CN112714782B

CN112714782B - Resin composition, resin film, and laminate

Info

Publication number: CN112714782B
Application number: CN201980060779.7A
Authority: CN
Inventors: 真岛启
Original assignee: Zeon Corp
Current assignee: Zeon Corp
Priority date: 2018-09-27
Filing date: 2019-09-06
Publication date: 2024-06-07
Anticipated expiration: 2039-09-06
Also published as: TWI799645B; CN112714782A; JP7334739B2; KR20210064203A; JPWO2020066554A1; WO2020066554A1; TW202024208A; KR102722808B1

Abstract

The present invention provides a resin composition comprising an alkoxysilyl modified product of a block copolymer hydride and an organometallic compound, wherein the block copolymer hydride is obtained by hydrogenating a block copolymer comprising a polymer block [ A ] and a polymer block [ B ], the polymer block [ A ] comprises an aromatic vinyl compound unit as a main component, and the polymer block [ B ] comprises an chain conjugated diene compound unit as a main component.

Description

Resin composition, resin film, and laminate

Technical Field

The present invention relates to a resin composition, a resin film, and a laminate.

Background

Conventionally, a resin layer has been laminated on a base film for use in an optical element or the like for the purpose of protecting the film or the like.

For example, as the polarizer protective film, a resin layer formed of a resin containing an alkoxysilyl-modified product of a predetermined block copolymer hydride is used (patent document 1).

Prior art literature

Patent document 1: international publication No. 2018/003715 (corresponding publication: U.S. patent application publication No. 2019/0162876).

Disclosure of Invention

Problems to be solved by the invention

However, the adhesion between the resin film formed from the resin of patent document 1 and the base film is insufficient.

Thus, there is a need for: a material capable of forming a resin film excellent in adhesion to a base film; a resin film having excellent adhesion to a base film; and a laminate of a resin film and a base film, which has excellent adhesion.

Solution for solving the problem

The inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, it has been found that the above-mentioned problems can be solved by a resin composition comprising a modified product of a prescribed polymer and an organometallic compound, and the present invention has been completed.

Namely, the present invention provides the following.

[1] A resin composition comprising an alkoxysilyl-modified block copolymer hydride and an organometallic compound,

The block copolymer hydrogenated product is obtained by hydrogenating a block copolymer comprising a polymer block [ A ] and a polymer block [ B ], wherein the polymer block [ A ] comprises an aromatic vinyl compound unit as a main component, and the polymer block [ B ] comprises a chain conjugated diene compound unit as a main component.

[2] The resin composition according to [1], wherein the block copolymer comprises at least two of the polymer blocks [ A ] and at least one of the polymer blocks [ B ] per molecule.

[3] The resin composition according to [1] or [2], wherein a ratio of a weight of the aromatic vinyl compound unit to a weight of the chain conjugated diene compound unit (aromatic vinyl compound unit/chain conjugated diene compound unit) in the block copolymer is 30/70 or more and 60/40 or less.

[4] The resin composition according to any one of [1] to [3], wherein the block copolymer hydride is obtained by hydrogenating 90% or more of aromatic carbon-carbon unsaturated bonds in the block copolymer and 90% or more of non-aromatic carbon-carbon unsaturated bonds in the block copolymer.

[5] The resin composition according to any one of [1] to [4], wherein the organometallic compound is a silane coupling compound.

[6] The resin composition according to [5], wherein the silane coupling compound contains an amino group which may have a substituent.

[7] The resin composition according to [6], wherein the above silane coupling compound contains two amino groups capable of having substituents per molecule.

[8] A resin film formed from the resin composition of any one of [1] to [7 ].

[9] A laminate comprising a base film and the resin film of [8], wherein the resin film is directly in contact with the surface of the base film.

Effects of the invention

According to the present invention, it is possible to provide: a resin composition capable of forming a resin film excellent in adhesion to a base film; a resin film having excellent adhesion to a base film; and a laminate of a resin film and a base film, which has excellent adhesion.

Drawings

Fig. 1 is a cross-sectional view schematically showing a laminate according to an embodiment of the present invention.

Detailed Description

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be arbitrarily modified and implemented within a range not departing from the scope of the present invention and the scope equivalent thereto.

In the following description, the term "long film" refers to a film having a length of 5 times or more, preferably 10 times or more, with respect to a width, and specifically to a film having a length of a degree that can be stored or transported in a roll form. The upper limit of the length of the film is not particularly limited, and may be, for example, 10 ten thousand times or less with respect to the width.

[1. Resin composition ]

The resin composition of the present embodiment contains an alkoxysilyl modified product of a block copolymer hydride and an organometallic compound.

[1.1. Alkoxysilyl modification of Block copolymer hydride ]

[1.1.1. Block copolymer hydride ]

The block copolymer hydrogenated compound is a compound obtained by hydrogenating a block copolymer comprising the polymer block [ A ] and the polymer block [ B ]. That is, the block copolymer hydride is a substance having a structure obtained by hydrogenating a block copolymer. However, the hydride is not limited by the method of producing the same.

(Polymer Block [ A ])

The polymer block [ A ] contains an aromatic vinyl compound unit as a main component. The term "comprising an aromatic vinyl compound unit as a main component" means that the content of the aromatic vinyl compound unit in the polymer block [ A ] is 50% by weight or more.

The aromatic vinyl compound unit means a structural unit having a structure formed by polymerizing an aromatic vinyl compound. The aromatic vinyl compound unit is not limited by the method of producing the same.

Examples of the aromatic vinyl compound corresponding to the aromatic vinyl compound unit of the polymer block [ A ] include: styrene; styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent such as α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 4-dimethylstyrene, 2, 4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; styrenes having a halogen atom as a substituent such as 4-chlorostyrene, dichlorostyrene and 4-monofluorostyrene; styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent such as 4-methoxystyrene; styrenes having an aryl group as a substituent such as 4-phenylstyrene; vinyl naphthalenes such as 1-vinyl naphthalene and 2-vinyl naphthalene. One of these may be used alone, or two or more of them may be used in combination in an arbitrary ratio. Among these, styrene and aromatic vinyl compounds containing no polar group such as styrene having an alkyl group having 1 to 6 carbon atoms as a substituent are preferable from the viewpoint of reducing hygroscopicity, and styrene is particularly preferable from the viewpoint of easy industrial availability.

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, still more preferably 98% by weight or more, and particularly preferably 99% by weight or more. In the polymer block [ A ], the hardness and heat resistance of a resin film formed from the resin composition can be improved by increasing the amount of the aromatic vinyl compound unit as described above.

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

Examples of the optional structural unit that the polymer block [ A ] may contain include chain conjugated diene compound units. Here, the chain conjugated diene compound unit means a structural unit having a structure formed by polymerizing a chain conjugated diene compound. Here, the chain conjugated diene compound may be a linear conjugated diene compound or a branched conjugated diene compound. Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit include the same examples as those given as examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit of the polymer block [ B ]. The chain conjugated diene compound unit is not limited by the method of producing the same.

Examples of the optional structural unit that the polymer block [ A ] may contain include a structural unit having a structure formed by polymerizing an optional unsaturated compound other than an aromatic vinyl compound and a chain conjugated diene compound. Examples of the optional unsaturated compound include: vinyl compounds such as chain vinyl compounds and cyclic vinyl compounds; unsaturated cyclic anhydrides; unsaturated imide compounds, and the like. 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, preferable is: a chain olefin having 2 to 20 carbon atoms per molecule, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, 4-methyl-1-pentene, and 4, 6-dimethyl-1-heptene; olefin compounds having no polar group such as cyclic olefins having 5 to 20 carbon atoms per molecule, e.g., vinylcyclohexane, 4-vinylcyclohexene, norbornene, etc., more preferably chain olefins having 2 to 20 carbon atoms per molecule, particularly preferably ethylene and propylene.

The content of any structural unit in the polymer block [ a ] is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 2% by weight or less, and particularly preferably 1% by weight or less.

The number of the polymer blocks [ A ] in the block copolymer of one molecule is preferably 2 or more, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, particularly preferably 2. In the case where the number of the polymer blocks [ A ] in the block copolymer of one molecule is 2 or more, the polymer blocks [ A ] may be the same or different from each other, for example, the composition and/or the number of the structural units contained in the polymer blocks [ A ] may be different from each other.

(Polymer Block [ B ])

The polymer block [ B ] contains chain conjugated diene compound units as a main component. The term "comprising the chain conjugated diene compound unit as a main component" means that the content of the chain conjugated diene compound unit in the polymer block [ B ] is 50% by weight or more.

The term "chain conjugated diene compound unit" means a structural unit having a structure formed by polymerizing a chain conjugated diene compound. The chain conjugated diene compound may be a linear conjugated diene compound or a branched conjugated diene compound. The chain conjugated diene compound unit is not limited by the method of producing the same.

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, and the like. One of these may be used alone, or two or more of them may be used in combination in an arbitrary ratio. Among them, in order to reduce hygroscopicity, a chain conjugated diene compound containing no polar group is preferable, and 1, 3-butadiene and isoprene are more preferable.

The content of the chain conjugated diene compound units in the polymer block [ B ] is preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more or 98% by weight or more. In the polymer block [ B ], the flexibility of the resin film formed from the resin composition can be improved by increasing the amount of the chain-like conjugated diene compound unit as described above.

The polymer block [ B ] may contain any structural unit in addition to the chain-like conjugated diene compound unit. The polymer block [ B ] may contain one arbitrary structural unit alone, or may contain two or more arbitrary structural units in any ratio in combination.

Examples of the optional structural unit that the polymer block [ B ] may contain include an aromatic vinyl compound unit and a structural unit having a structure formed by polymerizing an optional unsaturated compound other than an aromatic vinyl compound and a chain conjugated diene compound. Examples of the structural unit having a structure formed by polymerizing an arbitrary unsaturated compound and the aromatic vinyl compound include the same units as exemplified as the units that can be contained in the polymer block [ a ].

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, further preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 2% by weight or less. By reducing the content of any of the structural units in the polymer block [ B ], the flexibility of a resin film formed from the resin composition can be improved.

The number of the polymer blocks [ B ] in the block copolymer of one molecule is usually one or more, but may be two or more. In the case where the number of the polymer blocks [ B ] in one molecule of the block copolymer is two or more, the polymer blocks [ B ] may be the same or different from each other, for example, the composition of the structural units and/or the number of the structural units contained in the polymer blocks [ B ] may be different from each other.

(Block copolymer)

The block of the block copolymer may be in the form of a chain block or a radial block. Among them, chain-shaped blocks are preferable because they are excellent in mechanical strength. In the case where the block copolymer has a chain block form, it is preferable that the polymer block [ A ] is formed at both ends of the molecular chain of the block copolymer because the tackiness of the resin composition can be suppressed to a suitably low value.

The block copolymer preferably comprises at least two polymer blocks [ A ] per molecule and at least one polymer block [ B ] per molecule.

The particularly preferred block morphology of the block copolymer is: a triblock copolymer having a polymer block [ A ] bonded to both ends of the polymer block [ B ] as shown in [ A ] - [ B ] - [ A); a pentablock copolymer comprising a polymer block [ B ] bonded to both ends of the polymer block [ A ] as shown in [ A ] - [ B ] - [ A ] - [ B ] - [ A ], and further comprising a polymer block [ A ] bonded to the other ends of the two polymer blocks [ B ].

[A] the triblock copolymers of [ B ] - [ A ] are particularly preferred because they are easy to produce and can easily control physical properties within desired ranges.

In the block copolymer, it is preferable that the ratio (wA/wB) of the weight percentage wA of the aromatic vinyl compound unit to the weight percentage wB of the chain conjugated diene compound unit to the total weight of the block copolymer is controlled within a specific range. Specifically, the ratio (wA/wB) is preferably 30/70 or more, more preferably 40/60 or more, and usually 60/40 or less, preferably 55/45 or less. When the ratio wA/wB is equal to or greater than the lower limit of the above range, the hardness and heat resistance of a resin film formed from the resin composition can be improved or the birefringence can be reduced. Further, by setting the ratio wA/wB to the upper limit value or less of the above range, the flexibility of the resin film formed from the resin composition can be improved. Here, the weight percentage wA of the aromatic vinyl compound unit represents the weight percentage of the entire aromatic vinyl compound unit, and the weight percentage wB of the chain conjugated diene compound unit represents the weight percentage of the entire chain conjugated diene compound unit.

The above ratio (wA/wB) represents the ratio of the weight of the aromatic vinyl compound unit to the weight of the chain conjugated diene compound unit (aromatic vinyl compound unit/chain conjugated diene compound unit) in the block copolymer.

The weight average molecular weight (Mw) of the block copolymer is preferably 10000 or more, more preferably 20000 or more, further preferably 30000 or more, preferably 200000 or less, more preferably 100000 or less, further preferably 60000 or less.

The molecular weight distribution (Mw/Mn) of the block copolymer 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 the molecular weight distribution (Mw/Mn) of the block copolymer can be measured by Gel Permeation Chromatography (GPC) using Tetrahydrofuran (THF) as a solvent as a polystyrene equivalent.

The block copolymer can be produced by a conventionally known method. Examples of the method for producing the block copolymer include: a method of alternately polymerizing a monomer composition (a) containing an aromatic vinyl compound as a main component and a monomer composition (b) containing a chain conjugated diene compound as a main component by a living anion polymerization method or the like; a method in which a monomer composition (a) containing an aromatic vinyl compound as a main component and a monomer composition (B) containing a chain conjugated diene compound as a main component are polymerized in this order, and then the ends of the polymer block [ B ] are coupled to each other by a coupling agent.

The block copolymer can be produced by a method described in, for example, international publication No. 2018/003715.

(Block copolymer hydride)

The block copolymer hydrogenated product is obtained by hydrogenating the block copolymer, and more specifically, is a polymer obtained by hydrogenating at least a part of unsaturated bonds of the block copolymer. The unsaturated bond of the hydrogenated block copolymer includes aromatic and non-aromatic carbon-carbon unsaturated bonds of the main chain and side chains of the block copolymer.

By hydrogenating the block copolymer, a block copolymer hydride comprising a polymer block [ hA ] containing a structural unit obtained by hydrogenating at least a part of an aromatic carbon-carbon unsaturated bond contained in an aromatic vinyl compound unit and/or a polymer block [ hB ] containing a structural unit obtained by hydrogenating at least a part of a non-aromatic carbon-carbon unsaturated bond contained in an chain conjugated diene compound unit can be obtained.

The aromatic carbon-carbon unsaturated bond generally includes a carbon-carbon unsaturated bond of an aromatic ring of an aromatic vinyl compound unit included in the block copolymer.

The non-aromatic carbon-carbon unsaturated bond generally includes a carbon-carbon double bond of a chain conjugated diene compound unit included in the block copolymer.

The hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is preferably 90% or more, more preferably 97% or more, and still more preferably 99% or more of the non-aromatic carbon-carbon unsaturated bond in the block copolymer. By increasing the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond, the light resistance and oxidation resistance of the resin composition can be further improved.

The hydrogenation rate of the aromatic carbon-carbon unsaturated bond is preferably 90% or more, more preferably 97% or more, and still more preferably 99% or more of the aromatic carbon-carbon unsaturated bond in the block copolymer. By increasing the hydrogenation rate of the aromatic carbon-carbon unsaturated bond, the glass transition temperature of the polymer block obtained by hydrogenating the polymer block [ A ] becomes high, and therefore the heat resistance of the resin composition can be effectively improved. Further, the photoelastic coefficient of the resin composition can be reduced.

The hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is preferably 90% or more of the non-aromatic carbon-carbon unsaturated bond in the block copolymer, and the hydrogenation rate of the aromatic carbon-carbon unsaturated bond is preferably 90% or more of the aromatic carbon-carbon unsaturated bond in the block copolymer. The higher the hydrogenation ratio, the better the transparency, heat resistance and weather resistance of the resin composition can be made, and the birefringence can be easily reduced.

The hydrogenation ratio of the aromatic carbon-carbon unsaturated bond and the hydrogenation ratio of the non-aromatic carbon-carbon unsaturated bond in the block copolymer hydride can be determined by measuring ¹ H-NMR of the block copolymer and the block copolymer hydride.

The weight average molecular weight (Mw) of the block copolymer hydride is preferably 10000 or more, more preferably 20000 or more, further preferably 30000 or more, preferably 200000 or less, more preferably 100000 or less, further preferably 60000 or less. By controlling the weight average molecular weight (Mw) of the block copolymer hydride within the above range, the mechanical strength and heat resistance of the resin film can be improved, and further, the birefringence can be easily reduced.

The molecular weight distribution (Mw/Mn) of the block copolymer hydride is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more. By controlling the molecular weight distribution (Mw/Mn) of the block copolymer hydride within the above range, the mechanical strength and heat resistance of a resin film formed from the resin composition can be improved, and further, the birefringence can be easily reduced.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the block copolymer hydride can be measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent as polystyrene equivalent.

The block copolymer hydride may be produced by hydrogenating a block copolymer. The hydrogenation of the block copolymer can be carried out by a conventionally known method. As the hydrogenation method, a hydrogenation method capable of improving the hydrogenation rate and reducing the chain cleavage reaction of the block copolymer is preferable. Examples of such hydrogenation methods include those described in International publication No. 2011/096389 and International publication No. 2012/043708.

[1.1.2. Alkoxysilyl modification of Block copolymer hydride ]

The alkoxysilyl-modified block copolymer hydride is a polymer obtained by introducing an alkoxysilyl group into a block copolymer hydride. The introduced alkoxysilyl group may be directly bonded to the block copolymer hydride, or may be indirectly bonded to the block copolymer hydride via a 2-valent organic group such as an alkylene group or an alkylene oxycarbonyl alkylene group. The alkoxysilyl-modified product has excellent adhesion to a wide range of materials, and therefore can provide excellent adhesion to a resin composition containing the alkoxysilyl-modified product.

Examples of the alkoxysilyl group to be introduced include a tri (C ₁-C₆ alkoxy) silyl group such as trimethoxysilyl group and triethoxysilyl group; a (C ₁-C₂₀ alkyl) di (C ₁-C₆ alkoxy) silyl group such as a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, an ethyldiethoxysilyl group, a propyldimethoxysilyl group, and a propyldiethoxysilyl group; phenyl dimethoxysilyl, phenyl diethoxysilyl and other (aryl) di (C ₁-C₆ alkoxy) silyl groups, and the like.

The amount of the alkoxysilyl group to be introduced into the alkoxysilyl-modified block copolymer is preferably 0.1 part by weight or more, more preferably 0.2 part by weight or more, still more preferably 0.3 part by weight or more, preferably 5 parts by weight or less, more preferably 4 parts by weight or less, still more preferably 3 parts by weight or less, based on 100 parts by weight of the block copolymer hydride before introducing the alkoxysilyl group. When the amount of the alkoxysilyl groups to be introduced is controlled within the above range, it is possible to suppress the crosslinking degree of the alkoxysilyl groups, which are decomposed by moisture or the like, from becoming excessively high, and therefore, it is possible to maintain the adhesion of the resin composition high.

The amount of alkoxysilyl groups introduced can be measured by ¹ H-NMR spectroscopy. In addition, when the amount of alkoxysilyl groups to be introduced is measured, the number of times of accumulation can be increased to measure when the amount of alkoxysilyl groups to be introduced is small.

Since the amount of the alkoxysilyl group to be introduced is small, the weight average molecular weight (Mw) of the alkoxysilyl-modified product generally does not change much from the weight average molecular weight (Mw) of the block copolymer hydride before the introduction of the alkoxysilyl group. However, since the block copolymer hydride is subjected to a modification reaction in the presence of a peroxide when an alkoxysilyl group is introduced, the crosslinking reaction and the chain cleavage reaction of the block copolymer hydride proceed, and the molecular weight distribution tends to be greatly changed.

The weight average molecular weight (Mw) of the alkoxysilyl-modified product is preferably 10000 or more, more preferably 20000 or more, further preferably 30000 or more, preferably 200000 or less, more preferably 100000 or less, further preferably 60000 or less. The molecular weight distribution (Mw/Mn) of the alkoxysilyl-modified product is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less, and preferably 1.0 or more. When the weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the alkoxysilyl-modified product are within this range, good mechanical strength and tensile elongation of a resin film formed from the resin composition can be maintained.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the alkoxysilyl-modified product can be measured as polystyrene-equivalent values by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent.

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

As the ethylenically unsaturated silane compound, an ethylenically unsaturated silane compound which can be graft polymerized with a block copolymer hydride and can introduce an alkoxysilyl group into the block copolymer hydride can be used. Examples of such ethylenically unsaturated silane compounds include: vinyl-containing alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane and diethoxymethylvinylsilane; allyl-containing alkoxysilanes such as allyl trimethoxysilane and allyl triethoxysilane; alkoxysilanes having a p-styryl group such as p-styryl trimethoxysilane and p-styryl triethoxysilane; alkoxysilanes having 3-methacryloxypropyl groups, such as 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl triethoxy silane, and 3-methacryloxypropyl methyl diethoxy silane; alkoxysilanes having a 3-acryloxypropyl group, such as 3-acryloxypropyl trimethoxysilane and 3-acryloxypropyl triethoxysilane; and alkoxysilanes having 2-norbornene-5-yl group such as 2-norbornene-5-yl trimethoxysilane. Among these, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, and p-styryltrimethoxysilane are preferable from the viewpoint of more easily obtaining the effect of the present invention. The ethylenically unsaturated silane compound may be used alone or in combination of two or more kinds in any ratio.

The amount of the ethylenically unsaturated silane compound is preferably 0.1 part by weight or more, more preferably 0.2 part by weight or more, still more preferably 0.3 part by weight or more, preferably 5 parts by weight or less, more preferably 4 parts by weight or less, still more preferably 3 parts by weight or less, based on 100 parts by weight of the block copolymer hydride before introducing the alkoxysilyl group.

As the peroxide, a peroxide that functions as a radical reaction initiator can be used. As such peroxides, organic peroxides are generally used. Examples of the organic peroxide include dibenzoyl peroxide, t-butyl peroxyacetate, 2-di (t-butylperoxy) butane, t-butyl peroxybenzoate, t-butylcumene peroxide, diisopropylbenzene peroxide, di-t-hexyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxyisobutyrate, lauroyl peroxide, dipropyl peroxide, and p-terpene hydroperoxide. Of these, peroxides having a half-life temperature of 170℃to 190℃in one minute are preferable, and specifically t-butylcumene peroxide, diisopropylbenzene peroxide, di-t-hexyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide and the like are preferable. The peroxide may be used alone or in combination of two or more.

The amount of the peroxide is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, still more preferably 0.2 parts by weight or more, preferably 2 parts by weight or less, more preferably 1 part by weight or less, still more preferably 0.5 parts by weight or less, based on 100 parts by weight of the block copolymer hydride before introducing the alkoxysilyl group.

The alkoxysilyl-modified product can be produced, for example, by the method described in International publication No. 2018/003715.

[1.2. Organometallic Compounds ]

The organometallic compound is a compound containing at least one of a bond between a metal and carbon and a bond between a metal and oxygen, and is a compound having an organic group. Examples of the organometallic compound include organosilicon compounds, organotitanium compounds, organoaluminum compounds, and organozirconium compounds. Among these, organosilicon compounds, organotitanium compounds and organozirconium compounds are preferable, and organosilicon compounds are more preferable. The organometallic compound may be used singly or in combination of two or more.

Examples of the organometallic compound include, but are not limited to, compounds represented by the following formula (1).

R¹ _aSi(OR²)_4-a (1)

( In the formula (1), R ¹ and R ² each independently represent a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an epoxy group (ethylene oxide group, oxirany), an amino group, a mercapto group (sulfanyl), an isocyanate group, and an organic group having 1 to 10 carbon atoms, and a represents an integer of 0 to 4. In the case of having a plurality of R ¹, the plurality of R ¹ may be different from each other. In the case of having a plurality of R ², the plurality of R ² may be different from each other. )

R ¹ preferably represents an organic group having 1 to 10 carbon atoms, and more preferably represents an organic group having 1 to 10 carbon atoms containing one or more groups selected from the group consisting of an oxirane group, an amino group, a mercapto group, a vinyl group, an isocyanate group, an acryloyloxy group and a methacryloyloxy group.

R ² preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably represents a methyl group or an ethyl group.

A preferably represents 1 or 2, more preferably 1.

As the organometallic compound, a silane coupling compound is particularly preferable. The silane coupling compound means that it is an organosilicon compound and contains a reactive group, and an alkoxy group bonded to a silicon atom and/or a hydroxyl group bonded to a silicon atom.

Examples of the reactive group included in the silane coupling compound include a halogen atom, a vinyl group, a group having an oxirane ring structure, an acryloyloxy group, a methacryloyloxy group, an amino group which may have a substituent, a carbamoylamino group, an isocyanato group, a group having an isocyanurate ring structure, and a mercapto group (sulfanyl).

The group having an oxirane ring structure means a group having an oxirane ring in the structure, and may have an oxirane ring structure as a single ring or may have a ring condensed with another ring. Examples of the group having an oxirane ring structure include oxirane group, epoxycyclohexyl group (for example, 3, 4-epoxycyclohexyl group), and glycidoxy group.

By amino group which may have a substituent is meant an unsubstituted amino group (-a group represented by NH ₂), a group represented by-NH-R ³, -a group represented by NR ⁴R⁵, or a group represented by-n=r ⁶. Here, R ³、R⁴ and R ⁵ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³、R⁴ and R ⁵ include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and n-pentyl; cycloalkyl groups having 3 to 10 carbon atoms such as cyclopentyl and cyclohexyl; aryl groups having 6 to 10 carbon atoms such as phenyl groups; arylalkyl groups having 7 to 10 carbon atoms such as benzyl groups.

R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ⁶ include alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, propylene, butylene and pentylene.

Here, R ³、R⁴、R⁵ and R ⁶ each independently may further have a substituent. Examples of the substituent that R ³、R⁴、R⁵ and R ⁶ can have include amino and vinyl.

The reactive group contained in the silane coupling compound may be bonded directly to the silicon atom or may be bonded to the silicon atom via a linking group. In the silane coupling compound, examples of the linking group linking the reactive group to the silicon atom include a divalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms as the linking group include alkanediyl groups having 1 to 10 carbon atoms such as methylene, ethylene, propanediyl and butanediyl; cyclopentanediyl, cyclohexanediyl and other cycloalkanediyl groups having 3 to 10 carbon atoms; arylene groups having 6 to 10 carbon atoms such as phenylene groups are preferable, ethylene groups, propane diyl groups and phenylene groups.

Examples of the alkoxy group bonded to a silicon atom contained in the silane coupling compound include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, a tert-butoxy group, and a pentoxy group, and an alkoxy group having 1 to 5 carbon atoms is preferable, and methoxy and ethoxy groups are more preferable.

The alkoxy group bonded to a silicon atom may further have a substituent. Examples of the substituent that can be contained in the alkoxy group bonded to the silicon atom include an alkoxy group having 1 to 4 carbon atoms.

The silane coupling compound may be any one of an organosilicon compound in which one alkoxy group is bonded to a silicon atom, an organosilicon compound in which two alkoxy groups are bonded to a silicon atom, and an organosilicon compound in which three alkoxy groups are bonded to a silicon atom. In the case where the silane coupling compound includes a plurality of alkoxy groups bonded to a silicon atom, the plurality of alkoxy groups may be the same or different from each other, and the silane coupling compound is preferably the same as each other because the silane coupling compound is easily produced.

As the silane coupling compound as the organometallic compound, there may be mentioned, as an example thereof: vinyl-containing organosilicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; organosilicon compounds containing a group having an oxirane ring structure, such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, and 3-glycidoxypropyl triethoxysilane; an organic silicon compound containing a methacryloxy group such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane, etc.; organosilicon compounds containing an acryloxy group such as 3-acryloxypropyl trimethoxysilane; organosilicon compounds containing an amino group which may have a substituent(s), such as N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride; organosilicon compounds containing a carbamoylamino group such as 3-ureidopropyltrialkoxysilane; organosilicon compounds containing isocyanate groups such as 3-isocyanatopropyl triethoxysilane; an organosilicon compound containing a group having an isocyanurate ring structure, such as tris (trimethoxysilylpropyl) isocyanurate; and mercapto group-containing organosilicon compounds such as 3-mercaptopropyl methyl dimethoxy silane and 3-mercaptopropyl trimethoxy silane.

As the silane coupling compound, an organosilicon compound containing an amino group which can have a substituent is preferable, and an organosilicon compound containing two amino groups which can have substituents per molecule is more preferable. Here, the silane coupling compound includes an amino group having a substituent, and in the case where the substituent further has an amino group, the number of amino groups in the substituent including an amino group out of the number of amino groups capable of having a substituent included in the silane coupling compound.

As examples of the silane coupling compound containing two amino groups capable of having substituents per molecule, N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride can be given.

Examples of the organic titanium compound include titanium alkoxide such as tetraisopropyl titanate, titanium chelate such as titanium acetylacetonate, and titanium acylate such as titanium isostearate.

Examples of the organozirconium compound include zirconium alkoxide such as n-propyl zirconate, zirconium chelate such as zirconium tetra-acetylacetonate, and zirconium acylate such as zirconium stearate.

Examples of the organoaluminum compound include aluminum alkoxides such as aluminum sec-butoxide and aluminum chelate compounds such as aluminum triacetylacetonate.

The proportion of the organometallic compound to the alkoxysilyl-modified product is preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, still more preferably 0.03 parts by weight or more, preferably 1.0 parts by weight or less, more preferably 0.5 parts by weight or less, based on 100 parts by weight of the alkoxysilyl-modified product. By setting the ratio of the organometallic compound in the above range, the adhesion of the resin film formed from the resin composition can be further effectively improved.

As the organometallic compound, for example, commercial products such as KBE series and KBM series manufactured by the company of the singe chemical industry, ORGATIX (registered trademark) series manufactured by Matsumoto FINE CHEMICAL co.ltd.

[1.3. Optional ingredients ]

The resin composition may contain, in addition to the alkoxysilyl-modified product and the organometallic compound, any components such as additives and solvents.

Examples of the additives include: stabilizers such as antioxidants, ultraviolet absorbers, and light stabilizers; resin modifiers such as slip agents; colorants such as dyes and pigments; an antistatic agent. These additives can be used singly or in combination of two or more. The amount of the additive to be blended may be appropriately selected, and is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and still more preferably 10 parts by weight or less, based on 100 parts by weight of the alkoxysilyl-modified product. By setting the blending amount of the additive in the above range, the adhesion of the resin film formed from the resin composition can be further effectively improved.

Examples of the solvent that can be contained in the resin composition include: aliphatic and alicyclic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc., and aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc.; ether solvents such as tetrahydrofuran. The solvent can be used singly or in combination of two or more. The proportion of the solvent in the resin composition may be appropriately selected in consideration of the solubility of the components contained in the resin composition, and the like. The proportion of the solvent in the resin composition is, for example, preferably 150 parts by weight or more, more preferably 200 parts by weight or more, preferably 500 parts by weight or less, more preferably 400 parts by weight or less, based on 100 parts by weight of the alkoxysilyl-modified product.

[1.4 Process for producing resin composition ]

The resin composition can be produced by a conventionally known method depending on the nature of the components contained in the resin composition. For example, the resin composition can be produced by the following method or the like: a method of melt-mixing the components of the resin composition using an extruder or the like; a method of adding and mixing components of the resin composition other than the solvent to the solvent.

[2 Resin film ]

The resin film according to one embodiment of the present invention is formed from the above resin composition. Accordingly, the resin film may contain an alkoxysilyl-modified substance and an organometallic compound.

The resin film may be formed from the resin composition by any method such as a melt extrusion method, a solution casting method, a coating method, or the like.

In the case where the resin composition contains a solvent, the layer of the resin composition may be dried by forming the layer of the resin composition, thereby forming a resin film.

The thickness of the resin film can be arbitrarily set according to the application of the resin film, and is preferably 1 μm or more, more preferably 3 μm or more, and preferably 50 μm or less, and more preferably 20 μm or less.

The resin film is excellent in adhesion to various films as a base film, and is therefore useful as a protective film for various optical element films (for example, polarizer films).

[3. Laminate ]

In one embodiment of the present invention, the laminate comprises the resin film and a base film, and the resin film is in direct contact with the surface of the base film. Fig. 1 is a cross-sectional view schematically showing a laminate according to the present embodiment. The laminate 100 includes a base film 101 and a resin film 102 provided in contact with a surface 101U of the base film 101.

The material of the base film is not particularly limited, and resins containing various polymers can be used. Examples of the polymer include: an alicyclic structure-containing polymer; polyesters such as polyethylene terephthalate (PET); cellulose esters such as triacetyl cellulose; acrylic polymers such as polymethyl methacrylate; polyvinyl alcohol; a polycarbonate; polyimide; polysulfone; polyether sulfone; an epoxy polymer; a polystyrene; and combinations of these. The base film may be formed by any method such as a melt extrusion method, a solution casting method, a coating method, or the like. The substrate film may be subjected to any of surface treatments (for example, corona treatment, plasma treatment, saponification treatment, priming treatment, anchoring treatment), stretching treatment, dyeing treatment, and the like.

The substrate film may have a single-layer structure or a multilayer structure.

The thickness of the base film can be appropriately selected, and is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, preferably 1000 μm or less, more preferably 500 μm or less, further preferably 110 μm or less, and particularly preferably 100 μm or less.

The resin film included in the laminate of the present embodiment is a film formed from the resin composition containing the alkoxysilyl-modified product and the organometallic compound.

The laminate can be produced by a conventionally known method. As an example of the production method, (1) a method of producing a base film and a resin film, then laminating the base film and the resin film by pressure bonding or the like, and (2) a method of forming a layer of a resin composition by applying a resin composition containing a solvent to at least one surface of the base film, and then forming a resin film by drying the layer of the resin composition, are given. From the viewpoint of effectively exhibiting adhesion of the resin film to the base film, the laminate is preferably produced by the method of (2) above.

As examples of the method of coating the solvent-containing resin composition on the surface of the substrate film, there may be mentioned solution coating, emulsion coating, and melt extrusion coating, and from the viewpoint of enabling high-speed coating and obtaining a resin film of uniform thickness, solution coating is preferable. The thickness of the layer of the coated resin composition may be appropriately set according to a desired thickness required by the resin film.

Examples of the method for drying the layer of the resin composition include heat drying, reduced pressure drying, heat reduced pressure drying, and natural drying.

The laminate of another embodiment includes, in order, a 1 st resin film, a base material film, and a 2 nd resin film, wherein the 1 st resin film is in direct contact with one surface of the base material film, and the 2 nd resin film is in direct contact with the other surface of the base material film.

Since the laminate of the present embodiment is provided with resin films having excellent adhesion on both surfaces, both surfaces are well protected by the resin films.

Examples

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the embodiments described below, and may be arbitrarily modified and implemented within a range not departing from the scope of the present invention and the scope equivalent thereto.

In the following description, unless otherwise specified, "%" and "parts" representing amounts are based on weight. Unless otherwise specified, the operations described below are performed under normal temperature and normal pressure conditions.

[ Evaluation method ]

(Weight average molecular weight (Mw) and number average molecular weight (Mw/Mn))

The molecular weight of the block copolymer and the block copolymer hydride was measured at 38℃as a standard polystyrene equivalent of GPC using THF as an eluent. As a measurement device, "HLC8020GPC" manufactured by Tosoh corporation was used.

(Hydrogenation Rate)

The hydrogenation rate of the block copolymer hydride was calculated by measuring ¹ H-NMR spectra of the block copolymer and the block copolymer hydride.

(Method for measuring thickness)

The thickness of each film contained in the laminate was measured 5 times by using a thickness meter (trade name "ABS DIGIMATIC THICKNESS Gauge (547-401), manufactured by Mitutoyo corporation), and the average value was used as the thickness of each film.

(Evaluation of adhesion)

According to JIS K5400:1990 (checkerboard test) 100 cells of 1mm×1mm were drawn on a resin film (resin layer), and the checkerboard test was performed. When the number of peeled cells is more than 20, the adhesion is evaluated as poor. After the formation of the resin film (resin layer), the resin film was left to stand under the following conditions, and adhesion was evaluated.

(After 1 day) the resin film was allowed to stand in the atmosphere for 1 day

(After 5 days) the resin film was allowed to stand in the atmosphere for 5 days

(After the wet heat resistance test), the resin film was allowed to stand in the atmosphere for 5 days, and further allowed to stand in an atmosphere having a temperature of 60℃and a relative humidity of 90% for 500 hours

Production example 1 production of alkoxysilyl modified product of Block copolymer hydride [ S1]

(Production of Block copolymer)

A reactor equipped with a stirring device was prepared, and nitrogen substitution was sufficiently performed inside. 400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 parts of dibutyl ether were charged into the reactor. While stirring the vessel contents at 60℃0.90 parts of n-butyllithium (15% cyclohexane solution) was added thereto to initiate polymerization. Subsequently, 15 parts of dehydrated styrene was continuously added to the reaction solution for 40 minutes while stirring the reaction solution in the vessel at 60℃to carry out polymerization. After the addition of dehydrated styrene, the reaction mixture was stirred at 60℃for 20 minutes. The reaction solution at this time was analyzed by Gas Chromatography (GC), and as a result, the polymerization conversion was 99.5%.

Next, 50 parts of dehydrated isoprene was continuously added to the reaction solution over 130 minutes. After addition of dehydrated isoprene, the reaction solution was directly stirred for 30 minutes. The reaction solution at this time was analyzed by GC, and as a result, the polymerization conversion was 99.5%.

Subsequently, 25 parts of dehydrated styrene was continuously added to the reaction solution over 70 minutes. After the addition of dehydrated styrene, the reaction solution was directly stirred for 60 minutes. The reaction solution at this time was analyzed by GC, and as a result, the polymerization conversion was almost 100%.

Next, 0.5 part of isopropyl alcohol was added to the reaction solution to terminate the reaction, thereby obtaining a polymer solution containing a block copolymer. The block copolymer [ J1] contained in the polymer solution is a triblock copolymer of the type of a polymer block [ A ] containing styrene units, a polymer block [ B ] containing isoprene units, and a polymer block [ A ] containing styrene units. The weight average molecular weight (Mw) of the block copolymer [ J1] was 45300, the molecular weight distribution (Mw/Mn) was 1.04, and wA/wB=50/50.

Here, wA represents the weight percentage of the aromatic vinyl compound unit (styrene unit) in the block copolymer [ J1] as a whole, and wB represents the weight percentage of the chain conjugated diene compound unit (isoprene unit) in the block copolymer [ J1] as a whole.

(Production of Block copolymer hydride)

Then, the polymer solution was transferred to a pressure-resistant reactor having a stirring device. To the polymer solution, 7.0 parts of a kieselguhr-supported nickel catalyst (product name "E22U", manufactured by Nissk catalyst chemical Co., ltd., nickel loading amount of 60%) was added as a hydrogenation catalyst and 80 parts of dehydrated cyclohexane, and mixed to obtain a mixture. The inside of the reactor was replaced with hydrogen, and then the mixture was stirred while hydrogen was supplied into the reactor, and hydrogenation was carried out at a temperature of 150℃and a pressure of 3.0MPa for 1 hour, and then the temperature was raised to 190℃and a pressure of 4.5MPa, and hydrogenation was carried out for 6 hours, to obtain a reaction mixture containing a block copolymer hydride [ H1 ]. The block copolymer hydride [ H1] in the obtained reaction mixture had a weight average molecular weight (Mw) of 47900 and a molecular weight distribution (Mw/Mn) of 1.06.

After the completion of the hydrogenation reaction, the obtained reaction mixture was filtered to remove the hydrogenation catalyst to obtain a filtrate, and to the obtained filtrate, 2.0 parts of a xylene solution of pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (product name "AO60", manufactured by ADEKA corporation) as a phenolic antioxidant was added and dissolved to obtain a solution.

Subsequently, the solution was filtered through a metal fiber filter (pore size: 0.4 μm, NICHIDAI co., ltd.) to remove fine solid components. Then, cyclohexane, xylene and other volatile components were removed from the solution using a cylindrical concentration dryer (product name "Contro", manufactured by Hitachi Ltd.) at a temperature of 260℃and a pressure of 0.001MPa or less. The molten resin was extruded from a die directly connected to a concentration dryer, cooled with water, cut by a submerged cutter, and granulated, and about 100ppm of fine powder of ethylene bis stearamide was added as an antiblocking agent to prepare 95 parts of pellets of the block copolymer hydride [ H1 ].

The weight average molecular weight (Mw) of the obtained particulate block copolymer hydride [ H1] was 47400, the molecular weight distribution (Mw/Mn) was 1.10, and the hydrogenation ratio of the double bonds (the double bonds of the main chain and the side chains, the non-aromatic carbon-carbon unsaturated bonds) and the hydrogenation ratio of the aromatic carbon-carbon unsaturated bonds of the chain conjugated diene compound unit were almost 100%.

(Production of alkoxysilyl-modified product)

To 100 parts of the obtained pellets of the block copolymer hydride [ H1], 2.0 parts of vinyltrimethoxysilane (product name "KBM-1003", manufactured by Xinyue chemical industries, ltd.) and 0.1 part of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (product name "PERCEXA (registered trademark) 25B", manufactured by Nikko oil Co., ltd.) were added to obtain a mixture. The mixture was kneaded at a resin temperature of 210℃and a residence time of 60 seconds to 70 seconds using a biaxial extruder (product name "TEM37B", manufactured by Toshiba machinery Co., ltd.). The obtained kneaded material was extruded into a strand, cooled in air, and then cut by a granulator to obtain 96 parts of particles of an alkoxysilyl-modified block copolymer hydride [ S1] having an alkoxysilyl group introduced therein.

0.00001 Parts of particles of the alkoxysilyl-modified substance [ S1] were dissolved in 0.001 parts of cyclohexane, and then the resulting solution was poured into 0.004 parts of dehydrated methanol to coagulate the alkoxysilyl-modified substance [ S1], and the resultant coagulated substance was filtered. The filtered coagulum was dried in vacuo at 25℃to give 0.000009 parts of purified alkoxysilyl modification [ S1].

In the FT-IR spectrum of the alkoxysilyl modification [ S1], a new absorption band from Si-CH ₂ group was observed at 1090cm ^-1, from Si-OCH ₃ group at 825cm ^-1 and 739cm ^-1, at a position different from the absorption band from Si-OCH ₃ group, si-CH group (1075 cm ^-1、808cm^-1 and 766cm ^-1) of vinyltrimethoxysilane.

Furthermore, ¹ H-NMR spectrum (in deuterated chloroform) of alkoxysilyl-modified [ S1] was measured, and as a result, a peak of proton based on methoxy group was observed at 3.6 ppm. From the peak area ratio, it was confirmed that 1.8 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride [ H1 ].

Production example 2 production of alkoxysilyl modified product of Block copolymer hydride [ S2]

(Production of Block copolymer)

Except for the following modifications, a polymer solution containing a block copolymer [ J2] was obtained by the same procedure as in production example 1 (production of a block copolymer).

The amount of n-butyllithium (15% cyclohexane solution) was changed from 0.90 parts to 0.80 parts.

The block copolymer [ J2] contained in the polymer solution is a triblock copolymer of the type of a polymer block [ A ] containing styrene units, a polymer block [ B ] containing isoprene units, and a polymer block [ A ] containing styrene units. The weight average molecular weight (Mw) of the block copolymer [ J2] was 51900, the molecular weight distribution (Mw/Mn) was 1.04, and wA: wB=50:50.

Then, the polymer solution was transferred to a pressure-resistant reactor having a stirring device. To the polymer solution, a solution obtained by mixing 0.042 parts of bis (cyclopentadienyl) titanium dichloride and 0.122 parts of diethylaluminum chloride in 1.0 part of toluene was added as a hydrogenation catalyst, and mixed to obtain a mixture. The inside of the reactor was replaced with hydrogen, and then, the mixture was stirred while hydrogen was supplied into the reactor, and hydrogenation was carried out at a temperature of 90℃and a pressure of 1.0MPa for 5 hours, to obtain a reaction solution containing a block copolymer hydride [ H2 ].

The weight average molecular weight (Mw) of the block copolymer hydride [ H2] in the obtained reaction solution was 55000, and the molecular weight distribution (Mw/Mn) was 1.05.

After the completion of the hydrogenation reaction, 0.10 parts of water was added to the obtained reaction solution, and the mixture was stirred at 60℃for 60 minutes. Subsequently, the reaction solution was cooled to 30℃or lower, and 1.5 parts of activated clay (product name "GALLEON EARTH" (registered trademark), manufactured by water-jet chemical industry Co., ltd.) and 1.5 parts of talc (product name "Microace (registered trademark)", manufactured by Japanese talc Co., ltd.) were added and filtered, whereby insoluble matter was removed from the reaction solution to obtain a filtrate. To the obtained filtrate, 2.0 parts of a xylene solution in which 0.1 parts of pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] as a phenolic antioxidant was dissolved was added, and the mixture was dissolved to obtain a solution.

Next, the above solution was treated in the same manner as in production example 1 to produce 96 parts of particles of block copolymer hydride [ H2 ].

The obtained particulate block copolymer hydride [ H2] had a weight average molecular weight (Mw) of 54400, a molecular weight distribution (Mw/Mn) of 1.08, a hydrogenation ratio of double bonds (double bonds of a main chain and a side chain, non-aromatic carbon-carbon unsaturated bonds) of a chain conjugated diene compound unit of 99% and a hydrogenation ratio of aromatic carbon-carbon unsaturated bonds of less than 3%.

(Production of alkoxysilyl-modified product)

93 Parts of particles of an alkoxysilyl-modified product [ S2] were obtained by the same procedure as in production example 1 (production of an alkoxysilyl-modified product), except that the following matters were changed.

Instead of the block copolymer hydride [ H1], particles of the block copolymer hydride [ H2] are used.

As a result of measurement of ¹ H-NMR spectrum of the obtained alkoxysilyl-modified product [ S2], it was confirmed that 1.8 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride [ H2 ].

Example 1

(Preparation of coating liquid)

100 Parts by weight of the particles of the alkoxysilyl-modified substance [ S1] produced in production example 1 were dissolved in 300 parts by weight of cyclohexane to obtain a resin solution. Next, 0.05 part by weight of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane ("KBM 603", manufactured by Xinyue chemical industries, inc., organosilicon compound (silane coupling compound)) was added to the obtained resin solution, and the mixture was stirred for 1 hour to obtain a coating liquid for forming a resin film (for forming a resin layer) as a resin composition.

(Production of laminate)

A long polyethylene terephthalate (PET) film (manufactured by Toyobo Co., ltd., "A4300", thickness 50 μm) was prepared as a base film. A surface of one side of the base film was subjected to corona treatment, and a coating layer was formed by applying a coating liquid to the surface subjected to corona treatment using a die coater. The thickness of the coating layer was adjusted so that a resin film (resin layer) having a thickness of 10 μm could be obtained. Subsequently, the coating layer was dried by heating to form a resin film (resin layer) having a thickness of 10 μm, and a long laminate having a base film and a resin film with a width of 600mm was obtained. In the laminate, the resin film is in direct contact with the surface of the base film.

The obtained laminate was evaluated for adhesion by the above method.

Example 2

A laminate was obtained and evaluated for adhesion in the same manner as in example 1 except that the following matters were changed.

As a base film, a long triacetyl cellulose (TAC) film (FUJIFILM Corporation, "Fuji-TAC", thickness 40 μm) was used.

Example 3

As the base film, a long acrylic resin (Ac) film (thickness: 50 μm) was used.

The acrylic resin film was produced by the following procedure.

Polymethyl methacrylate resin (L) (trade name "Sumipex (registered trademark) HT20Y" manufactured by sumitomo chemical company) was prepared. In addition, a polymethyl methacrylate resin (H) (trade name "Sumipex MH" manufactured by sumitomo chemical company) having higher heat resistance than the resin (L) was prepared. The resin (L) and the resin (H) are supplied to a T-die of a multilayer coextrusion apparatus capable of forming a three-layer extruded film from two resins so as to obtain an extruded film of a resin (L)/resin (H)/resin (L) layer structure. Resin (L) and resin (H) were discharged from the T die at extrusion amounts of 20 kg/hr and 10 kg/hr, respectively, and the discharged films were cooled by mirror rolls to obtain a three-layer acrylic resin film having a thickness of 50. Mu.m.

Example 4

As the base film, a long polyvinyl alcohol (PVA) film (thickness: 60 μm) was used.

Example 5

As the base film, a long Polycarbonate (PC) film (trade name "OPCON", manufactured by Hui Co., ltd., thickness 110 μm) was used.

Example 6

In the preparation of the coating liquid, 3-aminopropyl trimethoxysilane (organosilicon compound "KBM903", manufactured by Xinyue chemical Co., ltd.) was used instead of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane ("KBM 603").

Example 7

In the preparation of the coating liquid, 3-glycidoxypropyl trimethoxysilane (organosilicon compound, "KBM403", manufactured by Xinyue chemical industries, inc.) was used instead of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane ("KBM 603").

Example 8

In the preparation of the coating liquid, N-propyl zirconate (Matsumoto FINE CHEMICAL Co. Ltd. "ORGATIX ZA-45", organozirconium compound) was used instead of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane ("KBM 603").

Example 9

In the preparation of the coating liquid, tetraisopropyl titanate (Matsumoto FINE CHEMICAL Co. Ltd. "ORGATIX TA-8, organic titanium compound) was used instead of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane (" KBM603 ").

Example 10

In the preparation of the coating liquid, the alkoxysilyl modified product [ S2] produced in production example 2 was used instead of the alkoxysilyl modified product [ S1 ].

Comparative example 1

In the preparation of the coating liquid, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane ("KBM 603") was used in an amount of 0 parts by weight.

Comparative example 2

As a base film, a long triacetyl cellulose film (FUJIFILM Corporation "Fuji-TAC", thickness 40 μm) was used.

Comparative example 3

As the base film, a long acrylic resin (Ac) film (thickness: 50 μm) was used. The acrylic resin film was the same as that produced in example 3.

Comparative example 4

Comparative example 5

[ Evaluation results ]

The results of examples and comparative examples are shown in the following table.

Abbreviations in the tables represent the following meanings.

"S1": alkoxysilyl modifier [ S1]

"S2": alkoxysilyl modifier [ S2]

"KBM603": n-2- (aminoethyl) -3-aminopropyl trimethoxysilane

"KBM903": 3-aminopropyl trimethoxysilane

"KBM403": 3-glycidoxypropyl trimethoxysilane

"PET": polyethylene terephthalate film

"TAC": triacetyl cellulose film

"Ac": acrylic resin film

"PVA": polyvinyl alcohol film

"PC": polycarbonate film

The adhesion evaluation in the table is expressed as a ratio (X/100) of the number of cells X in which peeling does not occur to 100 cells.

TABLE 1

From the above results, the following will be apparent.

The laminate of the example using the resin composition containing the predetermined resin and the organometallic compound has significantly better adhesion than the laminate of the comparative example using the resin composition containing no organometallic compound.

Further, the laminate of examples 1 to 6 and 10 using the silane coupling compound containing an amino group as the organosilicon compound was excellent in adhesion as compared with example 7 not containing the silane coupling compound containing an amino group. In particular, example 1 using a silane coupling compound having two amino groups per molecule was excellent in adhesion as compared with example 6 using a silane coupling compound having one amino group per molecule.

Further, examples 1 to 5 using a silane coupling compound containing two amino groups per molecule as an organosilicon compound and using the modified product [ S1] were superior to examples 6 to 10 in adhesion evaluation after the wet heat resistance test.

The above results show that a resin composition containing a predetermined alkoxysilyl-modified product and an organometallic compound can produce a resin film and a laminate excellent in adhesion.

Description of the reference numerals

100. Laminate body

101. Substrate film

102. Resin film

101U face

Claims

1. A resin film is formed from a resin composition,

The resin composition comprises:

Alkoxysilyl modifications of block copolymer hydrides; and

Silane coupling compounds and/or organometallic compounds,

The block copolymer hydride is obtained by hydrogenating a block copolymer comprising a polymer block [ A ] and a polymer block [ B ], wherein the polymer block [ A ] comprises an aromatic vinyl compound unit as a main component, the polymer block [ B ] comprises a chain conjugated diene compound unit as a main component,

The organic metal compound is at least one selected from organic titanium compounds and organic zirconium compounds,

The silane coupling compound contains an amino group which can have a substituent,

The ratio of the weight of the aromatic vinyl compound unit to the weight of the chain conjugated diene compound unit in the block copolymer is 40/60 or more and 60/40 or less,

The silane coupling compound and/or the organometallic compound is present in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the alkoxysilyl modified block copolymer hydride,

The amino group which may have a substituent is an unsubstituted amino group, -a group represented by NH-R ³, -a group represented by NR ⁴R⁵, or-a group represented by n=r ⁶, R ³、R⁴ and R ⁵ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.

2. The resin film according to claim 1, wherein the block copolymer comprises at least two of the polymer blocks [ a ] and at least one of the polymer blocks [ B ] per molecule.

3. The resin film according to claim 1 or 2, wherein the block copolymer hydride is obtained by hydrogenating 90% or more of aromatic carbon-carbon unsaturated bonds in the block copolymer and 90% or more of non-aromatic carbon-carbon unsaturated bonds in the block copolymer.

4. The resin film according to claim 1 or 2, wherein the silane coupling compound and/or the organometallic compound is a silane coupling compound,

5. The resin film according to claim 4, wherein the silane coupling compound contains two amino groups capable of having substituents per molecule,

6. A laminate comprising a base film and the resin film according to any one of claims 1 to 5, wherein the resin film is in direct contact with a surface of the base film.