TW201235213A - Barrier laminate and method for producing barrier laminate - Google Patents

Abstract

The invention provides a barrier laminate having a structure where an inorganic layer, an organic layer and another inorganic layer are adjacent to each other in sequence. The organic layer is formed by coating a polymerizable composition in a layer form and curing the same. The polymerizable composition contains a (meth)acrylate in an amount of 50 wt% or more in terms of the solid content, and a silane coupling agent having (meth)acryloyloxy groups. The (meth)acrylate is a liquid or a solid having a viscosity of 400 mPa.s or more at 25 DEG C and 1 atm before curing, and has a (meth)acryl equivalent of 260 or less. In the barrier laminate, bubble formation in the organic layer is inhibited.

Description

201235213 VI. Description of the Invention: [Technical Field] The barrier film is a barrier-type laminate and a gas barrier IV film using the same, and a method for producing the barrier laminate is described. [Prior Art] Various gas barrier films have been previously studied (Japanese Patent Laid-Open No. Hei 2 (9) No. 2-205354, No. 2010-30290, No. 2010-105321, No. Hei No. 278167, No. 2006-193596, No. 2007-76282). When it is known in the case of an organic layer, when a monomer having a large number of functional groups is photohardened, the organic layer is improved in barrier properties. Preferably, such a monomer is formed by coating to form a layer. [Invention] [,], and, if a monomer having a large number of functional groups is coated and formed into a layer and hardened, an organic layer is formed at a high temperature. The defect of the material causes damage to the adjacent inorganic layer, and the organic layer sandwiched between the two inorganic layers particularly causes damage to the adjacent inorganic layer. The present invention is to solve the problem: the object is to provide an organic A barrier layered product in which a layer is formed into a layer shape and which is less likely to cause defects such as running of an organic layer, and a method for producing the same. The inventors of the present invention have found that, if the polymerizable composition containing a polymerizable monomer having a specific viscosity or more is applied and cured to form an organic layer, the inventors can significantly reduce the defect rate of the organic layer during the temperature treatment. It is more pronounced when the alkoxyalkylene monomer composition is hardened to form an organic layer. Further, it has been found that when the amount of light irradiation for curing the light is a specific amount or less, defects such as foaming of the organic layer can be remarkably suppressed. Specifically, it is found that the above problems can be solved by the following means. 201235213 (1) A barrier laminated body having an inorganic layer 'organic layer and an inorganic layer sequentially adjacent to each other'. The organic layer is composed of (meth) acrylate containing 50 wt% or more of IU body component and The polymerizable composition of the (meth)acryloxyl decane coupling agent was applied in a layered form and cured, and the above (meth) acrylate was 25. 〇-liquid or solid before viscosity at atmospheric pressure is 4 〇〇 mPa s or more, and the (meth)acrylic equivalent is 26 〇 or less. (2) The barrier laminate according to (1), wherein the amount of the (meth) acryloyloxy group of the (meth) acrylate is from 3 to 5. (3) The barrier layered product according to (1) or (2), wherein the (meth)acrylic acid S is a liquid or a solid having a viscosity of from (7) to above at 25 C and at atmospheric pressure. (4) The barrier layered product according to (1) or (2), wherein the (meth)acrylic acid vinegar contains at least a compound which is solid at 25 ° C and at atmospheric pressure. (5) The barrier layered product according to any one of (1) to (4) wherein the number of (mercapto)acryloxyl groups of the (meth) acrylate is 4. (6) The barrier layered product according to any one of (1) to (5) wherein the inorganic layer contains an oxide and/or a nitride of aluminum and/or bismuth. (7) The barrier layered product according to any one of (1) to (6) wherein the polymerizable composition further contains an acidic monomer. (8) A gas barrier film which has the barrier layered product according to any one of (1) to (7). (9) The gas barrier film according to (8), wherein the substrate film is a substrate film having a glass transition temperature (Tg) of 10 ° C or more. (10) A device comprising the barrier product 4 201235213r layer body according to any one of (1) to (7), or the gas barrier film according to (8) or (9). (11) A method for producing a barrier laminate, which is a method for producing a barrier laminate having a structure in which an inorganic layer, an organic layer, and an inorganic layer are sequentially adjacent to each other, characterized in that it contains 5 〇wt based on solid content The polymerizable composition of the above (fluorenyl) acrylate is coated on the inorganic layer and hardened, and the (mercapto) acrylic acid vinegar has a viscosity of 4 〇〇 mPa s or more before hardening at 25 ° C and atmospheric pressure. Liquid or solid, and (mercapto) acrylic acid equivalent is 2 (9) or less. (12) The production method according to (11), wherein the polymerizable composition further contains a Shixiyuan coupling agent containing a (fluorenyl) acryloxy group. (13) The method for producing a barrier layered product according to the above aspect, wherein the polymerizable composition is photocured and irradiated under conditions of an illuminance at an ultraviolet wavelength of 365 nm of 1200 mW/sec or less. . (14) The method for producing a barrier laminate according to any one of the aspects of the present invention, wherein the cumulative amount of ultraviolet light when the polymerizable composition is cured is 1500 mj/sec or less. (15) The method for producing a barrier laminate according to any one of (11) to (14) wherein the inorganic layer is formed by a plasma chemical vapor deposition method. (16) The method for producing a barrier laminate according to any one of (11) to (15) wherein the (mercapto) acrylate has a (fluorenyl) acryloxy group in an amount of from 3 to 5. The method for producing a barrier laminate according to any one of (11) to (16), wherein the (mercapto) acrylate has a viscosity of 1000 mPa before hardening at 25 ° C under atmospheric pressure. Liquid or solid above s. (18) The method for producing a barrier laminate according to any one of (11) to (17) wherein the (meth) acrylate is contained in at least 25. (:, a compound which is solid at 201235213 under atmospheric pressure. The method for producing a gas includes: applying the barrier film described in (8) or (9), and treating it for 15 hours or more for 1 hour or more. [Effect of the invention] Further, an apparatus for suppressing the foaming of the organic layer and a gas barrier layer can be provided. [Embodiment] The content of the present invention will be described in detail below. In the present specification, "~ The residual value of the barrier layered body of the present invention has a structure in which the inorganic layer, the organic layer and the inorganic layer are adjacently adjacent to each other. The characteristic is: the organic content will contain (4) the body composition is 5 〇wt The (meth)acrylic acid vinegar w of /0 or more and the polymerizable composition of the Shixiayuan coupling agent containing a (meth)acryloyloxy group are coated and hardened, and this (meth)-propyl The dilute vinegar is a liquid or solid on the mPa.si^ at 25t, -A pressure, and the (meth)acrylic equivalent is 26〇 or less. Previously, it is believed that the shirt function is ) When Bray is used as a material for the organic layer, However, the inventors of the present invention have found that if the cloth is formed into an organic layer (inorganic layer) which is a good functional (meth) acrylate, the performance at the time of high temperature treatment is deteriorated. Therefore, the present invention adopts a specific polymerizable composition, and succeeds in producing a barrier layered body which maintains barrier properties and does not deteriorate in performance even if an organic layer is formed by coating, and thus does not affect the inorganic layer adjacent to the organic layer. The layer is damaged. This problem is less affected by vapor phase vapor deposition polymerization, and is caused by a large area of the organic layer by solvent coating. 6 201235213 Next, the polymerizable composition of the present invention is contained. Acrylic vinegar. ((Mercapto) acrylate) The polymerizable composition used in the present invention contains (meth) acrylate as an essential component, which is a viscosity of 400 mPa at 25 ° t at atmospheric pressure. .s liquid or solid on $s, and the (meth)acrylic acid equivalent is 260 or less. If 3 (meth) acrylate is used, the foaming can be suppressed even if the organic layer is formed by coating. Propylene The ester is a liquid or solid having a viscosity of 4 〇〇 mPa·s or more before hardening, more preferably a liquid or solid having a viscosity of 5 〇〇 mPa·s or more before hardening, and more preferably a viscosity of 1 〇〇〇 mPa.s or more before hardening. The liquid or solid is particularly preferably a solid. The upper limit of the viscosity in the case of a liquid is not particularly limited, and is usually preferably a liquid of 30,000 mPa·s or less. The (meth)acrylic equivalent of '(fluorenyl) acrylate is 260 or less. The high barrier property can be maintained by using such a compound. Here, the (meth)acrylic acid equivalent means the molecular weight per mole of fluorenyl fluorenyl group. In the present invention, '(sulfanyl) The acrylic acid equivalent is preferably 2 Å or less. The lower limit of the (fluorenyl) acrylic acid equivalent is not particularly limited, and is usually 70 or more. Further, the amount of the (meth)acryloxy group of 7 U k-Bu(1) used in the present invention is preferably from 3 to 5, more preferably 4. The (fluorenyl) acrylate used in the present invention preferably contains only a carbon atom, an oxygen atom, and a hydrogen atom, and more preferably a compound represented by the following formula (A) or (B).

Ac ί —丨—u—Ac

Ac General formula (A) 201235213^ (In the general formula (A), each Ac represents a (fluorenyl) acryloxy group, and each of L1, L2, L3 and L4 is -CH2-, -CH(0H)-, -0- Or a base containing the combination of these.) J

I 0

A U-AC Formula (B) (In the formula (B), each Ac represents a (fluorenyl) acryloxy group, and each of L1, L2, L3 and L4 is -CH2-, CH(OH)-, -0- Or a group containing such a combination, each of R1 and R2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) In the general formulae (A) and (B), Ι^1, ! ^,! Each of ^ and L4 is preferably -CH2-, -Ο- or a group comprising the combinations. In the formula (Β), R1 and R2 are each preferably an ethyl group. Examples of the (fluorenyl) acrylate used in the present invention are disclosed below, but the present invention is of course not limited to these.

201235213

l+m+n+o<4

201235213.

l+m+n+o<4

In the present invention, (〇-based) acrylic acid vinegar is contained in an amount of 5 〇 Wt% or more, preferably 70% by weight or more, based on the solid content of the polymerizable composition. The upper limit is not _, usually 95 (four) or less. The invention may contain two or more kinds of (fluorenyl) acrylates, and in this case, the total amount of the oxime may be 5 Qwt% or more. (Centane coupling agent) The polymerizable grade product used in the present invention is foamed with a fluorene-containing acetophenone, such as a propyl group. 201235213. The base is more preferably an alkoxyfluorenyl group or an alkoxyethyl group. The alkoxyalkyl group contained in the catalyst is preferably the following formula (1) Table 0^) m_Si-(R2)n Formula (1) [In the above formula, 'R1 is a hospitaloxy group, and R2 is a group (R2) Base) a propyl-oxy group. m is an integer of 1 to 3, and n = 4 m. When 111 is 2 or 3, 2 or 3 R1 may be the same or different from each other. Further, when η is 2 or 3, 2 or 3 R2 may be the same or different from each other. In the formula (1), R1 is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms. When a plurality of Ris are present in the formula (1), each R1 may be the same or different, and is preferably the same. In the formula (1), the organic group represented by R2 preferably has 2 to 18 carbon atoms, more preferably 3 to 14 carbon atoms, still more preferably 4 to 10 carbon atoms. When there are a plurality of R2 in the formula (1), R2 may be the same or different from each other, and is preferably the same. The (mercapto) acryloxy group is usually located at the end of the molecule. In the formula (1), m is an integer of 1 to 3, n = 4 to m, preferably m is 2 or 3, and η is 1 or 2. More preferably, m is 3 and η is 1. Examples of the decane coupling agent used in the present invention are disclosed below, but the present invention is of course not limited to these. 201235213

〇ch3

i<_ 〇ch3

In the present invention, it is preferred to contain 3 to 3 Gwt% of a coupling agent, more preferably 1 G to 25% by weight, based on the solid content of the polymerizable composition. Further, in the present invention, it is also possible to contain two or more kinds of zeaday couplers, and in this case, the total amount of these is within the above range. (Acid monomer) In the present invention, the polymerizable composition to be used may further contain an acidic monomer to further improve the interlayer adhesion of the resulting barrier layered product. Further, when used in combination with a blistering agent, hydrolysis of the Wei coupling agent can be promoted, and the present invention can be more effectively suppressed. Therefore, Wei Shanzheng is used in combination with a decane coupling agent. 〃 & π The so-called acidic monomer refers to a monomer containing an acidic group such as a ship, a continuous acid, a scaly acid or a scaly acid. The catalyst used in the present invention is: acid =; 'more preferably _-containing or carbyl-based oxime, more preferably a phosphate group-containing (fluorenyl) acrylate. 12 201235213, ((meth) propylene oxime containing a phosphate group) The (meth) acrylate containing a carboxylic acid group is more preferably a compound represented by the following formula (p). The (meth) acrylate containing a phosphate group can further improve the adhesion to the inorganic layer. 〇

II Α〇ι-〇-Χ1-〇_ρ~〇·_ζ1 1 Formula (Ρ) ο-ζ2 (In the formula (Ρ), Ζ1 represents ac2-〇-x2-, a substituent containing no polymerizable group Or hydrogen, Z2 represents Ac3-〇X3-, a substituent containing no polymerizable group or a hydrogen atom, and Ac1, Ac2 and Ac3 each represent an acryloyl group or a methyl propylene group i, x, x2 and X3 each The divalent linking group. The compound represented by the above formula (p) is preferably a monofunctional ii represented by the following formula (P-1), a bifunctional monomer represented by the following formula (p-2), and the following formula ( a trifunctional monomer represented by ρ·3), or a mixture thereof. 〇

II

One 〇 — P — 〇 — R General formula (P-1)

I O-R2 Ο 2-0 —A c

Ac O-R2 Formula (P-2) 13 201235213

Ac n—〇 — χ1_〇—p —Ο — X2 —O — Ac2 I ^ ^ 〇 —X3 —o —A c 3 General Formula (P-3)

The definitions of Ac, Ac2, Ac3, X!, X2 and X3 are the same as in the formula (p). In the general formulae (P-1) and (P_2), R1 represents a substituent or a hydrogen atom which does not contain a polymerizable group. R2 represents a substituent or a hydrogen atom which does not contain a polymerizable group. In the general formulae (P), (Ρ-1) to (Ρ-3), X1, X2 and χ3 represent a divalent linking group', and examples thereof include: a stretching base (such as an extended ethyl group, a 1,2_ stretching) Propyl, 2 2 extended propyl (also known as 2,2-propylene, 1,1-dimethyl fluorenylene), 13-propyl, 2,2-diindenyl-U·propyl, 2_butyl-2-ethyl-u-propyl, 1,6-extension, ι,9-extension, ι, ΐ2-extension, hexadecyl, etc. An extended aryl group (such as phenylene, anthranyl), an ether group, an imido group, a carbonyl group, a fluorenyl group, and a plurality of divalent residues in which the divalent groups are connected in series (eg, poly = Shen B Oxy-ethyl, poly-propoxy-propyl, 2,2-propyl phenyl, etc.). /Han base may also have a substituent. Wherein, it is preferably an alkyl extended aryl group and the poly(tetra)-bonded divalent group, more preferably an unsubstituted extended alkyl group, an unsubstituted 1 extended 2 aryl group, and the plurality of tandemly formed two Price base. X, x and X3 are preferably an alkylene or an alkyloxycarbonylalkylene group, and combinations thereof. The substituent which does not contain a polymerizable group in the case of (f) and (P-1) to (p_3) may, for example, be a group in which a calcining 'square group' is prepared. It is preferably an alkyl group. The carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 9, still more preferably from 1 to 6. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group 2012251313t. The alkyl group may be linear, branched or cyclic, and is preferably a linear alkyl group. The Hyun group can also be substituted by an alkoxy group, an aryl group, an aryloxy group or the like. The carbon number of the aryl group is preferably from 6 to 14, more preferably from 6 to 10. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. The aryl group may also be substituted with an alkyl group, an alkoxy group, an aryloxy group or the like. In the present invention, the monomers represented by the formula (P) may be used alone or in combination of two or more. Further, when used in combination, a monofunctional monomer represented by the formula (ρ-1), a bifunctional monomer represented by the formula (Ρ_2), and a trifunctional monomer represented by the formula (Ρ-3) may also be used. Two or more combinations are used. In the present invention, a commercially available compound such as a KAYAMER series manufactured by Nippon Kayaku Co., Ltd. or a Phosmer series manufactured by Uni-Chemical Co., Ltd. can be used as it is, and a newly synthesized compound can also be used. The acidic monomer is preferably contained in an amount of 0.5 to 10% by weight based on the solid content of the polymerizable composition, and more preferably contains 7% by weight. Further, in the present invention, two or more kinds of acidic monomers may be contained, and in this case, the total amount of these is within the above range. Specific examples of the acidic monomer preferably used in the present invention are disclosed below, but the present invention is not limited to these.

15 201235213

C〇(r"\^〇co(chy3〇 ΡΜ-21

μ The polymerizable compound contained in the polymerizable composition of the present invention is preferably at least 90% by weight of (mercapto)acrylic acid vinegar, a Wei coupling agent, and any one of acidic monomers. More preferably, polymerization is carried out. All of the functional components are (formic acid ester, sulphur-burning coupling agent, and any of acidic monomers. Soil (solvent) The polymerizable composition of the present invention usually contains a solvent, for example, a vinegar-based solvent, preferably 2-butanone, propylene glycol monoethyl ether acetate, cyclohexanone. The stem of the granule is preferably from 6 to 97 wt%, more preferably from 70 to 95 wt%, of the polymerizable composition. The polymerizable composition used in the present invention may further contain a polymerization initiator. When the photopolymerization initiator is used, the content thereof is preferably 〇i mol% or more of the total amount of the polymerizable compound, more preferably 0.5 to 2 mol%. 'The polymerization reaction via the active ingredient formation reaction is appropriately controlled by this. An example of the photopolymerization initiator can be exemplified by the Irgacure series sold by Ciba Specialty Chemicals Co., Ltd. (for example, jrgacure 651,

201235213t Λ. * ^ *L

Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.), Darocure series (eg Darocure TPO, Darocure 1173, etc.), Quantacure PDO, Ezacure series sold by Siber Hegner, Japan (eg Ezacure TZM) , Ezacure TZT, Ezacure KT046, etc.). (Method of Forming Organic Layer) The method for forming the organic layer is not particularly limited as long as it is applied by a solution, and for example, a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire bar coating method, or the like can be used. It is applied by a gravure coating method, a slide coating method (Slide c〇at mettiod), or an extrusion coating method using a hopper (h〇PPer) described in the specification of US Pat. No. 2,681,294. In the present invention, the composition containing the polymerizable compound is usually hardened by irradiation. The light to be irradiated is usually ultraviolet light of a high pressure mercury lamp or a low pressure mercury lamp. The illuminance at an ultraviolet wavelength of 365 nm is preferably 12 〇〇 mw/sec or less, more preferably 1 〇〇〇 mw/sec or less. The lower limit value is not particularly limited, and is usually preferably 50 mw/sec or more. When it is set within this range, the organic layer foaming can be more effectively suppressed. Further, in the present invention, it is preferable that the integrated light of the additional line when the polymerizable composition is cured is 1500 mj/sec or less, more preferably 1200 mj/sec or less. The lower-value..., special limit, is usually preferably 1 〇〇 (four) / 祀. the above. Setting within this range is more effective in suppressing organic layer foaming. In the present invention, since oxygen in the air interferes with polymerization, the oxygen concentration is preferably high. When the concentration of the poly: is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, more preferably 0.5% or less. When the oxygen partial pressure at the time of polymerization is decreased by the pressure reduction method, the total pressure is 17 201235213 Good for 1000 Pa or less, preferably 1 〇〇Pa or less. The organic layer in the present invention is smooth and has a high film hardness. Further, the polymerization rate of the polymerizable monomer is preferably 眺 or more, more preferably 88%. The above is more preferably 9 (%) or more, and particularly refers to a ratio occurring in all of the polymerizable groups (for example, an acrylonitrile group and a methacrylic acid group) in the polymerizable composition. The polymerization rate can be quantified by the infrared absorption method to quantify 4 ^ base. There is no mechanism to change the film thickness. If the film is too versatile, the film thickness is apt to decrease. Depending on the point, the thickness of the organic layer is preferably 5 〇 2 〇〇〇 nm, and more preferably 〜 15 〇〇 nm. Further, as described above, the organic layer is preferably smooth, and the smoothness thereof is preferably less than inm, more preferably less than 0.5 nm, in terms of an average roughness (Ra value) of 1 square. It is required that the surface of the organic layer is free of foreign matter such as particles and protrudes. Therefore, film formation of the organic layer is preferably carried out in a clean room. The cleanliness is preferably below 10,000 (class), and preferably below 1 。. The hardness of the organic layer is getting better and better. When the hardness of the organic layer is high, the inorganic layer can be smoothly formed into a film, and the barrier property can be improved. The hardness of the organic layer can be expressed as a minute hardness based on the nanoimprint method. The minute hardness of the organic layer is preferably 100 N/mm or more, more preferably i5 〇 N/mm or more. (Inorganic Layer) The inorganic layer is usually a layer of a film containing a metal compound. As the method of forming the inorganic layer, any method can be used as long as the target film can be formed. For example, a physical vapor deposition method such as a vapor deposition method, a sputtering method, or an ion plating method, or a liquid phase growth method such as a chemical vapor deposition method, a plating method, or a sol-gel method is preferably 18 201235213, a plasma chemical vapor phase. Deposition method. The component contained in the inorganic layer is not particularly limited as long as it satisfies the above properties, for example, a metal oxide, a metal nitride, a metal carbon compound, a metal oxynitride or a metal oxycarbide, and preferably used in a group selected from Shi Xi, Ming, An oxide, a nitride, a carbide, an oxygenated oxide or an oxycarbide of one or more metals of indium, tin, zinc, titanium, copper, and lanthanum is preferably selected from the group consisting of Shi Xi, Shao, and Indium. Oxides, nitrides or oxynitrides of metals in tin, rhetoric and chin, particularly preferably as stellite or nitride. These may also contain other elements as an accessory component. The present invention is similar in terms of average coarse sugar (Ra value) and less than 1 mn, more preferably 〇 5 M or less. Below the indoor level, it is better that the thickness of the β π side is less than 10,000. The thickness of the inorganic layer is not particularly limited, and it is preferably from 1 〇 to 200 nm per i. The inorganic layer 9 can also be a laminated structure. In this case, each sub-layer "the layer of the organic layer and the inorganic layer", ', and the composition may be different compositions. The organic layer and the inorganic layer are repeatedly formed with the inorganic layer, and the organic layer and the organic layer are organic. The layer and the inorganic layer are adjacent to each other and have an inorganic layer and an inorganic layer. Further, it may be further laminated (functional layer) in the device of the present invention, and has a functional layer. The functional layer is on the 曰 layer or in other bits of the _8 segment. Example 19 of the functional layer other than the gong*4. The 201235213 can be exemplified by a matting agent layer, a protective layer, a solvent resistant layer, and an anti-resistance layer. Electrostatic layer, smoothing layer, adhesion improving layer 'light shielding layer, antireflection layer, hard coat layer, stress relief layer, antifogging layer, antifouling layer, printed layer, easy adhesion layer, and the like. (Use of barrier laminate) The barrier laminate of the present invention is usually provided on a support, and the support can be selected for each viewpoint. In addition to the base, the support includes various devices, optical components, and the like. Specifically, the barrier laminate of the present invention can be used as a barrier layer of a gas barrier film. Further, the barrier layer and the gas barrier film of the present invention can also be used for sealing of a device requiring barrier properties. The resistive P early laminated body and the gas barrier film of the present invention can also be applied to an optical member. These matters are detailed below. <Gas Barrier Film> The gas barrier film has a substrate film and a barrier laminate formed on the substrate film. In the gas barrier film, the barrier laminate of the present invention may be provided only on one side of the base film or on both sides. Further, the gas barrier film of the present invention is a film substrate having a barrier layer having a function of blocking oxygen, moisture, nitrogen oxides, sulfur oxides, ozone, and the like in the atmosphere. The number of layers constituting the gas barrier film is not particularly limited, and is typically preferably from 2 to 30 layers, more preferably from 3 to 20 layers. <Substrate film> The gas barrier film of the present invention generally uses a plastic film as a substrate film. In particular, in the present invention, it is preferred to use a glass transition temperature (Tg) of 1 Å (a substrate film on rcu. If such a substrate film having high heat resistance is used, it is difficult to heat-treat even after the component is incorporated into 2012 20123213. Advantages of damage. Such a thermoplastic resin can be exemplified by polyethylene naphthalate (PEN: 120 ° C), polycarbonate (PC: 140 ° C), and alicyclic polyolefin (such as Zeon Corporation of Japan). made

Zeonor 1600: 160 ° C), polyarylate (PAr: 210 ° C), polyether oxime (PES: 220 ° C), polyfluorene (PSF: 190 ° C), cyclic olefin copolymer (COC: 曰 patent Compound No. 2001-150584: 162. (:), polyimine (such as Mitsubishi Gas Chemical Company's Neoprim: 260 ° C), 芴 ring modified polycarbonate (BCF-PC: 曰本专利专Compound No. 2000-227603: 225. (:), alicyclic modified polycarbonate (IP_PC: compound of Japanese Patent Laid-Open No. 2000-227603: 205 〇 propylene fluorenyl compound (Japanese Patent Laid-Open No. 2002-80616) Compound: 30 (TC or more) (Tg in parentheses). Particularly, when transparency is required, an alicyclic polyolefin or the like is preferably used. β The substrate of the present invention can be preferably used for water or oxygen, etc., even at room temperature. A sealing of an element which may deteriorate over the years is often used, and an organic electroluminescent element, a liquid crystal display element, a solar cell, a touch panel, etc. may be exemplified. A barrier laminated body of the present invention may be used for film sealing of a device. , that is, the method in which the member itself is a support, and the barrier layer of the present invention is provided on the surface thereof. The device is covered with a protective layer before the barrier layer is placed. The gas barrier film of the invention may also be used as a substrate of the device or a solid protective layer film; the solid sealing method refers to the device, and the agent is beneficial to the heart (4) A method for hardening a layer or a gas barrier surface. The vinegar resin can be exemplified as a thermosetting ring, and the photocurable two <devices> 201235213 air vent layer ruthenium barrier film can be preferably used for the cause Etc.) Causes Sexual Food 1 Inferior = Nitrogen Oxide 'Sulfur Oxide, Ozone Element, Liquid Crystalline Dry Element Plant 1° The above-mentioned examples of reading can be exemplified by organic EL, niobium, thin film transistor, touch Electronic devices such as control panel and electronic 铋=) can be preferably used for two-element devices == Sex: = Membrane seal for the device, that is, the transmissive layer of the disk is the FET device. The r-body sealing method refers to a method in which an adhesive film is formed on a device and a film is cured. Acrylic acid resin, etc., thermosetting epoxy resin, photocurability <organic EL device> An example of a film-transferred organic electroluminescence device is described in detail in Japanese Patent Laid-Open Publication No. 2007-30387. The display component> can be referred to the Japanese Patent Special Report No. 0044. "Others" Other applications can be exemplified: Japanese Patent Special Table 1〇_5121〇4 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application No. 22 201235213t • Μ. » ^ ^ A solar cell or the like described in Japanese Patent No. 7-160334. <Optical member> An example of the optical member using the gas barrier film of the present invention may, for example, be a circularly polarizing plate or the like. (Circular polarizing plate) The village barrier film of the present invention can be used as a substrate, and a W plate and a polarizing plate can be laminated to form a circularly polarizing plate. At this time, the slow axis of the plate is 45 with the absorption axis of the polarizing plate. Way to layer. Such a polarizing plate is preferably formed at 45 with respect to the length direction (MD). For the polarizing plate extending in the direction, for example, a polarizing plate described in Japanese Laid-Open Patent Publication No. 54 can be suitably used. In addition, when the conventional barrier laminate is incorporated into an organic EL device or the like, the organic layer may be defective to cause damage to itself or an adjacent inorganic layer if the heat is applied, but the present invention can also avoid such a problem. The problem is more meaningful in this regard. For example, even at 150. (: The above is carried out for more than one hour. It is preferably 170 to 20 (the TC is subjected to heat treatment for 丨 to 3 hours, and the gas barrier film can also maintain the barrier property. In the case of a bubble defect, the present invention is also significant in view of this point. Specifically, the barrier layered product and the gas barrier film of the present invention can maintain a barrier property even when heated at 20 (TC for 2 hours or more). The foaming defect of a size of 15 cm x 25 cm is 1 or less. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, and the materials, the amounts, the ratios, the treatment contents, the treatment order, and the like shown in the examples are not deviated from the present invention. The scope of the present invention is not limited to the specific examples shown below. 23 201235213r Production of gas barrier film PEN film (Te 〇nex q65FA manufactured by Teijin DuPont, thickness 1 〇〇 (4), Tg =113 C ) The A4 size was cut and the inorganic layer, the organic layer, and the inorganic layer were sequentially formed on the surface in the following order and evaluated. (Production of Inorganic Layer) Nitridation by plasma CVD on the surface of the PEN film Film (Preparation of polymerizable composition) 72 g of an acrylate compound having a composition shown in the following table, an ultraviolet polymerization initiator (KT046 manufactured by Siber Hegner Co., Ltd.), 0.6 g, and 2-butanone 11 g were prepared. Polymeric composition. In addition, when adding an additive, an acidic monomer (pM_21 manufactured by Nippon Kayaku Co., Ltd.) 0.5 g and/or 3-propenyloxypropyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.) was further blended. KBM5103) 1.6g. <Solvent Coating> The polymerizable composition prepared above was applied onto a PEN film by a spin coater, and the oxygen concentration was 〇1% or less by a nitrogen gas displacement method, and a high pressure mercury lamp was used as shown in the following table. The integrated light amount and illuminance are irradiated with ultraviolet rays to harden the organic layer to form an organic layer having a thickness of about 5 〇〇 nm. <Vapor Phase Film Formation> Polymerization prepared by flash evaporation on a PEN film under vacuum The composition is directly dried under vacuum using a high-pressure mercury lamp as shown in the following table to illuminate the organic layer by ultraviolet light to form an organic layer having a film thickness of about 5 Å. (Production of the inorganic layer) On the surface of the above organic layer The ruthenium nitride film was produced by a plasma CVD method. 24 201235213 The gas barrier film obtained was evaluated as follows. (Evaluation of barrier properties by calcium method) Using G. Nisato, PCP Bouten, P. J. Slikkerveer, etc. The method of measuring the water vapor transmission rate (g/m2/day) by the method described in the International Society for the Display of Information (SID) International Display Research Conference, pages 1435 to 1438. The temperature is set to 40 ° C and the relative humidity is set to 90%. . (Preparation of Secondary Stack) An organic layer and an inorganic layer are further laminated on the surface of the inorganic layer of the gas barrier film. (Heating evaluation) The number of bulging portions of the central 15 cm x 25 cm portion was counted in 20 (baked in a TC oven for 2 hours) in the secondary stack prepared as above. The compounds in the following table are as follows. Ught Acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd. has a functional group of 4 Μ 4〇8 Aronix M-408 manufactured by Toagosei Co., Ltd., and the number of functional groups is 3 A_BPE_4: NK Ester A-BPE manufactured by Shin-Nakamura Chemical Co., Ltd. 4, the number of functional groups is 2 M 350 East Asia Synthesis Co., Ltd. ΑΓ〇ηιχΜ·35〇, the number of functional groups is 3 NK Ester A-BPE-10 A-BPE-10: The number of functional groups manufactured by Shin-Nakamura Chemical Co., Ltd. is 2 7 〇1A ·Naka Nakamura Chemical Co., Ltd. NK Ester 701Λ, the number of functional groups is 2 A-600: Xinzhongcun Chemical ΝΚΕ^Α__, the number of functional groups is 2 The following table shows the state of solid or liquid is 25 ° C, - atmospheric pressure The shape of the lower 25 201235213 τ. The viscosity is 25 ° C, the viscosity measured by the ε-type viscosity meter at one atmosphere, the unit is mPa.s. When the additive is 〇, it means the above acidic monomer and 3-acryloxypropyl propyl group Both of the methoxylates are burned. The UV illuminance unit is "mw/sec".

As is apparent from the above table, when the polymerizable composition used in the present invention is used, even if the organic layer is layered and cured by coating, the number of bulging can be reduced to be the same as when the organic layer is formed by vapor phase vapor deposition. Level (Example 8 and Comparative Example 1). Further, it can be seen that the reduction in the number of bulges is more pronounced when the acrylate containing the oxynose group is added (Examples 1 and 3, Examples 4 and 8). It is also known that even if the organic layer is layered and hardened by coating, the viscosity of the (meth) acrylate contained in the composition of the poly 2 is low (Comparative Examples 2, 6, and ^) In particular, it is known from the comparison of Comparative Examples 2 and 4 that even a polymerizable composition mainly composed of an acrylate can be used outside the scope of the present invention at 26 201235213 < Λ. < ^/ ^/ The number of bulges in the polymerizable group film formation is very small. That is, * ^ 'The composition of the organic composition is formed by vapor phase evaporation to form an organic compound, which is Comparative Example 2', although it is added, Dabei offers a special number of gods _ poor. (4) Weiji's (four) sour vinegar, Rong knows that it will contain more than 5〇wt% of the solid content of the call for the ride as a thing (four) as a layer and Γ&quot ; θ g卩 can obtain the same excellent barrier layered body as the gas rider'. The (meth)acrylic acid vinegar is a liquid or solid which has a viscosity before the hardening at 2,500 atmospheres, and The base acid equivalent is 260 Å or less. It is also known that the effect is that the polymerizable composition contains (meth) propyl group. Further, it is more obvious that the oxime coupling agent of the fine oxime is more effective. When the ultraviolet illuminance when the organic layer is cured is set to 1000 mw/s or less, the number of bulging is further reduced. A conductive glass substrate (surface resistance of 1 〇 Ω / port) having an indium tin oxide film was prepared and washed with 2-propanol, and then subjected to ultraviolet ray treatment for 1 minute. Vacuum evaporation was performed on the substrate (anode). The following compound layer was vapor-deposited by plating (first hole transport layer) copper phthalocyanine: film thickness 10 nm (second hole transport layer) N, N'-diphenyl-N, N'-two Naphthylbenzidine: film thickness 4〇nm (light-emitting layer and electron transport layer) tris(8-hydroxyquinoline)aluminum: film thickness 60 nm 27 201235213 (electron injection layer) ratification clock. film thickness 1 nm on it A 100 nm metal aluminum was vapor-deposited as a cathode, and an organic rainbow element was formed by forming a 3 (4) thick nitride film by a parallel plate: VD method. Next, a thermosetting adhesive (Epotek 310 manufactured by Daizo-Nichimoly Co., Ltd.) was used. 'On the prepared organic EL element, the gas obtained by the example 阻J1 amniotic membrane was treated at 180 C for 2 hours, and then The barrier laminate was placed on the side of the organic EL element, and the adhesive was cured by heating at 65 ° C for 3 hours. The power measurement unit (SMU 2400 Source Measure Unit manufactured by Keithley Co., Ltd.) was applied to the organic EL element immediately after fabrication. The light was irradiated at a voltage of 7 V. The light-emitting surface was observed using a microscope, and it was confirmed that uniform light emission without a dark spot was provided. On the other hand, the gas barrier film was replaced with the gas barrier produced in Comparative Example 2. The film was produced under the same conditions, and in this case, dark spots were uneven, and uniform light emission could not be obtained. [Simple description of the diagram] Benefits [Description of main components] Yishun 28

Claims (1)

201235213 VII. Patent application scope: A kind of barrier-type laminated body with inorganic layer, organic layer and inorganic layer: structure, the financial layer will contain 5〇wt% of _ component; The propylene fondant brewing and the (meth) propylene oxide oxy group-forming polymer composition are applied in a layered form and hardened, and the (methyl) core brewing is at 25 ° C. A liquid or solid having a viscosity of 400 mPa·s or more before hardening at atmospheric pressure, and having a (meth)acrylic equivalent of 260 or less. 2. The barrier laminate according to claim 1, wherein the amount of the (meth) acryloxy group of the (meth) acrylate is from 3 to 5. 3. The barrier layered body according to the scope of the patent application, wherein the (meth) propyl group is a liquid or solid having a viscosity of 1000 mPa.s or more before hardening at 25 ° C and atmospheric pressure. . 4. The barrier laminate according to claim 2, wherein the (meth)acrylic acid S is at least a compound which is solid at hunger and atmospheric pressure. 5. The barrier laminate according to claim 1, wherein the amount of the (fluorenyl) acryloxy group of the (fluorenyl) acrylate is 4. 6. The barrier laminate according to claim 1, wherein the inorganic layer contains oxides and/or nitrides of the earth. 7. The barrier laminate according to claim 1, wherein the polymerizable composition further comprises an acidic monomer. A gas barrier film comprising the barrier laminate according to any one of claims 1 to 7 of the invention. 9. The gas barrier film according to claim 8, wherein the substrate 臈 is a substrate film having a glass transition temperature (Tg) of ioctc or more. A device comprising a barrier layered body according to any one of claims 1 to 7. 11. A method for producing a barrier layered product, which is a method for producing a barrier layered product having a structure in which an inorganic layer, an organic layer, and an inorganic layer are sequentially adjacent to each other, and is characterized by containing a solid content 50 wt% or more of a polymerizable composition of (fluorenyl) acrylate coated on an inorganic layer and cured, and the (mercapto) acrylate has a viscosity of 400 mPa·s or more before hardening at 25 ° C under atmospheric pressure. Liquid or solid, and the (fluorenyl) acrylic equivalent is 26 Å or less. 12. The production method according to claim 5, wherein the polymerizable composition further contains a (meth)acryloxy group-containing decane coupling agent. The method for producing a barrier laminate according to the invention of claim 11, wherein the polymerizable composition is photocured and irradiated under conditions of an illuminance at an ultraviolet wavelength of 365 nm of 1,200 mW/sec or less. 14. The method for producing a barrier laminate according to the invention of claim 5, wherein the cumulative amount of ultraviolet light when the polymerizable composition is cured is 1500 mj/sec or less. The method of producing a barrier laminate according to claim 11, wherein the inorganic layer is formed by a plasma CVD method. 16. The method for producing a barrier laminate according to claim n, wherein the amount of the (meth) acryloyloxy group of the (fluorenyl) acrylate is 3 to 5 〇 17. The method for producing a barrier layered product according to item n of the patent application, wherein the side (mercapto) propionate g is designed to have a hardness of 1000 mPa·s or more before hardening at 25 ° C and atmospheric pressure at 201235213. Liquid or solid. 18. The method for producing a barrier laminate according to claim 11, wherein the (meth) acrylate contains at least a compound which is solid at 25 ° C under atmospheric pressure. A method of manufacturing a device comprising: applying a gas barrier film as described in claim 8 of the invention, and treating at 150 ° C or higher for 1 hour or more. 31 201235213t same. The polymerizable composition contains a (meth)acrylate in an amount of 50 wt% or more in terms of the solid content, and a silane coupling agent having (meth)acryloyloxy groups. The (meth)acrylate is a liquid or a solid having a viscosity of 400 mPa-s or more at 25°C and 1 atm before curing, and has a (meth)acryl equivalent of 260 or less· In the barrier laminate, bubble formation in the organic layer is inhibited. The designated representative: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. If there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: none. 2 201235213 For the Chinese manual No. 101106050, there is no slash correction. Revision period: 1〇1牟¥日年月曰i + wall ί明 Patent Specification C〇06. 〇υ ^006, 〇J) ※Application number: ※Application曰: I. Name of the invention: (Chinese/English) Method for manufacturing P-resistant early laminate and barrier laminates BARRIER LAMINATE AND METHOD FOR ❾ PRODUCING BARRIER LAMINATE II. SUMMARY OF THE INVENTION The present invention provides a barrier layered body having a structure in which an inorganic layer, an organic layer and an inorganic layer are sequentially adjacent, wherein the organic layer will contain 50 wt% based on solid content. The polymerizable composition of the above (meth) acrylate and the fluorene coupling agent containing (fluorenyl) propylene oxy group is applied in a layered form and cured, and the above (meth) acrylate is at 25°. C. A liquid or solid having a viscosity of 400 mPa·s or more before hardening at an atmospheric pressure, and an equivalent weight of 260 of 260 or less. The foaming of the organic layer in the barrier laminate is suppressed. The invention provides a barrier laminate having a structure where an inorganic layer, an organic layer and another inorganic layer are adjacent to each other in sequence. The organic layer is formed by coating a polymerizable composition in a layer form and Curing the 1 201235213^ For the Chinese manual No. 101106050, there is no slash correction. The date of this revision is: May 1st, 1st, 2017. The invention is related to the invention. The present invention relates to a barrier layered body. And a gas barrier film using the same, and relates to a method for producing the barrier laminate. [Prior Art] Various gas barrier films have been previously studied (Japanese Patent Laid-Open No. 2〇〇2_205354, 2010-30290, 2010-105321, Pingm〇_278167 ❹, 2_-193596, 2007- Bulletin No. 76282). It is known that when an organic layer is produced, if a monomer having a large number of functional groups is photocured to form an organic layer, the barrier properties are improved. Such a monomer is preferably formed into a layer by coating. SUMMARY OF THE INVENTION However, it is known that when a monomer having a large number of functional groups is applied in a layered form and hardened, defects such as foaming of the organic layer may occur during the temperature treatment, causing damage to the adjacent inorganic layer, and being sandwiched between The organic layer between the two inorganic layers causes a large damage to the adjacent inorganic layer. The present invention has been made to solve the above problems, and an object of the invention is to provide a barrier laminate which is less likely to cause defects such as foaming of an organic layer even when a layer is formed by coating, and a method for producing the same. When the inventors of the present invention have studied the above-mentioned situation, it has been found that by forming and curing a polymerizable composition containing a polymerizable monomer having a specific viscosity or more to form an organic layer, the rate of occurrence of defects in the organic layer at the time of high-temperature treatment can be remarkably lowered. This effect is more pronounced when the oxide layer is coated and hardened to form an organic layer. Further, it has been found that when the amount of light irradiation for curing the light is a specific amount or less, defects such as foaming of the organic layer can be remarkably suppressed. Specifically, it has been found that the above problems can be solved by the following means. 201235213 Λ. Amendment date: May 1, 2011, No. 101106050 Chinese manual, no scribe correction (1) A barrier laminate with a structure in which an inorganic layer, an organic layer and an inorganic layer are adjacent to each other' In the organic layer, a polymerizable composition containing (5%) by weight or more of a (meth) acrylate and a (meth) acryloxy group-containing decane coupling agent as a solid component is applied as a layer and hardened. The above (mercapto) acrylic acid vinegar is a liquid or solid having a viscosity of 400 mPa·s or more before curing at 25 ° C under atmospheric pressure, and the (meth)acrylic equivalent is 26 Å or less. (2) The barrier laminate according to (1), wherein the (meth) acrylate (mercapto) acryloxy group is in an amount of from 3 to 5. (3) The barrier laminate according to (1) or (2), wherein the (mercapto)acrylic acid vinegar is 25. 〇—Liquid or solid with a viscosity of 1000 nipa.s or more before hardening at atmospheric pressure. (4) The barrier laminate according to (1) or (2), wherein the (meth) acrylate contains at least a compound which is solid at 25 t under atmospheric pressure. (5) The barrier layered product according to any one of (1) to (4) wherein the number of (mercapto)acryloxyl groups of the (meth) acrylate is 4. (6) The barrier layered product according to any one of (1) to (5) wherein the inorganic layer contains an oxide and/or a nitride of aluminum and/or bismuth. (7) The barrier layered product according to any one of (1) to (6) wherein the polymerizable composition further contains an acidic monomer. (8) A gas barrier film comprising the barrier layered product according to any one of (1) to (7). (9) The gas barrier film according to (8), wherein the substrate film has a glass transition temperature (Tg) of i〇 (a substrate film on TCa. (10) A device containing (1)~( 7) The barrier property described in any one of 201235213. Date of revision: May 1st, 1st, May 17th is the 101101050 Chinese manual without a slash correction of the layer body or (8) or (9) (11) A method for producing a barrier laminate, which is a method for producing a barrier laminate having a structure in which an inorganic layer, an organic layer, and an inorganic layer are sequentially adjacent to each other, characterized in that it contains a solid The polymerizable composition of (曱) acrylate having a composition of 5 〇 wt% or more is applied to the inorganic layer and hardened, and the (meth) acrylate is a viscosity before hardening at 25 ° C and an atmospheric pressure of 4 〇〇. The liquid or solid of 1111^8 or more, and the (meth)acrylic acid equivalent is 26 〇 or less. The production method according to (11), wherein the polymerizable composition further contains (meth) propylene oxide. (13) A method for producing a barrier layered product according to (11) or (12), wherein the ultraviolet ray wavelength is 365 The illuminance of rnn is 丨2〇〇mw/sec or less, and the polymerizable composition is photocured and irradiated. (14) The barrier layered product according to any one of (11) to (13) The method of producing a barrier layered product according to any one of (1) to (14), wherein the method of producing a barrier layered product according to any one of (1) to (14) The method for producing a barrier layered product according to any one of (11) to (15), wherein the inorganic layer is formed by a plasma chemical vapor deposition method, wherein the (meth)acrylic acid is produced. The (meth)acrylic acid g is a method for producing a barrier layered product according to any one of (11) to (16). The method for producing a barrier layered product according to any one of (11) to (17), wherein the method of producing a barrier layered product according to any one of (11) to (17), wherein (Mercapto) acrylate is contained in at least 25t: ' Under atmospheric pressure 201235213 is the 101106050 Chinese manual without a slash correction This revision period: 101 palladium < n " May 17 臼 is a solid compound. (19) A method of manufacturing a device comprising: applying the gas barrier film of (8) or (9) at 150. (: above treatment for more than 1 hour) [Effect of the Invention] According to the present invention, it is possible to provide a barrier laminate and a gas barrier film in which foaming of an organic layer is suppressed. [Embodiment] Hereinafter, the contents of the present invention will be described in detail. In the present specification, the "~" is a structure in which the inorganic layer, the organic layer, and the inorganic layer are sequentially adjacent to each other, and the barrier layered product of the present invention is used as the lower limit and the upper limit. In the organic layer, a polymerizable composition containing 50% by weight or more of a (meth) acrylate and a (meth) acryloxy group-containing ceramide coupling agent in a solid content is applied as a layer and hardened. The (meth)acrylic acid is a liquid or solid having a viscosity of 4 〇〇mPa.SJ^ before the hardening at 25t>, and the (fluorenyl)acrylic equivalent is 260 or less. It has been thought that when a polyfunctional (meth) acrylate is used as a material of the organic layer, the organic layer is preferably layered and hardened by coating. However, it is known that if the organic layer (the layer sandwiched by the inorganic layer) using polyfunctional (meth)propionic acid vinegar is formed by coating, the performance at high temperature treatment will be 2 °. Invented the materialized composition of the material, and successfully formed the second layer to form an organic layer, and also hindered the formation of the performance barrier of the miscellaneous material, so that the problem of the inorganic layer of the money layer is not vaporized in the gas phase. In the case of mineral polymerization, the influence is small, and it is a problem that occurs when a core piece or a large-area organic layer is produced. 201235213 .A is the Chinese version of the 10U06050 without a slash correction. Amendment date: May 17, 2011 Next, the (mercapto)propionate contained in the polymerizable composition of the present invention will be described. ((indenyl) acrylate) The polymerizable composition used in the present invention contains (mercapto) acrylate as a necessary component, which is at 25. (: a liquid or solid having a viscosity of 400 mPa·s or more before curing at a pressure of atmospheric pressure, and an equivalent of (meth)acrylic acid of 260 or less. If such a (meth) acrylate is contained, even if an organic layer is formed by coating, It can also inhibit foaming. 〇(曱) acrylate is a liquid or solid with a viscosity of 400 mPa·s or more before hardening, more preferably a liquid or solid having a viscosity of 5 〇〇 mpa.s or more before hardening, and more preferably hardening. The liquid or solid having a front viscosity of 1 〇 0 〇 mPa·s or more is particularly preferably a solid. The upper limit of the viscosity when the liquid is liquid is not particularly limited, and is usually preferably a liquid of 30,000 mPa·s or less. The (mercapto)acrylic acid equivalent of the acrylate is as follows. The high barrier property can be maintained by using such a compound. Here, the (mercapto)acrylic equivalent means per gram of mercapto fluorenyl group. In the present invention, the '(fluorenyl)acrylic acid equivalent is preferably 200 or less. The lower limit of the amount of U is not particularly limited, and is usually 70 or more. (meth) acrylate (1) (meth) propylene The amount of the oxime group is preferably from 3 to 5, more preferably 4. The (fluorenyl) acryl acid g used in the present invention preferably contains only a carbon atom, an oxygen atom or a hydrogen atom. S is preferably the following formula (4) Or the compound represented by (9). -L· L4 Ac Formula (A) 201235213ι is the first 〇l_5 中文 Chinese manual without a slash correction This revision period 〇1〇1年17月17 (Formula (A) Each Ac represents a (fluorenyl) acryloxy group, and L1, L2, [3 and L4 are each -CH2_, -CH(〇H)-, -〇_ or a group containing the combination of these.) I- 0 Ac-L3-C-L4-Ac^ General formula (B) (In the formula (B), each Ac represents a (fluorenyl) acryloxy group, and each of Li, L2, L3 and L4 is -CH2_, CH(OH) -, -〇_ or a group comprising such a combination, R1 and R2 are each a hydrogen atom or an alkyl group having a carbon number of 丨~3.) In the general formulae (A) and (B), ΐ^, ΐΛί3 and L4 Each of them is preferably -CH2-, -0- or a group containing the specific combination. In the formula (Β), each of 'R1 and R2 is preferably an ethyl group. The (meth) acrylate used in the present invention is disclosed below. For example, the invention is of course not limited to these. .i. 201235213 For the Chinese manual No. 101106050, there is no slash correction. Amendment date: May 17, 2011 9 201235213. Revision date: May 17, 101 is the 101106〇5〇 Chinese manual without line repair # t+m+n+〇<4 In the present invention, there is no limitation on the upper limit of the solid content of the (meth)acrylic acid of 5 Å or more of Wt% or more, and the content of f is 70 Wt% or more. Further, the present invention may also contain t/〇 or less. In this case, as long as the total amount of these is a base)-acid vinegar' (decane coupling agent) J, the polymerizable composition used in the present invention is oxygenated, and the coupling agent can be further based. The dilute coupling agent of the dilute oxy group preferably contains Oxygen Oxide 201235213, and the modified sputum period: May 17, 2011 is the 101101050 Chinese manual without a slash correction base, and more preferably contains an alkoxymethyl group. , alkoxyethyl. The alkoxyalkyl group contained in the decane coupling agent is preferably represented by the following formula (1). (Rl)m-Si_(R2)n General formula (1) [In the above formula, R1 is an alkoxy group, and r2 represents an organic group containing a (fluorenyl)acryloyloxy group. m is an integer of 1 to 3, and n = 4_m. When the melon is 2 or 3, R1 may be the same or different from each other. Further, when η is 2 or 3, 2 or 3 R2 may be the same or different from each other. ] ’ In the formula (1), 'R1 is preferably an alkoxy group of carbon: 2; There are a plurality of the formula (1), and each of them may be different, and is preferably the same. In the formula (1), the carbon number of the organic group represented by R2 is preferably from 3 to 14' and more preferably from 4 to 10. When there are a plurality of R2 in the formula (1), i: may be the same or different, and is preferably the same. (usually located at the end of the molecule. In the case of a milk-based general formula (1), m is 1 to 3 or 3, and η is 1 or 2. The following is not limited to the use of the present invention. Of course, the integer is n=4-m. Preferably, m is 2 1 , more preferably m is 3, and η is 1. An example of the flaming coupling agent, but the invention 201235213 is the 1011 〇 6 〇 5 中文 Chinese manual without a slash correction. Date: May 17, 101 In the present invention, it is preferred to contain 3 to 30% by weight of a decane coupling agent with respect to the solid content of the polymerizable composition, more preferably 丨〇255% by weight. Further, in the present invention, two or more kinds of decane coupling agents may be contained, and in this case, the total amount of these is within the above range. (Acid monomer) The polymerizable composition used in the present invention may contain an acidic monomer to further improve the interlayer adhesion of the resulting barrier laminate. Further, when used in combination with a decane coupling agent, hydrolysis of the decane coupling agent can be promoted, and foaming of the present invention can be more effectively suppressed. Therefore, the acidic monomer is preferably used in combination with the decane coupling agent used in the present invention. The acidic monomer refers to a monomer containing an acidic group such as a carboxylic acid, a sulfonic acid, a phosphoric acid or a phosphonic acid. The acidic monomer used in the present invention is preferably a carboxylic acid group or a phosphate group-containing monomer, more preferably a carboxylic acid group or a phosphate group (mercapto) acrylate, and more preferably a phosphate group (A) Base) acrylate. 12 201235213" Revision date: May, 2011, 7th, is the 101101050 Chinese manual, no scribe correction (phosphoric acid-based (meth)acrylic acid) (wei) vinegar-containing (methyl) diacid More preferably, it contains a compound represented by the following formula: (methyl group can be added) to improve the adhesion to the inorganic layer in one step. Ac Ί - 〇 - X1 - 〇 - p - o - 21 I ^ ο-z2 Formula (P) (In the formula (P), Z1 represents Ac2-〇_X2_, a substituent containing no polymerizable group, and a hydrogen atom 'Z2 represents Ac3-0-X3··, and does not contain polymerizability The substituent or the hydrogen atom of the group, Ac1, Ac2 and Ac3 each represent an acryloyl group or a methacryloyl group 'X1, X2 and X3 each represent a divalent linking group.) The compound represented by the formula (P) is preferably the following a monofunctional monomer represented by the formula (pl), a bifunctional monomer represented by the following formula (P-2), a trifunctional monomer represented by the following formula (P-3), or a mixture thereof. 〇-Xi_〇_p_〇_Ri I O-R2 General formula (P-1) 〇II Α〇1-〇-χΐ_〇_ρ_〇_χ2_〇_Α〇2 I 〇-rz pass (P-2) 13 201235213 Revision date: 1〇1年5月丨7th Ac is the 101106050 Chinese manual without a slash correction. Ac1—Ο—X1—Ο—P—〇—X2 —〇_ o-x3-oa General formula (P-3) Ac1, Ac2, Ac3, χΐ The definitions of χ2 and χ3 are the same as those in the formula (p). In the formulae (Ρ-1) and (P-2), R1 represents a substituent or a hydrogen atom which does not contain a polymerizable group, and R2 represents a a substituent of a polymerizable group or a hydrogen atom. In the formula (P), (IMHP-3), X, χ2 and χ3 represent a divalent linking group, and examples thereof include an alkyl group (e.g., an ethyl group).丨, 2_ propyl, 2, 2 _ propyl (also known as 2, 2- propylene, : u. dimercapto fluorenyl), ^ - propyl, 2, 2- dimethyl hydrazine Propyl, 2_butyl-2_ethyl·u•propyl, 1,6-extension, 1,9.Extension, U2·Extension 10: burnt base, ice-stretched hexadecane, etc.) , an extended aryl group (such as phenylene, anthranyl), screaming, imine = continuation ^, and a plurality of divalent residues of the divalent group in series (such as ^ base, poly-propoxy a propyl group, a 2,2-propyl group, and a terminal group 4). The group I may have a substituent. Among them, a preferred divalent group, more preferably an unsubstituted form: unsubstituted 1 a 2 square group and a plurality of tandem divalent groups, and a substituent of the oxime which is free of a polymerizable group in the (4) phenolic oxy-acid group, (P_l)~(Ρ_3) For example, a group or the like which is combined may be mentioned. It is preferably an alkyl group. The number of carbon atoms is preferably from 1 to 12 Å, more preferably from 1 to 9, more preferably from 1 to 6. Specific examples of the group include methyl group, ethyl group, propyl group, and butyl group H. 14 201235213 t A Revision period: May 17, 101 The stomach of the stomach No. 101106050 has no underline correction base. The alkyl group may be linear, branched or cyclic, and is preferably a linear alkyl group. The alkyl group f may be substituted with an alkoxy group, an aryl group, an aryloxy group or the like. The carbon number of the aryl group is preferably from 6 to 14, more preferably from 6 to 〇. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and an L-naphthyl group. The silk may also be substituted by a silk, a calcined oxygen group, an aryloxy group or the like. G Ο In the present invention, the monomers represented by the formula (P) may be used alone or in combination of two or more. Further, when used in combination, two of the monofunctional monomer represented by the formula (P1), the bifunctional monomer of the formula (p_2) filament, and the trifunctional monomer represented by the formula (P-3) may be used. The above combination is used. # The polymerizable monomer containing a phosphate group in the present invention may be a commercially available compound such as KAYAMER series manufactured by Nippon Kayaku Co., Ltd. or Ph=mer series manufactured by Uni-Chemieal Co., Ltd., or a newly synthesized compound. The acidic monomer preferably contains 〇5 to 10% by weight of the solid content of the polymerizable composition, and more preferably contains 1 to 7% by weight. Further, in the present invention, two or more kinds of acidic monomers may be contained, and in this case, the total amount of these is within the above range. The specific example of the use of the (IV) sex I in the invention of the invention is not limited to the above. COOH 15 201235213 Revision date: May 17, 2011 No. 101106050 Chinese manual no underline revision /?,5 ' PW-21 The polymerizable compound contained in the polymerizable composition of the present invention is preferably 3 or more and 90% by weight or more of (meth)acrylic acid vinegar, a Wei coupling agent, and an acidic one, and more preferably a polymerizable component. Any of various additives such as undoulate, decane coupling agent, and acidic monomer. (solvent) The polymerizable composition of the present invention usually contains a solvent, for example, a solvent, and is preferably a 2-top, a di-diol monoethyl acetate or a cyclohexane network. The content of the solvent is preferably 60 to 97% by weight of the polymerizable composition, and f is 70 to 95% by weight. (Polymerization Initiator) The polymerizable composition used in the present invention may further contain a polymerization initiator. The content of the first polymerization initiator is preferably 01 = 1% or more, more preferably 0.5 to 2% by weight based on the total amount of the polymerizable compound, whereby the reaction (4) reaction via the active ingredient is appropriately controlled. Examples of the photopolymerization starter can be exemplified by the Irgacure series sold by Ciba Specialty Chemicals Co., Ltd. (for example, __ 651, 16 201235213. Revision period: May 1st, 1st, May 17th, No. 101106050 Amend the Irzacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.), Darocure series (eg Darocure TPO, Darocure 1173, etc.), Quantacure PDO, Ezacure series sold by Siber Hegner, Japan (eg Ezacure TZM, Ezacure TZT, Ezacure KT046, etc.). (Method of Forming Organic Layer) The method for forming the organic layer is not particularly limited as long as it is applied by a solution, and for example, a dip coating method, an air knife coating method, a curtain coating method, a pro-coating method, or a bar coating method can be used. The method is applied by a method, an intaglio coating method, a slide coating method, or an extrusion coating method using a hopper (h〇PPer) described in the specification of US Pat. No. 2,681,294. In the present invention, the composition containing a polymerizable compound is usually hardened by light, and the light to be irradiated is usually ultraviolet rays of a high pressure mercury lamp or a low pressure mercury lamp. The illuminance at an ultraviolet wavelength of 365 nm is preferably 12 〇〇 mw/sec or less, and more preferably 1 〇〇〇 mW^eC or less. The lower limit value is not particularly limited, and usually 5 〇 mw/Sec is preferably 〇. When it is set within this range, the organic layer foaming can be more effectively suppressed. In addition, in the present invention, the total amount of the additional lines when the polymerizable composition is cured is preferably 1500 mj/sec or less, more preferably 12 〇〇mj/sec or less, and usually preferably 100 mj/sec or more. It is set in this 11 that 17 can more effectively suppress the foaming of the organic layer. It is the oxygen in the gas depressing which hinders the polymerization 'so the oxygen ratio or the partial pressure of oxygen is better. When the gas is replaced by the nitrogen gas replacement method. ^The agricultural degree is preferably 2% or less 'better than 0.5%. When the partial pressure of oxygen during polymerization is lowered by the decompression method, the total pressure is 17 um.曰期: May 17th, 1st, May, preferably less than 1000 Pa, more preferably 100 Pa or less. The organic layer in the present invention is preferably smooth and has a high film hardness. The polymerization rate of the polymerizable monomer constituting the organic layer is higher. Preferably, it is 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 92% or more. Here, the polymerization rate means all polymerizable groups in the polymerizable composition (for example, acrylonitrile). The ratio of the polymerizable group in which the reaction occurs in the group and the mercapto acrylonitrile group. The polymerization rate can be absorbed by infrared rays. The film thickness of the organic layer is not particularly limited, and if it is too thin, it is difficult to obtain film thickness uniformity, and if it is too thick, it is liable to be cracked by an external force, and the barrier property is lowered. According to the viewpoint, the organic layer is The thickness is preferably from 50 to 2000 nm, more preferably from 200 to 1500 nm. Further, as described above, the organic layer is preferably smooth, and the smoothness is preferably the average roughness (Ra value) of =lym square and less than 1 nm. More preferably, it is less than 0_5 nm. The surface of the organic layer is required to have no foreign matter or protrusions such as particles. Therefore, the film formation of the organic layer is preferably carried out in a clean room. The cleanliness is preferably 10,000 or less, 1〇〇. The hardness of the organic layer is preferably as high as possible. If the hardness of the organic layer is high, the inorganic layer can be smoothly formed into a film, and the barrier property is improved. The hardness of the organic layer can be expressed, based on nanoimprinting. The microhardness of the method. The microhardness of the organic layer is more than l〇〇N/mm or more 'more preferably 15〇N/mm or more. (Inorganic layer) The inorganic layer is usually a layer of a film containing a metal compound. The formation method is as long as the target film can be formed Any method, such as steaming, smelting, ion exchange, physical vapor deposition, physical chemical deposition, liquid deposition or sol-gel method, preferably 18 201235213 Period: May 17, 2011 is the No. 101106050 Chinese manual without electro-chemical vapor deposition. There are no special restrictions on the inorganic layer, such as metal servants & * centimeter to meet the above-mentioned properties, metal Oxynitride or gold = oxysulfide mountain: a compound of a mouse, a metal carbide L metal derivative, preferably a metalloide containing at least one selected from the group consisting of Li =, tin, zinc, titanium, copper, bismuth, and the like, Carbide, oxynitride or oxycarbide. f Select Ο 或 or gasified compounds of metals in Lu, indium, tin, zinc and titanium, especially metal oxides or rat compounds. , Hai special can also contain other elements as a secondary component. The average smoothness is preferably a value of 1 _ square 3) and less than 1 nm, more preferably 〇 5 nm or less 〇 : a difficult layer (4) of the machine layer. Below the level, more preferably below 1000. Reading the Hummer 10000 range Πΐίΐ is not particularly limited, each layer is usually in 5~ articles - the screen is connected to the raw soil 〇~200 nm. The inorganic layer may also be a laminate structure comprising a plurality of sublayers. In this case, each of the sub-layers may be the same layer (the layer of the organic layer and the inorganic layer) 4*, and the layered and the second layer and the inorganic layer. The conductive layer (functional layer) may also have a functional layer in the device of the present invention. The functional layer is detailed in the Japanese patent = body or other reported 0036 ~ section ^ ^ 627 public and other functional layers of the example 19 201235213 _ L revised period: May 17, 101 No. 101106050 Chinese specification without a scribe line correction example can be exemplified by matte, 'protective layer, solvent resistant layer, antistatic layer, flat layer, adhesion improving layer, light shielding layer, antireflection layer, hard coating layer, stress relief Layer, anti-fog layer, antifouling layer, printed layer, easy adhesion layer, and the like. (Use of barrier laminate) The barrier laminate of the present invention is usually provided on a support, and the support can be used for each cutting. The support body towel contains various benefits and optical components in addition to the base film. In other words, the barrier layer of the present invention can be used as a transfer layer for a gas transfer film. In addition, the present invention can also be used for sealing of barrier (four) parts. The barrier laminates and gas barrier films of the present invention can also be used to describe these matters in detail. Human <Gas Barrier Film> The integrated milk film has a barrier property formed on the substrate by the substrate, and the gas is turned into a gas. The film of the present invention can be provided only on the substrate film. Single side, can also be set on both sides. The gas barrier film of the present invention is a film-based f layer having a barrier layer having a function of blocking oxygen 'moisture, nitrogen oxides, sulfur emulsions, ozone, and the like in the atmosphere. Preferably, the number of layers constituting the gas barrier film is not particularly limited to 2 to 30 layers, more preferably 3 to 2 layers. <Substrate 臈> The gas barrier film of the present invention generally uses a plastic film as a substrate film. =, the present invention preferably uses a glass transition temperature (Tg) just. The substrate is 臈. If such a substrate film with high heat resistance is used, there is a correction period of 20 201235213": May 17, 2011, No. 101106050, the Chinese manual has no scribe line correction, and the heat treatment in the south of the group is not susceptible to heat treatment. The advantage of loss. Such a thermoplastic resin may, for example, be polyethylene naphthalate (PEN: 12 ° C), polycarbonate (PC. 140 ° C), or alicyclic polyolefin (such as Zeonor 1600 manufactured by Zeon Corporation of Japan: 160〇C), polyarylate (PAr: 21 (TC), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 19 (TC), cyclic olefin copolymer (C0C: 曰本专利特开2001 -150584 compound: 162. (:), polyamidiamine (such as Mitsubishi Gas Chemical Company's Neoprim: 26 (TC), anthracycline modified polycarbonate (BCF-PC: Japanese Patent Special Edition 2000_2276〇) Compound No. 3, 225 ° C), alicyclic modified polycarbonate (IP-PC: 曰 Patent No. 227603: 2Q5 ° C), acrylonitrile-based compound (Japanese Patent Laid-Open 2002) Compound No. -80616: 3(8).c or more) (including in the case of solitude. Especially when transparency is required, it is preferable to use a cyclic polyolefin such as a moon. The plate can be preferably used for water or oxygen, etc. Normally, the rhododendron is often sealed with 70 pieces of 35 years of deterioration. It can be exemplified by organic electro- _, 牛, 〉 night crystal display elements, solar cells, touch panels, etc. The ^2 layer can also be used for 11-piece film sealing, that is, the body of the body t body is disposed on the surface of the present invention. The gas barrier of the present invention is also provided with a protective layer. Covering the device. After the sealing method is used for 11 substrates or a solid protective layer, the solid sealing method refers to a method in which a coating agent is formed on 11 pieces without a special layer, a gas barrier film, and hardened. Glycolate resin, etc. β W shows thermosetting epoxy resin, photocurable propylene <device> 21 201235213 a L is the first 〇ι l〇6〇5 〇 Chinese manual without scribe correction This revision date: 101 On May 17th, the air laminate and gas barrier film can be preferably used for devices that can be degraded by specialization. Examples of the above devices can be exemplified = % battery 4 electronic reading, preferably used for organic EL The component of the crying layer can also be used for the membrane sealing of the device, that is, the body method. It can also be used in the body of the 罟 卩 卩 ^ a a a 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 ΒΒ The device is covered with a protective layer. The sealing _ is also used as a 11 piece plate, or a solid densely formed film. The method refers to a method of forming a ί=! on the device, overlapping the adhesive layer, the gas barrier film, and hardening. The gamma-acid material is mixed. 9 Wei coffee, first hardening <organic EL element> lion body resistance _ The organic electroluminescence 71 is described in detail in Japanese Laid-Open Patent Publication No. 2007-30387. <Liquid Crystal Display Element> ^〇^^^9^^ 2009-17299^^ <Others> For example, the touch panel described in Japanese Patent Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. The electronic paper described in the publication No. 98326, Japanese Patent Application No. 22 201235213, stipulated by the Japanese Patent Application No. 101106050, No. 101106050, No. <Optical member> An example of the optical member using the gas barrier film of the present invention may, for example, be a circularly polarizing plate or the like. (circular polarizer) 〇 The gas barrier film of the present invention can be used as a substrate, and an A/4 plate and a polarizing plate can be laminated to form a circularly polarizing plate. At this time, the slow axis of the [/4 plate is 45 with the absorption axis of the polarizing plate. Way to layer. Such a polarizing plate is preferably used at 45 with respect to the length direction (MD). For the polarizing plate extending in the direction, for example, a polarizing plate described in JP-A-2002-865554 can be suitably used. In addition, when the conventional barrier laminate is incorporated into an organic EL device or the like, if it is heated, the organic layer may be defective to cause damage to itself or an adjacent inorganic layer, but the present invention can also avoid such a problem. More meaningful in this regard. For example, 'even at 150. The heat treatment is carried out for 1 hour or longer, preferably at m to 20 (TC is subjected to heat treatment for 3 hours, and the gas barrier film can be maintained in a barrier property. In the case of a defect, the present invention is also significant in view of this point of view. Specifically, the barrier layered product and the gas barrier layer of the present invention are used in a range of 2 〇 0. (: heating for 2 hours or more is also maintained = barrier property) The foaming defect of the size of 15 cmx25 cm can be used below. The following system makes a more specific purchase of this M, and the examples show the materials, usage, _, processing content, processing order, etc. as long as they do not deviate from this 4 The subject matter of the stipulations can be changed as appropriate. Therefore, the scope of this _ is not limited to 23 201235213. The revised period: 1 5 1 5 May 17 第 is the 10th Π 06050 Chinese manual without a slash correction. Production of gas barrier film PEN film (Teonex Q65FA made by Teijin DuPont, thickness 1 〇〇 (4), Tg 113 C ) was cut into A4 size, and inorganic, organic and inorganic layers were sequentially formed on the surface in the following order. Evaluation. (Production of inorganic layer A tantalum nitride film was formed by plasma CVD on the surface of the PEN film. (Preparation of polymerizable composition) An acrylate compound containing 7 2 g of the composition shown in the following table was prepared, and an external starting agent was prepared. KT046) manufactured by Siber Hegner Co., Ltd. 聚合.6g and 2-butanone l10g polymerizable composition. In addition, when adding additives, it is also more acidic monomer (PM_21 manufactured by Nippon Kayaku Co., Ltd.) 0.5 g and / Or 3-propenyloxypropyltrimethoxydecane (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.6 g. <Solvent Coating> The above-prepared polymerizable composition was coated on a PEN film by a spin coater using nitrogen gas. In the replacement method, the oxygen concentration is 〇1〇/〇 or less, and the ultraviolet light is irradiated using the integrated light amount and illuminance shown in the following table of the high pressure mercury lamp, and the organic layer is cured to form an organic layer having a film thickness of about 500 nm. Membrane> The polymerizable composition prepared above was flash-deposited on a PEN film under vacuum, and the organic layer was hardened by ultraviolet light under a vacuum using a high-pressure mercury lamp as shown in the following table to form a thickness of about 5 犋. Nm has Layer (Production of Inorganic Layer) 24 201235213 _ . 1 Correction Period: May, 2011, No. 101106050 Chinese Manual, no scribe correction, the ruthenium nitride film is formed by plasma CVD on the surface of the above organic layer. The following evaluations were made on the obtained gas barrier 。. (Evaluation of barrier performance using the approximate method) International information using G. Nisato, P. C, P. B〇uten, R j. Slikkerveer, etc. The water vapor transmission rate (g/m2/day) was measured by the method described in the SID International Display Research Conference, pages 1435 to 1438. The % temperature is set to 4 〇 ° c and the relative humidity is set to 9 〇〇 / 0. (Preparation of Secondary Stack) An organic layer and an inorganic layer are further laminated on the surface of the inorganic layer of the gas barrier film. (Evaluation of heating) After the secondary stack prepared as above was baked in a 200 ° C oven for 2 hours, the number of bulging portions of the central portion of 15 cm x 25 cm was counted. The compounds in the table below are as follows. 4A, Light Acrylate PE-4A manufactured by Wings Chemical Co., Ltd., the number of functional groups is 4 M-408. The number of functional groups made by East Asia Synthetic Co., Ltd. is 3 Α·ΒΡΕ·4 · NK Ester, manufactured by Shin-Nakamura Chemical Co., Ltd. A-BPE-4, the number of functional groups is 2. Ar〇nixM_35〇 manufactured by Toagosei Co., Ltd., the number of functional groups is 3 ΒΡΕ·1〇: NK Ester A-BPE-10, s energy base number manufactured by Shin-Nakamura Chemical Co., Ltd. 2. New Nakamura Chemical Co., Ltd. NK Ester 7〇1Α, the number of functional groups is 2 _ 〇〇. New Nakamura Chemical NKEsterA-600, the number of functional groups is 2 25 201235213l is the 101106050 Chinese manual no line correction this amendment Date: In the following table on May 17, 101, the state of the solid or liquid is 25 ° C at a pressure of one atmosphere. The viscosity is 25 ° C, and the viscosity measured by an E-type viscosity meter at one atmosphere is mPa.s. When the additive is hydrazine, it means that both the above acidic monomer and 3-propenyloxypropyltrimethoxy sylvestre are contained. The UV illuminance unit is "mw/sec". Table 1 Acrylic acid vinegar state viscosity acrylic equivalent film forming method Adding Qi lj uv illuminance cumulative light amount barrier performance bulging number example 1 PE-4A solid - 88 solvent 〇 1000 1200 1.32E-04 0 Example 2 PE-4A solid - 88 Solvent 〇 2000 1800 1.35E-04 3 Example 3 PE-4A Solid - 88 Solvent X 1000 1200 1.36E-04 1 Example 4 M-408 Liquid 600-585 116.5 Solvent 〇 1000 1200 1.58E-04 3 Example 5 M -408 Liquid 600—589 116.5 Solvent KBM-503 1000 1200 1.78E-04 4 Example 6 M-408 Liquid 600—577 116.5 Solvent KBM-403 1000 1200 1.89E-04 6 Example 7 M-408 Liquid 600—585 116.5 Solvent 〇 2000 1800 1.55E-04 8 Example 8 M-408 Liquid 600 116.5 Solvent X 1000 1200 1.52E-04 5 Example 9 A-BPE-4 Liquid 1100—1091 256 Solvent 〇1000 1200 3.11E-04 1 Comparative Example 1 M-408 Liquid 600 116.5 Gas Phase X 1000 1200 1.68E-04 5 Comparative Example 2 M-350 Liquid 55-54 141 Solvent 〇 1000 1200 2.87E-04 25 Comparative Example 3 M-350 Liquid 55 141 Solvent X 1000 1200 3.27 E-04 34 Comparative Example 4 M-350 Liquid 55 141 Gas Phase X 1000 1200 2.78E-04 6 Comparative Example 5 A- BPE-10 Liquid 620-542 388 Solvent 〇1000 1200 1.33E-03 4 Comparative Example 6 701A Liquid 44-43 107 Solvent 〇1000 1200 4.31E-04 ----- 〇〇Comparative Example 7 A-600 Liquid 70— 67 354 Solvent 〇 1000 1200 5.31E-03 As is apparent from the above table, when the polymerizable composition used in the present invention is used, even if the organic layer is layered and cured by coating, the number of bulging can be reduced to The same level as in the formation of the organic layer by vapor phase evaporation (Example 8 and Comparative Example 1). Further, it is understood that the reduction in the number of bulges is more pronounced when the alkoxyalkyl group-containing acrylate is added (Examples 3 and 3, Examples 4 and 8). In addition, even if the organic layer is layered and hardened by coating, the viscosity of the (meth) acrylate contained in the polymerizable composition is low (Comparative Examples 2, 6, and the number of bulging) In particular, the comparison between Comparative Examples 2 and 4 is clear. 26 201235213, Revision date: May 1st, 1st, May, 2011, No. 101106050 Chinese manual, no scribe correction, even if it is also based on acrylate When a polymerizable composition other than the range of the present invention is used, the number of bulging of the organic layer formed by vapor phase vapor deposition is very small. The composition of the polymerizable composition used in the present invention is known. When the organic layer is formed by coating, there is a large contribution. In particular, in Comparative Example 2, although an alkoxyalkyl group-containing acrylate is added, the number of bulging is remarkably inferior. When the composition of the 0 (meth) acrylate having a solid content of 5 Å by weight or more is applied as a polymerizable composition in a layer form and an organic layer is provided, an excellent barrier layered product equivalent to gas vapor deposition can be obtained. (methyl) propyl The acid vinegar is a liquid or a solid having a viscosity of 400 mPa·s or more before curing at 25 ° C and an atmospheric pressure, and the (meth)acrylic acid equivalent is 260 or less. It is also known that the effect is contained in the polymerizable composition. Further, it is more obvious that the ultraviolet illuminance when the organic layer is cured is set to 1000 mw/s or less, and the number of bulges is further reduced. Production) Indium oxide in the lead glass substrate (the surface resistance is washed with 2_propanol, and then subjected to UV-ozone treatment for 10 minutes. The substrate (anode) is sequentially vapor-deposited by vacuum evaporation method. Compound layer (first hole transport layer) Copper phthalocyanine: film thickness 10 nm (2nd hole transport layer) Take '-diphenyl-fluorene, Ν'-dinaphthylbenzidine: film thickness 4〇 Nm (light-emitting layer and electron transport layer) 27 201235213 Revision date: May 17, 2011 is the younger brother 101106〇5〇 Chinese manual without scribe correction (3-Ji Kelin) Shao: 臈6〇nm (electron injection layer) lithium fluoride: a film thickness of 1 nm on which 100 nm metal is evaporated In the case of a flat CVD method, an organic EL element is formed by using a bismuth film which is thicker than the LU. The use of a hardening type adhesive (310 manufactured by Daizo_Nichimoly Co., Ltd.) is used to produce an organic EL element. The gas obtained in Example 1 was treated with an early j 18GC for 2 hours, and then bonded with a conductive laminate on the side of the organic EL member to heat the adhesive for 3 hours by blowing. The power measuring unit (Keithley) The company's SMU2400 Source Measure Unit) applies a voltage of 7 v to the newly fabricated organic EL element to emit light. The (10) micromirror was observed for the light-emitting surface, and as a result, it was confirmed that uniform light emission without a dark spot was provided. On the other hand, the gas barrier film was replaced with the gas barrier film produced in Comparative Example 2, and other conditions were the same, and in this case, dark spots were uneven, and uniform light emission could not be obtained. [Simple description of the schema] Benefits. [Description of main component symbols] 益〇 28 201235213 For the Chinese manual No. 101106050, there is no slash correction. Revision period: 1〇1牟¥日年月曰i + wall 明明 C〇06. 〇υ ^006, 〇J) ※Application number: ※Application曰: I. Name of the invention: (Chinese/English) Method for manufacturing P-resistant early laminate and barrier laminates BARRIER LAMINATE AND METHOD FOR ❾ PRODUCING BARRIER LAMINATE II. SUMMARY OF THE INVENTION The present invention provides a barrier layered body having a structure in which an inorganic layer, an organic layer and an inorganic layer are sequentially adjacent, wherein the organic layer will contain 50 wt% based on solid content. The polymerizable composition of the above (meth) acrylate and the fluorene coupling agent containing (fluorenyl) propylene oxy group is applied in a layered form and cured, and the above (meth) acrylate is at 25°. C. A liquid or solid having a viscosity of 400 mPa·s or more before hardening at an atmospheric pressure, and an equivalent weight of 260 of 260 or less. The foaming of the organic layer in the barrier laminate is suppressed. The invention provides a barrier laminate having a structure where an inorganic layer, an organic layer and another inorganic layer are adjacent to each other in sequence. The organic layer is formed by coating a polymerizable composition in a layer form and Curing the 1 201235213 . For the Chinese manual No. 101106050, there is no U-line correction. This revision date is May 17th, 2011. The polymerizable composition contains a (meth)acrylate in an amount of 50 wt% or more in terms of the Solid content, and a silane coupling agent having (meth)acryloyloxy groups. The (meth)acrylate is a liquid or a solid having a viscosity of 400 mPa-s or more at 25°C and 1 atm before curing, and has a ( Meth) acryl equivalent of 260 or less. In the barrier laminate, bubble formation in the organic layer is inhibited. IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. 201235213 L Λ Revision period: May 31, 2011 is the 101106050 Chinese manual without line _^ VII. Patent scope: - A kind of barrier layered body with inorganic layer, organic layer and inorganic layer in order _ In the structure, the organic layer is coated with a (meth)acrylic acid vinegar containing 5% by weight of methic acid and a symbiotic composition containing (meth)acryloxyloxy group. Layered and hardened, the (meth)acrylic acid material has a hardening degree of 4 GG mPa.s or more in a liquid or solid at 25t and a domain pressure, and the (meth)acrylic acid equivalent is fine or less. . The barrier laminate according to claim 1, wherein the (meth) acrylate has a (meth) acrylate methoxy group in an amount of from 3 to 5. 3. The barrier laminate according to claim 1, wherein the (meth)acrylic acid vinegar is a liquid or solid having a viscosity of 1000 mPa·s or more before hardening at 25 t at atmospheric pressure. 4. The barrier laminate according to claim 1, wherein the (meth)acrylic acid vinegar is at least contained in a pit and is a solid compound. 5. The barrier laminate according to claim 1, wherein the (meth) acrylate has a (meth) acryloxy group number of 4. The barrier laminate according to the first aspect of the invention, wherein the inorganic layer contains an oxide and/or a nitride of aluminum and/or bismuth. 7. The barrier laminate according to claim 1, wherein the polymerizable composition further comprises an acidic monomer. A gas barrier film comprising the barrier laminate according to any one of claims 1 to 7 of the invention. 9. The gas barrier film according to item 8 of the patent application scope, wherein the date is: 2012, 2012, the date of revision: May 17, 2011, No. 1, 〇6〇50 It is a substrate film having a glass transition temperature (Tg) of 1 〇〇 or more. A device comprising a barrier layered body according to any one of claims. A method for producing a barrier layered product, which is a method for producing a barrier layered product having a structure in which an inorganic layer, an organic layer, and an inorganic layer are adjacent to each other, and is characterized by containing a solid content of 5 The polymerizable composition of (fluorenyl) acrylate having a 〇wt% or more is coated on the inorganic layer and hardened, and the (mercapto) acrylate has a viscosity of 4 〇〇mPa.s at 25t: at atmospheric pressure. The above liquid or solid, and the (meth)acrylic equivalent is 26 Å or less. 12. The production method according to claim 5, wherein the polymerizable composition further contains a (meth)pyrene-oxygen-containing Wei coupling agent. 13. The method for producing a barrier laminate according to the above-mentioned item, wherein the polymerizable composition is photocured by irradiation with an illuminance of an ultraviolet wavelength of nm. 14. For example, please refer to the method of the barrier layered body of the Weiwei 11th article, which has a cumulative light quantity of 1500 mj/sec or less when the towel is hardened. 15. The method for producing a barrier laminate according to the application of the above-mentioned item (4), wherein the inorganic layer is formed by a plasma CVD method. The method for producing the barrier layer body described in the U-th article, and the number of (meth) propylene oxime groups of the 3 meth (meth) acrylate vinegar is 3 to 5.造二===== 30 201235213 L ± is the 101106050 Chinese manual without a slash correction. The revised period: May 17th, 101 液体 The liquid or solid with a viscosity before 1000 mPa.s. 18. The method of producing a barrier laminate according to claim 11, wherein the (mercapto) acrylate contains at least a compound which is solid at 25 ° C under atmospheric pressure. A method of manufacturing a device comprising: applying a gas barrier film according to claim 8 of the patent application, and treating at 150 ° C for 1 hour or more 31 201235213 . For the Chinese manual No. 101106050 No U-line correction This revision date: May 2011 17曰same. The polymerizable composition contains a (meth)acrylate in an amount of 50 wt% or more in terms of the solid content And a silane coupling agent having (meth)acryloyloxy groups. The (meth)acrylate is a liquid or a solid having a viscosity of 400 mPa-s or more at 25°C and 1 atm before curing, and has a (meth) The acryl equivalent of 260 or less. In the barrier laminate, bubble formation in the organic layer is inhibited. IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None.