JP2006095932A - Manufacturing method of laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of laminates, in which an inorganic compound layer formed of a silicon oxide film, a silicon nitride film or the like is provided on a flexible base composed of a polymer resin, and an organic protective film composed of an active energy ray-curable or a plasma irradiation-curable organic compound having excellent adherence is formed on the surface of the inorganic compound layer in vacuum. <P>SOLUTION: The laminate is formed by providing the inorganic compound layer and an organic compound layer on the base. The organic compound layer is provided by sequentially agglomerating two or more kinds of (meth)acrylic compounds in vacuum, and then active energy rays or plasma is irradiated for curing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a laminate having a high gas barrier property against permeation of oxygen and water vapor suitable for food / pharmaceutical packaging materials, film liquid crystal / electroluminescence element substrates, and the like.

  Conventionally, as a packaging material, a gas barrier performance against oxygen or water vapor is necessary for preservation of contents, and as a transparent packaging material, a packaging material provided with a gas barrier layer made of an inorganic compound is known. As a process for forming a gas barrier layer made of an inorganic compound on a polymer resin substrate, considering the controllability of the film quality, charging disturbance during film formation, and reduction of thermal damage to the polymer resin substrate A chemical vapor deposition (CVD) method is suitable, and depending on the film formation conditions, barrier performance at the measurement limit level by the mocon detection method can be realized. However, considering productivity, there are still many problems to be improved such as winding suitability and processing suitability after gas barrier film formation. Packaging materials such as food are usually deposited and transported at a speed of several hundreds of meters per minute. However, dust hidden inside the deposition system adheres to the deposition surface and comes into contact with the transport rollers and is rubbed or wound up. The film is damaged by being caught inside the roll. Mechanical and chemical stresses are also applied to the film in processing steps such as printing, lamination, and bag making.

Patent documents are described below.
Japanese Patent No. 3101682 Japanese Patent No. 2530350 U.S. Pat. No. 4,954,371.

  In order to improve this problem, a technique [Patent Document 1] is disclosed in which an organic substance is deposited in vacuum before film contact with another roller after film formation to protect the film expression. In addition, as a method for producing an organic material coating in a vacuum, a liquid organic material is instantaneously vaporized by spraying onto a heated substrate, and then condensed and solidified on the cooled surface of the coating, so-called flash deposition method [ Patent Document 2 and Patent Document 3]. Since this method is a method through a gas phase, an organic substance can be applied thinly and uniformly with a high purity, and it is one of the most promising methods for producing an organic substance coating. Compared with the system, in particular, the adhesion at the film interface with the gas barrier layer made of an inorganic compound such as silicon oxide or silicon nitride is weak, and there is a problem that delamination occurs in the post-processing step. In the above-mentioned patents, proposals for an organic vapor deposition process in a vacuum and an in-line organic / inorganic lamination process are specified, but a specific measure for improving the adhesion at the film interface is not specified.

  An object of the present invention is to solve the above-mentioned problems, and an inorganic compound layer such as a silicon oxide film or a silicon nitride film is provided on a flexible substrate made of a polymer resin, and adheres to the surface of the inorganic compound layer. An object of the present invention is to provide a method for producing a laminate, in which an organic protective film made of an organic compound that is cured by active energy rays or plasma irradiation having excellent strength is formed in a vacuum.

In order to solve the above problems, the present invention
Invention of Claim 1 is a manufacturing method of the laminated body which provides an inorganic compound layer and an organic compound layer on a base material,
The organic compound layer is formed by sequentially aggregating two or more kinds of (meth) acrylic compounds in a vacuum, and then irradiating with an active energy ray or plasma and curing the laminate. .

  The invention of claim 2 is characterized in that the two or more (meth) acrylic compounds have a (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600, and a compound having two or more (meth) acrylic groups. It is a manufacturing method of the laminated body of Claim 1 characterized by the above-mentioned.

  In the invention of claim 3, the organic compound layer comprises two or more kinds, and the organic compound layer A containing a (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600 on the substrate, It has the organic compound layer B containing the compound which has a 2 or more (meth) acryl group, It is a manufacturing method of the laminated body of Claim 2 characterized by the above-mentioned.

  Invention of Claim 4 is a manufacturing method of the laminated body of any one of Claims 1-3 with which the said organic compound layer is provided by the flash vapor deposition method.

  Invention of Claim 5 is a manufacturing method of the laminated body of any one of Claims 1-4 with which the said inorganic compound layer is provided by the chemical vapor deposition (CVD) method.

  Invention of Claim 6 is formed, without the said inorganic compound layer and organic compound layer being exposed to air | atmosphere in the same vacuum, The laminated body of any one of Claims 1-5 characterized by the above-mentioned. It is a manufacturing method.

  The method for producing a laminate of the present invention has a high water vapor barrier property and sufficient adhesion performance, prevents deterioration of the water vapor barrier property from mechanical rubbing that occurs during transportation, and stabilizes chemical resistance with excellent alkali resistance. Can be applied. In particular, the organic compound layer comprises two or more organic compound layers, and the organic compound layer A containing a (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600 on the substrate, two or more (meta ) By having the organic compound layer B containing a compound having an acrylic group, adhesion performance with an inorganic compound layer such as silicon oxide can be imparted, and further, alkali resistance performance and scratch resistance performance can be imparted. In addition, by sequentially aggregating these materials and then simultaneously curing, the two types of materials can be mixed appropriately at the interface, and peeling at the interface can be reduced. The adhesion performance, alkali resistance performance, and scratch resistance can be reduced. An excellent protective film having both performances can be formed.

  Hereinafter, a preferred embodiment of a method for producing a laminate according to the present invention will be described with reference to the drawings. FIG. 1 shows a production apparatus diagram as an example in the method for producing a laminate of the present invention, and FIG. 2 shows a laminate as a gas barrier material produced by the production method.

  In the following, the organic compound layer A in the present invention comprises two or more types, and the organic compound layer A containing a (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600 on the substrate is cured with active energy rays. The resin material layer A and the organic compound layer B containing a compound having two or more (meth) acryl groups on the outermost surface are referred to as an active energy ray curable resin material layer B. Also, the organic compound layer A and the organic compound layer B cured by active energy ray irradiation are referred to as an active energy ray curable resin layer A and an active energy ray curable resin layer B, respectively.

  The specific example of the manufacturing apparatus used with the manufacturing method of the laminated body of this invention is demonstrated. A process roll (3) is installed inside a vacuum film forming apparatus (1) connected to a vacuum pump A (2), and an unwinding roll (4) and a winding roll (5) are installed on the upper part. Around the process roll (3), a gas barrier layer forming device (6), a shielding plate A (7), an active energy ray curable resin raw material layer A resin vapor deposition device (8), and an active energy ray curable resin raw material layer B resin vapor deposition device. (9) An electron beam irradiation device (10) is installed. Further, an active energy ray curable resin raw material layer A resin vapor deposition device (8) is connected to an active energy ray curable resin layer A resin raw material supply device (11), and the active energy ray curable resin raw material layer B resin vapor deposition device (9). ) Is connected to the active energy ray-curable resin layer B resin raw material supply device (12), and the gas supply device (13) is connected to the electron beam irradiation device (10). Further, a vacuum pump B (14), a vacuum pump C (15), a pressure regulating valve A (16), and a pressure regulating valve B (17) are connected to the gas barrier layer forming device (6) and the electron beam irradiation device (10), respectively. The take-up roll (4) and the take-up roll (5) are shield plates B between the gas barrier film forming apparatus (6) and the active energy ray curable resin vapor deposition apparatus and the electron beam irradiation apparatuses (8) to (13). (18) The degree of vacuum suitable for each process is adjusted by the shielding plate C (19). Since the gas barrier layer and the active energy ray curable resin layer can be formed in the same vacuum film forming apparatus in this way, it is possible to easily optimize each film forming condition, and at the same time, a highly productive laminate with less dust and the like. Can be manufactured.

  The raw material of the polymer resin base material (101) is attached to the unwinding roll (4), and the raw material conveyance path reaching the winding roll (5) through the process roll (3) is formed. The vacuum film forming apparatus (1) is evacuated by a vacuum pump A (2), a vacuum pump B (14), and a vacuum pump C (15). Here, the example of the manufacturing apparatus in which the gas barrier layer and the active energy ray curable resin layers A and B are sequentially laminated has been described, but the present invention is not limited thereto.

  Hereinafter, the film forming process will be described. A gas barrier layer C (102) is provided on the surface of the polymer resin substrate (101) by chemical vapor deposition (CVD). As the polymer resin base material, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyacrylate, polycarbonate, polyethersulfone, cycloolefin-based material, etc. can be used. However, the present invention is not limited to this.

  The gas barrier layer C (102) was formed of any one of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film, and was activated by plasma using an organosilane material such as hexamethyldisiloxane (HMDSO) as a raw material. Formed by reaction with oxygen and nitrogen under atmosphere. The amount of the source gas and the reaction gas to be supplied is optimized depending on the film thickness, the degree of oxidation, the winding speed, the size of the vacuum film forming apparatus (1), and the like. Further, the film formation process of the gas barrier C layer (102) is not limited to the chemical vapor deposition (CVD) method, and may be formed by sputtering a target such as silicon oxide, silicon nitride, or silicon.

  The active energy ray curable resin layer AB (103) is formed by sequentially forming an active energy ray curable resin material layer by a vapor deposition method and then polymerizing it by irradiating one of electron beam, plasma, and ultraviolet rays. Compared with the polymerization method using heat, this method can perform polymerization in a short time, and has a feature that the elongation of the substrate and the deformation of the hardened layer are less caused by the heat load.

The active energy ray curable resin A layer is laminated on a gas barrier layer C (102) made of an inorganic compound such as silicon oxide or silicon nitride, thereby allowing adhesion between the inorganic compound layer and the active energy ray curable resin layer. It becomes a so-called primer layer that improves the properties. The (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600 is not particularly limited, and includes 1 trialkoxysilyl group and 1 to 3 (meth) acrylic groups in the molecule. good. When there is one (meth) acryl group, higher adhesion with the inorganic compound layer can be obtained. When the number is two or three, the film strength of the active energy ray-curable resin A layer can be increased by increasing the crosslinking density, but at the same time, the adhesion may be slightly decreased. Examples of the (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600 include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and other silane coupling agents; A compound obtained by reacting (meth) acrylic acid can be used. In the active energy ray-curable resin A layer, a monofunctional (meth) acrylate or a bifunctional or higher (meth) acrylic compound can be blended depending on purposes such as strength, flexibility, and scratch resistance. It is not specifically limited, For example, the compound which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Compounds having an amino group such as diethylaminoethyl (meth) acrylate, carboxyl groups such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hydrohexaphthalic acid (Meth) acrylate having a cyclic skeleton such as a compound, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. Rate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) Acrylic monofunctional compounds such as acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Acrylate, triethylene di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600 di (meth) acrylate, neopentyl Bifunctional (meth) acrylic compounds such as (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, etc., bifunctional epoxy (meth) acrylates, bifunctional urethane (meth) acrylates, etc. A functional (meth) acryl compound is mentioned. The compounds having three or more (meth) acryl groups include dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane triacrylate, and trimethylol. An acrylic polyfunctional monomer such as propanetetraacrylate, (meth) acryl polyfunctional epoxy acrylate, (meth) acryl polyfunctional urethane acrylate, and the like can be used.

The active energy ray curable resin B layer is a so-called protective layer that prevents scratching and rubbing of the inorganic compound layer contained in the flexible substrate by being laminated on the outermost surface. The active energy ray-curable resin B layer is not particularly limited as long as it has two or more (meth) acryl groups in the molecule. When it has 3 or more preferably, a crosslinking density becomes high and the outstanding protective property can be acquired. For example, as a compound having two (meth) acrylic groups, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 Nonanediol di (meth) acrylate, triethylene di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600 di (meth) acrylate, neopentyl di (meth) acrylate, dimethylol Bifunctional (meth) acrylic compounds such as bifunctional urethane (meth) acrylate such as acrylic bifunctional compounds such as tricyclodecane di (meth) acrylate, bifunctional epoxy (meth) acrylate, and the like. Examples of compounds having three or more (meth) acrylic groups include dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane triacrylate, and trimethylolpropanetetra. Acrylic polyfunctional monomers such as acrylate, (meth) acryl polyfunctional epoxy acrylate, (meth) acryl polyfunctional urethane acrylate, and the like can be used. Moreover, although the said active energy ray hardening resin B layer can also mix | blend a monofunctional (meth) acryl compound, it may produce the fall of protection performance.

A polymerization initiator can be blended with each of the active energy ray-curable resin layers A and B in order to allow the polymerization to proceed efficiently. The polymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with active energy. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,2- Dimethoxy-1,2-diphenylethane-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl 1-propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-Morpholinophenyl) butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be used.
In the present invention, the polymerization initiator is blended in an amount of 0.1 to 10 parts by weight, preferably 1 to 7 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the active energy ray-curable resin layer A and B. It is said.

  The active energy ray curable resin layer may be formed by laminating A and B, respectively, but the active energy ray curable resin is placed between the active energy ray curable resin layers A and B depending on purposes such as flexibility and impact resistance. Layer C can be provided. Active energy ray curable resin layer The active energy ray curable resin layer C is not particularly limited as long as it is a (meth) acrylic compound capable of obtaining desired characteristics.

  Next, specific examples of the present invention will be described.

A 125 μm thick polyethylene terephthalate film was mounted on the unwinding roll (4) of the vacuum film forming apparatus (1), and the inside of the vacuum film forming apparatus (1) was depressurized to 1.0 × 10 ⁻³ Pa. Chemical vapor deposition (CVD) on the surface of the polymer resin substrate (101) while introducing HMDSO flow rate: 10 sccm, O ₂ flow rate 100 sccm, generating plasma at a frequency of 13.56 MHz and power of 1000 W and adhering it to the process roll (3). ) Method was used to form a gas barrier layer C (102) made of a silicon oxide film.

  Further, 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM5103) is sequentially applied on the process roll (3) to the active energy ray curable resin raw material layer A resin vapor deposition apparatus (8). Acrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate TMP-A) is supplied to the active energy ray curable resin raw material layer B resin vapor deposition device (9), respectively, and the thickness of the cured active energy ray curable resin AB layer (103) is obtained. Was controlled to 1.0 μm. The acceleration voltage irradiated by the electron beam irradiation apparatus (10) was 10 kV.

As a comparative example for comparison with the manufacturing method of the laminate of the present invention,
A gas barrier layer C (102) is formed on the surface of the polymer resin substrate (101) under the same conditions as in Example 1, and 3-acryloxypropyltrimethoxysilane is applied to the gas barrier layer C (102) with active energy rays. A cured resin raw material layer A was supplied to a resin vapor deposition apparatus (8), and an active energy ray cured resin A layer (104) was formed while controlling the cured thickness to 1.0 μm. The active energy ray irradiation conditions were the same as those in Example 1.

As a comparative example for comparison with the manufacturing method of the laminate of the present invention,
A gas barrier layer C (102) is formed on the surface of the polymer resin substrate (101) under the same conditions as in Example 1, and trimethylolpropane triacrylate is formed on the gas barrier layer C (102) using an active energy ray-curable resin raw material. It supplied to the layer B resin vapor deposition apparatus (9), and formed active energy ray cured resin B layer (105), controlling so that the thickness after hardening might be set to 1.0 micrometer. The active energy ray irradiation conditions were the same as those in Example 1.

As a comparative example for comparison with the manufacturing method of the laminate of the present invention,
A gas barrier layer C (102) is formed on the surface of the polymer resin substrate (101) under the same conditions as in Example 1, and 3-acryloxypropyltrimethoxysilane is applied to the gas barrier layer C (102) with active energy rays. Cured resin raw material layer A was supplied to a resin vapor deposition apparatus (8) to form an active energy ray cured resin D layer (106). The active energy ray irradiation conditions were the same as those in Example 1. Next, using a roll coater in the atmosphere, 100 parts by weight of trimethylolpropane triacrylate and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy, Irgacure 184) as a photoinitiator are dissolved in methyl ethyl ketone. Then, after removing the solvent in an oven, it was applied so as to have an arbitrary film thickness and cured with a metal halide lamp to form an active energy ray-curable resin E layer (107). The film thicknesses of the D and E layers were controlled to be 1.0 μm in total.

As a comparative example for comparison with the manufacturing method of the laminate of the present invention,
50 parts by weight of 3-acryloxypropyltrimethoxysilane and 50 parts by weight of trimethylolpropane triacrylate are mixed and supplied to the active energy ray curable resin layer A resin supply device (8), and the cured active energy ray curable resin. The thickness of the F layer (108) was controlled to be 1.0 μm. The active energy ray irradiation conditions were the same as those in Example 1.

  About the laminated body obtained in said Examples 1-5, it evaluated based on the following evaluation method. The evaluation method is shown in Table 1.

<Evaluation method>
(1) Water vapor barrier property--A laminated body having a size of 100 × 400 mm is contacted 50 times with a free roller having a weight of 3.5 kg, a diameter of 80 mm, and a surface accuracy of 1.0 S, and then a temperature of 40 ° C. and a humidity of 90 It was measured with a Mocon Permatran W6 water vapor transmission rate measuring device (manufactured by Modern Control Co., Ltd.) in an atmosphere of% RH to obtain water vapor transmission rate. The unit of water vapor permeability in the table is g / m 2 · day.
(2) Adhesion evaluation A ··· Based on JIS5400, the coated surface was cut into 100 square grids with a 1 mm square, peeled at 180 ° C. with tape, and the residual rate (%) was measured. The gas barrier layer C (102) was The case where 100% remained on the base material was indicated as ◯, the case where about 50% remained as Δ, and the case where no residue remained as x.
(3) Adhesion evaluation B: A laminate having a size of 50 × 50 mm was immersed in a 3% aqueous sodium hydroxide solution at a water temperature of 25 ° C. for 10 minutes, washed with water, dried, and then evaluated for adhesion A The same test was performed, and the case where all of the gas barrier layer C (102) remained on the base on the peeled surface was indicated as ◯, and the case where it was not indicated as ×.

表中の層構成欄のＡｃは、アクリル化合物を表す。

Ac in the layer configuration column in the table represents an acrylic compound.

  From Table 1, the laminated body manufactured with the manufacturing method of the laminated body of this invention obtained in Example 1 compared with the laminated body manufactured with the comparative example of this invention in Examples 2-5, water vapor | steam. Excellent barrier properties, adhesion A and B performance, high water vapor barrier properties and sufficient adhesion performance, preventing deterioration of water vapor barrier properties due to mechanical rubbing that occurs during transportation, alkali resistance It was also confirmed that excellent chemical resistance was developed.

  Further, when the active energy ray-curable resin F layer (108) is formed by the production method as shown in Example 5, the friction resistance is obtained by mixing 3-acryloxypropyltrimethoxysilane and trimethylolpropane triacrylate. Even when trying to achieve both adhesion and interlayer adhesion, the various physical properties (vapor pressure, evaporation temperature, evaporation rate, latent heat of evaporation, etc.) of various materials are significantly different. 8) A part of the active energy ray-curable resin may remain without evaporating inside, or may be decomposed during evaporation and lose its original function, so it may be difficult to control the evaporation amount of each resin material. Yes, it does not reach the manufacturing method of Example 1 of the present invention.

It is a schematic explanatory drawing which shows an example of the manufacturing apparatus containing the vacuum film-forming apparatus (1) in the manufacturing method of the laminated body of this invention. It is a cross-sectional schematic diagram of the laminated body as one Example manufactured by the manufacturing method of the laminated body of this invention in Example 1. FIG. It is a cross-sectional schematic diagram of the laminated body as one Example manufactured by the manufacturing method of the laminated body in Example 2. FIG. It is a cross-sectional schematic diagram of the laminated body as one Example manufactured by the manufacturing method of the laminated body in Example 3. FIG. It is a cross-sectional schematic diagram of the laminated body as one Example manufactured by the manufacturing method of the laminated body in Example 4. FIG. It is a cross-sectional schematic diagram of the laminated body as one Example manufactured by the manufacturing method of the laminated body in Example 5. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Vacuum film-forming apparatus 2 ... Vacuum pump A
DESCRIPTION OF SYMBOLS 3 ... Process roll 4 ... Unwinding roll 5 ... Winding roll 6 ... Gas barrier layer forming apparatus 7 ... Shielding board A
8 ... Active energy ray curable resin raw material layer A resin vapor deposition device 9 ... Active energy ray curable resin raw material layer B resin vapor deposition device 10 ... Electron beam irradiation device 11 ... Active energy ray curable resin layer A resin Raw material supply device 12 ... Active energy ray curable resin layer B Resin raw material supply device 13 ... Gas supply device 14 ... Vacuum pump B
15 ... Vacuum pump C
16 ... Pressure regulating valve A
17 ... Pressure regulating valve B
18 ... Shield plate B
19 ... Shielding plate C
101 ... polymer resin base material 102 ... gas barrier layer C
103 ... Active energy ray curable resin AB layer 104 ... Active energy ray curable resin A layer 105 ... Active energy ray curable resin B layer 106 ... Active energy ray curable resin D layer 107 ... Active energy Wire curable resin E layer 108 ... Active energy ray curable resin F layer

Claims (6)

A method for producing a laminate comprising an inorganic compound layer and an organic compound layer on a substrate,
A method for producing a laminate, wherein the organic compound layer is formed by sequentially agglomerating two or more kinds of (meth) acrylic compounds in a vacuum, and then irradiating and curing with an active energy ray or plasma.   The two or more (meth) acrylic compounds include a (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600 and a compound having two or more (meth) acrylic groups. The manufacturing method of the laminated body of Claim 1.   The organic compound layer comprises two or more organic compound layers, the organic compound layer A containing a (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600 on the substrate, and two or more (meth) on the outermost surface It has the organic compound layer B containing the compound which has an acryl group, The manufacturing method of the laminated body of Claim 2 characterized by the above-mentioned.   The said organic compound layer is provided by the flash vapor deposition method, The manufacturing method of the laminated body of any one of Claims 1-3 characterized by the above-mentioned.   The said inorganic compound layer is provided by the chemical vapor deposition (CVD) method, The manufacturing method of the laminated body of any one of Claims 1-4 characterized by the above-mentioned.   The said inorganic compound layer and organic compound layer are formed in the same vacuum, without being exposed to air | atmosphere, The manufacturing method of the laminated body of any one of Claims 1-5 characterized by the above-mentioned.

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