TW202233759A - Curable silicone composition, release coating agent for silicone adhesive, release film and lamination body thereof - Google Patents

Abstract

To provide a curable silicone composition for a release agent that can form a release film in which, even when the film is thin, the release force is small from a silicone adhesive, particularly from a silicone adhesive having a low storage modulus at a low temperature. Further, to provide: a release film that has a low release force and that has superior smoothness of an adhesive layer surface after release; a laminate; and a method for producing said laminate. A curable silicone composition comprising: (A) a mixture of two or more types of fluoroalkyl group-containing organopolysiloxanes which are not compatible with each other, which each include a fluoroalkyl group and an alkenyl group, and in which the contained amounts of fluoroalkyl groups are different from each other; (B) an organohydrogen polysiloxane; (C) an organopolysiloxane that has a fluorine atom-containing organic group and that does not include a hydrosilylation reaction-causing group; (D) a catalyst for hydrosilylation reaction; and (E) an organic solvent. A use of a release film or the like provided with a cured product of said curable silicone composition.

Description

Curable polysiloxane composition, release coating agent for polysiloxane adhesive composed of the above composition, release film, and laminate

The present invention relates to a curable polysiloxane composition, a release coating agent comprising the composition, especially a release coating for a polysiloxane adhesive (pressure-sensitive adhesive) with low storage elastic modulus at low temperature A cloth, a release film using the release coating agent, especially a release film for a polysiloxane adhesive, and a laminate comprising the aforementioned release film, especially a laminate comprising a release film and a polysiloxane adhesive.

Polysiloxane adhesives (pressure-sensitive adhesives) have excellent heat resistance, cold resistance, weather resistance, chemical resistance and electrical insulation, etc., so they are used as industrial protective tapes, masking tapes, etc., or medical applications. Various functional tapes and other adhesives. In addition, in recent years, it has also been used for so-called assembly applications represented by bonding of optical components for liquid crystal displays (display devices, functional films, lenses, etc.). Since the polysiloxane adhesive will strongly adhere to the surface coated with polysiloxane rubber and polysiloxane-based materials, the usual polysiloxane-based release agent used in acrylic or organic rubber-based adhesives cannot be used. , Various curable polysiloxane peeling agent compositions are proposed to form a peeling film that can easily peel off the polysiloxane adhesive. The composition is applied as a release coating agent on a flexible substrate such as a plastic film to form a release film, and then the release film is laminated with a polysiloxane adhesive to laminate a sheet or roll tape. body use.

For example, Patent Document 1 proposes a curable coating composition comprising an organopolysiloxane, an organohydrogenpolysiloxane, a catalyst for hydrosilylation, and a silicon oxide as a release agent for a polysiloxane adhesive. A hydrogenation reaction inhibitor, the organopolysiloxane contains at least 300 silicon atoms, and has 0.5-2 mol % of vinyl-containing siloxane units and 30 mol % of fluoroalkyl-containing siloxane units. Each molecule of the organohydrogenpolysiloxane has on average at least 2 silicon atoms bonded to hydrogen atoms, and is compatible with the aforementioned organopolysiloxane.

In addition, Patent Document 2 proposes a release agent composition for a polysiloxane adhesive comprising two types of fluoroalkyl-modified polydimethylsiloxanes having different alkenyl groups for the purpose of lightening peeling, and a release sheet formed by applying the polysiloxane adhesive release agent composition to a base material.

Furthermore, Patent Document 3 proposes a release agent composition for a polysiloxane adhesive, and a release film formed by applying the release agent composition for a polysiloxane adhesive to a plastic film. For the purpose of adjusting the peeling force, the release agent composition includes: an organopolysiloxane having an organic group containing an alkenyl group and a fluoroalkyl group, an organohydrogen polymer having at least 3 silicon atoms bonded to hydrogen atoms in one molecule. Siloxanes, catalysts for hydrosilylation, organic solvents, and organopolysiloxanes with alkenyl groups and no fluoroalkyl groups.

Patent Document 4 proposes an organosiloxane peeling control agent having an organic group containing a fluorine atom and no hydrosilylation reactive group, a peeling agent composition containing the organosiloxane peeling control agent, and a A release sheet for the hardened layer of the hardened product.

In Patent Document 5, a curable polysiloxane composition is proposed, characterized in that, as an organopolysiloxane having a fluoroalkyl group and at least two alkenyl groups in the molecule, it is contained at 25° C. when mixed without a solvent. After stirring, and after standing for 24 hours, visually observe the combination of two or more kinds of organopolysiloxanes that are not completely compatible or completely incompatible; A peeling layer of a cured product obtained by curing an oxygen composition; a laminate comprising a structural unit in which a polysiloxane adhesive layer is laminated on the peeling layer.

However, in these documents, there is no description or suggestion about the combination of a specific peeling control agent and a specific curable polysiloxane composition. In particular, regarding the technical relationship between the storage elastic modulus at low temperature and the oligomeric siloxane adhesive, there is no record or suggestion about the exertion of various remarkable effects and their industrial significance. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-245031 [Patent Document 2] Japanese Patent Laid-Open No. 2005-60554 [Patent Document 3] Japanese Patent Laid-Open No. 2016-182391 [Patent Document 4] Patent WO2016-006252 [Patent Document 5] Patent WO2020-138413

[The problem to be solved by the invention]

The inventors and others discovered a new technical problem. That is, when the release film is used by peeling it from a release layered product containing a polysiloxane adhesive (also referred to as a "pressure-sensitive adhesive", the same hereinafter), in order to improve its work efficiency and prevent polymerization after peeling. The surface of the silicone adhesive is rough, etc., and a lower and stable peeling force is required. However, in recent years, the demand for polysiloxane-based optically transparent pressure-sensitive adhesive (OCA) has increased in the lamination or construction of display devices such as flexible displays/touch panels. (-20℃, etc.) Adhesive layer with sufficient viscoelasticity and low storage elastic modulus.

However, when a release film is formed using a conventionally known composition as a release coating layer and a laminate is formed, the polysiloxane adhesive layer with a low storage elastic modulus cannot be sufficiently reduced at a low temperature as described above and the The peeling force between the peeling layers, and even when peeled off, may cause defects such as roughness or wrinkles on the surface of the polysiloxane adhesive after peeling the peeling film, and transparency or visibility may occur. damage, or adversely affect yield or performance. If a peelable release agent layer can be realized by maintaining a sufficiently small peeling force and a good and smooth bonding surface for a polysiloxane adhesive with such new properties, it is possible to industrially utilize polysiloxane with excellent low-temperature properties more effectively. Silicone adhesive.

That is, the object of the present invention is to provide a release film, a release agent for the release film, a curable polysiloxane composition that can be used as a release agent, and a base material, a polysiloxane adhesive layer, and a layer of release agent, the release film can self-adhere to the polysiloxane adhesive of the release layer even if the release layer is a thin layer, especially the polysiloxane adhesive with low storage elastic modulus at low temperature The adhesive peels off with low peel force and has a stable peel force for polysiloxane adhesives. Furthermore, the release film generally has a release layer formed by coating a release agent on a flexible substrate such as a plastic film. [Technical means to solve the problem]

The present inventors have found that the above-mentioned problems can be solved by a hydrosilylation-curable polysiloxane composition comprising (A) having fluorine in the molecule, and completed the present invention. Organopolysiloxanes with alkyl groups and at least 2 alkenyl groups, i.e., two types that are not completely compatible or completely incompatible by visual observation after stirring at 25°C without solvent mixing and standing for 24 hours The above organopolysiloxane is used in combination with (C) an organopolysiloxane having an organic group containing a fluorine atom and not containing a hydrosilylation reactive group.

That is, the curable polysiloxane composition of the present invention is characterized in that it is curable by hydrosilylation reaction, and a mixture of organopolysiloxane having a specific fluorine-containing organic group and an alkenyl group is used as the main agent, and further added Organopolysiloxanes with fluorine-containing organic groups that do not contribute to the hydrosilation reaction. Furthermore, it is characterized in that the release layer obtained by curing the curable polysiloxane composition is used as a release layer for polysiloxane adhesives, especially polysiloxane adhesives with low storage elastic modulus at low temperature. A release coating agent, a release film, and a laminate.

Specifically, the curable polysiloxane composition of the present invention comprises: (A) A mixture of two or more fluoroalkyl group-containing organopolysiloxanes having a fluoroalkyl group and at least two alkenyl groups in one molecule and the contents of the fluoroalkyl groups being different from each other, and the aforementioned two or more fluorine-containing groups The organic polysiloxane of the alkyl group is a combination of those that are not completely compatible at 25°C when mixed without a solvent; (B) Organohydrogen polysiloxanes having at least 3 silicon atoms bonded to hydrogen atoms in one molecule; (C) Organopolysiloxanes having organic groups containing fluorine atoms and no hydrosilylation reactive groups; (D) catalysts for hydrosilylation; and (E) Organic solvent.

In addition, the above-mentioned problem can be used as the peeling property of the peeling layer for the polysiloxane adhesive whose storage elastic modulus at -20°C is 5 MPa or less by curing the curable polysiloxane composition. Coating agents, release films, and laminates are solved. [Effect of invention]

By using the curable polysiloxane composition of the present invention as a release coating agent, it is possible to form a release film which can adhere the polysiloxane adhesive, Especially the polysiloxane adhesive with low storage elastic modulus at low temperature can be peeled off from the peeling layer with low peeling force. In addition, the release film and laminated body of the present invention can attach the polysiloxane adhesive (including the release layer to the adhesive formed by the hardening reaction on the release layer, and the adhesive that has been formed on the release layer). It can be stably peeled off from the peeling layer with low peeling force, so that the surface of the polysiloxane adhesive after peeling can maintain a uniform adhesive surface with roughness or less wrinkles, so it can be preferably used for the uniformity of the adhesive surface. Components of display devices or electronic materials.

In particular, by using the release layer obtained by hardening the curable polysiloxane composition of the present invention, it is possible to provide a storage elastic mold at -20°C which is difficult to handle and manufacture the release laminate by the conventional release agent. Polysiloxane adhesives, especially sheet-like/film-like adhesives with a strength of 5 MPa or less, and peelable films and peelable laminates exhibiting low peeling force and good peeling properties, can achieve good performance at low temperatures. Viscoelastic polysiloxane adhesive and the expansion of its industrial application.

First, the curable polysiloxane composition of the present invention will be described in detail. [Curable polysiloxane composition]

The curable polysiloxane composition of the present invention is characterized in that it contains at least: (A) A mixture of two or more fluoroalkyl group-containing organopolysiloxanes having a fluoroalkyl group and at least two alkenyl groups in one molecule and the contents of the fluoroalkyl groups being different from each other, and the aforementioned two or more fluorine-containing groups The organic polysiloxane of the alkyl group is a combination of those that are not completely compatible at 25°C when mixed without a solvent; (B) Organohydrogen polysiloxanes having at least 3 silicon atoms bonded to hydrogen atoms in one molecule; (C) Organopolysiloxanes having organic groups containing fluorine atoms and no hydrosilylation reactive groups; (D) catalysts for hydrosilylation; and (E) organic solvent; (F) A hydrosilylation reaction control agent and other arbitrary components can also be contained arbitrarily. Hereinafter, these essential components and other components are demonstrated. [(A) Ingredient]

The component (A) is a mixture of two or more fluoroalkyl group-containing organopolysiloxanes having a fluoroalkyl group and at least two alkenyl groups in one molecule and having different fluoroalkyl groups from each other. Further, the two or more fluorine alkyl group-containing organopolysiloxanes need to be a combination that is not completely compatible at 25° C. when these components are mixed without a solvent. The meaning of "incomplete compatibility at 25°C when mixed without solvent" means that the mixture of two or more fluoroalkyl-containing organopolysiloxanes is put into a transparent glass vial with a lid, and the mixture is fully heated at 25°C. Immediately after stirring and after 24 hours, the mixture became cloudy or separated into two phases by visual observation, and did not show a uniform and transparent liquid state. Furthermore, when the fluoroalkyl group-containing organopolysiloxane is in a state other than a liquid state such as rubber or paste at 25°C, it refers to heating to a temperature at which the mixture becomes liquid, and then cooling to 25°C after thorough stirring. Immediately after and 24 hours later, the mixture became cloudy or separated into two phases by visual observation, and did not appear as a uniform and transparent liquid state. Using a mixture of these components in combination can obtain a lower peeling force for the polysiloxane adhesive than the peeling force to the polysiloxane adhesive estimated by the arithmetic mean of the results when each component is used alone. , can fully reduce the peeling force between the polysiloxane adhesive layer and the peeling layer with low elastic modulus stored at low temperature, and can maintain the surface of the peeled polysiloxane adhesive with a uniform adhesion with less roughness or less wrinkles noodle.

Specifically, the component (A) preferably has the following average composition formula (I): (R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c ( SiO _4/2 ) _d (I) (in the formula, R ¹ are the same or different and are independently an alkyl group with 1 to 12 carbons, an alkenyl group with 2 to 12 carbons, an aryl group with 6 to 12 carbons, and an aryl group with 6 to 12 carbons. An aralkyl group of 7-12 or a fluoroalkyl group having 1-12 carbon atoms, at least two R ¹ in a molecule are the aforementioned alkenyl groups, and at least one R ¹ in a molecule is a fluoroalkyl group having 1-12 carbon atoms, a is a positive number, b is a positive number, c is 0 or a positive number, and d is 0 or a positive number). Furthermore, in the formula (I), R ¹ may be a small amount of hydroxyl group and alkoxy group within the range not impairing the purpose of the present invention.

In formula (I), examples of the alkyl group having 1 to 12 carbon atoms that R ¹ can represent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, undecyl and dodecyl, preferably methyl.

In the formula (I), examples of the alkenyl group having 2 to 12 carbon atoms that can be represented by R ¹ include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl. , nonenyl, decenyl, undecenyl and dodecenyl, the alkenyl group is independently preferably vinyl or hexenyl, particularly preferably vinyl. Furthermore, in the formula (I), at least two R ¹ are alkenyl groups, and the content of the alkenyl groups in terms of vinyl groups is not particularly limited as long as they can be used to form a curable composition, but preferably 2.0 mass % or less, more preferably 1.0 mass % or less, still more preferably 0.5 mass % or less. The reason for this is that when the curable polysiloxane composition of the present invention is used as a release coating agent to form a release layer for a polysiloxane adhesive, if the content of the alkenyl group is greater than necessary, the release layer may be The peeling force from the polysiloxane adhesive layer becomes high. In addition, the vinyl group conversion content of an alkenyl group means the content calculated by converting the alkenyl group other than a vinyl group into the mass of an equimolar vinyl group.

In the formula (I), as the aryl group having 6 to 12 carbon atoms that can be represented by R ¹ , a phenyl group, a tolyl group, and a xylyl group can be exemplified, and a phenyl group is preferred.

In the formula (I), a benzyl group and a phenethyl group can be exemplified as the aralkyl group having 7 to 12 carbon atoms that can be represented by R ¹ .

In formula (I), 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluoro can be exemplified as examples of the fluoroalkyl group having 1 to 12 carbon atoms that can be represented by R ¹ . Butyl, 3,3,4,4,5,5,5-heptafluoropentyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4, 4,5,5,6,6,7,7,7-undecafluoroheptyl, 3,3,4,4,5,5,6,6,7,7,8,8,8-thirteen Fluorooctyl, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl, preferably 3,3,4, 4,5,5,6,6,6-Nonafluorohexyl.

Regarding a to d in the above formula (I), a is 2 or more, preferably an integer of 2 to 6, b is 1 or more, preferably an integer of 1 to 5,000, and more preferably an integer of 30 to 4,000, c is 0 or a positive number, and d is 0 or a positive number. Regarding the component (A), if the degree of siloxane polymerization is less than the lower limit of the aforementioned range, when the curable polysiloxane composition obtained by using the component is used as a release coating agent, it may be difficult to form a release layer, When the degree of siloxane polymerization exceeds the upper limit of the aforementioned range, the coating properties (especially the film coating properties) of the obtained curable polysiloxane composition may be lowered.

The two or more fluorine alkyl group-containing organopolysiloxanes constituting the component (A) are preferably a mixture of two or more organopolysiloxanes represented by the above formula (I), respectively, and further, the component (A) Especially preferred is a mixture of the following components (A1) and (A2).

(A1) One or more kinds of linear or linear or branched organopolysiloxanes; and (A2) One or more kinds of linear or linear or Branched organopolysiloxane.

That is, the component (A1) is a linear or branched organopolysiloxane, that is, in the above formula (I), two Rs of the unit represented by "R ¹ ₂ SiO _2/2 " At least one, preferably one, of ¹ is a fluoroalkyl group having 1 to 12 carbon atoms, particularly preferably 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and the formula ( The ratio of the mass of the fluorine atom to the mass of the entire compound represented by I) is 40 mass % or more, preferably 41 mass % or more, and more preferably 42 mass % or more.

In addition, the component (A2) is a linear or branched organopolysiloxane, that is, in the above formula (I), two R ¹ of the unit represented by "R ¹ ₂ SiO _2/2 " At least one, preferably one, is a fluoroalkyl group having 1 to 12 carbon atoms, particularly preferably 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and the formula (I ) in the mass of the entire compound represented by the ratio of the mass of the fluorine atom is less than 40 mass %, preferably 39 mass % or less, and more preferably 38 mass % or less.

Therefore, the content of fluorine atoms contained in the component (A1) and the component (A2) is different from each other. The difference between the fluorine atom content of the component (A1) and the fluorine atom content of the component (A2) is preferably a value larger than 3 mass %, and preferably 4 mass % or more. The reason for this is that the two components are likely to be incompatible because the difference in the fluorine atom content between the component (A1) and the component (A2) is the aforementioned value.

In addition, in one aspect of the present invention, it is preferable to satisfy the conditions of the content of fluorine atoms in the components (A1) and (A2), and the component (A1) is an organodisiloxane containing a fluorine-containing alkyl group. Unit, fluoroalkyl group is 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and this unit is 39 mol% or more of the whole organosiloxane unit or more than one kind of straight chain Organopolysiloxane with branched or branched chain, the component (A2) is an organodisiloxane unit containing a fluoroalkyl group, and the fluoroalkyl group is 3, 3, 4, 4, 5, 5, 6, 6, 6 -Nonafluorohexyl, the unit being 36 mol% or less of the whole organosiloxane unit of one or more linear or branched organopolysiloxanes.

As specific examples of the component (A1) and the component (A2), the fluoroalkyl group-containing organopolysiloxanes listed below can be exemplified, but are not limited to these. In the formula below, Me, Vi, Hex, Fa1, Fa2, and Fa3 represent methyl, vinyl, n-hexenyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, respectively , 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, and 3,3,3-trifluoropropyl. Organopolysiloxane represented by the average composition formula: (Me ₂ ViSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₇₅₀ (Me(Fa1)SiO _2/2 ) ₇₅₀ (MeViSiO _2/2 ) ₂₀ ; Average composition formula: (Me ₃ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₄₅₀ (Me(Fa1)SiO _2/2 ) ₃₅₀ (MeViSiO _2/2 ) Organopolysiloxane represented by ₁₀ ; Composition formula: organopolysiloxane represented by (Me ₂ (Fa1)SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₄₅₀ (Me(Fa1)SiO _2/2 ) ₃₅₀ (MeViSiO _2/2 ) ₁₀ ; Organopolysiloxane represented by the average composition formula: (Me ₂ HexSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₀₀₀ (Me(Fa1)SiO _2/2 ) ₁₀₀₀ (MeHexSiO _2/2 ) ₂₀ ; Average composition formula: organopolysiloxane represented by (Me ₂ ViSiO _1/2 ) ₄ (Me ₂ SiO _2/2 ) ₅₀₀ (Me(Fa1)SiO _2/2 ) ₅₀₀ (SiO _4/2 ) ₁ ; Composition formula: (Me ₂ ViSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₅₀₀ (Me(Fa2)SiO _2/2 ) ₅₀₀ (MeViSiO _2/2 ) Organopolysiloxane represented by ₁₀ ; average composition Formula: (Me ₂ ViSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₄₇₀ (Me(Fa1)SiO _2/2 ) ₁₁₀₀ (MeViSiO _2/2 ) ₈ Organopolysiloxane represented by the average composition formula : Organopolysiloxane represented by (Me ₂ ViSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₂₈₀ (Me(Fa1)SiO _2/2 ) ₁₂₇₀ (MeViSiO _2/2 ) ₇ ; with an average composition formula: Organopolysiloxane represented by (Me ₂ ViSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₉₀₀ (Me(Fa1)SiO _2/2 ) ₄₅₀ (MeViSiO _2/2 ) ₁₀ ; with an average composition formula: ( Organopolysiloxane represented by Me ₂ ViSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₁₀₀ (Me(Fa1)SiO _2/2 ) ₄₀₀ (MeViSiO _2/2 ) ₇ ; with an average composition formula: (Me ₂ ViSi O _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₁₀₀ (Me(Fa1)SiO _2/2 ) ₄₀₀ (Me(Fa3)SiO _2/2 ) ₁₀₀ (MeViSiO _2/2 ) Organopolysilicon represented by ₁₀ oxane.

In the curable polysiloxane composition of the present invention, the mass ratio of the component (A1) and the component (A2) contained in the composition is preferably 1/99 to 99/1 ((A1)/(A2)), More preferably, it is 10/90-90/10, More preferably, it is 20/80-80/20, Most preferably, it is 30/70-70/30. If the component (A1) and the component (A2) are used in combination, it is possible to obtain a higher value for polysiloxane than the results estimated by the arithmetic mean based on the results when the component (A1) or (A2) is used alone in place of the component (A), respectively. The peel force of the adhesive is low. [(B) Ingredient]

Component (B) is an organopolysiloxane having at least 3 silicon atoms-bonded hydrogen atoms (Si-H) in one molecule, and is formed by an addition reaction based on a hydrosilylation reaction with the component (A). A component that hardens the composition of the present invention. In particular, the component (B) may have a certain amount of fluorine-containing organic groups selected from fluoroalkyl groups having 1 to 12 carbon atoms and fluorine-containing (poly)ether-containing organic groups, and from the viewpoint of the technical effect of the present invention. speak better.

Examples of groups other than the hydrogen atom bonded to the silicon atom in the component (B) include an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an alkyl group having 7 to 12 carbon atoms. Fluoroalkyl groups of 1 to 12, and organic groups of fluorine-containing (poly)ethers having 2 to 100 carbon atoms. Furthermore, in the range which does not impair the objective of this invention, a small amount of hydroxyl group and alkoxy group may be couple|bonded with the silicon atom in (B) component.

The molecular structure of the component (B) is not limited, and can be exemplified by linear, branched, partially branched linear, resinous, and cyclic, and preferably linear or partially branched linear .

As such (B) component, the following average composition formula (II) can be exemplified: (R ² ₃ SiO _1/2 ) _aa (R ² ₂ SiO _2/2 ) _ab (R ² SiO _3/2 ) _ac (SiO _4/2 ) Organopolysiloxanes represented by _ad (II).

In formula (II), R ² is the same or different and independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an aralkyl group having 1 to 12 carbon atoms. A fluoroalkyl group of 12, or an organic group containing a fluorine (poly)ether, wherein at least 3 of R ² are hydrogen atoms. In addition, aa is positive, ab is positive, ac is 0 or positive, and ad is 0 or positive. Wherein, when aa is set to 2, the total of aa to ad is preferably in the range of 5 to 200, the lower limit is 10 or 15, and the upper limit is 150, 120, 100, 80, 70, 60, 50 or 40 within the range of any combination of upper and lower limits. The reason for this is that when aa is set to 2, the crosslinking of the present composition can be sufficiently advanced if the sum of aa to ad is equal to or greater than the lower limit of the above range, and on the other hand, if it is equal to or less than the upper limit of the above range, the present The workability of the composition was good.

Examples of the alkyl group having 1 to 12 carbon atoms that can be represented by R ² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecane. group and dodecyl group, preferably methyl group.

Moreover, as a C6-C12 aryl group which R< ² > can represent, a phenyl group, a tolyl group, and a xylyl group can be illustrated, and a phenyl group is preferable.

Moreover, as a C7-C12 aralkyl group which R< ² > can represent, a benzyl group and a phenethyl group can be illustrated.

Furthermore, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3-trifluorobutyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl can be exemplified as the fluoroalkyl group having 1 to 12 carbon atoms that can be represented by R ² . ,4,4,5,5,5-heptafluoropentyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4,4,5,5, 6,6,7,7,7-undecafluoroheptyl, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl and 3, 3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl, preferably selected from 3,3,4,4,5,5 ,5-heptafluoropentyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4,4,5,5,6,6,7,7, 7-undecafluoroheptyl and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, particularly preferably 3,3,4,4 ,5,5,6,6,6-Nonafluorohexyl.

In addition, as the organic group of the fluorine-containing (poly)ether represented by R ² , the organic group of the fluorine-containing (poly) ether exemplified by the aforementioned R ¹ can be preferably used.

The (B) component of the present invention may or may not have a group selected from the group consisting of a fluoroalkyl group and a fluorine-containing (poly)ether. Even if the organohydrogenpolysiloxane having a fluorine atom-containing group is not used as the component (B), by combining with the component (A) above, when the composition of the present invention is used as a coating agent and cured, it is possible to obtain A release layer having excellent releasability, especially excellent releasability for polysiloxane adhesives, from the viewpoint of the technical effect of the present invention, preferably has a certain amount of these fluorine atom-containing groups. As the component (B), an organic group represented by the above-mentioned average composition formula (II) in which R ² is a hydrogen atom, an alkyl group (especially a methyl group), and a fluoroalkyl group and/or a fluorine-containing (poly)ether is particularly preferable A combination of organic polyhydrosiloxanes.

When the component (B) of the present invention has a group selected from the group consisting of a fluoroalkyl group and an organic group containing a fluorine (poly)ether, the intramolecular source of the fluoroalkyl group and/or the fluorine-containing (poly)ether ) The content of the fluorine atom in the organic group of the ether is not particularly limited, but is preferably at least 20% by mass, at least 25% by mass, at least 30% by mass, or at least 35% by mass. Further, the upper limit of the content of the fluorine atoms in the component (B) is preferably at most 60% by mass or at most 50% by mass.

As a specific example of (B) component, although the organopolysiloxane listed below can be illustrated, it is not limited to these. In the formula below, Me, F2a, and F1b represent methyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, respectively, and the following formula: F[CF(CF ₃ )CF A group represented by ₂ O] ₂ CF(CF ₃ )CH ₂ O-(CH ₂ ) ₃ -. Organopolysiloxane represented by the average composition formula: (Me ₃ SiO _1/2 ) ₂ (Me(F2aSiO _2/2 ) ₁₂ (MeHSiO _2/2 ) ₂₇ ; by the average composition formula: (Me ₃ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₅₅ (Me(F1bSiO _2/2 ) ₂₅ (MeHSiO _2/2 ) ₂₅ represented by organopolysiloxane; with an average composition formula: (Me ₃ SiO _1/2 ) ₂ ( Organopolysiloxane represented by MeHSiO _2/2 ) ₅₀ ; Organopolysiloxane represented by average composition formula: (Me ₃ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₃₀ (MeHSiO _2/2 ) ₃₀ Organopolysiloxane represented by the average composition formula: (Me ₂ HSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₃₀ (MeHSiO _2/2 ) _30. One kind selected from these can be used Or two or more types are used in combination as (B) component.

The content of the component (B) in the curable polysiloxane composition of the present invention is such that the molar ratio of the silicon atom-bonded hydrogen atoms to the alkenyl group in the (A) component is 1 to 20 (silicon atom-bonded hydrogen atoms). The amount within the range of hydrogen atom/alkenyl), preferably the lower limit is 0.5, 0.8 or 1, and the upper limit is the range of the combination of any upper limit and lower limit of 18, 17, 16, 15, 14, 13 or 12 Inside. The reason for this is that when the content of the component (B) is more than the lower limit of the above-mentioned range, the crosslinking of the curable polysiloxane composition can sufficiently proceed, and on the other hand, when the content of the component (B) is below the upper limit of the above-mentioned range , which can stabilize the properties of the obtained peelable film. [(C) Ingredient]

Component (C) is an organopolysiloxane having an organic group containing a fluorine atom in its molecule and no hydrosilylation reactive group, and is used to impart excellent properties to a film obtained by curing a polysiloxane release agent composition The peeling control agent component of the peeling property. By using the release agent layer obtained by the curable polysiloxane composition of the present invention and its effects in combination with the above-mentioned (A) component and (C) component, not only a simple low release property but also a Polysiloxane adhesives that cannot achieve sufficient peeling properties from previous peeling agents, especially polysiloxane adhesives with low storage elastic modulus at low temperatures, have sufficiently low peeling force, and can maintain the uniformity of the adhesive surface after peeling state.

The molecular structure of the component (C) is not limited, and can be exemplified by linear, branched, partially branched linear, resinous, and cyclic, and preferably linear or partially branched linear . As such (C) component, the following average composition formula (III) is preferable: (R ³ ₃ SiO _1/2 ) _ba (R ³ ₂ SiO _2/2 ) _bb (R ³ SiO _3/2 ) _bc ( Organopolysiloxane represented by SiO _4/2 ) _bd (III).

In formula (III), R ³ is the same or different and independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and a fluorine group having 1 to 12 carbon atoms. Alkyl, or organic group of fluorine-containing (poly)ether. In addition, ba is a positive number, bb is a positive number, bc is 0 or a positive number, and bd is a 0 or a positive number. Among them, when ba is set to 2, the total of ba to bd is preferably in the range of 1 to 5,000, and more preferably an integer of 30 to 3,000.

Examples of the alkyl group having 1 to 12 carbon atoms that can be represented by R ³ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecane. group and dodecyl group, preferably methyl group.

Moreover, as a C6-C12 aryl group which R< ³ > can represent, a phenyl group, a tolyl group, and a xylyl group can be illustrated, and a phenyl group is preferable.

Moreover, as a C7-C12 aralkyl group which R< ³ > can represent, a benzyl group and a phenethyl group can be illustrated.

Furthermore, as the fluoroalkyl group having 1 to 12 carbon atoms that can be represented by R ³ , the fluoroalkyl group having 1 to 12 carbon atoms exemplified in the aforementioned R ² can be preferably used.

In addition, as the organic group of the fluorine-containing (poly)ether that can be represented by R ³ , the organic group of the fluorine-containing (poly) ether exemplified in the aforementioned R ¹ can be preferably used.

Furthermore, the content of the fluorine atom in the fluorine atom-containing organic group in the component (C) is preferably 20 to 40 mass %, more preferably 23 to 35 mass %, and particularly preferably 27 to 34 mass %. On the other hand, when the content of the fluorine atom-containing organic group in one molecule is less than the aforementioned lower limit or exceeds the aforementioned upper limit, excellent peelability may not be obtained.

The aforementioned organopolysiloxane is characterized in that it does not contain a hydrosilylation reactive group in the molecule except for the content of the organic group containing a fluorine atom. In the case of organopolysiloxane containing hydrosilylation reactive groups, especially in polysiloxane stripper compositions hardened by hydrosilylation, the organopolysiloxane is In the cured product, it is easy to form a covalent bond with a crosslinking agent or a main agent, and excellent peelability may not be achieved as a peeling control agent.

In addition, the molecular chain terminal of the organopolysiloxane is preferably a trimethylsiloxy group or a silanol group, and more preferably one or more of the molecular chain terminal is a trimethylsilyl group.

Specific examples of such organopolysiloxanes include methyl(3,3,3-trifluoropropyl)polysiloxanes terminated with trimethylsiloxy groups at both ends of the molecular chain, molecular Methyl (3,3,3-trifluoropropyl) siloxane-dimethylsiloxane copolymer terminated by trimethylsiloxy at both ends of the chain, both ends of the molecular chain by trimethylsiloxy Group-terminated methyl (3,3,4,4,5,5,6,6,6-nonafluorohexyl)siloxane-dimethylsiloxane copolymer, both ends of the molecular chain are composed of trimethyl Siloxy-terminated methyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)siloxane-dimethylsiloxane Alkane copolymer, methyl(3,3,3-trifluoropropyl)siloxane-dimethylsiloxane copolymer with silanol groups at both ends of the molecular chain, silanol groups at both ends of the molecular chain Terminated methyl (3,3,4,4,5,5,6,6,6-nonafluorohexyl)siloxane-dimethylsiloxane copolymer, both ends of the molecular chain are blocked by silanol groups Terminated methyl (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)siloxane-dimethylsiloxane copolymer, and a methyl group (3,3,4,4,5,5,6,6,6-nonafluorohexyl) with one end of the molecular chain capped by silanol and the other end capped by trimethylsiloxy Siloxane-dimethylsiloxane copolymer.

Content of (C)component exists in the range of 0.01-20 mass parts with respect to 100 mass parts of (A) components, Preferably it exists in the range of 0.1-10 mass parts. If the content of the (C) component is less than 0.01 part by mass relative to 100 parts by mass of the (A) component, the light peelability of the film (peelable cured film) obtained by curing may be remarkably reduced. Moreover, when content of (C)component exceeds 20 mass parts, the intensity|strength of the film obtained by hardening may fall remarkably, and it may become difficult to obtain a target release agent composition.

Moreover, as (C)component of this invention, 1 type of these organopolysiloxanes can be used individually or in mixture of 2 or more types. [(D) Ingredient]

The component (D) is a catalyst for a hydrosilylation reaction that promotes the curing of the curable polysiloxane composition based on a hydrosilylation reaction, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, preferably Platinum-based catalyst. Examples of the platinum-based catalyst include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, an alcohol solution of chloroplatinic acid, and a complex of platinum and olefin. and complexes of platinum and alkenyl siloxanes.

The content of component (D) is the amount used to promote the hardening of the curable polysiloxane composition, specifically, the metal atoms in the catalyst in mass units relative to the curable polysiloxane composition, preferably The amount of platinum atoms in the range of 0.1 to 1,000 ppm. The reason for this is that when the content of the component (D) is more than the lower limit of the above range, the curable polysiloxane composition obtained is sufficiently hardened, and on the other hand, when the content of the component (D) is below the upper limit of the above range, The obtained hardened product is not prone to coloration. [(E) Ingredient]

(E) component is an arbitrary organic solvent which can make the fluorine-containing organopolysiloxane mixture which is (A) component compatible uniformly, and can make the whole composition compatible. Here, "compatibility" means that a homogeneous and transparent liquid can be expressed without turbidity in the appearance at 25°C.

In addition, by adding an organic solvent, the viscosity of the curable polysiloxane composition can be reduced, and the coating workability and the wettability to the substrate can be improved.

As the component (E), it is preferably selected from diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, di2nd butyl ether, ditertiary butyl ether, and methyl tertiary butyl ether , ethyl tert-butyl ether, pentane, hexafluorom-xylene, methyl heptafluoropropyl ether, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, and 3-methoxy-1,1,1 ,2,2,3,4,4,5,5,6,6,6-tridecafluorohexane as one solvent or a mixed solvent containing two or more solvents.

As long as the appearance of the curable polysiloxane composition can be kept transparent and uniform at 25° C. after the composition is prepared and before use, other organic solvents may be used in addition to the above-mentioned organic solvents. Such an additional organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbon-based solvents such as toluene and xylene; hexane, heptane, octane, isooctane, decane, cyclohexane, and methylcyclohexane. , aliphatic hydrocarbon solvents such as isoparaffin; industrial gasoline (rubber volatile oil, etc.), petroleum ether, solvent naphtha and other hydrocarbon solvents; acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetone acetone, cyclohexanone and other ketone solvents; ethyl acetate, propyl acetate, isoacetate Propyl, butyl acetate, isobutyl acetate and other ester solvents; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, 2-butoxyethyl acetate Solvents having ester and ether moieties; hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxane) Siloxane-based solvents such as methyl) silane and tetrakis(trimethylsiloxy) silane; the aforementioned hexafluoro-m-xylene, methyl heptafluoropropyl ether, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether , and fluorine-modified solvents other than 3-methoxy-1,1,1,2,2,3,4,4,5,5,6,6,6-trifluorohexane, such as trifluorotoluene Isofluorine-modified aromatic hydrocarbon solvents, fluorine-modified ether-based solvents such as perfluoro(2-butyltetrahydrofuran), and fluorine-modified alkylamine-based solvents such as perfluorotributylamine and perfluorotriamylamine; and a mixed solvent of two or more selected from these.

The content of the component (E) is an amount required to make the entire curable polysiloxane composition uniformly compatible, and is 10,000 parts by mass or less, preferably 20 to 5,000 parts by mass relative to 100 parts by mass of the component (A) within the range. [(F) Ingredient]

In order to control the crosslinking reaction, (F) a hydrosilylation reaction control agent may be contained in the curable polysiloxane composition. As the component (F), 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3- Alcohol, 2-phenyl-3-butyn-2-ol and other alkynols; 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexen-1-yne, etc. Enyne compounds; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5 ,7-tetrahexenylcyclotetrasiloxane and other methylalkenylsiloxane oligomers; dimethylbis(3-methyl-1-butyn-3-oxy)silane, methylvinylbis (3-methyl-1-butyn-3-oxo)silane and other alkynyloxysilanes; methyltris(1-methyl-1-phenyl-propynyloxy)silane, dimethylbis(1- Methyl-1-phenyl-propynyloxy)silane, methyltris(1,1-dimethyl-propynyloxy)silane, dimethylbis(1,1-dimethyl-propynyloxy) alkynyloxysilane compounds such as alkynyl)silane; and benzotriazoles; diallyl maleate, diallyl fumarate, tris((1,1-dimethyl-2-propane) alkynyl)oxy)methylsilane.

The content of the component (F) is not limited, but in the case of using the component (F) in consideration of giving a sufficient pot life to the curable polysiloxane composition, the amount of the component is less than 100 parts by mass of the component (A). It is preferably within the range of 0.01 to 5 parts by mass, within the range of 0.05 to 5 parts by mass, or within the range of 0.05 to 3 parts by mass. [Other additives]

The curable polysiloxane composition can also be selected from the group consisting of photopolymerization initiators, antioxidants, reactive diluents, leveling agents, fillers, and antistatic agents within the range that can achieve the purpose of the present invention. , defoamer and additives in pigments, etc. [use]

The curable polysiloxane composition of the present invention is preferably used as a release coating agent, and is suitable for use as a release coating agent for a polysiloxane adhesive. In particular, it is most suitable as a release coating agent for polysiloxane adhesives with low storage elastic modulus at low temperature. Specifically, for the polysiloxane adhesive whose storage elastic modulus at -20°C is 5 MPa or less, preferably 2.5 MPa or less, and more preferably 1.0 MPa or less, it can maintain low peeling force and uniformity after peeling. In terms of the surface of the adhesive layer, the industrial applicability of the polysiloxane adhesive film/sheet for which sufficient workability cannot be ensured by the previous release agent has been greatly expanded.

The present invention also relates to a release film comprising: a substrate, especially a film-like substrate; and a release layer composed of a cured product obtained by curing the release coating agent of the present invention. Such a release film can be produced by, for example, applying the curable polysiloxane composition of the present invention to a film-like base material and curing the curable polysiloxane composition. The release film of the present invention is particularly suitable for use as a polysiloxane adhesive.

As the base material for the release film, a film-like base material selected from paper or plastic film, glass, and metal can be used. When the product provided with the release layer on the base material is used as the release film, the base material is preferably a plastic film, more preferably a polyester film. It is especially preferable that both the base material and the peeling layer are translucent.

The thickness of the peeling layer is preferably 2.0 µm or less, 1.0 µm or less, or 0.5 µm or less, more preferably 0.4 µm or less, and still more preferably 0.3 µm or less. In addition, it is preferably 0.05 µm or more, more preferably 0.1 µm or more. The reason for this is that when the film thickness is not less than the lower limit of the above-mentioned range, the peeling force of the obtained release layer is sufficiently reduced, and on the other hand, when the film thickness is not more than the upper limit of the above-mentioned range, the light transmittance of the release layer is particularly excellent. [Laminated body]

The present invention also relates to a laminate comprising at least a release layer formed of a cured product obtained by curing the curable polysiloxane composition of the present invention, and an adhesive layer disposed opposite to the release layer , especially the polysiloxane adhesive layer. In this case, the curable polysiloxane composition may also be referred to as a release coating agent. In this case, the meaning of "opposite" means that the release layer and the adhesive layer are in direct contact with each other. Therefore, generally, in this invention, a peeling layer and an adhesive bond layer are mutually opposingly arrange|positioned. In the following description, the structure of the layered product of the present invention will be described by citing a polysiloxane adhesive as the adhesive, but the adhesive is not limited to the polysiloxane adhesive.

The layered product of the present invention may be a layered product of any structure as long as it includes the above-mentioned structure in which the release layer and the polysiloxane adhesive layer are opposed to each other. An example of a specific laminated body will be described below.

The structure of the layered product of the present invention includes, for example, (a) to (d) shown below. These specific structures are, for example, the same as those disclosed by the applicant of the present application in the aforementioned Patent Documents 6 and 7, except that the peeling layer is replaced with a hardened layer obtained by hardening the curable polysiloxane composition of the present invention, The polysiloxane adhesive layer whose storage elastic modulus at -20°C is below 5 MPa can be preferably used as the polysiloxane adhesive layer. (a) The composition including the first base material/release layer/polysiloxane adhesive layer/second base material; (b) A composition comprising two or more constituent units of the base material/release layer/polysiloxane adhesive layer that are continuously stacked; (c) The composition comprising the first base material/the first release layer/polysiloxane adhesive layer/the second release layer/the second base material; (d) A structure consisting of two or more structural units of the base material/first peeling layer/polysiloxane adhesive layer/second peeling layer that are continuously stacked. In the constitutions (b) and (d), the substrate can be either discontinuous or continuous. Generally speaking, in the case of discontinuity, the laminate becomes a sheet, and in the case of continuous use, the laminate becomes a roll. shape.

The substrate is preferably in the form of a sheet or a film, particularly preferably in the form of a film, and the same substrate as that used for the above-mentioned release film can be used. In addition, any one of translucent and non-translucent can be used for the base material, and when a plurality of base materials are used, both can be arbitrarily combined according to the purpose.

The laminated body of the present invention may be a laminated sheet in which a plurality of sheet-like members of the base material/release layer/polysiloxane adhesive layer are laminated in the vertical direction, or may be in a roll-like shape, for example, wound around a suitable The roll shape of the cylindrical or cylindrical core.

In the laminated body of the present invention, the polysiloxane adhesive layer has a configuration in which the first peeling layer is arranged opposite to one of the two sides and the second peeling layer is arranged opposite to the other side (for example, equivalent to In the configuration (c) or (d)), at least one of the first peeling layer and the second peeling layer needs to be a peeling layer composed of a cured product obtained by curing the peeling coating agent of the present invention, but here Preferably, the peeling force (F1) when peeling the polysiloxane adhesive from the first peeling layer is different from the peeling force (F2) when peeling the polysiloxane adhesive from the second peeling layer.

When the peeling force difference between F1 and F2 is small, after the operation of peeling off one peeling layer from the polysiloxane adhesive layer (the peeling of the first opposite side), the operation of peeling off the other peeling layer (the second facing side) surface), when the first opposing surface is peeled off, the second opposing surface may be unintentionally peeled off, the polysiloxane adhesive layer may be destroyed, and the intended use as an adhesive may become difficult. The difference in peeling force is, for example, preferably 10 gf/inch or more, and more preferably 20 gf/inch or more.

As a method of realizing the above-mentioned difference in peeling force, a method of selecting the method for forming the opposing surface as described below, or a method of making the types of the two peeling layers different, etc. are mentioned.

In the layered product of the present invention, the thickness of the peeling layer is independently preferably 2.0 µm, 1.0 µm, or 0.5 µm or less, more preferably 0.4 µm or less, and still more preferably 0.3 µm or less. In addition, it is preferably 0.05 µm or more, more preferably 0.1 µm or more. The reason is that when the film thickness of the peeling layer is more than the lower limit of the aforementioned range, the peeling force of the peeling layer from the polysiloxane adhesive becomes sufficiently low, and on the other hand, if it is less than the upper limit of the aforementioned range, the light transmission of the peeling layer In particular, it is excellent in properties, and in addition, it is excellent in economical efficiency.

The polysiloxane adhesive composition or curable polysiloxane adhesive composition that can be used in the laminated body of the present invention is not limited to a specific one, and can be used in accordance with the intended use of the laminated body, such as the use as an adhesive tape Arbitrary, but it is especially preferable to use polysiloxane adhesives with low storage elastic modulus at low temperature.

The hardening mechanism of the curable polysiloxane adhesive is not particularly limited. Hydrosilylation curable, peroxide curable, and photocurable polysiloxane adhesives can be used. The following hydrosilylation curable adhesives can be preferably used. Polysiloxane adhesives can be hardened at relatively low temperatures and can reduce the thermal influence on the substrate or applied materials. On the other hand, it is also economical including the simplicity of the process.

In addition, the peeling layer of the present invention is extremely useful when applied to a polysiloxane adhesive with a low storage elastic modulus at low temperature. In assembly applications, especially OCA applications, sometimes high adhesion and high flexibility are required in a wider temperature range including low temperature. Therefore, it is preferable to use the following polysiloxane adhesives, which can be cured after curing. The glass transition temperature of the adhesive composition is low, for example, the composition is designed to be below room temperature, the storage elastic modulus at low temperature is suppressed low, and the elongation at break is sufficiently large. For example, the polysiloxane adhesive composition proposed by the applicant in International Publication No. 2017/188308, International Publication No. 2020/32285, International Publication No. 2020/32286, etc., is cured and heated at -20°C A polysiloxane adhesive layer having a storage elastic modulus of 5 MPa or less, preferably 2.5 MPa or less, and more preferably 1.0 MPa or less can be particularly preferably used in the present invention. Here, the peeling layer of the present invention is preferably used as a polysiloxane adhesive with low storage elastic modulus at low temperature, but does not prevent it from being applied to polysiloxane adhesive with high storage elastic modulus at low temperature , which can maintain the peeling force that is sufficiently reduced for the polysiloxane adhesive and the uniform surface of the adhesive layer after peeling.

The thickness of the polysiloxane adhesive layer of the laminate of the present invention is not particularly limited, but is preferably 0.1 to 300 µm, more preferably 0.5 to 200 µm.

In addition, in the laminated body of the present invention, the polysiloxane adhesive layer may be formed on the entire surface constituting the layer, or may be formed only on a part of the surface. The state of the polysiloxane adhesive layer formed only on a part of the surface is not particularly limited. For example, it can be formed in one or more dots, one or more straight lines or curves, concentric circles, etc., as well as in any shape. Cloth polysiloxane adhesive. The peeling layer may be formed on the entire surface constituting the peeling layer, or the peeling layer may be formed according to the shape of the polysiloxane adhesive formed on the polysiloxane adhesive layer. [Manufacturing method of laminated body]

The manufacturing method of the said laminated body of this invention is not specifically limited, Some preferable methods are listed below. First, when manufacturing the laminated body of this invention, as a method of preparing the opposing surface of a polysiloxane adhesive layer and a peeling layer, the following two methods can be illustrated. <Preparation method (1) of the opposite surface of the polysiloxane adhesive layer and the peeling layer>

The first preparation method of the opposite side includes: Process (1), wherein a release coating agent composed of the curable polysiloxane composition of the present invention is coated on a film-like substrate and cured, thereby forming a first release film having a first release layer; A polysiloxane adhesive layer is formed by coating a curable polysiloxane adhesive composition on the same film-like base material as the above-mentioned film-like base material or a second film-like base material different from the above-mentioned film-like base material and curing it process (2); and A process (3), comprising laminating the release layer of the first release film obtained by the above process (1) on the polysiloxane adhesive layer obtained by the above process (2). The preparation method is a method of contacting the hardened release layer and the hardened polysiloxane adhesive layer to form the opposite surfaces of the two layers. <Preparation method (2) of the opposite surface of the polysiloxane adhesive layer and the peeling layer>

The second preparation method of the opposite side includes: Process (1), wherein a release coating agent composed of the curable polysiloxane composition of the present invention is coated on a film-like substrate and cured, thereby forming a first release film having a first release layer; Process (2), which comprises coating a curable polysiloxane adhesive composition on the first release film obtained by the above-mentioned process (1) and curing it to form a polysiloxane adhesive layer; and Process (3), which consists of laminating the same film-like substrate as the above-mentioned film-like substrate or a film-like substrate different from the above-mentioned film-like substrate on the polysiloxane adhesive layer obtained by the above-mentioned process (2) material. The preparation method is a method of coating a hardening polysiloxane adhesive on the hardened release layer and hardening it to form the opposite surfaces of the two layers. In general, in many cases, the difference in peeling force between the polysiloxane adhesive and the release agent is higher in the second method than in the first method.

The above-mentioned structural examples (a) to (d) of the layered product of the present invention can be produced, for example, by the same production method as disclosed by the applicant of the present application in the aforementioned Patent Document 5. In this case, the peeling layer is Instead of a hardened layer formed by hardening the curable polysiloxane composition of the present invention, the storage elastic modulus at -20°C can preferably be 5 MPa or less, preferably 2.5 MPa or less, more preferably 1.0 The polysiloxane adhesive layer below MPa is used as the polysiloxane adhesive layer. In addition, it is suitable to use the method corresponding to the above-mentioned opposing surface preparation method (1) or (2) for the opposing surface of a polysiloxane adhesive agent and a release agent. [Example]

The curable polysiloxane composition and the release film of the present invention will be described in detail by way of examples, but the present invention is not limited by these examples. In addition, in the average composition formula shown below, symbol Me represents a methyl group, and Vi represents a vinyl group. In addition, the measurement method of the peeling force at the time of peeling a polysiloxane adhesive from a peeling film is as follows. <Reference Example 1> Preparation of "Hydrosilylation curable polysiloxane adhesive composition solution 1"

36.4 parts by weight of vinyl-functional polydimethylsiloxane (rubber-like (plasticization degree: 152), vinyl content: 0.013 mass %), containing (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/2 unit MQ polysiloxane resin with hydroxyl group (molecular weight of 3300, hydroxyl content of 3.5 mol% (0.8% by mass) of xylene solution (solid content of 75.5%)) 84.3 parts by weight, 101.6 parts by weight of toluene, both ends of the molecular chain are composed of three Methylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer (molecular weight 1600, SiH content 0.73%) 0.807 parts by weight, 1-ethynyl-1-cyclohexanol (20% toluene solution) 0.577 parts by weight were thoroughly mixed at room temperature, and 0.484 parts by weight of a platinum-based hydrosilylation catalyst (containing 0.62 mass % of platinum) was fully mixed into the mixture to prepare a uniform solution. Relative to the amount of alkenyl groups of vinyl-functional polydimethylsiloxane, the amount of dimethylsiloxane-methylhydrosiloxane copolymers in which both ends of the molecular chain are capped with trimethylsiloxy groups The molar ratio of the SiH group (SiH/Vi ratio) was 33.7, and the content of platinum metal relative to the solid content was 30 ppm. <Reference Example 2> Adhesion measurement of "hydrosilylation curable polysiloxane adhesive composition solution 1"

Using an applicator, the "hydrosilylation curable polysiloxane adhesive composition solution 1" of the above-mentioned reference example was applied to polyethylene terephthalate (hereinafter referred to as abbreviated as 50 µm) so that the film thickness after curing was 50 µm. PET) film (manufactured by Toray Co., Ltd., product name: Lumirror (registered trademark) S10, thickness 50 µm), heated at 150°C for 3 minutes and hardened to form a polysiloxane adhesive layer. After standing for 1 day, the sample was cut into a width of 20 mm, and the adhesive layer was attached to a PMMA plate (manufactured by PALTEK, Acrylite L001, 50×120×2 mm) using a roller, and used as a test piece. The test piece using the PMMA plate was measured using the RTC-1210 tensile tester manufactured by ORIENTEC Corporation, according to JIS Z0237, using the 180° peel test method to measure the adhesive force at a tensile speed of 300 mm/min (the measured value of 20 mm width was measured). Converted to display unit gf/inch), the result is 1490gf/inch. <Reference Example 3> Measurement of storage elastic modulus of "hydrosilylation curable polysiloxane adhesive composition solution 1"

Using an applicator, the "hydrosilylation curable polysiloxane adhesive composition solution 1" of the above-mentioned reference example was applied to the fluorine-modified organopolysiloxane release agent so that the film thickness after curing was 100 µm. On the release liner, it was heated at 150° C. for 3 minutes to harden to form a polysiloxane adhesive layer. Five or more sheets of the adhesive layer were stacked to obtain a film sample with a thickness of 500 µm or more sandwiched by release liners on both sides. The film was punched to a diameter of 8 mm and attached to a parallel plate probe of a dynamic viscoelasticity device (manufactured by Anoton Paar, MCR301), and the storage elastic modulus at -20°C was measured, and the result was 0.52 MPa. In addition, the measurement temperature was the range of -70 degreeC - 200 degreeC, and the frequency was set to 1 Hz and the temperature increase rate was set to 3 degreeC/min. <Measuring method of peeling force>

The curable polysiloxane release agent composition was coated on polyethylene terephthalate (hereinafter, abbreviated as PET) using a Mayer bar so that the thickness of the cured release agent layer was 0.2 µm. The film (manufactured by Toray Industries, Ltd., product name: Lumirror (registered trademark) S10, thickness 50 µm) was heated at 150°C for 3 minutes to prepare a "release film" having a cured polysiloxane release layer. Using an applicator, the "hydrosilylation curable polysiloxane adhesive composition solution 1" of the above reference example was applied on the release layer of the "release film" so that the film thickness after curing was 50 µm, and heated at 150°C It was hardened for 3 minutes to form a polysiloxane adhesive layer. Using a 2 kg hand roller, the aforementioned PET film was attached to the obtained polysiloxane adhesive layer. The obtained film was cut into a width of 1 inch, and the "release film 1" was stretched in the direction of 180° at a speed of 0.3 m/min using a tensile tester (RTC-1210 manufactured by ORIENTEC), and the measurement was carried out at The force (peeling force) required to peel off the "peeling film" from the polysiloxane adhesive layer at 25°C. <Surface state of polysiloxane adhesive layer after release of release liner>

After the measurement of the above-mentioned peeling force, the surface state of the polysiloxane adhesive layer after the peeling of the release liner was visually observed. The results are defined as follows. ○: The surface of the adhesive is uniform without roughness or wrinkles ×: Roughness and/or wrinkle on the surface of the adhesive [Examples 1 to 4] and [Comparative Examples 1 to 3]

The curable polysiloxane compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared by uniformly mixing each component according to the composition shown in Table 1 using the following components. Furthermore, in the formula, Me, Vi, and Pf represent methyl, vinyl, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl (C ₄ F ₉ CH ₂ CH ₂ , respectively) ).

( _A1 ) _{: Organopolysiloxane containing} a _fluorine alkyl group and an _alkenyl group with a fluorine atom content of 40% by mass or more The vinyl content represented by MePfSiO _2/2 ) ₁₁₀₀ (MeViSiO _2/2 ) ₁₀ is 0.060 mass %, the (MePfSiO _2/2 ) unit is 43 mol % of all diorganosiloxane units (D units), fluorine The content of 42% by mass of fluoroalkyl and alkenyl-containing organopolysiloxane. (A2): Organopolysiloxane containing a fluorine alkyl group and an alkenyl group having a fluorine atom content of less than 40% by mass The average composition formula is: (Me ₂ ViSiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₉₀₀ ( The vinyl content represented by Me(Pf)SiO _2/2 ) ₄₅₀ (MeViSiO _2/2 ) ₁₀ is 0.16% by mass, and the (Me(Pf)SiO _2/2 ) units are all diorganosiloxane units (D units). ) of 33 mol% and fluorine atom content of 38% by mass of fluorine alkyl and alkenyl-containing organopolysiloxane (B) with an average composition formula: (Me ₃ SiO _1/2 ) ₂ (MePfSiO _2/2 ) ₁₂ (MeHSiO _2/2 ) ₂₇ represented by 38 mass % of fluorine atoms and 0.50 mass % of silicon atom-bonded hydrogen atoms (C) is represented by an average composition formula: (Me ₃ Organopolysiloxane (D) 1,3-divinyl-1 represented by SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₉₀₀ (MePfSiO _2/2 ) ₃₀₀ and having a fluorine atom content of 32% by mass , 1,3,3-tetramethyldisiloxane platinum complex (the amount of platinum metal relative to the solid content in the curable composition is 270 ppm). (E) Diisopropyl ether (F) 2-Methyl-3-butyn-2-ol [Mixed Test]

The above-mentioned (A1) and (A2) were put into a transparent glass vial with a lid at a mass ratio of 1:1, and the mixture was sufficiently stirred and mixed at 25°C. As a result, the mixture was cloudy and did not become uniform and transparent. The mixture was left to stand at 25°C, and the external appearance was observed again after 24 hours, but it was still cloudy. In addition, (A1) and (A2) were each transparent liquid at 25 degreeC.

A curable polysiloxane composition was prepared according to the composition shown in the following Table 1, which was used as a release coating agent, a release film was prepared according to the above method, and the release film was measured when the release film was peeled from the polysiloxane adhesive layer. Peel force. In addition, the surface state of the polysiloxane adhesive layer after peeling the release film was visually observed.

〔Table 1〕 Element unit of ingredient Example 1 Example 2 Example 3 Example 4 (A) (A1) parts by mass 19.5 39.5 59.5 79.5 (A2) parts by mass 79.5 59.5 39.5 19.5 (B) parts by mass 4.2 4.4 4.6 4.9 (C) parts by mass 1.0 1.0 1.0 1.0 (D) ppm 250 250 250 250 (E) parts by mass 2665 2665 2665 2665 (F) parts by mass 3.0 3.0 3.0 3.0 The measurement results Peel force gf/inch 40 38 28 26 Surface state of polysiloxane adhesive layer - ○ ○ ○ ○ Element unit of ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) (A1) parts by mass - 60.0 99.0 (A2) parts by mass 99.0 40.0 - (B) parts by mass 6.0 4.6 5.1 (C) parts by mass 1.0 - 1.0 (D) ppm 250 250 250 (E) parts by mass 2665 2665 2665 (F) parts by mass 3.0 3.0 3.0 The measurement results Peel force gf/inch 58 75 53 Surface state of polysiloxane adhesive layer - × × ×

Furthermore, as mentioned above, the peeling layer of the present invention is preferably used as a polysiloxane adhesive with low storage elastic modulus at low temperature, but can also be applied to polysilicon with high storage elastic modulus at low temperature. Oxygen adhesives are shown in Reference Examples 4 to 7. <Reference Example 4> Preparation of "hydrosilylation curable polysiloxane adhesive composition solution 2"

100.0 parts by mass of DOWSIL(TM) 7657ADHESIVE (solid content 56% by mass), a hydrosilylation curable adhesive made by Dow Chemical, and 0.42 part by mass of 4000 CATALYST (a platinum-containing hydrosilylation catalyst) made by Dow Chemical , and 33.3 parts by mass of toluene were sufficiently mixed to prepare a uniform solution. <Reference Example 5> Adhesion measurement of "hydrosilylation curable polysiloxane adhesive composition solution 2"

In the above reference example 2, the "hydrosilylation curable polysiloxane adhesive composition solution 1" was changed to "hydrosilylation curable polysiloxane adhesive composition solution 2", and the heating and curing conditions were changed at 150°C for 3 minutes. The adhesive force was measured by the same method except that it was 140° C. for 5 minutes, and it was 1450 gf/inch. <Reference Example 6> Measurement of storage elastic modulus of "hydrosilylation curable polysiloxane adhesive composition solution 2"

In the above reference example 3, the "hydrosilylation curable polysiloxane adhesive composition solution 1" was changed to "hydrosilylation curable polysiloxane adhesive composition solution 2", and the heating and curing conditions were changed at 150°C for 3 minutes. The storage elastic modulus at -20°C was measured by the same method except that it was 140°C for 5 minutes, and the result was 9.5 MPa.

<Reference Examples 7-1, 7-2> According to the composition shown in Table 2 below, the composition was the same as that of Example 3, and the amount of component (C) was changed to 0.5 parts by mass (Example 3' ) to prepare a curable polysiloxane composition, use it as a release coating agent, and prepare a release film according to the above method, and measure the release force when the release film is peeled off from the polysiloxane adhesive layer. In addition, the surface state of the polysiloxane adhesive layer after peeling the release film was visually observed. The results are shown in Table 2.

〔Table 2〕 Element unit of ingredient Reference Example 7-1 Reference Example 7-2 hardened polysiloxane Example 3' 3 (A) (A1) parts by mass 59.7 59.5 (A2) parts by mass 39.8 39.5 (B) parts by mass 4.6 4.6 (C) parts by mass 0.5 1.0 (D) ppm 250 250 (E) parts by mass 2665 2665 (F) parts by mass 3.0 3.0 The measurement results Peel force gf/inch 41 25 Surface state of polysiloxane adhesive layer - ○ ○ [Summarize]

The curable polysiloxane compositions of Examples 1 to 4 of the present invention achieved peeling forces far lower than those of Comparative Examples 1 to 3. In addition, the surface of the polysiloxane adhesive layer after peeling of the release liners composed of the curable compositions of Examples 1 to 4 was in a uniform state, and no roughness or wrinkles were recognized. On the other hand, when the component (A) is used alone or when the component (C) is not used, a sufficient reduction in peel force cannot be achieved for a polysiloxane adhesive with a low storage elastic modulus at low temperature, especially It is because the peeled polysiloxane adhesive layer is in an uneven state, and there is a deep concern that the scope of industrial application is limited. (Comparative Examples 1 to 3) Furthermore, as confirmed in Reference Examples 7-1 and 7-2, the curable polysiloxane compositions of the embodiments of the present invention can also be sufficiently used to store polysiloxanes whose elastic modulus exceeds 5 MPa at low temperature. adhesive. [Industrial Availability]

As shown in the examples, the release film having the release layer formed by using the curable polysiloxane composition of the present invention as the release coating agent for the polysiloxane adhesive can peel off the polysiloxane adhesive with weak force, especially The polysiloxane adhesive with low storage elastic modulus at low temperature can keep the surface of the polysiloxane adhesive after peeling off the release film uniformly and prevent the generation of roughness or wrinkles. Therefore, the curable polysiloxane of the present invention The oxygen composition can be used not only as a previously commercially available polysiloxane adhesive, but also as a release coating agent for release films for polysiloxane adhesives with low storage elastic modulus at low temperatures. In addition, the polysiloxane adhesive with low storage elastic modulus at low temperature is contrary to its excellent performance, and there are few release agents with good compatibility, so its application development is often limited, but by using the release coating of the present invention The cloth agent is easily provided in the form of a polysiloxane adhesive film/sheet with good peeling properties and low peeling properties, and its industrial application is strongly expected to expand.

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Claims (15)

A curable polysiloxane composition comprising: (A) A mixture of two or more fluoroalkyl group-containing organopolysiloxanes having a fluoroalkyl group and at least two alkenyl groups in one molecule, and the contents of the fluoroalkyl groups are different from each other, and the aforementioned two or more kinds contain The fluoroalkyl organopolysiloxane is a combination of those that are not completely miscible at 25°C when mixed without a solvent; (B) Organohydrogen polysiloxanes having at least 3 silicon-bonded hydrogen atoms in one molecule; (C) Organopolysiloxanes having organic groups containing fluorine atoms and no hydrosilylation reactive groups; (D) catalysts for hydrosilylation; and (E) Organic solvent. The curable polysiloxane composition of claim 1, wherein the component (A) is a mixture of the following components: (A1) One or more linear or branched organopolysiloxanes containing an organodisiloxane unit containing a fluorine-containing alkyl group and having a fluorine atom content of 40% by mass or more, and (A2) One or more linear or branched organopolysiloxanes containing an organodisiloxane unit containing a fluorine alkyl group and having a fluorine atom content of less than 40% by mass. The rigid polysiloxane composition of claim 2, wherein the difference between the fluorine atom content (mass %) of the (A1) component and the fluorine atom content (mass %) of the (A2) component is 3 mass % or more. The curable polysiloxane composition according to any one of claims 1 to 3, wherein the component (A) is a mixture of the following components: (A1) An organodisiloxane unit comprising a fluoroalkyl group, the aforementioned fluoroalkyl group is 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and the aforementioned unit is an organosiloxane 39 mol% or more of the whole unit of one or more linear or branched organopolysiloxanes; and (A2) An organodisiloxane unit comprising a fluoroalkyl group, the aforementioned fluoroalkyl group is 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and the aforementioned unit is an organosiloxane One or more kinds of linear or branched organopolysiloxanes of 36 mol% or less of the whole unit. The curable polysiloxane composition of claim 4, wherein the mass ratio of the above-mentioned (A1) component and (A2) component is a mass ratio of (A1)/(A2)=1/99 to 99/1. The curable polysiloxane composition according to any one of claims 1 to 5, wherein at least one of the (C) component molecular chain ends is a trimethylsilyl group, The fluorine atom-containing organic group is one or more groups selected from the group consisting of fluoroalkyl groups having 1 to 12 carbon atoms and organic groups containing fluorine (poly)ethers, The organopolysiloxane in which the content of the fluorine atom in the fluorine atom-containing organic group in the molecule is in the range of 20 to 40 mass %. The curable polysiloxane composition according to any one of claims 1 to 6, wherein the component (B) is an organic hydrogen further having a fluoroalkyl group having 1 to 12 carbon atoms or an organic group containing a fluorine (poly)ether Polysiloxane. The curable polysiloxane composition according to any one of claims 1 to 7, which contains 0.1 to 40 parts by mass of (B) component and 0.01 to 20 parts by mass of (C) component with respect to 100 parts by mass of (A) component (D) Component platinum metal content is 0.1 to 500 ppm, and (E) component is 20 to 10,000 parts by mass. A release coating agent for polysiloxane adhesives, comprising the curable polysiloxane composition of any one of claims 1 to 8. As claimed in claim 9, the release coating agent for polysiloxane adhesives is a polysiloxane adhesive whose storage elastic modulus at -20°C is below 5 MPa. A release film comprising: film substrates; and A peeling layer consisting of a cured product obtained by curing the curable polysiloxane composition of any one of claims 1 to 8. A release film for polysiloxane adhesive, comprising: film substrates; and A release layer consisting of a cured product obtained by curing the release coating agent for a polysiloxane adhesive according to claim 9 or 10. A layered product having a structure in which a polysiloxane adhesive layer and at least one release layer are arranged to face each other, and the release layer is cured by curing the release coating agent for a polysiloxane adhesive according to claim 9 The peeling layer composed of the material. According to the laminate of claim 13, the polysiloxane adhesive layer is a polysiloxane adhesive layer whose storage elastic modulus at -20°C is 5 MPa or less. The layered product according to claim 13 or 14, wherein the entire layered product has at least one shape selected from i) a layered sheet shape and ii) a roll shape.