JPS59171948A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To simplify a heating step and to speed up a manufacturing process by using a photosensitive resin compsn. comprising an alkali-soluble polyfunctional polyester acrylate monommer or oligomer, a photopolymn. initiator, and a sensitizer, as a photoresist for a printed circuit plate. CONSTITUTION:An alkali-soluble polyfunctional polyester acrylate monomer or oligomer used for the essential component of a phototsensitive resin compsn. gives superior physical property to a coating film and ahrdenability characteristics and permits easy peeling of the unhardened part and hardened part due to exposure using an aq. alkaline soln. Said polyfunctional polyester acrylate is a compd. having plural acryloyloxy groups, such as (CH2=CHCOOCH2)2C(CH3)2 or (CH2=CHCOOCH2)3C-C2H5. Preferably, it has 150-1,000mol.wt. As a polymn. initiator, benzoin or benzoin ethyl ether initiating photopolymn. reaction with UV rays is used in an amt. of 1-20pts.wt. per 100pts.wt. of said monomer or oligomer. As said sensitizer, alkylamines, such as triethylamine, and ethyleneamines, such as triethylenetetraamine, are used in an amt. of 1-2pts.wt. per 100pts.wt. of said monomer or oligomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition that is polymerized by light, and more particularly to a photosensitive resin composition that can be used as a photoregimen during esotinction by pattern exposure.

- Generally, when manufacturing printed wiring boards, a photosensitive resin composition is coated on a conductive foil such as copper foil.
and exposed the first resist layer.

This is developed to obtain a first and second pattern, and this pattern is used as an etching mask to create a fine conductive pattern.

The fluorenosts used in the above applications have conventionally been made of ene-thiol-based photosensitive materials, azide-thiol resin mixed-based photosensitive materials, and cyclized rubber-subazide resin mixed-based photosensitive materials. Material phases, α-diazoketone based photosensitive materials, acrylic resin based photosensitive materials, etc. are known.

By the way, the ene-thiol-based photosensitive material is
・When used as a resist, it requires heating processes such as semi-cure and post-cure before exposure and after development, and generally requires 25 m J
／（：＋j＜） 2. Because it requires high illuminance, pattern exposure takes a long time, and it cannot meet the demands for shortening and simplifying the manufacturing process.Furthermore, the photosensitive material has a high viscosity. When applying coach ink, use Photoren λ1 layer (which also eliminates the drawback that the pores are raw).

In addition, when using an acid-phenol resin mixed light-sensitive material, a cyclized rubber-bisazide resin mixed light-sensitive material, or an α-diazoketone light-sensitive material, each of these light-sensitive materials is of the so-called solvent type dissolved in a solvent. In addition, a no-heakening process is required to volatilize the solvent used to form the coating film, making it difficult to shorten or simplify the manufacturing process, as in the case of the first enthiol-based photosensitive material. Furthermore, when a cured product that is cured by pattern exposure and used as an ethotink mask is to be finally removed, it cannot be removed with an alkaline solution.

However, it is necessary to use organic solvents such as trichlorethylene and methylene chloride to peel off these cured products, which may adversely affect the health of the workers. During the process, it becomes troublesome, etc. Furthermore, these photosensitive paulownia materials are very m l1
Since it is a liiα product, it also has the disadvantage of increased manufacturing costs.

Also, since the acrylic resin photosensitive material is solvent type,
After painting one model, a kink step is required to evaporate the solvent, and furthermore, the after-kink process after the first appearance is also slow.

Therefore, as a result of intensive research to eliminate the above-mentioned drawbacks of the prior art, the outside invention η et al. has developed a method using an alkali-soluble polyfunctional polyester or acrylate monomer or oligomer as the main component of the photosensitive resin composition. The present invention was completed based on the discovery that this composition has excellent coating film properties and curing properties, and that the uncured portions and hardened portions caused by exposure to light can be easily peeled off using an aqueous alkaline solution.

That is, the photosensitive resin composition according to the present invention contains an alkali-soluble polyfunctional polynitride acrylate monomer or olicomer, a photopolymerization initiator, and a sensitizer. Note that the polyfunctional polyester and steracrylate herein refer to a plurality of anj1 royloxy groups (Cl-
12=CHCOO).

As the alkali-soluble polyalcoholic polyester acrylate used in the present invention, the following compounds can be used.

(1) CHz=CI-ICOO(CH2)nOcO
cH=cHz (I] is an integer from 1 to 6) (2,1(C)(z=CHCOOCH2)zC(CH3
)2(3) (CH2= CHCOOCH2) 3C
-C2l-1s(4,I Cl-12=CHCOO-
(CHzCHO)3-cOcI-J=CHz product 3 (7) Cl-l2=CHCO(J(CH12)so
-0(J (a) CH2=C00(CH,C1-120)rL
COCH=CH2 (however, the number is 4 or 14) The molecular weight of the alkali-soluble polyfunctional polyester acrylate hexamer or oricomer shown above is 150 to 1.
Preferably, it is 000. If the molecular weight is less than 150, the degree of polymerization of the photosensitive resin composition will decrease, and the physical properties of the coating film will deteriorate. Moreover, when the molecular weight exceeds 1000, it becomes difficult to remove the photosensitive resin composition with alkali.

As the polymerization initiator used in the present invention, any initiator that is photoexcited when irradiated with ultraviolet rays and easily initiates a photopolymerization reaction can be used. Examples include ehachenzoin, benzoin methyl able, benzoin ethyl ether, Acilloin and its derivatives, such as henzoin inobrobil ether, henzoin isofthyl ether, tesylfuromide, and α-methylhenzoin; carbonyl compounds, such as 2-methylan I-laquinone, cyclohexanone, and 9-fluorenone; henlu and diacetyl Diketones such as diphenyl monosulfide, diphenyl disulfite, tenruphenyl sulfite, and organic sulfides such as tetramethyl ten ram monosulfide 1 to 1; -methylaminohenozophenone and.・Phenone m such as P, P'-tetramethyldiaminosonphenone: P-h luenesulfonylchloride 1,]-naphthalenesulfonylchloride 1-12-
Examples include sulfonyl halides such as naphthalenesulfonyl chloride, 1,3-hensendisulfonyl chloride, '2,4-nonitrobenzenesulfonyl bromite, and P-acetamitohensensulfonyl chloride. Particularly preferred are Group J luponyl compounds).

The amount of polymerization initiator added depends on the alkali-soluble polyfunctional group.
Ester acrylate monomer (or oligomer 10)
It is preferable that 1 to 20 parts by weight per part by weight of 1b to 20 parts by weight. If the amount added is less than 1 part by weight, the photosensitive resin composition will not be easily cured by light, and if the added amount exceeds 20 parts by weight, the coating properties of the photosensitive resin composition will deteriorate.

Examples of the sensitizer used in the present invention include alkylamines such as ethylamine, and ethyleneamines such as triethylenetetraamine, tetraethylenepentamine, penkethylenehexamine, and diethylenetetramine. The I sound sensitizer used by Jiro is one that prevents the oxygen force in the air (photosensitive branch due to ultraviolet irradiation) from delaying the surface hardening of the resin composition.The sensitizer's The amount added is preferably 1 to 2 parts by weight per 100 parts by weight of the monomer or oligomer of the polyfunctional polyester acrylate I.If the amount added is less than 1 part by weight, The above effects cannot be achieved, and if the amount added exceeds 2 parts by weight, the photosensitive resin composition will condense.

Further, a polyvinylphenol derivative may be added to the photosensitive resin composition according to the present invention. Polyvinylphenol derivatives act as alkaline hoof stripping accelerators. Examples of polyvinylphenol derivatives include compounds having repeating units represented by the general formula (wherein Ro represents a substituent selected from the group consisting of -H, -CH2 and -C2H5) or substituted compounds selected from the general formula. represents a group. ) Compounds having a repeating unit shown in the following are mentioned. The molecular weight of this polyvinylphenol derivative is preferably 5,000 to 11,000.

The photosensitive resin composition according to the present invention is a so-called solvent-free type that does not require a solvent, and in order to achieve high physical properties of the coating film, it requires heating processes such as bre-bake and after-bake.
10 (1=30
Since it has a low viscosity of 00CP8, it can be applied by various coating methods such as spinner coating, roll coach ink, isopink, etc., without the risk of pinholes or the like occurring in the coating film.

Moreover, the photosensitive resin composition according to the present invention has a power of 8 to 10 mJ/c.
It is an extremely sensitive photosensitive material that cures at low illuminances of .
Manufacturing efficiency can be significantly improved.

Further, the photosensitive resin composition according to the present invention can be developed with a dilute aqueous alkaline solution, and the cured product can be peeled off with a highly concentrated aqueous alkaline solution.

Examples of the alkali used for this development and stripping include sodium hydroxide and potassium hydroxide, but the alkali is not particularly limited to these, and any alkali can be used. For example, when thorium hydroxide is used as the alkali, it is preferable to use an aqueous solution with a concentration of 0.5 to 1 w/v% for the development, and 41% for peeling off the cured product. /V
It is preferable to use an aqueous solution with a concentration higher than 50%. Here, if a thorium hydroxide solution with a concentration of 05 W/v% or less is used for development, it will be difficult to remove the uncured resin, and if a solution with a concentration of IW/v% or more is used, it will harden by exposure. There is a risk that the resin in the exposed areas may also be removed. On the other hand, a thorium hydroxide solution having a concentration of 4 W/v% or more may be used to peel off the cured product; if it is less than that, the peeling will be insufficient.

In this way, the uncured portions and hardened portions of the photosensitive resin composition due to exposure to light can be sequentially removed by changing the concentration of the alkaline aqueous solution, eliminating the need to use a curing solvent at all and improving the health of workers. It becomes very desirable.

Furthermore, since polynisdel acrylate monomer or oligomer is used as the main component of the photosensitive resin composition, the photosensitive material is extremely cheap.

Moreover, the photosensitive resin composition according to the present invention is 20011m to 3
00. Since it is sensitive to ultraviolet rays with known wavelengths of L-, it has not been used conventionally.1. UV #, i! (Wavelength 3007., n
-4007zm), there is less blurring of the image due to diffraction and interference, making it possible to perform high-resolution exposure.

Hereinafter, specific examples of the present invention will be described.

〔Example〕

A monomer or oligomer of one compound among the alkali-soluble polyfunctional polyester acrylates shown in Table 1, one compound among the photopolymerization initiators shown in Table 2, and one of the sensitizers shown in Table 3. These compounds were mixed at any of the composition ratios shown in Table 4, and the resulting mixture was sufficiently stirred to prepare a liquid photosensitive resin composition.

The obtained liquid photosensitive resin composition was used as a first resist, and a 10 μm coating was applied onto a copper foil-coated substrate using a bar coater.
Coating to a thickness of m to form a photoresist film and
Using a KW (7) ultra-high pressure mercury lamp as a light source, the photoresist film was exposed to light through glass transfer. The exposure time was 1 second (illuminance 8 rrLJ/cffl).

After developing the photoresist film of the exposure agent with 1% NaOH aqueous solution and etching the copper foil with ferric chloride solution, 4% N
a The photoresist 119λ was removed using an OH aqueous solution.

As a result, a striped copper foil pattern with a line width of 50 μm was obtained.

Note that a photosensitive resin composition having similar effects could be obtained by any combination of the above-mentioned compounds.

In this way, the photosensitive resin composition according to the present invention can be used as the first resist for printed wiring boards. It is possible to simplify the heating process, and since it can be cured at relatively low illuminance, the line can be made lighter, which is a great manufacturing advantage.

Furthermore, although the photosensitive resin composition of the present invention is a solvent-free type, it has a low viscosity of 100 to 3000 CP S, so it can be applied using a divine coating method.
Also, there are no pinholes in the paint film. In addition, the photosensitive resin composition according to the present invention can develop the uncured portion with a dilute alkaline solution, and furthermore, the cured product of this composition can be peeled off with a highly concentrated alkaline solution. There is no need to use a solvent, and there is no risk of adverse effects on the health of workers.

Table 1 Table 2 Table 3 Table 4

Claims (1)

[Claims] A photosensitive resin composition comprising an alkali-soluble multifunctional polyester acrylate monomer or oligomer, a photopolymerization initiator, and a sensitizer.