JP2017065086A - Multilayer film - Google Patents

Abstract

A multi-layer film comprising a first resin layer and a second resin layer, wherein deformation of the first resin layer can be suppressed when the second resin layer is separated from the first resin layer. offer. A resin containing an alkoxysilyl group-modified product of a hydride obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds of the main chain and side chains of the block copolymer and the carbon-carbon unsaturated bonds of the aromatic ring. and a second resin layer provided on at least one side of the first resin layer, wherein the peel strength between the first resin layer and the second resin layer is 0.1 N / 25 mm or less There is a multi-layer film. [Selection drawing] Fig. 1

Description

  The present invention relates to a multilayer film.

  Conventionally, an alkoxysilyl group-modified product in which an alkoxysilyl group is introduced into a hydride obtained by hydrogenating a block copolymer of an aromatic vinyl compound and a chain conjugated diene compound is known (Patent Documents 1 and 2).

International Publication No. 2012/043708 Japanese Patent Laying-Open No. 2015-104859

  The alkoxysilyl group-modified product may be molded and used as a resin film. This resin film is usually wound into a roll and stored and transported. At this time, the resin film may be bonded to the protective film in order to prevent blocking and scratching. Here, blocking refers to a phenomenon in which films rolled up in a roll shape are closely attached. Thus, the film by which the resin film and the protective film were bonded is a film having a multilayer structure including these resin film and protective film.

  Usually, when using a resin film, the protective film is peeled off from the resin film. However, the conventional protective film is difficult to peel off from the resin film. For this reason, when the protective film is peeled from the resin film, the resin film stretches and deformation such as wrinkles easily occurs.

  The present invention has been made in view of the above problems, and is a predetermined alkoxysilyl group-modified product in which an alkoxysilyl group is introduced into a hydride of a block copolymer of an aromatic vinyl compound and a chain conjugated diene compound. When the second resin layer is peeled from the first resin layer, the first resin layer comprising a first resin layer comprising a resin and a second resin layer provided on at least one side of the first resin layer Another object of the present invention is to provide a multilayer film capable of suppressing the occurrence of deformation in the first resin layer.

As a result of intensive studies to solve the above problems, the present inventor has made a first resin layer comprising a resin containing an alkoxysilyl group-modified product of a hydride of a block copolymer of an aromatic vinyl compound and a chain conjugated diene compound. And by making the peel strength with the second resin layer provided on at least one side of the first resin layer within a predetermined small range, it is possible to suppress deformation such as wrinkles in the first resin layer at the time of peeling. Discovered and completed the present invention.
That is, the present invention is as follows.

[1] Alkoxysilyl group of hydride [2] in which 90% or more of carbon-carbon unsaturated bond of main chain and side chain of block copolymer [1] and carbon-carbon unsaturated bond of aromatic ring are hydrogenated A first resin layer made of a resin [I] containing a modified product [3], and a second resin layer provided on at least one side of the first resin layer,
The block copolymer [1] is composed mainly of an aromatic vinyl compound unit, and the block copolymer [1] includes two or more polymer blocks [A] per molecule and a chain conjugated diene compound unit. The block copolymer [1] having at least one polymer block [B] per molecule,
The weight fraction wA of the polymer block [A] in the entire block copolymer [1], and the weight fraction wB of the polymer block [B] in the entire block copolymer [1]. The ratio (wA / wB) to 20/80 to 60/40,
The multilayer film whose peeling strength of said 1st resin layer and said 2nd resin layer is 0.1 N / 25mm or less.
[2] The multilayer film according to [1], wherein the resin [I] contains 1 to 30 parts by weight of a plasticizer with respect to 100 parts by weight of the modified alkoxysilyl group [3].
[3] The multilayer film according to [1] or [2], wherein the second resin layer includes a layer made of an olefin resin or a polyester resin.

  According to the present invention, a first resin layer made of a resin containing a predetermined alkoxysilyl group-modified product in which an alkoxysilyl group is introduced into a hydride of a block copolymer of an aromatic vinyl compound and a chain conjugated diene compound; A multilayer film comprising a second resin layer provided on at least one side of the first resin layer, and when the second resin layer is peeled off from the first resin layer, deformation occurs in the first resin layer Can be provided.

FIG. 1 is a cross-sectional view schematically showing a multilayer film according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and exemplifications, and can be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the equivalents thereof.
In the following description, the “polarizing plate” includes not only a rigid member but also a flexible member such as a resin film, unless otherwise specified.

[1. Overview of multilayer film]
FIG. 1 is a cross-sectional view schematically showing a multilayer film 100 according to an embodiment of the present invention.
As shown in FIG. 1, the multilayer film 100 according to an embodiment of the present invention includes a first resin layer 110 and a second resin layer 120 provided on at least one surface 110U of the first resin layer 110.

  The first resin layer 110 is made of a resin [I] containing an alkoxysilyl group-modified product [3] of a hydride [2] obtained by hydrogenating an unsaturated bond of a predetermined block copolymer [1]. Since the resin [I] is flexible, the first resin layer 110 tends to be easily deformed such as wrinkles. However, in the multilayer film 110, the peel strength between the first resin layer 110 and the second resin layer 120 is a small value equal to or less than a predetermined value. Therefore, even if the second resin layer 120 is peeled off from the first resin layer 110, the first resin layer 110 is unlikely to be stretched, so that the occurrence of deformation such as wrinkles can be suppressed.

[2. First resin layer]
The first resin layer is a layer made of a resin [I] containing an alkoxysilyl group-modified product [3] of a hydride [2] obtained by hydrogenating an unsaturated bond of a predetermined block copolymer [1].

[2.1. Block copolymer [1]]
The block copolymer [I] comprises two or more polymer blocks [A] per molecule of the block copolymer [1] and one or more polymer blocks [B] per molecule of the block copolymer [1]. ] Is a block copolymer.

  The polymer block [A] is a polymer block having an aromatic vinyl compound unit as a main component. Here, the aromatic vinyl compound unit refers to a structural unit having a structure formed by polymerizing an aromatic vinyl compound.

  Examples of the aromatic vinyl compound corresponding to the aromatic vinyl compound unit contained in the polymer block [A] include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4 -Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; 4-chloro Styrenes having a halogen atom as a substituent, such as styrene, dichlorostyrene, 4-monofluorostyrene; Styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; 4-phenylstyrene Styrenes having an aryl group as a substituent, such as 1-vinylnaphthalene, 2-vinylnaphthal Vinyl naphthalenes such emissions; and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio. Among these, from the viewpoint of hygroscopicity, aromatic vinyl compounds that do not contain a polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable, and are easy to obtain industrially. Styrene is particularly preferred.

  The content of the aromatic vinyl compound unit in the polymer block [A] is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 99% by weight or more. The heat resistance of the first resin layer can be increased by increasing the amount of the aromatic vinyl compound unit in the polymer block [A] as described above.

  The polymer block [A] may contain an arbitrary structural unit in addition to the aromatic vinyl compound unit. The polymer block [A] may contain any structural unit alone or in combination of two or more at any ratio.

  As an arbitrary structural unit that the polymer block [A] may contain, for example, a chain conjugated diene compound unit may be mentioned. Here, the chain conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a chain conjugated diene compound. Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit include, for example, the same examples as those exemplified as the chain conjugated diene compound corresponding to the chain conjugated diene compound unit included in the polymer block [B]. Is mentioned.

  Moreover, as an arbitrary structural unit which the polymer block [A] can contain, for example, a structural unit having a structure formed by polymerizing an arbitrary unsaturated compound other than an aromatic vinyl compound and a chain conjugated diene compound is used. Can be mentioned. Examples of the optional unsaturated compound include vinyl compounds such as chain vinyl compounds and cyclic vinyl compounds; unsaturated cyclic acid anhydrides; unsaturated imide compounds; These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group. Among these, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, It does not have a polar group such as a chain olefin having 2 to 20 carbon atoms such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; a cyclic olefin having 5 to 20 carbon atoms such as vinylcyclohexane; Vinyl compounds are preferred, chain olefins having 2 to 20 carbon atoms are more preferred, and ethylene and propylene are particularly preferred.

  The content of any structural unit in the polymer block [A] is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less.

  The number of polymer blocks [A] in one molecule of block copolymer [1] is preferably 2 or more, preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less. The plurality of polymer blocks [A] in one molecule may be the same as or different from each other.

  When a plurality of different polymer blocks [A] are present in one molecule of the block copolymer [1], the weight average molecular weight of the polymer block having the maximum weight average molecular weight in the polymer block [A] is expressed as Mw. (A1), and the weight average molecular weight of the polymer block having the smallest weight average molecular weight is Mw (A2). At this time, the ratio “Mw (A1) / Mw (A2)” between Mw (A1) and Mw (A2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. It is. Thereby, the dispersion | variation in various physical-property values can be suppressed small.

  The polymer block [B] is a polymer block mainly composed of a chain conjugated diene compound unit. As described above, the chain conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a chain conjugated diene compound.

  Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit of the polymer block [B] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1, 3-pentadiene etc. are mentioned. One of these may be used alone, or two or more of these may be used in combination at any ratio. Among these, in terms of hygroscopicity, a chain conjugated diene compound not containing a polar group is preferable, and 1,3-butadiene and isoprene are particularly preferable.

  The content of the chain conjugated diene compound unit in the polymer block [B] is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. By increasing the amount of the chain conjugated diene compound unit in the polymer block [B] as described above, the flexibility of the first resin layer can be improved.

  The polymer block [B] may contain an arbitrary structural unit in addition to the chain conjugated diene compound unit. The polymer block [B] may contain any structural unit alone or in combination of two or more at any ratio.

  As an arbitrary structural unit that can be contained in the polymer block [B], for example, it is formed by polymerizing an aromatic vinyl compound unit and any unsaturated compound other than the aromatic vinyl compound and the chain conjugated diene compound. Examples include structural units having a structure. Examples of the structural unit having a structure formed by polymerizing these aromatic vinyl compound units and any unsaturated compound include those exemplified as those which may be contained in the polymer block [A]. The same example is given.

  The content of any structural unit in the polymer block [B] is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less. The flexibility of the first resin layer can be improved by reducing the content of any structural unit in the polymer block [B].

  Block copolymer [1] The number of polymer blocks [B] in one molecule is usually 1 or more, but may be 2 or more. When the number of polymer blocks [B] in the block copolymer [1] is 2 or more, the polymer blocks [B] may be the same as or different from each other.

  When a plurality of different polymer blocks [B] are present in one molecule of the block copolymer [1], the weight average molecular weight of the polymer block having the maximum weight average molecular weight in the polymer block [B] is expressed as Mw. (B1), and the weight average molecular weight of the polymer block having the smallest weight average molecular weight is Mw (B2). At this time, the ratio “Mw (B1) / Mw (B2)” between Mw (B1) and Mw (B2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. It is. Thereby, the dispersion | variation in various physical-property values can be suppressed small.

  The form of the block of the block copolymer [1] may be a chain type block or a radial type block. Among these, a chain type block is preferable because of its excellent mechanical strength. When the block copolymer [1] has a chain-type block form, it is desired that both ends of the molecular chain of the block copolymer [1] are polymer blocks [A], so that the resin [I] is not sticky. Is preferable because it can be suppressed to a low value.

  A particularly preferable block form of the block copolymer [1] is that the polymer block [A] is bonded to both ends of the polymer block [B] as represented by [A]-[B]-[A]. A triblock copolymer; [A]-[B]-[A]-[B]-[A], the polymer block [B] is bonded to both ends of the polymer block [A]. And a pentablock copolymer in which the polymer block [A] is bonded to the other end of each of the polymer blocks [B]. In particular, a triblock copolymer of [A]-[B]-[A] is particularly preferable because it can be easily produced and the physical properties can be easily within a desired range.

  In the block copolymer [1], the weight fraction wA of the polymer block [A] in the entire block copolymer [1] and the polymer block [B] in the entire block copolymer [1]. The ratio (wA / wB) to the weight fraction wB falls within a predetermined range. Specifically, the ratio (wA / wB) is usually 20/80 or more, preferably 25/75 or more, more preferably 30/70 or more, particularly preferably 40/60 or more, and usually 60/40. Hereinafter, it is preferably 55/45 or less. By setting the ratio wA / wB to be equal to or higher than the lower limit of the above range, the heat resistance of the first resin layer can be improved or the birefringence can be reduced. Moreover, the softness | flexibility of a 1st resin layer can be improved by making it into an upper limit or less. Here, the weight fraction wA of the polymer block [A] indicates the weight fraction of the whole polymer block [A], and the weight fraction wB of the polymer block [B] is the whole polymer block [B]. The weight fraction is shown.

The weight average molecular weight (Mw) of the block copolymer [1] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, preferably 200,000 or less. More preferably, it is 150,000 or less, Most preferably, it is 100,000 or less.
The molecular weight distribution (Mw / Mn) of the block copolymer [1] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more. Here, Mn represents a number average molecular weight.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the block copolymer [1] were determined as polystyrene-converted values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. It can be measured.

  As a method for producing the block copolymer [1], for example, a monomer mixture (a) containing an aromatic vinyl compound as a main component and a chain conjugated diene compound as a main component are contained by a method such as living anion polymerization. Method of alternately polymerizing the monomer mixture (b); after sequentially polymerizing the monomer mixture (a) containing an aromatic vinyl compound as a main component and the monomer mixture (b) containing a chain conjugated diene compound as a main component And a method of coupling ends of the polymer block [B] with a coupling agent.

  The content of the aromatic vinyl compound in the monomer mixture (a) is usually 90% by weight or more, preferably 95% by weight or more, more preferably 99% by weight or more. The monomer mixture (a) may contain any monomer component other than the aromatic vinyl compound. Examples of the optional monomer component include a chain conjugated diene compound and an arbitrary unsaturated compound. The amount of the optional monomer component is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the monomer mixture (a).

  The content of the chain conjugated diene compound in the monomer mixture (b) is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more. The monomer mixture (b) may contain any monomer component other than the chain conjugated diene compound. Optional monomer components include aromatic vinyl compounds and arbitrary unsaturated compounds. The amount of the optional monomer component is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, based on the monomer mixture (b).

  As a method for polymerizing the monomer composition to obtain each polymer block, for example, radical polymerization, anion polymerization, cation polymerization, coordination anion polymerization, coordination cation polymerization and the like can be used. From the viewpoint of facilitating the polymerization operation and the hydrogenation reaction in the subsequent step, a method in which radical polymerization, anion polymerization, cation polymerization and the like are performed by living polymerization is preferable, and a method in which living polymerization is performed by living anion polymerization is particularly preferable.

  The polymerization can be carried out in the presence of a polymerization initiator. For example, in living anionic polymerization, as a polymerization initiator, monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium; dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio A polyfunctional organolithium compound such as 2-ethylcyclohexane; One of these may be used alone, or two or more of these may be used in combination at any ratio.

  The polymerization temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower, particularly preferably 70 ° C. or lower.

As the form of the polymerization reaction, for example, solution polymerization and slurry polymerization can be used. In particular, when solution polymerization is used, reaction heat can be easily removed.
When solution polymerization is performed, an inert solvent in which the polymer obtained in each step can be dissolved can be used as the solvent. Examples of the inert solvent include aliphatic hydrocarbon solvents such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, decalin, bicyclo And alicyclic hydrocarbon solvents such as [4.3.0] nonane and tricyclo [4.3.0.1 ^2,5 ] decane; aromatic hydrocarbon solvents such as benzene and toluene; One of these may be used alone, or two or more of these may be used in combination at any ratio. Among these, it is preferable to use an alicyclic hydrocarbon solvent as the solvent because it can be used as it is as an inert solvent for the hydrogenation reaction and the solubility of the block copolymer [1] is good. The amount of the solvent used is preferably 200 to 2000 parts by weight with respect to 100 parts by weight of all the monomers used.

  When each monomer composition contains two or more monomers, a randomizer can be used to prevent a single component chain from becoming long. In particular, when the polymerization reaction is performed by anionic polymerization, it is preferable to use, for example, a Lewis base compound as a randomizer. Examples of Lewis base compounds include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, and ethylene glycol methyl phenyl ether; and tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, Tertiary amine compounds; alkali metal alkoxide compounds such as potassium-t-amyl oxide and potassium-t-butyl oxide; phosphine compounds such as triphenylphosphine; One of these may be used alone, or two or more of these may be used in combination at any ratio.

[2.2. Hydride [2]]
The hydride [2] is a polymer obtained by hydrogenating a predetermined amount or more of the unsaturated bond of the block copolymer [1]. Here, the unsaturated bond of the block copolymer [1] to be hydrogenated includes aromatic and non-aromatic carbon-carbon unsaturation of the main chain and side chain of the block copolymer [1]. Includes any bond.

The hydrogenation rate is usually 90% or more, preferably 97% or more, and more preferably 97% or more of the carbon-carbon unsaturated bond of the main chain and side chain of the block copolymer [1] and the carbon-carbon unsaturated bond of the aromatic ring. Is 99% or more. The higher the hydrogenation rate, the better the transparency, heat resistance and weather resistance of the first resin layer, and the easier it is to reduce the birefringence of the first resin layer. Here, the hydrogenation rate of the hydride [2] can be obtained by measurement by ¹ H-NMR.

  In particular, the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is preferably 95% or more, more preferably 99% or more. By increasing the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond, the light resistance and oxidation resistance of the first resin layer can be further increased.

  The hydrogenation rate of the aromatic carbon-carbon unsaturated bond is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. Since the glass transition temperature of the polymer block obtained by hydrogenating the polymer block [A] is increased by increasing the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring, the heat resistance of the first resin layer is increased. Can be effectively increased. Furthermore, the photoelastic coefficient of the first resin layer can be lowered.

The weight average molecular weight (Mw) of the hydride [2] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, preferably 200,000 or less, more preferably 150. 1,000 or less, particularly preferably 100,000 or less. By keeping the weight average molecular weight (Mw) of the hydride [2] within the above range, the mechanical strength and heat resistance of the first resin layer can be improved, and the birefringence of the first resin layer can be reduced. easy.
The molecular weight distribution (Mw / Mn) of the hydride [2] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more. By keeping the molecular weight distribution (Mw / Mn) of the hydride [2] within the above range, the mechanical strength and heat resistance of the first resin layer can be improved, and the birefringence of the first resin layer can be reduced. Easy to do.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the hydride [2] can be measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

  The hydride [2] described above can be produced by hydrogenating the block copolymer [1]. As the hydrogenation method, a hydrogenation method that can increase the hydrogenation rate and causes little chain-breaking reaction of the block copolymer [1] is preferable. Examples of such a hydrogenation method include the methods described in International Publication No. 2011/096389 and International Publication No. 2012/043708.

  Examples of specific hydrogenation methods include, for example, hydrogenation using a hydrogenation catalyst containing at least one metal selected from the group consisting of nickel, cobalt, iron, rhodium, palladium, platinum, ruthenium, and rhenium. The method of performing is mentioned. A hydrogenation catalyst may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used. The hydrogenation reaction is preferably performed in an organic solvent.

The heterogeneous catalyst may be used as it is, for example, as a metal or a metal compound, or may be used by being supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride, and the like. The supported amount of the catalyst is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less based on the total amount of the catalyst and the carrier. is there. The specific surface area of the supported catalyst is preferably 100m ² / g~500m ² / g. Further, the average pore diameter of the supported catalyst is preferably 100 mm or more, more preferably 200 mm or more, preferably 1000 mm or less, more preferably 500 mm or less. Here, the specific surface area can be obtained by measuring the nitrogen adsorption amount and using the BET equation. The average pore diameter can be measured by a mercury intrusion method.

  Examples of homogeneous catalysts include catalysts in which nickel, cobalt, or iron compounds and organometallic compounds (eg, organoaluminum compounds, organolithium compounds) are combined; organometallics including rhodium, palladium, platinum, ruthenium, rhenium, etc. Complex catalysts; and the like can be used.

Examples of the nickel, cobalt, or iron compound include acetylacetonate compounds, carboxylates, cyclopentadienyl compounds, and the like of various metals.
Examples of the organoaluminum compound include alkylaluminums such as triethylaluminum and triisobutylaluminum; aluminum halides such as diethylaluminum chloride and ethylaluminum dichloride; alkylaluminum hydrides such as diisobutylaluminum hydride; and the like.

  Examples of organometallic complex catalysts include transition metal complexes such as dihydrido-tetrakis (triphenylphosphine) ruthenium, dihydrido-tetrakis (triphenylphosphine) iron, bis (cyclooctadiene) nickel, and bis (cyclopentadienyl) nickel. Is mentioned.

  The amount of the hydrogenation catalyst used is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, particularly preferably 0.1 parts by weight or more with respect to 100 parts by weight of the block copolymer [1]. Preferably, it is 100 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less.

  The temperature of the hydrogenation reaction is preferably 10 ° C or higher, more preferably 50 ° C or higher, particularly preferably 80 ° C or higher, preferably 250 ° C or lower, more preferably 200 ° C or lower, particularly preferably 180 ° C or lower. . By performing the hydrogenation reaction in such a temperature range, the hydrogenation rate can be increased, and the molecular cleavage of the block copolymer [1] can be reduced.

  The hydrogen pressure during the hydrogenation reaction is preferably 0.1 MPa or more, more preferably 1 MPa or more, particularly preferably 2 MPa or more, preferably 30 MPa or less, more preferably 20 MPa or less, and particularly preferably 10 MPa or less. By performing the hydrogenation reaction at such a hydrogen pressure, the hydrogenation rate can be increased, the molecular chain scission of the block copolymer [1] can be reduced, and the operability is improved.

  The hydride [2] obtained by the above-described method is usually obtained as a reaction liquid containing a hydride [2], a hydrogenation catalyst, and a polymerization catalyst. Therefore, the hydride [2] may be recovered from the reaction solution after removing the hydrogenation catalyst and the polymerization catalyst from the reaction solution by a method such as filtration and centrifugation. As a method for recovering the hydride [2] from the reaction solution, for example, a steam coagulation method in which the solvent is removed from the reaction solution containing the hydride [2] by steam stripping; direct solvent removal to remove the solvent under reduced pressure heating And a solidification method in which the reaction solution is poured into a poor solvent of hydride [2] to precipitate or solidify.

  The recovered hydride [2] is preferably in the form of a pellet so that it can be easily subjected to a subsequent silylation modification reaction (reaction for introducing an alkoxysilyl group). For example, the molten hydride [2] may be extruded from a die into strands, cooled, and then cut into pellets by a pelletizer, and used for various moldings. In the case of using a solidification method, for example, the obtained solidified product may be dried and then extruded in a molten state by an extruder and may be formed into pellets in the same manner as described above and used for various moldings.

[2.3. Modified alkoxysilyl group [3]]
The alkoxysilyl group-modified product [3] is a polymer obtained by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above. In this case, the alkoxysilyl group may be directly bonded to the hydride [2] described above, and may be indirectly bonded, for example, via a divalent organic group such as an alkylene group. The alkoxysilyl group-modified product [3] is particularly excellent in adhesion to inorganic materials such as glass and metal. Therefore, the first resin layer is usually excellent in adhesiveness with the inorganic material. Therefore, the first resin layer can maintain a high adhesive force to the inorganic material even after being exposed to a high temperature and high humidity environment for a long time.

The introduction amount of the alkoxysilyl group in the modified alkoxysilyl group [3] is preferably 0.1 parts by weight or more, more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the hydride [2] before introduction of the alkoxysilyl group. 2 parts by weight or more, particularly preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less. When the amount of alkoxysilyl groups introduced is within the above range, the degree of cross-linking between the alkoxysilyl groups decomposed by moisture or the like can be prevented from being excessively high, so the adhesiveness of the first resin layer to the inorganic material is kept high. can do.
The amount of alkoxysilyl group introduced can be measured by ¹ H-NMR spectrum. In addition, when the introduction amount of the alkoxysilyl group is measured, if the introduction amount is small, the number of integrations can be increased.

Since the weight average molecular weight (Mw) of the alkoxysilyl group-modified product [3] is small in the amount of alkoxysilyl groups introduced, usually the weight average molecular weight (2) of the hydride [2] before introducing the alkoxysilyl group ( Mw) does not change significantly. However, when the alkoxysilyl group is introduced, the hydride [2] is modified in the presence of a peroxide, so that the hydride [2] undergoes a crosslinking reaction and a cleavage reaction, and the molecular weight distribution changes greatly. Tend to. The weight average molecular weight (Mw) of the alkoxysilyl group-modified product [3] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, and preferably 200,000 or less. Preferably it is 150,000 or less, Most preferably, it is 100,000 or less. The molecular weight distribution (Mw / Mn) of the modified alkoxysilyl group [3] is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less, preferably 1.0. That's it. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the alkoxysilyl group-modified product [3] are within this range, good mechanical strength and tensile elongation of the first resin layer can be maintained.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the alkoxysilyl group-modified product [3] can be measured as values in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. .

  The alkoxysilyl group-modified product [3] can be produced by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above. Examples of the method for introducing an alkoxysilyl group into the hydride [2] include a method in which the hydride [2] and an ethylenically unsaturated silane compound are reacted in the presence of a peroxide.

  As the ethylenically unsaturated silane compound, those capable of graft polymerization with hydride [2] and capable of introducing an alkoxysilyl group into hydride [2] can be used. Examples of such ethylenically unsaturated silane compounds include: vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane and other alkoxy silanes; allyltrimethoxysilane, allyltriethoxysilane Alkoxysilanes having an allyl group such as p-styryltrimethoxysilane, p-styryltriethoxysilane and the like alkoxysilanes having a p-styryl group; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane Alkoxysilanes having a 3-methacryloxypropyl group such as 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; 3-acryloxypropyl Alkoxysilanes having a 3-acryloxypropyl group such as limethoxysilane and 3-acryloxypropyltriethoxysilane; alkoxysilanes having a 2-norbornen-5-yl group such as 2-norbornene-5-yltrimethoxysilane; Etc. Among these, since the effects of the present invention are more easily obtained, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxy Silane is preferred. Moreover, an ethylenically unsaturated silane compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The amount of the ethylenically unsaturated silane compound is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, particularly 100 parts by weight of the hydride [2] before introducing the alkoxysilyl group. The amount is preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less.

  As the peroxide, one that functions as a radical reaction initiator can be used. As such a peroxide, an organic peroxide is usually used. Examples of the organic peroxide include dibenzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, t-butylcumyl peroxide, Dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxyhexane), di-t-butyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane-3, t-butylhydroperoxide, t-butylperoxyisobutyrate, lauroyl peroxide, dipropionyl peroxide, p-menthane hydroperoxide and the like. Among these, those having a 1-minute half-life temperature of 170 ° C. to 190 ° C. are preferable, and specifically, t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl. -2,5-di (t-butylperoxyhexane), di-t-butylperoxide and the like are preferable. Moreover, a peroxide may be used individually by 1 type and may be used in combination of 2 or more type.

  The amount of the peroxide is preferably 0.01 parts by weight or more, more preferably 0.2 parts by weight or more, particularly preferably 0 parts by weight based on 100 parts by weight of the hydride [2] before introducing the alkoxysilyl group. .3 parts by weight or more, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.

  The method of reacting the hydride [2] of the block copolymer [1] with the ethylenically unsaturated silane compound in the presence of a peroxide can be performed using, for example, a heating kneader and a reactor. As a specific example, a mixture of a hydride [2], an ethylenically unsaturated silane compound and a peroxide is heated and melted at a temperature equal to or higher than the melting temperature of the hydride [2] in a biaxial kneader to obtain a desired value. By kneading for this time, the alkoxysilyl group-modified product [3] can be obtained. The specific temperature during kneading is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, particularly preferably 200 ° C. or higher, preferably 240 ° C. or lower, more preferably 230 ° C. or lower, particularly preferably 220 ° C. or lower. It is. The kneading time is preferably 0.1 minutes or more, more preferably 0.2 minutes or more, particularly preferably 0.3 minutes or more, preferably 15 minutes or less, more preferably 10 minutes or less, particularly preferably. 5 minutes or less. When using a continuous kneading facility such as a twin-screw kneader or a single-screw extruder, kneading and extrusion can be performed continuously with the residence time being in the above range.

  The amount of the alkoxysilyl group-modified product [3] in the resin [I] is preferably 95% by weight or more, more preferably 97% by weight or more, still more preferably 98% by weight or more, and particularly preferably 99% by weight or more. By keeping the amount of the alkoxysilyl group-modified product [3] in the resin [I] within the above range, the desired effect of the present invention can be stably exhibited.

[2.4. (Optional ingredients)
Resin [I] contained in the first resin layer may contain an arbitrary component in combination with the alkoxysilyl group-modified product [3] of the hydride [2] of the block copolymer [1] described above. Arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Optional components include plasticizers. Since the glass transition temperature and elastic modulus of the resin [I] can be adjusted by using the plasticizer, the heat resistance and mechanical strength of the resin [I] can be adjusted. The plasticizer is preferably one that can be easily mixed with the alkoxysilyl group-modified product [3] and does not impair the transparency of the first resin layer by mixing with the plasticizer. Examples of such plasticizers include polyisobutene, hydrogenated polyisobutene, hydrogenated polyisoprene, hydrogenated 1,3-pentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, hydrogenated styrene / indene petroleum resin, and the like. Can be mentioned. Moreover, a plasticizer may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  The amount of the plasticizer is preferably 1 part by weight or more, more preferably 3 parts by weight or more, particularly preferably 5 parts by weight or more, preferably 30 parts by weight with respect to 100 parts by weight of the alkoxysilyl group-modified product [3]. Parts or less, more preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less. By keeping the amount of the plasticizer within the above range, the glass transition temperature and elastic modulus of the resin [I] can be easily adjusted to an appropriate range.

  Moreover, antioxidant is mentioned as an arbitrary component. By using the antioxidant, when the first resin layer is produced by melt-extruding the resin [I], it is possible to suppress the oxidative degradation product of the resin [I] from adhering to the lip portion of the die. Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Moreover, antioxidant may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Among the antioxidants, phenolic antioxidants, particularly alkyl-substituted phenolic antioxidants are preferable. Specific examples of the alkyl-substituted phenolic antioxidant include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4- Methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6- Dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t- Hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, stearyl β- (3,5-di-t-butyl-4-hydride Monocyclic phenolic antioxidants such as xylphenyl) propionate; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-t -Butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis [3- (3-t-butyl-4-hydroxy-5-methylpheny ) Propionate], triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) Isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t Butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc. And tricyclic phenolic antioxidants; tetracyclic [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] tetracyclic phenolic antioxidants such as methane; and the like.

  The amount of the antioxidant is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, particularly preferably 0.05 parts by weight or more with respect to 100 parts by weight of the alkoxysilyl group-modified product [3]. It is preferably 1.0 part by weight or less, more preferably 0.5 part by weight or less, and particularly preferably 0.3 part by weight or less.

  Furthermore, optional components include: heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers, near infrared absorbers and other stabilizers; resin modifiers such as lubricants; colorants such as dyes and pigments; An inhibitor etc. are mentioned. These amounts can be appropriately selected within a range not impairing the object of the present invention.

  As a method of mixing the alkoxysilyl group-modified product [3] and an optional component, for example, (i) hydride [2] of the block copolymer [1] can be prepared by dissolving the optional component in an appropriate solvent. After mixing with the solution, the solvent is removed to recover the hydride [2] and a composition containing optional components, and this composition is reacted with the ethylenically unsaturated silane compound in the presence of a peroxide. A method; (ii) a method of kneading an arbitrary component in a molten state with the alkoxysilyl group-modified product [3] in a kneading apparatus such as a twin-screw kneader, a roll, a Brabender, or an extruder; (iii) a hydride [2] A method of kneading an ethylenically unsaturated silane compound with an optional component when they are reacted in the presence of a peroxide; (iv) Uniformly adding an optional component to the hydride [2] Dispersed into pellets and alkoxysilyl group changes And a method of mixing the material [3] in a pellet form, and melt-kneading and uniformly dispersing.

[2.5. Physical properties of resin [I]]
The resin [I] is preferably transparent. The first resin layer made of such a transparent resin [I] can be suitably used for optical applications. Here, the transparent resin refers to a resin having a total light transmittance of 70% or more, preferably 80% or more, more preferably 90% or more, measured using the resin as a test piece having a thickness of 1 mm. The total light transmittance can be measured in a wavelength range of 400 nm to 700 nm using an ultraviolet / visible spectrometer.

  The glass transition temperature of the resin [I] is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, particularly preferably 70 ° C. or higher, preferably 200 ° C. or lower, more preferably 180 ° C. or lower, particularly preferably 160 ° C. It is as follows. When the resin has a plurality of glass transition temperatures, the highest glass transition temperature of the resin is preferably within the above range. By keeping the glass transition temperature of the resin [I] within the above range, the balance between the adhesiveness and heat resistance of the first resin layer can be improved. The glass transition temperature of the resin [I] can be obtained as the peak top value of tan δ in the viscoelastic spectrum.

[2.6. Physical properties of first resin layer)
Since the first resin layer is a layer made of the above-mentioned resin [I], it is usually exposed to a low moisture absorption, non-hydrolyzability, weather resistance, transparency, flexibility, and high temperature and high humidity environment for a long time. It has excellent properties such as excellent adhesion to glass after heating.

  The first resin layer is preferably flexible. When the first resin layer is flexible, the first resin layer can be used for a wide range of applications, such as a polarizing plate protective film and a sealing film for a light emitting device. The specific tensile elastic modulus of the first resin layer is preferably 1500 MPa or less, more preferably 1000 MPa or less, and particularly preferably 800 MPa or less. This tensile elastic modulus is a value measured at 23 ° C. Although there is no restriction | limiting in particular in the minimum of the said tensile elasticity modulus, Preferably it is 0.1 Mpa or more.

  The storage elastic modulus at 90 ° C. of the first resin layer is preferably 10 MPa or more, more preferably 20 MPa or more, and particularly preferably 50 MPa or more. Since the storage elastic modulus at 90 ° C. of the first resin layer is large as described above, the durability of the first resin layer can be increased, and the performance degradation particularly in a high temperature environment can be effectively suppressed. The upper limit of the storage elastic modulus at 90 ° C. of the first resin layer is not particularly limited, but is preferably 1000 MPa or less.

  The transparency of the first resin layer is not particularly limited. However, it is preferable that the transparency of the first resin layer is high from the viewpoint that the first resin layer is useful in a portion that is required to transmit light. In this case, the total light transmittance of the first resin layer is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

  The haze of the first resin layer is not particularly limited. However, when the first resin layer is used for an optical application that does not specifically intend to diffuse light, the haze is generally preferably low. In this case, the haze of the first resin layer is preferably 3.0% or less, more preferably 1.0% or less. Haze can be measured using a film piece obtained by cutting the first resin layer into 50 mm × 50 mm in accordance with JIS K7136.

  The first resin layer preferably has sufficiently high adhesiveness with the inorganic material. For example, when the first resin layer is directly bonded to the glass plate, the peel strength required to peel the first resin layer from the glass plate is preferably 5 N / cm or more, more preferably 10 N / cm or more. is there. Although there is no restriction | limiting in particular in the upper limit of the said peeling strength, Preferably it is 200 N / cm or less.

[2.7. (Dimension and surface smoothness of first resin layer)
The thickness of the first resin layer is preferably 5 μm or more, more preferably 10 μm or more, preferably 100 μm or less, more preferably 50 μm or less.

  Moreover, the thickness variation of the first resin layer is preferably within 3%, more preferably within 2.5%. Here, the thickness variation of the first resin layer is calculated from [(| “maximum or minimum thickness of the first resin layer” − “average thickness of the first resin layer” |) / “average thickness of the film”] × 100. Is the value to be By setting the thickness variation of the first resin layer within the above range, when the first resin layer is incorporated into an organic electroluminescence element or a liquid crystal display element, uneven bonding due to air biting can be reduced.

  Usually, the first resin layer is excellent in surface smoothness. Specifically, the surface roughness of both surfaces of the first resin layer is expressed by an average roughness Ra, preferably 0.2 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. Here, the average roughness Ra is the same as the “arithmetic average height Ra” defined by JIS B 0601: 2001. For example, a color 3D laser microscope (product name “VK-9500”, manufactured by Keyence Corporation) ) And the like. When the average roughness Ra is in this range, microscopic unevenness is not observed on the surface of the first resin layer, which is preferable as an optical film. On the other hand, when the first resin layers are in contact with each other, Inferior in nature and easily scratched on the surface.

[2.7. Method for producing first resin layer]
The first resin layer can be produced by molding the resin [I] into a layer shape by an arbitrary molding method. As the molding method, for example, a melt molding method, a solution casting method, or the like can be used. More specifically, the melt molding method can be classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these methods, in order to obtain a first resin layer having excellent mechanical strength and surface accuracy, an extrusion molding method, an inflation molding method, and a press molding method are preferable. Among them, a viewpoint that the first resin layer can be produced efficiently and easily. Therefore, the extrusion molding method is particularly preferable.

  In the extrusion molding method, the pellet of the resin [I] is usually melted by an extruder and extruded from a die attached to the extruder into a sheet shape, and the extruded sheet-shaped resin [I] is at least one It can be manufactured by being brought into close contact with the cooling drum, molded and taken up. In this case, for example, the surface roughness Ra having an average value of the surface roughness Ra of the die slip of 0.05 μm or less and a range of the distribution of the surface roughness Ra in the entire width of the die slip is ± 0.025 μm or less of the average value. By using a small die, the first resin layer having excellent surface smoothness as described above can be obtained.

  The melting temperature of the resin [I] in the extruder is preferably Tg + 50 ° C. or higher, more preferably Tg + 70 ° C. or higher, preferably Tg + 160 ° C. or lower, more preferably Tg + 140 ° C. or lower. Here, Tg represents the glass transition temperature of the resin [I]. When the melting temperature in the extruder is equal to or higher than the lower limit value of the range, the fluidity of the resin [I] can be sufficiently increased, and when the melting temperature is equal to or lower than the upper limit value of the range, the resin [I] is decomposed. It is possible to suppress a decrease in molecular weight due to.

  The resin [I] extruded from the opening of the die is cooled by being in close contact with the cast roll, and a film-like first resin layer is obtained. Normally, the degree of adhesion of the extruded film-like resin [I] to the cast roll varies depending on the temperature of the cast roll. Specifically, when the temperature of the cast roll is raised, the adhesion is improved. However, when the temperature is raised too much, the film-like resin [I] is hardly peeled off from the cast roll and may be wound around the roll. Therefore, the temperature of the cast roll is preferably (Tg-80 ° C) or higher, more preferably (Tg-60 ° C) or higher, and preferably (Tg + 10 ° C) or lower, more preferably (Tg-5 ° C) or lower, Particularly preferably (Tg-10 ° C.) or less. By doing so, it is possible to suppress problems such as slipping and scratching.

[3. Second resin layer]
The second resin layer is a layer provided on at least one side of the first resin layer. In the multilayer film, since the second resin layer protects the first resin layer, it is possible to suppress scratching of the first resin layer, or it is possible to suppress blocking when the multilayer film is rolled up. . You may provide a 2nd resin layer on both surfaces of a 1st resin layer as needed.

  The second resin layer has a predetermined range of peel strength with respect to the first resin layer. The specific peel strength between the first resin layer and the second resin layer is usually 0.1 N / 25 mm or less, preferably 0.08 N / 25 mm or less, more preferably 0.06 N / 25 mm or less. By keeping the peel strength within such a range, the occurrence of deformation in the first resin layer can be suppressed when the second resin layer is peeled from the first resin layer. Moreover, normally, it is possible to make it difficult to leave a peeling mark on the surface of the first resin layer. The lower limit of the peel strength is preferably 0.005 N / 25 mm or more, more preferably 0.01 N / 25 mm or more, and particularly preferably 0.015 N / 25 mm or more. The peel strength can be measured at a temperature of 23 ° C. according to JIS Z 0237.

  As the second resin layer, a resin layer including a base material layer made of resin can be used. Preferable examples of the resin included in the base material layer include olefin resins and polyester resins. Since these resins are excellent in mechanical strength, when the second resin layer includes a base material layer made of these resins, they can be easily transported to the first resin layer without deformation.

  Examples of the olefin resin include a chain olefin resin containing a chain olefin polymer such as polyethylene, polypropylene, ethylene / α-olefin copolymer; and a cyclic olefin polymer such as norbornene polymer and hydrogenated product thereof. Cyclic olefin resin containing. Polyester resins include polyethylene terephthalate and polybutylene terephthalate. These resins may be used alone or in combination of two or more.

  In addition, the second resin layer may be a single-layered layer composed only of the base material layer, or may be a multilayered layer provided with an arbitrary layer in combination with the base material layer. For example, the second resin layer may include a base material layer and a release layer provided on the base material layer. The second resin layer including the release layer can easily have the peel strength with respect to the first resin layer within the above-described range.

  The release layer is a layer containing a material having releasability. As the material having such a release property, a material obtained by curing a release agent containing a curable silicone resin is preferable. Here, the release agent may be a type mainly composed of a curable silicone resin, or a modified silicone type that can be modified by a polymerization reaction such as graft polymerization with an organic resin such as a urethane resin, an epoxy resin, or an alkyd resin. .

  As the curable silicone resin, any curing reaction type such as an addition type, a condensation type, an ultraviolet curable type, an electron beam curable type, and a solventless type may be used. Specific examples of the curable silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847, KS-847T, KS-856, X-62-2422, manufactured by Shin-Etsu Chemical Co., Ltd. X-62-2461; DKQ3-202, DKQ3-203, DKQ3-204, DKQ3-205, DKQ3-210 manufactured by Dow Corning Asia, Inc. YSR-3022, TPR-6700, TPR-6720, TPR manufactured by Toshiba Silicone -6721; SD7220, SD7226, SD7229 manufactured by Toray Dow Corning. Moreover, these mold release agents may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Furthermore, in order to adjust the peelability of the release layer, a release control agent may be used in combination with the release agent. Usually, a catalyst is used in combination with a release agent.

  The release layer can be formed, for example, by applying a release agent to the surface of the base material layer and curing it. Examples of the release agent coating method include a roll coating method, a die coating method, a gravure coating method, a bar coating method, and a doctor blade coating method.

  Although there is no special restriction | limiting in the thickness of a release layer, Usually, they are 0.1 micrometer-2.0 micrometers.

  Furthermore, the bending elastic modulus at 23 ° C. of the resin contained in the layer on the surface of the second resin layer is preferably 3500 MPa or less, more preferably 3000 MPa or less, and particularly preferably 2500 MPa or less. By keeping the bending elastic modulus in the above range, it is possible to effectively suppress damage to the first resin layer when the multilayer film is wound into a roll. The bending elastic modulus can be measured according to JIS K 7171.

  The thickness of the second resin layer is preferably 15 μm or more, more preferably 20 μm or more, particularly preferably 30 μm or more, preferably 100 μm or less, more preferably 80 μm or less, and particularly preferably 60 μm or less. Since the thickness of the second resin layer is not less than the lower limit value of the above range, the handling property of the multilayer film can be improved, and the weight of the multilayer film can be reduced by being not more than the upper limit value of the above range. Can be improved, and economic efficiency can be improved.

  The second resin layer can be manufactured by a manufacturing method including a step of obtaining a base material layer by forming an appropriate resin into a layer shape. At this time, as a molding method, any method selected from the range described in the method for manufacturing the first resin layer may be employed. Moreover, the manufacturing method of the 2nd resin layer may include the process of forming a release layer as needed.

[4. Method for producing multilayer film]
The multilayer film can be manufactured by laminating the first resin layer and the second resin layer. When the second resin layer includes a release layer, bonding is usually performed so that the surface of the second resin layer on the release layer side is in contact with the first resin layer.

  In particular, when a multi-layer film is wound up and obtained in a roll state, the first resin layer and the second resin layer are bonded together by winding the first resin layer and the second resin layer on top of each other. You may combine them. Thereby, since bonding and winding can be performed simultaneously, the manufacturing efficiency of a multilayer film can be made favorable.

[5. Application]
The above-mentioned multilayer film is usually manufactured as a long film, wound up in a roll shape, and stored and transported. Here, the long film refers to a film having a length of usually 5 times or more, preferably 10 times or more, specifically a roll shape with respect to the width of the film. A film having a length that is wound around and stored or transported. When wound up in this way, the second resin layer functions as a protective film, so that damage to the surface of the first resin layer can be suppressed. Moreover, when using a multilayer film, a 2nd resin layer is normally peeled from a 1st resin layer, and a 1st resin layer is used as an optical film. Since the peel strength between the first resin layer and the second resin layer is small as described above, the occurrence of deformation such as wrinkles due to the elongation of the first resin layer can be suppressed at the time of peeling.

  The first resin layer from which the second resin layer has been peeled off is, for example, a polarizing plate protective film, a retardation film, a brightness enhancement film, a transparent conductive film, a touch panel substrate, a liquid crystal substrate, a light diffusion sheet, a prism sheet, and organic electroluminescence. It can be used as an optical film such as an element sealing film. In particular, the first resin layer is preferably used as a sealing film for organic electroluminescence elements.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.
In the following description, “%” and “part” representing amounts are based on weight unless otherwise specified. Further, the operations described below were performed in a normal temperature and pressure atmosphere unless otherwise specified.

[Evaluation method]
[1. Method for measuring weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured as standard polystyrene equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. The measurement was performed at 38 ° C. Further, “HLC8020GPC” manufactured by Tosoh Corporation was used as a measuring apparatus.

[2. (Measurement method of hydrogenation rate)
The hydrogenation rate of the carbon-carbon unsaturated bond of the main chain and side chain of the hydride of the block copolymer and the carbon-carbon unsaturated bond of the aromatic ring was calculated by measuring a ¹ H-NMR spectrum.

[3. (Measurement method of glass transition temperature)
A sample polymer was press-molded to prepare a test piece having a length of 50 mm, a width of 1170 mm, and a thickness of 1 mm. Using this test piece, the following method was performed based on the method defined in JIS-K7244-4.
Using a loss elastic modulus measuring device (“DMS6100” manufactured by Seiko Instruments Inc.) and a viscoelasticity measuring device (“ARES” manufactured by TA Instruments Japan Co., Ltd.), temperatures from −100 ° C. to + 150 ° C. The viscoelastic spectrum was measured at a temperature rising rate of 5 ° C./min. From this viscoelastic spectrum, the peak top temperature on the high temperature side of the loss coefficient tan δ was determined, and this peak top temperature was taken as the glass transition temperature.

[4. (Measurement method of peel strength)
Resin film containing a modified alkoxysilyl group (resin film (a-1) or (a-2); film corresponding to the first resin layer) and protective film (protective film (PET-1), (PET-2) ) Or (COP); a film corresponding to the second resin layer) and a laminator was used to produce a plate having a thickness of 50 μm to 70 μm. This plate was cut into a length of 150 mm and a width of 25 mm.

  Using an autograph (“AGS-10NX” manufactured by Shimadzu Corporation), in accordance with JIS Z 0237, a 180 ° peel test is performed to peel the protective film part from the resin film part containing the alkoxysilyl group-modified product. The strength was measured. The measurement conditions at this time were a peeling rate of 300 mm / min and a temperature of 23 ° C.

[5. (Evaluation method of deformation)
The protective film was peeled from the resin film of the multilayer film provided with the resin film containing the alkoxysilyl group-modified product and the protective film. The resin film after peeling was observed visually to determine the presence or absence of wrinkles.

[Production Example 1. Production of Resin Film (a-1) Corresponding to First Resin Layer]
[1-1. Synthesis of block copolymer (a1)]
A block copolymer was produced by the following procedure using styrene as the aromatic vinyl compound and isoprene as the chain conjugated diene compound. In the following description, the polymerization conversion rate was measured by gas chromatography unless otherwise specified.

  550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.475 part of n-dibutyl ether were placed in a reactor equipped with a stirrer in which the inside was sufficiently replaced with nitrogen. Polymerization was initiated by adding 0.68 parts of butyl lithium (15% cyclohexane solution). The mixture was reacted at 60 ° C. for 60 minutes with stirring. The polymerization conversion rate at this point was 99.5%.

  Next, 50.0 parts of dehydrated isoprene was added and stirring was continued for 30 minutes. At this time, the polymerization conversion rate was 99%. Thereafter, 25.0 parts of dehydrated styrene was further added and stirred for 60 minutes. The polymerization conversion rate at this point was almost 100%. Here, 0.5 part of isopropyl alcohol was added to stop the reaction to obtain a polymer solution containing the block copolymer (a1). The weight average molecular weight (Mw) of the block copolymer (a1) was 61,700, and the molecular weight distribution (Mw / Mn) was 1.05.

[1-2. Hydrogenation of block copolymer (a1)]
Next, the polymer solution containing the block copolymer (a1) is transferred to a pressure-resistant reactor equipped with a stirrer, and a silica-alumina-supported nickel catalyst (“T-K” manufactured by Sud Chemie Catalysts) is used as a hydrogenation catalyst. 8400RL ") 3.0 parts and 100 parts dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was carried out at a temperature of 170 ° C. and a pressure of 4.5 MPa for 6 hours. Thereby, the block copolymer (a1) in a solution was hydrogenated, and the reaction solution containing the hydride (a2) of a block copolymer (a1) was obtained. The hydride (a2) had a weight average molecular weight (Mw) of 65,300 and a molecular weight distribution (Mw / Mn) of 1.06.

  After completion of the hydrogenation reaction, the reaction solution containing the hydride (a2) was filtered to remove the hydrogenation catalyst. Thereafter, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetrakis-, which is a phosphorus antioxidant, was added to the filtered reaction solution. Add 1.0 part of a xylene solution in which 0.1 part of t-butyldibenzo [d, f] [1.3.2] dioxaphosfepine (“Sumilyzer (registered trademark) GP” manufactured by Sumitomo Chemical Co., Ltd.) was dissolved. And dissolved.

  Next, the reaction solution was filtered with a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Co., Ltd.) to remove minute solids. Thereafter, from the filtered reaction solution, using a cylindrical concentrating dryer (“Contro” manufactured by Hitachi, Ltd.), the temperature is 260 ° C. and the pressure is 0.001 MPa or less, and the solvents cyclohexane and xylene, and other volatile components are used. Was removed. And from the die | dye directly connected to the said concentration dryer, the solid content of the said reaction solution is extruded in the shape of a strand in a molten state, cooled, and cut with a pelletizer to obtain 90 parts of hydride (a2) pellets. It was. The obtained hydride (a2) had a weight average molecular weight (Mw) of 64,600 and a molecular weight distribution (Mw / Mn) of 1.11. The hydrogenation rate was almost 100%.

[1-3. Mixing of compounding agents)
Next, 100 parts of the hydride (a2) pellets and N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hindered amine light stabilizer. Polymers of hexanediamine and 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine 1.0 part of the reaction product (“Chimassorb (registered trademark) 2020” manufactured by Ciba Japan) and 2- (2H-benzotriazol-2-yl) -4- (1) which is a benzotriazole-based ultraviolet absorber , 1,3,3-tetramethylbutyl) phenol (“Tinvin (registered trademark) 329” manufactured by Ciba Japan) and 0.05 part of a twin screw extruder (“TEM35B” manufactured by Toshiba Machine Co., Ltd.) And kneading at a resin temperature of 250 ° C. to obtain a resin containing a hydride (a2). This resin was extruded in a strand form from a twin screw extruder, cooled with water, and then cut by a pelletizer to obtain 98 parts of pellets.

[1-4. Introduction of alkoxysilyl group into hydride (a2)]
To 100 parts of the resin pellets, 2.0 parts of vinyltrimethoxysilane and 0.2 part of di-t-butyl peroxide were added. This mixture was kneaded using a twin screw extruder (“TEM37B” manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 210 ° C. and a residence time of 80 seconds to 90 seconds. Thereafter, the kneaded resin is extruded in a strand shape, air-cooled, and then cut by a pelletizer, and an alkoxysilyl group-modified product in which an alkoxysilyl group is introduced into a hydride (a2) obtained by hydrogenating the block copolymer (a1) ( 97 parts of pellets of resin (a4) containing a3) were obtained.

[1-5. Extrusion molding)
90 parts of the resin (a4) pellets and 10 parts of hydrogenated polybutene (“SH10” manufactured by NOF Corporation) as a plasticizer were added to a T-die film melt extrusion molding machine (T-die) equipped with a 25 mmφ screw. The resin film (a-1) corresponding to the first resin layer was obtained by extrusion from this extruder. The extrusion molding conditions were a molten resin temperature of 210 ° C., a T die temperature of 210 ° C., and a roll temperature of 50 ° C. The obtained resin film (a-1) had a thickness of 20 μm and a width of 120 mm.

[Production Example 2. Production of resin film (a-2) corresponding to first resin layer]
In the step [1-5], the amount of the pellet of the resin (a4) was changed to 80 parts, and the amount of hydrogenated polybutene (“SH10” manufactured by NOF Corporation) as a plasticizer was changed to 20 parts. A resin film (a-2) was produced in the same manner as in Production Example 1 except for the above items.

[Example 1]
A pellet of polyethylene terephthalate (“TRN-8550FF” manufactured by Teijin Limited) was heat-treated at 120 ° C. for 4 hours using a hot air dryer in which air was circulated. Thereafter, this pellet was extruded into a film using a T-die type film melt extrusion molding machine (T-die width 600 mm) having an extruder equipped with a 40 mmφ screw, and a PET film (thickness 38 μm) was obtained. Obtained. The obtained PET film was rolled up and collected.

  100 parts of curable silicone resin (“KS-847” manufactured by Shin-Etsu Chemical Co., Ltd.), 1400 parts of a mixed solvent of toluene and methyl ethyl ketone (toluene / MEK = 1/1), and a catalyst (“CAT-PL manufactured by Shin-Etsu Chemical Co., Ltd.) −50T ”) A coating solution for forming a release layer containing 0.3 part was prepared. The PET film was unwound from the roll, and the release layer-forming coating solution was applied to one side of the unrolled PET film with a die coater. Then, it was dried at 150 ° C. for 30 seconds to form a release layer having a thickness of 0.3 μm. Thereby, the protective film (PET-1) provided with a PET film and the release layer formed in the single side | surface of this PET film was obtained.

  The resin film (a-1) produced in Production Example 1 and the protective film (PET-1) are bonded together under a load of 0.3 MPa, and the resin film corresponding to the first resin layer ( A multilayer film provided with a-1) and a protective film (PET-1) corresponding to the second resin layer was obtained. The bonding was performed so that the surface on the release layer side of the protective film (PET-1) was in contact with the resin film (a-1).

About the multilayer film obtained in this way, the deformation | transformation of the resin film (a-1) when peeling a protective film (PET-1) from the resin film (a-1) was evaluated by the method mentioned above.
Moreover, the peeling strength of the resin film (a-1) and the protective film (PET-1) was measured using the resin film (a-1) and the protective film (PET-1).

[Example 2]
The pellets of cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd .; Tg = 126 ° C.) were heat-treated at 80 ° C. for 4 hours using a hot air dryer in which air was circulated. The pellets were extruded using a T-die film melt extruder (T-die width 600 mm) having an extruder equipped with a 40 mmφ screw to obtain a protective film (COP) having a thickness of 45 μm. The obtained protective film (COP) was rolled up and collected.

  Corresponding to the resin film (a-1) corresponding to the first resin layer and the second resin layer, in the same manner as in Example 1, except that the protective film (COP) was used instead of the protective film (PET-1). A multilayer film provided with a protective film (COP) to be obtained was obtained.

About the multilayer film obtained in this way, the deformation | transformation of the resin film (a-1) when peeling a protective film (COP) from the resin film (a-1) was evaluated by the method mentioned above.
Moreover, the peeling strength of the resin film (a-1) and the protective film (COP) was measured using the resin film (a-1) and the protective film (COP).

[Example 3]
Resin film (a-2) corresponding to the first resin layer in the same manner as in Example 1 except that the resin film (a-2) produced in Production Example 2 was used instead of the resin film (a-1). ) And a protective film (PET-1) corresponding to the second resin layer was obtained.

About the multilayer film obtained in this way, the deformation | transformation of the resin film (a-2) when peeling a protective film (PET-1) from the resin film (a-2) was evaluated by the method mentioned above.
Moreover, the peeling strength of the resin film (a-2) and the protective film (PET-1) was measured using the resin film (a-2) and the protective film (PET-1).

[Comparative Example 1]
The PET film produced in Example 1 was prepared as a protective film (PET-2) without forming a release layer on the surface of the PET film.
Resin film (a-1) and second resin layer corresponding to the first resin layer in the same manner as in Example 1 except that the protective film (PET-2) was used instead of the protective film (PET-1). The multilayer film provided with the protective film (PET-2) corresponded to was obtained.

About the multilayer film obtained in this way, the deformation | transformation of the resin film (a-1) when peeling a protective film (PET-2) from the resin film (a-1) was evaluated by the method mentioned above.
Moreover, the peeling strength of the resin film (a-1) and the protective film (PET-2) was measured using the resin film (a-1) and the protective film (PET-2).

[result]
The results of the examples and comparative examples are shown in the table below.

100 multilayer film 110 first resin layer 120 second resin layer

Claims (3)

Alkoxysilyl group-modified product of hydride [2] obtained by hydrogenating 90% or more of carbon-carbon unsaturated bond of main chain and side chain of block copolymer [1] and carbon-carbon unsaturated bond of aromatic ring [ 3] and a second resin layer provided on at least one side of the first resin layer,
The block copolymer [1] is composed mainly of an aromatic vinyl compound unit, and the block copolymer [1] includes two or more polymer blocks [A] per molecule and a chain conjugated diene compound unit. The block copolymer [1] having at least one polymer block [B] per molecule,
The weight fraction wA of the polymer block [A] in the entire block copolymer [1], and the weight fraction wB of the polymer block [B] in the entire block copolymer [1]. The ratio (wA / wB) to 20/80 to 60/40,
The multilayer film whose peeling strength of said 1st resin layer and said 2nd resin layer is 0.1 N / 25mm or less.   The multilayer film according to claim 1, wherein the resin [I] contains 1 to 30 parts by weight of a plasticizer with respect to 100 parts by weight of the modified alkoxysilyl group [3].   The multilayer film of Claim 1 or 2 with which the said 2nd resin layer is provided with the layer which consists of an olefin resin or a polyester-type resin.

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