JPS6065005A - Partial impartment of hydrophilicity to polymeric material - Google Patents

Abstract

PURPOSE:To facilitate the formation of a printing plate material suitable for relief printing or the like, by applying light of a specified wavelength through a pattern mask against a polymeric material capable of undergoing phot-Fries rearrangement and thereby introducing thereto hydroxyl or amino groups after the pattern. CONSTITUTION:A polymeric material is prepared from a polymerix compound having an aryl ester, aryl amide, or aryl carbonate unit in the main chain or a side chain and being capable of undergoing photo-Fries rearrangement (e.g., polyphenyl methacrylate or poly-N-acetylaminostyrene). Near-ultraviolet to far-ultraviolet light of a wavelength of 210-390nm is applied through a pattern mask against the polymeric material to effect Fries rearrangement after the pattern to introduce hydroxyl or amino groups to render the material hydrophilic after the pattern. A negative or positive pattern can be obtained by developing the material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for partially hydrophilizing polymeric materials useful as photoresists or in letterpress or lithographic printing.

Conventional photoresists include polyvinyl cinnamate resists, cyclized rubber resists, etc. as negative resists, and naphthoquinone diazide resists as positive resists, but both of these are so-called negative resists or It can only be used as a positive resist, and cannot be used as a negative resist or as a negative resist.

In addition, methods for making the surface of polymeric materials hydrophilic include, for example, oxygen plasma treatment or graft polymerization of hydrophilic monomers such as acrylamide, N-vinylpyrrolidone, and acrylic acid onto the surface of polymeric materials. In the former case, the surface of the polymer material is severely damaged and unless the conditions are selected, the material will turn into ash. cannot be made hydrophilic in a pattern, and the equipment for grafting M must be large-scale.

The present invention has solved these technical problems, and it uses a polymer property capable of optical Fries rearrangement;
In combination with irradiation, at least the surface of the polymer material is hydrophilized in a pattern, so it can be used as a positive resist or a negative resist, and can also be used as a letterpress printing material. The object of the present invention is to provide a method for partially hydrophilizing a polymer I material that can also be used for printing.

That is, the present invention is characterized in that a hydroxyl group or an amine group is introduced into at least the surface of the polymer material by irradiating the polymer Hamura capable of photo-Fries rearrangement with light having a wavelength of 210 to 390 nm through a pattern mask. This is a method for partially hydrophilizing polymeric materials.

The present invention provides a partially hydrophilized polymeric material useful as a photoresist or letterpress or lithographic printing material by irradiating a polymeric material capable of photo-Fries rearrangement with light through a pattern mask to make it hydrophilic. Has characteristics.

Fries rearrangement generally refers to the acyl group of a phenol ester or aromatic acid azide being rearranged to the di-ortho or para position by the action of a catalyst such as aluminum chloride or zinc chloride to produce 0- or p-acylphenol. However, in the present invention, such Fries rearrangement is applied to a polymer material, and a hydrophilic treatment is carried out by optical Fries rearrangement.

In the present invention, polymeric materials capable of photo-Fries rearrangement include (i) aryl ester; -Ar-0-C-(Ar
Id-1 A polymer having an aryl residue (the same applies hereinafter) in the main chain or side chain.

(b) Ori-ruamide: A polymer having -A r -N H-C- in the main chain or side chain.

(c) Aryl carboner); -Ar -0-C-
A polymer having 0-1 in the main chain or side chain.

Specifically, the following general formula (1)
-M) Polymers or copolymers containing at least one type of repeating unit can be exemplified.

(However, R is a hydrogen atom or a methyl group, R2 is C1-C
4 lower alkyl group, phenyl group, naphthyl group, or tolyl group) R1 (However, R1 is the same as above, horse~lt7 represents a hydrogen atom, a halogen atom, or a 01-C4 lower alkyl group) ・-pot・(II CH5 (However, X is -C-1-CH2-, -8-,
-SO2-.

H3CH5 10- or -C-) 2H5 ■Maru.

- CH2- , --- @, (However, R1 and l are the same as above) l: Ll (However, R1 and it2 are the same as above) The above-mentioned button knob applied to the present invention is as follows: It is sufficient if the MfT repeating unit is preferably 10 molar or more, particularly preferably 30 molar or more, and most preferably 50 molar or more, and other repeating units such as styrene, α-
Methyl styrene, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate,
It may contain repeating units such as styrene monomers such as vinylpyridine and N-vinylpyrrolidone, acrylic monomers, and nitrogen-containing vinyl monomers.

If the number of repeating units is less than 10 moles, hydrophilization will not proceed sufficiently.

Next, the polymer constituting the polymeric material capable of photo-7-Riess rearrangement and its polymerization method will be explained by giving specific examples.

<Polyphenyl methacrylate> Using phenyl methacrylate, for example, azobisin butyronitrile as an initiator and benzene as a solvent,
Polymerization is carried out at around 0.degree. C., and after the polymerization, it is precipitated with a non-solvent and then purified by reprecipitation to obtain polyphenyl methacrylate C (hereinafter referred to as "PPMAJ").

When this PPMA is irradiated with light, which will be described later, the ester in the side chain undergoes photo-Fries rearrangement and becomes a hydrophilic polymer.

<Acetylated polyhydroxystyrene> Polyhydroxystyrene is dissolved in dried pyridine using, for example, potassium hydroxide, and acetyl chloride is added dropwise while stirring and cooling the reaction solution so that it does not exceed 10°C. After the reaction is completed, a gelatin-like The reaction solution is precipitated with methanol and further reprecipitated with methyl ethyl ketone to obtain diacetylated polyhydroxystyrene (hereinafter 'i' A c P ) (referred to as S J). ◎ This A c P H8 has a side chain of The aryl ester undergoes photo-Fries rearrangement and turns into a hydrophilic polymer.

A c P H8 <Poly→oxycarbonyloxy-1,4-7enylene ingropylidene-1,4-phenylene)> Phosgene is reacted with bisphenol A and carbonic acid ester or bisphenol AVc in the presence of an alkali according to a conventional method. obtained by acting on

Poly+oxycarbonyloxy-1,4-phenylene ingropylidene-1,4-phenylene) (hereinafter referred to as "PC")
), the aryl carbonate in the main chain undergoes photo-Fries rearrangement and changes into a hydrophilic polymer.

Poly-N-acetyl-aminostyrene> Obtained by reacting acetic acid and aminostyrene in anhydrous pyridine in the presence of silicon tetrachloride. , using tetrahydrofuran as the solvent and 60”0
Make a pattern needle at the front and back. Next, the polymerization solution was added dropwise into methanol, which is a non-solvent, to obtain precipitated poly-N-acetyl-aminostyrene (hereinafter referred to as rPNAAs). The aryl ester in the chain undergoes photo-Fries rearrangement and becomes a hydrophilic polymer.

The above is just a few examples of polymers constituting the polymeric material capable of photo7-Riess rearrangement applied to the present invention, and the present invention is not limited thereto.

In the present invention, the above-mentioned polymeric material capable of optical Fries dislocation is molded by itself, or it is coated onto a substrate using a roll coater, a spinner, etc. and dried, and then the surface of the polymeric material or By irradiating the vicinity of the surface with light having a wavelength of 210 to 390 nm in a pattern through a pattern mask, at least the irradiated surface of the polymer material is made hydrophilic by causing optical Fries dislocation. If the wavelength is as short as 21 Q nm, this is undesirable as it may cause the main chain in the polymer to break, while if it exceeds 39 Q nm, the energy is insufficient and optical Fries rearrangement is difficult to occur. The preferred wavelength is 250-3651 m. If light is irradiated in a pattern through a pattern mask as described above, it can be used as a negative or positive photoresist or a printing plate for letterpress printing or planographic printing.

Next, to describe a specific application method of the present invention, a polymeric material capable of optical Fries rearrangement is prepared as a solution with a solid content concentration of 5 to 60% by weight using an organic container, a silicon wafer, a metal substrate, or a letterpress. A film is formed by applying the coating onto a plate material for printing or lithography using a roll coater or a spinner. A pattern mask having a predetermined pattern is placed on this film and light is irradiated. Thus, the irradiated area undergoes photo-Fries rearrangement and becomes a hydrophilic polymer.A developer is used that does not dissolve the hydrophilic polymer but dissolves the polymer before photo-Fries rearrangement (hereinafter referred to as "pre-rearranged polymer"). On the other hand, it is possible to obtain a positive pattern by using a developer that dissolves the hydrophilized polymer but does not dissolve the polymer before rearrangement. Moreover, without using such a developer, the hydrophilized polymer and pre-rearranged polymer (
(This is also an oleophilic polymer) forms a specific pattern, so it is possible to apply this directly to lithographic printing.

As described above, according to the present invention, by irradiating a polymeric material capable of photo-fries conversion with light to make it hydrophilic, it can be made into either a negative type or a positive type depending on the combination of developer. In addition to being able to obtain a pattern, this method also provided a method for making polymers hydrophilic, allowing the plate material after light irradiation to be directly used in lithographic printing. The significance is extremely great.

The present invention will be explained in more detail below using Examples.

Example 1 Phenyl methacrylate was dried using anhydrous barium sulfate and then purified by vacuum distillation (48°C/0.2 mmHP). The obtained monomer 10.4F and azobisin butyronitrile 02661% as an initiator were charged into a glass ampoule with an internal volume of 1 o orrt, and the contents became a homogeneous solution. After confirming this, polymerization was carried out at 60°C for 10 hours. After polymerization, 53 ml of tetrohydrone (THF) was added to the contents to make a homogeneous solution, which was then precipitated in 1500 m/m of methanol to obtain 1) PMA. The obtained polymer is again 1
It was dissolved in 00ml of THF and purified by reprecipitation using 1500ml of methanol. When the polystyrene equivalent average molecular weight of the gel permeation chromatograph 7 (GPC) (Waters 150C bottle) was calculated, the number average molecular weight: lt (Mn) was 8.80.
0, and the weight average molecular weight (Mw) was 25,000.

The polymer thus obtained was made into a 20% solution by weight using chloroform as a solvent, and the solution was coated on a rock salt plate, dried at 60°C and under reduced pressure of 1 mm) (y) for 12 hours, and then coated on the rock salt plate. A film with a thickness of 10 μm was formed.

This sample was irradiated in nitrogen for 0.5 hours using a 20 W low-pressure mercury lamp that generates light with wavelengths of 254 nm and 311 nm, and changes in the IR spectrum of the polymer were examined.

As a result, when PPMA was irradiated with light, the absorption due to the ester group at 1760 cm decreased, the absorption due to the hydroxyl group centered on 344Qn increased, and the absorption due to the hydroxyl group at 1635 cm increased.
A sharp absorption occurs at c1n (absorption due to o-hydroxyacetophenone) and at 1670cm (absorption due to p-hydroxyacetophenone), and PP MA
It was found that 0-Fries rearrangement and p-Fries rearrangement occurred to transform the polymer into a hydrophilic polymer.

Next, this PPMA was made into a chloroform solution in the same manner as above, and coated on an aluminum lithographic plate material of thickness Q, 51111 using a roll coater, and dried to a thickness of 100 μm.
A film of m was formed. This was irradiated with light through a positive-type no-turn mask using the same low-pressure mercury lamp as described above to print the image, and then the planographic plate was subjected to lithographic printing according to the usual method, and the printing durability at 10,000 sheets was confirmed. and the printed matter was clear.

Example 2 Polyhydroxystyrene (manufactured by Maruzen Oil Co., Ltd., Mn =
10,000) 24y was dissolved in dried pyridine/120 using potassium hydroxide and then cooled to 50°C. While stirring the reaction solution, the reaction solution temperature IW reaches ioo'c.
236 g of acetyl chloride was added dropwise over 2 hours so as not to exceed After the dropwise addition was completed, the reaction was continued for 1 hour at room temperature,
The gelatinous reaction solution was poured into 2000 ml of methanol, and the precipitated polymer (AcPH8) was recovered.

Furthermore, the polymer obtained was dissolved in 20 Qme of methyl ethyl ketone, purified by reprecipitation using 1,000 m/m of methanol, and then dried under reduced pressure. ) The acetylation rate determined by l-NMlt was 92 molti. When the molecular weight of the polymer thus obtained was determined by OPC, Mn==6,000, Mw==15.
It was ooo.

This polymer was applied on a rock salt plate in the same manner as in Example 1,
When irradiated with light and examined the changes in the polymer by IR spectrum, the absorption due to the ester group of 1760cIn decreased, and the absorption due to the hydroxyl group of 344Qcm decreased.
An increase in absorption due to the O-hydroxyphenone structure of 1640 cm was observed, and it was confirmed that a hydrophilic polymer was generated due to 0-7 Lis rearrangement.

Next, this polymer was dissolved in 1.1.2-) dichloroethane to make a 10 weight solution, and this solution was applied to a silicon wafer with a silicon oxide film using a spinner to a thickness of 0.
It was applied to a thickness of 5 μm and dried at 80 to 90° C. for 15 minutes. Apply this to a mask aligner (wavelength 210-300n)
The image was printed through a resolution test chart chrome mask using a 100 m) irradiation energy of 50 mJ/c4.

When the image was developed using toluene as a developer (unirradiated portions were dissolved and removed), a pattern with a line width of 1 μm could be resolved.

Example 3 As poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4 phenylene) (PC), Nipiron S 2000 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used.
Mn = 16.000, Mw = measured by GPC
53,000) WO-USEIRI TIT (flJ 1) In the same manner as above, it was applied on a rock salt plate, irradiated with light, and changes in the polymer were investigated using an iR spectrum. Dihydroquine benzophenone was found to have a 7-Ries rearrangement in the main chain of the polymer. It was confirmed that a hydrophilic polymer was produced.

Next, a 100 μm thick PC film was used as a lithographic plate material, and a positive pattern mask was placed on the film. After irradiating the film with light using the same low-pressure mercury lamp as in Example 1 and printing an image, this lithographic plate was used. When lithographic printing was carried out according to a conventional method, it had a printing durability of more than 10,000 sheets and the printing was clear.

Patent issuer M+ person Japan Synthetic Rubber Co., Ltd. Representative Patent Attorney Takashi Shirai

Claims (1)

[Claims] 1. By irradiating a polymeric material capable of optical Fries rearrangement with near-ultraviolet light to far-ultraviolet light with a wavelength of 210 to 39 Qnm through a pattern mask, a water group or an amino group is added to at least the surface of the polymeric material. 1. A method for partially hydrophilizing a polymeric material, the method comprising: