KR20110105346A - Gas barrier laminated film - Google Patents

Abstract

Provided is a gas barrier laminate film that is excellent in transparency, heat resistance, impact resistance and dimensional stability.
It consists of curable resin composition containing curable resin which has cage type silsesquioxane structure, The tensile elasticity modulus in a tensile stress-strain curve is 2000 Mpa or more, the linear expansion coefficient is 80 ppm / K or less, and the glass transition temperature is 300 degreeC or more. It consists of a curable resin composition comprising a curable resin having a first layer and a cage-type silsesquioxane structure, and has a yield point at a tensile modulus of 100 MPa or more in a tensile stress-strain curve, less than the tensile modulus of the first layer, and having a yield point. The 2nd layer which shows a deformation | transformation is laminated | stacked, The gas barrier layered film characterized by the gas barrier layer provided in one or both surfaces of this laminated body.

Description

Gas barrier laminate film {GAS BARRIER LAMINATED FILM}

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 represented by liquid crystal displays, organic EL displays, plasma displays, electronic paper and the like. However, in recent years, displays are required to be thinner, lighter, larger screens, design, impact resistance, plastic instead of glass materials that have the problems such as fragile, high specific gravity, lack of flexibility and workability due to bending and impact Adaptation of the film is under consideration. Plastic films are lighter than glass materials, are less susceptible to bending and impact, and are adaptable to roll to roll production. It is especially preferable when it aims at manufacture of a flexible display.

However, a plastic film has a problem that it is low in heat resistance compared with glass, and inferior in dimensional stability by thermal expansion and absorption and dehydration of water vapor. For example, when a plastic film is used as a display substrate, high process temperature and water washing in various manufacturing processes, such as a color filter formation process, a thin film transistor formation process, a panel bonding process, an orientation film formation process, and a transparent electrode formation process, are mentioned. Since it is repeatedly exposed to a process, it is difficult to produce a display with high precision, since the damage to the board | substrate by thermal oxidation deterioration, the dimensional fluctuation behavior by thermal expansion, or water absorption and dehydration are large.

In order to prevent the influence on the substrate which is subjected to the thermal process as described above, a thin film made of an inorganic or organic compound (called a gas barrier layer) is formed on the plastic film to examine the gas barrier film provided with gas barrier properties. have. By providing the gas barrier layer, it is possible to block the contact between the substrate and oxygen to prevent thermal oxidation deterioration, to lower the water absorption rate of the substrate, and to suppress the dimensional variation behavior. In addition, the gas barrier layer serves to prevent the deterioration of light emission performance by blocking contact between elements formed in a liquid crystal display panel, an EL display panel, or the like, and gases invading from outside such as oxygen or water vapor.

As a material for such a request, a material in which a gas barrier layer is formed on a transparent plastic film such as a polycarbonate film or a polyester film is proposed (see Patent Documents 1 and 2). In addition, as a laminate, a material having a laminated structure obtained by sequentially laminating 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 on one or both surfaces of a flexible substrate is also provided. It is proposed (refer patent document 3). However, although such a material can obtain a film having excellent transparency and flexibility, the film has a glass transition temperature of 200 ° C. or lower, and therefore, it is difficult to break the gas barrier layer due to thermal expansion of the substrate in a high temperature process of 150 ° C. to 200 ° C. or higher. As a result, gas barrier properties cannot be maintained and problems such as deformation of the substrate due to heat occur.

Japanese Unexamined Patent Publication No. 2000-338901 Japanese Unexamined Patent Publication No. 2007-268711 Japanese Laid-Open Patent Publication 2005-313560

When the gas barrier layer is formed on a substrate such as a plastic film, the gas barrier layer is formed at a high temperature as much as possible, whereby it becomes possible to obtain a dense film structure and to increase the gas barrier performance. In addition, assuming that the heating process is small, the absolute amount of the dimensional change caused by thermal expansion of the substrate is reduced, so that stress to the gas barrier layer is suppressed and cracks in the gas barrier layer are prevented. Therefore, the gas barrier film which is excellent in heat resistance and provided the gas barrier layer in the low thermal expansion plastic film is calculated | required.

An object of the present invention is to provide a gas barrier laminate film excellent in transparency, heat resistance, impact resistance and dimensional stability.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in view of the above-mentioned prior art problem, and, as a result, the gas barrier layer was laminated | stacked on the laminated body which laminated | stacked the layer which consists of curable resin containing cage-type silsesquioxane structure. By providing the present invention, the present inventors have found that the present invention can be solved, and have completed the present invention.

That is, the present invention is composed of a curable resin composition containing a curable resin having a cage-type silsesquioxane structure, the tensile modulus of elasticity in the tensile stress-strain curve is 2000MPa or more, the linear expansion coefficient is 80ppm / K or less, And a curable resin composition comprising a first layer having a glass transition temperature of 300 ° C. or higher and a curable resin having a cage-type silsesquioxane structure, wherein the tensile modulus in the tensile stress-strain curve is 100 MPa or more. A second layer having a yield point and exhibiting plastic deformation while being less than the tensile modulus of elasticity is laminated, and a gas barrier layered film is provided on one or both sides of the laminate.

Since the gas barrier laminate film of the present invention is excellent in gas barrier property, transparency, heat resistance, impact resistance and dimensional stability, it is lightweight, difficult to be broken against bending and impact, and also adaptable to roll to roll production, It is especially suitable as a display substrate for the purpose of manufacture of a flexible display. Therefore, this invention is very high in the industrial use value.

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

EMBODIMENT OF THE INVENTION Hereinafter, the gas barrier laminate film of this invention is demonstrated in detail based on preferable embodiment.

(1st floor)

The first layer (inner layer material) restrains thermal expansion of the second layer, which is the other layer, suppresses thermal expansion in the in-plane direction of the gas barrier laminate film, and at the same time, the gas barrier laminate film against surface impact. It is responsible for reducing the amount of deflection. Therefore, the condition is made of a material having excellent dimensional stability and high rigidity.

Specifically, a molded product obtained by curing a curable resin containing a cage-type silsesquioxane structure, the tensile modulus of elasticity in the tensile stress-strain curve is 2000 MPa or more, the linear expansion coefficient is 80 ppm / K or less, and the glass transition temperature is 300 It is required to be a film that satisfies at least C, and it is preferable that the light transmittance at a wavelength of 550 nm is 90% or more.

When the tensile modulus of the first layer is less than 2000 MPa, the amount of warpage of the inner layer increases with respect to the surface impact, and sufficient impact resistance is not obtained as the gas barrier laminate film.

In the in-plane direction of the gas barrier laminate film, the first layer restrains the expansion of the second layer, whereby the coefficient of linear expansion as the gas barrier laminate film can be suppressed to the value of the first layer. Therefore, if the coefficient of linear expansion of the first layer is more than 80 ppm / K, the coefficient of linear expansion of the gas barrier laminate film is 80 ppm / K or more, and when the gas barrier laminate film is heat treated, the gas barrier layer and Since the difference in thermal expansion between the laminate composed of the first layer and the second layer (hereinafter also referred to as a "laminated film") becomes large, cracks are generated in the gas barrier layer, so that a sufficient gas barrier function cannot be exhibited.

It is a gas barrier laminated body film obtained when it is less than 300 degreeC with respect to the glass transition temperature of a 1st layer, and lacks important heat resistance in a display manufacturing process.

When the light transmittance at the wavelength of 550 nm of a 1st layer is less than 90%, as a gas barrier laminated body film obtained, light transparency which is important in transparent film applications, such as a liquid crystal display and an organic electroluminescent display, falls short, and the visibility of an image problems such as; visibility).

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

Preferably, in curable resin composition used for formation of a 1st layer, following General formula (1)

_{[RSiO 3/2] n (} 1)

[Wherein n represents an integer of 8 to 14, and R or General Formula (2), (3) or (4)

(3)

(3)

(4)

(4)

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

The cage-type silsesquioxane resin used for formation of the first layer has a reactive functional group composed of an organic functional group having a (meth) acryloyl group, a glycidyl group or a vinyl group on all silicon atoms, and the molecular weight distribution and molecular structure are controlled. Although it is preferable that it is a cage type silsesquioxane resin, even if one part may be substituted by the alkyl group, the phenyl group, etc., it may be a structure which does not interfere and is not a completely closed polyhedral structure but a part cleaved structure.

Moreover, curable resin composition containing cage-type silsesquioxane resin used for formation of a 1st layer uses curable resin which has compatibility and reactivity with this cage-type silsesquioxane resin other than cage-type silsesquioxane resin. It is good that it is the curable resin composition mixed. As such curable resin composition, what is necessary is just a resin composition which can be hardened by heat processing, or the resin composition which can harden | cure by irradiating an active energy ray, and is not specifically limited.

As curable resin which is compatible and reactive with cage-type silsesquioxane resin, the reactive oligomer which is a polymer of the repeating number of a structural unit about 2-20, or the reactive monomer of low molecular weight, low viscosity is mentioned, for example. Specific examples of the reactive oligomer include epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, Polystyryl ethyl methacrylate etc. can be illustrated. As the reactive monomer, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, and dish Monofunctional monomers such as clofentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate or dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate , Bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxy pivalic acid neopentyl glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di Polyfunctional monomers, such as pentaerythritol hexaacrylate, can be illustrated. .

As curable resin which has compatibility and reactivity with cage-type silsesquioxane resin, various reactive oligomers and monomers can be used other than what was illustrated above, These may be used individually, or may be used in mixture of 2 or more types.

Curable resin composition containing cage-type silsesquioxane resin used for formation of a 1st layer can add various additives in the range which does not deviate from the objective of this invention. As various additives, organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, release agents, foaming agents, nucleating agents, coloring agents, Although a crosslinking agent, a dispersal adjuvant, etc. can be illustrated, it is not limited to these.

Moreover, although curable resin composition containing cage-type silsesquioxane resin used for formation of a 1st layer needs to contain cage-type silsesquioxane resin, content of such cage-type silsesquioxane resin is 3 It is preferable that it is the quantity used as the mass% or more. When the said content is less than 3 mass%, when using the gas barrier laminated body film obtained for the use which requires a high temperature process, sufficient heat resistance will not be obtained.

Moreover, the curable resin composition containing cage-type silsesquioxane resin used for formation of a 1st layer may contain the polymerization initiator as needed. As such a polymerization initiator, what is necessary is just a photoinitiator or a thermal polymerization initiator, and a commercially available thing can be selected suitably and can be used. As a photoinitiator, an alkynphenone type, an acyl phosphine oxide type, a titanocene type, etc. are mentioned, for example. As a thermal polymerization initiator, a ketone peroxide type, a peroxy ketal type, a hydroperoxide type, a dialkyl peroxide type, a diacyl peroxide type, a peroxydicarbonate type, a peroxy ester type, etc. are mentioned, for example.

In the present invention, a suitable solvent may be used as a diluent to adjust the viscosity of the curable resin composition, but in consideration of the volatilization removal process of the solvent, time is required to reduce production efficiency, and is also obtained after curing. It is preferable that the content of the solvent in the curable resin composition to be applied is only 5% or less, and more preferably no solvent is contained due to the presence of a residual solvent or the like in the resin layer, leading to deterioration of the properties of the molded film. It is good to use. Moreover, it is preferable that such curable resin composition does not generate | occur | produce a volatile matter at the time of hardening.

(2nd floor)

When used as a gas barrier laminate film, the second layer (outer layer material) plays a role as a shock absorbing layer for preventing crack propagation of the gas barrier layer generated due to surface impact and preventing breakage of the film. Therefore, it is a necessary condition that it is a material which disperses a stress by the yielding behavior which changes by plastic deformation instead of breaking directly beyond an elastic limit with respect to external stress.

Specifically, a molded article obtained from a curable resin containing a cage-type silsesquioxane structure, wherein the tensile modulus in the tensile stress-strain curve is 100 MPa or more and is less than the tensile modulus of the first layer, but has a yield point and exhibits plastic deformation. It is necessary to be composed of, and the light transmittance at a wavelength of 550 nm is preferably 90% or more. The upper limit of the tensile modulus is about 3000 MPa.

When the tensile modulus of elasticity of the second layer is less than 100 MPa, the warpage amount of the second layer increases with respect to the surface impact, so that sufficient impact resistance cannot be obtained as the gas barrier laminate film. If the tensile modulus is a value exceeding the modulus of elasticity of the first layer, when the gas barrier laminate film is heated, the thermal expansion of the laminate film becomes large because the first layer cannot suppress thermal expansion of the second layer. As a result, the difference in thermal expansion between the gas barrier layer and the laminated film also becomes large, so that cracks occur in the gas barrier layer, so that a sufficient gas barrier function cannot be exhibited.

In addition, if the second layer is a material having a yield point in the tensile stress-strain curve and showing no plastic deformation, crack propagation of the gas barrier layer caused by the surface impact cannot be suppressed and the film breaks easily. Specifically, in the tensile stress-strain curve, it is necessary to have tensile yield elongation and tensile fracture elongation, and the tensile yield elongation is not particularly limited, and tensile elongation elongation is preferably 5% or more, more preferably 10%. The material having a tensile yield strength of preferably 10 MPa or more, more preferably 30 MPa or more, and tensile strength of preferably 10 MPa or more, and more preferably 30 MPa or more is preferable.

If the light transmittance at the wavelength of 550 nm of a 2nd layer is less than 90%, as a gas barrier laminated body film obtained, important light transmittance will run short in transparent film applications, such as a liquid crystal display and an organic electroluminescent display, and a problem, such as image visibility, will arise. .

When forming such a 2nd layer, curable resin composition containing cage-type silsesquioxane containing curable silicone copolymer resin is used.

Curable resin composition which forms a 2nd layer, Preferably it is 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 -ZY (5)

[Where R ² and R ³ are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and in R ² or R ³ , each substituent is the same as Although it may be different or it may be sufficient, at least 1 of R <^3> contained in 1 molecule is any of the group which has a vinyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring. In addition, a and b are numbers of 0 to 3, satisfying a relationship of 1≤a + b≤4, k represents a number of 8 to 14, and when k is odd, a and b are an even number including zero When odd is an even number and k is an even number, a and b are even number combinations including zero, and l represents the number of 1-2000. In addition, Z is the following general formula (6)

(Wherein R ⁴ is a group having a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R ⁴ may be the same or different from each other, and p is 0 to Represents a number of 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 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring, and in R ⁶ or R ⁷ , each substituent is the same or different. R ⁵ may be selected from a hydrogen atom, a methyl group or an ethyl group, c and e are 0 to 3, d is 8 to 14, and when d is odd, c and e are each independently. Is 0 or 2, and d is an even number, c and e are each independently 1 or 3.). It is preferable to contain a cage-type silsesquioxane-containing curable silicone copolymer having a structural unit represented by

As curable resin composition used for formation of a 2nd layer, if it is resin which has compatibility and reactivity with cage type silsesquioxane containing curable silicone copolymer, and this cage type silsesquioxane containing curable silicone copolymer, it will be specifically limited. no.

Examples of curable resins having compatibility and reactivity with cage-type silsesquioxane-containing curable silicone copolymers include reactive oligomers or polymers having a repeating number of structural units of about 2 to 20 or low molecular weight and low viscosity reactive monomers. Can be. Specific examples of the reactive oligomer include epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, Polystyryl ethyl methacrylate etc. can be illustrated. As the reactive monomer, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, and dish Monofunctional monomers such as clofentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate or dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate , Bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxy pivalic acid neopentyl glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di Polyfunctional monomers such as pentaerythritol hexaacrylate; These may be used independently, respectively, or may mix and use two or more types.

Moreover, various additives can be added in the range which does not impair the characteristic of gas barrier laminated body films, such as transparency, heat resistance, an optical characteristic, and dimensional stability. As various additives, thermoplastic resins and thermosetting elastomers, rubbers, organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, coloring agents, crosslinking agents, dispersion aids, etc. Although it can illustrate, it is not limited to these.

Content of cage-type silsesquioxane containing curable silicone copolymer in curable resin composition used for formation of a 2nd layer becomes like this. Preferably it is 3 mass% or more, More preferably, it is 15 mass% or more. When the said content is less than 3 mass%, when using the obtained laminated | multilayer film for the use which requires a high temperature process, sufficient heat resistance will not be obtained.

Moreover, you may further have a polymerization initiator in the curable resin composition containing the cage-type silsesquioxane containing curable silicone copolymer used for formation of a 2nd layer. As such a polymerization initiator, what is necessary is just a photoinitiator and a thermal polymerization initiator, and what is marketed can be selected suitably, and can be used. As a photoinitiator, an alkynphenone type, an acyl phosphine oxide type, a titanocene type, etc. are mentioned, for example. As a thermal polymerization initiator, a ketone peroxide type, a peroxy ketal type, a hydroperoxide type, a dialkyl peroxide type, a diacyl peroxide type, a peroxydicarbonate type, a peroxy ester type, etc. are mentioned, for example.

In the present invention, a suitable solvent may be used as a diluent to be used for viscosity adjustment of the curable resin composition, but in consideration of the volatilization removal process of the solvent, time is required and production efficiency decreases, and remains in the resin layer obtained after curing. Due to the presence of a solvent and the like, leading to a deterioration of the properties of the molded film, the content of the solvent in the curable resin composition to be applied is preferably only 5% or less, and more preferably, a solvent is not contained. Moreover, it is preferable that such curable resin composition does not generate | occur | produce a volatile matter at the time 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. Moreover, it is good to make thickness ratio (thickness of the 2nd layer / thickness of a 1st layer) of a 2nd layer and a 1st layer of laminated | multilayer film become 0.01 or more and 5.0 or less. 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 the first layer cannot suppress thermal expansion of the second layer by heating, and when the gas barrier layered film is provided with a gas barrier layer, the gas barrier layer Cracking becomes easy to occur. On the other hand, when the thickness ratio is less than 0.01, the second layer becomes too thin, so that the effect as the shock absorbing layer cannot be exhibited, and sufficient impact resistance is not obtained.

It is preferable to set it as the laminated | multilayer film which consists of a three-layered structure which made the 1st layer inside, and provided the 2nd layer in the outer both surfaces. The warpage, deformation, and the like can be further reduced as compared with the laminate film provided with only one outer layer material.

The linear expansion coefficient in the plane direction of the laminated film is preferably 80 ppm / K or less, and more preferably 60 ppm / K or less. If the value exceeds 80 ppm / K, when the gas barrier laminate film provided with the gas barrier layer is heated, the difference in thermal expansion between the gas barrier layer and the laminate film becomes large, so that cracks may occur in the gas barrier layer, thereby providing sufficient gas barrier function. It becomes impossible. In addition, since the thermal expansion in the in-plane direction of the outer layer material is constrained by the inner layer material having excellent low thermal expansion property with respect to the thermal expansion coefficient of the laminated film, even if the single layer exhibits the same thermal expansion behavior in the in-plane direction and the thickness direction, the outer layer can be made into a laminated film. Part of the thermal expansion of the ash appears as an increase in the thermal expansion in the thickness direction, so that the thermal expansion coefficient of the laminated film shows different values in the surface direction and the thickness direction. Therefore, the thermal expansion coefficient of the said laminated | multilayer film calculate | requires the thermal expansion coefficient of the in-plane direction in the state of a laminated | multilayer film.

There is no restriction | limiting in particular in the manufacturing method of laminated | multilayer film, For example, a 2nd layer is formed in both surfaces of the film molding which hardened curable resin composition containing cage-type silsesquioxane resin used as a 1st layer (inner layer material). Cage-type silsesquioxane-containing curable silicone used as a method of manufacturing laminated | multilayer film by apply | coating and hardening curable resin composition containing cage-type silsesquioxane containing curable silicone copolymer resin, or 2nd layer (outer layer material) A method of producing a laminated film by sandwiching a curable resin composition containing a cage-type silsesquioxane resin serving as an inner layer material between the film moldings cured curable resin composition containing a copolymer resin, and further, an outer layer material and a resin serving as an inner layer material. The method of making into a laminated | multilayer film by apply | coating and hardening simultaneously is mentioned.

(Gas barrier layer)

When the gas barrier layer is used as a member that requires a manufacturing process that is repeatedly exposed to a high process temperature or water cleaning process, it prevents thermal oxidation deterioration by blocking contact between the laminated film and oxygen, and decreases the water absorption of the laminated film, thereby causing dimensional variation. It suppresses the behavior and further prevents the deterioration of the luminous performance by blocking the contact between the elements formed in the liquid crystal display panel, the EL display panel and the like and the gas invading from outside such as oxygen or water vapor.

The gas barrier layer is preferably formed by laminating at least one or more layers, and examples thereof include silicon oxide, silicon nitride, silicon nitride oxide, aluminum oxide, tantalum oxide, and an aluminum film. It is preferable to mainly use silicon oxide, silicon nitride, and silicon nitride oxide from the viewpoint of excellent dimensional stability, which is important for barrier performance and high precision display. In addition, the thickness of the gas barrier layer is preferably 1 nm to 1000 nm, particularly preferably 10 nm to 300 nm. These gas barrier layers can also be laminated and multilayered with an organic layer. In addition, 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 the gas barrier laminate film in which the gas barrier layer is laminated on the laminate (lamination film) in which the first layer and the second layer are laminated is 90%. It is preferable to be comprised so that it may have transparency. Since the transmittance of visible light also affects the composition and thickness of the gas barrier layer, both are considered in consideration.

(Gas barrier laminate film)

It is preferable that a crack does not generate | occur | produce the gas barrier layered film in this invention, when heated up to 150 degreeC from normal temperature. When it is less than 150 degreeC with respect to a crack generation temperature, when it uses for the use which requires a high temperature process, a crack will generate | occur | produce in a gas barrier layer and it will not be able to exhibit sufficient gas barrier function.

The gas barrier laminate film preferably has a water absorption of less than 1%, more preferably 0.5% or less. When the water absorption rate is 1% or more, the dimensional change behavior of the gas barrier laminate film increases, so when used in applications requiring a high process temperature or a manufacturing process that is repeatedly exposed to water washing, cracks may occur in the gas barrier layer. It becomes impossible to exert sufficient gas barrier function.

The gas barrier laminate film preferably has a dimensional change rate of 0.1% or less in a heating test heated to 160 ° C. and then cooled under the condition of 23 ° C. 50% RH. More preferably, it is 0.01% or less. If the rate of dimensional change is 0.1% or more, the element is not formed on the substrate as the design drawing, and the position is shifted.

Hereinafter, although the gas barrier laminate film of this invention is demonstrated in detail by an Example and a comparative example, this invention is not limited to the following Example.

[Example]

Synthesis Example 1: Production of curable resin used to form first layer (inner layer material)

The cage-type silsesquioxane resin used for forming an inner layer material was synthesize | combined as follows by the method of Unexamined-Japanese-Patent No. 2004-143449.

In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 40 ml of 2-propanol (IPA) as a solvent and 3.1 g of 5% aqueous tetramethylammonium hydroxide solution (TMAH aqueous solution) as a basic catalyst were charged. 15 ml of IPA and 12.7 g of 3-methacryloxypropyltrimethoxysilane were added to the dropping funnel, and the IPA solution of 3-methacryloxypropyltrimethoxysilane was added dropwise over 30 minutes while the reaction vessel was stirred. After completion | finish of 3-methacryloxypropyl trimethoxysilane dripping, it returned to room temperature gradually 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 dehydrated with anhydrous magnesium sulfate. 8.6 g of a hydrolysis product (silsesquioxane) was obtained by filtering anhydrous magnesium sulfate and concentrating. This silsesquioxane was a colorless viscous liquid soluble in various organic solvents.

Next, 5.0 g of silsesquioxane, 20.5 ml of toluene and 0.75 g of a 10% TMAH aqueous solution were added to a reaction solvent equipped with a stirrer, Dean-Stark, and a cooling tube, and water was distilled off at 130 ° C. While toluene was heated to reflux to carry out a recondensation reaction. After stirring for 3 hours after refluxing toluene, the reaction was returned to room temperature to complete the reaction. The reaction solution was neutralized with 10% citric acid, washed with saturated brine and dehydrated with anhydrous magnesium sulfate. 4.5 g of recondensates were obtained by filtering anhydrous magnesium sulfate and concentrating. The obtained recondensate was a colorless viscous liquid soluble in various organic solvents, and mass spectrometry (LC-MS) and 1 H-NMR were measured, and it was confirmed that the resin mainly had a cage silsesquioxane structure.

Production Example 1: Preparation of Inner Layer Material 1

Cage-type silsesquioxane resin obtained by the synthesis example 1: 20 mass parts, trimethylol propane triacrylate: 25 mass parts, dicyclopentanyl diacrylate: 55 mass parts, 1-hydroxycyclohexyl phenyl ketone as a photoinitiator : 2.5 parts by mass was mixed and degassed to obtain a liquid curable resin composition. Next, using a roll coater, the sheet was cast to have a thickness of 100 μm, cured to a cumulative exposure amount of 2000 mJ / cm 2 using a high-pressure mercury lamp of 80 W / cm, and a sheet-shaped molded article having a predetermined thickness was formed. Got it. The obtained molded article was a material having a tensile modulus of 3000 MPa, a linear expansion coefficient of 45 ppm / K, a glass transition temperature of 300 ° C or higher, and satisfying physical properties as an inner layer material.

Production Example 2: Preparation of Inner Layer Material 2

Cage-type silsesquioxane resin obtained in the synthesis example 1: 30 mass parts, dicyclopentanyl diacrylate: 70 mass parts, 1-hydroxycyclohexyl phenyl ketone: 2.5 mass parts as a photoinitiator, mixed, defoaming, and liquid Except having set it as curable resin composition, the molded object was obtained by operation similar to the manufacture example 1 of an inner layer material. The obtained molded product was a material having a tensile modulus of 2500 MPa, a linear expansion coefficient of 60 ppm / K, a glass transition temperature of 300 ° C or higher, and satisfying 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 shown in Table 1.

Evaluation Method: Tensile Modulus

The tensile elastic modulus of each film molded object in 25 degreeC was measured using the tensile tester (RTE-1210 by ORIENTEC company). At this time, it was measured under the condition of the distance between the chuck 50mm and the tensile speed 2mm / min.

[Evaluation method: thermal expansion coefficient]

Using a thermomechanical analyzer (TMA4030SA, manufactured by Bruker AXS), the change in the amount of thermal expansion at 50 ° C to 150 ° C was measured under the condition of a temperature increase rate of 5 ° C / min based on the thermomechanical analysis (TMA) method.

[Evaluation method: glass transition temperature]

It measured using the dynamic viscoelasticity analyzer (DVE-V4 type | mold by the rheology company) on the conditions of the temperature increase rate of 5 degree-C / min, and the distance between chucks.

[Evaluation method: light transmittance]

The light transmittance spectrum in 400-800 nm light of each film was measured using the ultraviolet visible spectrophotometer (U4000 by Hitachi Seisakusho Co., Ltd.), and the transmittance | permeability of the light of wavelength 550 nm was shown as a representative value.

Inner layer
Produce Tensile modulus
[GPa] Thermal expansion coefficient
[ppm / K] Glass transition temperature
[° C] Transmittance
[%] Preparation Example 1 3000 45 ＞ 300 91 Production Example 2 2500 60 ＞ 300 90

Synthesis Example 2: Production of curable resin used to form second layer (outer layer material)

Cage-type silsesquioxane containing curable silicone copolymer resin used for forming an outer layer material was synthesize | combined as follows by the method of Unexamined-Japanese-Patent No. 2009-227863.

250 ml of toluene and 52.5 g of phenyltrichlorosilane were charged to the reaction vessel, and it cooled to 0 degreeC. Water was added dropwise and stirred until hydrolysis was complete. After washing the hydrolysis product, 8.3 ml of a commercially available 30% benzyltrimethylammonium hydroxide solution was added and the mixture was heated to reflux for 4 hours. The whole was then cooled and left for about 96 hours. The slurry obtained after this time was again heated to reflux for 24 hours, then cooled and filtered to obtain 37.5 g of octaphenylsilsesquioxane as a white powder.

Subsequently, 100 ml of toluene, 0.123 g (1.35 mmol, 0.49 g as a 25% methanol solution), 20.3 g (19.7 mmol) of the octaphenylsilsesquioxane and 3 were added to a reaction vessel equipped with a Deanstock and a cooling tube. 5.12 g (19.7 mmol) of methacryloxypropyl diethoxymethylsilane were added, the mixture was heated at 80 ° C for 1 hour to distill off methanol, further heated to 100 ° C, and returned to room temperature after 2 hours to complete the reaction. The reaction solution was judged that the reaction proceeded completely because the white powder of octaphenylsilsesquioxane disappeared.

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

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

Production Example 3: Production of Outer Layer Material 1

Cage-type silsesquioxane containing curable silicone copolymer resin obtained by the synthesis example 2: 30 mass parts, dicyclopentanyl diacrylate: 70 mass parts, 2-hydroxy-2-methylpropiophenone as a photoinitiator: 1.5 mass The curable resin composition obtained by mixing the parts and degassing was cast so as to have a thickness of 100 μm, and cured at an integrated exposure dose of 2000 mJ / cm 2 using an 80 W / cm high-pressure mercury lamp to form a sheet-shaped molded article having a predetermined thickness. Got it. In the tensile stress-strain curve obtained by performing a tensile test, the molded body was a material having a tensile modulus of 1650 MPa, a yield point and a plastic strain region, and satisfying physical properties as an outer layer material. The tensile stress-strain curve of the molded object obtained in FIG. 1 is shown.

Production Example 4: Manufacture of Outer Layer Material 2

Cage-type silsesquioxane containing curable silicone copolymer resin obtained by the synthesis example 2: 45 mass parts, trimethylol propane triacrylate: 55 mass parts, 2-hydroxy-2-methylpropiophenone as a photoinitiator: 1.5 mass The curable resin composition obtained by mixing the parts and degassing was cast so as to have a thickness of 100 μm, and cured at an integrated exposure dose of 2000 mJ / cm 2 using an 80 W / cm high-pressure mercury lamp to form a sheet-shaped molded article having a predetermined thickness. Got it. In the tensile stress-strain curve obtained by performing a tensile test, the molded body was a material having a tensile modulus of 1300 MPa, a yield point, and a plastic strain region, which satisfied physical properties as an outer layer material. The tensile stress-strain curve of the molded object obtained in FIG. 2 is shown.

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

[Evaluation method: tensile modulus, tensile yield strength, tensile fracture strength, tensile fracture elongation]

The tensile elastic modulus of each film molded object in 25 degreeC was measured using the tensile tester (RTE-1210 by ORIENTEC company). At this time, it was measured under the condition of the distance between the chuck 50mm and the tensile speed 2mm / min.

[Evaluation method: light transmittance]

The light transmittance spectrum in 400-800 nm light of each film was measured using the ultraviolet visible spectrophotometer (U4000 by Hitachi Seisakusho Co., Ltd.), and the transmittance | permeability of the light of wavelength 550 nm was shown as a representative value.

Manufacture of inner layer material Tensile modulus
[MPa] Tensile yield strength
[GPa] Tensile strength
[GPa] Tensile failure elongation
[%] Transmittance
[%] Production Example 3 1650 46 45 10 92 Preparation Example 4 1300 30 29 12 91

Example 1: Preparation of Gas Barrier Layered Film 1

The curable resin composition containing cage-type silsesquioxane resin obtained by the same formulation as Production Example 1 (preparation of inner layer material 1) was cast (flexible) to a thickness of 50 μm using a roll coater, and the high pressure was 80 W / cm. It hardened | cured by the accumulated exposure amount of 2000mJ / cm <2> using a mercury lamp, and the sheet-like molded object made into the predetermined thickness was obtained. Subsequently, the curable resin composition containing the cage-type silsesquioxane containing curable silicone copolymer obtained by the same formulation as the manufacture example 3 (production of the outer layer material 1) was cast on both surfaces of the obtained molded object so that it might become each 15 micrometers in thickness, It hardened | cured by the accumulated exposure amount of 2000mJ / cm <2> using the high pressure mercury lamp of 80W / cm, and the sheet-like laminated material which made it into predetermined thickness was obtained. Furthermore, the SiNO film (gas barrier layer) was formed in the surface layer both surfaces of this laminated body by the CVD method by thickness of 150 nm, and the gas barrier laminate film 1 was obtained. In addition, the film forming conditions of the gas barrier layer were set at a film forming temperature of 120 ° C., a film forming 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 Layered Films 2 to 12]

A gas barrier laminate film was prepared in the same manner as in Example 1 except that the combination of the inner layer materials (Manufacture Examples 1 and 2) and the outer layer materials (Manufacture Examples 3 and 4) or the thickness configuration were changed. Got it.

Comparative Example 1

The curable resin composition containing cage-type silsesquioxane resin obtained by the same formulation as in Production Example 1 was cast (flexible) to a thickness of 50 μm using a roll coater, and 2000 mJ using a high-pressure mercury lamp of 80 W / cm. The sheet-shaped molded object which hardened | cured by the integrated exposure amount of / cm <2> and made it into predetermined thickness was obtained. Subsequently, the curable resin composition containing the cage-type silsesquioxane containing curable silicone copolymer obtained by the same formulation as the manufacture example 3 on both surfaces of the obtained molded object was cast so that each thickness might be 15 micrometers, and the high pressure mercury lamp of 80 W / cm was cast It hardened | cured by the accumulated exposure amount of 2000mJ / cm <2>, and the sheet-like laminated film which made into predetermined thickness was obtained.

Comparative Example 2

SiNO film was formed in the molded object surface layer both surfaces on the molded object obtained by the method similar to manufacture example 1, and the gas barrier film was obtained.

Comparative Example 3

SiNO film was formed in the molded object surface layer both surfaces on the molded object obtained by the method similar to manufacture example 3, and the gas barrier film was obtained.

[Comparative Example 4]

Trimethylolpropane triacrylate (light acrylate TMP-A manufactured by Kyoeisha Kagaku Co., Ltd.) is used for the inner layer material, and dicyclopentanyl diacrylate (light acrylate manufactured by Kyoeisha Kagaku Co., Ltd.) is used as the outer layer material. Except having used DCP-A), it carried out similarly to Example 1, and obtained the gas barrier laminated body film as shown in Table 3.

The film obtained by the said Example and the comparative example ('film' said here including a laminated | multilayer film, a gas barrier laminate film, and a gas barrier film) was evaluated as follows. The results are shown in Table 3.

Evaluation Method: Saturation Absorption Test

The film cut | disconnected to 10 mm x 10 mm was heated and dried at 200 degreeC for 1 hour using the hot air oven (initial drying). Subsequently, it was immersed in pure water, completely immersed in water in the environment of 23 degreeCx50% RH, and the mass of the film after predetermined time was measured. The measurement was performed every 24 hours, and the value at the time point of reaching saturation was taken as the water absorption. Absorption rate was computed using the following formula.

c = {(b-a) / a} × 100

C: water absorption (%), a: sample mass (g) after initial drying and before immersion, and b: sample mass (g) after immersion.

Evaluation Method: Dimensional Change Rate of Film

The fine cross marking was performed so that the distance between the markings adjacent to the four corners of the film cut | disconnected by 150 mm x 150 mm might be about 100 mm, and the distance between each marking was measured correctly (precision +/- 1micrometer). After heating the film to 160 ° C. for 1 hour using a hot air oven, and leaving it to cool for 15 minutes under the condition of 23 ° C. 50% RH, the distance between the markings was measured as before the heating, and the dimensional change rate was calculated from the values. It was. The dimensional change rate was calculated using the following equation.

f = {(d-e) / d} × 100

Where f is dimensional change rate (%), d is distance between markings before heating (mu m), and e is distance between markings after heating (mu m).

[Evaluation method: heat resistance test]

The obtained film was heat-treated at predetermined temperature for 1 hour using the hot air oven, respectively, it cooled to room temperature after that, and the presence or absence of the crack of the film surface was observed with the polarization microscope. At that time, the occurrence of cracks was confirmed on the surface of the film while raising the temperature of the hot air oven at 100 ° C. for 1 hour, 110 ° C. for 1 hour, and 120 ° C. for 1 hour. The heat-resistant evaluation test which continued this until it was carried out was carried out, and Table 3 recorded the temperature before crack generation was confirmed.

[Evaluation method: Fall impact test]

Five or more tests were conducted to freely drop 10 g of the weight (R = 2.5 mm) perpendicular to the surface of the film at any height, and a height of 50% or more was evaluated to evaluate the height when the laminate film was broken.

[Evaluation method: light transmittance]

The light transmittance spectrum in 400-800 nm light of each film was measured using the ultraviolet visible spectrophotometer (U4000 by Hitachi Seisakusho Co., Ltd.), and the transmittance | permeability of the light of wavelength 550 nm was shown as a representative value.

[Evaluation method: thermal expansion coefficient]

Using a thermomechanical analyzer (TMA4030SA, manufactured by Bruker AXS), the change in the amount of thermal expansion at 50 ° C to 150 ° C was measured under the condition of a temperature increase rate of 5 ° C / min based on the thermomechanical analysis (TMA) method.

Evaluation Method: Tensile Modulus

The tensile elastic modulus of each film molded object in 25 degreeC was measured using the tensile tester (RTE-1210 by ORIENTEC company). At this time, it was measured under the condition of the distance between the chuck 50mm and the tensile speed 2mm / min.

Since the gas barrier laminate film of the present invention is excellent in gas barrier property, transparency, heat resistance, impact resistance and dimensional stability, a plastic substrate for liquid crystal display elements, a substrate for color filters, a plastic substrate for organic EL display elements, a substrate for electronic paper And a display substrate, such as a solar cell board | substrate.

Claims (4)

A curable resin composition comprising a curable resin having a cage-type silsesquioxane structure, the tensile modulus of elasticity of which is at least 2000 MPa, the coefficient of linear expansion of 80 ppm / K or less, and glass in a tensile stress-strain curve The first layer having a transition temperature of 300 ° C. or higher,
A curable resin composition comprising a curable resin having a cage-type silsesquioxane structure, the tensile modulus of which is at least 100 MPa in the tensile stress-strain curve and less than the tensile modulus of the first layer, having a yield point and exhibiting plastic deformation Two layers are stacked,
A gas barrier laminate film, wherein a gas barrier layer is provided on one or both surfaces of the laminate. The method of claim 1,
Curable resin composition which forms a 1st layer is following General formula (1)
_{[RSiO 3/2] n (} 1)
[Wherein n represents an integer of 8 to 14 and R represents the following General Formula (2), (3) or (4)
[Formula 1]

(2)

(3)

(4)
(Wherein m is an integer of 1 to 3, R ¹ represents a hydrogen atom or a methyl group), and a cage silsesquioxane resin Gas barrier laminate film. The method of claim 1,
Curable resin composition which forms a 2nd layer is 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 -ZY (5)
[Wherein R ² and R ³ are a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and in R ² or R ³ , the substituents may be the same or different. And at least one of R ³ contained in one molecule is any one of a group having a vinyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring. In addition, a and b are numbers of 0 to 3, satisfying a relationship of 1≤a + b≤4, k represents a number of 8 to 14, and when k is odd, a and b are an even number including zero When odd is an even number and k is an even number, a and b are even number combinations including zero, and l represents the number of 1-2000. In addition, Z is the following general formula (6)
(2)

(6)
(Wherein R ⁴ is a group having a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R ⁴ may be the same or different from each other, and p is 0 to Represents a number of 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 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring, and in R ⁶ or R ⁷ , each substituent is the same or different. R ⁵ may be selected from a hydrogen atom, a methyl group or an ethyl group, c and e are 0 to 3, d is 8 to 14, and when d is odd, c and e are each independently. And 0 or 2, and when d is even, c and e are each independently 1 or 3.), and a cage-type silsesquioxane-containing curable silicone copolymer having a structural unit represented by A gas barrier laminate film. The method of claim 1,
A gas barrier laminate film, wherein the gas barrier layer is composed of a layer containing at least one of silicon oxide, silicon nitride, and silicon nitride oxide as a main component.

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