JP2006036904A - Method for producing protective film and protective film produced by the same production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of applying effect equivalent to knurling treatment also to an extremely inexpensive substrate at low price and to provide a substrate not only providing the substrate, but also capable of bringing about an effect equivalent to optimized in-line formed film also in a conventional off-line formed film. <P>SOLUTION: The present invention provides a method, etc., for forming a protective film by aggregating a (meth)acrylic compound in vacuum at both ends of a polymer resin substrate, irradiating the (meth)acrylic compound with electron beam or plasma to cure the (meth)acrylic compound and forming an active energy beam-cured resin layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a protective film for 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, and a method for producing the same It is.

  Conventionally, as a packaging material, a gas barrier performance against oxygen and 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 a thin film 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 deposition method (CVD method) is suitable, and it is known that barrier performance at a measurement limit level by the mocon detection method can be realized depending on the surface state of the polymer resin substrate and the film forming conditions.

  However, considering productivity, there are still many problems to be improved such as winding suitability and processing suitability after gas barrier film formation. In addition, packaging materials used for foods are usually deposited and transported at a speed of several hundreds of meters per minute. At that time, dust hidden inside the deposition apparatus adheres to the deposition surface and enters the winding roll. Entrainment causes significant stress on the film, damages the film itself, and significantly limits the gas barrier performance. Also, mechanical and chemical stresses are applied to the film itself in processing steps such as printing, lamination, and bag making. Recently, in order to provide a high gas barrier property against permeation of oxygen and water vapor suitable for an electroluminescence element, a protective film for protecting a surface to be formed in advance on a polymer resin substrate is provided and supplied. There are many cases.

  This plays a role of protecting a film forming surface necessary for an electro device application from dust and the like generated during winding and transporting, and preventing winding tightening due to smoothing of the substrate surface. As an alternative means for carrying out this protection, there is a method of winding while applying a processing step called knurling to both end faces of the polymer substrate at the time of manufacturing the substrate.

  This method is a processing method in which both ends in the width direction of the support, i.e., both ear ends are sandwiched by uneven rollers, and the uneven pattern is caused to deform on the support ears. It is manufactured in a band shape along the longitudinal direction on both sides of the support, and the support subjected to the knurling treatment has an action of preventing excessive adhesion with the pass roller even in a vacuum and reducing peeling electrification. However, there is a necessity for the processing step to be performed at the time of manufacturing the base material and a work according to the width of the base material, which leads to a significant increase in cost as a base material for packaging materials. In addition, as another inexpensive method for protecting the substrate surface, a method for producing an organic coating in vacuum is disclosed.

  In this method, a uniform vapor of a polymerizable substance is continuously supplied by supplying at a polymerization temperature / decomposition temperature or lower, continuously atomizing, and evaporating by contacting with a heating surface not lower than the boiling point and lower than the decomposition point. A so-called Patent Document 1 or Patent Document, in which liquid organic substances represented by monomers are vaporized on a heated substrate, as represented by a method, are instantly vaporized and then condensed and solidified on the cooled coating surface. This is called a flash vapor deposition method as shown in FIG.

For example, since it is a method via a gas phase, an organic substance can be applied thinly, uniformly and at high speed with high purity, and is one of the most promising methods for producing an organic coating. Using this principle, a method of filling a submicron-order dust adhering to a film surface immediately before film formation by forming an organic substance such as acrylic on the surface of a polymer substrate in vacuum is disclosed in Patent Document 3. Etc. are disclosed.

  However, when the film is formed by the above method, the smoothness of the film before the film formation deteriorates more than before the film formation (that is, the surface of the base material), or the covering material is covered, so that the film can be wound and transported thereafter. Unless the film thickness is significantly deteriorated or the film thickness uniformity in the width direction of the film is not controlled, the take-up tension is biased to the side where the film is formed thick, and wrinkles and meandering occur. In addition, the organic film design requires extremely elaborate process conditions, such as the adhesion performance with the base material and the gas barrier layer formed directly thereon.

  Also disclosed is a method of laminating a gas barrier layer on a polymer substrate and then sequentially manufacturing an acrylic protective film without contacting other guide rollers, etc. The inorganic barrier film forming process conditions and organic protective film forming process conditions (film forming speed conditions, film forming pressure conditions, process drum temperature conditions, etc.) must be optimally controlled. It is limited to.

Patent documents are as follows.
Japanese Patent No. 2530350 U.S. Pat. No. 4,954,371 Japanese Patent No. 3101682

  The object of the present invention is to solve the above-mentioned problems, and by forming an organic thin film having excellent adhesion on both ends of the polymer resin substrate surface, an effect equivalent to that of the narlink treatment (on both ends treated surfaces) Concentration of winding tension prevents stress concentration and winding deviation on the film formation surface due to dust entrainment, and enables stable winding film formation and conveyance without damaging the surface of the polymer substrate. In addition to providing a method and a substrate that can be applied to extremely inexpensive substrates at a low price, a base that can provide the same effect as optimized in-line deposition in normal offline deposition The material is provided.

  The present invention is for solving the above-mentioned problems. The invention according to claim 1 is directed to an electron beam or an electron beam after aggregating (meth) acrylic compounds in vacuum at both ends in the width direction of the polymer resin substrate. It is the manufacturing method of the protective film which irradiated plasma and hardened the said acrylic compound and manufactured the active energy ray hardening resin layer.

  The invention according to claim 2 is based on the aggregate thickness of the acrylic compound produced on the both end portions in the vacuum and the (meth) acryl compound on the both end portions in the vacuum on both ends in the width direction of the polymer resin substrate. The active energy ray-curable resin layer is produced by irradiating an electron beam or plasma after thinning the aggregation thickness of the acrylic compound produced on the inner surface further than the both ends, and then curing the acrylic compound. 1 is a method for producing a protective film according to 1.

  The invention according to claim 3 is the method for producing a protective film according to claim 1 or 2, wherein the protective film contains a compound having two or more (meth) acrylic groups.

  The invention according to claim 4 is a protective film manufactured by the manufacturing method according to any one of claims 1 to 3.

  The invention according to claim 5 is the protection according to claim 1 or claim 2, wherein the method of applying the active energy ray-curable resin layer to the surface of the polymer resin substrate is a flash vapor deposition method. It is a manufacturing method of a film.

  In the invention according to claim 6, the step of forming the active energy ray-curable resin layer and the step of forming the gas barrier layer on the polymer resin substrate are all exposed to the atmosphere in the same vacuum apparatus. It is manufactured sequentially, The manufacturing method of the protective film of Claim 1 or Claim 2 characterized by the above-mentioned.

  The invention according to claim 7 is the step of forming the active energy ray curable resin layer on the polymer resin substrate, the step of forming a gas barrier layer, and forming the active energy ray curable resin layer on the barrier layer. 3. The method for producing a protective film according to claim 1, wherein all the film forming steps are sequentially produced without being exposed to the atmosphere in the same vacuum apparatus.

  The invention according to claim 8 is the protective film according to claim 4, wherein a gas barrier thin film made of an inorganic compound is produced directly on the film according to claim 3.

  The invention according to claim 9 is directed to irradiate an electron beam or plasma after aggregating the acrylic compound comprising a compound containing the compound having two or more (meth) acrylic groups directly on the film according to claim 8. And a protective film obtained by curing the acrylic compound to produce an active energy ray-curable resin layer.

  The laminates achieved by the present invention, ie, Example and Comparative Example 2, have a high water vapor barrier property and sufficient adhesion performance as compared with the method shown in Comparative Example 3 produced by a generally considered method. Further, it is possible to prevent deterioration of the water vapor barrier property due to mechanical rubbing and dust contamination that occur during transportation. This is because an organic thin film with excellent adhesion is produced on both ends of the polymer resin substrate surface, and the same effect as that of the nerlink treatment, that is, the winding tension is concentrated on the treatment surfaces on both ends, thereby entraining dust. It is possible to prevent stress concentration and winding deviation on the film formation surface, and to realize stable winding film formation and conveyance without damaging the surface of the polymer substrate. In addition, this method is a method that can be easily applied to an inexpensive polymer resin substrate, and can provide an effect equivalent to that of optimized in-line film formation even in normal off-line film formation. The body can be created.

  The manufacturing method and manufacturing apparatus of the protective film of the present invention will be described below with reference to the apparatus diagram shown in FIG. 1 and the active energy ray curable resin layer A, gas barrier layer, and active energy as shown in FIGS. A gas barrier material obtained by sequentially laminating the wire curable resin layer B will be described as an example.

A specific example of the manufacturing apparatus will be described below with reference to the apparatus diagram of FIG. A process roll A (3) and a process roll B (4) are disposed inside the vacuum film forming apparatus (1), and an unwinding roll (5), a winding roll (6), and a guide roll (20) are disposed thereon. The raw material of the polymer resin base material (101) is mounted on the unwinding roll (5), and the winding roll (6) through the process roll A (3), the guide roll (20), and the process roll B (4). The raw material conveyance path leading to is manufactured. When the slightly adhesive film is bonded in advance to the polymer resin substrate (101) installed on the unwinding roll, the adhesive film is peeled off via the nip roll (7), and the winding roll (8) Manufactures a raw fabric pass for winding an adhesive film. Process role A (
3) The active energy ray curable resin A raw material supply device (12) and the active energy ray resin A raw material control device A (13) are sequentially provided around the shielding plates A (9), B (16), and C (19). ) Connected to an active energy ray-curable resin vapor deposition apparatus A (11), an electron beam irradiation apparatus A (14) connected to a gas supply apparatus A (15), an electron beam heating vapor deposition apparatus (17), and a crucible (18). ) Is arranged. In addition, a gas barrier layer manufacturing apparatus is comprised with an electron beam heating type vapor deposition apparatus (17) and a crucible (18).

  Around the process roll B (4), an active energy ray curable resin B raw material supply device (22) and an active energy ray curable resin raw material control device B (23) are sequentially provided through shielding plates C (20) and D (27). Are connected to an active energy ray-curable resin vapor deposition apparatus B (21) connected to each other and an electron beam irradiation apparatus B (25) connected to a gas supply apparatus B (24). Further, the space between the shielding plates A (9), C (20) and D (27) is exhausted by the vacuum pump A (2), and the space between the shielding plates A (9) and B (16) is vacuum pump B ( 10), the space between the shielding plates B (16) and C (20) is evacuated by the vacuum pump C (19), and the space between the shielding plates C (20) and D (27) is a vacuum pump D (26). The degree of vacuum suitable for each process is adjusted by evacuating at. Since the gas barrier layer and the active energy ray curable resin layer can be manufactured 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.

  Hereinafter, the film forming process will be described. As the polymer resin substrate (101), polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyacrylate, polycarbonate, polyethersulfone, cycloolefin-based material, or the like can be used. However, it is not particularly limited to this. After the active energy ray-curable resin layer A (102) is sequentially produced on the surface of the polymer resin substrate (101) by the flash vapor deposition method, one of electron beam, plasma and ultraviolet rays is irradiated. To produce by polymerization.

  Compared with the thermal polymerization method, this method can perform the polymerization in a short time, and has a feature that the elongation of the base material and the deformation of the hardened layer are less caused by the thermal load. FIG. 2 shows a cross-sectional shape of the injection port in the substrate width direction of the active energy ray-curable resin A vapor deposition apparatus. Normally, the clearance C and the clearance D are matched so that the film thickness of the cured active energy ray-cured resin A is as uniform as possible, but the fluctuation of the clearance due to thermal expansion, the aggregation of the film on the polymer resin base material The film thickness uniformity in the width direction is limited to about ± 3% due to efficiency.

The present invention is characterized in that both ends of the base material produce thick films by setting the values of clearances C and D to C >> D. FIG. 4 shows an example of the structure of a film manufactured when the value of the clearance D is 0 (zero), and FIG. 5 shows an example of the structure of a film manufactured when the clearance C = D. In this case, if the minimum tension value required at the time of winding is F ₁ and F ₂ , F ₂ / F ₁ = (2A + B) / (2A), and as B becomes larger (wider), it occurs at the time of winding. The stress value is also reduced, and as a result, the stress concentration due to the dust contained in the vacuum being caught or rubbed can be reduced. Further, by adjusting the clearance (28) and the clearance (29) of FIG. 2 using a material (ceramic material or the like) having a small thermal expansion, the uniformity of the film at both ends can be controlled relatively easily, and the meandering is performed. It has the effect of suppressing wrinkling without deviation of the roll and the winding material.

The active energy ray curable resin A (102) layer is formed under the gas barrier layer B (103) made of an inorganic compound such as aluminum oxide or silicon oxide, thereby forming the polymer resin substrate (101) and the gas barrier. This is a so-called primer layer that improves adhesion between the layer B (103). The resin raw material is not limited to a (meth) acrylic compound having a trialkoxysilyl group having a molecular weight of 150 to 600, but 1 trialkoxysilyl group and (meth) acrylic group in the molecule are 1 to Just include three. 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 trimethoxypropyl (meth) acrylate, trimethoxypropyl methacrylate, and other silane coupling agents, and (meth) acrylic acid. A compound obtained by reacting can be used.

  In the active energy ray curable resin A (102) layer, a monofunctional (meth) acrylate or a bifunctional or higher (meth) acrylic compound can be blended depending on the purpose such as strength, flexibility, and scratch resistance. , Not particularly limited, for example, compounds having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate A compound having an amino group such as diethylaminoethyl (meth) acrylate, a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid Compound, glycidyl (meth) acrylate, tetrahydride (Meth) acrylate having a cyclic skeleton such as furfuryl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylic monofunctional compounds such as acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) 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 di (meth) acrylate, dimethylol tricyclodecane di (meth) ) Bifunctional (meth) acrylic compounds such as bifunctional (meth) acrylic compounds such as bifunctional epoxy (meth) acrylate, bifunctional epoxy (meth) acrylate, and other bifunctional (meth) acrylic compounds. 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 gas barrier layer C (102) is manufactured from an inorganic film such as an aluminum film, an aluminum oxide film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, and the film formation process of the gas barrier B layer (102) is a physical process. It is not limited to the vapor deposition method, but may be manufactured by sputtering using a chemical deposition method or a target such as silicon oxide, silicon nitride, or silicon.

The active energy ray-curable resin B layer (103) 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 (103) is a compound having two or more (meth) acryl groups, and is not particularly limited, and has two or more (meth) acryl groups in the molecule. Just do it. When it is preferably 3 or more, the crosslinking density is increased, and excellent protective properties can be obtained. For example, as a compound having two (meth) acryl 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 Acrylic bifunctional compounds such as # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600 di (meth) acrylate, neopentyl di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, And bifunctional (meth) acrylic compounds such as bifunctional epoxy (meth) acrylate and the like, and bifunctional urethane (meth) acrylate. 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.

  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.

<Example 1> A polyethylene terephthalate film having a width of 600 mm and a thickness of 25 μm is mounted on the unwinding roll (5) of the vacuum film forming apparatus (1), and the inside of the vacuum film forming apparatus (1) is 1.0 × 10 ⁻³ Pa. The pressure was reduced to. Acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM5103) is supplied to the active energy ray curable resin raw material layer A resin deposition apparatus (11), and the active energy ray curable resin A is placed on the polymer resin substrate (101). The evaporation amount of the resin raw material A was controlled so that the film thickness of both end portions (A portion in FIG. 6) of the layer (102) was 0.7 μm. At this time, the value of A was 20 mm. The film thickness of part B in FIG. 6 was about 0.25 μm, and the acceleration voltage irradiated by the electron beam irradiation apparatus (14) was about 8 kV. Further, the crucible (18) filled with aluminum is heated with an electron beam heating device (17), and the gas barrier layer C (103) is successively introduced while introducing oxygen gas so that the transmittance of the aluminum oxide film is around 85%. Manufactured. Further, trimethylolpropane triacrylate is supplied onto the gas barrier layer C (103) to the active energy ray curable resin raw material layer B resin deposition apparatus (21), and the thickness after curing is controlled to be 0.2 μm. Thus, an active energy ray-curable resin B layer (104) was produced. At this time, the minimum tension that can be wound was 2 kg over the entire width.
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 ·· Based on JIS5400, after cutting the coated surface into 100 mm grids at 1 mm each, the tape was peeled 180 ° and the residual rate (%) was measured, and the gas barrier layer C (103) 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) Winding suitability evaluation: The laminated roll wound up after film formation was taken out, and the number of wrinkles generated in the film forming effective surface was visually observed.

  The evaluation results for the laminates obtained in Example 1 and Comparative Example 1 are shown in Table 1 below. As shown in Table 1, the laminates shown in Examples and Comparative Example 2 had a high water vapor barrier property and sufficient adhesion performance as compared with the laminates shown in Comparative Examples 1 and 3, and were excellent. It was confirmed that the winding property was expressed. Further, it was confirmed that the water vapor barrier performance of Comparative Example 3 was deteriorated despite the same film configuration as that of Comparative Example 1. This is because the surface of the active energy ray-curing resin B layer covers the lubricant and hides the lubricant, and therefore the rewinding operation is performed in an environment where the slipping property at the time of winding is extremely deteriorated. Wrinkles are generated due to the uneven winding tension caused by variations in the film thickness of A and B, and the film itself is subjected to great stress, and dust is mixed into the surface during rewinding work. This suggests that the effect of stress on tightening cannot be ignored. The difference in the surface state due to the rewinding work can be easily estimated from the difference in barrier performance between Comparative Example 2 and Comparative Example 3.

<Comparative Example 1>
The active energy ray-curable resin A layer (102) is controlled on the surface of the polymer resin substrate (101) using a slit having the same clearance C and clearance D in FIG. 2 while controlling the film thickness to be 0.25 μm. Manufactured. Further, a gas barrier layer C (102) was formed under the same conditions as in Example 1, acryloxypropyltrimethoxysilane was formed on the gas barrier layer C (102), and an active energy ray curable resin raw material layer A resin deposition apparatus (8 The active energy ray-cured resin B layer (104) was produced while controlling the thickness after curing to 0.2 μm. The active energy ray irradiation conditions were the same as those in Example 1, but the minimum tension that could be wound was 6 kg over the entire width.

<Comparative Example 2>
Under the same conditions as in Example 1, winding film formation was performed off-line. (Films were formed while rewinding each layer for each pass.

<Comparative Example 3>
Under the same conditions as in Comparative Example 1, winding film formation was performed off-line. (Films were formed while rewinding each layer for each pass.

  TECHNICAL FIELD The present invention relates to 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, and a method for producing the same.

It is a schematic explanatory drawing explaining an example of the manufacturing apparatus which concerns on manufacture of the laminated body of this invention and contains a vacuum film-forming apparatus (1). It is a schematic explanatory drawing explaining the cross-sectional shape of the injection nozzle in the base-material width direction of the vapor deposition apparatus for manufacturing the active energy ray hardening resin layer A manufactured by this invention. It is a schematic explanatory drawing explaining the cross-sectional shape of the injection nozzle in the base-material width direction of the vapor deposition apparatus for manufacturing the active energy ray hardening resin layer B manufactured by this invention. It is a schematic explanatory drawing explaining the manufacture example of the protective film manufactured by this invention. It is a schematic explanatory drawing explaining the comparative example of the protective film manufactured by this invention. It is a schematic explanatory drawing explaining the laminated body example manufactured by this invention. It is a schematic explanatory drawing explaining the comparative example of the laminated body manufactured by this invention.

Explanation of symbols

1 Vacuum deposition system 2 Vacuum pump A
3 Process role A
4 Process role B
5 Unwinding roll 6 Winding roll 7 Nip roll 8 Winding roll 9 Shielding plate A
10 Vacuum pump B
11 Active energy ray curable resin vapor deposition equipment A
12 Active energy ray curable resin A raw material supply device 13 Active energy ray resin A raw material control device A
14 Electron beam irradiation device A
15 Gas supply device A
16 Shielding plate B
17 Electron beam heating vapor deposition device 18 Crucible 19 Shield plate C
20 Guide roll

Claims (9)

  Protect the polymer resin base material by agglomerating the (meth) acrylic compound in a vacuum at both ends in the width direction, and then irradiating with an electron beam or plasma to cure the acrylic compound to produce an active energy ray curable resin layer A method for producing a film.   A surface further inside than the both ends of the aggregate thickness of the acrylic compound produced in the (meth) acryl compound at the both ends in a vacuum on both ends in the width direction of the polymer resin substrate and on the surfaces inside the both ends The method for producing a protective film according to claim 1, wherein the agglomerated thickness of the acrylic compound produced in 1 is thinly agglomerated and then irradiated with an electron beam or plasma to cure the acrylic compound and produce an active energy ray-curable resin layer. .   The said protective film contains the compound which has a 2 or more (meth) acryl group, The manufacturing method of the protective film of Claim 1 or Claim 2 characterized by the above-mentioned.   The protective film manufactured with the manufacturing method in any one of Claims 1-3.   The method for producing a protective film according to claim 1 or 2, wherein a method of applying the active energy ray-curable resin layer to the surface of the polymer resin substrate is a flash vapor deposition method.   The step of forming the active energy ray-curable resin layer on the polymer resin substrate and the step of forming the gas barrier layer are all sequentially manufactured without being exposed to the atmosphere in the same vacuum apparatus. The manufacturing method of the protective film of Claim 1 or Claim 2 characterized by the above-mentioned.   The step of forming the active energy ray curable resin layer on the polymer resin substrate, the step of forming the gas barrier layer, and the step of forming the active energy ray curable resin layer on the barrier layer are all the same vacuum apparatus. The method for producing a protective film according to claim 1, wherein the protective film is produced sequentially without being exposed to the atmosphere.   The protective film according to claim 4, wherein a gas barrier thin film made of an inorganic compound is produced directly on the film according to claim 3.   The acrylic compound comprising a compound containing a compound having two or more (meth) acrylic groups is aggregated immediately on the film according to claim 8, and then the acrylic compound is cured by irradiating with an electron beam or plasma. The protective film which manufactured the active energy ray hardening resin layer.

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