JPH0734220A - Formation of vapor-deposited film - Google Patents

Abstract

PURPOSE:To provide a method for forming a vapor-deposited film of an inorganic material sufficient in adhesion in the method for forming a vapor- deposited film of an inorganic material such as a metal or metal oxide or the like on a resin substrate or resin layer by vapor deposition. CONSTITUTION:A substrate is coated with a resin composition contg. ionizing radiation hardening tape resin to form an intermediate resin coating film, and the state of the coating film is formed into a semihard one. The intermediate resin coating film in a semihard state is vapor-deposited with an inorganic material to form a vapor-deposited film. Next, ionizing radiation is applied to perfectly harden the semihard coating film. The obtd. vapor-deposited film is sufficient in adhesion to prevent the peeling of the vapor-deposited film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a vapor deposition film of an inorganic material which is used for various functional vapor deposition films such as gas barrier sheet materials such as food packaging materials, conductive films and antireflection films.

[0002]

2. Description of the Related Art Conventionally, in the production of gas barrier sheet materials such as food packaging materials, conductive films, antireflection films, etc.
BACKGROUND ART A vapor-deposited film of an inorganic material such as a metal or a metal oxide is formed by vapor deposition on a resin substrate or on a resin layer having various functions laminated on a substrate.

[0003]

However, a method of forming a vapor deposition film of an inorganic material such as a metal or a metal oxide on a resin base material or a resin layer by the vapor deposition is as follows. Since the two materials are different materials in joining, the adhesiveness was not sufficient and peeling sometimes occurred.

Therefore, the present invention is not particularly limited to the material of the base material, and even when the base material is made of resin, the vapor deposition film of the inorganic material is formed on the surface of the various base materials. Also, it is an object of the present invention to provide a method for forming a vapor-deposited film capable of achieving sufficient adhesion.

[0005]

In order to solve the above-mentioned problems, the present invention is to apply a resin composition containing an ionizing radiation curable resin onto a substrate to form a coating film. In a semi-cured state, the semi-cured coating film is vapor-deposited with an inorganic material to form a vapor-deposited film, and the semi-cured coating film is completely cured by irradiation with ionizing radiation. The formation method of

In the present invention, a resin composition containing an ionizing radiation curable resin is applied onto a substrate to form an intermediate resin coating film in a semi-cured state, while a vapor deposition layer is formed on a release paper. The release paper on which the vapor deposition layer is formed, and the transparent resin substrate on which the intermediate resin coating film is formed are closely bonded to each other so that the intermediate resin coating film and the vapor deposition layer face each other, and the semi-cured A method for forming a vapor deposition film, characterized in that the vapor deposition layer is transferred to the intermediate resin coating film by completely curing the intermediate resin coating film and then peeling off the release paper.

Further, according to the present invention, a vapor deposition layer is formed on a release paper, a resin composition containing an ionizing radiation curable resin is applied on the vapor deposition layer to form an intermediate resin coating film in a semi-cured state, With respect to the release paper on which the vapor deposition layer and the intermediate resin film are formed, the base material is closely adhered and bonded with the intermediate resin coating film inside,
The semi-cured intermediate resin coating film is completely cured, and then the release layer is peeled off to transfer the vapor deposition layer to the intermediate resin coating film.

The type of substrate used in the method for forming a vapor deposited film of the present invention is not particularly limited, and any type of substrate can be used as long as it can form a resin coating film. Can be applied particularly effectively when an inorganic material is vapor-deposited on a resin base material that has conventionally been poor in adhesiveness.

In the present invention, a resin composition containing an ionizing radiation curable resin can be preferably used as the resin capable of bringing the vapor deposition film into close contact with the intermediate resin coating film in a semi-cured state. Examples of such resins include the following. That is, the ionizing radiation curable resin alone, a mixture of an ionizing radiation curable resin and an adhesive resin, a mixture of an ionizing radiation curable resin and a thermosetting resin, and a solid-phase reaction type ionizing radiation curable resin. Is used.

Ionizing radiation-curable resin: Examples of the ionizing radiation-curable resin used for forming the intermediate resin coating film are preferably those having an acrylate-based functional group, for example, relatively low. Molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin,
Urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin, polythiol polyene resin,
Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N as reactive diluents
-Monofunctional and polyfunctional monomers such as vinylpyrrolidone, eg trimethylolpropane tri (meth)
Acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. which contain a relatively large amount can be used.

Further, in order to use the above ionizing radiation curable resin as an ultraviolet curable resin, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester and tetramethyl are used as photopolymerization initiators in the resin. Thiuram monosulfide, thioxanthone, and n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used as a photosensitizer. Particularly in the present invention, it is preferable to mix urethane acrylate as the oligomer and dipentaerythritol hexaacrylate as the monomer.

Adhesive resin: The adhesive resin mixed with the above-mentioned ionizing radiation-curable resin imparts viscosity to the ionizing radiation-curable resin, and is composed of an adhesive and an ionizing radiation-curable resin. It is preferable that the resin is formed from a mixture thereof, but it can be used as it is if the ionizing radiation-curable resin is not crosslinked in a liquid state and has an adhesive property. In particular, in order to keep the hardness of the coating film high, thermoplastic resins such as polymethyl methacrylate and polybutyl methacrylate can be preferably used.

The other resin may be one that has been used for a conventionally known adhesive tape or adhesive seal.
Rubber-based resins such as polyisoprene rubber, polyisobutylene rubber, styrene-butadiene rubber, butadiene-acrylonitrile rubber, (meth) acrylic acid ester-based resin, polyvinyl ether-based resin, polyvinyl acetate-based resin, polyvinyl chloride / vinyl acetate copolymer-based Resin, polystyrene resin, polyamide resin, polychlorinated olefin resin,
Suitable tackifiers for polyvinyl butyral resin and the like, for example, rosin, dammar, polymerized rosin, partially hydrogenated rosin,
Ester rosin, polyterpene-based resin, modified terpene, petroleum-based resin, cyclopentadiene-based resin, phenol-based resin, coumarone-indene-based resin are appropriately added, and if necessary, a softener, a filler, an antiaging agent, etc. It was added.

The purpose of mixing the ionizing radiation-curable resin with the resin having tackiness is to semi-cure the coating film and to impart tackiness. The mixing ratio of the resin having adhesiveness to the ionizing radiation curable resin is preferably 50 parts by weight or less with respect to 100 parts by weight of the ionizing radiation curable resin for the purpose of semi-curing the coating film. .

Thermosetting resin: The thermosetting resin contained in the mixture of the ionizing radiation curing resin and the thermosetting resin includes phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, Unsaturated polyester resin, polyurethane resin, epoxy resin,
Amino alkyd resin, melamine / urea co-condensation resin, silicon resin, polysiloxane resin, etc. are available.
A crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, and an extender pigment are added as additives. As the curing agent, usually, isocyanate is an unsaturated polyester resin or polyurethane resin, and peroxide such as methyl ethyl ketone peroxide and a radical initiator such as azobisisobutyronitrile are often used for the unsaturated polyester resin. . Furthermore, as the isocyanate as the curing agent, divalent or higher valent aliphatic or aromatic isocyanate can be used.

Solid-phase reaction-type ionizing radiation-curable resin: The above-mentioned solid-phase-reaction type ionizing-radiation-curable resin is solid at room temperature in the uncrosslinked state, and has thermoplasticity and solvent solubility. It is mainly composed of an ionizing radiation curable resin that gives a coating that is non-fluid (drying to the touch) even when touched by hand by coating and drying, and that is non-adhesive. is there. Specifically, for example, the following two types of resins (a) and (b) are exemplified. A similar resin is disclosed in JP-A-1-202492. Furthermore, the resins shown in (a) and (b) below can be mixed and used, and a radically polymerizable unsaturated monomer can also be added thereto for use.
Reactive diluents, sensitizers and the like used in ordinary ionizing radiation curable resins are added to these resins. Further, a non-crosslinking thermoplastic resin may be added in order to impart flexibility to the cured resin product.

(A) A resin having a radically polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C.

Specifically, it is a resin obtained by polymerizing or copolymerizing the monomers listed below and introducing a radical copolymerizable unsaturated group by the methods a) to d) described below.

Monomers having hydroxyl groups: For example, N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy. Examples include propyl (meth) acrylate.

Monomers having a carboxyl group: For example,
Examples include (meth) acrylic acid and (meth) acryloyloxyethyl monosuccinate.

Monomers having epoxy groups: For example, glycidyl (meth) acrylate and the like.

Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate and the like.

Monomers having amino groups: (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like.

Monomers having sulfone groups: 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like.

Monomers having isocyanate groups: 2,4
-Toluene diisocyanate and 2-hydroxyethyl (meth) acrylate 1 mole to 1 mole adduct and the like, and the like, the adduct of diisocyanate and a radical copolymer having active hydrogen, and the like.

Further, in order to control the glass transition temperature of the copolymer and the physical properties of the cured film, each of the monomers listed above and the following compounds can be copolymerized. Examples of such a copolymerizable monomer include methyl (meth) acrylate and propyl (meth).
Examples thereof include acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, gt-butyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

An ultraviolet-curable resin or a resin obtained by polymerizing or copolymerizing each of the above-mentioned monomers is introduced by introducing a radically polymerizable unsaturated group by the following methods a) to d). An ionizing radiation curable resin such as an electron beam curable resin can be obtained.

A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.

B) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the above-mentioned monomer having a hydroxyl group is subjected to a condensation reaction.

C) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or a monomer having a carboxyl group is subjected to an addition reaction. .

D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group, a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing acrylate ester Addition reaction is performed with 1 mol of monomer to 1 mol of adduct.

In order to carry out the above reaction, it is desirable to add a trace amount of a polymerization inhibitor such as hydroquinone and to carry out it while sending dry air.

(B) A resin having a radical-polymerizable unsaturated group and a melting point of room temperature (20 ° C.) to 250 ° C.

Specific examples include stearyl acrylate, stearyl (meth) acrylate, triacrylic isocyanate, cyclohexanediol (meth) acrylate, spiroglycol diacrylate, and spiroglycol (meth) acrylate.

Method for curing coating film: In the present invention, a semi-cured layer is formed by bringing an intermediate resin coating film layer applied on a transparent resin substrate into a semi-cured state such as touch-drying or half-cure. An inorganic material such as a metal or a metal oxide is vapor-deposited thereon to form a vapor deposition layer. The reason for semi-curing the intermediate resin coating film layer in the present invention is that even if a vapor deposition layer made of an inorganic material is formed on the completely cured intermediate resin coating film layer, since both layers are different materials, adhesion between layers is improved. Since the intermediate resin coating layer mainly composed of the resin layer is dry to the touch or half-cured in a semi-cured state, it is obliquely vapor-deposited onto the substrate. This is because the formed oblique vapor deposition layer has good adhesion to the intermediate resin coating film layer.

(1) Solvent drying type semi-curing a. Solvent-drying semi-curing The coating film formed by applying a solvent to a normal ionizing radiation-curing resin and drying the solvent is a semi-cured state, and the ionizing radiation-curing resin is a curing reaction. Is not completed.

Since the above composition alone cannot maintain a sufficient viscosity, a solvent drying type thermoplastic resin is added to adjust the viscosity suitable for coating. When a coating film is formed using this resin composition, the solvent is released and diffused during drying, and the coating film is in a semi-cured state.

As the solvent-drying type thermoplastic resin to be added to the ionizing radiation-curable resin, those which are usually used are used. Particularly, when polymethyl methacrylate or polybutyl methacrylate is used, the hardness of the coating film is high. Can be kept.

B. Solid-state reaction-type ionizing radiation-curable semi-curing This semi-curing is a state of semi-curing by the solid-state reaction-type ionizing radiation-curing resin, which is solid at room temperature in the uncrosslinked state, and is thermoplastic and solvent It refers to a state in which the resin has solubility, is non-fluid and non-tacky by appearance and by touching with coating and drying, and the curing reaction of the ionizing radiation curable resin is not completed.

(2) Half cure type semi-curing a. Ionizing radiation curable resin semi-crosslinking type semi-curing It is formed by applying a normal ionizing radiation-curable resin and adjusting the irradiation conditions of the ionizing radiation such as ultraviolet rays or electron beams to the coating film to carry out semi-crosslinking. A semi-cured state.

B. Ionizing radiation curable resin / thermosetting resin blend type semi-curing Semi-cured state formed by mixing the ionizing radiation curable resin with the thermosetting resin, applying the resin composition, and applying heat to the coating film. Say.

C. Solvent-drying / half-cure composite semi-curing This is a state in which the solvent-drying semi-curing state (1) is further irradiated with ionizing radiation to be a semi-curing state. This semi-cured state is the same as the semi-cured state described in JP-A-1-20249.

Method of Curing Coating Film: In the present invention, the resin composition containing the ionizing radiation-curable resin applied on the substrate is completely cured by irradiation with ionizing radiation. An inorganic material such as a metal or a metal oxide is deposited on the resin layer in a semi-cured state to form a vapor deposition film, and then ionizing radiation is performed, so that the inorganic material is bonded to the resin with sufficient adhesion. It

Irradiation device: The ionizing radiation curable resin used in the present invention can be cured by a usual method for curing an ionizing radiation curable resin, that is, an electron beam or an ultraviolet ray. For example, in the case of electron beam curing, Cockloft-Walton type, Van de Graaff type, resonance transformation type,
50-1000 emitted from various electron beam accelerators such as insulating core transformer type, linear type, dynamitron type, high frequency type
An electron beam or the like having an energy of KeV, preferably 100 to 300 KeV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc and a metal halide lamp are used. Available.

[0045]

【Example】

[Example 1] Ionizing radiation curing having the property that a film can be formed on the surface of a triacetyl cellulose film (FT-UV-80: trade name, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 µm by solvent drying. 5g of acrylic polymer-containing polyester acrylate) as mold resin
/ Dry was applied and dried at 60 ° C for 1 minute to form an uncrosslinked but semi-cured coating film.

[0046] was placed the film at an angle of 85 ° with respect to the deposition source composed of MgF _2, and MgF ₂ was oblique evaporation, to form a oblique deposition film having a thickness of 1600 Å. By irradiating this film with an electron beam at 5 Mrad, the coating film was completely cured to obtain an antireflection film.

Table 1 below shows values for each of the test items of the refractive index, the transmittance, the cellophane tape adhesion test using a grid and the surface hardness of the MgF ₂ film of the antireflection film obtained in this Example 1.

Example 2 In the above Example 1, Mg
The same treatment as in Example 1 was performed except that MgF ₂ was vapor-deposited in a normal direction, that is, MgF ₂ was vapor-deposited in the normal direction instead of obliquely vapor-depositing F ₂ . The antireflection film of Example 1 was obtained.

Table 1 below shows values for each of the test items such as the refractive index, the transmittance, the cellophane tape adhesion test using a grid and the surface hardness of the MgF ₂ film of the antireflection film obtained in Comparative Example 1.

[Comparative Example 1] A coating film coated with the same ionizing radiation curable resin as in Example 1 was irradiated with 5 Mrad of an electron beam to completely cure the coating film, and MgF ₂ was obliquely added onto the completely cured coating film. An antireflection film was produced under the same conditions as in Example 1 except that the oblique vapor deposition was performed to form a diagonal vapor deposition film having a film thickness of 1600Å. Table 1 below shows the values of the MgF ₂ film of the antireflection film obtained in Comparative Example 1, the refractive index, the transmittance, the cellophane tape adhesion test by cross-cutting, and the surface hardness.

[0051]

[Table 1] According to Table 1, the antireflection film formed by vapor deposition on the semi-cured intermediate resin coating film of the present invention (the above-mentioned Example 1,
It can be seen that in Example 2), the adhesion of the vapor deposition layer to the intermediate resin coating film is better than in the ordinary vapor deposition method of Comparative Example 1.

Example 3 An antireflection film was produced under the same conditions as in Example 1 with respect to a polyethylene terephthalate film (HP-7: trade name, manufactured by Teijin Limited) having a thickness of 125 μm.

Table 2 below shows the values of the MgF ₂ film of the antireflection film obtained in Example 3 for each of the refractive index, the transmittance, the cellophane tape adhesion test by cross-cutting, and the surface hardness.

Example 4 In the above Example 3, Mg
Instead of performing oblique vapor deposition of F ₂ , the same process as in Example 3 was performed except that MgF ₂ was vapor-deposited by a normal vapor deposition method, that is, vapor deposition was performed on the substrate in the normal direction. The antireflection film of Example 4 was obtained.

Table 2 below shows values for the respective test items of the refractive index, the transmittance, the cellophane tape adhesion test by cross-cutting and the surface hardness of the MgF ₂ film of the antireflection film obtained in this Example 4.

[Comparative Example 2] A coating film coated with the same ionizing radiation curable resin as in Example 3 was irradiated with an electron beam of 5 Mrad to completely cure the coating film, and MgF ₂ was obliquely added onto the completely cured coating film. An antireflection film was manufactured under the same conditions as in Example 3 except that the oblique vapor deposition film having a film thickness of 1600Å was formed by vacuum vapor deposition. Table 2 below shows the values for the respective test items of the refractive index, the transmittance, the cellophane tape adhesion test by cross-cutting, and the surface hardness of the MgF ₂ film of the antireflection film obtained in Comparative Example 42.

[0057]

[Table 2] According to Table 2, the antireflection films formed by the oblique vapor deposition of the present invention (Examples 3 and 4 above) were obtained by depositing an inorganic material such as MgF ₂ on the semi-cured intermediate coating layer. Since the vapor deposition film was formed and then the intermediate coating film was completely cured, the adhesion of the vapor deposition layer to the intermediate coating film layer was good.

[0058]

According to the present invention, a vapor-deposited film is formed by vapor-depositing an inorganic material on a semi-cured resin layer, and then the semi-cured coating film is completely cured by ionizing radiation. Therefore, the vapor deposition film made of the inorganic material is bonded to the resin layer with sufficient adhesion without peeling.

Claims (4)

[Claims] 1. An intermediate resin coating film is formed by coating a resin composition containing an ionizing radiation curable resin on a substrate, and (2) the intermediate resin coating film is semi-cured. 3) Vapor deposition of an inorganic material on the semi-cured intermediate resin coating film to form a vapor deposition film, and (4) irradiation of ionizing radiation to completely cure the semi-cured coating film. Method of forming a film. 2. (1) A resin composition containing an ionizing radiation-curable resin is applied on a substrate to form an intermediate resin coating film in a semi-cured state. (2) On the other hand, a vapor deposition layer is formed on a release paper. (3) The release paper having the vapor deposition layer formed thereon and the transparent resin base material having the intermediate resin coating film formed thereon are bonded to each other so that the intermediate resin coating film and the vapor deposition layer face each other. Then, the semi-cured intermediate resin coating film is completely cured, and then (4) the vapor deposition layer is transferred to the intermediate resin coating film by peeling off the release paper. (1) A vapor deposition layer is formed on a release paper, and a resin composition containing an ionizing radiation curable resin is applied on the vapor deposition layer to provide an intermediate resin coating film in a semi-cured state. (2) The substrate is closely adhered to the release paper on which the vapor deposition layer and the intermediate resin film are formed, with the intermediate resin coating film inside, and the semi-cured intermediate resin coating film is completely cured. (3) Next, a method for forming a vapor deposition film, characterized in that the vapor deposition layer is transferred to the intermediate resin coating film by peeling off the release paper. 4. The substrate according to claim 1, wherein the substrate is a resin substrate.
2. The method for forming a vapor deposition film according to 2 or 3.