Polyorganosiloxane

Abstract

The present application can provide a polyorganosiloxane and a release composition capable of forming a release layer capable of ensuring solvent resistance by maximizing the bonding strength between a base film and a release layer. In addition, the present application can provide a polyorganosiloxane and a release composition capable of forming a release layer having an appropriate release strength even under room temperature and high temperature conditions, and having little change in release strength even under high temperature and ultraviolet irradiation conditions, and capable of ensuring an excellent residual adhesion rate. In addition, the present application can provide a release layer and a release film and an adhesive film including the release layer as applications of the polyorganosiloxane and the release composition.

Description

[Technical field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0017903, filed on February 11, 2022, and all contents disclosed in the documents of the Korean Patent Application are incorporated as part of this specification.

[0002] The present application relates to a polyorganosiloxane, a release composition, a release layer, a release film, and an adhesive film. [Background technology]

[0003] The release layer is a layer that exhibits low peel strength against a pressure-sensitive adhesive or adhesive. Such a release layer or a release film containing the same is used for various purposes such as a protective film for a pressure-sensitive adhesive layer, a process film for manufacturing a resin sheet, a process film for forming a ceramic green sheet, and a process film for manufacturing synthetic leather.

[0004] Release films are generally produced by applying a release composition to a substrate film such as paper, glass, or a polymeric film, and curing the composition to form a release layer.

[0005] Patent Document 1 (Japanese Unexamined Patent Publication No. 2011-52207) discloses a release sheet having a release layer (mold release layer) formed from a release agent composition (mold release composition) containing at least a polyolefin, an isocyanate compound, and a polyolefin polyol.

[0006] A release layer is basically required to have low peel strength against a pressure-sensitive adhesive or adhesive, but additionally needs to have solvent resistance. Since organic solvents are often used in the process of forming a release film and / or in the process of forming a pressure-sensitive adhesive or adhesive on the release layer, the release layer is required to have solvent resistance.

[0007] In addition, since it is not appropriate for the peel strength of the release layer to change with respect to the adhesive or bonding agent after the release layer is exposed to heat or ultraviolet light, it is important that the release layer has appropriate heat resistance and ultraviolet light resistance. Summary of the Invention [Problem to be solved by the invention]

[0008] The present application provides a polyorganosiloxane, a release composition, a release layer, a release film, and an adhesive film. The present application can provide a polyorganosiloxane capable of forming a release layer exhibiting an appropriately low peel strength against a pressure-sensitive adhesive or adhesive, and a release composition, a release layer, a release film, and an adhesive film containing the same.

[0009] Another object of the present application is to make the release layer stably maintain a low peel strength against the pressure-sensitive adhesive or adhesive over time.

[0010] In addition, the present application aims to form a release layer that, when formed on a base film for the purpose of forming a release film, shows excellent adhesion to the base film, has excellent heat resistance, solvent resistance, and UV resistance, and maintains a high residual adhesion rate. [Means for solving the problem]

[0011] In the present specification, when the measurement temperature affects a physical property, the physical property is measured at room temperature, unless otherwise specified.

[0012] The term "room temperature" refers to a natural temperature without artificial heating or cooling, and may mean, for example, any one temperature within the range of 10° C. to 30° C., or a temperature that is about 15° C. or higher, about 18° C. or higher, about 20° C. or higher, or about 23° C. or higher, and about 27° C. or lower, or a temperature of about 25° C. Unless otherwise specified in this specification, the unit of temperature is Celsius (° C.).

[0013] When the measurement pressure affects the physical properties mentioned in this application, unless otherwise specified, the physical properties are those measured at normal pressure.

[0014] The term "normal pressure" refers to the natural pressure without artificial pressurization or depressurization, and can mean, for example, any one pressure within the range of 0.9 atm to 1.2 atm or any one pressure within the range of about 740 mmHg to 780 mmHg.

[0015] In this specification, the terms "weight average molecular weight (Mw)" and "number average molecular weight (Mn)" are physical properties measured using GPC (Gel permeation chromatography), and the term "polydispersity index (PDI)" is the value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). The units of the weight average molecular weight (Mw) and number average molecular weight (Mn) mentioned in this specification are g / mol.

[0016] In this specification, the number average molecular weight (M n ) and weight average molecular weight (Mw) can be measured by putting the sample in a 20 mL vial, diluting it with THF (tetrahydrofuran) to a concentration of about 20 mg / mL, and then filtering the calibration standard sample and the sample to be analyzed with a syringe filter (pore size: 0.2 μm). As the analysis program, ChemStation of Agilent technologies can be used, and the number average molecular weight (M n ) and weight average molecular weight (M w ) can be obtained by comparing the elution time of the sample with the calibration curve.

[0017] <GPC measurement conditions> Instrument: 1200 series of Agilent technologies Column: Use TL Mix.A&B of Agilent technologies Solvent: THF Column temperature: 40℃ Sample concentration: 20mg / mL, 10μl injection Standard samples used MP: 364000, 91450, 17970, 4910, 1300

[0018] The term "alkyl group" in this specification, unless otherwise specified, can mean a straight or branched alkyl group having 1 to 20 carbon atoms, or 1 to 16 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or can mean a cyclic alkyl group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0019] As used herein, unless otherwise specified, the term "alkoxy group" can mean a straight-chain or branched-chain alkoxy group having 1 to 20 carbon atoms, or 1 to 16 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or a cyclic alkoxy group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0020] As used herein, the terms "alkylidene group" and "alkylene group" both refer to a divalent residue formed by removing two hydrogen atoms from an alkane, with the proviso that an alkylidene group refers to a divalent residue formed by removing two hydrogen atoms from one carbon atom of an alkane, and an alkylene group refers to a divalent residue formed by removing one hydrogen atom each from two different carbon atoms of an alkane.

[0021] In this specification, unless otherwise specified, the term "alkylidene group" can mean a straight-chain or branched-chain alkylidene group having 1 to 20 carbon atoms, or 1 to 16 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or it can mean a cyclic alkylidene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0022] In this specification, unless otherwise specified, the term "alkylene group" can mean a straight-chain or branched-chain alkylene group having 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms, or 2 to 4 carbon atoms, or it can mean a cyclic alkylene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0023] In this specification, unless otherwise specified, the term "alkenyl group" or "alkenylene group" may mean a straight-chain or branched-chain alkenyl group or alkenylene group having 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms; or an alkenyl group or alkenylene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0024] As used herein, unless otherwise specified, the term "alkynyl group" or "alkynylene group" refers to a straight-chain or branched-chain alkynyl group or alkynylene group having 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms, or an alkynyl group or alkynylene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0025] In this specification, the term "aryl group" means a monovalent residue derived from an aromatic compound, and the term "arylene group" means a divalent residue derived from an aromatic compound, unless otherwise specified. The aromatic compound may be a compound or derivative thereof containing a structure in which benzene or two or more benzenes are linked to each other or condensed or bonded while sharing one or two or more carbon atoms. For example, the term "aryl group" in this specification may include not only functional groups commonly referred to as aryl groups, but also so-called aralkyl groups or arylalkyl groups. The aromatic compound forming the aryl group or arylene group may be, for example, an aromatic compound having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms, or benzene.

[0026] As used herein, the term "monovalent hydrocarbon group" can mean, unless otherwise specified, a compound consisting of carbon and hydrogen or a monovalent residue derived from a derivative of such a compound. For example, the monovalent hydrocarbon group can contain 1 to 25 carbon atoms. Examples of the monovalent hydrocarbon group include the alkyl group, alkenyl group, alkynyl group, and aryl group described above.

[0027] The alkyl group, alkoxy group, alkylidene group, alkylene group, alkenyl group, alkenylene group, alkynyl group, alkynylene group, aryl group, arylene group or monovalent hydrocarbon group may be optionally substituted with one or more substituents. In this case, the substituent may be one or more selected from the group consisting of halogen (chlorine (Cl), iodine (I), bromine (Br) or fluorine (F)), epoxy group, glycidyl group, glycidyloxy group, aryl group, heteroaryl group, alkoxy group, cyano group, carboxyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carbonyl group and hydroxyl group, but is not limited thereto.

[0028] The term "heteroaryl group" as used herein refers to an aromatic ring substituent containing one or more atoms other than carbon (heteroatoms) in the ring structure, and the heteroatoms may be exemplified by one or more selected from the group consisting of nitrogen (N), oxygen (O), sulfur (S), selenium (Se) and tellurium (Te). In the present specification, the atoms constituting the ring structure of the heteroaryl group may be referred to as ring atoms. The heteroaryl group may include a monocyclic structure or a polycyclic ring structure. The heteroaryl group may be, for example, a heteroaryl group having 2 to 30 carbon atoms, or 2 to 26 carbon atoms, or 2 to 22 carbon atoms, or 1 to 20 carbon atoms, or 2 to 18 carbon atoms, or 2 to 15 carbon atoms. The heteroaryl group is not particularly limited in the number of ring atoms, but the number of ring atoms may be about 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, or 5 to 8. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, an acridyl group, a pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinolinyl group, an indole group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuran group, a dibenzofuran group, a benzosilole group, a dibenzosilole group, a phenanthrolinyl group, Examples of the alkyl group include, but are not limited to, one or more selected from the group consisting of an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a phenoxazinyl group, and condensed structures thereof.

[0029] As used herein, the term "heteroarylene group" refers to a divalent moiety formed by removing an additional hydrogen atom from a heteroaryl group defined above.

[0030] The heteroaryl group or heteroarylene group may be optionally substituted with one or more substituents. In this case, the substituent may be one or more selected from the group consisting of halogen (chlorine (Cl), iodine (I), bromine (Br) or fluorine (F)), epoxy group, glycidyl group, glycidyloxy group, aryl group, heteroaryl group, alkoxy group, cyano group, carboxyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carbonyl group and hydroxyl group, but is not limited thereto.

[0031] The present application relates to polyorganosiloxanes. The term "polyorganosiloxane" means, as is known, a polymer comprising chains formed by siloxane bonds (Si-O-Si).

[0032] Polyorganosiloxanes are usually formed containing one or more siloxane units selected from the group consisting of so-called M units, D units, T units and Q units.

[0033] In this specification, M units are generally defined as (RSiO 1 / 2 ), which is a so-called monofunctional siloxane unit (i.e., a siloxane unit in which a silicon atom is linked to one oxygen atom), and the D unit is usually represented by (RSiO 2 / 2 ), and the T unit is usually represented by (RSiO 3 / 2 ), which is a so-called trifunctional siloxane unit (i.e., a siloxane unit in which a silicon atom is linked to three oxygen atoms), and the Q unit is usually represented by (SiO 4 / 2 ), which are so-called tetrafunctional siloxane units (i.e., siloxane units in which a silicon atom is linked to four oxygen atoms).

[0034] The polyorganosiloxane of the present application contains specific siloxane units, which allows the formation of the release layer intended in the present application.

[0035] The polyorganosiloxane may be one molecule of polyorganosiloxane or a mixture of two or more molecules of polyorganosiloxane. For example, the one molecule of polyorganosiloxane or the mixture of two or more molecules of polyorganosiloxane may have an average unit (average unit of chemical formula 5) described below.

[0036] The polyorganosiloxane may include a siloxane unit of the following formula 1: (R 1 m R 2 n SiO (4-m-n) / 2 ) (chemical formula 1)

[0037] In formula 1, R 1 and R 2 are each a substituent bonded to the silicon atom of the siloxane unit. 1 may be a functional group containing a carbon-carbon double bond, R 2 may be hydrogen, a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group. In Chemical Formula 1, m is a number of 1 or more, n is a number of 0 or more, and m+n may be a number in the range of 1 to 3.

[0038] In Chemical Formula 1, when m+n is 1, 2, or 3, it means that the siloxane unit of Chemical Formula 1 is a T unit, a D unit, or an M unit, respectively. The siloxane unit of Chemical Formula 1 may be the T unit, the D unit, or the M unit.

[0039] In formula 1, R 1 is a functional group containing a carbon-carbon double bond, and in one example, the functional group may be a functional group containing an alkenyl group or a functional group containing a (meth)acryloyl group.

[0040] As used herein, the term "(meth)acrylic" refers to both acrylic and methacrylic.

[0041] In one example, the functional group containing a carbon-carbon double bond may be a functional group represented by the following formula 3:

[0042] [ka]

[0043] In Formula 3, L1 may be a single bond, an alkylidene group or an alkylene group, L2 may be an alkylidene group or an alkylene group, and R5 and R6 may each independently be a hydrogen atom, an alkyl group or an aryl group.

[0044] In the above, the single bond refers to the case where L1 is absent. Thus, for example, when L1 is a single bond, the nitrogen atom of Formula 3 is directly connected to the silicon atom of the siloxane unit of Formula 1.

[0045] As a suitable example, L1 and L2 in Formula 1 may each independently be an alkylidene group or an alkylene group.

[0046] In Chemical Formula 3, specific types of the alkyl group, alkylidene group, alkylene group and aryl group are as described at the beginning of this specification.

[0047] Either L1 or the nitrogen atom (when L1 is a single bond) of Chemical Formula 3 can be linked to the silicon atom of the siloxane unit of Chemical Formula 1.

[0048] In formula 1, R 2 may be hydrogen, a hydroxyl group, an alkoxy group, or a monovalent hydrocarbon group, which may be an alkyl group, an alkenyl group, an alkynyl group, or an aryl group as described above, and a suitable example may be an alkyl group, but is not limited thereto.

[0049] Specific types of the alkoxy group, monovalent hydrocarbon group, alkyl group, alkenyl group or alkynyl group are as described at the beginning of this specification.

[0050] In Chemical Formula 1, the lower limit of m may be 1, 2, or 3, and the upper limit may be 3, 2, or 1. The m may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. In one example, the m may be 1.

[0051] In Chemical Formula 1, the lower limit of n may be 0, 1, or 2, and the upper limit may be 2, 1, or 0. The n may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. In one example, the n may be 1 or 2.

[0052] The lower limit of the molar percentage of the siloxane unit of the chemical formula 1 relative to the total number of moles of the entire siloxane units contained in the polyorganosiloxane (the total number of moles of M, D, T and Q units) may be about 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol%, and the upper limit may be about 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, or 3 mol%. The mole percent may be greater than or equal to any one of the lower limits recited above, less than or equal to any one of the upper limits recited above, or within a range that is greater than or equal to any one of the lower limits recited above and less than or equal to any one of the upper limits recited above.

[0053] In addition, the lower limit of the molar percentage of the functional group containing a carbon-carbon double bond contained in the siloxane unit of the formula 1 relative to the total number of moles of the silicon-bonded organic groups contained in the polyorganosiloxane may be about 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, or 10 mol%, and the upper limit may be about 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, or 2 mol%. The molar percentage may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0054] The polyorganosiloxane may include a siloxane unit of the following formula 2: (R3 p R 4 q SiO (4-p-q) / 2 ) (chemical formula 2)

[0055] In formula 2, R 3 and R 4 are each a substituent bonded to the silicon atom of the siloxane unit. 3 may be a ketone group-containing functional group, R 4 may be hydrogen, a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group. In Chemical Formula 2, p is a number of 1 or more, q is a number of 0 or more, and p+q may be a number in the range of 1 to 3.

[0056] In Chemical Formula 2, when p+q is 1, 2, or 3, it means that the siloxane unit of Chemical Formula 2 is a T unit, a D unit, or an M unit, respectively. The siloxane unit of Chemical Formula 2 may be the T unit, the D unit, or the M unit.

[0057] In formula 2, R 3 may be a ketone group-containing functional group.

[0058] In one example, the ketone group-containing functional group may be a functional group represented by the following formula 4: [ka]

[0059] In Formula 4, L3 may be a single bond, an alkylidene group or an alkylene group, L4 may be an arylene group, R7 may be hydrogen or an alkyl group, and R8 may be an aryl group.

[0060] In the above, the single bond refers to the case where L3 is not present. Thus, for example, when L3 is a single bond, the nitrogen atom of Formula 4 is directly connected to the silicon atom of the siloxane unit of Formula 2.

[0061] As a suitable example, L3 in Formula 2 may be an alkylidene group or an alkylene group.

[0062] In Chemical Formula 4, specific types of the alkyl group, alkylidene group, alkylene group, aryl group and arylene group are as described at the beginning of this specification.

[0063] Either L3 or the nitrogen atom (when L3 is a single bond) of formula 4 can be linked to the silicon atom of the siloxane unit of formula 2.

[0064] In formula 2, R 4 may be hydrogen, a hydroxyl group, an alkoxy group, or a monovalent hydrocarbon group, which may be an alkyl group, an alkenyl group, an alkynyl group, or an aryl group as described above, and a suitable example may be an alkyl group, but is not limited thereto.

[0065] Specific types of the alkoxy group, monovalent hydrocarbon group, alkyl group, alkenyl group or alkynyl group are as described at the beginning of this specification.

[0066] In Chemical Formula 2, the lower limit of p may be 1, 2, or 3, and the upper limit may be 3, 2, or 1. The p may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. In one example, the p may be 1.

[0067] In Chemical Formula 2, the lower limit of q may be 0, 1, or 2, and the upper limit may be 2, 1, or 0. The q may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. In one example, the q may be 1 or 2.

[0068] The lower limit of the molar percentage of the siloxane unit of the chemical formula 2 relative to the total number of moles of the entire siloxane units contained in the polyorganosiloxane (the total number of moles of M, D, T and Q units) may be about 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol%, and the upper limit may be about 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, or 3 mol%. The mole percent may be greater than or equal to any one of the lower limits recited above, less than or equal to any one of the upper limits recited above, or within a range that is greater than or equal to any one of the lower limits recited above and less than or equal to any one of the upper limits recited above.

[0069] In addition, the lower limit of the molar percentage of the functional group containing a carbon-carbon double bond contained in the siloxane unit of Chemical Formula 2 relative to the total number of moles of the entire silicon-bonded organic groups contained in the polyorganosiloxane may be about 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, or 10 mol%, and the upper limit is about 50 mol%, 45 mol%, 40 mol%, , 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, or 2 mol%. The mol% may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0070] In the polyorganosiloxane, the lower limit of the ratio of the number of moles of the siloxane units of the formula 2 to the number of moles of the siloxane units of the formula 1 may be about 0.1, 0.3, 0.5, 0.7 or 0.9, and the upper limit may be about 2, 1.8, 1.6, 1.4, 1.2 or 1.1. The ratio may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0071] The polyorganosiloxane as described above may have a specific average unit. In this specification, the term "average unit of polyorganosiloxane" means a unit that indicates the ratio of other atoms or functional groups when the total silicon atoms contained in the polyorganosiloxane are converted to 1. Such an average unit may be for one molecule of polyorganosiloxane or for a mixture of two or more molecules of polyorganosiloxane. When the average unit is for a mixture of two or more molecules of polyorganosiloxane, the ratio of other functional groups or atoms is calculated assuming that the number of all silicon atoms contained in the mixture is 1. In the process of producing polyorganosiloxane, it is rare that only one molecule of polyorganosiloxane is substantially produced, and usually a mixture of two or more molecules of polyorganosiloxane is produced.

[0072] The polyorganosiloxane may have an average unit of formula 5: R 1 a R 3 b R 5 c SiO (4-a-b-c) / 2 (Chemical formula 5)

[0073] In formula 5, R 1 is R in formula 1 1 is the same as R 3 is R in chemical formula 2 3 is the same as R 5 is hydrogen, a hydroxyl group, an alkoxy group, or a monovalent hydrocarbon group. The monovalent hydrocarbon group may be an alkyl group, an alkenyl group, an alkynyl group, or an aryl group as described above, and a suitable example may be an alkyl group, but is not limited thereto.

[0074] In Chemical Formula 5, a, b, and c are any numbers.

[0075] In one example, the lower limit of a may be 0.001, 0.005, 0.01, 0.015, 0.02, 0.05, 0.1, 0.15, 0.2, 0.25, or 0.3, and the upper limit may be about 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, or 0.03. a may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0076] In one example, the lower limit of b may be 0.001, 0.005, 0.01, 0.015, 0.02, 0.05, 0.1, 0.15, 0.2, 0.25, or 0.3, and the upper limit may be about 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, or 0.03. The b may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0077] In one example, the lower limit of c may be about 0.1, 0.5, 1, 1.5, or 2, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3, 2.5, or 2. The c may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0078] The lower limit of the number of silicon atoms contained in the polyorganosiloxane of the average unit as described above may be about 2, 3, 5, 10, 15, 20, 25, 30, 35 or 40, and the upper limit may be about 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 or 5. The number of silicon atoms may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0079] The polyorganosiloxane may have a substantially linear structure. In this case, the polyorganosiloxane may have a structure that is substantially composed of only M units and D units, or that contains T and / or Q units together with M units and D units, but the proportion of the T and / or Q units is below a certain level.

[0080] For example, in the polyorganosiloxane, the upper limit of the ratio of the total moles of the T and Q units to the total moles of the siloxane units contained in the polyorganosiloxane (100 × (moles of T units + moles of Q units) / total moles of siloxane units) may be about 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol% or 0.5 mol%, and the lower limit may be 0 mol%. The ratio may be less than or equal to any one of the upper limits described above, or may be greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0081] The lower limit of the weight average molecular weight of the polyorganosiloxane may be about 500, 1,000, 1,500, 2,000, 2,500, 3,000 or 3,500, and the upper limit may be about 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500 or 4,000. The weight average molecular weight may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0082] The present application also relates to a release composition. The term "release composition" means a composition capable of forming a release layer.

[0083] The mold release composition can include a silicone resin component. The term "silicone resin component" means a component that is comprised of one polyorganosiloxane or a mixture of two or more polyorganosiloxanes.

[0084] The silicone resin component may be a curable silicone resin component, in which case the release composition may be a curable composition.

[0085] As used herein, the term "curable composition" may include components that can be converted to a resin via a curing or polymerization reaction, as well as components commonly known as resins.

[0086] The release composition may contain, together with the silicone resin component, a polyorganosiloxane containing the siloxane units of the above-mentioned formula 1 and / or 2. The polyorganosiloxane containing the siloxane units of the above-mentioned formula 1 and / or 2 contained in the release composition may be called an added polyorganosiloxane to distinguish it from the polyorganosiloxane contained in the silicone resin component.

[0087] In one example, the silicone resin component can have a weight average molecular weight greater than that of the additive polyorganosiloxane.

[0088] The release composition may be a solvent-based, water-based or solventless release composition.

[0089] When the release composition is curable, the composition may be of an active energy ray (e.g., ultraviolet ray) curable type, a moisture curable type, a heat curable type, or a room temperature curable type, and in some cases, may be a hybrid type in which two or more of the above are combined. When the release composition is of an active energy ray curable type, the release composition is cured by irradiation of an active energy ray such as ultraviolet ray, when the release composition is of a moisture curable type, the release composition is cured by maintaining the release composition under appropriate humidity, when the release composition is of a heat curable type, the release composition is cured by applying appropriate heat, or when the release composition is of a room temperature curable type, the release composition is cured by maintaining the release composition at room temperature.

[0090] In the release composition of the present application, the lower limit of the proportion of the silicone resin component may be about 10% by weight, 11% by weight, 12% by weight, 14% by weight, 16% by weight, or 18% by weight, and the upper limit may be about 40% by weight, 39% by weight, 38% by weight, 36% by weight, 34% by weight, 32% by weight, 30% by weight, 28% by weight, 26% by weight, 24% by weight, 22% by weight, or 20% by weight. The proportion may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. Within the above range, a release composition that can ensure appropriate release force and excellent residual adhesion rate may be provided.

[0091] In another example, in the release composition of the present application, the lower limit of the ratio of the silicone resin component may be about 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, or 90% by weight, and the upper limit may be about 100% by weight, 99% by weight, 98% by weight, 96% by weight, 95% by weight, 94% by weight, 93% by weight, 92% by weight, 91% by weight, 90% by weight, 89% by weight, or 88% by weight. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. Within the above range, a release composition that can ensure appropriate release force and excellent residual adhesion rate may be provided. The above ratios are based on the solid content, and therefore, in the case where the release composition contains a solvent, the ratios are based on the total weight of the release composition excluding the weight of the solvent.

[0092] In one example, the silicone resin component of the mold release composition may be a so-called addition curing type component. Such a resin component may include, for example, a polyorganosiloxane including a siloxane unit having an alkenyl group bonded to a silicon atom (hereinafter, may be referred to as a first polyorganosiloxane or a first polyorganosiloxane component).

[0093] In the release composition according to one embodiment of the present application, the lower limit of the ratio of the first polyorganosiloxane component based on the total weight of the curable silicone resin component may be about 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight or 98% by weight, and the upper limit may be about 100% by weight, 99.9% by weight or 99% by weight. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. When the curable silicone resin component contains the first polyorganosiloxane component within the above range, an appropriate release force can be ensured.

[0094] In one example, the first polyorganosiloxane component may have an average unit of the following formula 6. Such an average unit may be for one molecule of polyorganosiloxane or for a mixture of two or more molecules of polyorganosiloxane. When the average unit is for a mixture of two or more molecules of polyorganosiloxane, the ratio of other functional groups or atoms is calculated assuming that the number of all silicon atoms contained in the mixture is 1. P a Q b SiO (4-a-b) / 2 (Chemical formula 6)

[0095] In Formula 6, P may be an alkenyl group and Q may be an alkoxy group, a hydroxy group, or a monovalent hydrocarbon group.

[0096] In Chemical Formula 6, specific types of the alkenyl group, alkoxy group, and monovalent hydrocarbon group are as described at the beginning of this specification.

[0097] In Chemical Formula 6, a and b are any numbers.

[0098] In one example, the lower limit of a may be about 0.0001, 0.0005, 0.001, 0.002, 0.005, or 0.01, and the upper limit may be about 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, 0.009, 0.008, 0.007, 0.006, 0.005, 0.004, or 0.003. a may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0099] In one example, the lower limit of b may be about 0.5, 1, 1.5, 1.7, or 1.9, and the upper limit may be about 4, 3.5, 3, 2.5, or 2. The b may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and within a range of less than or equal to any one of the upper limits described above.

[0100] The lower limit of the ratio of the total number of moles of alkenyl groups contained in the average unit of the formula 6 based on the total number of moles of silicon-bonded organic groups contained in the average unit of the formula 6 may be about 0.01 mol%, 0.05 mol%, 0.1 mol%, 0.15 mol%, 0.2 mol%, 0.25 mol%, 0.3 mol%, 0.35 mol%, 0.4 mol%, 0.45 mol%, or 0.5 mol%, and the upper limit may be about 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.8 mol%, 0.7 mol%, or 0.6 mol%. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. At such a ratio, appropriate curing properties can be ensured, and a release layer having the desired release properties can be formed.

[0101] Such alkenyl groups can be present, for example, in siloxane units of the following formula 8 and / or siloxane units of the following formula 9: ViR 6 2SiO 1 / 2 (Chemical formula 8) ViR 6 SiO 2 / 2 (Chemical formula 9)

[0102] In formulas 8 and 9, Vi is an alkenyl group and R 6 is a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group. Specific types of the alkenyl group, the alkoxy group, and the monovalent hydrocarbon group are as described at the beginning of this specification.

[0103] The lower limit of the ratio of the siloxane units of the chemical formula 8 based on the total siloxane units in the first polyorganosiloxane component may be about 0.001 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.03 mol%, 0.04 mol%, 0.05 mol%, 0.06 mol%, 0.07 mol%, 0.08 mol%, 0.09 mol%, or 0.095 mol%, and the upper limit may be about 0.5 mol%, 0.4 mol%, 0.3 mol%, 0.2 mol%, 0.1 mol%, 0.09 mol%, 0.08 mol%, or 0.07 mol%. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to or greater than any one of the lower limits described above and within a range of less than or equal to any one of the upper limits described above.

[0104] The lower limit of the ratio of the siloxane units of the formula 9 based on the total siloxane units in the first polyorganosiloxane component may be about 0.01 mol%, 0.05 mol%, 0.1 mol%, 0.15 mol%, 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.5 mol%, 0.6 mol%, 0.7 mol%, 0.8 mol%, or 0.9 mol%, and the upper limit may be about 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, or 1 mol%. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0105] The first organosiloxane component may include all of the siloxane units of formulas 8 and 9. In this case, the lower limit of the molar ratio of the siloxane units of formula 9 to the siloxane units of formula 8 may be about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 9.5, and the upper limit may be about 20, 18, 16, 14, 12, 11, 10, 9, 8, 7, 6, 5, 4, or 3. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0106] The lower limit of the number of silicon atoms contained in the first polyorganosiloxane component may be about 500, 1,500, 2,000, 2,500 or 3,000, and the upper limit may be about 10,000, 5,000, 4,000, 3,500, 3,000, 2,500 or 2,100. The number of silicon atoms may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0107] The first polyorganosiloxane component may have a substantially linear structure. In such a case, the polyorganosiloxane may have a structure that is substantially composed of only M and D units, or that contains T and / or Q units in addition to M and D units, but the proportion of the T and / or Q units is below a certain level.

[0108] For example, in the first polyorganosiloxane component, the upper limit of the ratio of the total moles of the T and Q units to the total moles of the siloxane units contained in the polyorganosiloxane (100 × (moles of T units + moles of Q units) / total moles of siloxane units) may be about 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol% or 0.5 mol%, and the lower limit may be 0 mol%. The ratio may be less than or equal to any one of the upper limits described above, or may be greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0109] The lower limit of the weight average molecular weight of the first polyorganosiloxane component may be about 100,000, 150,000, 200,000, 250,000, 300,000 or 350,000, and the upper limit may be about 1,000,000, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000 or 400,000. The weight average molecular weight may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to or greater than any one of the lower limits described above and within a range of less than or equal to any one of the upper limits described above.

[0110] The first polyorganosiloxane component may have a polydispersity index (PDI) lower limit of about 1, 1.25, or 1.5, and the upper limit may be about 5, 3.5, or 2.5. The polydispersity index may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0111] In one embodiment, the first polyorganosiloxane component may include a compound represented by Formula A below.

[0112] [ka]

[0113] In the chemical formula A, R a , R b and R 21 may each independently be an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, 2 to 4 carbon atoms, or 2 or 3 carbon atoms.

[0114] In the chemical formula A, R 16 , R 17 , R 18 , R 19 , R 20 , R 22 and R 23 may each independently be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 or 2 carbon atoms.

[0115] In the chemical formula A, m and n may each independently be a number within the range of 1 to 10,000, 1 to 8,000, 1 to 6,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, or 1 to 1,000. Specifically, in the chemical formula A, m may be within the range of 1 to 5,000, 10 to 4,500, 50 to 5,000, 100 to 4,500, 500 to 4,000, or 1,000 to 3,000. In the chemical formula A, n may be within the range of 1 to 100, 2 to 75, 3 to 50, or 4 to 25.

[0116] The first polyorganosiloxane component may include 100 wt% of the compound represented by formula A based on the total weight of the first polyorganosiloxane component. In another example, the first polyorganosiloxane component may include 90 wt% or more, 92.5 wt% or more, 95 wt% or more, 97.5 wt% or more, or 99 wt% or more of the compound represented by formula A based on the total weight of the first polyorganosiloxane component.

[0117] The first polyorganosiloxane component may further include a compound having an alkenyl group at the other end, other than the compound represented by formula A, and including a dialkylsiloxane repeat unit.

[0118] In one example, the silicone resin component of the mold release composition can further include a polyorganosiloxane component having a hydrogen atom bonded to a silicon atom, which can be referred to as a second polyorganosiloxane component.

[0119] The second polyorganosiloxane component is capable of forming a crosslinked structure with the first polyorganosiloxane component.

[0120] In one example, the second polyorganosiloxane component may have an average unit of the following formula 7. Such an average unit may be for one molecule of polyorganosiloxane or for a mixture of two or more molecules of polyorganosiloxane. When the average unit is for a mixture of two or more molecules of polyorganosiloxane, the ratio of other functional groups or atoms is calculated assuming that the number of all silicon atoms contained in the mixture is 1. H c Q d SiO (4-c-d) / 2 (Chemical formula 7)

[0121] In Chemical Formula 7, Q is the same as Q in Chemical Formula 6.

[0122] In Chemical Formula 7, c and d are any numbers.

[0123] In one example, the lower limit of c may be about 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, or 0.6, and the upper limit may be about 2, 1.5, 1, 0.9, 0.8, 0.7, or 0.65. The c may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0124] In one example, the lower limit of d may be about 0.5, 1, or 1.5, and the upper limit may be about 4, 3.5, 3, 2.5, 2, or 1.5. The d may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and within a range of less than or equal to any one of the upper limits described above.

[0125] The lower limit of the ratio of the number of moles of all silicon-bonded hydrogen atoms contained in the average unit of the chemical formula 7 based on the number of moles of all silicon-bonded organic groups contained in the average unit of the chemical formula 7 may be about 1 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, or 30 mol%, and the upper limit may be about 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, or 20 mol%. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. Under such a ratio, appropriate curability can be ensured, and a release layer having the desired release properties can be formed.

[0126] The silicon-bonded hydrogen atoms may be present, for example, at least in the siloxane unit of the following chemical formula 10: HR 6 SiO 2 / 2 (Chemical formula 10)

[0127] In formula 10, R 6 is a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group. Specific types of the alkenyl group, the alkoxy group, and the monovalent hydrocarbon group are as described at the beginning of this specification.

[0128] The lower limit of the ratio of the number of moles of the siloxane units of the silicon chemical formula 10 based on the total number of moles of the siloxane units containing silicon-bonded hydrogen atoms among all the siloxane units contained in the second polyorganosiloxane component may be about 85 mol%, 90 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, 99 mol% or 99.5 mol%, and the upper limit may be about 100 mol%. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0129] The lower limit of the ratio of the siloxane units of the formula 10 based on the total siloxane units in the second polyorganosiloxane component may be about 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol% or 60 mol%, and the upper limit may be about 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol% or 50 mol%. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0130] The lower limit of the number of silicon atoms contained in the second polyorganosiloxane component may be about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or 90, and the upper limit may be about 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55 or 50. The number of silicon atoms may be greater than or equal to any one of the lower limits described above, or less than or equal to any one of the upper limits described above, or may be within a range of greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0131] The second polyorganosiloxane component may have a substantially linear structure. In such a case, the polyorganosiloxane may have a structure that is substantially composed of only M and D units, or that contains T and / or Q units in addition to M and D units, but the proportion of the T and / or Q units is below a certain level.

[0132] For example, in the second polyorganosiloxane component, the upper limit of the ratio of the total moles of the T and Q units to the total moles of the siloxane units contained in the polyorganosiloxane (100 × (moles of T units + moles of Q units) / total moles of siloxane units) may be about 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol% or 0.5 mol%, and the lower limit may be 0 mol%. The ratio may be less than or equal to any one of the upper limits described above, or may be greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0133] The lower limit of the weight average molecular weight of the second polyorganosiloxane component may be about 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000 or 9,500, and the upper limit may be about 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 45,000, 40,000, 30,000, 20,000 or 15,000. The weight average molecular weight may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0134] The lower limit of the polydispersity index (PDI) of the second polyorganosiloxane component may be about 1, 1.25, or 1.5, and the upper limit may be about 5, 3.5, or 2.5. The polydispersity index may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0135] The second polyorganosiloxane component may include a compound represented by the following formula B:

[0136] [ka]

[0137] In the chemical formula B, R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 and R 32may each independently be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 or 2 carbon atoms.

[0138] In chemical formula B, a and b may each independently be a number within the range of 1 to 10,000, 1 to 8,000, 1 to 6,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, or 1 to 1,000. Specifically, in chemical formula B, a and b may each independently be a number within the range of 2 to 500, 5 to 250, 10 to 200, 15 to 150, 20 to 100, or 25 to 50.

[0139] In the silicone resin component, the lower limit of the weight ratio of the second polyorganosiloxane component to 100 parts by weight of the first polyorganosiloxane component may be about 0.1 parts by weight, 0.25 parts by weight, 0.5 parts by weight, 0.75 parts by weight, 1 part by weight, 1.25 parts by weight, 1.5 parts by weight, 1.75 parts by weight, or 2 parts by weight, and the upper limit may be about 10 parts by weight, 8 parts by weight, 6 parts by weight, 4 parts by weight, or 3.5 parts by weight, 3 parts by weight, or 2.5 parts by weight. The ratio may be less than or equal to any one of the upper limits described above, or greater than or equal to any one of the lower limits described above, or greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. When the second polyorganosiloxane component is contained within the above range, it is possible to improve the appropriate crosslink density and ensure excellent durability.

[0140] The release composition according to one embodiment of the present application can include a (meth)acrylate-modified silicone compound together with the silicone resin component. The (meth)acrylate-modified silicone compound may be the additive polyorganosiloxane described above.

[0141] The specific details of the added polyorganosiloxane are as described above.

[0142] In one embodiment, the (meth)acrylate-modified silicone compound may be a compound represented by the following formula C. In another embodiment, the silicone compound of the release composition may include a compound represented by the following formula C.

[0143] The compound of the following formula C is one example of the added polyorganosiloxane.

[0144] [ka]

[0145] In the formula C, A may be a functional group having a ketone group. The A may be derived from a polymerization initiator having a ketone group.

[0146] In another embodiment of the present application, in formula C, A can be represented by formula D below.

[0147] [ka]

[0148] In the chemical formula D, R 15 may be an aryl group having 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 8 or 5 or 6 carbon atoms; or a heteroaryl group having 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 8 or 5 or 6 ring atoms.

[0149] In chemical formula D, L1 is an arylene group having 5 to 30 carbon atoms, 5 to 25 carbon atoms, 5 to 20 carbon atoms, 5 to 15 carbon atoms, 5 to 10 carbon atoms, 5 to 8 carbon atoms, or 5 or 6 carbon atoms; or a heteroarylene group having 5 to 30 ring atoms, 5 to 25 ring atoms, 5 to 20 ring atoms, 5 to 15 ring atoms, 5 to 10 ring atoms, 5 to 8 ring atoms, or 5 or 6 ring atoms, and * represents a site bonded to Q in chemical formula C.

[0150] In formula C, Q may be CR5R6 or NR7. The Q may be derived from a substituent contained in a polymerization initiator having a ketone group.

[0151] The polymerization initiator having a ketone group capable of forming A and Q is, for example, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4-aminobenzo Examples of the compound that can be used include, but are not limited to, phenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, and oligo[2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]propanone].

[0152] The polymerization initiator having a ketone group capable of forming A and Q may be a compound having a structure of the following chemical formula E. That is, A and Q may be derived from a compound having a structure of the following chemical formula E.

[0153] [ka]

[0154] In the chemical formula E, R p1may be an aryl group having 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 8 or 5 or 6 carbon atoms; or a heteroaryl group having 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 8 or 5 or 6 ring atoms.

[0155] In the chemical formula E, R p2 may be an aryl group having 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 8 or 5 or 6 carbon atoms, having one or more substituents selected from the group consisting of an amine group and an alkyl group having 1 to 4 carbon atoms; or a heteroaryl group having 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 8 or 5 or 6 ring atoms, having one or more substituents selected from the group consisting of an amine group and an alkyl group having 1 to 4 carbon atoms. p2 The aryl and heteroaryl groups may additionally have a hydroxy group as a substituent.

[0156] A compound with the structure of formula E is R p1 is the chemical formula D and R 15 In addition, the compound having the structure of the above chemical formula E may be represented by the formula R p2 The substituents of (one of the substituents, if multiple) can be Q in the chemical formula C, and R excluding the substituents p2 can be L1 in formula D.

[0157] Since the compound represented by chemical formula C is derived from a polymerization initiator having a ketone group, the release composition according to an embodiment of the present application can initiate polymerization by including the (meth)acrylate-modified silicone compound without including a separate polymerization initiator.

[0158] In chemical formula C, R1 to R 13 may each independently be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 or 2 carbon atoms.14 may be a hydrogen atom or a methyl group.

[0159] In the chemical formula C, H p may be a peptide bond. The compound represented by formula C having a peptide bond can be endowed with strong cohesive force due to hydrogen bonds and hydrophilic properties.

[0160] In formula C, a, b, c, p and q are each independently a number within the range of 1 to 100, 1 to 80, 1 to 60, 1 to 40, 1 to 20, 1 to 10, 1 to 5, or 1 to 3.

[0161] The compound represented by formula C according to an embodiment of the present application or the additive polyorganosiloxane described above has a siloxane unit, which ensures soft and flexible properties while at the same time imparts hydrophobic properties, and has a (meth)acryl group at the end, which can induce a curing reaction by ultraviolet light.

[0162] By using the compound of formula C or the added polyorganosiloxane in an appropriate amount, it is possible to obtain a cured product that has strong cohesive force due to hydrogen bonds and soft and flexible properties, and at the same time has both hydrophilic and hydrophobic properties, so that the cured product has an appropriate peel strength under room temperature and high temperature conditions, has little change in peel strength even under high temperature and ultraviolet irradiation conditions, and has excellent residual adhesion rate.

[0163] The compound represented by formula C according to an embodiment of the present application may have a weight average molecular weight (Mw) of 1,000 g / mol or more, 1,250 g / mol or more, 1,500 g / mol or more, 1,750 g / mol or more, 2,000 g / mol or more, 2,250 g / mol or more, 2,500 g / mol or more, 2,750 g / mol or more, 3,000 g / mol or more, 3,250 g / mol or more, 3,500 g / mol or more, or 3,750 g / mol or more, or 10,000 g / mol or less, 9,000 g / mol or less, 8,000 g / mol or less, 7,000 g / mol or less, 6,000 g / mol or less, 5,000 g / mol or less, or 4,000 g / mol or less. When the compound represented by formula C has a weight average molecular weight within the above range, a suitable viscosity for application is ensured, and excellent coatability is ensured.

[0164] The compound represented by formula C according to one embodiment of the present application may have a polydispersity index (PDI) of 1 or more, 1.2 or more, 1.4 or more, 1.6 or more, or 1.8 or more, or 3 or less, 2.8 or less, 2.6 or less, 2.4 or less, 2.2 or less, or 2 or less. When the compound represented by formula C has a polydispersity index within the above range, a suitable viscosity for application can be ensured, thereby ensuring excellent coatability.

[0165] The compound or added polyorganosiloxane represented by formula C according to one embodiment of the present application can be prepared by reacting a siloxane resin containing a terminal hydroxyl group with an isocyanate compound containing a (meth)acrylate group under a catalyst, and then adding a polymerization initiator having a ketone group to the reactant. For the specific preparation process, please refer to the following example part.

[0166] In the mold release composition, the upper limit of the weight ratio of the added polyorganosiloxane to 100 parts by weight of the silicone resin component may be 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 parts by weight, 11 parts by weight, or 10 parts by weight, and the lower limit may be about 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight. The ratio may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0167] When the added polyorganosiloxane is contained in the above weight ratio, the adhesive has an appropriate peel strength even at room temperature and at high temperature, and the peel strength changes little even at high temperature and under ultraviolet irradiation conditions, ensuring an excellent residual adhesion rate.

[0168] The release composition according to an embodiment of the present application may further include a catalyst for a curing reaction, for example, a metal catalyst. The metal catalyst may include at least one selected from the group consisting of aluminum, bismuth, lead, mercury, tin, zinc, platinum, silver, and zirconium as a central metal element. In addition, the metal catalyst may have a siloxane group, an ester group, an ether group, or a carboxyl group bonded to the central metal element. The metal catalyst may be, for example, Bis[1,3-bis(2-ethenyl)-1,1,3,3-tetramethyldisiloxane]platinum (CAS No. 81032-58-8), dibutyltin dilaurate, or dimethyltin diacetate, but is not particularly limited thereto, and any metal catalyst commonly used in the art may be used without limitation.

[0169] Considering the components contained in the mold release composition, the metal catalyst may be a platinum catalyst containing platinum (Pt) as a central metal element. In addition, the mold release composition may contain the platinum catalyst in an amount of 0.1 parts by weight or more, 0.5 parts by weight or more, 1 parts by weight or more, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, or 4.5 parts by weight or more, or 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less, based on 100 parts by weight of the curable silicone resin component. In addition, when the content ratio of the platinum catalyst satisfies the above range, it is possible to effectively promote the progress of the cured product formation reaction while reducing side reactions.

[0170] The release composition according to an embodiment of the present application may further include an organic solvent. That is, the release composition may be dispersed in the organic solvent. The term "dispersion" used in the present application may refer to a state in which a solute is dissolved in a solvent, or may refer to a state in which a solute is uniformly spread even if it is not dissolved in the solvent.

[0171] The organic solvent is not particularly limited as long as it is one commonly used in the art. Examples of the organic solvent that can be used include tetrahydrofuran, methyl ethyl ketone, toluene, heptane, and the like, and organic solvents obtained by mixing these in an appropriate weight ratio.

[0172] The organic solvent can be used to the extent that the mold release composition is sufficiently dispersed.Specifically, the mold release composition can contain 200 parts by weight or more, 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, or 400 parts by weight or more of the organic solvent relative to 100 parts by weight of the curable silicone resin component, but is not particularly limited.The upper limit can be determined in consideration of the viscosity appropriate for the process, but is not particularly limited.The mold release composition can contain 2,000 parts by weight or less, 1,500 parts by weight or less, or 1,000 parts by weight or less of the organic solvent relative to 100 parts by weight of the curable silicone resin component.

[0173] The release composition according to one embodiment of the present application may further include one or more additives as exemplified below in order to secure additional physical properties. However, the additives may be any additives commonly used in the art and are not necessarily limited to the additives exemplified below.

[0174] The release composition according to an embodiment of the present application may further include a dispersant. The dispersant may be, for example, polyamidoamine and its salt, polycarboxylic acid and its salt, modified polyurethane, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid-formaldehyde condensate, polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, pigment derivative, etc., but any dispersant known in the art may be used without limitation. For example, Disperbyk-1799 (BYK) may be used.

[0175] The release composition according to an embodiment of the present application may further include a plasticizer. The type of the plasticizer is not particularly limited, and may be, for example, one or more selected from the group consisting of phthalic acid compounds, phosphoric acid compounds, adipic acid compounds, sebacic acid compounds, citric acid compounds, glycolic acid compounds, trimellitic acid compounds, polyester compounds, epoxidized soybean oil, chlorinated paraffin, chlorinated fatty acid esters, fatty acid compounds, and vegetable oils.

[0176] The phthalic acid compound may be one or more of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-n-octyl fullerate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, n-hexyl n-decyl phthalate, n-octyl phthalate, and n-decyl phthalate. The phosphoric acid compound may be one or more of tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, and trichloroethyl phosphate. The adipic acid compound may be one or more of dibutoxyethoxyethyl adipate (DBEEA), dioctyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, diisononyl adipate (DINA), diisodecyl adipate (DIDP), n-octyl n-decyl adipate, n-heptyl adipate, and n-nonyl adipate. The sebacic acid compound may be one or more of dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, and butyl benzyl. The citric acid compound may be one or more of triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate. The glycolic acid compound may be one or more of methylphthalyl ethyl glycolate, ethylphthalyl ethyl glycolate, and butylphthalyl ethyl glycolate.The trimellitic acid compound may be one or more of trioctyl trimellitate and tri-n-octyl n-decyl trimellitate.The polyester compound may be a reaction product of a diol selected from butanediol, ethylene glycol, propane 1,2-diol, propane 1,3 diol, polyethylene glycol, glycerol, a diacid (selected from adipic acid, succinic acid, succinic anhydride) and a hydroxy group (e.g., hydroxystearic acid).

[0177] The release composition according to an embodiment of the present application may further include a reaction accelerator as necessary. The reaction accelerator may function to accelerate the curing reaction of the release composition. The type of the reaction accelerator is not particularly limited, and for example, dimethyl-p-toluidine (N,N-Dimethyl-p-toluidine; DMPT) may be used.

[0178] The release composition according to an embodiment of the present application may further include a viscosity modifier, such as a thixotropy imparting agent, a diluent, a surface treatment agent, a dispersion stabilizer, or a reaction control agent, for adjusting the viscosity, for example, to increase or decrease the viscosity or to adjust the viscosity due to shear force, as necessary. The thixotropy imparting agent can adjust the viscosity due to the shear force of the release composition. Examples of the thixotropy imparting agent that can be used include fumed silica. The diluent is generally used to reduce the viscosity of the release composition, and various types of agents known in the industry can be used without limitation as long as they can exhibit the above-mentioned action. The surface treatment agent is for surface treatment of the filler composition introduced into the cured product of the release composition, and various types of agents known in the industry can be used without limitation as long as they can exhibit the above-mentioned action. The dispersion stabilizer can be used to stabilize the dispersibility between the components in the release composition, and various types of agents known in the industry can be used without limitation as long as they can exhibit the above-mentioned action. The reaction control agent can be used to control a chemical reaction, such as the curing of the release composition, and various types of agents known in the industry can be used without limitation as long as they can exhibit the above-mentioned action. In addition, various kinds of materials known in the industry can be used without any restrictions as long as they can exhibit the above-mentioned action.

[0179] The release composition according to one embodiment of the present application may be substantially free of a silane coupling agent and / or a crosslinking agent. Even if the release composition does not contain a silane coupling agent and / or a crosslinking agent, the combination of the curable silicone resin component and the silicone compound described above can ensure adhesion to the substrate film described below and maximize solvent resistance.

[0180] The term "substantially free" used in this application means that the relevant substance is not added artificially, and when present naturally, it can mean that the substance is contained in an amount of 1% by weight or less, or 0.1% by weight or less based on the total weight of the target.

[0181] The silane coupling agent is not particularly limited as long as it is one generally used in the art. Examples of the coupling agent include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, γ-acetoacetatepropyltrimethoxysilane, γ-acetoacetatepropyltriethoxysilane, β-cyanoacetyltrimethoxysilane, β-cyanoacetyltriethoxysilane, and acetoxyacetotrimethoxysilane.

[0182] The crosslinking agent is not particularly limited as long as it is one generally used in the art. Examples of the crosslinking agent include epoxy crosslinking agents such as ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidylethylenediamine, and glycerin diglycidyl ether; aziridine crosslinking agents such as N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), triethylenemelamine, bisisoprotoyl-1-(2-methylaziridine), and tri-1-aziridinylphosphine; metal chelate crosslinking agents in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium is coordinated to acetylacetone or ethyl acetoacetate; isophorone diisocyanate; diisocyanate, methylene dicyclohexyl diisocyanate, cyclohexane diisocyanate, and the like; derivatives thereof such as dimers or trimers; or a reaction product of any one of the above with a polyol (e.g., trimethylolpropane); alkylene diisocyanate compounds having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms, such as hexamethylene diisocyanate (HMDI), and derivatives thereof such as dimers or trimers; or a reaction product of any one of the above with a polyol (e.g., trimethylolpropane).

[0183] The present application also relates to a release layer. The release layer may include the release composition or a cured product thereof.

[0184] Therefore, the release layer may include the silicone resin component and the silicone compound or the added polyorganosiloxane. The release layer may be formed by curing the release composition according to the embodiment of the present application described above. The curing may be appropriately performed by various methods as described above. The release layer may include a residual component after curing the release composition according to the embodiment of the present application described above.

[0185] The release layer according to one embodiment of the present application may contain a silicone resin component in the range of 80% to 95% by weight based on the total weight. In another embodiment, the release layer may contain a silicone resin component in the range of 81% by weight or more, 82% by weight or more, 83% by weight or more, 84% by weight or more, or 85% by weight or more, or 94% by weight or less, 93% by weight or less, 92% by weight or less, 91% by weight or less, or 90% by weight or less based on the total weight. When the release layer contains a silicone resin component within the above range, it is possible to ensure an excellent residual adhesion rate as well as an appropriate release peel force.

[0186] The curable silicone resin component of the release layer according to one embodiment of the present application may include a first polyorganosiloxane component containing an alkenyl group at its terminal and including a dialkylsiloxane repeat unit, and may additionally include a second polyorganosiloxane component containing a dialkylsiloxane repeat unit and a monoalkylsiloxane repeat unit.

[0187] The first polyorganosiloxane component and the second polyorganosiloxane component are the same as those described in the release composition according to the example of the present application, and therefore, detailed description thereof will be omitted.

[0188] The silicone compound of the release layer according to one embodiment of the present application may include a (meth)acrylate-modified silicone compound or an added polyorganosiloxane. The (meth)acrylate-modified silicone compound is the same as that described in the release composition according to one embodiment of the present application, and therefore the detailed description is omitted.

[0189] In the release layer according to one embodiment of the present application, the absolute value of the rate of change (ΔP1) of the peel force according to the following formula 1 may be within a predetermined range. For example, the upper limit of the absolute value of the rate of change may be about 30%, 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, or 13%, and the lower limit may be about 0.001%, 0.01%, or 0.1%. The absolute value may be equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The ΔP1 may be a negative number or a positive number. ΔP1=100X(P2-P1) / P1(Formula 1)

[0190] In Equation 1, P1 is the release force measured by maintaining the release layer attached to the pressure-sensitive adhesive layer at 25°C for 24 hours and then peeling it at a peel angle of 180° and a peel speed of 0.3 m / min at 25°C, and P2 is the release force measured by irradiating the release layer attached to the pressure-sensitive adhesive layer with ultraviolet light, maintaining the layer at 60°C for 24 hours, and then peeling it at a peel angle of 180° and a peel speed of 0.3 m / min at 25°C.

[0191] The method for measuring the peeling forces P1 and P2 in the formula 1 is described in the Examples section of this specification. For example, the peeling force P1 is calculated by the peeling force A in the Examples section. RT(1d) and the peel force P2 is the peel force A of the example item 21 Or A 22 It is.

[0192] The order of irradiation with ultraviolet light and maintaining at 60° C. for measuring the peel force P2 in Equation 1 is not limited. That is, maintaining at 60° C. may be performed after irradiation with ultraviolet light, or conversely, irradiation with ultraviolet light may be performed after maintaining at 60° C.

[0193] When ultraviolet light is applied to the release layer to confirm Equation 1, the ultraviolet light is about 1 J / m2 ~3J / m 2 The irradiation can be performed for about 15 to 90 seconds using light having an energy of about 150 to 200 nm and a wavelength of about 300 to 400 nm.

[0194] The release layer according to one example of the present application may have a predetermined range of residual adhesion rate (Ad) according to the following formula 2. For example, the lower limit of the residual adhesion rate may be about 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96% or 97%. The closer the residual adhesion rate (Ad) according to the following formula 2 is to 100%, the better the performance is. Therefore, the upper limit of the residual adhesion rate (Ad) is not particularly limited, and may be, for example, about 100%, 99.9% or 99%. The residual adhesion rate may be equal to or greater than any one of the lower limits described above, or may be equal to or greater than any one of the lower limits described above and be equal to or greater than any one of the upper limits described above. Residual adhesion rate (Ad)=100XA f / A i (Formula 2)

[0195] In Equation 2, A i A is a peel strength measured by attaching an adhesive tape to the release layer and peeling the adhesive tape at a peel angle of 180 degrees at 25° C. and a peel speed of 0.3 m / min. f is the peel force A i The peel force A was measured on the release layer. i The peel strength was measured by attaching an adhesive tape in the same manner as in measuring the peel strength, and peeling the adhesive tape at 25° C. at a peel angle of 180° and a peel speed of 0.3 m / min.

[0196] The residual adhesion rate (Ad) according to the above formula 2 can be specifically measured according to the examples.

[0197] In the release layer according to one embodiment of the present application, the peel force P1 in the formula 1 may be in the range of 10 gf / inch to 30 gf / inch. In other examples, the release force P1 may be 11 gf / inch or more, 12 gf / inch or more, 13 gf / inch or more, 14 gf / inch or more, 15 gf / inch or more, 16 gf / inch or more, or 17 gf / inch or more, or 29 gf / inch or less, 28 gf / inch or less, 27 gf / inch or less, 26 gf / inch or less, 25 gf / inch or less, 24 gf / inch or less, 23 gf / inch or less, 22 gf / inch or less, 21 gf / inch or less, 20 gf / inch or less, or 19 gf / inch or less.

[0198] When the peel strength P1 of the release layer satisfies the above range, it can be regarded as having an appropriate peel strength such that when attached to an adherend, it is not easily peeled off as the process progresses, but is easily peeled off when it is required to be peeled off from the adherend.

[0199] The release layer according to one embodiment of the present application may have a release force in the range of 10 gf / inch to 45 gf / inch, measured at a peel angle of 180 degrees and a peel speed of 0.3 m / min after maintaining the release layer attached to the pressure-sensitive adhesive layer at 60° C. for 24 hours. In other examples, the release force may be 11 gf / inch or more, 12 gf / inch or more, 13 gf / inch or more, 14 gf / inch or more, 15 gf / inch or more, 16 gf / inch or more, or 17 gf / inch or more, or 44 gf / inch or less, 42 gf / inch or less, 40 gf / inch or less, 38 gf / inch or less, 36 gf / inch or less, 34 gf / inch or less, 32 gf / inch or less, 30 gf / inch or less, 28 gf / inch or less, 26 gf / inch or less, 24 gf / inch or less, 22 gf / inch or less, or 20 gf / inch or less. The method for measuring the release peel force is described in the Examples section of this specification. The release force is the peel force A measured in the Examples section of this specification. 60(1d) This applies.

[0200] When the release layer satisfies the above peeling force, it can be considered to have an appropriate peeling force such that when attached to an adherend, even in a high-temperature process, it is not easily peeled off as the process progresses, but is easily peeled off when it is required to be peeled off from the adherend.

[0201] The present application also relates to a release film or adhesive film including the release layer. The release film may include a base film and the release layer attached to one or both sides of the base film. The adhesive film may include the release layer and an adhesive layer attached to the release layer.

[0202] The types of the base film and the adhesive layer applied to the release film and the adhesive film are not particularly limited, and any known base film of a release film or adhesive layer of an adhesive film may be applied.

[0203] Examples of the base film include papers such as fine paper, clay-coated paper, cast-coated paper, and kraft paper; laminated papers obtained by laminating thermoplastic resins such as polyethylene resins to these papers; paper sheets such as synthetic paper; glass sheets; polyolefin resins such as polyethylene resin and polypropylene resin; polyester resins such as polybutylene terephthalate resin, polyethylene terephthalate resin, and polyethylene naphthalate resin; polyesterimide resins; acetate resins; polystyrene resins; and vinyl chloride resins. Examples of the adhesive layer include known acrylic, urethane, or silicone adhesive layers.

[0204] The thicknesses of the release layer, the base film and the adhesive layer are appropriately selected depending on the application and are not particularly limited. For example, the base film can be usually formed to a thickness of 5 μm to 500 μm or 10 μm to 100 μm.

[0205] The release layer of the release film according to this example of the present application is the same as the release layer according to the example of the present application described above, and therefore a detailed description thereof will be omitted.

[0206] The thickness of the release layer is appropriately selected depending on the application, and is not particularly limited, and may be usually formed to a thickness of 30 nm to 5 μm.

[0207] The release film according to an example of the present application can be manufactured by applying the release composition according to an example of the present application to one surface of a base film, and then curing the release composition to form a release layer.

[0208] The method of applying the release composition is not particularly limited as long as it is a method used in the art. For example, Mayer bar coating, knife coating, reverse roll coating, roll coating, calendar coating, curtain coating, cast coating, dip coating, etc. can be used.

[0209] In addition, the curing may be appropriately performed in various ways as described above, and here, the curing may be appropriately performed by thermal curing. The thermal curing may be appropriately performed in consideration of the components contained in the release layer, their content ratios, thickness, etc., and may be performed, for example, at 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher for 15 seconds to 60 minutes. If necessary, ultraviolet irradiation may be performed for the curing, as in the method performed to measure the peel force P2 described above. Effect of the Invention

[0210] The present application can provide a polyorganosiloxane and a release composition that can form a release layer that can ensure solvent resistance by maximizing the bonding strength between a substrate film and a release layer.

[0211] In addition, the present application can provide a polyorganosiloxane and a release composition that can form a release layer that has an appropriate peel strength even at room temperature and high temperature conditions, exhibits little change in peel strength even at high temperature and under ultraviolet irradiation conditions, and can ensure an excellent residual adhesion rate.

[0212] In addition, the present application can provide a release layer, and a release film and an adhesive film that include the release layer, as applications of the polyorganosiloxane and the release composition. [Brief description of the drawings]

[0213] FIG. 1 shows the polyorganosiloxane produced in the production example. 1 1 H NMR measurement data. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0214] Hereinafter, the present application will be described through examples and comparative examples, but the scope of the present application is not limited to the contents presented below.

[0215] 1. Evaluation of release strength A test specimen was prepared by laminating an adhesive layer of an adhesive tape for measuring release force (TESA7475 PV2, TESA) on the release layer of the release film of the Examples or Comparative Examples. The adhesion was performed by placing the adhesive tape on the release layer and then moving a roller with a load of 2.5 kg back and forth three times. Thereafter, the adhesive tape (TESA7475) was peeled at a peel angle of 180 degrees and a peel speed of 0.3 m / min at room temperature (about 25° C.) using a physical property measuring device (AR-1000, Cheminstruments) to measure the release force.

[0216] 2. Evaluation of residual adhesion rate (Ad) The residual adhesion rate Ad was determined by the following formula A. Ad=100XAf / Ai (formula A)

[0217] In the formula A, Ai is the release peel force measured after maintaining the test piece prepared according to the method for evaluating the release peel force at room temperature (about 25° C.) for about 24 hours.

[0218] In Equation A, Af is the release force measured after a standard tape (TESA7475, TESA) is attached to the release layer of the release film after measuring the release force Ai in the same manner as for measuring the release force Ai to prepare a test specimen, and the test specimen is kept at room temperature (about 25° C.) for about 24 hours.

[0219] The release peel strengths Ai and Af were measured by peeling an adhesive tape (TESA7475) at a peel angle of 180 degrees and a peel speed of 0.3 m / min at room temperature (about 25° C.) using a physical property measuring device (AR-1000, Cheminstruments) in the same manner as in the measurement method of the release peel strength.

[0220] 3. Evaluation of solvent resistance The release layer of the release film of the Example or Comparative Example was rubbed with a cloth soaked in toluene until even a part of the release layer was peeled off to evaluate the solvent resistance. The rubbing with the cloth was performed using No. 542-AB equipment (Yasauda). The evaluation criteria for solvent resistance are as follows.

[0221] <Evaluation criteria for solvent resistance> P: The number of friction cycles is 8 or more until even a part of the release layer is peeled off. N: The number of friction cycles until even a part of the release layer is peeled off is less than 8

[0222] Production Example 1. Production of Silicone Compound (A) A polyorganosiloxane (KF-6001, Shinetsu Silicone) represented by the following chemical formula K1 was prepared.

[0223] [ka]

[0224] In the chemical formula K1, a was about 30, and the weight average molecular weight was about 2,000 g / mol.

[0225] A mixture was prepared by mixing polyorganosiloxane of formula K1, MOI (methacryloyloxyethyl isocyanate) and THF (tetrahydrofuran) in a weight ratio of 10:0.39:10 (K1:MOI:THF). The mixing ratio was adjusted so that about half of the total hydroxyl groups present in the polyorganosiloxane of formula K1 reacted with the MOI. Then, 0.14 parts by weight of DBTDL (dibutyltin dilaurate) was added to 100 parts by weight of the polyorganosiloxane and reacted at 60°C. Through the reaction, the hydroxyl group of the polyorganosiloxane of formula K2 reacts with the isocyanate of the MOI to form a polyorganosiloxane having the structure of formula K2 below, in which a methacryloyloxyethyl group is linked to the end of the polyorganosiloxane by a peptide (urethane) bond.

[0226] [ka]

[0227] In the chemical formula K2, a is the same as in the chemical formula K1, and R1 and R2 are each independently a hydroxyl group or a functional group of the following chemical formula K2-1.

[0228] [ka]

[0229] In formula K2-1, the leftmost nitrogen atom is linked to the rightmost or leftmost carbon atom of formula K2.

[0230] Considering the actual reaction, the resultant product after the reaction may be a mixture of polyorganosiloxanes in which R1 and R2 in the structure of formula K2 are all hydroxyl groups, polyorganosiloxanes in which R1 and R2 are all functional groups of formula K2-1, and / or polyorganosiloxanes in which one of R1 and R2 is a hydroxyl group and the other is a functional group of formula K2-1.

[0231] The reaction product (containing polyorganosiloxane of formula K2) and 4-ABP (4-aminobenzophenone) were mixed in a weight ratio of 100:4.2 (result:4-ABP) to prepare a mixture, which was then reacted at about 60°C. The mixing ratio was adjusted to an equivalent ratio such that most of the hydroxyl groups present in the reaction product reacted with the 4-ABP. Through the reaction, the amino groups of the 4-ABP reacted with the hydroxyl groups present in the reaction product, thereby obtaining a polyorganosiloxane (weight average molecular weight: about 3,800 g / mol) having an average unit of approximately formula 1A below. The following average unit is the ratio of each siloxane unit when the total number of moles of all siloxane units contained in the polyorganosiloxane is set to 1. (R a Me2SiO 1 / 2 ) 0.03 (R b Me2SiO 1 / 2 ) 0.03 (MeSiO 2 / 2 ) 0.94 (Chemical formula 1A)

[0232] In formula 1A, R a is a functional group of the following chemical formula K2-2, R b is a functional group of the above chemical formula K2-1, and Me is a methyl group.

[0233] [ka]

[0234] [ka]

[0235] In the formula K2-2, the leftmost carbon atom is linked to the silicon atom of the siloxane unit of the formula 1A, and the leftmost carbon atom of the formula 1A-1 is linked to the silicon atom of the siloxane unit of the formula 1A.

[0236] FIG. 1 shows the polyorganosiloxane of formula 1A. 1 1 H NMR measurement results. 1 H NMR analysis was performed using a known measuring instrument (Avance Neo, Bruker), and chemical transitions (shifts) were expressed using dilute tetramethylsilane in CDCl (TMS) as the reference compound (RC).

[0237] <Example 1> A curable composition was prepared by mixing polyorganosiloxane of the following formula 2A (KS-847H, Shinetsu Silicone) (weight average molecular weight of about 350,000 g / mol), polyorganosiloxane of the following formula 3A (X-92-122, Shinetsu Silicone) (weight average molecular weight of about 10,000 g / mol), polyorganosiloxane having an average unit of formula 1A in Preparation Example 1, platinum catalyst (PL-50L, Shinetsu Silicone), and solvent (S) in the weight ratio shown in Table 1 below. As the solvent (S), a mixture of THF (tetrahydrofuran), MEK (methylethyl ketone), toluene (T) and n-heptane (H) in a weight ratio of 30:20:30:20 (THF:MEK:T:H) was used.

[0238] [ka]

[0239] In Chemical Formula 2A, m is a number of about 1,500, and n is a number of about 12 to 13.

[0240] [ka]

[0241] In Chemical Formula 3A, a and b are each a number of about 34 to 36.

[0242] The curable composition was Meyer bar coated on one side of a substrate film (PET (polyethylene terephthalate) film (SG00, SKC)) having a thickness of about 50 μm, and cured in an oven at about 150° C. for about 3 minutes to prepare a release film having a release layer.

[0243] <Examples 2 and 3 and Comparative Example 1> A curable composition, a release layer and a release film were prepared in the same manner as in Example 1, except that the weight ratio during mixing was changed as shown in Table 1 below. The percentages in Table 1 below are percentages by weight.

[0244] [Table 1]

[0245] The physical property evaluation results for the release films of the examples and comparative examples are summarized in the following Table 2. In the following Table 2, the unit of the release peeling force is all gf / inch.

[0246] [Table 2]

[0247] In Table 2, A RT(1d) , A 60(1d) and A 22 All of the values ​​are the release peel strengths measured by the above-mentioned release peel strength evaluation method, and the unit is gf / inch.

[0248] In Table 2, A RT(1d) A is the release peel strength measured after maintaining the test piece prepared according to the method for evaluating release peel strength at room temperature (about 25°C) for about 24 hours. 60(1d) is the release peel strength measured after the test piece prepared according to the method for evaluating the release peel strength was kept at 60° C. for about 24 hours.

[0249] In Table 2, A 21A is the peel strength measured after irradiating the test piece prepared according to the method for evaluating the peel strength with ultraviolet light and maintaining it at 60°C for 24 hours. 22 is the release peel strength measured after the test piece prepared according to the method described in the evaluation method for release peel strength was kept at 60°C for 24 hours and then irradiated with ultraviolet light. The ultraviolet light irradiation was performed using a metal halide lamp with ultraviolet light having a wavelength of about 300 nm to 400 nm at about 3 J / m 2 The sample was irradiated with a light intensity of .

[0250] In Table 2, △A1 is the peel force A RT(1d) and A 21 The formula is 100X(A 21 -A RT(1d) ) / A RT(1d) △A2 is the value obtained by substituting RT(1d) and A 22 The formula is 100X(A 22 -A RT(1d) ) / A RT(1d) This value is obtained by substituting

[0251] In Table 2, Ad is the residual adhesion rate Ad calculated by the above formula A.

[0252] In Table 2, the solvent resistance is organized according to the criteria of the solvent resistance evaluation method described above, and the solvent resistance number is the number of times rubbed until even a part of the release layer is peeled off in the solvent resistance evaluation described above.

Claims

1. A polyorganosiloxane comprising a siloxane unit of the following formula 1 and a siloxane unit of the following formula 2: (R １ ｍ R ２ ｎ SiO （４－ｍ－ｎ）／２ ) (Chemical formula 1) In Formula 1, R １ and R ２ are each a substituent bonded to a silicon atom, R １ is a functional group containing a carbon-carbon double bond, R ２ is a hydrogen atom, a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group, m is a number equal to or greater than 1, n is a number equal to or greater than 0, and m+n is a number ranging from 1 to 3: (R ３ ｐ R ４ ｑ SiO （４－ｐ－ｑ）／２ ) (Chemical formula 2) In formula 2, R ３ and R ４ are each a substituent bonded to a silicon atom, R ３ is a ketone group-containing functional group, R ４ is a hydrogen atom, a hydroxyl group, an alkoxy group, or a monovalent hydrocarbon group, p is a number of 1 or more, q is a number of 0 or more, and p+q is a number in the range of 1 to 3.

2. The polyorganosiloxane according to claim 1, characterized in that the functional group containing a carbon-carbon double bond is represented by the following chemical formula 3: 【Chemistry 1】 In Chemical Formula 3, L 1 is a single bond, an alkylidene group or an alkylene group; L ２ is an alkylidene group or an alkylene group, R ５ and R ６ are each independently hydrogen or an alkyl group; 1 Or the nitrogen atom is connected to the silicon atom of the siloxane unit of formula (3).

3. The polyorganosiloxane of claim 1, characterized in that the ketone group-containing functionality is represented by the following chemical formula 4: 【Chemistry 2】 In Chemical Formula 4, L ３ is a single bond, an alkylidene group or an alkylene group; L ４ is an arylene group, R ７ is hydrogen or an alkyl group; R ８ is an aryl group, and L in the above formula 4 ３ is connected to the silicon atom of the siloxane unit.

4. The polyorganosiloxane of claim 1, characterized in that it has an average unit of the following chemical formula 5: R １ ａ R ３ ｂ R ５ ｃ SiO （４－ａ－ｂ－ｃ）／２ (Chemical formula 5) In Chemical Formula 5, R １ is R in Chemical Formula 1 １ is the same as R ３ is R in Chemical Formula 2 ３ is the same as R ５ is a hydrogen atom, a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group, a is a number in the range of 0.001 to 1, b is a number in the range of 0.001 to 1, and c is a number in the range of 0.1 to 10.

5. 2. The polyorganosiloxane according to claim 1, characterized in that the weight average molecular weight is in the range of 500 g / mol to 10,000 g / mol.

6. a curable silicone resin component; and A mold release composition comprising a polyorganosiloxane as defined in any one of claims 1 to 5.

7. 7. The mold release composition according to claim 6, wherein the curable silicone resin component is an addition-curable silicone resin component.

8. The mold release composition according to claim 6, characterized in that the curable silicone resin component contains a polyorganosiloxane having an average unit of the following chemical formula 6 and a polyorganosiloxane having an average unit of the following chemical formula 7: P ａ Q ｂ SiO （４－ａ－ｂ）／２ (Chemical formula 6) In Chemical Formula 6, P is an alkenyl group, Q is an alkoxy group, a hydroxy group, or a monovalent hydrocarbon group, a is a number in the range of 0.0001 to 0.1, and b is a number in the range of 1 to 4: H ｃ Q ｄ SiO （４－ｃ－ｄ）／２ (Chemistry 7) In Chemical Formula 7, Q is an alkoxy group, a hydroxy group, or a monovalent hydrocarbon group; c is a number in the range of 0.01 to 0.9; and d is a number in the range of 1 to 4.

9. The mold release composition according to claim 8, wherein the polyorganosiloxane of formula 6 comprises one or more siloxane units selected from the group consisting of a siloxane unit of formula 8 below and a siloxane unit of formula 9 below: ViR ６ ２ SiO １／２ (Chemical formula 8) ViR ６ SiO ２／２ (Chemical formula 9) In formulas 8 and 9, Vi is an alkenyl group, R ６ is a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group.

10. The release composition according to claim 8, wherein the polyorganosiloxane of formula 7 contains a siloxane unit of formula 10: HR ６ SiO ２／２ (Chemical formula 10) In formula 10, R ６ is a hydroxy group, an alkoxy group, or a monovalent hydrocarbon group.

11. 7. The mold release composition according to claim 6, comprising up to 19 parts by weight of polyorganosiloxane per 100 parts by weight of the curable silicone resin component.

12. The mold release composition according to claim 8, wherein the polyorganosiloxane having an average unit of the chemical formula 6 has a weight average molecular weight in the range of 100,000 g / mol to 1,000,000 g / mol.

13. The release composition according to claim 8, wherein the polyorganosiloxane having an average unit of the formula 7 has a weight average molecular weight in the range of 1,000 g / mol to 50,000 g / mol.

14. A release layer comprising the release composition defined in claim 7 or a cured product thereof.

15. The release layer according to claim 14, wherein the absolute value of the peel force change rate ΔP1 according to the following formula 1 is 30% or less: ΔP1=100X(P ２ -P １ ) / P １ (Formula 1) In Equation 1, P １ is the release force measured while peeling the release layer at a peel angle of 180° and a peel speed of 0.3 m / min at 25° C. after maintaining the release layer attached to the pressure-sensitive adhesive layer at 25° C. for 24 hours, and P ２ is the release force measured by irradiating the release layer with the pressure-sensitive adhesive layer attached thereto with ultraviolet light, maintaining the layer at 60° C. for 24 hours, and then peeling the layer at a peel angle of 180° and a peel speed of 0.3 m / min at 25° C.

16. The release layer according to claim 14, wherein the residual adhesion rate Ad according to the following formula 2 is 80% or more: Ad=100XAf / Ai (Formula 2) In Equation 2, Ai is the release force measured by attaching an adhesive tape to the release layer and peeling the adhesive tape at a peel angle of 180° at 25° C. and a peel speed of 0.3 m / min, and Af is the release force measured by attaching the same adhesive tape to the release layer used to measure the release force Ai, and peeling the adhesive tape at a peel angle of 180° at 25° C. and a peel speed of 0.3 m / min.

17. A release film comprising a base film and a release layer as defined in claim 14 attached to one or both sides of said base film.

18. 15. An adhesive film comprising: a release layer as defined in claim 14; and an adhesive layer attached to said release layer.

Images