JPH0545881A - Positive type visible light-sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain high sensitivity and to improve resolution and storage stability by constituting the resin compsn. of a specified polymer compd., specified compd. which promotes decomposition of the polymer compd., diaryl iodonium salt and specified P-aminobenzylidene deriv. CONSTITUTION:The resin compsn. consists of 1 pts.wt. of polymer compd. of 1000-1000000 mol.wt. having at least one structural unit expressed by formula I, 0.1-0.5 pts.wt. of compd. expressed by formula II, 0.03-0.3 pts.wt. of diaryl iodonium salt, and 0.03-0.3 pts.wt. of P-aminobenzylidene deriv. expressed by formula III. In formula I, R is 2-tetrahydrofurfuryl group or tetrahydropyranyl group. In formula II, R is tert-butyl group or tetrahydropyranyl group, and n is 1-4. In formula III, R1 and R2 are lower alkyl groups, X is a residue selected from hydrogen, phenyl group, acyl group, cyano group, ammonia group, etc., Y is a residue selected from acyl group, cyano group, ammoia group, etc., and n is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type visible light resin composition which is highly sensitive to visible light, particularly laser light, and has excellent resolution and storage stability.

[0002]

2. Description of the Related Art A visible light resin composition is used as a recording material using a laser having a visible oscillation wavelength as a light source. Since recording by laser light can be controlled by an electronic computer, direct drawing is possible and it is used for printing plate making, optical video disc original plate making, and the like. Furthermore, high-resolution hologram recording derived from the monochromaticity of laser light is also important.

A recording material suitable for such a purpose is required to be highly sensitive to laser light and exhibit high resolution. Further, in actual use, it is also necessary that the storage stability is excellent for a long period of time.

Since the photosensitive resin has a feature in forming a relief image, it is useful as a recording material that takes advantage of this point. However, most of the conventional photosensitive resins are used as a photoresist material, an ink,
It is used in paints, varnishes, printing plate-making materials, etc., and their photosensitive wavelengths remained in the ultraviolet region.

As a resin which is sensitive to visible laser light, photopolymerization and photocrosslinking materials have been proposed so far.
For example, in JP-A-52-134692, a photopolymerizable composition comprising a polycyclic quinone and a tertiary amine, JP-A-5-134690
JP-A-4-151024 discloses a composition containing a merocyanine and a triazine derivative as a photopolymerization initiator.
No. 155292, a photopolymerization composition using an imidazolyl dimer and a cyclic ketone having an aminophenyl group as an initiator, and JP-A No. 60-22129, p-.
A photocrosslinkable polymer composed of a phenylenediacrylic acid residue and a sensitizer such as a pyrylium salt is shown. Although these are sensitive to visible light with relatively high sensitivity,
It belongs to the so-called negative type and has a drawback that it is inferior in resolution.

On the other hand, the photo-soluble resin composition (positive type) has very excellent resolution, and as a typical example thereof.
It is well known that o-naphthoquinonediazides are put to practical use. However, this photosensitive material has not been known to perform optical sensitization, and has a problem of extremely low sensitivity in the visible region. Therefore, in recent years, a high-sensitivity photosoluble resin composition that does not use o-naphthoquinonediazides has been proposed. JP-A-57-1
Japanese Patent No. 76035 discloses a composition comprising a polymer having an olefin introduced into a methacrylate side chain, a mercapto acid and a reaction initiator, and Japanese Laid-Open Patent Publication No. 59-45439 discloses a polymer which causes hydrolysis using an acid generated by light irradiation as a catalyst. A composition comprising -p-tert-butoxycarbonylstyrene, and JP-A-61-167945 discloses a composition comprising a compound having a silyl ether group which causes hydrolysis using an acid generated by light irradiation as a catalyst. ing.

However, none of them are sensitive to visible light, and much higher sensitivity has been desired for use as a recording material for a laser or a substitute material for a silver salt. Further, if a material having a high resolution can be produced, the range of application can be expanded, and therefore a high resolution recording material for visible light has been desired.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made by paying attention to the above problems, and the problem is that it is sensitive to visible light, especially laser light, Moreover, it is an object of the present invention to provide a positive-type visible light sensitive resin composition having excellent resolution and storage stability.

[0009]

The inventor of the present invention has completed the present invention as a result of earnest studies to obtain a recording material having high sensitivity and high resolution.

That is, the present invention has at least one structural unit represented by the general formula (A) (formula 1) (wherein R is a 2-tetrahydrofurfuryl group or a tetrahydropyranyl group). 1 part by weight of a polymer compound having a molecular weight of 1,000 to 1,000,000, and (B) general formula 2:
R is a tert-butyl or tetrahydropyranyl group. n is 1
4. ) 0.1 to 0.5 parts by weight of the compound represented by
0.03 to 0.3 parts by weight of (C) diaryliodonium salt, and (D) general formula 3: (Chemical formula 3) (in the formula, R ₁ and R ₂
Is a lower alkyl group. X is a residue selected from a hydrogen atom, a phenyl group, an acyl group, a cyano group, an ammonio group or an alkoxycarbonyl group. Y is a residue selected from an acyl group, a cyano group, an ammonio group or an alkoxycarbonyl group. n is 0 or 1. The present invention provides a visible light resin composition, which comprises 0.03 to 0.3 part by weight of a p-aminobenzylidene derivative represented by the formula (1).

The compound of the component (B) contained in the positive-type visible light sensitive resin composition of the present invention and the polymer compound (A) are mixed in a ratio of 1: 1 to 1: 6. The amount of the diaryliodonium salt of the component (C) is the same as that of the component (B).
Compound: diaryliodonium salt in a weight ratio of 1:
It can range from 0.03 to 1: 0.2. Further, the weight ratio of the compound of component (B) to the sensitizer is in the range of 1: 0.02 to 1: 0.2.

The positive-type visible light resin composition of the present invention comprises
If desired, known additives such as binders, pigments and plasticizers may be added.

As a light source suitable for the positive-type visible light resin composition of the present invention, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a high pressure xenon lamp, a halogen lamp, a helium-cadmium laser, and an algo laser can be used.

After exposure using these light sources for a predetermined time, the resin composition is heated in the dark. Heating temperature is 60-1
50 degreeC, Preferably it is 90-120 degreeC. If it is less than this, the time required for image formation becomes significantly long,
Even if it is more than this, the time for image formation cannot be shortened. The heating time depends on the heating temperature, but 1 to 20 minutes,
It is preferably 5 to 10 minutes. After heating, the exposed portion is solubilized by developing with a solvent containing an alkaline aqueous solution, and a high resolution image is formed.

[0015]

The action of each component in the present invention and its action will be described below. Examples of the polymer compound (general formula 1) having at least one ester residue constituting the positive visible light resin composition of the present invention include acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid. It has the characteristic that the ester bond is cleaved. In particular,
Examples thereof include 2-tetrahydrofurfuryl ester and 2-tetrahydropyranyl ester of these carboxylic acids.

As the polymer compound used in the present invention, in addition to these monomers, vinyl type monomers such as (meth) acrylic ester, (meth) acrylamide, substituted (meth) acrylamide, styrene and methylstyrene are used. The thing which copolymerized the body is used. By selecting the type and copolymerization ratio of these copolymerizable monomers, the characteristics of the intended photosensitive resin composition can be adjusted.

Examples of the compound giving the structural unit of the general formula 2 include benzoic acid in which n is 1 in the formula, wherein R is a tert-butyl group or a tetrahydropyranyl group, and terephthalic acid in which n is 2. R is a tert-butyl group or a tetrahydropyranyl group, n is 3 trimesic acid of three R is a tert-butyl group or a tetrahydropyranyl group, n is 4 of four pyromellitic acid R Can be, but is not limited to, a tert-butyl group or a tetrahydropyranyl group. The structural feature of these compounds is that they contain a bond that is easily cleaved by an acid, and the cleavage results in an acid.

The component (C), a diaryliodonium salt, has a property of generating an acid upon irradiation with light. The compounds used in the present invention include Macromolecules, 10, 1307
(1977). Described in, for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium,
Examples thereof include chloride salts such as bis (p-tert-butylphenyl) iodonium, bromide salts, borofluoride salts, hexafluorophosphate salts, and hexafluoroarsenate salts.

The p-dialkylaminobenzylidene derivative which is the component (D) has a function of spectrally sensitizing the photolysis of the diaryl iodonium salt. Examples of the dialkylaminobenzylidene compound represented by the general formula 3 include the following compounds.

[0020]

[Chemical 4]

[0021]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

<Examples 1 to 3> trimesic acid 21.0 g
And 0.25 g of p-toluenesulfonic acid pyridine salt were dissolved in 100 ml of chloroform, and 37.8 g of 3,4-dihydro-2H-pyran diluted with 30 ml of chloroform was added thereto with stirring. After stirring for 1 hour, the reaction solution was washed with saturated aqueous sodium hydrogen carbonate solution and water. After drying and distilling off the solvent,
The crude product was separated and purified by subjecting it to silica gel column chromatography, and tris (tetrahydropyranyl) trimesinate (hereinafter referred to as compound [A]).
was gotten.

Compound [A] and tetrahydropyranyl methacrylate-α-methylstyrene copolymer (Mn: 3
10,000) 1: 5 mixture is dissolved in diethylene glycol dimethyl ether, and diphenyliodonium hexafluorophosphate and a sensitizer are added to the above solution in an amount of 20% by weight and 10% by weight based on the copolymer. Thus, a photosensitive solution was prepared. This is spin-coated on an anodized aluminum plate, prebaked at 90 ° C for 20 minutes, and then a step tablet (Eastman
1 minute exposure (488n) with a xenon lamp through Kodak
m; 10.8 mJ / cm ² ). This was post-baked at 110 ° C. for 10 minutes and then developed with a 7% aqueous sodium hydroxide solution.

The same sensitivity measurement was carried out for the photosensitive solution containing no compound [A]. The number of solubilization stages is summarized in Table 1.

[0025]

[Table 1]

The resin composition after development was allowed to stand at 180 ° C. for 30 minutes, but no change in relief pattern was observed.

Examples 4 to 6 1 g of trimesic acid was suspended in 10 ml of dioxane, and 1 ml of concentrated sulfuric acid was added. The mixture was cooled in a dry ice-acetone bath, about 3.5 times the amount of isobutylene was added, and the mixture was left overnight in a pressure bottle at room temperature. After cooling, the mixture was poured into a 2 molar aqueous sodium hydroxide solution, extracted with ether, dried and the solvent was distilled off to obtain tri (tert-butyl) trimesinate (hereinafter referred to as compound [B]).

Table 2 shows the results of evaluation using the same formulation as in Examples 1 to 3 using the compound [B].

[0029]

[Table 2]

The resin composition after development was allowed to stand for 30 minutes at 180 ° C., but no change in relief pattern was observed.

<Examples 7 to 9> Benzoic acid 12.2 g, p-
Tetrahydropyranyl benzoate synthesized from 0.25 g of toluenesulfonic acid pyridine salt and 10.1 g of 3,4-dihydro-2H-pyran in the same manner as in Examples 1 to 3 (hereinafter,
Let it be a compound [C]. )was gotten.

Table 3 shows the results of evaluation using the same formulation as in Examples 1 to 3 using the compound [C].

[0033]

[Table 3]

The resin composition after development was allowed to stand at 180 ° C. for 30 minutes, but no change in relief pattern was observed.

[0035]

The positive type visible light sensitive resin composition of the present invention comprises
Since it has a higher sensitivity than conventional visible light resins, it can be applied to a wide range of fields such as plate-making materials for lithographic and letterpress using a visible-light laser, various reliefs, holograms and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/029 9019-2H H01L 21/027

Claims (1)

[Claims] 1. (A) General formula 1: (In the formula, R is a 2-tetrahydrofurfuryl group or a tetrahydropyranyl group.) 1 part by weight of a polymer compound having a molecular weight of 1,000 to 1 million and having at least one structural unit represented by the following formula: B) General formula 2: (In the formula, R is a tert-butyl or tetrahydropyranyl group.
n is 1 to 4. 0.1 to 0.5 parts by weight of the compound represented by the formula (4), 0.03 to 0.3 parts by weight of the (C) diaryl iodonium salt, and (D) the general formula 3: (In the formula, R ₁ and R ₂ are lower alkyl groups, X is a hydrogen atom,
A residue selected from a phenyl group, an acyl group, a cyano group, an ammonio group or an alkoxycarbonyl group. Y is a residue selected from an acyl group, a cyano group, an ammonio group or an alkoxycarbonyl group. n is 0 or 1. ) A visible light resin composition comprising 0.03 to 0.3 part by weight of a p-aminobenzylidene derivative represented by the formula (1).