JPS61282835A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve an adhesion property of the titled composition and to improve a definition of a picture image by incorporating a resin composed of a alpha,beta-unsatd. ethylenic monomer, a polymerizable monomer which is a liquid state at an room temperature, a photopolymerization initiator and a compd. shown by the specific formula to the titled composition. CONSTITUTION:The titled composition is prepared by compounding 100pts.wt. the resin comprising the alpha,beta-unsatd. eethylenic monomer as an repeating unit, 10-300pts.wt. the polymerizable monomer which is the liquid state at the room temperature, 0.1-20pts.wt. the photopolymerizable initiator, and 0.01-1pts.wt. the compd. shown by formula I wherein R1 is an ortho aromatic hydrocarbon, X1 is O, S or N-R3 (N is a nitrogem atom, R3 is a hydroxy group, a halogen atom or an alkyl group contg. 1-4 carbon atoms per a molecule), R2 is a hydrogen atom or an alkyl group contg 1-4 carbon atoms per a molecule, X2 is O or S atom, Z is a nitrogen atom.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to photosensitive compositions.

(Prior Art) Conventionally, a film of a photosensitive material is formed by coating a photosensitive composition on a completely transparent support film, etc., and the film of the film is formed. is brought into contact with the surface of the substrate from which the entire image is to be extracted, and adhered by heat fusion, etc., and the original image is passed through with the transparent support film left on the top layer or with the support film removed. After exposing the surface of the film to active light, the unexposed portion is eluted with a solvent. Alternatively, when applying the above support film t = flJ #i, the film (peeling method in which the unexposed portion is attached and removed) is used. An image on an original image is developed by a developing method, and this is applied to the manufacture of printed wiring boards, for example, or to the manufacture of relief plates, by the photoresist method.

One of the important problems when using photosensitive compositions for the above-mentioned applications is that their adhesion to the substrate on which the image is to be formed is still insufficient, which makes it difficult to obtain satisfactory and excellent resolution. The point is that there is no. In particular, when used as a resist material for printed wiring, for example when large bags of IC chips are placed on printed wiring boards, a resolution of Fi50μ or less may be required; Have difficulty.

Also, if the adhesion between the resist and the copper substrate is not strong enough,
The etching solution or plating solution penetrates between the resist and the copper substrate, causing the resist to float away from the copper substrate. As a result, the edges of the resist are damaged due to etching, and the plating sinks (the plating extends to the bottom of the resist). phenomenon) occurs, leading to blurring of the linearity of the image cross section, and making it impossible to move around the copper substrate on which a good image has been formed.In order to improve this point, various methods have been tried.
For example, an adhesive layer may be provided between the photosensitive composition layer and the substrate to improve adhesion, or sulfonitrile chloride, phosphate, etc. may be added to the composition in the peel development method. has also been proposed, but in the former case, steps are required to uniformly apply the adhesive layer and dry it when creating the image forming material, which complicates the manufacturing process and is therefore undesirable. In the latter case, the long-term storage stability is poor due to bleeding of the above-mentioned additives, and furthermore, the resolution cannot be said to be sufficiently satisfactory.

Furthermore, for example, it has been proposed to add benzotriazole additives as described in JP-A No. 47-13475, but the adhesion between the resist and the steel is insufficient and it takes several days for development after exposure. If left untreated, the resolution tends to drop significantly. Furthermore, as described in JP-A-53-702, the 2-mercaptobenzimidazole derivative t? It has also been proposed to add copper, but this is thought to react at the mercapto group and the copper interface, and even if the resist is removed, a trace amount of deposits will remain and cannot be removed by post-processing such as soft etching, which poses a problem.

(Problems to be Solved by the Invention) In view of the above-mentioned current situation, the present invention provides a photosensitive material that improves adhesion to a substrate, improves resolution, and can be easily processed into an image forming material. This was made for the purpose of providing Composition 1.

(Means for Solving the Problems) The gist of the present invention is as follows: L (a) 100 parts by weight of a resin containing an α,β-unsaturated ethylenic monomer as a constituent unit; 10 to 300 parts by weight of polymer, (c) 1 to 20 parts by weight of photopolymerization initiator, (d) 1 to 1 part by weight of carpenter's compound α0, t [wherein, C is carbon, N is nitrogen, R1 is ortho] aromatic hydrocarbon;
- represents an alkyl group containing 4 carbon atoms), R2 is hydrogen, an alkyl group containing 1 to 4 carbon atoms per molecule, a phenyl group, or F'i is a carbon atom containing 1 to 4 carbon atoms ), x2 is oxygen, sulfur or NH (however, N is nitrogen and H is hydrogen), Z is nitrogen or #: tcR4C, where C is carbon, R4 is hydrogen or #-t (indicates an alkyl group containing 1 to 4 carbon atoms per molecule)] or a photosensitive composition characterized by containing these as a main component of gold.

As the resin component in the present invention, a polymer substance having α,β-unsaturated ethylenic monomer as a constituent unit is used. , O-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-
Ethylstyrene, 2,4-dimethylstyrene, p-n-
hexylstyrene, p-n-octyl
-Methoxystyrene, p-722styrene, 3-4-
Styrenes such as dimethylchlorostyrene; vinylnaphthalenes; ethylene, propylene, butylene, C6-C
α-olefins such as so and D'; vinyl halides such as vinyl chloride, vinyl bromide, and vinyl fluoride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, methyl diacrylate, ethyl acrylate,
Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, acrylic acrylate, A9! J tv II) α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl, phenyl methacrylate, dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile,
Acrylic acid or a/tuff acrylic acid derivatives such as acrylic acid amide F; Vinyl ethers such as vinyl methyl nitrate, vinyl ethyl ether, etc.; Vinyl ketone necks such as vinyl methyl ketone and vinyl ethyl ketone; N-vinyl pyrrole, N-vinyl carbazole , N-vinyl compounds such as N-vinylindole, and the like.

The photopolymerizable monomer used in the present invention is a room-temperature liquid monomer that initiates polymerization and hardens with light 1ζ in the presence of a photopolymerization initiator, and is typically pentaerythritol triacrylate, polyethylene glycol di Polyacrylate or polymethacrylate monomers such as acrylate, triethylene glycol diacrylate, polyethylene dimethacrylate, trimethylolprono-triacrylate, and trimethylolprono-trimethacrylate are preferably used.

The amount of the polymerizable monomer is 10 to 300 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the resin component.
Used in parts by weight. The amount of the monomer used is 101
If the amount is less than 1 part of tff, curing after exposure will be insufficient,
Also, if the exposure time is longer than that of 3001i Sunbe, the unexposed areas will be too sticky, making it impossible to obtain a good image.

The photopolymerization initiator in the present invention may be any one having the property of activating the photopolymerizable monomer and initiating polymerization when exposed to actinic rays; for example, the following compounds are effectively used. Namely, iodine compounds such as sodicum methyl dithiocarpamate iodine, tetranotyl thicum monosulfide, diphenyl monopur 7-ide, dipenzothiazoyl monosulfide and glutylphide; hydrazone, azoisobutylnitrile, benzenediazonicum Azo and diazo compounds such as chloride; Inorganic compounds such as zinc oxide, magnesium oxide, and tetraethyl lead:
Aromatic carbonyl compounds such as vinyl acetylene, benzoin methyl ether, benzoin ethyl ether, benzophenone, benzaldehyde, benzoin, benzyl anthraquinone, 2-methyl anthraquinone, 2-amino anthraquinone, 2-chloro anthraquinone, tele-7 taraldehyde, etc. ; benzoyl beak oxide, ditertiary glutyl peroxide, dicumyl peroxide,
Peroxides such as cumene hydroperoxide: Examples include inorganic ion complex compounds such as cobalt chloride, cobalt acetate, vinegar l1efI11% iron chloride, iron oxalate, cobalt acetylacetate, cobalt naphthenate, zinc naphthenate, etc. .

The photopolymerization initiator is used in an amount of α1 to 20 parts by weight based on 100 parts by weight of the resin component. If the amount of the photopolymerization initiator is less than 1 part of α1li, the photosensitivity will decrease, and if it is more than 20 parts by weight, the initiator will tend to precipitate from the composition.

The compound that improves adhesion in the present invention has the general formula 1, [wherein C is carbon, N is nitrogen, sR1 is an orthoaromatic hydrocarbon such as orthophenylene, alkyl orthophenylene, or naphthylene, and xtt- is oxygen, sulfur or N-Rs
(However, N represents nitrogen, a hydroxy group, a halogen group, or an alkyl group containing 1 to 4 carbon atoms per molecule)
s Rz represents hydrogen, carbon per molecule and an alkyl group containing 1 to 4 carbon atoms, phenyl group, or alkylene phenylene group having an alkyl group containing 1 to 4 carbon atoms), islands are oxygen , sulfur-crossed NH (however, N-nitrogen, H-hydrogen), 2 is nitrogen-crossed C-R4 (however, C
represents carbon, R4 hydrogen or an alkyl group containing 1 to 4 carbon atoms per molecule], for example, 2-(4-thiazoyl)pendioquinazole, 2-(4-thiazoyl) ) Benzothiazole, 2-(4-thiazoyl)benzimidazole, 2-(
4-Oxacyyl)benzimidazole, 2-(4-thiazoyl)benzimidazole, 2-(4-imidazoyl)benzimidazole, 2-(4-1 riazoyl)benzimidazole, 1-hydroxy-2-(4thiazoyl)benzimidazole , 1-chloro-2-(4-thiazoyl)benzimidazole, 1-methyl-2-(4-
Thiazoyl)benzimidazole, 1-ethyl-2-(
4-Thiazoyl)benzimidazole, 1-propyl-
2-(4-thiazoyl)benzimidazole, 1-gethyl-2-(4-thiazoyl)benzimidazole, 2-
(4-thiazoyl)-5-ethylbenzimidazole,
2-(4-thiazoyl)-s-furobylbenzimidazole, 2-(4-thiazoyl)-5-butylbenzimidazole, 2-(4-thiazoyl)nacoxazole, 2-(4-thiazoyl)natuthiazole, 2 −
Examples include (4-thiazoyl)nac-imidazole and 2-(4-thiazoyl)7tatriazole.

The compound is used in an amount of α01 to 1 part by weight based on 100 parts by weight of the resin component. If it is less than α01 part by weight, no improvement in adhesion can be expected, and 111!
If the amount is more than 1 part, phase separation with the resin component is likely to occur.
As a result, sufficient resolution cannot be obtained.

In the present invention, a color-forming agent such as a leuco dye may be included.

(Function) The photosensitive composition of the present invention is usually dissolved in a solvent and applied to a support film such as a polyethylene terephthalate film and dried to form a photosensitive layer, which is then used as an image forming material. . The image-forming modified material can then be used for forming photoresist images and relief images in the same manner as conventional products. In forming such an optical image,
When the composition of the present invention is used, images with excellent resolution can be obtained due to the action of the copolymer contained in the composition.

This is considered to be because the addition of the above-mentioned copolymer improves the adhesion between the cured photosensitive layer and the substrate surface, which brings about good resolution in peel development or solvent development.

Furthermore, when used as a photoresist material, the photosensitive hardened layer has excellent etching resistance due to improved adhesion.
A high resolution image can be obtained, and there is little decrease in resolution even if the image is left unused after exposure. Furthermore, when used as a metal resist, it does not cause plating to deteriorate, making it effective for use in applications that require high precision, such as in the manufacture of printed wiring boards.

Below margin (5E example) The present invention will be explained in detail below.

<Example 1> Polymethyl methacrylate 60? , Pentaeri Sri
1 s
t, tetraethylene glycol diacrylate 15t.

Benzophenone 39. Dimethylaminobenzophenone α
49. Ethyl violet α2f.

Compound 1: 2-(4-thiazoyl)benzimidazole, Compound 2: 2-(4-
Thiazoyl)benzoxazole, compound 3:2-(4
-Thiazoyl)benzthiazole compound 0. ．． 2t was added to prepare photosensitive solutions of three types of photosensitive compositions.

In addition, for comparison, photosensitive solutions were also prepared containing the above compound and a photosensitive composition containing benzotriazole a29 (in place of the above compound).

These photosensitive solutions were dried on a polyethylene terephthalate film with a thickness of 25 μm, and the thickness of the photosensitive layer after drying was 50 μm.
A cylindrical image material was prepared by coating the material so as to have a thickness of .mu. and drying at 80.degree. C. for 10 minutes.

Next, the surface of this image-forming material was cleaned and laminated under pressure on the surface of a double-sided copper-clad substrate for a printed wiring board having nine through-horns. In this state, place the negative with the wiring circuit-turn tightly on the support and place it 1m away from a 400W high-pressure mercury lamp.
It was exposed to 300 millijoules square centimeter. Next, the polyethylene terephthalate film of the support was peeled off at room temperature, and spray development was performed with trichloroethane.

As a result, in all cases in which Compounds 1 to 3 of Examples of the present invention were added, images up to a fine line of 40 μm were reproduced.

However, in the case of the comparative example, the one without the addition of the compound was 5
In the case of 0μ and benzatriazole added, the image was reproduced down to a fine line of 45μ and was only 9.

Next, using these as metal resists, copper pyrophosphate plating was performed under the following plating conditions, followed by solder plating.

Plating conditions Piro 7 male 7 ate steel common copper Cu”+ 309/
epi(t71X7.z-to R(%'-200P
/ l! Ny) rate N0s-8? /11
Ammonia N & 2r/4
1st ylxyz-) HPO♂-(Ll?/4'
pH 112, 50° C., 30 Altltd, 30 minutes As a result, almost no plating was observed when Compounds 1 to 3 of Examples of the present invention were added.

However, in the case of the comparative example, the one without the addition of the compound was
The plating had largely sunk in from the end face, and the plating with benzotriazole added was also seen to have sunk in considerably.

In addition, in the above development step, when left for 3 days after pressure lamination and 3 days after exposure, when Compounds 1 to 3 of Examples of the present invention were added, the image up to a fine line of 50μ was obtained. was reproduced. However, in the case of the comparative examples, the image without the addition of the compound and the one with the addition of benzotriazole were only able to reproduce images up to 70μ l1m1A, and the resolution was low. As a result of plating using as a metskiresist, Compounds 1 to 3 of Examples of the present invention were obtained.
In all the cases where , plating was hardly observed. However, in the case of the comparative example, large plating cavities were eventually observed.

<Execution N2> Example 10 A photosensitive solution was prepared by adding 51 styrene-maleic anhydride half-propyl ester (acid value: 18 G, ring and ball softening temperature: about 180'C) to each of the three photosensitive compositions, and the experiment was carried out. Development and plating were performed in the same manner as in Example 1.

In the case of the embodiment of the present invention, the image after development is
The layer was imaged down to a fine MA of 25 μm, and then washed with running water, neutralized with 20% HNO3, and washed with water. This is V, =
1 using a sinusoidal alternating waveform current under the condition of 12.7V.
% nitric acid aqueous solution with an electric charge of 160 corons/dm2. When the surface roughness was measured, it was 0.6μ (expressed as Ra). Continue to 30%
After being immersed in an aqueous solution of H2SO4 and desmutted for 2 minutes at 55°C, the thickness was 2.7 g/m2 at a current density of 2 A/dm2 in an aqueous solution of 20%) 12SO4.
It was anodized for 2 minutes so that After that, it was immersed in a 2.5% sodium silicate aqueous solution at 70°C for 1 minute, washed with water,
Dry.

The following photosensitive solution (1) was prepared.

Photosensitive liquid (1) 0 Behenic acid 1g This photosensitive liquid (
After filtering 1), it was coated onto the substrate using a spin coater so that the weight after drying was 2.0 g/m2. Drying was carried out at 80° C. for 2 minutes, and this was designated as sample 8.

As a comparative example, a photosensitive solution containing no behenic acid was prepared from photosensitive solution (1), coated and dried in the same manner, and designated as Sample B.

In order to compare the degree of influence of oxygen on these plates, we placed a PS step guide (gray scale in which the transmission density changes discontinuously at ΔD = 0.15) manufactured by Fuji Photo Film @ on the sample, and Exposure was performed using a Nuark printer (light source: 2KW metal halide lamp). At this time, change the vacuum of the printing frame of the printer and expose, and apply 1 liter of developer for PS plate negatives DN-3C manufactured by Fuji Photo Film ■.
:1, diluted with water, and the unexposed areas were removed.

As shown in Table 1, Sample A was not affected by vacuum and had high sensitivity as shown in Table 1 regarding the number of step guides on the plate after development.

Table 1 Effect of degree of vacuum on sensitivity (gray scale step guide peta stage number) When this sample A was printed using a printing machine Heidelberg KOR-RI, more than 100,000 prints were obtained. 5 in sample B
A printing failure occurred after 10,000 copies were printed.

Example 2 Sample C was obtained by applying and drying a plate in the same manner using the following photosensitive liquid (2) instead of the photosensitive liquid of Example 1.

Photosensitive liquid (2) 0 Photopolymerization initiator with the following structure 2gCCj!
.

Claims (1)

[Scope of Claims] 1. (a) 100 parts by weight of a resin containing an α,β-unsaturated ethylenic monomer as a constituent unit, (b) 10 to 300 parts by weight of a polymerizable monomer that is liquid at room temperature, (
c) 0.1 to 20 parts by weight of photopolymerization initiator, (d) 0.01 to 1 part by weight of the compound of formula I, ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ Formula I [In the formula, C is carbon, N is nitrogen, R_1 is orthoaromatic hydrocarbon, X_1 is oxygen, sulfur, or N-R_3 (however, N
is nitrogen, hydroxyl group, halogen group, or 1 to 1 per molecule
(represents an alkyl group containing 4 carbon atoms), R_2 is hydrogen, an alkyl group containing 1 to 4 carbon atoms per molecule, a phenyl group, or an alkyl group containing 1 to 4 carbon atoms per molecule (indicates an alkylenephenylene group having),
X_2 is oxygen, sulfur or NH (however, N is nitrogen and H is hydrogen), Z is nitrogen or C-R_4 (however, C is carbon,
R_4 represents hydrogen or an alkyl group containing 1 to 4 carbon atoms per molecule] A photosensitive composition characterized by comprising or having these as a main component.