JP6971650B2 - Surface-treated resin film manufacturing method - Google Patents

Description

The present invention relates to a method for producing a surface-treated resin film.

Inorganic materials such as glass substrates and silicon wafers, which have high heat resistance, are generally used for the substrates of electronic devices. On the other hand, plastic substrates (resin films, etc.) made of organic materials, such as displays to which organic electroluminescence (organic EL) is applied, have come to be used as substrates for electronic devices.
However, the plastic base material has problems that the heat resistance is lower than that of the inorganic material, the wear resistance of the surface and the adhesion to the adjacent thin film are inferior, and the use thereof is limited. To solve this problem, it is required to improve the functionality of the plastic base material.

As a technique for improving the functionality of a plastic base material, a method of modifying the surface of the plastic base material has been developed.
Conventionally, a corona discharge treatment method, a plasma treatment method, or the like has been used to modify the surface of a plastic base material. However, in these treatment methods, it is difficult to treat a large area at one time and to treat without damaging.

Further, Patent Document 1 proposes a plastic surface treatment method for modifying the surface of a plastic by decomposing hydrogen molecules into atomic hydrogen under reduced pressure and bringing the atomic hydrogen into contact with the plastic. There is. According to such a plastic surface treatment method, it is said that hydrophilicity or hydrophobicity can be imparted, abrasion resistance, mechanical strength, or adhesion to a thin film can be improved.

Japanese Unexamined Patent Publication No. 2007-154050

By the way, in recent years, electronic components such as semiconductor elements are increasingly required to be smaller and more sophisticated. Along with this, the characteristics required for the substrate of the electronic device are becoming higher than those in the past.
Based on the studies so far, the present inventors have determined that it is important to form the fine uneven structure provided on the plastic surface more regularly in order to satisfy the required characteristics of the electronic device for the substrate. I found it.
In the plastic surface treatment method described in Patent Document 1, although a fine uneven structure can be formed on the plastic surface, the regularity of the structure is low and there is still room for improvement.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a surface-treated resin film having a fine structure having a high regularity on the surface.

The first aspect of the present invention is a method for producing a surface-processed resin film having a plurality of regular fine structures composed of uneven surfaces, so that the pitch between the fine structures is 1 μm or less. On the other hand, it is a method for producing a surface-processed resin film, which comprises a step of irradiating atomic hydrogen.

According to the present invention, it is possible to provide a method for producing a surface-treated resin film having a fine structure having a high regularity on the surface.

It is a figure which shows the SEM image which shows one Embodiment of the surface-treated resin film manufactured by the manufacturing method of this embodiment. It is a figure explaining the pitch (length per cycle) between microstructures 1a and 1b. It is a schematic diagram which shows an example of the atomic hydrogen irradiation apparatus. It is a figure which shows the relationship between the irradiation time at an initial temperature of 50 degreeC, the thickness of the residual resin film, and the resin film temperature. It is a figure which shows the relationship between the irradiation time at an initial temperature of 70 degreeC, the thickness of the residual resin film, and the resin film temperature. It is a figure which shows the SEM image of the PMMA film (final temperature 120 degreeC, 150 degreeC) after atomic hydrogen irradiation. It is a figure which shows the relationship between the irradiation time and the resin film temperature in the resin film of each initial temperature. It is a figure which shows the SEM image of the PMMA film (final temperature 140 degreeC, 160 degreeC) after atomic hydrogen irradiation. It is a figure which represented the roughness curve by y = f (x). Ra is a value determined by the equation in FIG. 9 as expressed in nanometers (n m). It is a figure which shows the AFM image which the irradiation time of a sample was 5 minutes and 30 minutes when it exposed at ^{50 mJ / cm 2 about} the epoxy resin film after the atomic hydrogen irradiation. It is a figure which shows the AFM image of the epoxy resin film after the atomic hydrogen irradiation ^{, when the sample was exposed at 1000 mJ / cm 2 and the irradiation time was 5 minutes.} It is a schematic diagram which shows the other example of the atomic hydrogen irradiation apparatus. It is a figure which shows the relationship between the irradiation time and the resin film temperature.

In the present specification and claims, "aliphatic" is defined as a concept relative to aromatics and means a group, a compound or the like having no aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of the hydrogen atom of the alkyl group or the alkylene group is substituted with a fluorine atom.
The “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When describing "may have a substituent", a case where a hydrogen atom (-H) is substituted with a monovalent group and a case where a methylene group (-CH _2- ) is substituted with a divalent group. Including both.
"Exposure" is a concept that includes general irradiation of radiation.

(Manufacturing method of surface-treated resin film)
The manufacturing method of the present embodiment is a method of manufacturing a surface-treated resin film having a plurality of regular microstructures composed of uneven surfaces.
Such a manufacturing method includes a step of irradiating the resin film with atomic hydrogen (hereinafter, this step is referred to as "step (α)").

FIG. 1 is a diagram showing an SEM image showing an embodiment of a surface-treated resin film produced by the production method of the present embodiment.
The surface-treated resin film 10 shown in FIG. 1 is a resin film having an uneven surface having a fine structure in which a plurality of concave portions and convex portions are regularly arranged. In the surface-treated resin film 10, the pitch between the individual microstructures is set to 1 μm or less.

FIG. 2 shows the pitch (length per cycle) between the fine structures 1a and 1b. The height h of the convex portion in the fine structure is appropriately set according to the application and the like, and is set to, for example, 0.1 to 1 μm.

"Pitch" refers to the length of a plurality of regular microstructures per cycle. In the present invention, it means the pitch (length per cycle) between the fine structures 1a and 1b shown in FIG.
This "pitch" is a value calculated by using PSD (power spectral density function) based on the surface data obtained by AFM for the surface-treated resin film.

<Process (α)>
In the step (α), the resin film is irradiated with atomic hydrogen so that the pitch between the plurality of regular fine structures composed of the uneven surface is 1 μm or less.

≪Resin film≫
The thickness of the resin film is determined in consideration of the intended use and the like, and is preferably 10 μm or less, more preferably 1 to 6 μm.
When the thickness of the resin film is not more than the upper limit of the above-mentioned preferable range, the easiness of deformation is further enhanced. On the other hand, if it is at least the lower limit of the above-mentioned preferable range, the strength is further increased.

The resin film contains a resin component as a main component and, if necessary, various additives.
The resin component may be any as long as it can form a fine structure on the surface of the resin film by irradiation with atomic hydrogen. For example, acrylic resin, epoxy resin, polyethylene resin, polyvinyl chloride resin, polypropylene. Examples include based resins.
Among these, as the resin component, an acrylic resin and an epoxy resin are preferable because a fine structure is easily formed.

-Acrylic resin As an acrylic resin, a structural unit derived from acrylic acid in which a hydrogen atom bonded to the α-position may be substituted with a substituent, or a hydrogen atom bonded to the α-position is a substituent. Examples thereof include polymers having a repeating structure of structural units derived from optionally substituted acrylic acid esters.

The “constituent unit derived from acrylic acid” means a structural unit composed by cleavage of the ethylenic double bond of acrylic acid.
The “constituent unit derived from the acrylic acid ester” means a structural unit formed by cleaving the ethylenic double bond of the acrylic acid ester.
The "acrylic acid ester" is a compound in which the hydrogen atom at the terminal of the carboxy group of _{acrylic acid (CH 2 = CH-COOH) is replaced with an organic group.}
^{The substituent (R α} ) that replaces the hydrogen atom bonded to the α-position is an atom or group other than the hydrogen atom. Examples of the group other than the hydrogen atom bonded to the α-position include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group having 1 to 5 carbon atoms.
The alkyl group as the substituent bonded to the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, etc.). Examples thereof include an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group).
Further, the alkyl halide group as a substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as a substituent bonded to the α-position" is substituted with a halogen atom. Can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
Further, the hydroxyalkyl group as a substituent bonded to the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned “alkyl group as a substituent at the α-position” is substituted with a hydroxyl group. Be done. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.
Unless otherwise specified, the α-position in an acrylic resin refers to a carbon atom constituting a main chain to which a carbonyl group is bonded.

Examples of acrylic acid in which the hydrogen atom bonded to the α-position may be substituted with a substituent include acrylic acid, methacrylic acid, ethacryllic acid, and 2-propylacrylic acid.
Examples of the acrylate ester in which the hydrogen atom bonded to the α-position may be substituted with a substituent include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethyl methacrylate, ethyl methacrylate, and methacrylic. Examples thereof include propyl acid and butyl methacrylate.

As a preferable acrylic resin, a polymer (P1) having a structural unit (u1) represented by the following general formula (u1) or a weight having a structural unit (u2) represented by the general formula (u2). Coalescence (P2) can be mentioned.
In the structural unit (u1), a substituent (R ^α1 ) other than a hydrogen atom is bonded to the α-position.
In the structural unit (u2), a hydrogen atom is bonded to the α-position.

［式（ｕ１）中、Ｒ^α１は、炭素数１〜５のアルキル基である。Ｒ^ｕ１は、有機基又は水素原子である。式（ｕ２）中、Ｒ^ｕ２は、有機基又は水素原子である。］

[In the formula (u1), R ^α1 is an alkyl group having 1 to 5 carbon atoms. R ^u1 is an organic group or a hydrogen atom. In formula (u2), ^Ru2 is an organic group or a hydrogen atom. ]

-Regarding the polymer (P1) In the above formula (u1), R ^α1 is an alkyl group having 1 to 5 carbon atoms.
The alkyl group in R ^α1 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. , Tert-Butyl group, pentyl group, isopentyl group, neopentyl group and the like. Among these, R ^α1 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the formula (u1), ^Ru1 is an organic group or a hydrogen atom.
^{Examples of the organic group in Ru1} include a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include a chain hydrocarbon group and a cyclic hydrocarbon group.

The ^{chain hydrocarbon group in Ru1} may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
As the chain hydrocarbon group, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.
The branched-chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group and a 2,2-dimethylbutyl group.

The ^{cyclic hydrocarbon group in Ru1} may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

In R ^u1, if the cyclic hydrocarbon group is an aromatic hydrocarbon group, aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a polycyclic group or a monocyclic group. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specifically, the aromatic ring is an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, or phenanthrene; an aromatic heterocycle in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom or the like. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
^{Specifically, as the aromatic hydrocarbon group in Ru1,} a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; two or more aromatic rings are used. A group obtained by removing one hydrogen atom from an aromatic compound (eg, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (eg, a benzyl group, etc.). Examples thereof include an arylalkyl group such as a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

Among the above, ^{the organic group in Ru1} is preferably a chain hydrocarbon group, more preferably a linear or branched alkyl group, further preferably a linear alkyl group, and particularly preferably a methyl group. be.

^{The hydrocarbon group in Ru1} may have a substituent. Examples of the substituent include a halogen atom, an oxo group (= O), a hydroxyl group (-OH), an amino group (-NH ₂ ), -SO _2- NH _{2 and the} like, and among these, the hydroxyl group (-OH) is used. preferable.

A specific example of the structural unit (u1) represented by the above general formula (u1) is shown below.

The structural unit (u1) contained in the polymer (P1) may be one kind or two or more kinds.
Further, the polymer (P1) may have a structural unit other than the structural unit (u1), if necessary.
The ratio of the structural unit (u1) in the polymer (P1) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% with respect to the total of all the structural units constituting the polymer (P1). The above is more preferable, and it may be 100 mol% (homopolymer).

-Regarding the polymer (P2) In the above formula (u2), ^Ru2 is an organic group or a hydrogen atom.
^Examples of the organic group in ^{Ru2 include the same organic groups as in Ru1.} A chain hydrocarbon group is preferable, a linear or branched alkyl group is more preferable, and a linear alkyl group is preferable. Is more preferable, and particularly preferably a methyl group.

A specific example of the structural unit (u2) represented by the above general formula (u2) is shown below.

The structural unit (u2) contained in the polymer (P2) may be one kind or two or more kinds.
Further, the polymer (P2) may have a structural unit other than the structural unit (u2), if necessary.
The ratio of the structural unit (u2) in the polymer (P2) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% with respect to the total of all the structural units constituting the polymer (P2). The above is more preferable, and it may be 100 mol% (homopolymer).

Among the above-mentioned acrylic resins, an acrylic resin in which a substituent other than a hydrogen atom is bonded to the α-position of the acrylic acid ester is preferable because a fine structure is more easily formed, and a polymer having the above-mentioned structural unit (u1) is preferable. It is particularly preferable to use (P1).

-Epoxy-based resin Examples of the epoxy-based resin include resins having an epoxy group in the molecule and capable of forming a crosslinked structure.
For example, examples of the epoxy resin include polyfunctional phenol / novolak type epoxy resin, polyfunctional orthocresol novolac type epoxy resin, polyfunctional triphenyl type novolak type epoxy resin, and polyfunctional bisphenol A novolak type. Epoxy resin and the like can be mentioned.

Preferred epoxy-based resins include resins (P3) represented by the following general formula (p3).

In the above formula (p3), R ^p1 and R ^p2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
^Examples of the alkyl group in R ^p1 and R p2 include linear, branched or cyclic alkyl groups. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. A linear alkyl group is preferable, and a methyl group is more preferable. Examples of such a cyclic alkyl group include a cyclobutyl group and a cyclopentyl group.
Among them, as R ^p1 and R ^p2 , a hydrogen atom or a linear or branched alkyl group is preferable.
In the above formula (p3), the plurality of R ^p1s may be the same or different from each other. The plurality of R ^p2s may be the same as or different from each other.

In the formula (p3), R ^EP is an epoxy group-containing group.
The epoxy group-containing group for R ^EP, is not particularly limited, groups composed of only an epoxy group; group consists of only alicyclic epoxy group; and an epoxy group or an alicyclic epoxy group, a divalent linking group A group having and can be mentioned.
The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a 3-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure.

The alicyclic group which is the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. Further, the hydrogen atom in these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group or the like.

In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, the epoxy group or the alicyclic epoxy group is via a divalent linking group bonded to an oxygen atom (-O-) in the formula. It is preferable that the groups are bonded.
Here, the divalent linking group is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like are preferable.

For divalent hydrocarbon groups that may have substituents:
The hydrocarbon group in the divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group as the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, −CH (CH ₃ ) −, −CH (CH ₂ CH ₃ ) −, and −C (CH ₃ ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups;- CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂₎ CH ₃ ) _2- CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

As the aliphatic hydrocarbon group containing a ring in the above structure, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or linear. Examples thereof include a group bonded to the end of a branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group as a divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n + 2) π electrons, and may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic containing two or more aromatic rings. A group obtained by removing two hydrogen atoms from a compound (for example, biphenyl, fluorene, etc.); a hydrogen atom of a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group in which one is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.) A group from which one atom is further removed) and the like can be mentioned. The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

Such a divalent hydrocarbon group may have a substituent.
The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group and the like.

The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure as a divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. A methoxy group and an ethoxy group are particularly preferable.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
Further, in the alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure, a part of the carbon atom constituting the ring structure may be substituted with a substituent containing a heteroatom. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

As the aromatic hydrocarbon group as a divalent hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
Examples of the alkoxy group, the halogen atom, and the alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the alicyclic hydrocarbon group.

About divalent linking groups containing heteroatoms:
The hetero atom in the divalent linking group including the hetero atom is an atom other than the carbon atom and the hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

Among the divalent linking groups containing a heteroatom, the preferred linking groups are -O-, -C (= O) -O-, -C (= O)-, -O-C (= O). -O-; -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H is a substitution of an alkyl group, an acyl group, etc.) it may be substituted with a _{group); - S -, - S} (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 - ^{O -, - Y 21 -C (} = O) -O -, - C (= O) -O-Y 21, - [Y 21 -C (= O) -O] m "-Y 22 - or -Y ^{21 -O-C (= O)} -Y 22 - group represented by ^{wherein, Y 21} and ^{Y 22} are each independently may be substituted divalent hydrocarbon group, O is an oxygen atom and m "is an integer of 0 to 3. ] And so on.

When the divalent linking group containing the hetero atom is -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)- , The H may be substituted with a substituent such as an alkyl group or an acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 -C _{(= O) -O] m "} -Y 22 - or ^{-Y 21 -O-C (= O} ) -Y 22 - ^{in, Y 21} and ^{Y 22} each independently have a substituent It is also a good divalent hydrocarbon group. As the divalent hydrocarbon group, the "divalent hydrocarbon group which may have a substituent may have a substituent" mentioned in the above description of the divalent linking group. The same thing can be mentioned.
The Y ^21, preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, a linear alkylene group is more preferred, a methylene group or an ethylene group having 1 to 5 carbon atoms, especially preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
Formula _{^{- [Y 21 -C (= O}} ) -O] m "-Y 22 - In the group represented by, m" is an integer of 0 to 3, preferably an integer of 0 to 2, 0 or 1 is more preferred, and 1 is particularly preferred. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m "-Y 22 represented by A group is particularly preferable. Among _{them, a group represented by the formula − (CH 2} ) _{a ′} −C (= O) −O− (CH ₂ ) _{b ′} − is preferable. In the formula, a ′ is 1 to 10 An integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b'is an integer of 1 to 10 and 1 to 8. An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is more preferable, and 1 is most preferable.

Among them, the epoxy group-containing group for R ^EP, a glycidyl group are preferable.
In the formula (p3), the plurality of R ^EPs may be the same as or different from each other.
As the epoxy-based resin, one in which the epoxy ring in the molecule is opened and cross-linking is advanced is preferable, and one in which the epoxy ring in the molecule is completely opened and cross-linking is completely advanced is more preferable.

As the resin component contained in the resin film, an acrylic resin and an epoxy resin are preferable.
Among these, since the fine structure is more easily formed, a resin film containing an acrylic resin in which a substituent other than a hydrogen atom is bonded to the α-position of the acrylic acid ester, or an epoxy resin having a crosslinked structure formed. A resin film containing the above is preferable.
Among them, a resin film containing an acrylic resin in which a substituent other than a hydrogen atom is bonded to the α-position of the acrylic acid ester is more preferable because a fine structure is particularly easy to form, and a weight having the above-mentioned structural unit (u1) is preferable. A resin film containing a coalescence (P1) is particularly preferable.

Among the resin films, the resin film containing an acrylic resin in which a substituent other than a hydrogen atom is bonded to the α-position of the acrylic acid ester is particularly easy to form a fine structure by irradiation with atomic hydrogen as follows. Is guessed.
In an acrylic resin in which a substituent other than a hydrogen atom is bonded to the α-position, a double bond is formed between the carbon atom at the α-position and the substituent bonded to the α-position by irradiation with atomic hydrogen. , The main chain is easily decomposed. By such decomposition of the main chain, the resin matrix constituting the resin film is partially destroyed, and the surface state of the resin film is changed (the minute portion on the surface of the resin film has fluidity). It is considered that the fine structure is easily formed because the removal rate of the resin by irradiation with atomic hydrogen changes depending on the difference in the surface state of the resin film.

The molecular weight of the resin component contained in the resin film is preferably 10,000 or more, more preferably 1,000,000 to 1,000,000, and even more preferably 500,000 to 1,000,000.
When the molecular weight of the resin component is at least the lower limit of the above-mentioned preferable range, the fine structure is more likely to be formed.
The molecular weight of the resin component referred to here means a mass average molecular weight (Mw), and indicates a polystyrene-equivalent value by gel permeation chromatography (GPC).

The resin component contained in the resin film may be one kind or two or more kinds.
The ratio of the resin component to the resin film is 50% by mass or more, preferably 90% by mass or more.

The resin film may contain various additives in addition to the resin component, if necessary.
Examples of this additive include phthalates, isophthalates and the like.

For such a resin film, for example, a resin composition in which the above resin components and various additives are dissolved in an organic solvent is used, and this resin composition is applied onto a support by spin coating or the like and baked. The resin film is produced by performing the treatment (preferably at a temperature condition of 80 to 150 ° C. for 40 to 120 seconds).

[Operation to irradiate the resin film with atomic hydrogen]
In the operation of the present embodiment, the resin film is irradiated with atomic hydrogen so that the pitch between the plurality of regular fine structures composed of the uneven surface is 1 μm or less.
Atomic hydrogen is produced by contacting a heated catalyst body (for example, 1500 ° C. or higher) with a hydrogen-containing gas.

FIG. 3 is a schematic view showing an example of an atomic hydrogen irradiation device.
The atomic hydrogen irradiation device 100 is composed of a chamber 102 and a bottom 112, and has a housing in which a space is formed. A gas supply port 104 is formed in the upper portion of the chamber 102, and an exhaust port 106 is formed in the bottom portion 112.
The catalyst body 108 is attached to the space inside the housing. The catalyst body 108 is formed of a tungsten filament (tungsten wire). A power supply 110 for heating the catalyst body 108 is attached to the catalyst body 108.
Further, in the space inside the housing, the heater 114 is arranged on the bottom 112. A power supply 115 for raising the temperature of the heater 114 to heat the resin film 14 is attached to the heater 114. A thermocouple 116 for measuring the temperature of the surface of the heater 114 is also attached to the heater 114. The thermocouple 116 is connected to the temperature monitor 118. The thermocouple 116 measures the temperature of the surface of the heater 114 (resin film 14).

The operation of irradiating the resin film with atomic hydrogen is performed, for example, as follows (Hot-Wire method).
In the atomic hydrogen irradiation device 100, a processing gas containing hydrogen is supplied from the gas supply port 104. In FIG. 3, a hydrogen / nitrogen mixed gas (H ₂ / N ₂ gas) is used as the processing gas.
With the supply of the processing gas, hydrogen molecules in the supplied processing gas come into contact with the catalyst body 108 and decompose to generate atomic hydrogen 50. Specifically, the dissociated hydrogen atom is adsorbed on the dangling bond of each tungsten atom on the surface of the catalyst body 108. After that, the hydrogen atom is thermally desorbed to generate atomic hydrogen 50. Then, the generated atomic hydrogen 50 advances toward the resin film 14 arranged on the heater 114.
In this way, the surface of the resin film 14 is irradiated with atomic hydrogen 50, and a surface-treated resin film having a fine structure in which a plurality of concave portions and convex portions are regularly arranged is manufactured.

In the operation of the present embodiment, in order to irradiate the resin film with atomic hydrogen so that the pitch between the fine structures is 1 μm or less, for example, the following (I) or (II) can be controlled. good.

(I) The temperature rise of the surface of the heater 114 (resin film 14) is controlled at the time when the irradiation of the atomic hydrogen 50 is started and after the irradiation of the atomic hydrogen 50 for a predetermined time.
In order to control such a temperature rise, the temperature of the catalyst body 108 and the distance from the substrate are changed, and the temperature of the resin film 14 is controlled by using the radiant heat generated by the heat generation of the catalyst body 108, or the atomic hydrogen 50 is used for a predetermined time. After irradiation, the temperature of the surface of the heater 114 (resin film 14) is set to, for example, "Tg plus 20 ° C." or more and "Tg plus 50 ° C." or less of the resin component contained in the resin film 14 based on the measured value.

(II) The etching rate of the resin film generated by irradiation with atomic hydrogen is controlled.
In order to control such an etching rate, the type of resin component contained in the resin film 14 is selected. For example, the number of carbon atoms at the end of the side chain of the resin, Tg, and the like are selected.
Alternatively, the temperature of the catalyst body 108 and the distance from the substrate are changed, and the temperature of the resin film 14 is controlled by using the radiant heat generated by the heat generated by the catalyst body 108. Alternatively, the etching rate is controlled by changing the temperature of the catalyst body 108 to change the amount and energy of atomic hydrogen generated. Alternatively, the temperature of the surface of the heater 114 (resin film 14) at the time of starting the irradiation of the atomic hydrogen 50 is, for example, "Tg minus 20 ° C." or more "Tg plus" of the resin component contained in the resin film 14 based on the measured value. The temperature shall be 20 ° C. or lower.

When the resin residual film 22 is attached to the surface of the resin film 14, the atomic hydrogen 50 decomposes the residual film 22 and removes it from the surface of the resin film 14.
The atomic hydrogen 50 is irradiated to the surface of the resin film 14, and then discharged from the exhaust port 106 to the outside of the atomic hydrogen irradiation device 100.

Hereinafter, the conditions for irradiating the resin film 14 with the atomic hydrogen 50 using the atomic hydrogen irradiation device 100 will be described.

As the treatment gas, a gas having a single composition containing hydrogen such as hydrogen gas or ammonia gas; or a mixed gas of hydrogen and an inert gas such as a hydrogen / nitrogen mixed gas or a hydrogen / argon mixed gas can be used.
The hydrogen concentration in the processing gas is not particularly limited. For example, from the viewpoint of resin removal efficiency, the higher the hydrogen concentration is, the more preferably 100% by volume is preferable with respect to the total volume of the processing gas. Considering the balance between safety and the generation efficiency of atomic hydrogen 50, the hydrogen concentration in the processing gas is particularly preferably 1 to 10% by volume or 75 to 100% by volume.
Further, the flow rate of hydrogen gas may be determined in consideration of the exhaust speed of the vacuum exhaust device and the partial pressure of hydrogen gas during processing, and can be selected from the range of 1 sccm or more and 300 sccm or less. Among these, it can be selected from a range of preferably 1 sccm or more and 200 sccm or less, more preferably 1 sccm or more and 150 sccm or less, and further preferably 1 sccm or more and 50 sccm or less.
Further, the partial pressure of the hydrogen gas may be determined in consideration of the removal speed of the residual film 22 of the resin and the influence on the resin film 14 of the portion to which the residual film 22 does not adhere, and is 0.5 Pa or more and 10 Pa. You can select from the following range. Further, the pressure in the system (inside the chamber 102) can be selected from a range of 0.5 Pa or more and 50 Pa or less, and more preferably 0.5 Pa or more and 30 Pa or less, for example, from the viewpoint of resin removal efficiency.

The temperature of the catalyst body 108 is not particularly limited, and for example, the balance between the removal efficiency of the residual film 22 and the influence on the resin film 14 of the portion to which the residual film 22 does not adhere and the heat resistance of the resin film 14 is taken into consideration. It should be decided.
The temperature of the catalyst body 108 is preferably 1500 ° C. or higher and 2500 ° C. or lower. If the temperature of the catalyst body 108 is less than 1500 ° C., the generation efficiency of the atomic hydrogen 50 may decrease, and the removal efficiency of the residual film 22 may decrease. On the other hand, if the temperature exceeds 2500 ° C., the durability of the resin film 14 may decrease.

The distance between the catalyst body 108 and the resin film 14 is not particularly limited, and for example, the removal efficiency of the residual film 22, the influence on the resin film 14 of the portion to which the residual film 22 does not adhere, and the heat resistance of the resin film 14. It should be decided in consideration of the balance of.
The distance between the catalyst body 108 and the resin film 14 is preferably 5 mm or more and 120 mm or less. If the distance exceeds 120 mm, the efficiency of removing the residual film 22 may decrease. On the other hand, if it is less than 5 mm, the durability of the resin film 14 may decrease.

In the atomic hydrogen irradiation device 100 shown in FIG. 3, a catalyst body 108 formed of a tungsten filament is used, but the catalyst body 108 is not limited to this, and a tantalum filament, a molybdenum filament, or an iridium filament is formed. A medium can also be suitably used. However, from the viewpoint of the generation efficiency of the atomic hydrogen 50, it is preferable to use a catalyst formed from a tungsten filament.

In the above-described embodiment, the atomic hydrogen irradiation device 100 for generating the atomic hydrogen 50 using the catalyst 108 is used, but the method for generating the atomic hydrogen 50 is not limited to this. For example, plasma may be used to generate atomic hydrogen 50. However, the method of generating atomic hydrogen 50 using the catalyst body 108 (Hot-Wire method) as in the present embodiment can minimize the decrease in the durability of the resin film and also treats the resin film. It is more preferable because the time can be shortened and the device can be miniaturized.

According to the manufacturing method of the present embodiment described above, it is possible to manufacture a surface-treated resin film having a plurality of regular fine structures composed of uneven surfaces having a pitch of 1 μm or less. For example, the production method of the present embodiment produces an acrylic resin film having an uneven pattern having a pitch of several hundred nm.
In addition, according to the production method of the present embodiment, a resin film having a modified surface can be obtained. By adopting the surface-treated resin film obtained by the manufacturing method of the present embodiment, it is possible to improve the abrasion resistance, the mechanical strength, or the adhesion to the thin film of the plastic substrate.

≪Surface-treated resin film≫
_{Preferred Ra} , R _zjis , R _max , and pitch of the surface-treated resin film produced by the production method of the present embodiment are shown below. Definitions of R _a , R _zjis , R _max , and pitch will be described later in Examples.
The R _a, preferably 100nm or less, more preferably 60nm or less, particularly preferably 30 nm.
The R _zjis is preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less.
The R _max is preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less.
The pitch is 1 μm or less, preferably 800 nm or less, more preferably 400 nm or less, and particularly preferably 200 nm or less.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
In this embodiment, OAPM-400 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is the same device as the embodiment shown in FIG. 3, was used as the atomic hydrogen irradiation device.
A hydrogen / nitrogen mixed gas (hydrogen concentration: 10% by volume) was used as the treatment gas. The flow rate of hydrogen gas was 30 sccm, the partial pressure of hydrogen gas was 3.2 Pa, the distance between the catalyst body and the resin film was 100 mm, and the resin film was irradiated with atomic hydrogen.

(Example 1)
As a polymer, an alkyl polymethacrylate in which the number of carbon atoms of the side chain terminal alkyl group was changed was used, and the formation of a fine structure was examined. The polyalkyl methacrylate used is as follows.

Polymethyl methacrylate (PMMA, Mw = 120,000)
Ethyl polymethacrylate (PEMA, Mw = 250,000)
Polypropyl methacrylate (PPrMA, Mw = 150,000)
Butyl Polymethacrylate (PBuMA, Mw = 370,000)
Isobutyl polymethacrylate (PiBuMA, Mw = 70,000)

Ethyl lactate was used as a solvent, and a solution prepared by dissolving various polymers in the solvent was spin-coated on a Si wafer and baked at 100 ° C. for 60 seconds to prepare a resin film (sample).
Each sample was irradiated with atomic hydrogen under the conditions of W-wire energization 20A, continuous irradiation time of 9 minutes and 12 minutes, and initial temperature of the resin film of 50 ° C. and 70 ° C.

FIGS. 4 and 5 show the relationship between the irradiation time at the initial temperatures of 50 ° C. and 70 ° C., the thickness of the remaining resin film, and the resin film temperature.
Table 1 shows the average removal rate (etching rate) at a continuous irradiation time of 9 minutes when each polymer was used at an initial temperature of 50 ° C. and 70 ° C. In Table 1, "substrate" means a resin film.

As shown in Table 1, it was confirmed that the removal rate decreased as the carbon number of the side chain terminal alkyl group increased. It is considered that this is because the increase in the number of carbon atoms in the side chain terminal alkyl group increases the number of side chain cleavage sites due to atomic hydrogen, and thus the main chain cleavage efficiency decreases.
Further, since the removal rate of the resin film increases with the increase in the initial temperature of the resin film, it is considered that the reactivity between the atomic hydrogen and the polymer increases as the initial temperature increases.

Further, the PMMA film (final temperature 120 ° C./150 ° C.) after irradiation with atomic hydrogen was observed by SEM under the above conditions. The SEM observation conditions are gold vapor deposition for 30 seconds, an acceleration voltage of 4 kv, and a current value of 6 A. The result is shown in FIG.

As shown in FIG. 6, the formation of a fine structure was confirmed in the PMMA film.

Considering that the Tg (glass transition temperature) of the polymer is involved in the formation of the fine structure, the Tg of PMMA, PEMA, and PPrMA was actually measured and found to be PMMA: 100 ° C, PEMA: 65 ° C, and PPrMA: 45 ° C. rice field. From these results, it was confirmed that the larger the Tg, the easier it is for the fine structure to be formed.
Considering from the viewpoint of the surface condition (fluidity of minute parts) of the resin film, when the temperature of the resin film rises due to the irradiation of atomic hydrogen, if the temperature does not greatly exceed Tg, the movement of the main chain It is considered that the surface condition of the resin film changes (the minute part has fluidity) and the fine structure is formed without being so violent.

(Example 2)
[Examination of Tg using PMMA film]
17% by mass of a solution prepared by dissolving polymethyl methacrylate (PMMA, Mw = 120,000) in ethyl lactate was spin-coated on a Si wafer at 2000 rpm for 30 seconds, and then baked at 100 ° C. for 60 seconds to obtain a film thickness of 5. A sample (thin film) of .54 μm was prepared.
This sample was irradiated with atomic hydrogen under the conditions of W-wire energization 20A, irradiation time 9 minutes, and initial temperature of the resin film 50 ° C., 70 ° C., 85 ° C., 110 ° C., 120 ° C., and 130 ° C., respectively. ..

FIG. 7 shows the relationship between the irradiation time and the resin film temperature in the resin film at each initial temperature.
As shown in FIG. 7, it was confirmed that the temperature of the resin film during irradiation increased with the increase of the initial temperature of the resin film.
Table 2 shows the initial temperature, the final temperature, the film thickness of the resin film after 9 minutes of continuous irradiation with atomic hydrogen, and the removal rate. In Table 2, "substrate" means a resin film.

As shown in Table 2, 170 to 180 ° C. was measured under the strictest conditions. This is 70 ° C. higher than the PMMA Tg (about 100 ° C.).

Further, the PMMA film (final temperature 140 ° C. and 160 ° C.) after the atomic hydrogen irradiation was observed by SEM under the above conditions.
The SEM observation conditions are gold vapor deposition for 30 seconds, an acceleration voltage of 4 kv, and a current value of 6 A. The result is shown in FIG.

As shown in FIG. 8, the formation of a fine structure was confirmed at the final temperature of the resin film of 140 ° C to 160 ° C. It was confirmed that the optimum temperature of the resin film exists in the formation of the fine structure of PMMA.
From the above, it is considered that fine structures can be formed in various polymers by controlling the amount of atomic hydrogen produced and irradiating the resin with atomic hydrogen at the final temperature near Tg.

[Definition of Ra, Rzjis, Rmax, Pitch]
Ra extracts only the reference length L from the roughness curve in the direction of the average line, takes the x-axis in the direction of the average line of the extracted portion, and takes the y-axis in the direction of the vertical magnification, and sets the roughness curve as y =. when expressed in f (x), it refers to those expressed in nanometers (n m) the value determined by the equation in FIG.
Rzjis has 5 points farthest in the positive direction from the average line (elevation of the 5th peak from the highest peak) and 5 points farthest in the negative direction (5th valley bottom from the lowest peak). It is the sum of the averages of the absolute values of (elevation).
Rmax is the absolute value of the difference between the Y value of the point farthest in the positive direction from the average line and the Y value of the point farthest in the negative direction from the average line.
Pitch is the length per cycle calculated by using PSD (Power Spectral Density Function) for the surface data obtained by AFM. For example, it is shown in FIG.

(Example 3)
[Investigation of molecular weight using PMMA film]
Atomic hydrogen was applied to a sample prepared in the same manner as in Example 1 using each polymethylmethacrylate having Mw = 120,000, 350,000, and 996,000, W-ware energization 20A, irradiation time 3 minutes, 6 minutes. Irradiation was carried out for 9 minutes under each condition of the initial temperature of the resin film of 50 ° C.
Under the above conditions, the surface data of the PMMA film after irradiation with atomic hydrogen was obtained by AFM. The results are shown in Table 3. In Table 3, n. d. ^a means not determined.

(Example 4)
A solution prepared by dissolving ethyl polymethacrylate (PEMA, Mw = 250,000) in ethyl lactate was spin-coated on a Si wafer at 2000 rpm for 30 seconds and then baked at 100 ° C. for 60 seconds to achieve a film thickness of 1.7 μm. Samples were prepared.
This sample was irradiated with atomic hydrogen under the conditions of W-wire energization 20A, irradiation time of 3 minutes, 6 minutes, and 9 minutes, and an initial temperature of the resin film of 50 ° C.

Further, a solution prepared by dissolving 2-hydroxyethyl polymethacrylate (PHEMA, Mw = 300,000) in DMF (dimethylformamide) is placed on a Si wafer at 2000 rpm for 30 seconds, spin-coated, and then baked at 100 ° C. for 60 seconds. This was performed to prepare a sample having a film thickness of 1.82 μm.
This sample was irradiated with atomic hydrogen under the conditions of W-wire energization 20A, irradiation time of 3 minutes, 6 minutes, and 9 minutes, and an initial temperature of 70 ° C. of the resin film.
Under the above conditions, the surface data of the PEMA film and PHEMA film after irradiation with atomic hydrogen were obtained by AFM. The results are shown in Table 4. In Table 4, n. d. ^a means not determined.

(Example 5)
Photosensitive composition (epoxy resin: trade name JER157S70 (manufactured by Mitsubishi Chemical Corporation) 100 parts, photoacid generator: trade name CPI-100P (manufactured by Sun Appro Co., Ltd.) 3 parts, PGMEA (propylene glycol monomethyl acetate) 1250 parts) Was spin-coated on a Si wafer at 2000 rpm for 30 seconds and then baked at 100 ° C. for 60 seconds to prepare an epoxy resin film (sample) having a film thickness of 1.7 μm. The sample was exposed at ^{50mJ / cm 2 · 1000mJ / cm} 2.
This sample was irradiated with atomic hydrogen under the conditions of W-wire energization 22.2A, 25A, 30A, irradiation time of 5 minutes, 10 minutes, 15 minutes, and 30 minutes, and an initial temperature of the resin film of 50 ° C.
Under the above conditions, the surface data of the epoxy resin film after irradiation with atomic hydrogen was obtained by AFM. Table 5 shows the surface data of the sample when exposed at 50 mJ / cm ^2. Table 6 shows the surface data of the sample when exposed at 1000 mJ / cm ^2. In Tables 5-6, n. d. ^a means not determined.

Further, the epoxy resin film after the atomic hydrogen irradiation was observed by AFM under the above conditions. FIG. 10 shows images of the sample irradiation time of 5 minutes and 30 minutes when exposed at 50 mJ / cm ^2. Further, FIG. 11 shows an image of the sample with an irradiation time of 5 minutes when exposed at 1000 mJ / cm ^2.

In the examples described below, the same device as that of the embodiment shown in FIG. 12 was used as the atomic hydrogen irradiation device.
FIG. 12 is a schematic view showing another example of the atomic hydrogen irradiation device.
The atomic hydrogen irradiation device 200 includes a chamber 202, and has a housing in which a space is formed. A gas supply port 204 is formed above the side surface of the chamber 202, and an exhaust port 206 is formed below the same side surface.
A catalyst 208 is attached to the space inside the chamber 202. The catalyst body 208 is formed of a tungsten filament (tungsten wire). A power supply 210 for heating the catalyst body 208 is attached to the catalyst body 208 above the chamber 202.
A stage 220 is arranged near the center of the bottom of the chamber 202. The stage 220 is connected to an external temperature controller 214. In FIG. 12, a laminate of a Si wafer 212 and a resin film 14 formed on the Si wafer 212 is placed on the stage 220. In the stage 220, both heating and cooling are possible, and the temperature of the resin film 14 can be controlled to be constant.
Further, a thermocouple 216 for measuring the temperature of the surface of the stage 220, that is, the temperature of the resin film 14, is also attached to the bottom of the chamber 202. The thermocouple 216 is connected to the temperature monitor 218.

The operation of irradiating the resin film with atomic hydrogen by the atomic hydrogen irradiation device 200 is performed, for example, as follows (Hot-Wire method).
In the atomic hydrogen irradiation device 200, the processing gas containing hydrogen is supplied from the gas supply port 204 above the side surface of the chamber 202.
With the supply of the processing gas, hydrogen molecules in the supplied processing gas come into contact with the catalyst body 208 and decompose to generate atomic hydrogen 50. Then, the generated atomic hydrogen 50 advances toward the resin film 14 placed on the stage 220. At that time, in the atomic hydrogen irradiation device 200, the resin film 14 can be kept at a constant temperature.
In this way, the surface of the resin film 14 is irradiated with atomic hydrogen 50, and a surface-treated resin film having a fine structure in which a plurality of concave portions and convex portions are regularly arranged is manufactured.

Hydrogen gas (hydrogen concentration 100% by volume) was used as the treatment gas. The flow rate of hydrogen gas was 30 sccm, the hydrogen gas pressure was 30 Pa, the distance between the catalyst and the resin film was 100 mm, and the resin film was irradiated with atomic hydrogen.

(Example 6)
[Examination of film temperature using PMMA film]
17% by mass of a solution prepared by dissolving polymethyl methacrylate (PMMA, Mw = 120,000) in ethyl lactate was spin-coated on a Si wafer at 2000 rpm for 30 seconds, and then baked at 100 ° C. for 60 seconds to obtain a film thickness of 5. A sample (thin film) of .54 μm was prepared.
This sample is irradiated with atomic hydrogen using an atomic hydrogen irradiation device 200 at a W-wire energization of 20 A, an irradiation time of 20 minutes or more, and an initial temperature of the resin film of 50 ° C., and the temperature of the resin film is 80 ° C. The resin film was irradiated with atomic hydrogen while being cooled so as to be maintained at 100 ° C., 120 ° C., and 140 ° C.

The relationship between the irradiation time and the resin film temperature is shown in FIG.
As shown in FIG. 13, it was confirmed that the temperature of the resin film during irradiation was kept substantially constant.

Under the above conditions, the surface data of the PMMA film after irradiation with atomic hydrogen was obtained by AFM. The results are shown in Table 7. In Table 7, n. d. ^a means not determined.

From the results in Table 7, by irradiating the resin film with atomic hydrogen so that the pitch is 1 μm or less, the roughness is reduced and the surface has a fine structure with high regularity. It was confirmed that a processed resin film could be manufactured.

(Example 7)
[Examination of hydrogen gas flow rate using PMMA film]
17% by mass of a solution prepared by dissolving polymethyl methacrylate (PMMA, Mw = 120,000) in ethyl lactate was spin-coated on a Si wafer at 2000 rpm for 30 seconds, and then baked at 100 ° C. for 60 seconds to obtain a film thickness of 5. A sample (thin film) of .54 μm was prepared.
This sample is irradiated with atomic hydrogen using an atomic hydrogen irradiation device 200 at a W-wire energization of 20 A, an irradiation time of 30 minutes, and an initial temperature of the resin film of 50 ° C., and the temperature of the resin film reaches 120 ° C. The resin film was irradiated with atomic hydrogen while being cooled so as to be maintained. At this time, the resin film was irradiated with atomic hydrogen while flowing hydrogen gas at a constant pressure of 30 Pa and changing the flow rates to 3 sccm, 30 sccm, 150 sccm, and 300 sccm, respectively.

According to this embodiment, it was confirmed that a surface-treated resin film having a plurality of regular fine structures composed of uneven surfaces having a pitch of 1 μm or less can be produced.

1a Fine structure,
1b microstructure,
14 Resin film,
50 Atomic hydrogen,
100 Atomic Hydrogen Irradiator,
102 chamber,
104 gas supply port,
106 Exhaust port,
108 catalyst,
110 power supply,
112 bottom,
114 heater,
115 power supply,
116 thermocouple,
118 temperature monitor,
220 stages.

Claims (5)

A method for producing a surface-treated resin film having a plurality of regular fine structures composed of uneven surfaces.
The above-mentioned regular fine structure has Ra, Rzjis and Rmax defined below having Ra of 0.6 nm or more and 100 nm or less, Rzjis of 5.2 nm or more and 300 nm or less, and Rmax of 42 nm or more and 300 nm or less, respectively. can be,
As the pitch between the fine structure is 1μm or less, have a step of irradiating the resin film, atomic hydrogen,
In the above step
The temperature of the resin film after being irradiated with the atomic hydrogen for a predetermined time is adjusted to be "Tg plus 20 ° C." or more and "Tg plus 50 ° C." or less of the resin component contained in the resin film.
A method for producing a surface-treated resin film, which comprises controlling a temperature rise of the resin film caused by irradiation with atomic hydrogen.
Ra extracts only the reference length L from the roughness curve in the direction of the average line, takes the x-axis in the direction of the average line of the extracted portion, and takes the y-axis in the direction of the vertical magnification, and sets the roughness curve as y =. When expressed in f (x), the value obtained by the following formula is expressed in nanometers (nm).

Rzjis is the 5 points farthest from the average line in the positive direction (elevation of the highest peak to the 5th peak) and the 5 points farthest from the average line in the negative direction (5th from the lowest peak). It is the sum of the averages of the absolute values of each of the valley bottoms up to.
Rmax is the absolute value of the difference between the Y value of the point farthest in the positive direction from the average line and the Y value of the point farthest in the negative direction from the average line.
The pitch is the length per cycle calculated by using PSD (power spectral density function) from the surface data obtained by AFM (atomic force microscope). In the above step
The number of carbon atoms or Tg at the end of the side chain of the resin contained in the resin film is selected.
Or,
The temperature of the resin film at the time of starting the irradiation of the atomic hydrogen is adjusted to be "Tg minus 20 ° C." or more and "Tg plus 20 ° C." or less of the resin component contained in the resin film.
The method for producing a surface-treated resin film according to claim 1, wherein the etching rate of the resin film generated by irradiation with the atomic hydrogen is controlled. The method for producing a surface-processed resin film according to claim 1 or 2 , wherein the resin film contains an acrylic resin, an epoxy resin, a polyethylene resin, a polyvinyl chloride resin, or a polypropylene resin. The method for producing a surface-processed resin film according to any one of claims 1 to 3 , wherein the resin film contains an acrylic resin in which a substituent other than a hydrogen atom is bonded to the α-position of the acrylic acid ester. The method for producing a surface-treated resin film according to any one of claims 1 to 3 , wherein the resin film contains an epoxy resin having a crosslinked structure formed therein.

Images