12,500 cst Organic polysiloxane 5 (Ruisil) Vinyl-free polydimethylsiloxane, trimethylsilyl, trimethylsilyloxy-terminated

[0199] As shown in Tables 1 and 2, the polysiloxane adhesive protective film according to the present invention has a good effect in protecting the adherend, exhibiting a low peel strength increase rate, good wettability, and good step embedding. The polysiloxane adhesive protective film according to the present invention does not cause contamination or damage to the adherend when removed from it. Conversely, as shown in Table 2, the adhesive protective films of Comparative Examples 1 to 3, prepared without the organic polysiloxane resin according to the present invention, do not meet the peel strength increase rate according to the present invention, or exhibit poor step embedding. Furthermore, each adhesive protective film of Comparative Examples 4 and 5, containing only component (i) or only component (ii), exhibits poor step embedding properties or does not meet the peel strength increase rate according to the present invention. Furthermore, the adhesive protective film of Comparative Example 6, prepared using vinyl-free polydimethylsiloxane instead of component (ii), does not meet the peel strength increase rate or improve the residual peel strength reduction rate according to the present invention.

[0200] Furthermore, as shown in Table 3, the polysiloxane adhesive protective film according to the present invention has a good effect in protecting the adherend, and has a low peel strength increase rate, good wettability, good step embedding and low residual peel reduction rate, thereby preventing contamination and damage to the adherend when the polysiloxane adhesive protective film is removed from the adherend.

[0201] Conversely, the adhesive protective film of Comparative Example 7, prepared without the organic polysiloxane resin, exhibits a high peel strength increase rate. The adhesive protective film of Comparative Example 8, prepared without component (ii), exhibits poor wettability and cannot be used as a polysiloxane adhesive protective film. The adhesive protective film of Comparative Example 9, prepared without component (i), has a high peel strength increase rate and a high residual peel reduction rate, thus causing contamination and damage to the adhered object when removing the polysiloxane adhesive protective film from the adhered object.

[0202] It should be understood that, without departing from the spirit and scope of the present invention, those skilled in the art can make various modifications, alterations, changes and equivalent embodiments. [Simplified Explanation of the Diagram]

[0203] Figure 1 is a plan view of the sample used to measure the tensile strength of the polysiloxane adhesive protective film in the example. Figure 2 is a cross-sectional view of the sample with stepped embedding of the polysiloxane adhesive protective film used to measure the tensile strength of the polysiloxane adhesive protective film in the example.

Claims

1. A polysiloxane adhesive protective film, formed from a composition comprising an alkenyl-containing organic polysiloxane mixture, an organic polysiloxane resin, a crosslinking agent, and a hydrogenated silanizing catalyst, wherein the alkenyl-containing organic polysiloxane mixture comprises a mixture of component (i) and component (ii), wherein component (i) is an organic polysiloxane having at least one silicon bond in a C3 to C10 alkenyl group, and component (ii) is an organic polysiloxane having at least one silicon bond in a vinyl group; the organic polysiloxane resin comprises an MQ resin composed of RaRbRcSiO1 / 2 units and SiO4 / 2 units; and Ra, Rb, and Rc are each independently C1 to C6 alkyl or C2 to C10 alkenyl, wherein at least one of Ra, Rb, and Rc in the MQ resin is a C2 to C10 alkenyl group.

2. The polysiloxane adhesive protective film as claimed in claim 1, wherein the polysiloxane adhesive protective film has a peel strength increase rate of 50% or less calculated by Equation 1: [Equation 1] Peel strength increase rate = (P2 - P1) / P1 × 100, where P1 represents the initial peel strength (in grams per inch) of the polysiloxane adhesive protective film relative to the adhered object in the sample of the polysiloxane adhesive protective film and the adhered object; and P2 represents the peel strength (in grams per inch) of the polysiloxane adhesive protective film relative to the adhered object of the sample measured after the sample has been stored at 23°C and 50% relative humidity for 14 days.

3. The polysiloxane adhesive protective film as claimed in claim 1, wherein the polysiloxane adhesive protective film has a peel strength increase rate of 100% or less than 100% calculated by Equation 1-1: [Equation 1-1] Peel strength increase rate = (P3-P1) / P1×100, where P1 represents the initial peel strength (in grams per inch) of the polysiloxane adhesive protective film relative to the adhered object in the sample of the polysiloxane adhesive protective film and the adhered object; and P3 represents the peel strength (in grams per inch) of the polysiloxane adhesive protective film relative to the adhered object of the sample measured after the sample has been placed at 50°C for 7 days.

4. The polysiloxane-based adhesive protective film according to claim 1, wherein the polysiloxane-based adhesive protective film has a residual peel strength change rate of less than 20% calculated by Equation 2: [Equation 2] Residual peel strength change rate = (1 - (M2 / M1)) × 100, where M1 represents the peel strength of the adhesive tape relative to the adherend (unit: g / inch); and M2 represents the peel strength of the adhesive tape relative to the adherend when the adhesive film is removed from the adherend of the sample (unit: g / inch), and the peel strength is measured after removing the polysiloxane-based adhesive protective film from the sample, attaching the adhesive tape to the surface of the sample from which the polysiloxane-based adhesive protective film has been removed, and leaving it for 24 hours under the conditions of 23°C and 50% relative humidity, wherein the sample is prepared by stacking and attaching the polysiloxane-based adhesive protective film and the release film to the adherend via the polysiloxane-based adhesive protective film, and leaving it at 50°C for 14 days.

5. The polysiloxane-based adhesive protective film according to claim 1, wherein the polysiloxane-based adhesive protective film has a residual peel strength reduction rate of -50% or greater than -50% calculated by Equation 2-1: [Equation 2-1] Residual peel strength reduction rate = (M3 - M4) / M4 × 100, where M3 represents the peel strength of the adhesive tape when the adhesive film is removed from the adherend of the sample (unit: g / inch), and the peel strength is measured after removing the polysiloxane-based adhesive protective film from the sample, attaching the adhesive tape to the surface of the sample from which the polysiloxane-based adhesive protective film has been removed, and leaving it for 30 minutes at 25°C, wherein the sample is prepared by stacking and attaching the polysiloxane-based adhesive protective film and the release film to the adherend via the polysiloxane-based adhesive protective film, leaving it at 50°C for 7 days, and cooling it at 25°C for 30 minutes; and M4 represents the peel strength of the adhesive tape relative to the initial adherend without attaching the polysiloxane-based adhesive protective film (unit: g / inch).

6. The polysiloxane-based adhesive protective film according to claim 1, wherein the polysiloxane-based adhesive protective film has a peel strength of 3 g / inch or less relative to the adherend.

7. The polysiloxane-based adhesive protective film according to claim 1, wherein the C3 to C10 alkenyl group is a hexenyl group.

8. The polysiloxane-based adhesive protective film according to claim 7, wherein the hexenyl group is 5-hexenyl.

9. The polysiloxane-based adhesive protective film according to claim 1, wherein the component (i) comprises an organopolysiloxane represented by Formula 1: [Formula 1] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y, in Formula 1, R1 is a C3 to C10 alkenyl group; R2 is a C1 to C10 alkyl group; R3 and R4 are each independently a C1 to C10 alkyl group; and 0 < x < 1, 0 < y < 1, and x + y = 1.

10. The polysiloxane-based adhesive protective film according to claim 9, wherein in Formula 1, x and y satisfy 0.001 ≤ x ≤ 0.4 and 0.6 ≤ y ≤ 0.

999.

11. The polysiloxane-based adhesive protective film according to claim 1, wherein the component (ii) comprises at least one of the organopolysiloxanes represented by Formula 2, Formula 3, and Formula 4: [Formula 2] R5R6R7SiO(R1R2SiO2 / 2)x(R3R4SiO2 / 2)ySiR8R9R10. In Formula 2, R1, R2, R3, and R4 are each independently a C1-C10 alkyl group; R5, R6, and R7 are each independently a vinyl group or a C1-C10 alkyl group, and at least one of R5, R6, and R7 is a vinyl group; R8, R9, and R10 are each independently a vinyl group or a C1-C10 alkyl group, and at least one of R8, R9, and R10 is a vinyl group; and 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, and x + y = 1; [Formula 3] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y(R5R6SiO2 / 2)z. In Formula 3, R1, R2, R3, R4, R5, and R6 are each independently a C1-C10 alkyl group, a vinyl group, or a C6-C10 aryl group, and at least one of R1 and R2 is a vinyl group; and 0 < x ≤ 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1; [Formula 4] (R1R2SiO2 / 2)x(R3R4SiO2 / 2)y. In Formula 4, R1, R2, R3, and R4 are each independently a C1-C10 alkyl group, a vinyl group, or a C6-C10 aryl group, and at least one of R1 and R2 is a vinyl group; and 0 < x ≤ 1, 0 < y < 1, and x + y = 1.

12. The polysiloxane-based adhesive protective film according to claim 11, wherein the organopolysiloxane of Formula 2 is Vi(CH3)2SiO-((CH3)2SiO2 / 2)n-Si(CH3)2Vi [Vi is vinyl, and n is an integer greater than 0 to 5,000].

13. The polysiloxane-based adhesive protective film according to claim 11, wherein in Formula 3, both R3 and R4 are C6-C10 aryl groups; both R5 and R6 are C1-C10 alkyl groups; and x, y, and z satisfy the relationship: 0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1.

14. The polysiloxane-based adhesive protective film according to claim 11, wherein in Formula 4, both R3 and R4 are C1-C10 alkyl groups; and x and y satisfy the relationship: 0 < x < 1, 0 < y < 1, and x + y = 1.

15. The polysiloxane-based adhesive protective film according to claim 1, wherein relative to 100 parts by weight of the alkenyl-containing organopolysiloxane mixture, the component (i) is present in an amount of 10 parts by weight to 70 parts by weight, and the component (ii) is present in an amount of 30 parts by weight to 90 parts by weight.

16. The polysiloxane-based adhesive protective film according to claim 1, wherein the RaRbRcSiO1 / 2 unit and the SiO4 / 2 unit are present in the organopolysiloxane resin in a molar ratio (RaRbRcSiO1 / 2 unit:SiO4 / 2 unit) of 0.25:1 to 2.5:

1.

17. The polysiloxane adhesive protective film as claimed in claim 1, wherein the organopolysiloxane resin comprises a mixture of component (iii) and component (iv): component (iii): an organopolysiloxane resin comprising RaRbRcSiO1 / 2 units and SiO4 / 2 units, wherein in component (iii), Ra, Rb and Rc are each independently C1 to C6 alkyl or C2 to C10 alkenyl, and at least one of Ra, Rb and Rc is C2 to C10 alkenyl; and component (iv): an organopolysiloxane resin comprising RdReRfSiO1 / 2 and SiO4 / 2 units, wherein Rd, Re and Rf are each independently C1 to C6 alkyl.

18. The polysiloxane adhesive protective film as claimed in claim 1, wherein the organic polysiloxane resin is present in an amount of 0.01 parts by weight to 20 parts by weight relative to 100 parts by weight of the alkenyl-containing organic polysiloxane mixture.

19. The polysiloxane adhesive protective film as claimed in claim 1, wherein the composition further comprises an anchoring agent.

20. An optical element, comprising: Optical film; And a polysiloxane adhesive protective film as described in any one of claims 1 to 19, formed on one surface of the optical film.

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