JPH0426848A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve mechanical strength of a relief image and to obtain sufficient sensitivity to ultraviolet rays by adding an azido compound or quinonediazido compound as a photosensitivity donor to a polymer having specified structural units in the molecule. CONSTITUTION:The polymer having in the molecule the structural units represented by formula I (R1 is H, methyl, or ethyl; (n) is an integer of >=1; and (m) is an integer of 1 - 4) contains as the photosensitivity donor the azido compound or the quinonediazido compound. The weight average molecular weight of the polymer is not especially limited but it is generally preferred that it is 5X10<3> - 5X10<5> in terms of the molecular weight of the polystyrene. The content of this donor in the photosensitive composition is not especially limited but it is generally preferred to be 10 - 30pts.wt. of the quinonediazido per 100pts.wt. of the polymer and 5 - 10pts.wt. of the azido per 100pts.wt. of the polymer, thus permitting the relief image to be improved in the mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to photosensitive compositions. More specifically, it relates to a photosensitive composition for forming relief images. The photosensitive composition according to the present invention can be used in general photoresist application fields such as parts processing in the electronics field and plate-making materials in the printing industry. .

[Prior Art] Conventionally, photosensitive compositions commonly used in parts processing in the electronics field and plate-making materials in the printing industry include 0-
naphthoquinonediazide sulfonic acid ester or 0-
2,6-di(4-azidobenzal) is a photosensitive composition in which a quinonediazide such as naphthoquinonediazide sulfonamide is used as a photosensitive component in combination with a phenol resin.
There are photosensitive compositions in which an azide compound such as -4-methylcyclohexanone is used as a photosensitive component in combination with a phenol resin.

The 0-naphthoquinonediazide sulfonic acid compound is decomposed by the action of light to produce a compound having a carboxylic acid group, resulting in a difference in solubility between exposed and unexposed areas. Monoazide and diazide compounds have photocrosslinking properties with phenol groups, and the exposed areas are hardened by the action of light, resulting in a difference in solubility.

Utilizing this property, a photosensitive material containing a photosensitive composition containing these quinonediazide compounds or azide compounds as a photosensitive component is layered on a suitable support and is exposed to light and developed using an alkaline water-soluble or organic solvent. By processing, it is possible to dissolve and remove the exposed area in the former case and the unexposed area in the latter case, and obtain a positive or negative relief image for the i-image used for each image exposure.

[ff that the invention tries to solve! l! ] However, since the novolak resin, which is a phenolic resin conventionally used as a component of photosensitive compositions, has a relatively low molecular weight, there is a problem that the mechanical strength of the resulting relief image is insufficient. Although polyvinylphenol resin has good mechanical strength for relief images, it has a problem in that it does not have sufficient sensitivity to ultraviolet light when forming negative relief images.

[Means for Solving the Problems] The present inventor has proposed a photosensitive material containing a polymer compound obtained by polymerizing a compound represented by the following general formula as an active ingredient and a quinonediazide compound or an azide compound as a photosensitizer. It has been found that the composition solves the problems mentioned above.

That is, the present invention provides a compound represented by the general formula (wherein R represents a hydrogen atom, CH, or a CxHs group, n is an integer from 1 to This is a photosensitive composition characterized in that it is made by adding an azide compound or a quinone diazide compound as a photosensitizer to a polymer compound having a structural unit in its molecular structure.

The polymer compound in the composition of the present invention is characterized by having a structural unit represented by the above general formula in its molecular structure, and is a homopolymer consisting only of this structural unit or a polymer consisting of this structural unit and other vinyl. It has a copolymer-type structure having a repeating structure that is a combination of monomers and one or more types of structural units having a structure in which an unsaturated double bond is cleaved.

Structural units used in combination with the structural unit represented by the above general formula in the polymer compound of the present invention having a copolymer type structure include, for example, styrenes such as styrene and methylstyrene, acrylic acid, methacrylic acid, etc. Esters of α-methylene aliphatic monocarboxylic acids such as methyl meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, vinyl esters such as vinyl acetate Examples include structures of vinyl monomers with cleaved unsaturated double bonds.

The method for polymerizing the compound represented by formula [11] or the method for copolymerizing the compound represented by formula [1] and the vinyl monomer may be any of solution polymerization, suspension polymerization, and emulsion polymerization, [1]
] The polymerization form of the copolymer produced when the compound represented by the formula and the vinyl monomer is copolymerized is not particularly limited,
Any of random copolymers, block copolymers, graft copolymers, etc. may be used.

There is no particular restriction on the molecular weight of the polymer compound used in the composition of the present invention, but since it is necessary to coat the photosensitive composition as a uniform film on a support, the weight average molecular weight in terms of polystyrene is usually s, A range of ooo to soo or ooo is preferable, but it is also possible to select a polystyrene equivalent weight average molecular weight outside the above range depending on the thickness of the film to be formed, the coating method, and the purpose of use.

Known compounds can be effectively used as the quinonediazide compound and azide compound as the photosensitizer used in the present invention.

Table 1 shows the representative I will give a concrete example.

No.! Table: The amount of the photosensitizer in the photosensitive composition of the present invention is not particularly limited, but is usually 10 to 30 parts by weight for quinone diazides and 5 to 10 parts by weight for azides per 100 parts by weight of the polymer compound. If the amount is less than the range of parts by weight of each photosensitizer, the effect of inhibiting dissolution in alkaline solvents will not be sufficient (quinonediazides).
However, there are drawbacks such as insufficient curing speed of the film (azides), and if the range is exceeded, problems such as precipitation of the photosensitizer may occur.

In the photosensitive composition of the present invention, a sensitizer can be added to the above-mentioned monoazides and diazides as necessary. Specific examples of sensitizers include naphthothiazocines and benzothiazolines represented by 1-methyl-2-benzoylmethylene-β-naphthothiazoline;
Ketocoumarins represented by 3.3°-carbonylbis(7-dinithylaminocoumarin) are preferred.

The amount of the sensitizer to be added is not particularly limited, but is usually in the range of 0.2 to 15 parts by weight, preferably in the range of 0.5 to 10 parts by weight, per 100 parts by weight of the polymer compound. 0.2
If it is less than 15 parts by weight, the effect of the sensitizer will be small and the curing speed will not be as fast as when it is not added. If it exceeds 15 parts by weight, the solubility of the unexposed area in an alkaline aqueous solution will decrease6.
By mixing predetermined amounts of each of the above constituent materials, a photosensitive material, that is, a photosensitive composition of the present invention can be obtained.

When using the above-mentioned photosensitive materials, conventional methods have been used. For example, a transparent original image containing a line image is exposed in close contact with a photosensitive surface, and then developed with an alkaline aqueous solution to produce positive or negative effects on the original image. A relief image of the mold is obtained.

The photosensitive composition of the present invention can be coated onto a support using a conventional coating method and then irradiated with ultraviolet rays to form a desired relief image due to the photodenaturation of quinone diazides and the crosslinking properties of azides. .

The relief image thus obtained has high chemical resistance and excellent mechanical strength. In addition, it has strong adhesion to the support.

As described above, the photosensitive composition according to the present invention is extremely useful.

Next, the present invention will be illustrated by giving Examples, but the implementation of the present invention is not limited thereto.

Example 1 154 g of hydroxyethoxyphenol, 430 g of methacrylic acid, 3 g of hydroquinone monomethyl ether, and 3 g of phenothiazine were placed in a flask with stirring and heated to 50°C, stirred and dissolved.Next, 3g of concentrated sulfuric acid was added and dissolved at 150°C.
Water is produced as the reaction progresses after heating and stirring for hours. Thereafter, excess methacrylic acid was distilled off under reduced pressure. A 1:1 mixture of ethanol and water was added to this residue, treated with activated carbon, and then water was added for recrystallization. Repeat this process until the irritating odor disappears, then recrystallize twice with hexane.
2-(4-hydroxyphenoxy) at -63°C to 64°C
108 g of ethyl methacrylate was obtained.

Next, 20 g of 2-(4-hydroxyphenoxy)ethyl methacrylate and 0.1 g of α,α゛-azobisisobutyronitrile were dissolved in 60 g of methyl cellosolve and heated at 65°C for 6 hours in a sealed tube purged with nitrogen gas to form a polymer. A solution was obtained. This polymer solution was poured into 1200 mjl of hexane, and the resulting white precipitate was filtered and dried to obtain 12 g of a white polymer.

1.5g of the obtained polymer was added to 91L of methyl cellosolve.
The mixture was stirred and dissolved. After dissolving 0.0453 of the sonoacyto compound of Zaraani (a-1) in N-methyl-2-pyrrolidone l ■1, mix it with the previous solution and filter it, then rotate this filtrate on a glass substrate. Apply using an applicator and apply for 80 minutes.
After drying by heating for 10 minutes at °C, it was exposed to light through a striped pattern mask. The exposure amount at which the film thickness after development with a 2.0% aqueous tetramethylammonium hydroxide solution became constant at about 1.0 μl was defined as the sensitivity. (All exposures were performed in air.) The sensitivity at this time was 60 J/cm''.

Example 2 The diazide compound (a-3) was used in place of the monoazide compound of Example 1, and exposure and development were carried out in the same manner. The sensitivity at this time was 70 mJ/c2.

Example 3 1.5 g of the polymer of Example 1 and 0.3 g of (n-1) naphthoquinonediazide sulfonic acid ester compound were added to 10 m
Stir and dissolve in J2 methyl cellosolve and filter.

Thereafter, this filtrate was applied to a glass substrate using a rotary coater, dried by heating at 80° C. for 10 minutes, and then exposed to light. The exposure amount is 8
It was 0 mj/cm'. Subsequently, it was developed with a 135% aqueous tetramethylammonium hydroxide solution. The remaining film thickness was approximately 1.0 μI.

Example 4 Polymer 1.58 of Example 1 was converted into methyl cellosolve 9-1
The mixture was stirred and dissolved. Furthermore, 0.045 g of the diazide compound (a-3) and 0.0754 g of 1-methyl-2-benzoylmethylene-β-naphthothiazoline as a sensitizer were added to the N-
Methyl-2-Hyrolidone 1 Meal A&: The dissolved product was mixed with the previous solution and filtered, then the filtrate was applied to a glass substrate using a rotary coater, and heated and dried at 80°C for 10 minutes. It was exposed to ultraviolet light of 436 na.

(Exposure was performed in air.) After development with a 2.0% tetramethylammonium hydroxide aqueous solution, the film thickness was approximately 1.0%.
The exposure amount that became constant in μm was defined as the sensitivity. The sensitivity at this time was 300 mj/c 2.

Comparative Example 1 1.5 g of polyvinylphenol was added to methyl cellosolve 9
mL with stirring. Furthermore, 0.045 g of the diazide compound (a-3) and 0.075 g of 1-methyl-2-benzoylmethylene-β-naphthothiazoline were dissolved in N-methyl-2-pyrrolidone 11 times and mixed with the above solution. After dissolving and passing through a filtration, this filtrate was applied to a glass substrate using a rotary coater, and after heating and drying at 80°C for 20 minutes,
Exposure to UV light from Fitv. (Exposure was performed in air.) Developed with a 0.95% aqueous tetramethylammonium hydroxide solution. Exposure amount 800J/Cl112
However, no cured images were obtained.

Application example 1 12 g of 2-(4-hydroxyphenoxy)ethyl methacrylate, 24 g of N-(3-dimethylaminopropyl) methacrylamide, 4 g of 2-hydroxyethyl methacrylate and α,α°-azobisisobutyronitrile O,
18 g was dissolved in 111 g of methyl cellosolve and heated in a sealed tube purged with nitrogen gas at 65° C. for 6 hours to obtain a polymerization solution. This polymerization solution was poured into 2000a+jl of ethyl acetate, and the white precipitate formed was filtered and dried to obtain white polymer 15.
I got g.

Next, 1.5 g of the obtained polymer was added to methyl cellosolve 9
(1) Stir and dissolve in 1. Furthermore, (a-3) 0.045 g of QD diazide compound was added to tomethyl-2-pyrrolidone 1
The solution dissolved in Soybean A was mixed and dissolved with the previous solution and filtered to obtain a photosensitive solution. Using this photosensitive liquid, a good stripe pattern relief image was obtained in the same manner as in Example 1.

Red 24c (Nippon Kayakuryu) uses this relief image as a dye.
,! 151p (Nippon Kayaku), blue 43p (Nippon Kayaku)
was used for staining at 60°C. Clear color tones were obtained for each color, demonstrating that the photosensitive composition of the present invention is useful as a base material for color filters used in color liquid crystal display devices and the like.

[Effects of the Invention] The photosensitive composition of the present invention has good mechanical strength of the resulting relief image, and is sensitized even in air with a small amount of exposure, so it has higher productivity and better productivity than conventional photosensitive compositions. It is advantageous in terms of energy saving and equipment. Furthermore, the exposed or unexposed areas can be easily removed with an alkaline aqueous solution, resulting in high process safety.

[Brief explanation of the drawing]

The IR spectrum of the homopolymer of Example 1 of the present invention is shown in FIG. that's all

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼... [1] (In the formula, R_1 is a hydrogen atom, CH_3 or C_2H_
5 groups, n is an integer from 1 to m, and m is an integer from 1 to 4. ) A photosensitive composition characterized in that it is formed by adding an azide compound or a quinonediazide compound as a photosensitizer to a polymer compound having a structural unit represented by the following in its molecular structure. (2) Structural units constituting polymeric compounds include styrene, methylstyrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, and methacrylic acid. Claim No. 1 which uses one or more compounds selected from ethyl, n-butyl methacrylate, isobutyl methacrylate, or vinyl acetate.
The photosensitive composition described in .