JP2003291156A - Manufacturing method for laminated film having self assembly type fine structure and composition used for it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminated film having a self assembly type fine structure to assemble a fine structure (IC chip) on the flexible film, while maintaining a higher accuracy of form for the fine structure as well as a better production efficiency, optimum materials for that manufacture and the laminated film itself made of them. <P>SOLUTION: In the method, a reliably-adhesive UV cure resin composition- coated layer is provided on the film consisting of a circular olefin resin having highest heat resistance/dimensional stability and better UV permeability. Then the film is laminated with a die containing a protrusion fitted to the fine structure, UV irradiation from the film side cures the composition, finally the laminated film for assembly comprising both the film and the composition is peeled from the die. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a recess complementary to the shape of a microstructure on an organic plastic film or substrate used for self-assembling a microstructure (such as an integrated circuit device). A method for producing a laminated film or substrate having a recess (hereinafter, this laminated film or substrate is simply referred to as a laminated film), an ultraviolet curable resin composition used for the production, and a laminated film produced by the same. Regarding

[0002]

2. Description of the Related Art In recent years, proposals and developments regarding electronic paper have become active as portable electronic displays that combine the advantages of paper and PDAs (portable terminals) (Nikkei Microdevices, February 2001, p. .113
etc). There, elements having a display function, such as liquid crystal, organic EL, and electrophoresis, are mentioned. On the other hand, as a method of forming an integrated circuit element for driving these display elements on a substrate, (1) an inorganic polycrystalline silicon layer or an amorphous silicon layer is formed on a glass substrate to form an inorganic transistor. (2) A method of forming a thin film organic transistor by crystallizing an organic substance such as pentacene on a film (Nikkei Electronics,
October 8, 2001 issue, p. 55), (3) A truncated pyramid block-shaped IC chip (generally, a fine structure) is formed and placed, and the IC chip is dispersed in an alcohol aqueous solution to form a slurry. A substrate having recesses / depressions (referred to as a self-assemble type fine structure) having a shape complementary to the shape of the IC chip is dipped in the slurry, and I
Self-assemble C chip. As a result, a method of embedding an IC chip on the substrate (AM-LCD'01,
P. 81), etc.

The method (1) has a drawback that it requires a high temperature process for forming a silicon layer and cannot be applied to a flexible plastic substrate as a substrate. In (2), it is extremely difficult to form a large-area organic crystal, and the carrier mobility is 3 cm ² / Vs.
Is considered to be the limit (JH Shon et al., Sci.
ence, Vol. 287, P.I. 1022, 2000
Year), (hole) mobility of inorganic single crystal silicon 500 cm
Compared with ² / Vs, there is a drawback that the mobility is orders of magnitude lower and the display operating frequency cannot be increased.

In contrast to the former two, (3) uses a high mobility single crystal silicon or the like, and a large number of ICs are formed on one substrate such as single crystal silicon or the like by an already established integrated circuit forming process. Is formed, and then cut out as individual IC chips in the shape of a truncated pyramid. This method has a feature that a high-performance silicon IC chip can be easily and inexpensively assembled (self-assemble) on a film or a substrate while applying an existing silicon integrated circuit process or the like. Details of the process of the method (3) are disclosed in US Pat. No. 5,545,291, US Pat. No. 5,783,856, JP-A-9-120943, and US Pat. No. 6,274,508.

Here, in particular, US Pat. No. 6,274,508
Discloses a method for producing a film having a self-assembled fine structure which is a recess for assembling an IC chip. The method is polyethersulfone (PE
It is a web process in which a thermoplastic resin film such as S) or polyethylene terephthalate (PET) is passed through a template or a roller. However, this method cannot form an accurate self-assemble type fine structure at high speed, and a method with higher productivity has been demanded.

[0006]

In view of the above situation, an object of the present invention is to provide a laminated film having a self-assembled fine structure for assembling an IC chip on a flexible film. The present invention provides a manufacturing method for manufacturing a structure with high shape accuracy and good production efficiency, a material suitable for the manufacturing, and a laminated film manufactured by them.

[0007]

In order to solve the above-mentioned problems, the inventors of the present invention have adhered a film made of a cyclic olefin resin having high heat resistance and dimensional stability and excellent ultraviolet ray transparency to an adhesive. A self-assembled microstructure is created by providing a layer of UV curable resin with good properties, bonding it to the mold, then UV curing through the film, and finally peeling the film from the mold (generally Two
This method is called a P molding method).

That is, the present invention is directed to a laminated film or substrate (hereinafter referred to as a laminated film or substrate, which comprises a film made of a cyclic olefin resin as a lower layer material and a cured film of an ultraviolet curable resin composition as an upper layer material. , Simply referred to as a laminated film), at least one or more concave portions are formed on the surface of the upper layer, which is one surface side of the laminated film, to form a concave portion for self-assembling the microstructure. A method for producing a laminated film having a self-assembled fine structure, comprising: a film made of a cyclic olefin resin;
Alternatively, a step of applying the ultraviolet curable resin composition onto a mold having at least one or more protrusions formed thereon, and a film made of the cyclic olefin resin coated with the composition and the composition are not yet applied. A step of attaching the die which is coating, or a step of attaching the composition and the die coated with the composition and a film made of the cyclic olefin resin not applied, A film / composition / mold, that is, a structure in which a film and a mold are bonded together via the composition by either of the two steps, and then from the film side made of the cyclic olefin resin. A step of irradiating ultraviolet rays through the film to cure the composition to form a cured film, and a step of irradiating the composition with ultraviolet rays to form a cured film, and then using a cyclic olefin system By peeling a laminated film composed of a film made of a fat and a cured film of an ultraviolet curable resin composition from the mold, a recess in a state where the convex part of the mold is punched out as a mold, A self-assembling process in which a self-assembling recess, which is a recess having a shape complementary to a certain fine structure, is formed on a surface of a cured film of an ultraviolet-curable resin composition as one surface / upper layer. A method for producing a laminated film having an assemble type fine structure.

The present invention also provides an ultraviolet-curable resin composition containing a polymerizable compound and a photopolymerization initiator, wherein the photopolymerization initiator is a compound having a benzophenone structure in its molecule, It is an ultraviolet curable resin composition as a material used in the manufacturing method.

Furthermore, the present invention uses the above-mentioned ultraviolet-curable resin composition and is manufactured by the above-mentioned manufacturing method, and has a concave portion for assembling a microstructure as a one-sided / upper-layer ultraviolet-cured resin. A self-assembling laminated film having at least one cured film formed of a mold resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION A film made of a cyclic olefin resin used as a lower layer material in a laminated film for self-assembly of the present invention is a resin having high transparency and heat resistance. As this resin, for example, the product name "Zeonor" is put on the market from Nippon Zeon Co., Ltd. as a film of a cyclic olefin resin having a norbornene derivative as a monomer (see "Functional Material" published by CMC).
2000 August issue). Also, from JSR
The product name “Arton” (“Functional Material” January 1993 issue) is marketed as a film of a cyclic olefin resin having a norbornene structure having a polar group in the molecule. These cyclic olefin-based resins are characterized by high transmittance in the ultraviolet region. Therefore, even when the ultraviolet curable resin composition is applied as an upper layer of the film and the composition is cured by being irradiated with ultraviolet rays through the film from the film side, the composition is efficiently treated. Can be cured well.

In addition to the above-mentioned cyclic olefin resin film, as the resin having high transparency and heat resistance, there are films made of polyether sulfone (PES), polysulfone (PSF) and polyimide (PI). However, since these have a large number of aromatic rings as a chemical structure, they have low transmittance in the ultraviolet region (200-400 nm, particularly 200-300 nm) and are used for the purpose of curing the ultraviolet curable resin composition through a film. It was an unsuitable resin.

However, the film made of the cyclic olefin resin has the following drawbacks and is a problem to be solved. That is, when a film made of the cyclic olefin resin is used as a lower layer and a cured film of an ultraviolet curable resin composition is formed as an upper layer to form a laminated film, it is not possible to use a conventional ultraviolet curable resin composition. , The adhesion between the film and the cured film is poor, so the adhesive strength of both layers is low, the mechanical properties as a film are poor,
The problem is that only laminated films that cannot be put to practical use can be produced.

On the other hand, the present inventors have solved the above problems and completed the present invention. That is, to find a UV curable resin composition having excellent adhesion to a film made of a cyclic olefin resin, by using it as a material to provide a laminated film that can fully withstand practical use, and at the same time. The present invention provides a method for manufacturing a laminated film having a self-assembled fine structure.

Further, the above-mentioned manufacturing method means that an ultraviolet curable resin composition containing at least a photopolymerization initiator having a benzophenone structure in a molecule is applied onto a film made of a cyclic olefin resin, and at least one or more protrusions are applied. By a 2P molding method, in which the composition is attached to a mold having parts, and then the composition is irradiated with ultraviolet rays to cure the composition, and the convex parts of the mold are transferred as concave parts into the cured film layer of the ultraviolet curable resin composition. A method for manufacturing a laminated film having an assemble type fine structure. And here, the recesses of the cured film as the self-assembled microstructure in the manufactured laminated film have a complementary shape to the microstructure, and when actually assembling the microstructure, it is highly efficient. Precision that can be fitted is required.

Further, the reason why the ultraviolet-curable resin composition of the present invention firmly adheres to the cyclic olefin resin film is that the cyclic olefin-based resin film is hydrogen-absorptive by the benzophenone structure of the photopolymerization initiator as described later. It is presumed that the crosslinking with the resin is promoted and the adhesiveness is improved.

The ultraviolet curable resin composition of the present invention comprises
It comprises at least (A) a photopolymerization initiator having a benzophenone structure in the molecule, (B) a polymerizable compound, and (C) other components.

Component (A) Radical polymerization type photopolymerization initiators industrially used for ultraviolet curing are roughly classified into a cleavage type and a hydrogen abstraction type. As a result of examining the adhesiveness of the ultraviolet curable resin to the cyclic olefin resin film, it was found that it is essential to use at least a photopolymerization initiator having a benzophenone structure in the molecule as the photopolymerization initiator.

The photopolymerization initiator as the component (A) used in the composition of the present invention includes benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, 1,4-dibenzoylbenzene, 4 −
Benzoylnaphthalene, 4-benzoylbiphenyl, 4
-Benzoyl diphenyl ether, 2,4,6-trimethylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. When a benzophenone compound other than 4-benzoyl-4′-methyldiphenyl sulfide is used alone, depending on the component (B), the coating film may be cracked or the like and a normal coating film may not be obtained. By using benzoyl-4′-methyldiphenyl sulfide in combination, such a problem can be avoided. Alternatively, trialkylamine compounds such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, and methylethyl-n-propylamine as photopolymerization initiation aids, 2-diethylaminoethanol, methyldiethanolamine, triethanol. Alkanolamine compounds such as amines, N,
Allylamine compounds such as N-dimethylallylamine, methyldiallylamine and triallylamine, diamine compounds such as tetramethylethylenediamine and tetramethyl-1,3-diaminopropane, pentamethyldiethylenetriamine, N, N, N ′, N ′, N ″ -Triamine compounds such as pentamethyldipropylenetriamine, piperidine compounds such as N-methylpiperidine and N-ethylpiperidine, dimethylbenzylamine, N, N-dimethylcyclohexylamine; having a polymerizable reactive group with a (meth) acrylate compound N, N-dimethylamino (meth) acrylamide as an aliphatic tertiary amine compound,
N, N-diethylamino (meth) acrylamide, N,
It has been found that the above problems can be avoided by using N-alkyl (meth) acrylamide compounds such as N-dimethylaminoethyl (meth) acrylamide and aliphatic amine compounds such as acryloylmorpholine and morpholinoethyl acrylate together. It was However, when an aromatic amine compound generally used as a photopolymerization initiation aid is used in combination, the benzophenone compound easily forms an exciter, and the benzophenone compound promotes adhesion to a cyclic olefin resin. Therefore, it is not preferable to use the aromatic amine compound in combination.

In addition to the above photopolymerization initiator, a photopolymerization initiator belonging to the cleavage type can be used in combination. However, the adhesiveness to the film tends to deteriorate and decrease. In particular, when the coating film becomes thick, the adhesiveness of the ultraviolet curable resin to the film becomes worse. For that reason,
These should be limited to 10% by mass or less in the total amount of the photopolymerization initiator. Examples of the cleavage type photopolymerization initiator include benzoin monomethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, ethylphenyl glyoxylate, and 2 Examples include acylphosphine oxide such as -hydroxy-2-methyl-1-phenylpropan-1-one and 2,4,6-trimethylbenzoylphenylphosphine oxide. Among these, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, ethylphenyl glyoxylate, and 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferable from the viewpoint of transparency and curability. .

In addition to the photopolymerization initiator having a benzophenone structure in the molecule, hydrogen abstraction type photopolymerization initiators include thioxanthone photopolymerization initiators such as 2,4-diethylxanthone and isopropylthioxanthone. There are agents and they can be used together in the same manner. Contrary to the above, the adhesiveness of the UV-curable resin to the film is improved, but the cured film is colored, and therefore, when transparency is required for the film appearance, the combined use is very small. Should be limited.

The proportion of component (A) used is from (A) to (C).
It is 3 to 8 parts by mass, preferably 4 to 6 parts by mass, relative to 100 parts by mass of the composition. If the amount of the component (A) is less than this range, it becomes impossible to sufficiently secure the adhesiveness of the ultraviolet curable resin to the cyclic olefin resin film,
On the contrary, when the coating amount is large, when the coating thickness of the ultraviolet curable resin is large, curing of the coating film portion in the direction away from the light source (depth) becomes insufficient.

Component (B) The polymerizable compound used in the present invention includes (B-1)
A polyfunctional oligomer having two or more (meth) acryloyl groups in one molecule, (B-2) a polyfunctional monomer having three or more (meth) acryloyl groups in one molecule, (B
-3) One or two functional monomers having one or two (meth) acryloyl groups in one molecule can be mentioned.

Examples of the component (B-1) include polyester (meth) acrylate, polyurethane (meth) acrylate and epoxy (meth) acrylate. As the oligomer component contained in the ultraviolet curable composition of the present invention, the use of one having a polyether structure in its structure is not very preferable. An oligomer having a polyether structure can be blended depending on the blending amount of the photopolymerization initiator, the polyether concentration in the oligomer and the like, but a small blending amount is preferable. This is because it is presumed that the adhesion to the cyclic olefin resin film is due to the hydrogen abstraction action. When a polyether structure is present, the hydrogen abstraction action of the photopolymerization initiator contained acts on the polyether portion, and the adhesiveness between the cyclic olefin resin film and the ultraviolet curable resin is deteriorated or lowered. The film of the present invention is required to have flexibility. Therefore, urethane (meth) acrylate is preferable as the oligomer component from the viewpoint of the cured film elastic modulus and toughness of the ultraviolet curable resin.

Examples of the component (B-2) include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, tris ((meth) acryloyloxyethyl) isocyanurate. , Tris ((meth) acryloyloxypropyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol Rupenta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth)
Acrylate etc. are mentioned. The component (B-2) is good in terms of scratch resistance, chemical resistance, and heat resistance improvement, and can be used alone or in combination of two or more kinds, but it increases the elastic modulus of the cured coating film. , Tends to deteriorate the flexibility of the film. Therefore, there is an upper limit to the amount used, as will be described later. In addition, as preferable component (B-2), trimethylolpropane triacrylate,
There are tris (acryloyloxyethyl) isocyanurate, tris (acryloyloxypropyl) isocyanurate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate. Curing shrinkage is small, and from the viewpoint of film curl prevention,
Tris (acryloyloxyethyl) isocyanurate and tris (acryloyloxypropyl) isocyanurate having a cyclic structure are particularly preferable.

Examples of the component (B-3) include cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyloxy. Ethyl (meta)
Acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, isoamyl (meth) acrylate, t-butyl (meth) acrylate,
Methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, (meth)
Monofunctional (meth) acrylate monomers such as acryloylmorpholine; ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolethane di ( (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth)
Examples thereof include bifunctional (meth) acrylate monomers such as acrylate and bis- (2-methacryloyloxyethyl) phthalate. The blending amount of the above-mentioned mono- and bifunctional monomers is determined from the viewpoint of film curl, required coating film physical properties, curability and the like. Among the above-mentioned monomers, as the bifunctional monomer, ethylene oxide-modified bisphenol A di (meth) acrylate (modification mole number n is preferably 6 or less), neopentyl glycol-modified trimethylolpropane di (meth) acrylate, tricyclode It is preferable to add a monomer having a cyclic structure such as candimethanol di (meth) acrylate. Examples of monofunctional monomers having a cyclic structure include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and tricyclodecanyl (meth) acrylate. Since the elastic modulus of the cured coating film increases depending on the combination with the monomer and the compounding amount, the compounding amount has an upper limit. These mono- and bifunctional monomers can be used alone or in combination of two or more.

(B-1), (B-2) in the component (B),
The ratio of the component (B-3) varies depending on the required physical properties (elastic modulus etc.) of the cured coating film, but is generally a cyclic olefin used as the base material (lower layer) of the ultraviolet curable resin composition. It is preferable that the elastic modulus of the resin film is smaller than that of the resin film in terms of curl of the film and flexibility of the film. Therefore, (B-1) is 0 to 30 mass% in the component (B). (B
-2) is 0 to 30 mass% in the component (B). The component (B-3) is preferably added in the range of 40 to 100 mass% in the component (B).

Component (C) The ultraviolet-curable resin composition used in the present invention can be used as it is, but since the cyclic olefin resin film has a low energy surface, it can be applied satisfactorily when applied to the film. To obtain quality, it is necessary to add surfactants and paint additives. For example, by adding a fluorine-based nonionic surfactant, a modified silicone-based surfactant, a vinyl-based polymer coating additive, an acrylic polymer-based coating additive, etc., alone or in combination to an ultraviolet-curable composition, an ultraviolet-curable resin The wetting of the composition is improved. Moreover, since the 2P molding die is generally made of a metal such as Ni (nickel), it is necessary to avoid adding an adhesion enhancer with the metal to the ultraviolet curable resin composition. For example, ethylene oxide-modified succinic acid (meth) acrylate, ethylene oxide-modified phthalic acid (meth) acrylate, and other (meth) acrylates having a carboxyl group, ethylene oxide-modified phosphoric acid (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate. Addition of a (meth) acrylate having a phosphate group in the molecule such as a caprolactone-modified phosphate group di (meth) acrylate should be avoided because it enhances the adhesion of the ultraviolet curable resin composition to a metal. I won't.

Although the viscosity of the ultraviolet curable resin composition of the present invention depends on the coating method, it is 100 to 800 mPa · s due to factors such as transferability of 2P molding and film thickness variation due to film lamination on a mold. A viscosity of s is preferred. 10
When the viscosity is lower than 0 mPa · s, the 2P molding transferability is good, but the ultraviolet curable resin composition flows due to lamination, and the film thickness is likely to vary. On the other hand, when the viscosity is higher than 800 mPa · s, the variation in the film thickness is reduced, but when air bubbles or the like are mixed in, there is a problem such that defects cannot be completely removed and defects occur.

The method of applying the ultraviolet-curable resin composition of the present invention to a cyclic olefin resin film or a mold is not particularly limited, but since the IC chip is self-assembled with high precision, the surface other than the recess is Must be smooth. Therefore, it is preferable to coat the film with a microgravure coater, a roll coater or the like.

The IC chip self-assembled into the fine structure of the film of the present invention is made into one truncated pyramid shape by utilizing the <111> crystal orientation. And
The chip thickness according to the chip size is determined in consideration of the dispersion state of the chips dispersed in a liquid such as an alcoholic aqueous solution and chip defects. Therefore, the UV-curable resin composition of the present invention is provided so that this IC chip is not exposed in the fine structure of the film and is not in a dented state, and the thickness for forming the properly arranged recesses is secured. It is necessary to form a cured film layer of the product on the cyclic olefin resin film. Generally, it is formed by coating with a thickness of 20 to 100 μm.

The ultraviolet curable resin composition of the present invention is cured by an ultraviolet curing lamp through a cyclic olefin resin film. As the curing lamp, a metal halide lamp having a high ultraviolet intensity on the long wavelength side where a large curing depth can be obtained is preferable. Furthermore, regarding the adhesion of the ultraviolet curable resin composition to the cyclic olefin resin film, it is preferable that the ultraviolet intensity is high, and it is preferable that the lamp input power is 120 W / cm or more and the ultraviolet curing is performed.

[0033]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. First, solventless UV curable resin compositions having the compositions shown in Tables 1 and 2 were prepared.

[0034]

[Table 1] Table 1. Paints A to D: Examples 1 to 4

[0035]

[Table 2] Table 2. Paint E: Example 5, Paints FH: Comparative Examples 1-3

Here, the abbreviations in the formulations refer to the following compounds, respectively. BPE4-A: ethylene oxide modified (n = 4) bisphenol A diacrylate CBA: 2 (2-ethoxyethoxy) ethyl acrylate IAA: isoamyl acrylate DMAA: N, N-dimethylaminoacrylamide BP: benzophenone BMDS: 4-benzoyl-4 '-Methyldiphenyl sulfide DBE: ethyl N, N-dimethylaminobenzoate Irg. 184: 1-Hydroxycyclohexyl phenyl ketone FZ-2188: Polyether-modified silicone oil manufactured by Nippon Unicar Co., Ltd.

<Evaluation Method and Evaluation Results> Next, a laminated film was prepared from each of the composition paints of Examples and Comparative Examples prepared above and evaluated by the following evaluation methods. (Evaluation of adhesiveness to J-R's cyclic olefin film) J-R's "Arton G" film (glass transition temperature 171 ° C, 100 μm by DSC) with cellophane tape with a width of about 3 mm attached to a part of the surface
(Thickness), paint is dripped on the
The ultraviolet curable coating material was applied so that the coating film thickness was 0 μm. Then, using a conveyor type ultraviolet curing device (condensing cold mirror manufactured by Eye Graphics Co. + metal halide lamp M03-L31; input power 120 W / cm), 1
UV curing was performed in 3 passes under the conditions of 0.5 J / cm ² pass (measured by UVPF-36, an ultraviolet photometer manufactured by Eye Graphics Co., Ltd.). Next, peel off the cellophane tape attached to the surface to expose the part without a coating film on the film,
Starting from that portion, a cellophane tape was newly attached on the coating film to try to peel the coating film (hereinafter referred to as cellophane tape gap-cellophane tape peeling method). When the 80 μm coating film was peeled off together with the peeled cellophane tape, it was evaluated as NG (adhesion failure), and when the coating film remained on the film and only the cellophane tape was peeled off, it was evaluated as OK (adhesion good).

(Evaluation of Adhesion to Cyclic Olefin Film Made by Nippon Zeon Co., Ltd.) "Zeonor 1600" manufactured by Nippon Zeon Co., Ltd.
R ”film (glass transition temperature 163 ° C. by DSC,
The surface of 100 μm thickness) is plasma-treated by KEYENCE ST-7000 for 1 second of plasma irradiation under the conditions of gap setting 5 mm, irradiation level High, and external air to improve the wettability of the surface. Adhesiveness evaluation (cellophane tape gap-cellophane tape peeling method) was performed under the same conditions as the evaluation of adhesiveness to the above-mentioned "Arton" film. "Arton G", "Zeonor 1600
Table 3 shows the evaluation results of the adhesiveness to the "R" film.

[0039]

[Table 3] Table 3. Adhesion evaluation result

It can be seen from Table 3 above that all of the coating materials A to E according to the present invention have good adhesiveness to any cyclic olefin resin film. On the other hand, the coating material F containing as little as 2 parts by mass of the benzophenone-based photopolymerization initiator (total amount of two kinds) has a coating film thickness of 80 μm.
It can be seen that at m, it does not adhere to the cyclic olefin resin film. This is because the photopolymerization initiator used in the present invention is
It is presumed that since the number of cross-linking points formed by acting on the film surface is small and the film cannot withstand the internal stress caused by the thickness of the coating film, the adhesion becomes NG. On the other hand, in the case of the coating material G using 1-hydroxycyclohexyl phenyl ketone which is a general cleavage type photopolymerization initiator, even a thin film having a coating film thickness of about 10 μm does not adhere to the cyclic olefin film. Further, even if benzophenone is used as the photopolymerization initiator, in the case of the coating H using an aromatic amine compound as the photopolymerization initiation aid, it is the same as the one using a normal open-line photopolymerization initiator. It does not adhere to the cyclic olefin resin film.

(Evaluation method and evaluation result regarding 2P molding)
Similarly to the above, the coating materials of Tables 1 and 2 were applied to a Ni stamper having a large number of truncated pyramids (convex structure) so as to have a coating film thickness of 80 μm. After that, a cyclic olefin resin film ("ARTON G" and "ZEONOR 1600R" which was subjected to plasma surface treatment under the same conditions as described above was evaluated) was laminated so as not to contain air bubbles, and the film was conveyed from the conveyor side. Type UV curing device (condensing cold mirror made by igraphics + metal halide lamp M03-L31; input power 120 W / cm) 1 pass 0.5 J / cm ² (ultraviolet photometer UVPF-made by eyegraphics) (Measured at 36), UV curing was performed in 3 passes.

After curing the ultraviolet curable resin, the film was peeled from the Ni stamper, and the peeled state was observed and the shape transferability after peeling was evaluated by microscopic observation. The peeled state is "good" when the transfer-molded UV-curable resin composition is peeled off in a form that is cleanly attached to the film,
If even a part of the ultraviolet curable resin composition was peeled off from the film and remained in the mold, it was determined to be "defective". Regarding the shape transfer property, the case where there is no large difference between the size of the truncated pyramid and the shape of the recessed part transferred is defined as “good”, and the case where there is a large difference due to shape collapse or the like is defined as “poor”. The evaluation results of the peeled state and the shape transfer property are shown in Table 4 and Table 5, respectively.

[0043]

[Table 4] Table 4. Evaluation result of peeling state

[0044]

[Table 5] Table 5. Evaluation result of shape transferability

From the results shown in Tables 4 and 5 above, when the 2P molding was performed using the ultraviolet curable resin composition of the present invention, the peeled state was good and the shape transfer property was excellent. I understand. Therefore, when the ultraviolet curable resin composition of the present invention is used, it is possible to form a self-assemble type fine structure at a high speed and with high accuracy on the surface of the composition by the 2P molding method. It can be seen that a self-assembled laminated film having a resin film as the lower layer can be produced.

[0046]

According to the present invention, an organic plastic film or a film having a fine structure used for self-assembling integrated circuit devices on an organic plastic substrate can be produced with high precision and at high speed. It will be possible.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B29L 31:34 B29L 31:34 F term (reference) 2H025 AB11 AB20 AC01 AD01 BC13 DA19 4F204 AA21 AA43 AA44 AB04 AD05 AD08 AF01 AG03 AG05 AH33 EA03 EA04 EB13 EB29 EK17 EK18 4J011 QA02 QA03 QA12 QA13 QA22 QA23 QA24 QA33 QA34 QA39 QA45 QA46 QB14 QB19 QB23 SA22 SA23 SA24 SA26 SA29 UA01 VA01 WA02 5F5

Claims (5)

[Claims] 1. A laminated film or substrate comprising a film made of a cyclic olefin resin as a lower layer material and a cured film of an ultraviolet curable resin composition as an upper layer material (hereinafter, this laminated film or substrate is simply laminated. (Referred to as a film), in which at least one recess is formed on the surface of the upper layer, which is one side of the laminated film, to form a recess for self-assembling the microstructure. A method for producing a laminated film having a mold fine structure, comprising the step of forming the ultraviolet-curable resin composition on a film made of a cyclic olefin resin, or on a mold having at least one or more protrusions. The step of applying, a film made of the cyclic olefin resin coated with the composition and the composition not yet coated Two steps, a step of attaching a mold, or a step of attaching the composition-uncoated film made of the cyclic olefin-based resin and the mold coated with the composition, A film / composition / mold, that is, a structure in which a film and a mold are bonded to each other through the composition by any of the steps, and then the film is passed from the film side made of the cyclic olefin resin. And irradiating with ultraviolet light to cure the composition to form a cured film, and after irradiating with ultraviolet light to form the cured film, a film made of a cyclic olefin resin and an ultraviolet curable resin composition A microstructure that is an assembly part that is a recess in the state where the convex part of the mold is punched out as a mold by peeling the laminated film composed of the cured film of the object from the mold. And a concave portion for self-assembling, which is a recess having a shape complementary to that of the laminated film formed on the surface of the cured film of the ultraviolet curable resin composition as one side / upper layer. A method for producing a laminated film having a self-assembled fine structure. 2. An ultraviolet curable resin composition containing a polymerizable compound and a photopolymerization initiator, wherein the photopolymerization initiator is a compound having a benzophenone structure in its molecule, and the laminated film according to claim 1. An ultraviolet-curable resin composition, which is a material used in the method for producing. 3. The ultraviolet curable resin composition according to claim 2, wherein the content of the photopolymerization initiator is 3 to 8 mass% with respect to the composition. 4. The ultraviolet curing according to claim 2 or 3, wherein the polymerizable compound contains a polyfunctional (meth) acrylate compound having two or more polymerizable functional groups and a cyclic structure in the molecule. Type resin composition. 5. The ultraviolet curable resin composition according to any one of claims 2 to 4 is used and is manufactured by the manufacturing method according to claim 1, and a concave portion for assembling a fine structure is provided on one side. A self-assembling laminated film having at least one cured film formed of an ultraviolet curable resin composition as an upper layer.