JP2011194648A - Gas barrier laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate film excellent in transparency, heat resistance, impact resistance and dimensional stability.SOLUTION: In the gas barrier laminate film, a first layer which comprises a curable resin composition including a curable resin having a cage-type silsesquioxan structure and has ≥2,000 MPa tensile elastic modulus in a tensile stress-strain curve thereof, ≤80 ppm/K linear expansion coefficient and ≥300°C glass transition temperature, and a second layer which comprises another curable resin composition including another curable resin having the cage-type silsesquioxan structure, has ≥100 MPa tensile elastic modulus in the tensile stress-strain curve thereof, the linear expansion coefficient less than that of the first layer and a yield point and exhibits plastic deformation are laminated, wherein a gas barrier layer is provided on one or both surfaces of the obtained laminate.

Description

  The present invention relates to a gas barrier laminate film excellent in transparency, heat resistance, impact resistance, and dimensional stability.

  Conventionally, glass materials have been used for flat panel displays such as liquid crystal displays, organic EL displays, plasma displays, and electronic paper. However, in recent years, displays are required to be thinner, lighter, larger in screen size, designability, impact resistance, easily breakable with respect to bending and impact, high specific gravity, poor flexibility and workability, etc. As an alternative to glass materials having the above, application of plastic films is being studied. A plastic film is lighter than a glass material, has a feature that can be easily applied to roll-to-roll production, and is less susceptible to bending and impact. It is particularly suitable for the purpose of manufacturing a flexible display.

  However, the plastic film has a problem that it has lower heat resistance than glass and is inferior in dimensional stability due to thermal expansion and absorption / dehydration of water vapor. For example, when using a plastic film as a substrate for a display, in various manufacturing processes such as a color filter forming process, a thin film transistor forming process, a panel bonding process, an alignment film forming process, and a transparent electrode forming process, Because of repeated exposure, damage to the substrate due to thermal oxidative degradation, dimensional fluctuation behavior due to thermal expansion, water absorption and dehydration is large, and it is difficult to produce a highly accurate display.

  In order to prevent the influence of the thermal process on the substrate as described above, a gas barrier film that has a gas barrier property by forming a thin film (gas barrier layer) made of an inorganic or organic compound on a plastic film has been studied. ing. By providing the gas barrier layer, it is possible to prevent contact between the substrate and oxygen to prevent thermal oxidation deterioration, reduce the water absorption rate of the substrate, and suppress the dimensional variation behavior. Further, the gas barrier layer has a role of blocking the contact between an element formed in a liquid crystal display panel, an EL display panel, or the like and a gas entering from the outside such as oxygen or water vapor, thereby preventing deterioration in light emission performance.

  As materials for the above requirements, materials in which a gas barrier layer is formed on a transparent plastic film such as a polycarbonate film or a polyester film have been proposed (see Patent Documents 1 and 2). In addition, as a laminated body, a material provided with a laminated structure in which an acrylic resin layer having a thickness of 0.1 to 10 μm and an inorganic gas barrier layer having a thickness of 20 to 100 nm are sequentially laminated on one surface or both surfaces of a flexible substrate. It has been proposed (see Patent Document 3). However, although such a material can obtain a film having excellent transparency and flexibility, since the glass transition temperature of the film is 200 ° C. or less, the thermal expansion of the substrate in a high temperature process of 150 ° C. to 200 ° C. Due to the cracking of the gas barrier layer, the gas barrier property cannot be maintained, and the substrate is deformed by heat.

JP 2000-338901 A JP 2007-268711 A JP 2005-313560 A

  When the gas barrier layer is formed on a substrate such as a plastic film, the gas barrier layer is formed at a temperature as high as possible, whereby a dense film structure can be obtained and the gas barrier performance can be improved. Furthermore, assuming a heating process, reducing the absolute amount of dimensional change due to thermal expansion of the base material suppresses stress on the gas barrier layer and prevents cracking of the gas barrier layer. Therefore, a gas barrier film having a gas barrier layer on a plastic film having excellent heat resistance and low thermal expansion is required.

  An object of this invention is to provide the gas-barrier laminated body film excellent in transparency, heat resistance, impact resistance, and dimensional stability.

  As a result of intensive studies in view of the above-described problems of the prior art, the present inventors provide a gas barrier layer on a laminate in which layers made of a curable resin containing a cage silsesquioxane structure are laminated. Thus, the present inventors have found that the above problems can be solved, and have completed the present invention.

  That is, the present invention comprises a curable resin composition containing a curable resin having a cage-type silsesquioxane structure, a tensile elastic modulus in a tensile stress-strain curve of 2000 MPa or more, and a linear expansion coefficient of 80 ppm / K. A tensile elasticity in a tensile stress-strain curve comprising: a first layer having a glass transition temperature of 300 ° C. or higher; and a curable resin composition containing a curable resin having a cage silsesquioxane structure. A layer having a modulus of 100 MPa or more and less than the tensile modulus of the first layer and having a yield point and exhibiting plastic deformation, one side of the laminate, or both The gas barrier layered film is characterized in that a gas barrier layer is provided on the surface.

  Since the gas barrier laminate film of the present invention is excellent in gas barrier properties, transparency, heat resistance, impact resistance, and dimensional stability, it is lightweight, and is difficult to bend against bending and impact, It is particularly suitable as a display substrate for the purpose of manufacturing flexible displays, such as being adaptable to roll-to-roll production. Therefore, the present invention has extremely high industrial utility value.

FIG. 1 shows a tensile stress-strain curve of a molded body (second layer) obtained in Production Example 3. FIG. 2 shows a tensile stress-strain curve of the molded body (second layer) obtained in Production Example 4.

  Hereinafter, the gas barrier laminate film of the present invention will be described in detail based on preferred embodiments.

(First layer)
The first layer (inner layer material) restrains the thermal expansion of the other second layer, suppresses the thermal expansion in the in-plane direction of the gas barrier laminate film, and prevents the gas barrier laminate from surface impact. Plays the role of reducing the amount of film deflection. Therefore, it is necessary to be made of a material having excellent dimensional stability and high rigidity.

  Specifically, it is a molded article obtained by curing a curable resin containing a cage silsesquioxane structure, and has a tensile modulus of elasticity of 2000 MPa or more and a linear expansion coefficient of 80 ppm / K in a tensile stress-strain curve. Hereinafter, it is necessary that the film satisfies a glass transition temperature of 300 ° C. or higher, and the light transmittance at a wavelength of 550 nm is preferably 90% or higher.

  If the tensile modulus of the first layer is less than 2000 MPa, the amount of deflection of the inner layer with respect to the surface impact increases, and sufficient impact resistance as a gas barrier laminate film cannot be obtained.

  The thermal expansion in the in-plane direction of the gas barrier laminate film suppresses the linear expansion coefficient as the gas barrier laminate film to the value of the first layer by the first layer constraining the expansion of the second layer. It becomes possible. Therefore, when the linear expansion coefficient of the first layer exceeds 80 ppm / K, the linear expansion coefficient of the gas barrier laminate film becomes 80 ppm / K or more, and when the gas barrier laminate film is heat-treated, the gas barrier layer And a laminate composed of the first layer and the second layer (hereinafter sometimes referred to as “laminated film”), the gas barrier layer is cracked and a sufficient gas barrier The function cannot be demonstrated.

  About the glass transition temperature of a 1st layer, as a gas-barrier laminated body film obtained as it is less than 300 degreeC, the heat resistance important in a display manufacturing process is insufficient.

  If the light transmittance at a wavelength of 550 nm of the first layer is less than 90%, the obtained gas barrier laminate film has insufficient light transmittance, which is important in the use of transparent films such as liquid crystal displays and organic EL displays. Problems arise in the visibility of the image.

  In forming the first layer as described above, a curable resin composition containing a cage-type silsesquioxane resin having curability is used.

（但し、ｍは１〜３の整数であり、Ｒ¹は水素原子又はメチル基を示す）のいずれか一つから選ばれる有機官能基）である〕で表される籠型シルセスキオキサン樹脂を含有させるのが良い。 Preferably, the curable resin composition used for forming the first layer includes the following general formula (1):
[RSiO _3/2 ] _n (1)
[However, n represents an integer of 8 to 14, and R represents the following general formula (2), (3) or (4)

(Wherein m is an integer of 1 to 3 and R ¹ represents a hydrogen atom or a methyl group), a cage silsesquioxane resin represented by It is good to contain.

  The vertical silsesquioxane resin used for forming the first layer has a reactive functional group consisting of an organic functional group having a (meth) acryloyl group, a glycidyl group or a vinyl group on all silicon atoms, and has a molecular weight distribution. In addition, a cage-type silsesquioxane resin having a controlled molecular structure is preferable, but it may be partially substituted with an alkyl group, a phenyl group, or the like, and it is not a completely closed polyhedral structure. The structure may be such that the part is cleaved.

  Moreover, the curable resin composition containing the cage silsesquioxane resin used for forming the first layer is compatible with and reacts with the cage silsesquioxane resin as well as the cage silsesquioxane resin. A curable resin composition in which a curable resin having properties is mixed is preferable. Such a curable resin composition is not particularly limited as long as it is a resin composition that can be cured by heat treatment or a resin composition that can be cured by irradiation with active energy rays.

  Examples of the curable resin having compatibility and reactivity with the cage silsesquioxane resin include a reactive oligomer or a low molecular weight, low viscosity reactivity which is a polymer having about 20 to 20 structural units. Monomer. Specifically, reactive oligomers include epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyrylethyl methacrylate. Etc. can be illustrated. As reactive monomers, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate Monofunctional monomers such as phenoxyethyl acrylate and trifluoroethyl methacrylate, or dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate Acrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylolpropane triacrylate, penta Risuri tall triacrylate, pentaerythritol tetraacrylate, can be exemplified polyfunctional monomers such as dipentaerythritol hexaacrylate.

  As the curable resin having compatibility and reactivity with the cage silsesquioxane resin, in addition to those exemplified above, various reactive oligomers and monomers can be used. Two or more types may be mixed and used.

  Various additives can be added to the curable resin composition containing the cage silsesquioxane resin used for forming the first layer without departing from the object of the present invention. Various additives include organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, Examples thereof include, but are not limited to, a crosslinking agent and a dispersion aid.

  Further, the curable resin composition containing the cage silsesquioxane resin used for forming the first layer is required to contain the cage silsesquioxane resin. The content of the cage silsesquioxane resin is preferably 3% by mass or more. When the content is less than 3% by mass, sufficient heat resistance cannot be obtained when the obtained gas barrier laminate film is used for an application requiring a high-temperature process.

  Moreover, the curable resin composition containing the cage silsesquioxane resin used for forming the first layer may contain a polymerization initiator, if necessary. Such a polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, and commercially available ones can be appropriately selected and used. Examples of the photopolymerization initiator include alkynephenone, acylphosphine oxide, and titanocene. Examples of the thermal polymerization initiator include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.

  In the present invention, an appropriate solvent can be used as a diluent to adjust the viscosity of the curable resin composition. In addition, the content of the solvent in the applied curable resin composition is 5% or less because the residual solvent is present inside the resin layer obtained after curing, resulting in deterioration of the properties of the molded film. However, it is preferable to use one that does not contain a solvent. Moreover, it is preferable that such curable resin composition is a thing which does not generate | occur | produce a volatile matter in the case of hardening.

(Second layer)
When the second layer (outer layer material) is used as a gas barrier laminate film, the second layer (outer layer material) plays a role as an impact absorbing layer for suppressing crack propagation of the gas barrier layer caused by surface impact and preventing the film from breaking. Therefore, it is a necessary condition that the material disperses the stress by the yield behavior that changes to plastic deformation, rather than breaking immediately beyond the elastic limit with respect to external stress.

  Specifically, it is a molded body obtained from a curable resin containing a cage silsesquioxane structure, and has a tensile elastic modulus in a tensile stress-strain curve of 100 MPa or more, and a tensile elastic modulus of the first layer. And having a yield point and exhibiting plastic deformation, and the light transmittance at a wavelength of 550 nm is preferably 90% or more. The upper limit of the tensile elastic modulus is about 3000 MPa.

  If the tensile modulus of the second layer is less than 100 MPa, the amount of deflection of the second layer will increase with respect to the surface impact, so that sufficient impact resistance as a gas barrier laminate film cannot be obtained. Moreover, when the tensile modulus is a value exceeding the elastic modulus of the first layer, the first layer cannot suppress the thermal expansion of the second layer when the gas barrier laminate film is heated. The thermal expansion of the laminate film is increased. As a result, the difference in thermal expansion between the gas barrier layer and the laminated film also increases, so that the gas barrier layer cracks, and a sufficient gas barrier function cannot be exhibited.

  Also, if the second layer is a material that has a yield point and does not show plastic deformation in the tensile stress-strain curve, it is difficult to suppress the crack propagation of the gas barrier layer caused by the surface impact, and the film breaks easily. End up. Specifically, in the tensile stress-strain curve, it is necessary to have a tensile yield elongation and a tensile fracture elongation. The tensile yield elongation is not particularly limited, and the tensile fracture elongation is preferably 5% or more, more preferably 10 %, And a material having a tensile yield strength of preferably 10 MPa or more, more preferably 30 MPa or more, and a tensile fracture strength of preferably 10 MPa or more, more preferably 30 MPa or more.

  If the light transmittance at a wavelength of 550 nm of the second layer is less than 90%, the obtained gas barrier laminate film has insufficient light transmittance, which is important in the use of transparent films such as liquid crystal displays and organic EL displays. Problems arise in the visibility of the image.

  In forming the second layer as described above, a curable resin composition containing a cage-type silsesquioxane-containing curable silicone copolymer resin is used.

（但し、Ｒ⁴は水素原子、ビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基であって、Ｒ⁴は互いに同じか異なるものであってもよく、また、ｐは0〜30の数を示す。）で表される２価の基であり、Ｙは下記一般式（７）〜（１０）から選ばれるいずれかの１価の基である。
[(Ｒ⁵Ｏ)Ｒ⁶ ₂ＳｉＯ_1/2]_c−[Ｒ⁷ＳｉＯ_3/2]_d−[Ｏ_1/2]− （７）
[Ｒ⁵Ｏ_1/2]_e−[Ｒ⁷ＳｉＯ_3/2]_d−[Ｏ_1/2−Ｒ⁶ ₂ＳｉＯ_1/2]− （８）
(Ｒ⁵Ｏ_1/2)− （９）
(Ｒ⁵ ₃ＳｉＯ_1/2)− （１０）
（但し、Ｒ⁶及びＲ⁷はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基、又はオキシラン環を有する基であって、Ｒ⁶又はＲ⁷において、各置換基は互いに同じか異なるものであってもよく、Ｒ⁵は水素原子、メチル基又はエチル基から選ばれ、また、ｃ及びeは0〜3の数であり、dは8〜14の数であり、ｄが奇数の場合は、ｃとeはそれぞれ独立に０又は２であり、ｄが偶数の場合は、ｃとeはそれぞれ独立に１又は３である。）〕で表される構成単位を有する籠型シルセスキオキサン含有硬化性シリコーン共重合体を含有するのが良い。 The curable resin composition forming the second layer is preferably the following general formula (5)
^{_{Y- [Z- (O 1/2 -R 2}} 2 SiO 1/2) a - (R 3 SiO 3/2) k - (O 1/2) b] l -Z-Y
(5)
[However, R ² and R ³ are vinyl group, alkyl group, phenyl group, (meth) acryloyl group, allyl group or group having an oxirane ring, and in R ² or R ³ , are each substituents the same as each other? Although it may be different, at least one of R ³ contained in one molecule is any of a vinyl group, a (meth) acryloyl group, an allyl group, or a group having an oxirane ring. Further, a and b are numbers from 0 to 3, satisfying the relationship of 1 ≦ a + b ≦ 4, k is a number from 8 to 14, and when k is an odd number, a and b are zero. When k is an even number, a and b are even number combinations including zero, and l represents a number from 1 to 2000. Furthermore, Z is the following general formula (6)

(However, R ⁴ is a hydrogen atom, vinyl group, alkyl group, phenyl group, (meth) acryloyl group, allyl group or a group having an oxirane ring, and R ⁴ may be the same or different from each other, P is a divalent group represented by 0 to 30), and Y is any monovalent group selected from the following general formulas (7) to (10).
[(R ⁵ O) R ⁶ ₂ SiO _1/2 ] _c- [R ⁷ SiO _3/2 ] _d- [O _1/2 ]-(7)
[R ⁵ O _1/2 ] _e- [R ⁷ SiO _3/2 ] _d- [O _1/2 -R ⁶ ₂ SiO _1/2 ]-(8)
(R ⁵ O _1/2 ) − (9)
(R ⁵ ₃ SiO _1/2 ) − (10)
(However, R ⁶ and R ⁷ are vinyl groups, alkyl groups, phenyl groups, (meth) acryloyl groups, allyl groups, or groups having an oxirane ring, and in R ⁶ or R ⁷ , each substituent is the same as each other. R ⁵ is selected from a hydrogen atom, a methyl group or an ethyl group, c and e are a number from 0 to 3, d is a number from 8 to 14, and d is In the case of an odd number, c and e are each independently 0 or 2, and in the case where d is an even number, c and e are each independently 1 or 3.)] It is preferable to contain a silsesquioxane-containing curable silicone copolymer.

  The curable resin composition used for forming the second layer includes a cocoon-type silsesquioxane-containing curable silicone copolymer, and compatibility and reaction with the cocoon-type silsesquioxane-containing curable silicone copolymer. The resin is not particularly limited as long as it has a property.

  Examples of the curable resin having compatibility and reactivity with the cage-type silsesquioxane-containing curable silicone copolymer include, for example, a reactive oligomer that is a polymer having about 2 to 20 repeating structural units, or a low Examples thereof include reactive monomers having a low molecular weight and low molecular weight. Specifically, reactive oligomers include epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyrylethyl methacrylate. Etc. can be illustrated. As reactive monomers, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate Monofunctional monomers such as phenoxyethyl acrylate and trifluoroethyl methacrylate, or dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate Acrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylolpropane triacrylate, penta Risuri tall triacrylate, pentaerythritol tetraacrylate, can be exemplified a multifunctional monomer such as dipentaerythritol hexaacrylate, be used each of which alone or may be used in combination of two or more.

  Moreover, various additives can be added in the range which does not impair the characteristics of the gas barrier laminate film such as transparency, heat resistance, optical characteristics and dimensional stability. Various additives include thermoplastic resins and thermosetting elastomers and rubbers, organic / inorganic fillers, plasticizers, flame retardants, thermal stabilizers, antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, release agents. Examples of the molding agent, foaming agent, nucleating agent, coloring agent, cross-linking agent, and dispersion aid may be mentioned, but the invention is not limited thereto.

  The content of the cocoon-shaped silsesquioxane-containing curable silicone copolymer in the curable resin composition used for forming the second layer is preferably 3% by mass or more, more preferably 15% by mass or more. When the content is less than 3% by mass, sufficient heat resistance cannot be obtained when the obtained laminate film is used for an application requiring a high temperature process.

  Moreover, the curable resin composition containing the cage-type silsesquioxane-containing curable silicone copolymer used for forming the second layer may further have a polymerization initiator, if necessary. . Such a polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, and commercially available ones can be appropriately selected and used. Examples of the photopolymerization initiator include alkynephenone, acylphosphine oxide, and titanocene. Examples of the thermal polymerization initiator include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.

  In the present invention, an appropriate solvent can be used as a diluent to adjust the viscosity of the curable resin composition, etc., but it takes time when considering the solvent volatilization removal process, and the production efficiency is lowered. In the curable resin composition to be applied, it is preferable to keep the content of the solvent at 5% or less because a residual solvent or the like is present inside the resin layer obtained later and leads to deterioration of the properties of the molded film. More preferably, it is preferable to use one that does not contain a solvent. Moreover, it is preferable that such curable resin composition is a thing which does not generate | occur | produce a volatile matter in the case of hardening.

(Laminated film)
As for the thickness of the laminated body (laminated body film) which laminated | stacked the 1st layer and the 2nd layer, 1-400 micrometers is preferable, More preferably, it is 10-200 micrometers, More preferably, it is 50-100 micrometers. good. The thickness ratio of the second layer and the first layer of the laminated film (the thickness of the second layer / the thickness of the first layer) should be 0.01 or more and 5.0 or less. good. More preferably, it is 0.01 or more and 2.0 or less. When the thickness ratio is 5.0 or more, the second layer becomes too thick, and it becomes impossible for the first layer to suppress the thermal expansion of the second layer by heating, and the gas barrier property provided with the gas barrier layer When a laminate film is used, cracks are likely to occur in the gas barrier layer. On the other hand, if the thickness ratio is less than 0.01, the second layer becomes too thin, and the effect as the shock absorbing layer cannot be exhibited, and sufficient impact resistance cannot be obtained.

  The laminated film is preferably a laminated film having a three-layer structure in which the first layer is on the inner side and the second layer is provided on both outer sides. Warpage, deformation, and the like can be further reduced as compared with a laminate film in which the outer layer material is provided only on one side.

  The linear expansion coefficient in the plane direction of the laminated film is preferably 80 ppm / K or less, more preferably 60 ppm / K or less. When the gas barrier laminate film provided with a gas barrier layer is heated to a value exceeding 80 ppm / K, the difference in thermal expansion between the gas barrier layer and the laminate film increases, so that the gas barrier layer is cracked and has a sufficient gas barrier function. Cannot be demonstrated. Regarding the thermal expansion coefficient of this laminated film, the thermal expansion in the in-plane direction of the outer layer material is constrained by the inner layer material excellent in low thermal expansion, so that the single layer has the same thermal expansion behavior in the in-plane direction and in the thickness direction. Even when the laminated film is used, a part of the thermal expansion of the outer layer material appears as an increase in the thermal expansion in the thickness direction, and the thermal expansion coefficient of the laminated film differs between the surface direction and the thickness direction. Will be shown. Therefore, the thermal expansion coefficient of the laminated film is obtained by obtaining the thermal expansion coefficient in the in-plane direction in the state of the laminated film.

  There is no restriction | limiting in particular in the production method of a laminated | multilayer film, For example, on both surfaces of the film molded object which hardened | cured the curable resin composition containing the vertical silsesquioxane resin used as a 1st layer (inner layer material), it is 2nd A method for producing a laminated film by applying and curing a curable resin composition containing a cocoon-type silsesquioxane-containing curable silicone copolymer resin that forms a layer, or a second layer (outer layer A film molded body obtained by curing a curable resin composition containing a cocoon-type silsesquioxane-containing curable silicone copolymer resin, and a curable resin containing a cocoon-type silsesquioxane resin used as an inner layer material. Examples thereof include a method of sandwiching a resin composition to produce a laminated film, and a method of forming a laminated film by applying and simultaneously curing an outer layer material and a resin that becomes an inner layer material.

(Gas barrier layer)
When used as a member that requires a manufacturing process that is repeatedly exposed to high process temperatures and water washing processes, the gas barrier layer prevents contact between the laminated film and oxygen to prevent thermal oxidative degradation, and reduces the water absorption rate of the laminated film. To prevent the deterioration of luminous performance by suppressing contact between the elements formed in liquid crystal display panels and EL display panels, etc., and gases entering from outside such as oxygen and water vapor. Take on.

  The gas barrier layer is preferably formed by laminating at least one layer, for example, silicon oxide, silicon nitride, silicon nitride oxide, aluminum oxide, tantalum oxide, aluminum film, etc., particularly optical characteristics, gas barrier performance. In view of excellent dimensional stability, which is important for high-definition displays, those mainly composed of silicon oxide, silicon nitride, and silicon nitride oxide are preferable. The thickness of the gas barrier layer is preferably 1 nm to 1000 nm, and particularly preferably 10 nm to 300 nm. These gas barrier layers can be laminated or multilayered with an organic layer. The gas barrier layer can be formed by a known method such as vapor deposition, sputtering, PECVD, CatCVD, coating or laminating.

  The gas barrier layer is preferably transparent, and the light transmittance at a wavelength of 550 nm in a gas barrier laminate film in which a gas barrier layer is laminated on a laminate (laminated film) obtained by laminating a first layer and a second layer. However, it is preferable to be configured to have a transparency of 90% or more. Since the visible light transmittance is affected by the composition and thickness of the gas barrier layer, both are considered.

(Gas barrier laminate film)
The gas barrier laminate film of the present invention preferably has no cracks in the gas barrier layer when heated from room temperature to 150 ° C. When the crack generation temperature is less than 150 ° C., the crack is generated in the gas barrier layer when the high temperature process is required, and a sufficient gas barrier function cannot be exhibited.

  The gas barrier laminate film preferably has a water absorption of less than 1%, more preferably 0.5% or less. When the water absorption is 1% or more, the dimensional change behavior of the gas barrier laminate film increases, so cracks are present in the gas barrier layer when used in applications that require a high process temperature or a manufacturing process that is repeatedly exposed to a water washing process. Is generated, and a sufficient gas barrier function cannot be exhibited.

  In the heating test in which the gas barrier laminate film is heated to 160 ° C. and then cooled at 23 ° C. and 50% RH, the dimensional change rate is preferably 0.1% or less. More preferably, it is 0.01% or less. If the dimensional change rate is 0.1% or more, the element cannot be formed on the substrate as shown in the design drawing, causing a positional shift.

  Hereinafter, the gas barrier laminate film of the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1: Production of curable resin used to form first layer (inner layer material)]
The cage silsesquioxane resin used for forming the inner layer material was synthesized as follows by the method described in JP-A-2004-143449.
A reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer was charged with 40 ml of 2-propanol (IPA) as a solvent and 3.1 g of a 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. . To the dropping funnel, 15 ml of IPA and 12.7 g of 3-methacryloxypropyltrimethoxysilane were added, and an IPA solution of 3-methacryloxypropyltrimethoxysilane was added dropwise at room temperature over 30 minutes while stirring the reaction vessel. After completion of dropwise addition of 3-methacryloxypropyltrimethoxysilane, the mixture was gradually returned to room temperature and stirred for 2 hours without heating. After stirring, IPA was removed under reduced pressure and dissolved in 50 ml of toluene. The reaction solution was washed with saturated brine until neutral, and then dehydrated with anhydrous magnesium sulfate. 8.6 g of hydrolysis product (silsesquioxane) was obtained by filtering off anhydrous magnesium sulfate and concentrating. This silsesquioxane was a colorless viscous liquid soluble in various organic solvents.

  Next, 5.0 g of the silsesquioxane obtained above, 20.5 ml of toluene and 0.75 g of 10% TMAH aqueous solution are put in a reaction solvent equipped with a stirrer, a Dean stack, and a cooling tube, and water is added at 130 ° C. While distilling off, toluene was heated to reflux to carry out a recondensation reaction. After stirring for 3 hours after refluxing toluene, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 10% citric acid, washed with saturated brine, and dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 4.5 g of a recondensate. The obtained recondensate is a colorless viscous liquid that is soluble in various organic solvents. As a result of mass spectrometry (LC-MS) and 1H-NMR measurement, the recondensation product mainly has a cage silsesquioxane structure. The resin was confirmed.

[Production Example 1: Production of inner layer material 1]
Vertical silsesquioxane resin obtained in Synthesis Example 1: 20 parts by mass, trimethylolpropane triacrylate: 25 parts by mass, dicyclopentanyl diacrylate: 55 parts by mass, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator : 2.5 parts by mass were mixed and defoamed to obtain a liquid curable resin composition. Next, the film was cast (cast) to a thickness of 100 μm using a roll coater, and cured at an integrated exposure amount of 2000 mJ / cm ² using an 80 W / cm high-pressure mercury lamp to obtain a predetermined thickness. A sheet-like molded body was obtained. The obtained molded body had a tensile modulus of 3000 MPa, a linear expansion coefficient of 45 ppm / K, a glass transition temperature of 300 ° C. or higher, and was a material satisfying the physical properties as an inner layer material.

[Production Example 2: Production of inner layer material 2]
The cage silsesquioxane resin obtained in Synthesis Example 1: 30 parts by mass, dicyclopentanyl diacrylate: 70 parts by mass, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator: 2.5 parts by mass, A molded body was obtained by the same operation as in Production Example 1 for the inner layer material, except that the liquid curable resin composition was defoamed. The obtained molded body had a tensile modulus of 2500 MPa, a linear expansion coefficient of 60 ppm / K, a glass transition temperature of 300 ° C. or higher, and a material satisfying the physical properties as an inner layer material.

  The inner layer candidate material films (molded bodies) obtained in Production Examples 1 and 2 were evaluated as follows, and the results are summarized in Table 1.

[Evaluation method: Tensile modulus]
Using a tensile tester (ORITEEC RTE-1210), the tensile modulus of each film molded body at 25 ° C. was measured. At this time, the measurement was performed under the conditions of a distance between chucks of 50 mm and a tensile speed of 2 mm / min.

[Evaluation method: Thermal expansion coefficient]
Using a thermomechanical analyzer (TMA4030SA manufactured by Bruker Ax), a change in the amount of thermal expansion from 50 ° C. to 150 ° C. was measured based on a thermomechanical analysis (TMA) method at a temperature rising rate of 5 ° C./min.

[Evaluation method: Glass transition temperature]
Using a dynamic viscoelasticity analyzer (DVE-V4 type manufactured by Rheology), the measurement was performed under the conditions of a heating rate of 5 ° C./min and a distance between chucks of 10 mm.

[Evaluation method: Light transmittance]
Using a UV-visible spectrophotometer (U4000 manufactured by Hitachi, Ltd.), the light transmittance spectrum of each film with light of 400 to 800 nm was measured, and the transmittance of light having a wavelength of 550 nm was shown as a representative value.

[Synthesis Example 2: Production of curable resin used to form second layer (outer layer material)]
A cage-type silsesquioxane-containing curable silicone copolymer resin used for forming the outer layer material was synthesized by the method described in JP-A-2009-227863 as follows.
The reaction vessel was charged with 250 ml of toluene and 52.5 g of phenyltrichlorosilane and cooled to 0 ° C. An appropriate amount of water was added dropwise and stirred until hydrolysis was complete. After the hydrolysis product was washed with water, 8.3 ml of a commercially available 30% benzyltrimethylammonium hydroxide solution was added, and the mixture was heated to reflux temperature for 4 hours. The whole was then cooled and left for about 96 hours. The slurry obtained after the elapse of time was heated again to the reflux temperature for 24 hours, then cooled and filtered to obtain 37.5 g of octaphenylsilsesquioxane as a white powder.

  Next, 100 ml of toluene, 0.123 g of tetramethylammonium hydroxide (1.35 mmol, 0.49 g as a 25% methanol solution), 20.3 g of the above octaphenylsilsesquioxane ( 19.7 mmol) and 5.12 g (19.7 mmol) of 3-methacryloxypropyldiethoxymethylsilane were added, heated at 80 ° C. for 1 hour to distill off methanol, further heated to 100 ° C., and returned to room temperature after 2 hours. The reaction was terminated. In the reaction solution, it was judged that the white powder of octaphenylsilsesquioxane disappeared and the reaction was completely progressed.

  The reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 19.7 g of a colorless and transparent viscous liquid in a yield of 78%. The structure of the obtained cage silsesquioxane was confirmed by GPC and NMR measurement. Furthermore, under a nitrogen atmosphere, in a reaction vessel equipped with a dropping funnel and a condenser tube, 15 ml of toluene, 9.0 g (7 mmol) of the above obtained silsesquioxane, and 4 mg (0.044 mmol, tetramethylammonium hydroxide) 153 mg) as a 2.5% methanol solution. While stirring the reaction solution at 70 ° C., 4.6 g of silanol-terminated polydimethylsiloxane (DMS-S12: Mn (number average molecular weight) = 400-700: Asmax Corporation) was added dropwise from a dropping funnel over 3 hours. The mixture was further stirred for 3 hours and then cooled to room temperature.

  The reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 12.5 g of a cocoon-type silsesquioxane-containing curable silicone copolymer as a colorless and transparent viscous liquid. As a result of measuring GPC of the obtained cocoon-shaped silsesquioxane-containing curable silicone copolymer, the weight average molecular weight (Mw) was 14000. Moreover, as a result of measuring 1H-NMR, it confirmed that it was resin which mainly used the cage silsesquioxane containing curable silicone copolymer.

[Production Example 3: Production of outer layer material 1]
Cage-type silsesquioxane-containing curable silicone copolymer resin obtained in Synthesis Example 2: 30 parts by mass, dicyclopentanyl diacrylate: 70 parts by mass, 2-hydroxy-2-methylpropio as a photopolymerization initiator Phenone: A liquid curable resin composition obtained by mixing 1.5 parts by mass and removing it is cast to a thickness of 100 μm, and an integration of 2000 mJ / cm ² using an 80 W / cm high-pressure mercury lamp. A sheet-like molded body having a predetermined thickness was obtained by curing with an exposure amount. The molded body is a material having a tensile elastic modulus of 1650 MPa, a yield point, and a plastic deformation region in a tensile stress-strain curve obtained by performing a tensile test, and satisfying physical properties as an outer layer material. there were. FIG. 1 shows a tensile stress-strain curve of the molded body obtained.

[Production Example 4: Production of outer layer material 2]
Cage-type silsesquioxane-containing curable silicone copolymer resin obtained in Synthesis Example 2: 45 parts by mass, trimethylolpropane triacrylate: 55 parts by mass, 2-hydroxy-2-methylpropiophenone as a photopolymerization initiator : Mixing 1.5 parts by mass and casting the liquid curable resin composition obtained by degassing so as to have a thickness of 100 μm, and using an 80 W / cm high-pressure mercury lamp, integrated exposure of 2000 mJ / cm ² A sheet-like molded body having a predetermined thickness was obtained by curing in an amount. The molded body is a material satisfying the physical properties as an outer layer material by performing a tensile test and having a tensile elastic modulus of 1300 MPa, a yield point, and a plastic deformation region in a tensile stress-strain curve obtained. It was. FIG. 2 shows a tensile stress-strain curve of the obtained molded body.

  The outer layer candidate material films (molded bodies) obtained in Production Examples 3 and 4 were evaluated as follows, and the results are summarized in Table 2.

[Evaluation methods: Tensile modulus, tensile yield strength, tensile fracture strength, tensile fracture elongation]
Using a tensile tester (ORITEEC RTE-1210), the tensile modulus of each film molded body at 25 ° C. was measured. At this time, the measurement was performed under the conditions of a distance between chucks of 50 mm and a tensile speed of 2 mm / min.

[Evaluation method: Light transmittance]
Using a UV-visible spectrophotometer (U4000 manufactured by Hitachi, Ltd.), the light transmittance spectrum of each film with light of 400 to 800 nm was measured, and the transmittance of light having a wavelength of 550 nm was shown as a representative value.

[Example 1: Production of gas barrier laminate film 1]
A curable resin composition containing a vertical silsesquioxane resin obtained by the same composition as in Production Example 1 (production of inner layer material 1) was cast (flowed) to a thickness of 50 μm using a roll coater. And cured using an 80 W / cm high-pressure mercury lamp with an integrated exposure amount of 2000 mJ / cm ² to obtain a sheet-like molded body having a predetermined thickness. Next, a curable resin composition containing a cage-type silsesquioxane-containing curable silicone copolymer obtained by the same formulation as in Production Example 3 (Production of outer layer material 1) on both surfaces of the obtained molded body. Each sheet was cast so as to have a thickness of 15 μm, and cured using an 80 W / cm high-pressure mercury lamp with an integrated exposure amount of 2000 mJ / cm ² to obtain a sheet-like laminate having a predetermined thickness. Furthermore, a SiNO film (gas barrier layer) was formed to a thickness of 150 nm on both surface layers of the laminate by a CVD method to obtain a gas barrier laminate film 1. The film formation conditions for the gas barrier layer were a film formation temperature of 120 ° C., a film formation gas introduction pressure of 10 Pa, a monosilane flow rate of 8 sccm, an ammonia flow rate of 20 sccm, a hydrogen flow rate of 200 sccm, and an oxygen flow rate of 30 sccm.

[Examples 2 to 12: Production of gas barrier laminate films 2 to 12]
A gas barrier laminate film as shown in Table 3 in the same manner as in Example 1 except that the combination of the inner layer material (Production Examples 1 and 2) and the outer layer material (Production Examples 3 and 4) or the thickness configuration was changed. Got.

[Comparative Example 1]
A curable resin composition containing a bowl-shaped silsesquioxane resin obtained by the same composition as in Production Example 1 was cast (cast) to a thickness of 50 μm using a roll coater, and 80 W / cm. The sheet-shaped molded body having a predetermined thickness was obtained by curing with an integrated exposure amount of 2000 mJ / cm ² using a high-pressure mercury lamp. Next, a curable resin composition containing a cocoon-shaped silsesquioxane-containing curable silicone copolymer obtained by the same formulation as in Production Example 3 on both surfaces of the obtained molded product is set to have a thickness of 15 μm. It was cast and cured using an 80 W / cm high-pressure mercury lamp with an integrated exposure amount of 2000 mJ / cm ² to obtain a sheet-like laminate film having a predetermined thickness.

[Comparative Example 2]
A SiNO film was formed on both surfaces of the molded body under the same conditions as in Example 1 on the molded body obtained by the same method as in Production Example 1 to obtain a gas barrier film.

[Comparative Example 3]
SiNO films were formed on both surfaces of the molded body under the same conditions as in Example 1 on the molded body obtained by the same method as in Production Example 3 to obtain a gas barrier film.

[Comparative Example 4]
Trimethylolpropane triacrylate (Kyoeisha Chemical Co., Ltd. light acrylate TMP-A) was used for the inner layer material, and dicyclopentanyl diacrylate (Kyoeisha Chemical Co., Ltd. light acrylate DCP-A) was used for the outer layer material. Except for this, a gas barrier laminate film was obtained in the same manner as in Example 1 as shown in Table 3.

  The films obtained in the above Examples and Comparative Examples (herein, “film” includes a laminated film, a gas barrier laminate film, and a gas barrier film) were evaluated as follows. The results are shown in Table 3.

[Evaluation method: Saturated water absorption test]
The film cut to 10 mm square was heat-dried at 200 ° C. for 1 hour using a hot air oven (initial drying). Thereafter, the film was immersed in pure water and completely immersed in water in an environment of 23 ° C. × 50% RH, and the mass of the film after a predetermined time was measured. The measurement was performed every 24 hours, and the value at the time when saturation was reached was defined as the water absorption rate. The water absorption was calculated using the following formula.
c = {(b−a) / a} × 100
Here, c: water absorption (%), a: sample mass (g) after initial drying and before immersion, b: sample mass (g) after immersion.

[Evaluation method: Dimensional change rate of film]
Fine cross-shaped markings were applied so that the distance between adjacent markings at the four corners of the film cut to 150 mm square was about 100 mm, and the distance between each marking was measured accurately (accuracy ± 1 μm). This film was heated at 160 ° C. for 1 hour using a hot air oven, then allowed to cool for 15 minutes under conditions of 23 ° C. and 50% RH, and then the distance between each marking was measured in the same manner as before heating. The dimensional change rate was determined from the value. The dimensional change rate was calculated using the following equation.
f = {(d−e) / d} × 100
Here, f: dimensional change rate (%), d: distance between markings before heating (μm), e: distance between markings after heating (μm).

[Evaluation method: Heat resistance evaluation test]
Each of the obtained films was heat-treated at a predetermined temperature for 1 hour using a hot air oven, then cooled to room temperature, and the presence or absence of cracks on the film surface was observed with a polarizing microscope. At that time, the temperature of the hot air oven is increased to 100 ° C. for 1 hour, 110 ° C. for 1 hour, 120 ° C. for 1 hour, and the temperature of the heat treatment is increased from 100 ° C. in increments of 10 ° C. on the film surface. The heat resistance evaluation test was continued until the occurrence of cracks was confirmed. Table 3 shows the temperatures just before the occurrence of cracks.

[Evaluation method: Drop weight impact test]
Tested to allow a 10g weight (R = 2.5mm) to fall freely on the surface of the film from an arbitrary height 5 times or more, and evaluate the height at which this laminate film breaks with a probability of 50% or more did.

[Evaluation method: Light transmittance]
Using a UV-visible spectrophotometer (U4000 manufactured by Hitachi, Ltd.), the light transmittance spectrum of each film with light of 400 to 800 nm was measured, and the transmittance of light having a wavelength of 550 nm was shown as a representative value.

[Evaluation method: Thermal expansion coefficient]
Using a thermomechanical analyzer (TMA4030SA manufactured by Bruker Ax), a change in the amount of thermal expansion from 50 ° C. to 150 ° C. was measured based on a thermomechanical analysis (TMA) method at a temperature rising rate of 5 ° C./min.

[Evaluation method: Tensile modulus]
Using a tensile tester (ORITEEC RTE-1210), the tensile modulus of each film molded body at 25 ° C. was measured. At this time, the measurement was performed under the conditions of a distance between chucks of 50 mm and a tensile speed of 2 mm / min.

  Since the gas barrier laminate film of the present invention is excellent in gas barrier properties, transparency, heat resistance, impact resistance, and dimensional stability, a plastic substrate for a liquid crystal display element, a substrate for a color filter, an organic EL display element It is suitable as a display substrate such as a plastic substrate, an electronic paper substrate, and a solar cell substrate.

Claims (4)

It consists of a curable resin composition containing a curable resin having a cage-type silsesquioxane structure, has a tensile modulus of elasticity of 2000 MPa or more, a linear expansion coefficient of 80 ppm / K or less, and a glass transition temperature in a tensile stress-strain curve. A first layer having a temperature of 300 ° C. or higher;
It consists of a curable resin composition containing a curable resin having a cage-type silsesquioxane structure, and has a tensile elastic modulus in a tensile stress-strain curve of 100 MPa or more and lower than the tensile elastic modulus of the first layer. And a second layer having a yield point and exhibiting plastic deformation is laminated,
A gas barrier laminate film, wherein a gas barrier layer is provided on one surface or both surfaces of the laminate. The curable resin composition forming the first layer is represented by the following general formula (1).
[RSiO _3/2 ] _n (1)
[However, n represents an integer of 8 to 14, and R represents the following general formula (2), (3) or (4)

(Wherein m is an integer of 1 to 3 and R ¹ represents a hydrogen atom or a methyl group), a cage silsesquioxane resin represented by The gas barrier laminate film according to claim 1, comprising: The curable resin composition forming the second layer is represented by the following general formula (5).
^{_{Y- [Z- (O 1/2 -R 2}} 2 SiO 1/2) a - (R 3 SiO 3/2) k - (O 1/2) b] l -Z-Y
(5)
[However, R ² and R ³ are vinyl group, alkyl group, phenyl group, (meth) acryloyl group, allyl group or group having an oxirane ring, and in R ² or R ³ , are each substituents the same as each other? Although it may be different, at least one of R ³ contained in one molecule is any of a vinyl group, a (meth) acryloyl group, an allyl group, or a group having an oxirane ring. Further, a and b are numbers from 0 to 3, satisfying the relationship of 1 ≦ a + b ≦ 4, k is a number from 8 to 14, and when k is an odd number, a and b are zero. When k is an even number, a and b are even number combinations including zero, and l represents a number from 1 to 2000. Furthermore, Z is the following general formula (6)

(However, R ⁴ is a hydrogen atom, vinyl group, alkyl group, phenyl group, (meth) acryloyl group, allyl group or a group having an oxirane ring, and R ⁴ may be the same or different from each other, P is a divalent group represented by 0 to 30), and Y is any monovalent group selected from the following general formulas (7) to (10).
[(R ⁵ O) R ⁶ ₂ SiO _1/2 ] _c- [R ⁷ SiO _3/2 ] _d- [O _1/2 ]-(7)
[R ⁵ O _1/2 ] _e- [R ⁷ SiO _3/2 ] _d- [O _1/2 -R ⁶ ₂ SiO _1/2 ]-(8)
(R ⁵ O _1/2 ) − (9)
(R ⁵ ₃ SiO _1/2 ) − (10)
(However, R ⁶ and R ⁷ are vinyl groups, alkyl groups, phenyl groups, (meth) acryloyl groups, allyl groups, or groups having an oxirane ring, and in R ⁶ or R ⁷ , each substituent is the same as each other. R ⁵ is selected from a hydrogen atom, a methyl group or an ethyl group, c and e are a number from 0 to 3, d is a number from 8 to 14, and d is In the case of an odd number, c and e are each independently 0 or 2, and in the case where d is an even number, c and e are each independently 1 or 3.)] The gas barrier laminate film according to claim 1, comprising a silsesquioxane-containing curable silicone copolymer.   2. The gas barrier laminate film according to claim 1, wherein the gas barrier layer is a layer mainly composed of at least one of silicon oxide, silicon nitride, and silicon nitride oxide.

Images