JP7115501B2 - Laminated barrier film. - Google Patents

Description

TECHNICAL FIELD The present invention relates to a transparent barrier film that is used as a gas-barrier material or a packaging material that is required to be airtight, such as foods, medicines, and electronic parts, which has excellent gas barrier properties.

Films with excellent gas barrier properties are known in which plastic films are laminated with aluminum, and films in which vinylidene chloride or ethylene-vinyl alcohol copolymer is coated. Also, as a material using an inorganic thin film, there is known a material in which thin films of silicon oxide, aluminum oxide, etc. are laminated (see, for example, Patent Document 1).
However, since the inorganic layer formed on the plastic film is very thin, it may be deteriorated when the inorganic thin film layer is subjected to post-processing such as printing. For example, in the printing process, the inorganic layer may be scratched due to friction with a gravure roll or pigment particles contained in the ink, resulting in a decrease in barrier properties. For this improvement, there is a method of coating an organic layer on an inorganic layer. A coating agent dissolved in a solvent is applied and dried to form an organic layer. There is also a method using a vacuum process (see Patent Document 2, for example).

However, since the adhesion between the inorganic layer and the organic layer is weak in the method using a vacuum process, a method has been proposed in which the organic layer is formed into two layers, a primer layer and a protective layer (see, for example, Patent Document 3). .
However, in this method, each layer is laminated in a liquid phase before cross-linking, so it is difficult to always mix the two layers uniformly. Moreover, a mechanism for evaporating two kinds of monomers is required, which complicates the apparatus.

Japanese Patent No. 2700019 Japanese Patent No. 4604674 JP-A-2006-95932

The present invention is intended to solve the above problems, and relates to a transparent barrier film in which an inorganic layer and an organic layer are provided on one side of a plastic film. To provide a transparent barrier film suitable for packaging.

That is, the present invention has a structure in which an inorganic layer and an organic layer having a thickness of 50 nm or more and 150 nm or less are laminated in this order on at least one side of a plastic film, and the organic layer contains an acryloyl group and/or a methacryloyl group. A structure obtained by cross-linking copolymerization of a compound (A) that is not a silane coupling agent and a compound (B) that is a silane coupling agent having an acryloyl group and/or a methacryloyl group, and has an acryloyl group and/or methacryloyl The weight of the compound (B) having a group and being a silane coupling agent is 5% by weight or more with respect to the total weight of the compounds (A) and (B) having an acryloyl group or a methacryloyl group. It is a barrier film.

In this case, it is preferable that the organic layer is formed by vapor-depositing the compound (A) and the compound (B) on an inorganic layer by flash vapor deposition, followed by electron beam irradiation. be.

Moreover, in this case, it is preferable that the inorganic layer mainly consists of aluminum oxide and silicon oxide.

The transparent barrier film of the present invention has excellent adhesion between the organic layer and the inorganic layer, and does not deteriorate in barrier properties even after processing such as printing or lamination with other films. Alternatively, it can be used as a gas barrier material.

Schematic diagram of a transparent barrier film produced by the production method of the present invention Schematic diagram of an example of an apparatus used in the production method of the present invention Schematic diagram of an example of an organic vapor deposition source used in the production method of the present invention

(plastic film)
The plastic film (1) referred to in the present invention is a film obtained by melt extruding an organic polymer, stretching it in the longitudinal direction and/or the width direction, cooling, and heat setting as necessary. Examples include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic polyamide, polyamideimide, Examples include polyimide, polyetherimide, polysulfone, polyphenylene sulfide, and polyphenylene oxide. In addition, these (organic polymers) organic polymers may be copolymerized or blended with other organic polymers in small amounts.

Furthermore, known additives such as ultraviolet absorbers, antistatic agents, plasticizers, lubricants, and colorants may be added to the organic polymer, and the transparency is not particularly limited. When used as a transparent gas barrier film, it preferably has a transmittance of 50% or more.
The plastic film (1) of the present invention is subjected to corona discharge treatment, glow discharge treatment, or other surface roughening treatment prior to lamination of the thin film layers, as long as the object of the present invention is not impaired. Alternatively, known anchor coating treatment, printing, and decoration may be applied.

The thickness of the plastic film (1) in the present invention is preferably in the range of 1 μm to 300 μm, more preferably in the range of 9 μm to 25 μm.

(Inorganic layer)
The inorganic layer (2) in the present invention includes metals such as Al, Si, Ti, Zn, Zr, Mg, Sn, Cu, and Fe, and oxides, nitrides, fluorides, and sulfides of these metals. Specific examples include SiOx (x=1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, zirconia, cerium oxide, or mixtures thereof. The inorganic layer (2) may be a single layer or a laminate of two or more layers.

In the present invention, a particularly preferred inorganic layer (2) is a composite oxide layer formed by vapor-depositing aluminum oxide and silicon oxide, or a composite oxide layer formed by vapor-depositing aluminum oxide and magnesium oxide.
In the case of a composite oxide prepared by vapor deposition of aluminum oxide and silicon oxide, the weight ratio of aluminum oxide contained in the inorganic compound thin film is not particularly limited. The ratio of aluminum oxide is preferably 10% by weight or more, more preferably 20% by weight or more, further preferably 30% by weight or more, relative to the total 100% by weight of magnesium). Also, the proportion of aluminum oxide is preferably 90% by weight or less, more preferably 75% by weight or less, and further preferably 65% by weight or less.
If the proportion of aluminum oxide exceeds 75% by weight, the flexibility tends to be poor, so cracks are likely to occur during handling, and it may be difficult to obtain stable barrier properties. On the other hand, when the proportion of aluminum oxide is less than 30% by weight, the barrier properties tend to be lowered.

The film thickness of the inorganic layer (2) of the present invention is not particularly limited, but is preferably 5 to 500 nm, more preferably 8 nm or more and 100 nm or less. On the other hand, even if the thickness exceeds 500 nm, the corresponding effect of improving the gas barrier property cannot be obtained, and it is rather disadvantageous in terms of bending resistance and manufacturing cost. becomes.

As a method for forming the inorganic layer (2) of the present invention, known methods such as physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition methods such as PECVD are employed.

In the vacuum deposition method, metals such as aluminum, silicon, titanium, magnesium, zirconium, cerium, zinc, etc., as deposition materials, SiOx (x=1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, Compounds such as zirconia and mixtures thereof are used. As a heating method, resistance heating, induction heating, electron beam heating, or the like is adopted. Also, a reactive vapor deposition method may be employed in which oxygen or the like is introduced as a reactive gas, ozone is added, ion assist is used, or the like.

(Organic layer)
The organic layer (3) referred to in the present invention includes a compound (A) having an acryloyl group and/or a methacryloyl group and not a silane coupling agent and a compound (B) having an acryloyl group and/or a methacryloyl group and being a silane coupling agent. It consists of a structure obtained by cross-linking copolymerization.

The compound (A) which has an acryloyl group and/or a methacryloyl group and is not a silane coupling agent is not particularly limited. Acrylates, 2-hydroxybutyl methacrylate, methacrylic acid, glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, triethylene glycol dimethacrylate, PEG #200 dimethacrylate, PEG #400 dimethacrylate, methoxypolyethylene glycol methacrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxydipropylene glycol acrylate, 2-hydroxybutyl acrylate, 2 -hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl-phthalate, 2-acryloyloxyethyl acid phosphate, triethylene glycol Diacrylate, PEG200# diacrylate, PEG400# diacrylate, PEG600# diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalate acrylic acid adduct, trimethylolpropane triacrylate, EO modified Examples include trimethylolpropane triacrylate, pentaerythritol triacrylate, and the like.
At this time, one having two or more acryloyl groups and/or methacryloyl groups per molecule is preferable.

The compound (B), which has an acryloyl group and/or a methacryloyl group and is a silane coupling agent, refers to an organosilicon compound having at least an acryloyl group or a methacryloyl group and a hydrolyzable group. Examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like. can be done.

In the present invention, a compound (A) having an acryloyl group and/or a methacryloyl group and not a silane coupling agent and a compound (B) having an acryloyl group and/or a methacryloyl group and being a silane coupling agent are crosslinked and copolymerized. The weight ratio of the compound (B), which has an acryloyl group and/or a methacryloyl group and is a silane coupling agent, in the organic layer obtained is preferably 5% by weight or more.

Acryloyl group and/or methacryloyl group relative to the total weight of the compound (A) having an acryloyl group and/or methacryloyl group and not a silane coupling agent and the compound (B) having an acryloyl group and/or methacryloyl group and being a silane coupling agent The weight ratio of compound (B), which is a silane coupling agent, can be calculated by measuring the amount of silicon atoms contained in the organic layer.

The compound (B), which has an acryloyl group and/or a methacryloyl group and is a silane coupling agent, contributes to improving the adhesion between the inorganic layer and the organic layer, and its content is preferably 5% by weight or more. More preferably, it is 10% by weight or more. If the content of the compound (B), which has an acryloyl group and/or a methacryloyl group and is a silane coupling agent, increases, the adhesion improves, but the compound (B), which has an acryloyl group and/or a methacryloyl group and is a silane coupling agent ) is expensive, and more than 50 wt. 40% by weight or less is more preferable, and 30% by weight or less is most preferable.

The organic layer has a function of protecting the inorganic layer and a function of improving the adhesive force when sticking with a sealant or the like with an adhesive. In order to satisfy the protective function, the thickness of the organic layer is preferably 50 nm or more. If it is 50 nm or less, the inorganic layer cannot be protected from pigment particles and the like contained in the pigment ink. In addition, when the film thickness is 150 nm or more, the protective function is increased, but the stress of the organic layer and defects included therein are increased, resulting in a decrease in adhesion.

As a method for forming the organic layer, flash vapor deposition, which is a vacuum process, is suitable. Flash vapor deposition is a method in which a material to be vapor-deposited is brought into contact with a heated plate or the like little by little and vaporized instantaneously. A known technique can be used as a method for heating the heating plate. Examples include a method in which a heating wire is installed on the opposite side of the heating plate where the vapor deposition material contacts so as to ensure good thermal contact, a method in which a heat medium is circulated, and a method in which IR heaters are used for heating.

As a method for cross-linking and curing a compound having an acryloyl group or a methacryloyl group formed on an inorganic layer of a plastic film by flash vapor deposition, curing by electron beam irradiation is suitable. There is also a curing method by ultraviolet irradiation, but the compound must be mixed with a photopolymerization initiator, and in this case storage in a cool and dark place is required, which is a problem.
A known radiation source can be used as the electron beam source. For example, an electron gun type source can scan the electron beam to irradiate a range of areas. Alternatively, a linear electron source may be placed on the running film to irradiate it.

At least one layer of various films or papers may be laminated on the transparent barrier film of the present invention.
Lamination of the heat-sealable resin layer is usually carried out by an extrusion lamination method or a dry lamination method. As the thermoplastic polymer for forming the heat-sealable resin layer, any polymer can be used as long as it can exhibit sufficient sealant adhesiveness. Polymers, ethylene-α-olefin random copolymers, ionomer resins and the like can be used.

The printing ink for forming the printing layer on the transparent barrier film of the present invention may be a water-based resin-containing printing ink or a solvent-based resin-containing printing ink. Examples of resins used in printing inks include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. Antistatic agents, light shielding agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, cross-linking agents, anti-blocking agents, antioxidants, and other known additives are used in printing inks. may contain additives. The printing method for forming the printed layer is not particularly limited, and known printing methods such as offset printing, gravure printing, and screen printing can be used. For drying the solvent after printing, a known drying method such as hot air drying, hot roll drying, or infrared drying can be used.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
The film properties obtained in each example were measured and evaluated by the following methods.

(1) Adhesion Strength A 40 μm-thick polyethylene film (L4102, manufactured by Toyobo Co., Ltd.) was adhered to a transparent deposition barrier film using a dry lamination adhesive (TM590, CAT56, manufactured by Toyo-Morton Co., Ltd.) to prepare a laminate film.
The adhesive strength of the laminate is measured by cutting the laminate film to a width of 15 mm, peeling off a part of the laminate film, pulling the peeled piece at a speed of 300 mm / min using a universal material testing machine (Tensilon), and peeling it 180 °. did.

(2) Measurement of oxygen permeation amount and water vapor permeation amount Oxygen permeation amount is prepared according to JIS K7126-2 A method, oxygen permeation amount measuring device (OXTRAN 2/21 manufactured by MOCOM), temperature 23 degrees, humidity 65%. Measured under RH atmosphere.
The amount of water vapor transmission was measured according to JIS K7129 B method using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCOM) under an atmosphere of 40° C. temperature and 90% RH.

In addition, for the measurement after printing, white ink (Fine Star R641 White, manufactured by Toyo Ink Co., Ltd.) was printed on one side by gravure printing.

(3) Measurement of Film Thickness and Composition of Inorganic Layer A method for measuring the composition of each content of aluminum oxide and silicon oxide in the inorganic layer will be described below.
First, a film having an inorganic compound thin film composed of aluminum oxide and silicon oxide was prepared, and the deposition amount of each of aluminum oxide and silicon oxide was determined by an inductively coupled plasma emission method (ICP method). The composition of the prepared inorganic oxide thin film was calculated from the obtained adhesion amounts of aluminum oxide and silicon oxide.
The film thickness was calculated assuming that the density of the inorganic oxide thin film was 80% of the bulk density, and that the volume of each of the aluminum oxide and silicon oxide was maintained even in a mixed state.
The content wa (%) of aluminum oxide in the film and the content ws (%) of silicon oxide in the film are defined by Ma (g/cm 2 ), which is the adhesion amount per unit area of aluminum oxide, and Ma (g/cm ² ), which is the amount of silicon oxide per unit area. Assuming that the adhesion amount per unit is Mm (g/cm ² ), it is obtained by the following formulas (1) and (2).
wa=100×[Ma/(Ma+Mm)] (1)
ws=100-wa (2)
Let Ma (g/cm ² ) be the adhesion amount of aluminum oxide per unit area, ρa (3.97 g/cm ³ ) be its bulk density, and Ms (g/cm ² ) be the adhesion amount of silicon oxide per unit area. ) and its bulk density is ρs (2.65 g/cm ³ ), the film thickness t (nm) is obtained by the following equation (3).
t = ((Ma/(ρa×0.8)+Ms/(ρs×0.8))×10 ⁻⁷ Equation (3)
Several kinds of inorganic oxide thin films with specified film thickness and composition were prepared, and a calibration curve was prepared by measuring them with a fluorescent X-ray apparatus.
Using a fluorescent X-ray spectrometer (“ZSX100e” manufactured by Rigaku Corporation), the film thickness composition was measured according to a calibration curve prepared in advance. The conditions for the excitation X-ray tube were 50 kV and 70 mA.

(4) Measurement of thickness and composition of organic layer Compound (A) having an acryloyl group and/or methacryloyl group and not a silane coupling agent and Compound (B) having an acryloyl group and/or a methacryloyl group and being a silane coupling agent ) was calculated by measuring the amount of silicon atoms contained in the organic layer.
An organic layer cured by electron beam irradiation consisting of compound (B) alone, which has an acryloyl group and/or a methacryloyl group and is a silane coupling agent, is previously formed in various thicknesses. This organic layer was measured by a fluorescent X-ray spectrometer, and a calibration curve was prepared from the fluorescent X-ray intensity of silicon atoms and the thickness of the organic layer consisting of compound (B) alone, which is a silane coupling agent.
Film thickness of an organic layer obtained by cross-linking copolymerization of a compound (A) having an acryloyl group and/or a methacryloyl group and not a silane coupling agent and a compound (B) having an acryloyl group and/or a methacryloyl group and being a silane coupling agent was measured. Further, the fluorescent X-ray intensity was measured, and the measured value was used to calculate the equivalent film thickness of the compound (B) having an acryloyl group and/or a methacryloyl group and being a silane coupling agent from the calibration curve.
As a method for measuring the film thickness of the organic layer, there is a method of directly measuring a cross section with a transmission electron microscope (TEM). Alternatively, an ellipsometer or a reflection spectroscopic film thickness meter can be used for measurement using interference. In this case, a correlation is taken with the value obtained by TEM, and the value is converted to that value.
The content was calculated by dividing the equivalent film thickness of the compound (B), which is a silane coupling agent having an acryloyl group and/or a methacryloyl group, by the total film thickness of the organic layer.
At this time, an organic layer consisting solely of the compound (B) which has an acryloyl group and/or a methacryloyl group and is a silane coupling agent, the compound (A) which has an acryloyl group and/or a methacryloyl group and is not a silane coupling agent, and an acryloyl group. And/or the density of the organic layer obtained by cross-linking copolymerization with the compound (B), which has a methacryloyl group and is a silane coupling agent, was calculated as the same.

A method for producing a transparent vapor-deposited barrier film of the present invention will be described with reference to the schematic diagrams of FIGS. 2 and 3. FIG. A roll of substrate plastic film is set on the unwind roll (4). The unwound plastic film (1) passes through a plasma processor (5) to treat the surface. An electron gun (6) heats and evaporates the ceramic in the crucible (7) to form an inorganic layer on the plastic film running on the inorganic coating roll (8).

A mixed compound (13) composed of at least two compounds having an acryloyl group or a methacryloyl group and at least one of which is a silane coupling agent is placed in a liquid container (14). The mixed compound (13) is transported inside the organic deposition source (16) by a liquid pump (15). The transferred mixed compound (13) comes into contact with a heating plate (18) heated by a heating wire (17) and becomes vapor. The vapor travels through an organic evaporation source (16) which is heated so as not to condense and reaches an organic nozzle (9).

An inorganic layer running on an organic coating roll (10) is vapor-deposited from a heated organic nozzle (9) onto the laminated plastic film. A mixed compound liquid layer is formed on the inorganic layer. The formed liquid layer is irradiated with an electron beam using an electron beam irradiation device (11) to crosslink and cure. In this way, the organic layer is formed on the inorganic layer and wound up on the winding roll (12).

(Example 1)
A polyethylene terephthalate film (E5100, thickness 12 μm, manufactured by Toyobo Co., Ltd.) was used as the plastic film. Aluminum oxide and silicon oxide were charged separately into a crucible and individually heated by an electron gun for vapor deposition. The formed inorganic layer had a thickness of 15 nm and an aluminum oxide content of 38% by weight.
Subsequently, on the inorganic layer, 9 parts of PEG200# diacrylate (Kyoeisha Chemical Co., Ltd. Light Ester 4EG) and a silane coupling agent 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-503) 1 part was deposited by flash vapor deposition and cured by electron beam. The content of the silane coupling agent in the organic layer was 10% by weight. This film was laminated and the adhesive strength was measured. Table 1 shows the results.

(Example 2)
Example 1 was carried out in the same manner as in Example 1, except that the silane coupling agent in the mixed compound was 50% by weight.

(Example 3)
The procedure of Example 1 was repeated except that the silane coupling agent in the mixed compound was changed to 70% by weight.

(Example 4)
The procedure of Example 1 was repeated except that the silane coupling agent in the mixed compound was 90% by weight.

(Comparative example 1)
Example 1 was carried out in the same manner as in Example 1, except that only the PEG200# diacrylate compound was used without mixing the silane coupling agent.

(Example 5)
A polyethylene terephthalate film (E5100, thickness 12 μm, manufactured by Toyobo Co., Ltd.) was used as the plastic film. Aluminum oxide and silicon oxide were charged separately into a crucible and individually heated by an electron gun for vapor deposition. The formed inorganic layer had a thickness of 19 nm and an aluminum oxide content of 37% by weight.
A compound obtained by mixing 9 parts of PEG200# diacrylate and 1 part of silane coupling agent 3-methacryloxypropyltrimethoxysilane was vapor-deposited on the inorganic layer by flash vapor deposition and cured by electron beams to form a film thickness of 50 μm. The content of the silane coupling agent in the organic layer was 10% by weight. This film was laminated and the adhesive strength was measured.
Further, printing was performed on the organic layer and lamination was performed. The oxygen permeation amount and the water vapor permeation amount of the laminate film and the printed laminate film were measured. Table 2 shows the results.

(Example 6)
Example 5 was the same as Example 5, except that the film thickness of the organic layer was 75 nm.

(Example 7)
Example 5 was the same as Example 5, except that the film thickness of the organic layer was 100 nm.

(Example 8)
Example 5 was the same as Example 5, except that the film thickness of the organic layer was 150 nm.

(Comparative example 2)
Example 5 was the same as Example 5, except that the film thickness of the organic layer was 30 nm.

(Comparative Example 3)
Example 5 was the same as Example 5, except that the film thickness of the organic layer was 300 nm.

Table 2 shows the above results.

According to the present invention, it is possible to provide a transparent barrier film which is excellent in printing resistance and adhesion.

1: Plastic film 2: Inorganic layer 3: Organic layer 4: Unwinding roll 5: Plasma processor 6: Electron gun 7: Crucible 8: Inorganic coating roll 9: Organic nozzle 10: Organic coating roll 11: Electron beam irradiation device 12 : winding roll 13: mixed compound 14: liquid container 15: liquid pump 16: organic vapor deposition source 17: heating wire 18: heating plate

Claims (1)

A transparent barrier film having a structure in which an inorganic layer having a thickness of 8 nm or more and 100 nm or less and an organic layer having a thickness of 50 nm or more and 150 nm or less are laminated in this order on at least one side of a polyethylene terephthalate film having a thickness of 25 μm or less; A laminated barrier film obtained by laminating a heat-sealable resin layer, wherein the organic layer has a compound (A) that has an acryloyl group and/or a methacryloyl group and is not a silane coupling agent, and an acryloyl group and/or a methacryloyl group. It consists of a structure obtained by cross-linking copolymerization with the compound (B) which is a silane coupling agent, does not contain a photopolymerization initiator,
The compound (A) which has an acryloyl group and/or a methacryloyl group and is not a silane coupling agent includes phenoxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, methacrylic acid, glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, triethylene glycol dimethacrylate, PEG #200 dimethacrylate, PEG #400 dimethacrylate, methoxypolyethylene glycol methacrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxydipropylene glycol acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3 phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl-phthalic acid, 2-acryloyloxyethyl acid phosphate, triethylene glycol diacrylate, PEG200# diacrylate, The group consisting of PEG400# diacrylate, PEG600# diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalate acrylic acid adduct, EO-modified trimethylolpropane triacrylate, and pentaerythritol triacrylate At least one compound selected from
Compound (B), which is a silane coupling agent having an acryloyl group and/or a methacryloyl group, includes 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -Methacryloxypropyltriethoxysilane, and at least one compound selected from the group consisting of 3-acryloxypropyltrimethoxysilane, wherein the weight of (B) is an acryloyl group or a compound (A ) and (B) in an amount of 5% by weight or more.

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