JP6686774B2 - Laminated film - Google Patents

Description

  The present invention relates to a laminated film.

  A release film with a surface layer of silicone resin is used as a base film when forming an adhesive layer used in the production of films for optical applications such as liquid crystal polarizing plates and retarders, and as an adhesive layer protection until the above optical film is laminated. Functions as a film.

  The adhesive layer of the optical film exerts its function by being peeled off from the release film and attached to a predetermined adherend. Therefore, the basic function of the release film is that the peeling force between the adhesive layer and the release film or between the adhesive layer and the adherend does not change depending on various environments and periods with the release layer attached to the adhesive layer. (Hereinafter referred to as “change in peeling force between adhesive layers during heating” and “residual adhesion rate of adhesive layer”).

  Furthermore, in addition to the above-mentioned basic functions, the additional function of the release film is that the peeling force is sufficiently low from the viewpoint of shortening the work load and working time of the adhesive layer laminating process (hereinafter referred to as “light peeling property”). That is, the peeling force has a small peeling speed dependence (hereinafter, referred to as “peeling speed dependence”).

  On the other hand, it is not technically easy to satisfy all of the above requirements, and various studies have been made so far. Patent Document 1 discloses that "a base material film has a release layer composed of a silicone-based resin film on at least one surface, and the silicone-based resin film contains a silicone compound obtained by reacting a silicone oil having a hydroxyl group with an isocyanate compound. Release film ".

  In Patent Document 2, "a laminated film having a coating layer containing polyvinyl alcohol on at least one surface of a polyester film and a release layer and an adhesive layer on one surface in this order, wherein the release layer is at least 1 A laminated film containing at least one kind of silicone resin having alkenyl groups and alkyl groups as functional groups and containing at least one kind of siloxane having a molecular weight of 1,000 or less in an amount of 3.0 to 15.0% by weight is proposed.

  Patent Document 3 discloses a "polyester film having a silicone-based release layer containing a silicone resin having an alkenyl group and an alkyl group as a functional group, a low-molecular-weight silicone compound having a molecular weight of 1000 or less, and a platinum-based catalyst." The layer has a low speed peeling force in the range of 10 to 20 mN / cm in the 300 mm / min speed range, and a high speed peeling force in the 10,000 mm / min speed range of 2.5 times or less the low speed peel force. A release polyester film for a polarizing plate in which the release film has an MOR value of 1.5 to 3.0 is proposed.

JP, 2005-313601, A JP, 2014-226922, A JP2012-137568A

  TECHNICAL FIELD The present invention relates to a laminated film which is excellent in change of peeling force during heating, residual adhesion rate of an adhesive layer after peeling a release layer, light peelability, and peeling speed dependency.

  The problems to be solved by the present invention are: Small change in peeling force during heating, 2. 2. The adhesive layer has a high residual adhesion ratio. 3. Good light peelability That is, the peeling speed dependency is small. On the other hand, the above-mentioned known technique is in the following situation.

  First, when the inventors of the present invention confirmed the technique of Patent Document 1, it was confirmed that the light peeling property of 3 and the peeling speed dependency of 4 were good. The release force was significantly large when the release layer and the pressure-sensitive adhesive layer were peeled off.

  Regarding the technologies of Patent Documents 2 and 3, it was confirmed that the light peeling property of 3 and the peeling speed dependency of 4 were excellent, but the peeling force at the time of heating 1 was reduced, and the residual adhesion ratio of 2 was It was a small one.

As a result of intensive studies conducted by the present inventors to solve the above problems, the following inventions have been completed. That is, the present invention is as follows.
1. There is a resin layer on at least one surface of the supporting substrate, the resin layer contains a polyorganosiloxane, the polyorganosiloxane contains a dimethylsiloxane segment, an alkylene-methylsiloxane segment and a fluoroalkyl-methylsiloxane segment, and A laminated film which satisfies the following condition 1 and condition 2.

Condition 1. The elastic modulus measured from the surface side of the resin layer by an atomic force microscope is 15 MPa or less Condition 2. Receding contact angle of hydroxypropyl acrylate in the resin layer surface 30 ° or more on
2 . 1 the ratio of fluorine atom / silicon atom of the resin layer is equal to or less than 0.005 than 0.1. The laminated film according to.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated film which is excellent in the peeling force change at the time of heating, the residual adhesiveness of the adhesive layer after peeling a resin layer, light peelability, and peeling speed dependence can be obtained.

It is a measurement conceptual diagram of the receding contact angle of hydroxypropyl acrylate on the resin layer surface. It is a measurement conceptual diagram of the receding contact angle of hydroxypropyl acrylate on the resin layer surface. It is an example of a graph showing the relationship between the liquid suction amount and the contact angle obtained by the measurement of the receding contact angle. It is a measurement conceptual diagram of the receding contact angle of hydroxypropyl acrylate on the resin layer surface. It is an example of a graph showing the relationship between the liquid suction amount and the contact angle obtained by the measurement of the receding contact angle.

  Before describing the modes for carrying out the present invention, the problems of the prior art will be considered from the viewpoint of the present inventor, and the mechanism of the present invention will be described.

  First, the reason why the laminated film described in Patent Document 1 has a large change in peeling force during heating is that the silicone oil having a hydroxyl group is immobilized in the resin layer by crosslinking reaction with an isocyanate compound in order to reduce the peeling force. Therefore, a high residual adhesion rate can be obtained by immobilization, but the crosslinking reaction of the silicone oil having hydroxyl groups progresses during heating storage, the elastic modulus of the resin layer increases, and the peeling force after heating storage increases. I believe.

  The reason why the laminated films described in Patent Documents 2 and 3 have a large change in peeling force when heated at 1 and a small residual adhesion ratio at 2 is that the invention relates to a silicone resin having an alkenyl group and an alkyl group as functional groups. In addition, since a low molecular weight siloxane having a molecular weight of 1,000 or less is mixed, the low molecular weight siloxane migrates to the interface between the adhesive layer and the resin layer, and as a result, the peeling force at heating and the residual adhesion rate are reduced. thinking.

  As an overview of these conventional technologies, when trying to enhance additional functions as a laminated film such as light peeling property and peeling speed dependency, peeling force change during heating, residual adhesion rate of adhesive layer after resin layer peeling, etc. The basic function as a laminated film is deteriorated, and there is a trade-off relationship.

  Therefore, the inventors once returned to the peeling process of the resin layer and the pressure-sensitive adhesive, and as a result of detailed observation, found that the magnitude of the peeling energy corresponding to the peeling force is governed by two phenomena.

  One is the effect of relieving the large deformation of the adhesive layer that occurs in the early stage of the peeling process between the resin layer and the adhesive layer by the deformation of the resin layer. The more easily the resin layer deforms with a small force, the smaller the deformation of the adhesive layer can be. As a result, the peeling energy is reduced and the peeling force is reduced.

  The other is the ease of movement of the peeling point on the surface of the resin layer that occurs in the latter part of the peeling process. This is because in the latter part of the peeling process, the deformation of the adhesive layer is completed and the force is transmitted to the interface between the two layers, and the peeling proceeds while the peeling point between the adhesive layer and the resin layer moves. Therefore, the ease of movement of the peeling end of the adhesive layer on the surface of the resin layer affects the peeling force, and the easier the movement, the lower the peeling force.

  Based on the knowledge of the newly obtained peeling process, the present inventors maintain basic functions as a laminated film such as change in peeling force during heating and deterioration of residual adhesion ratio of an adhesive layer after resin layer peeling. In the meantime, we devised a method to improve the additional function.

  Specifically, as a result of diligent studies by the inventors of the present invention on the physical property index of the laminated film that controls the above-mentioned two phenomena, the elastic modulus measured from the resin layer surface side by an atomic force microscope was found for the former. I found that it was effective to make it within a certain range. The significance of using this method is that the apparent elastic modulus including the influence of the thickness of the resin layer and the hardness of the base material can be measured with high accuracy, and the peeling energy in the initial stage of the peeling process is more likely to be affected. It is difficult to evaluate the elastic modulus of the recovery process, which has characteristics and is measured by a conventional nanoindenter or the like.

  For the latter, it was found that it is effective to set the receding contact angle of the resin layer to a typical acrylic monomer (hydroxylpropyl acrylate) contained in the adhesive layer within a specific range.

  The receding contact angle is called a dynamic contact angle, unlike a static contact angle which is generally called a contact angle. The dynamic contact angle characterizes the shape of the liquid as it moves along the surface, and the contact angle when the liquid expands is called the advancing contact angle, and the contact angle when the liquid contracts is called the receding contact angle. The receding contact angle is an index that integrates not only the affinity between the resin layer and the adhesive layer but also the shape of the resin layer surface and the composition uniformity of the resin layer surface, and therefore corresponds to the peeling energy at the final stage of the peeling process. Therefore, even if the static contact angle on the surface of the resin layer is high, the effect of reducing the peeling energy cannot be obtained if the receding contact angle is low.

  Details of the receding contact angle measurement conditions will be described later. There are several methods of measuring the receding contact angle value, but methods that are in principle affected by the droplet mass, such as the falling angle method, should be avoided. Here, measurement by the expansion-contraction method will be described with reference to FIGS. 1 to 5. FIG. 1 shows the initial state of the receding contact angle measurement. A measurement solution is supplied onto the surface 1 of the resin layer through a syringe needle 2 to form a solution solution 3. The contact angle 4 at this time corresponds to a static contact angle.

  FIG. 2 shows a measurement state of the surface of the resin layer having a high receding contact angle. When the measurement solution is sucked from the solution solution through the syringe needle 6, the solution solution on the surface of the resin layer 5 is reduced, but the contact angle is high, and thus the spreading area of the measurement solution is reduced. The change in contact angle at this time is shown in FIG. The abscissa plots the measurement time or the amount of the aspirated measurement liquid, and the ordinate plots the contact angle at each time point. Immediately after the start of measurement, the contact angle slightly decreases, but thereafter it becomes relatively high and constant. This constant value is called the receding contact angle.

  FIG. 4 shows a measurement state of the resin layer surface having a low receding contact angle. When the liquid to be measured is sucked, the liquid suitability is reduced, but the end of the liquid suitability does not move much and the height of the liquid suitability decreases. The change in contact angle at this time is shown in FIG. The contact angle decreases greatly from the start of measurement and becomes constant when it decreases. Further, it may not be constant depending on the sample, and in this case, the receding contact angle is 0 °.

  The contact angle in the expansion / shrinkage method can be measured using, for example, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.).

  These methods can be achieved by setting the viscoelasticity and surface physical properties of the resin layer within a specific range, so that different reaction systems can be brought into the resin layer or migration to the adhesive layer side as in the prior art. There is a feature that additional functions such as light peeling property and peeling speed dependency can be improved without using a material having a high heat resistance.

  Hereinafter, modes for carrying out the present invention will be specifically described.

The above problems, namely 1. Small change in peeling force during heating, 2. 2. The adhesive layer has a high residual adhesion ratio. 3. Good light peelability In order to satisfy all that the peeling speed dependency is small, the laminated film of the present invention is a laminated film having a resin layer on at least one surface of a supporting substrate, and satisfies the following Condition 1 and Condition 2. Is preferred.
Condition 1. 1. The elastic modulus measured from the resin layer surface side by an atomic force microscope is 15 MPa or less. The receding contact angle of hydroxypropyl acrylate on the resin layer surface is 30 ° or more.

  From the viewpoint of reducing the absolute value of the peeling force, the elastic modulus measured from the resin layer surface side by an atomic force microscope is preferably 15 MPa or less, more preferably 10 MPa or less, and particularly preferably 5 MPa or less. When the elastic modulus measured from the resin layer surface side is larger than 15 MPa, the peeling force may increase. Although the elastic modulus measured from the resin layer surface side is low, there is no problem, but when it becomes significantly low, for example, 0.1 MPa or less, the cohesive force of the resin layer decreases, so the resin layer is destroyed when the adhesive layer is peeled off, The residual adhesion rate may decrease.

  The elastic modulus measured from the resin layer surface side by this atomic force microscope shows the influence of the viscoelasticity of the resin layer itself, the thickness of the resin layer, and the hardness of the supporting base material in addition to the composition and curing conditions of the resin layer itself. Therefore, they can be controlled by using these.

  From the viewpoint of reducing the peeling speed dependency of the peeling force, the receding contact angle of hydroxypropyl acrylate on the surface of the resin layer is preferably 30 ° or more, and more preferably 40 ° or more. When the receding contact angle of hydroxypropyl acrylate on the surface of the resin layer is lower than 30 °, the peeling speed dependency may increase. Although the receding contact angle of hydroxypropyl acrylate on the surface of the resin layer is high, there is no problem, but the limit is actually about 60 °.

  Further, the resin layer preferably contains a polyorganosiloxane, and the polyorganosiloxane preferably contains a dimethylsiloxane segment, an alkylene-methylsiloxane segment and a fluoroalkyl-methylsiloxane segment. Here, the dimethylsiloxane segment is exemplified by the chemical formula 1, the alkylene-methylsiloxane segment is exemplified by the chemical formula 2, and the fluoroalkyl-methylsiloxane segment is exemplified by the chemical formula 3.

  The dimethylsiloxane segment is a segment that affects the flexibility of the polyorganosiloxane contained in the resin layer. As the proportion of the dimethylsiloxane segment increases, the elastic modulus measured from the resin layer surface side by an atomic force microscope can be reduced, but on the other hand, sufficient cohesive force cannot be obtained with only this segment, and the resin layer It may not be possible to form.

  The alkylene-methylsiloxane segment is a segment that affects the three-dimensional crosslinking of the polyorganosiloxane contained in the resin layer, and is responsible for adjusting the elastic modulus and cohesive force of the resin layer. As n in the chemical formula 2 is larger, the reactivity of the alkenyl-methylsiloxane segment exemplified in the chemical formula 4 and the hydrogensilyl segment exemplified in the chemical formula 5 in the hydrosilylation reaction is improved when the polyorganosiloxane is formed, and the unreacted The migration of the cross-linking component to the adhesive layer is reduced.

  In Chemical Formula 2, n is preferably 2 or more, more preferably 6 or more, and in Chemical Formula 4, n may be 0, but is preferably 2 or more, more preferably 3 or more. There is a preferable range for the ratio of the alkylene-methylsiloxane segment in the resin layer, and about 10 to 25% by mass of the dimethylsiloxane segment is 100% by mass of the fluoroalkyl-methylsiloxane segment, which is too high. The crosslink density may be too high, and as a result, the elastic modulus of the resin layer may be too high. On the other hand, if it is too low, the cohesive force of the coating film may be insufficient.

  The fluoroalkyl-methylsiloxane segment has a function of increasing the receding contact angle of hydroxylpropyl acrylate on the surface of the resin layer, and in the chemical formula 3, n is preferably 3 or more and 8 or less. In Chemical Formula 3, the larger n is, the longer the fluoroalkyl chain length is, and the receding contact angle of hydroxylpropyl acrylate on the resin layer surface can be increased. On the other hand, when n is too large, the resin precursor for the resin layer is formed. In some cases, the solubility in the coating composition for a resin layer may be reduced, or the uniformity on the surface of the coating film on a fine scale can be reduced, and the receding contact angle can be reduced.

  The presence of the above segment in the resin layer and the quantitative analysis can be confirmed by the TOF-SIMS method for the resin layer.

  Further, regarding the existence state of the above segment in the resin layer, it is preferable that the ratio of the fluoroalkyl-methylsiloxane segment occupying on the surface side is larger than that on the inner side, and the fluoroalkyl-methylsiloxane segment is the most. It is more preferable that it is segregated only very thinly on the surface. By segregating the fluoroalkyl-methyl siloxane segment on the surface side, the surface can be uniformly covered with the fluoroalkyl chain, so that the receding contact angle can be increased and the flexible dimethyl siloxane segment is formed on the substrate side from the surface. By occupying most of the thickness, it becomes possible to reduce the elastic modulus of the entire resin layer. The method of forming the distribution of the segments in the thickness direction will be described later.

  Further, the ratio of fluorine atom / silicon atom of the resin layer has a preferable range, and is preferably 0.005 or more and less than 0.1, more preferably 0.01 or more and less than 0.05.

  When the ratio of fluorine atom / silicon atom is 0.1 or more, the receding contact angle of hydroxylpropyl acrylate increases, but the elastic modulus of the resin layer surface may increase.

  The ratio of fluorine atoms / silicon atoms in the resin layer is the ratio of fluorine atoms / silicon atoms in the resin layer, and the ratio of fluorine atoms / silicon atoms in the resin layer should be determined by XPS. Is possible.

[Laminated film and resin layer]
The laminated film of the present invention may have a resin layer satisfying the above conditions on at least one surface of the supporting base material, and may have a resin layer on both surfaces of the supporting base material. However, one or more intermediate layers may be provided between the supporting base material and the resin layer in order to impart adhesion, antistatic property, solvent resistance, etc. of the resin layer to the supporting base material.

  The thickness of the resin layer described above is preferably 10 to 500 nm, more preferably 20 to 200 nm. By setting the resin layer in the above range, it is possible to realize the basic function and additional function as a stable laminated film that is unlikely to reduce productivity.

  The resin layer of the laminated film of the present invention is not particularly limited as long as the above conditions can be satisfied, but is preferably formed of a resin composition for a resin layer described below, and is supported by a method for manufacturing a laminated film described below. It is preferably formed by coating, drying and curing a resin layer coating composition described below on a substrate.

  Here, the “layer” in the present invention refers to the boundary between the surface of the laminated film in the thickness direction, the composition of constituent elements with adjacent portions, the shape of inclusions such as particles, and the physical properties in the thickness direction that are discontinuous. A part having a finite thickness that is distinguished by having a surface. More specifically, various composition / elemental analyzers (FT-IR, XPS, XRF, EDAX, SIMS, EPMA, EELS, etc.), electron microscopes (transmission type, scanning type) or the above-mentioned laminated film in the thickness direction from the surface are used. This refers to a portion having a finite thickness, which is distinguished by the discontinuous boundary surface when the cross-section is observed with an optical microscope.

  As described above, in the thickness direction of the resin layer, the structure in which the amount of fluoroalkyl-methylsiloxane segments is larger on the surface side than on the inner side is more preferable. 1. A layer structure is spontaneously formed in a drying step by using a compatibility difference between resin precursors in a resin layer coating composition described later. 2. A layer containing no fluoroalkyl-methylsiloxane segment is formed on the substrate side and a layer containing a fluoroalkyl-methylsiloxane segment is formed on the surface side by sequential coating. It can be formed by a method such as forming a layer containing no fluoroalkyl-methylsiloxane segment on the substrate side by simultaneous coating and forming a layer containing a fluoroalkyl-methylsiloxane segment on the surface side. And the method of simultaneous coating are preferred. Details of the manufacturing method will be described later.

[Resin layer resin composition]
The above-mentioned resin composition for resin layer refers to a resin composition preferable for the resin layer of the above-mentioned laminated film of the present invention. The composition of the resin layer, or the resin composition for the resin layer is not particularly limited as long as the above conditions can be satisfied, but alkyd resin, polyolefin resin, long chain alkyl group-containing resin, fluorine resin, silicone resin, A mixture of an organic type and a silicone type or a copolymer resin is preferable, a silicone type resin is more preferable because of excellent mold releasability and heat resistance, and a curable silicone type resin is particularly preferable.

  The curable silicone resin is an "addition reaction type" in which an organohydrogenpolyroxane and an organopolysiloxane containing an alkenyl group are heat-cured under a platinum catalyst, an organohydrogenpolyroxane and a hydroxyl group at the end. "Polycondensation reaction type" obtained by heating and curing an organopolysiloxane containing an organotin catalyst, an organopolysiloxane containing an alkenyl group and an organopolysiloxane containing a mercapto group using a photopolymerization catalyst. There are "radical addition type" for curing and "cationic polymerization type" for photo-opening and curing an epoxy group with an onium salt initiator, and either may be used, but from the viewpoint of productivity and peeling power, organo Hydrogen polyroxane and an alkenyl group-containing organopolysiloxane are added under a platinum catalyst. Cured addition reaction type are preferred.

  The resin composition for a resin layer in the present invention can be preferably formed by removing a solvent in a drying step, if necessary, and then curing the resin composition for a resin layer described below.

[Resin layer coating composition, resin layer resin precursor]
The above-mentioned resin layer coating composition is a resin layer of the above-mentioned laminated film, or a mixture exhibiting a liquid state at room temperature capable of forming the above-mentioned resin layer resin composition, and at least the below-mentioned laminated film. By a method capable of forming a resin composition for a resin layer (hereinafter referred to as a resin precursor), a polymerization initiator, a curing agent, and a curing catalyst, and further includes a solvent, particles, an antistatic agent, and the like. Various additives may be included.

The composition of the resin layer coating composition is not particularly limited as long as it can satisfy the above-mentioned conditions, but as described above, a silicone resin, particularly a curable silicone resin, can be formed from the viewpoint of releasability and heat resistance. A resin precursor is preferable, and a coating composition containing an "addition reaction type", "polycondensation reaction type", "radical addition type", "cationic polymerization type" resin precursor, and a polymerization initiator, a curing agent, and a curing catalyst. The thing is more preferable, and "addition reaction type" is the most preferable.

  Further, the resin layer coating composition in the present invention preferably contains a resin precursor A and a resin precursor B described later. When the resin layer contains a polyorganosiloxane and the polyorganosiloxane contains a dimethylsiloxane segment, an alkylene-methylsiloxane segment, and a fluoroalkyl-methylsiloxane segment, the resin layer coating composition has a resin precursor described below. It is preferable that the resin precursor C is contained in addition to A and the resin precursor B.

  In the method for producing a laminated film described below, only one type of resin layer coating composition may be used, or a plurality of resin layer coating compositions may be used to form the resin layer by sequential coating or simultaneous coating. May be. Therefore, one type of resin layer coating composition may or may not include all of the resin precursor A, the resin precursor B, and the resin precursor C, and the method for producing a laminated film and the resin layer used Depends on the resin precursor.

  The resin precursor A preferably contains an organohydrogenpolysiloxane α and an alkenyl group-containing organopolysiloxane β. The resin precursor A preferably has a viscosity of 10,000 (mPa · s) or more in the state of a toluene solution containing the resin precursor A at a solid content concentration of 30% by mass.

  The resin precursor B preferably contains an organohydrogenpolysiloxane X and an alkenyl group-containing organopolysiloxane Y. Further, the resin precursor B preferably has a viscosity of 5,000 (mPa · s) or less in the state of a toluene solution containing the resin precursor B in a solid content concentration of 30% by mass.

  The resin precursor C preferably contains the organohydrogenpolysiloxane 1 and a fluoroalkyl-modified organopolysiloxane containing an alkenyl group and a fluoroalkyl group.

  Specific examples of the organohydrogenpolysiloxanes α, X, and 1 include methylhydrogenpolysiloxane having trimethylsiloxy groups blocked at both molecular chain terminals, and dimethylsiloxane / methylhydrogensiloxane copolymer having trimethylsiloxy groups blocked at both molecular chain terminals. Examples thereof include dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane having molecular chain terminals at both ends, and dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer having dimethylhydrogensiloxy group at both molecular chain terminals.

  The organohydrogenpolysiloxane α and the organohydrogenpolysiloxane X used in the present invention may be the same or different.

  Specific examples of the alkenyl group-containing organopolysiloxanes β and Y include a dimethylsiloxy / methylhexenylsiloxane copolymer (dimethylsiloxane unit: 96 mol%, methylhexenylsiloxane unit: 4 mol%) capped with trimethylsiloxy groups at both molecular chain ends. ), A dimethylvinylsiloxy group-capped dimethylsiloxane / methylhexenylsiloxane copolymer having molecular chain terminals at both ends (dimethylsiloxane unit: 97 mol%, a methylhexenylsiloxane unit: 3 mol%), a dimethylhexenylsiloxy group-capped dimethylsiloxane at each molecular chain terminal: methyl Examples thereof include hexenyl siloxane copolymers (dimethyl siloxane unit: 95 mol%, methylhexenyl siloxane unit: 5 mol%).

  The alkenyl group-containing organopolysiloxane β and the alkenyl group-containing organopolysiloxane Y used in the present invention are preferably different.

  Further, it is preferable that the alkenyl group-containing organopolysiloxane β and the alkenyl group-containing organopolysiloxane Y have a viscosity difference in the state of a toluene solution containing a solid content concentration of 30% by mass. It is preferable that the organopolysiloxane β has a viscosity of 10,000 (mPa · s) or more and the alkenyl group-containing organopolysiloxane Y has a viscosity of 5,000 (mPa · s) or less.

  The fluoroalkyl-modified organopolysiloxane containing an alkenyl group and a fluoroalkyl group has at least one alkenyl group in one molecule and at least one fluoroalkyl group in one molecule. The content of the alkenyl group contained in the fluoroalkyl-modified organopolysiloxane is preferably 0.02 to 0.20 mol / 100 g, and more preferably 0.03 to 0.15 mol / 100 g. When the alkenyl content contained in the fluoroalkyl-modified polydimethylsiloxane is about 0.02 mol / 100 g or less, the degree of crosslinking becomes insufficient and curing failure may occur. When the alkenyl content is about 0.20 mol / 100 g or more, the release properties of this cured product may be impaired.

  The organohydrogenpolysiloxane and the alkenyl group-containing organopolysiloxane include KS-3650, KS843, KS847, KS847H, KS847T, X62-2829, KS838 and Toray manufactured by Shin-Etsu Chemical Co., Ltd. -SD7333, SRX357, SRX345, LTC310, LTC303E, LTC300B, LTC350G, LTC750A, LTC851, LTC759, LTC755, LTC761, LTC856 etc. by Dow Corning Co., Ltd. are mentioned.

Examples of the organohydrogenpolysiloxane and the fluoroalkyl group-containing organopolysiloxane include BY24-900, BY24-903, SYL-OFF ^R 3062 manufactured by Toray Dow Corning Co., Ltd., Shin-Etsu Chemical Co., Ltd. Examples include X-41-3035 manufactured by Co., Ltd.

The resin layer coating composition in the present invention preferably contains a resin precursor A and a resin precursor B, and more preferably contains a resin precursor C. Specific examples of the resin precursor A include LTC750A, LTC851, LTC759, LTC755, LTC761, LTC856, specific examples of the resin precursor B, LTC310, LTC303E, LTC300B, LTC350G, and specific examples of the resin precursor C, SYL-OFF ^R 3062, X-41-3035 and the like can be mentioned.

  The solid content concentration of the resin layer coating composition in the present invention is not particularly limited to this, but when the resin layer coating composition contains a solvent, it is usually 10% by mass or less, and further, It is preferably 0.5 to 5 mass%. If it is less than 0.5% by mass, cissing tends to occur on the supporting base material or the intermediate layer described later, while if it exceeds 10% by mass, the surface may become rough.

[Middle layer]
In the laminated film of the present invention, the interlayer adhesion between the supporting base material and the resin layer is improved, the antistatic property of the laminated film, the solvent resistance of the resin layer, and the surface migration of the low molecular weight component from the supporting base material are suppressed (hereinafter For the purpose of providing an oligomer block property, one or more intermediate layers may be provided between the supporting base material and the resin layer.

  The method for forming the intermediate layer is not particularly limited as long as the intermediate layer that achieves the above-mentioned purpose can be formed. After forming a film on which the coating composition for an intermediate layer to be described later is applied during film formation of the supporting substrate, the resin layer may be applied in another step. After forming the supporting substrate, the coating composition for the intermediate layer is formed. The material may be applied to the supporting substrate, dried, and wound, and then the resin layer may be applied, dried, and wound (sequential application), but preferably, the intermediate layer coating composition is applied and the solvent is removed. It is preferable to apply the resin layer immediately afterwards from the viewpoints of adhesion between the supporting base material and the resin layer, and coating film quality.

  The dry coating thickness of the intermediate layer is preferably 10 to 500 nm, more preferably 20 to 200 nm, and further preferably 20 to 100 nm. When the coating thickness is 10 nm to 500 nm, the original release performance of the resin layer is stable, and the function desired by the intermediate layer is to improve the adhesion between the support substrate and the resin layer, oligomer blockability, and charging. It is possible to obtain excellent coating film quality with prevention property and solvent resistance.

[Intermediate layer coating composition]
The coating composition for the intermediate layer is not particularly limited, but contains an organosilicon compound and / or a condensate of an organosilicon compound hydrolyzate for the purpose of imparting adhesiveness between the supporting base material and the resin layer. Is preferred.

  Examples of the organosilicon compound include alkoxysilane compounds such as ethyl silicate and methyl silicate, and silanes such as γ-methacryloxy group-containing organoalkoxysilane, epoxy group-containing organoalkoxysilane, vinyl group-containing organoalkoxysilane, and vinyl group-containing acetoxysilane. Coupling agents and mixtures thereof are preferred.

  The condensate of the hydrolyzate of the organosilicon compound is a condensate of the above-mentioned alkoxysilane or a dimer of the hydrolyzate of the silane coupling material, and is a so-called silicone oligomer, silicone resin, siloxane polymer or the like.

  The coating composition for an intermediate layer may contain an organometallic compound in addition to the above organosilicon compound, from the viewpoint of improving the adhesiveness of the resin layer and imparting solvent resistance. The organic metal compound is preferably an organic acid salt of a metal such as aluminum, zinc, cobalt, manganese, zirconium, iron or indium, a chelate compound, an alkoxide and an oligomer thereof, and particularly preferably an organic aluminum compound.

Examples of the organic aluminum compound include aluminum alcoholates such as (MeO) ₃ Al, (EtO) ₃ Al, and (n-Pro) ₃ Al; aluminum salts such as naphthenic acid, stearic acid, octylic acid, and benzoic acid; Examples thereof include aluminum chelates obtained by reacting acetic acid ester or dialkyl malonate, organic acid salts of aluminum oxide, and aluminum acetylacetonate. Further, as the organic aluminum compound, an aluminum chelate compound is preferable. Specifically, examples of the organoaluminum compound include aluminum tris (acetylacetonate) and aluminum monoacetylacetonate hist (ethyl acetoacetate).

  The solid content concentration of the coating composition for an intermediate layer in the present invention is not particularly limited to this, but when the coating composition for an intermediate layer contains a solvent, it is usually 10% by mass or less, and further, It is preferably 0.5 to 5 mass%. If it is less than 0.5% by mass, cissing may easily occur on the substrate film, while if it exceeds 10% by mass, the surface may be roughened.

[Other paint composition additives]
The above-mentioned resin layer coating composition and intermediate layer coating composition may contain a solvent, and preferably contains a solvent from the viewpoint of production suitability. Here, the solvent refers to a substance that is a liquid at room temperature and atmospheric pressure that can evaporate almost the entire amount in the drying step after coating. The coating composition suitable for the laminated film of the present invention may contain a solvent. The number of kinds of solvent is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and further preferably 1 or more and 6 or less.

  The type of solvent depends on the molecular structure of the solvent. That is, those having the same elemental composition and different bonding relationships even if the type and number of functional groups are the same (structural isomers), but not the above structural isomers, but what conformation in three-dimensional space Those that do not overlap exactly with each other (stereoisomers) are treated as different kinds of solvents. For example, 2-propanol and n-propanol are treated as different solvents.

  Further, for the purpose of imparting antistatic properties to the laminated film, the resin layer and the intermediate layer may contain various antistatic materials. As the antistatic agent, cationic antistatic agents typified by ammonium group-containing compounds, polyether compounds, nonionic compounds typified by siloxane compounds, fluorine compounds, anionic compounds typified by sulfonic acid compounds, betaine compounds And ion conductive polymer compounds such as amphoteric compounds, π-electron conjugated polymer compounds such as polyacetylene, polyphenylene, polyaniline, polypyrrole, polyisothianaphthene and polythiophene, and ionic liquids.

[Supporting substrate]
Examples of the supporting substrate in the present invention include polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyethylene films, polypropylene films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, ethylene-vinyl acetate. Copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyphenylene sulfide film, polyetherimide film, polyimide film, fluororesin film, polyamide film, acrylic Resin film, norbornene resin film, cycloolefin Examples of the supporting base material used for the laminated film include a biaxially stretched polyester film which is excellent in mechanical strength, heat resistance, thermal dimensional stability and chemical resistance, and economical. The surface of a preferable supporting substrate may be subjected to various surface treatments before forming the resin layer. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferable, and glow discharge treatment and ultraviolet treatment are more preferable.

[Method for producing laminated film]
The resin layer present on the surface of the laminated film of the present invention is preferably formed by applying the coating composition onto a supporting base material or a supporting base material provided with an intermediate layer. Similarly, when an intermediate layer is provided between the resin layer, the supporting base material, and the resin layer, a method of forming the intermediate layer coating composition on the supporting base material is also preferable.

  The method for applying the coating composition onto the supporting substrate is not particularly limited, but the coating composition may be applied by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Pat. No. 2,681,294). It is preferable to form a layer by applying the composition to a supporting base material or the like by the method described above. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.

When the composition of the surface side is different from that of the inner side in the thickness direction of the resin layer, for example, the resin layer contains a fluoroalkyl-methylsiloxane segment, and the fluoroalkyl-methylsiloxane segment forms a structure in which the surface side is larger than the inner side. In such a case, it is preferable to form by sequential coating or simultaneous coating. When they are formed by sequential coating, different coating compositions are applied one by one by a gravure coating method or a die coating method to form a plurality of layers. When they are formed by simultaneous coating, different coating compositions are formed by using a coating die having a plurality of slits.
Next, the liquid film applied on the supporting substrate or the like is dried. In addition to completely removing the solvent from the obtained laminated film, it is preferable to heat the liquid film in the drying step from the viewpoint of accelerating the curing of the coating film.

  Examples of the drying method include heat transfer drying (adhesion to a hot object), convective heat transfer (hot air), radiant heat transfer (infrared), and others (microwave, induction heating). Among these, in the production method of the present invention, a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to precisely make the drying rate uniform in the width direction.

  Furthermore, you may perform the further hardening operation (hardening process) by irradiating heat or an energy ray. In the curing step, when curing with heat, the temperature is preferably from room temperature to 200 ° C, more preferably 100 ° C or higher and 200 ° C or lower, and further preferably 130 ° C or higher and 200 ° C or higher, from the viewpoint of activation energy of the curing reaction. It is the following.

Further, in the case of curing with energy rays, from the viewpoint of versatility, electron rays (EB rays) and / or ultraviolet rays (UV rays) are preferable. Moreover, examples of the type of ultraviolet lamp used when irradiating with ultraviolet rays include a discharge lamp system, a flash system, a laser system, and an electrodeless lamp system. When ultraviolet curing is performed using a high-pressure mercury lamp which is a discharge lamp system, the illuminance of ultraviolet rays is 100 to 3,000 (mW / cm ² ), preferably 200 to 2,000 (mW / cm ² ), and more preferably 300 to It is preferable to perform ultraviolet irradiation under the condition of 1,500 (mW / cm ² ), and the integrated amount of ultraviolet light is 100 to 3,000 (mJ / cm ² ), preferably 200 to 2,000 (mJ / m ² ). cm ^2), more preferably it is more preferable to carry out ultraviolet irradiation under the condition that the 300~1,500 (mJ / cm ^2). Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and changes depending on the lamp output, the light emission spectrum efficiency, the diameter of the light emission bulb, the design of the reflecting mirror, and the light source distance from the irradiation target. However, the illuminance does not change depending on the transport speed. Further, the ultraviolet integrated light quantity is irradiation energy received per unit area and is the total quantity of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of times of irradiation and the number of lamps.

[Use]
The laminated film of the present invention can be suitably used as a release film. In particular, it can be suitably used as a release film for protecting a pressure-sensitive adhesive used in the production of an optical film such as a liquid crystal polarizing plate and a retardation plate.

Next, the present invention will be described based on examples, but the present invention is not necessarily limited to these. The same product was used for the same compound unless otherwise specified. In addition, below, Examples 1-5 and 14-19 shall be read as reference examples 1-5 and 14-19.

[Preparation of coating composition]
[Intermediate Layer Coating Composition 1]
The following materials were mixed and diluted with a 2-propanol / toluene mixed solvent (mass mixing ratio 50/50) to obtain a coating composition 1 for intermediate layer having a solid content concentration of 4% by mass.
・ Epoxy group-containing organosilicon compound (BY24-846B: manufactured by Toray Dow Corning Co., Ltd.) 5 parts by mass ・ Methacrylic group-containing organosilicon compound (OFS-6030: manufactured by Toray Dow Corning Co., Ltd.) 5 parts by mass ・ Aluminum chelate compound (BY24-846E: manufactured by Toray Dow Corning Co., Ltd.) 1 part by mass.

[Resin layer coating composition A1]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A1 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 9 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 1 part by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A2]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A2 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 8 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 2 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A3]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A3 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A3-2]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A3-2 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass Silicone resin precursor C
(SYL-OFF3062 Coating: manufactured by Toray Dow Corning Co., Ltd.) 0.5 parts by mass Platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A3-3]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A3-3 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass Silicone resin precursor C
(X-41-3035: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A3-4]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A3-4 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass Silicone resin precursor C
(SYL-OFF3062 Coating: Toray Dow Corning Co., Ltd.) 0.1 parts by mass platinum catalyst (SRX212: Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A3-5]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A3-5 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass Silicone resin precursor C
(SYL-OFF3062 Coating: manufactured by Toray Dow Corning Co., Ltd.) 10 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A4]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A4 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 6 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 4 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.
[Resin layer coating composition A5]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A5 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC759: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A6]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A6 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC759: manufactured by Toray Dow Corning Co., Ltd.) 9 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 1 part by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A7]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A7 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC300B: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A8]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A8 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC856: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.
[Resin layer coating composition A9]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A9 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 10 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A10]
The following materials were mixed and diluted with n-heptane / toluene (50/50) to obtain a resin layer coating composition A10 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 10 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A11]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A11 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 5 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 5 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A12]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A12 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 9.5 parts by mass Silicone resin precursor B
(LTC303E: manufactured by Toray Dow Corning Co., Ltd.) 0.5 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A13]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A13 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC759: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A14]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A14 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 7 parts by mass Silicone resin precursor B
(LTC750A: manufactured by Toray Dow Corning Co., Ltd.) 3 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A15]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A15 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC750A: manufactured by Toray Dow Corning Co., Ltd.) 10 parts by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass.

[Resin layer coating composition A16]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A16 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(LTC761: manufactured by Toray Dow Corning Co., Ltd.) 9 parts by mass Silicone resin precursor B
(BY24-850: manufactured by Toray Dow Corning Co., Ltd.) 1 part by mass platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass.

[Resin layer coating composition A17]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition A17 having a solid content concentration of 2% by mass.
・ Silicone resin precursor A
(KS847H: manufactured by Shin-Etsu Chemical Co., Ltd.) 9 parts by mass / additive (X92-183: manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by mass Platinum catalyst (SRX212: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts by mass .

[Resin layer coating composition B1]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a resin layer coating composition B1 having a solid content concentration of 0.1% by mass.
・ Silicone resin precursor C
(SYL-OFF3062 Coating: Toray Dow Corning Co., Ltd.) 10 parts by mass cross-linking agent (3062C CROSSLINKER: Toray Dow Corning Co., Ltd.) 0.08 parts by mass platinum catalyst (SRX212: Toray Dow Corning Co., Ltd.) ) 0.05 part by mass.

[Creation of laminated film]
[Method 1 of producing laminated film]
The coating composition for the intermediate layer was applied to a polyester film having a thickness of 38 (μm) (trade name: “Lumirror” (registered trademark) R60, manufactured by Toray Industries, Inc.) to 0.1 (μm) after drying and curing. Then, the peripheral speed of the gravure roll and the number of gravure lines were adjusted by a gravure coater to apply, and the coating was dried and cured at 100 ° C. for 3 seconds. The resin layer coating composition A is applied within 5 minutes by adjusting the peripheral speed of the gravure roll and the number of gravure lines with a gravure coater so that the coating thickness after drying becomes the specified thickness, and the coating is performed at 120 ° C for 30 seconds. It was dried and cured to obtain a laminated film.

[Method 2 of producing laminated film]
Gravure the coating composition A for the resin layer onto a 38 (μm) thick polyester film (trade name “Lumirror” (registered trademark) R60 manufactured by Toray Industries, Inc.) so that the coating thickness after drying is the specified thickness. The peripheral speed of the gravure roll and the number of gravure lines were adjusted by a coater and applied, and dried and cured at 120 ° C. for 30 seconds to obtain a laminated film.

[Method 3 of producing laminated film]
A 38 (μm) thick polyester film (trade name “Lumirror” (registered trademark) R60 manufactured by Toray Industries, Inc.) is coated with the coating composition A for the resin layer so that the coating thickness after drying becomes a specified thickness. Then, the peripheral speed of the gravure roll and the number of gravure lines were adjusted and applied, and the coating was dried and cured at 120 ° C. for 30 seconds. Next, the surface of the coating film is subjected to corona treatment, and the coating composition A for resin layer is applied by adjusting the peripheral speed of the gravure roll and the number of gravure lines with a gravure coater so that the coating thickness after drying becomes a specified thickness. Then, it was dried and cured at 120 ° C. for 30 seconds to obtain a laminated film.

[Method 4 of producing laminated film]
A two-layer die coater was used for a polyester film having a thickness of 38 (μm) (trade name “Lumirror” (registered trademark) R60 manufactured by Toray Industries, Inc.), and a resin layer coating composition A was used as a lower layer and a resin layer coating composition. B was applied to the upper layer with a two-layer die coater so that the coating thickness after drying would be the specified thickness, and dried and cured at 120 ° C. for 30 seconds to obtain a laminated film.

[Method 5 of producing laminated film]
Gravure the coating composition B for the resin layer onto a 38 (μm) thick polyester film (trade name “Lumirror” (registered trademark) R60 manufactured by Toray Industries, Inc.) so that the coating thickness after drying becomes the specified thickness. The peripheral speed of the gravure roll and the number of gravure lines were adjusted by a coater and applied, and dried and cured at 120 ° C. for 30 seconds to obtain a laminated film.

  Table 1 shows the method for producing the laminated film, the intermediate layer coating composition, and the resin layer coating compositions A and B used in each of the examples and comparative examples.

  The laminated films of Examples 1 to 19 and Comparative Examples 1 to 10 were produced by the above method.

[Evaluation of laminated film]
The performance evaluation shown below was carried out on the produced laminated film, and the obtained results are shown in Table 2. Unless otherwise specified, in each of the examples and comparative examples, the measurement was performed three times at different locations for each sample, and the average value was used.

[Elastic modulus measured from resin layer surface]
The resin layer surface of the laminated film was measured in PeakForceQNM mode using AFM (Burker Corporation DimensionIcon), and the obtained force curve was analyzed using the attached analysis software "NanoScope Analysis V1.40" to determine the JKR contact theory. Based on the above, the elastic modulus distribution was obtained.

  Specifically, according to the PeakForce QNM mode manual, after configuring the cantilever's warp sensitivity, spring constant, and tip curvature, measurement was performed under the following conditions, and the obtained DMT Modulus channel data was used to calculate the surface elastic modulus. Adopted as. Although the spring constant and the tip curvature vary depending on the individual cantilevers, the spring constant is 0.3 (N / m) or more and 0.5 (N / m) or less, and the tip curvature radius is 15 ( nm) A cantilever satisfying the following conditions was adopted and used for measurement.

The measurement conditions are shown below.
Measuring device: Atomic force microscope (AFM) manufactured by Burker Corporation
Measurement mode: PeakForceQNM (force curve method)
Cantilever: Bruker AXS SCANASYST-AIR
(Material: Si, spring constant K: 0.4 (N / m), tip radius of curvature R: 2 (nm))
Measurement atmosphere: 23 ° C, measurement range in air: 3 (μm) square resolution: 512 × 512
Cantilever moving speed: 10 (μm / s)
Maximum pushing load: 10 (nN).

  Then, the obtained DMT Modulus channel data was analyzed with the analysis software "NanoScope Analysis V1.40", and the value of Image Raw Mean of the Results tab obtained by processing with Roughness was measured from the resin layer surface side. Was set as the elastic modulus. The elastic modulus of the resin layer surface is summarized in two significant figures.

[Measurement of receding contact angle of resin layer surface]
The receding contact angle was measured by the expansion-contraction method, and a contact angle meter Drop Master DM-501 manufactured by Kyowa Interface Science Co., Ltd. was used, and the expansion-contraction method measurement manual of the device was followed.

  With respect to the receding contact angle, a droplet of hydroxylpropyl acrylate having an initial droplet volume of 50 μL is once created on the surface of the resin layer, and then the liquid ejection speed is 8.5 μL / s with the syringe needle tip being pointed at the droplet. The droplets were continuously sucked, and the shape of the droplet in the shrinking process was continuously photographed every 100 milliseconds to determine the contact angle in each process.

  The contact angle during the contraction process of the droplets first changed with contraction and then became constant, and the contact angle at that time was defined as the receding contact angle. The method for determining that the contact angle has become constant is that when the contact angles are arranged in the direction in which the droplet contracts and five consecutive points are selected, the standard deviation of the consecutive five points is first 1 The average value when it became less than ° was defined as the receding contact angle of the measurement.

  This measurement was performed 5 times for each sample, and the average value was used as the receding contact angle of the sample. Note that, depending on the sample, the contact angle during the contraction process of the droplets is not constant and continuously decreases, but the receding contact angle was set to 0 ° for this.

[Peeling force of laminated film]
An adhesive tape (polyester tape manufactured by Nitto Denko Corp., product name 31B: 31B tape below) is pressure-bonded to the surface of the resin layer of the laminated film by reciprocating a 5 kg rubber roller once, and then at 23 ° C. and 65% RH environment. After standing for a period of time, a resistance value was measured using a tensile tester when peeled 180 degrees at a speed of 300 (mm / min) and 100,000 (mm / min). The resistance value when peeling at a speed of 300 (mm / min) was taken as the low speed peeling force, and the resistance value when peeling at a speed of 100,000 (mm / min) was taken as the high speed peeling force.

[Release force increase rate after heating]
An adhesive tape (polyester tape manufactured by Nitto Denko Corp., product name 31B: 31B tape below) is pressure-bonded to the surface of the resin layer of the laminated film by reciprocating a 5 kg rubber roller once, and then at 23 ° C. and 65% RH environment. After being left for a period of time, a resistance value obtained by peeling 180 degrees at a speed of 300 (mm / min) using a tensile tester was defined as a peeling force before heating.

  Next, an adhesive tape (polyester tape manufactured by Nitto Denko KK, product name 31B: 31B tape below) was pressure-bonded to the surface of the resin layer of the laminated film by reciprocating a 5 kg rubber roller once, and at 70 ° C and 65% RH After being left for 24 hours at 80 ° C, the resistance value when peeled 180 degrees at a speed of 300 (mm / min) using a tensile tester is taken as the peeling force after heating, and the peeling force after heating is calculated using the following formula. The rate of increase was calculated. A peeling force increase rate of 150% or less after heating was regarded as acceptable.

Peel force increase rate (%) after heating = A / B × 100
A: Peeling force after heating B: Peeling force before heating.

[Residual adhesion rate]
A polyester pressure-sensitive adhesive tape (31B tape) was pressure-bonded to the surface of the resin layer by reciprocating a 5 kg rubber roller once, and allowed to stand for 20 hours in an environment of 70 ° C and 20 g / cm ² . Then, after cooling at room temperature for 1 hour, the 31B tape was carefully peeled off, the tape was again stuck to the copper plate and left still for 1 hour, and then the resistance value when peeled 180 degrees at a speed of 300 m / min was measured. This value is (f). The same procedure was applied to a tetrafluoroethylene resin ("Toyofuron" (registered trademark) manufactured by Toray Film Co., Ltd.) to measure the peel resistance value, and this value was used as a blank value (fo). The residual adhesion rate was calculated by applying this result to the following formula. If the calculated value is 90% or more, it can be said to be good.
Residual adhesion rate (%) = (f) / (fo) × 100.

[Fluorine atom / silicon atom ratio measurement]
It was measured under the following conditions by X-ray photoelectron spectroscopy (XPS).
Measuring device: PHI5000 VersaProbe manufactured by ULVAC-PHI, Inc.)
X-ray source: mono-Al
Output: 24.2W
X-ray beam diameter: 100 μm
Extraction angle: 45 °
Pass energy: 23.50 eV
For the composition ratio of each atom, the peak area was measured from a high-resolution spectrum, the relative sensitivity coefficient set by the method described in JIS 0167: 2011 was used, and the attached software was used for the analysis.

  Specifically, measurement by XPS is performed from the outermost surface of the laminated film under the above conditions, and at measurement points existing in the range of 5 nm to 15 nm from the outermost surface, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm from the outermost surface. , 11 nm, 12 nm, 13 nm, 14 nm, and 15 nm were selected, and the fluorine atom strength and the silicon atom strength at these 11 points were averaged to obtain the fluorine atom / silicon atom ratio. If there are two measurement points that are closest to a point located at a specific distance from the outermost surface, the average value of the two points is used.

1, 5, 10: Resin layer surfaces 2, 6, 11: Syringe needles 3, 7, 12: Droplets 4, 8, 13: Contact angle 9, 14: Relationship between contact angle and liquid suction amount

  The laminated film of the present invention makes use of the change in peeling force when heated, the residual adhesion ratio of the adhesive layer after peeling the resin layer, the light peeling property, and the improvement of the peeling speed dependency, and is used for optical applications such as liquid crystal polarizing plates and retardation plates. It can be preferably used for protecting the pressure-sensitive adhesive used during film production.

Claims (2)

There is a resin layer on at least one surface of the supporting substrate, the resin layer contains a polyorganosiloxane, the polyorganosiloxane contains a dimethylsiloxane segment, an alkylene-methylsiloxane segment and a fluoroalkyl-methylsiloxane segment, and A laminated film which satisfies the following condition 1 and condition 2.
Condition 1. The elastic modulus measured from the surface side of the resin layer by an atomic force microscope is 15 MPa or less Condition 2. The receding contact angle of hydroxypropyl acrylate on the resin layer surface is 30 ° or more The laminated film according to claim 1 , wherein a ratio of fluorine atoms / silicon atoms of the resin layer is 0.005 or more and less than 0.1.