JPH0453839A - Manufacturing method of uneven pattern - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a manufacturing method that has excellent scratch resistance and can easily produce an uneven pattern on the surface at low cost. The present invention relates to a method for manufacturing a concavo-convex pattern that can be used in the field.

[Conventional technology]

There are two types of photoresist materials, positive type and negative type. Since high resolution is required to form fine uneven shapes on a resist film, positive type resist materials are particularly suitable.

The following method has been conventionally known for producing fine irregularities in a resist film using a high-resolution positive resist.

That is, a photoresist dissolved in an organic solvent is coated on glass to create a positive resist film, a mask pattern with fine irregularities is layered, and a low-pressure mercury lamp, high-pressure mercury lamp,
An ultra-high-pressure mercury lamp or the like is used as an exposure light source to irradiate ultraviolet rays, and after exposure, the resist film is etched to form a fine uneven pattern on the resist film.

[Problem to be solved by the invention]

A plate or a film is used as a photomask in the process of forming an uneven shape on a resist film. Further, as the exposure light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, etc. are used, but these light sources have a 0. 8
μm to 1. Heat radiation also occurs in the near-infrared region of 0 μn1, and the photomask material may be heated and thermally deformed by this heat radiation. Therefore, it is difficult to accurately form uneven shapes on the resist film according to the fine patterns made on the photomask.

Films used as photomask materials are very useful for producing large-area patterns at low cost compared to glass, but thermal deformation of these films is a very serious problem.

Furthermore, in the prior art, there was no technique for etching while maintaining the hardness of the cured film, so when the photomask and the resist film are exposed in close contact, the resist film is very likely to be scratched. This is because the solvent remains inside, causing problems such as swelling caused by the solvent.

This invention was made based on the above background,
The purpose of this is to form an uneven shape accurately according to the fine pattern of the photomask, so that the unevenness can exhibit excellent hardness and durability, and can be performed using simple processes and inexpensive equipment. An object of the present invention is to provide a method for manufacturing a pattern.

[Means to solve the problem]

As a result of extensive studies, the inventors of the present invention have found that ultraviolet irradiation under a specific atmosphere is effective in achieving the object of the present invention, and has completed the present invention.

That is, the method for producing a concavo-convex pattern with excellent scratch resistance according to the present invention includes: (a) a polyfunctional monomer having at least two (meth)acryloyloxy groups in one molecule; a step of forming at least a surface layer of the molded article; (b) a step of overlaying a mask pattern on the surface layer of the molded article consisting of a portion that transmits ultraviolet light including a wavelength of 300 nm or less and a portion that does not transmit; (c) a step of forming at least a surface layer of the molded article. (d) irradiating the surface layer of the molded product through the mask pattern surface with ultraviolet rays of 300 nm or less that pass through water; (e) irradiating the surface layer of the molded product with the irradiated surface layer of the molded product. This method is characterized by including a step of alkali treatment.

In addition, in this specification, a "molded object" means an object having a certain shape. Also, "(meth)acryloyloxy" is "acryloyloxy or metaglylooxy"
means.

[For production]

In this invention having the above structure, at least the surface layer of a molded product obtained by polymerizing a polyfunctional monomer having two or more (meth)acryloyloxy groups in one molecule is formed, and a wavelength of 300 nm or less is formed. A mask pattern consisting of a portion that transmits ultraviolet rays and a portion that does not transmit the ultraviolet rays is superimposed on the surface layer of the molded article.

Next, in the present invention, the surface layer portion of the molded article and the mask pattern are immersed in water, and ultraviolet rays are irradiated in the water.

The wavelength range from the ultraviolet irradiation device is generally from the far ultraviolet region to 0. 8-1. It has a wide wavelength distribution up to the near infrared region of 0 μm. However, because this ultraviolet light passes through water, the water absorbs the heat from the heat radiation in the long wavelength range, and the heat transfer does not reach the mask pattern and molded product, causing no thermal deformation and allowing stable irradiation. will be carried out.

Next, the molded product after being irradiated with ultraviolet rays is subjected to alkali treatment, and by this treatment, only the portions irradiated with ultraviolet rays are etched to form recesses.

[Detailed description of the invention]

Hereinafter, the manufacturing method of the present invention will be explained in more detail.

Examples of polyfunctional monomers having two or more (meth)acryloyloxy groups in one molecule used in the present invention include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and polyethylene glycol diacrylate. , polypropylene glycol diacrylate, 1.3-butylene glycol diacrylate, 1.4 butylene glycol diacrylate, neopentyl glycol diacrylate, 1.6-hexane glycol diacrylate,
Pentaerythritol diacrylate, 2,2-bis(
4-acryloxyprobyloxyphenyl)propane, 2
．． 2-bis(4-acryloxyshed bovine diphenyl)propane, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate,
Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate,
1.3-butylene glycol dimethacrylate, 1,4
-butylene glycol neopentyl glycol dimethacrylate, 1,6-hexane glycol diacrylate,
Examples include 2,2-bis(4-methacryloxyshedquinphenyl)propane, trimethylolethane trimethacrylate, and trimethylolpropane trimethacrylate.

These may be used alone or in combination of two or more.

These monomers may be made into a sheet as they are, but -
For boat fishing, a hardened layer is formed on the surface layer of a material with relatively low scratch resistance by means such as photocuring or heat curing.

Figure 1 shows a schematic diagram in which a surface layer (1) of a polymer using at least a polyfunctional monomer having two or more (meth)acryloyloxy groups in one molecule is laminated on a base material (2). show.

In the present invention, the polymer may be used alone, but it is preferable to use it in combination with the base material because it can have the same properties as the base material.

A plate with excellent transparency can be produced by using polymethyl methacrylate, polypropylene, polyethylene, polyethylene terephthalate, etc., which have excellent transparency, as the base material.

Other base materials may also be selected depending on the intended use, such as polyvinyl chloride, polystyrene, ABS resin, and polyvinylidene chloride.

The polymer surface layer part (1) shown in FIG. 1 is JISK5400
From the viewpoint of scratch resistance, it is desirable that the hardness be 2H or more, preferably 4H or more in the Empi hardness test based on .

In addition, in the method of coating and polymerizing the above-described polyfunctional monomer on the surface of the substrate, the thickness of the polymer layer on the surface is preferably 1.0 μm or more, more preferably 3.0 μm or more.

However, as mentioned above, this base material is not necessarily necessary, and depending on the purpose of the molded product, the entire molded product may be composed of a polymer of the above-mentioned polyfunctional monomer.

Next, a mask pattern consisting of a part that transmits ultraviolet rays of 300 nm or less and a part that does not transmit is overlaid on the surface layer of the molded product formed by polymerizing a polyfunctional monomer, and ultraviolet rays of 300 nm or less are transmitted through the mask pattern surface. Irradiates ultraviolet light containing wavelengths.

At this time, in the present invention, as shown in FIG. 2, the atmosphere for irradiating ultraviolet rays is such that the surface layer (1) of the molded article has a transparent area and a non-transparent area for ultraviolet rays containing wavelengths of 300 nm or less. The mask patterns (4) are immersed in water (5) in an overlapping state, and ultraviolet light having a wavelength of 300 nm or less is irradiated from an ultraviolet light source (3) above the water surface.

This underwater ultraviolet irradiation is the most significant feature of the present invention. As is well known, high-pressure mercury lamps are generally used as ultraviolet irradiation equipment, and the wavelength range is from the far ultraviolet region to 0.
．． It has a wide wavelength distribution up to the near infrared region of 8 to 1.0 μm.

For this reason, water absorbs the heat generated by heat radiation in the long wavelength range, so heat transfer does not reach the molded product as well as the mask pattern consisting of the ultraviolet ray transmitting portion and non-transmitting portion.
Irradiation is performed in a stable state without thermal deformation.

Ultraviolet rays containing wavelengths of 300 nm or less are applied to the surface portion formed by polymerizing a polyfunctional monomer from above the water surface through a mask pattern consisting of a transparent part and a non-transparent part of UV rays containing wavelengths of 300 nm or less. irradiate. The ultraviolet rays may be carried out by appropriately selecting a wavelength range and irradiation time that can impart enough energy to cleave some of the ester bonds of the polymer. Since the bonding energy between molecules differs depending on the composition of the polymer, it is desirable to use an ultraviolet region that imparts energy of about 4 eV or more, although it cannot be generally specified.

Preferably, this ultraviolet light includes a wavelength within 180 nm to 300 nm. As the mask pattern consisting of ultraviolet transmitting parts and non-transmitting parts used in the present invention, for example, olefin-based films such as polypropylene and polyethylene, polyester-based films, acrylic-based films, PVC-based films, etc. are used. There is no particular limitation as long as it forms a mask pattern consisting of a transparent part and a non-transparent part for ultraviolet rays of 300 nm or less.

For example, a wide range of patterns can be selected by the method of the present invention, such as mask patterns having micro holes or designs.

Next, when the molded product after being irradiated with ultraviolet rays is taken out of water and subjected to alkali treatment after drying, the mask pattern may or may not be removed.

By this alkali treatment, only the portions previously irradiated with ultraviolet rays are etched to form recesses.

Examples of aqueous alkaline solutions used in this alkaline treatment include aqueous solutions of sodium hydroxide, potassium hydroxide, etc.
Examples include alkaline aqueous solutions in which various solvents such as alcohol are added. The conditions for alkali treatment after UV irradiation cannot be specified as they vary depending on the composition of the UV irradiated area, the form of the molded product, the desired performance, etc., but for example, when using sodium hydroxide, 0.1 It is desirable to use it as an aqueous solution with a concentration of ~50% by weight, more preferably 1~30% by weight. In addition, the temperature of the alkali treatment is usually 0 to 100°C, and 2
A temperature of 0 to 80°C is desirable. The time for alkali treatment is 0.0
The time is preferably 1 to 100 hours, more preferably 0.1 to 10 hours.

The surface layer having an uneven pattern obtained by the present invention shows no decrease in hardness and has excellent scratch resistance.

〔Example〕

This invention will be explained more specifically by the following examples.

Example trimethylolethanediacryl) 40% by weight, 1.
A solution consisting of 58% by weight of 6-hexanediol diacrylate and 2% by weight of benbuine isobutyl ether was prepared. A polymethyl methacrylate resin plate with a thickness of 2.0 mm was immersed in this solution, and then slowly pulled up at a speed of 0.5 cm/sec to form a liquid film on the surface of the resin plate. Polyethylene terephthalate film (
A film with a center wavelength of 365 cm was placed at a distance of 20 cm from both sides of the film.
using a high-pressure mercury lamp with nm 760 m J/c
Irradiation was carried out at a dose of g.

As a result, a molded article having a cured film with a thickness of 30 μm was obtained. This cured film had a 60° specular gloss of 149 and was highly glossy. And the total light transmittance is 9
2% and the minimum load by steel wool rotation test is 5
It was 00g.

The diameter of the circle is 1.3 mm, and the thickness of 200 mesh is 100 μm.
Using a polypropylene film as a mask pattern, superimpose the film on the molded product prepared above, and place it in a water tank (6) filled with water (5) as shown in Figure 2, with the film part at a distance of 20 mm from the water surface. immersed in the position of wavelength 2
300m from the water surface using a high-pressure mercury lamp with a wavelength of 54nm.
Irradiation was performed at a dose of 15,000 m J/crd from a position of m.

Next, this molded product was immersed in a 10% by weight aqueous sodium hydroxide solution at 60°C for 60 minutes, washed with water, dried, and then
It was immersed in a % by weight aqueous hydrochloric acid solution at room temperature for 5 minutes, washed with water, and dried. As shown in FIG. 3, fine irregularities (1-) corresponding to the pattern of the mask pattern were formed on the surface layer (1) of the molded product.

That is, part of the film remains as a convex part, and the openings, which are micropores, are etched to a depth of 0.5 in terms of average roughness Ra.
It showed a circular concave shape with a diameter of 2 μm. The diameter of the formed circle was 1.3 mm, which was the same as the mask pattern, and the same size was formed.

C Effect of the Invention] As demonstrated in the above examples, the production method of the present invention forms an uneven shape on the surface layer of a specific polymer having excellent hardness, and the unevenness has excellent durability. In addition, a concavo-convex shape that accurately corresponds to the mask pattern is formed.

Moreover, the process is simple and can be carried out using inexpensive equipment.

FIG. 1 is a cross-sectional view of an example of a molded article including the surface layer of the molded article in the manufacturing method of the present invention, FIG. 2 is a cross-sectional view schematically showing the ultraviolet irradiation step, and FIG. 3 is the manufacturing method of the present invention. It is a sectional view of the example of unevenness obtained by.

l...Surface layer of polymer 1-...Unevenness 2...Base material 3...UV light source 4...Mask pattern 5...Water 6...Aquarium

[Brief explanation of drawings]

Claims (1)

[Claims] 1. Forming at least the surface layer of a molded product obtained by polymerization using at least a polyfunctional monomer having two or more (meth)acryloyloxy groups in one molecule, and having a diameter of 300 nm or less A mask pattern consisting of a UV-transmissive part and a non-transmissive part including wavelengths is overlaid on the surface layer of the molded article, and at least the surface layer of the molded article and the mask pattern are immersed in water to prevent ultraviolet rays of 300 nm or less that are transmitted through the water. A method for producing an uneven pattern with excellent scratch resistance, comprising: irradiating the surface layer of the molded article through the mask pattern surface, and treating the irradiated surface layer of the molded article with an alkali.