KR920005772B1 - Photosensitive resin composition - Google Patents

Abstract

The photosensitive resin compsn. comprises binder polymer, photo- polymerization initiator and polyfunctionalmonomer, Acrylic copolymer (I) is used 40-90 wt.% of total compsn. as binder and polyfunctional monomer. Acrylic copolymer is obtained by copolymerization acrylic acid, methacrylic acid, glycidyl acrylate and glycidlyl methacerylate. In (I), R1,R2,R3,R4,R5, and R8 are each hydrogen atom or methyl; R6 and R7 is COOZ; Y= (a); Z= alkyl; X= carboxyl group; n = 100-2000. Acrylic monomer contains 0.1-0.7 mol acrylic acid and 0.2-0.9 mol glycidyl acrylate. The compsn. has a good resolving power and tenting property.

Description

Photosensitive resin composition

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, and more particularly, to a binder polymer and a polyfunctional monomer, a resolution and ten using an acrylic copolymer represented by the following general formula (I), which is an aqueous alkali solution developability. It relates to a photosensitive resin composition which is excellent in ting property.

Z기(여기서, Z기는 C₁~C₄인 알킬기이다)이고, X는 카르복실기이고, Y는 글리시딜기와 아크릴산의 결합에 의해 형성되는[Wherein R ₂ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₈ are each a hydrogen atom or a methyl group, and R ₆ and R ₇ are

Z group (where Z group is an alkyl group having ₁ to ₄ carbon atoms), X is a carboxyl group, and Y is formed by the bonding of glycidyl group and acrylic acid

N is a natural number selected from 100 to 2,000, and R ₁ to R ₈ , X, and Y may be mutually changed.

As the electronic industry develops, photosensitive resin compositions are widely used in the production of printed circuit boards, and thus, researches on such photosensitive resin compositions have been widely conducted by many researchers in various countries. U.S. Pat. Since the resin composition is prepared, even when exposed to an aqueous alkali solution after exposure, even the exposed portion is swelled and there is a problem in that resolution and tenting properties are lowered.

On the other hand, U.S. Patent No. 3,418,295 discloses a photosensitive resin composition in which an acrylic group is introduced into a binder polymer so that the acrylic group bonds with the multifunctional monomer to form crosslinks during exposure. However, in developing this photosensitive resin composition, since a toxic organic solvent such as methyl ethyl ketone or methylene chloride must be used, there is a problem that it is not only toxic to the human body but also has a fatal effect on the working environment and the like.

On the other hand, in order to solve the problems described above, US Patent No. 4,783,518, in preparing a photosensitive resin composition using an alkaline aqueous solution as a developer, by introducing a glycidyl group into the binder polymer, By ring-opening, crosslinking of binder polymers is formed, and it tries to minimize the problem that the exposed part swells at the time of image development. However, in this photosensitive resin composition, since the crosslinking of binder polymers must be formed by the ring-opening of the epoxy group in the glycidyl group introduce | transduced into the binder polymer, there exists a problem of adding a cation initiator like diacrylonitrile salt separately. Moreover, since the photosensitivity of such a cationic initiator and the photosensitivity of the radical photoinitiator used for radical polymerization of the polyfunctional monomer are different from each other, it is not only difficult to control the sensitivity during exposure, but also the degree of crosslinking depending on the exposure dose. There is a problem that it is difficult to control.

The present invention has been made to solve the problems of the prior art as described above, an object of the present invention, by allowing the acrylic copolymer used as the binder polymer to perform the role of not only a support agent, but also a multifunctional monomer at the same time, It is possible to develop with an aqueous alkali solution, and to provide a photosensitive resin composition with improved resolution and tentability.

In order to achieve the above object, the present invention provides a photosensitive resin composition comprising a binder polymer, a photopolymerization initiator, and a polyfunctional monomer, wherein the binder polymer and the polyfunctional monomer are represented by the following general formula (I). It provides a photosensitive resin composition characterized by using the acrylic copolymer represented:

(여기서, Z는 C₁~C₄인 알킬기이다)기 이고, X는

기 이고, Y는 글리시딜기와 아크릴산의 결합에 의해 형성되는[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₈ are hydrogen atoms or methyl groups, and R ₆ and R ₇ are

(Wherein Z is an alkyl group having ₁ to ₄ carbon atoms) and X is

Y is formed by bonding a glycidyl group and acrylic acid

N is a natural number selected from 100 to 2,000, and R ₁ to R ₈ , X, and Y may be mutually changed.

Moreover, in this invention, the compound represented by said general formula (I) provides the photosensitive resin composition characterized by adding in the quantity of 40 to 90 weight% with respect to the total amount of the photosensitive resin composition. Furthermore, in the present invention, the acrylic copolymer represented by the general formula (I) is acrylic acid, acrylic acid, methacrylic acid, or a mixture thereof, glycidyl acrylate, glycidyl methacrylate or a combination thereof. Characterized in that the mixture glycidyl acrylate is composed of a copolymer. In the present invention, in addition to the acrylic acid and glycidyl acrylate described above, the acrylic copolymer may be selected from alkyl acrylate, which is any one or a mixture of two or more of methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Characterized in that further comprises.

On the other hand, in the present invention, in the acrylic copolymer of general formula (I), the content of each component is 0.1 to 0.7 mole fraction of acid and 0.2 to 0.9 mole fraction of glycidyl acrylate relative to the total amount of monomers added. It is done. Moreover, in this invention, it is preferable that the said acryl-type copolymer has a molecular weight of about 20,000-400,000.

On the other hand, the acrylic copolymer of the general formula (I) as described above may be prepared by the following method. As mentioned above, the acrylic acid component which is acrylic acid, methacrylic acid, or mixtures thereof, and the glycidyl acrylate component which is acrylic acid glycidyl, methacrylic acid glycidyl, or a mixture thereof are a ketone compound such as methyl ethyl ketone or tetra It is dissolved in a reaction solvent of ethers such as hydrofuran. At this time, if necessary, an alkyl acrylate which is one or a mixture of two or more of methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate may be added. N, N'- azo-bis-isobutyronitrile is added as a thermal polymerization initiator, and it is made to react for 5 to 10 hours and cooled in the temperature range of 70-80 degreeC. Subsequently, a polymerization inhibitor such as phenyl-α-naphthylamine or N-N'-di-2-naphthyl-p-phenylenediamine is added, followed by diacrylodinium salt, diacrylchloronium salt, and diacrylbromonium salt. When a cation initiator such as these is added and acrylic acid is added again, a desired acrylic copolymer of the general formula (I) is obtained. The polymerization inhibitor added after the completion of the polymerization reaction is added for the purpose of preventing the acrylic acid added subsequently from causing the addition polymerization reaction.

The polymerization reaction process of the acrylic copolymer of the general formula (I) as described above is as follows.

The acrylic copolymer of the general formula (I) synthesized as described above is in the photosensitive resin composition, and acts as a binder polymer, a support agent, and a polyfunctional monomer to improve resolution and tentability.

In order to perform this role, the copolymer must satisfy the following conditions: Firstly, in order for the non-exposed portion to be developed by an aqueous alkali solution, an appropriate amount of acidic groups must be present in the acrylic copolymer. In the synthesis of the compound represented by the general formula (I), the addition amount of the acrylic acid component should be added in 0.1 to 0.7 mole fraction relative to the amount of the total monomers; Secondly, in order to perform the role of the polyfunctional monomer when the compound of the general formula (I) receives actinic light, the amount of the glycidyl acrylate component that is a parent thereof is 0.2 to 0.9 mole fraction based on the total monomer amount. Should be.

As described above, when the amount of the acid component added to the acrylic copolymer having the general formula (I) is less than 0.1 mole fraction, the developability of the photosensitive resin composition is deteriorated, and when the addition amount exceeds 0.7 mole fraction, development The problem is that too much swelling and removal of the exposed portion occurs.

In addition, when the amount of the glycidyl acrylate component added to the acrylic copolymer is less than 0.2 mole fraction, the polymerization reaction during exposure by actinic light, that is, the degree of crosslinking is low, so that the intensity of the exposure site is low, and thus the exposure site during development Is partially swelled and removed, and if the amount of addition exceeds 0.9 mole fraction, a polymerization reaction, that is, crosslinking occurs excessively, and a problem that the peeling step of removing the exposed portion after the etching step becomes difficult.

On the other hand, since the acrylic copolymer of the general formula (I) as described above functions as a binder polymer, a support agent and a polyfunctional monomer in the photosensitive resin composition, only the photopolymerization initiator, the photosensitizer, Only dyes, colorants, cationic photoinitiators and other additives are added and dissolved in the organic solvent to form the final photosensitive resin composition.

As various additives and organic solvents as mentioned above, the general compound of a predetermined use added to a normal photosensitive resin composition can be applied as it is.

In recent years, in order to make use of such a photosensitive resin composition simpler, the photosensitive resin composition is produced and used for the film form of predetermined thickness.

In order to meet such an objective, the molecular weight of the above-described acrylic copolymer used in the present invention is preferably about 20,000 to 400,000. If the acrylic copolymer has a molecular weight of less than 20,000, it is difficult to maintain the photosensitive resin composition as a final product in the form of a film. If the molecular weight exceeds 400,000, the developability of the resin composition is sharply low. The problem arises.

On the other hand, as for content of the acrylic copolymer of said general formula (I), 40-90 weight% is preferable with respect to the photosensitive resin composition whole quantity.

When the addition amount of the acrylic copolymer is less than 40% by weight, it is difficult to maintain and control the coating amount of about 40㎛ thickness during film production or coating, and when the addition amount exceeds 90% by weight, the photosensitive resin composition is in the form of a film. Flexibility when manufactured and used is reduced, resulting in a problem that the adhesion to the copper substrate is poor.

The method for producing the photosensitive resin composition of the present invention into a dry film is as follows.

Applying the photosensitive resin composition in a solvent in a volatile organic solvent such as methyl ethyl ketone or tetrahydrofuran at a coating amount of about 40 μm on a polyester support film having a thickness of about 25 μm and drying, and then applying the photosensitive resin composition In order to protect a layer, about 35 micrometers of polyethylene protective films are stuck on this application layer.

When the resin composition produced in the form of such a dry film is used for manufacture of a printed circuit board etc., the protective film on a resin composition is removed, and a resin composition film is laminated on the circuit board with a copper thin film.

Without removing the supporting film, a negative photomask circuit diagram is provided thereon and then exposed to actinic light for a predetermined time. After completion of the exposure, the mask circuit diagram is removed, and after the support film on the photosensitive resin composition film is removed, development is performed using an aqueous alkali solution such as sodium carbonate.

When the development is completed, copper plating and lead plating are performed on the developing part, and the exposed part is peeled with an aqueous alkali solution such as sodium hydroxide, which is much stronger than when developing the exposed part, and then the copper of the peeling part is removed using a suitable etching solution. After etching, the lead plated and the like that have been plated off are removed to obtain a desired printed circuit board.

In this series of processes for manufacturing a printed circuit board, first, a thin circuit line of 10 μm or less should be preserved as it is. For this purpose, the resolution of the photosensitive resin composition should be good, and during the plating process, holes The part of the exposed photosensitive resin composition layer which is blocking the portion must be preserved without being removed. For this purpose, the tentability of the photosensitive resin composition should be good.

In the present invention, by using the acrylic copolymer of the general formula (I) as described above, this compound simultaneously serves as a binder polymer, a support agent and a polyfunctional monomer, thereby providing a resin composition excellent in resolution and tentability. Providing.

That is, the acrylic copolymer of general formula (I) which comprises the main component of the photosensitive resin composition of this invention contains the acid group in the member, and since it can develop with aqueous alkali solution, it is less harmful to a human body. In addition, since the acrylic copolymer used functions as a binder polymer, a support agent, and a polyfunctional monomer at the same time, since crosslinking is easily formed throughout the exposure area at the time of exposure even without the addition of a crosslinking agent at the time of development, It has the advantage that an exposed part does not swell and excellent in tentability.

In addition, even if a very fine pattern is exposed once, sufficient crosslinking occurs over the entire exposed area, and thus the photosensitive resin composition of the present invention is not removed but maintained and preserved not only during development but also during crosslinking. This has the advantage that the resolution is excellent because the exposed portion and the non-exposed portion are clearly different in developability.

Next, a preferred embodiment of the present invention is described.

However, these examples are only for illustrating the present invention in more detail, the scope of the present invention is not limited only to these examples.

<Production of Photosensitive Resin Composition>

Example 1

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate)... … … … … 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loiko Crystal Violet (dye) … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone (solvent). … Add the total resin composition to 200 parts by weight.

In preparing the photosensitive resin composition having the above composition, 100 parts by weight of the acrylic copolymer [poly (methyl acrylate / acrylic acid / glycidyl acrylate)] used as the binder polymer and the multifunctional monomer is 0.4 mole fraction of methyl acrylate. , 0.4 mole fraction of acrylic acid and 0.2 mole fraction of glycidyl acrylate were taken and prepared by the production method described above was used.

Example 2

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl methacrylate / acrylic acid / glycidyl methacrylate)... … … 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl methacrylate / acrylic acid / glycidyl methacrylate), which is an acrylic copolymer of general formula (I) used in preparing the photosensitive resin composition of the present embodiment, has 0.1 mole fraction of methyl methacrylate and 0.6 mole fraction of acrylic acid. And those prepared using 0.3 mole fraction glycidyl methacrylate were used.

Example 3

The photosensitive resin composition was manufactured with the following composition.

Poly (ethyl acrylate / methacrylic acid / glycidyl acrylate / acrylic acid). 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (ethyl acrylate / methacrylic acid / glycidyl acrylate / acrylic acid), which is an acrylic copolymer of general formula (I) used in preparing the photosensitive resin composition of this embodiment, is 0.2 mole fraction of ethyl acrylate and 0.3 mole fraction of methacrylic acid. , 0.25 mole fraction of acrylic acid glycidyl, and 0.25 mole fraction of acrylic acid were used.

Example 4

The photosensitive resin composition was manufactured with the following composition.

Poly (propyl acrylate / methacrylic acid / methacrylic acid glycidyl / acrylic acid)

… … … … … … … … … … … … … … … … … … … … … … … 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … … … The total resin composition was added to 200 parts by weight.

Poly (propyl acrylate / methacrylic acid / glycidyl methacrylate / acrylic acid), which is an acrylic copolymer of general formula (I) used in preparing the photosensitive resin composition of this embodiment, is 0.1 mole fraction of acrylic acid profile and 0.3 mole fraction of meta What was prepared using methacrylic acid, 0.3 mole fraction glycidyl methacrylate, and 0.3 mole fraction acrylic acid was used.

Example 5

The photosensitive resin composition was manufactured with the following composition.

Poly (ethyl acrylate / methyl acrylate / methacrylic acid / glycidyl acrylate / acrylic acid)

… … … … … … … … … … … … … … … … … … … … … 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (ethyl acrylate / methyl acrylate / methacrylic acid / glycidyl acrylate / acrylic acid), which is an acrylic copolymer of general formula (I) used in preparing the photosensitive resin composition of this embodiment, is 0.15 mole fraction of ethyl acrylate, 0.05 mole fraction. Those prepared using methyl acrylate, 0.4 mole fraction methacrylic acid, 0.2 mole fraction acrylic acid glycidyl, and 0.2 mole fraction acrylic acid were used.

Example 6

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate)... … … … … 120 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.5 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl acrylate / acrylic acid / acrylic acid glycidyl), an acrylic copolymer of general formula (I), used in preparing the photosensitive resin composition of this embodiment is 0.4 mole fraction of methyl acrylate, 0.4 mole fraction of acrylic acid, and 0.2 mole fraction of acrylic acid. What was prepared using glycidyl was used.

Example 7

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate)... … … … … 150 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 1.0 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.5 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl acrylate / acrylic acid / acrylic acid glycidyl), an acrylic copolymer of general formula (I), used in preparing the photosensitive resin composition of this embodiment is 0.4 mole fraction of methyl acrylate, 0.4 mole fraction of acrylic acid, and 0.2 mole fraction of acrylic acid. What was prepared using glycidyl was used.

Comparative Example 1

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl methacrylate / methyl acrylate / acrylic acid). … … … … 100 parts by weight,

Benzoyl methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl methacrylate / methyl acrylate / acrylic acid) used in preparing the photosensitive resin composition of Comparative Example 1 was prepared using 0.3 mole fraction methyl methacrylate, 0.3 mole fraction methyl acrylate, and 0.4 mole fraction acrylic acid. Was used.

Comparative Example 2

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl methacrylate / methyl acrylate / acrylic acid / glycidyl acrylate)

… … … … … … … … … … … … … … … … … … … … 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … … … 1.0 parts by weight,

Diacrylic iodonium salt... … … … … … … … … … … … … … … … … … … … 5.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … … 1.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl methacrylate / methyl acrylate / acrylic acid / glycidyl acrylate) used in preparing the photosensitive resin composition of this comparative example is 0.2 mole fraction methyl methacrylate, 0.2 mole fraction methyl acrylate, 0.2 mole fraction acrylic acid, and One prepared using 0.4 mole fraction glycidyl acrylate was used.

Comparative Example 3

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate)... … … … … 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate) used in preparing the photosensitive resin composition of this Comparative Example was prepared using 0.85 mole fraction methyl acrylate, 0.1 mole fraction acrylic acid, and 0.05 mole fraction acrylic glycidyl. Used.

[Comparative Example 4]

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate)... … … … … 100 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate) used in preparing the photosensitive resin composition of this comparative example was prepared using 0.94 mole fraction methyl acrylate, 0.04 mole fraction acrylic acid, and 0.02 mole fraction acrylic glycidyl. Used.

[Comparative Example 5]

The photosensitive resin composition was manufactured with the following composition.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate)... … … … … 30 parts by weight,

Benzoin methyl ether... … … … … … … … … … … … … … … … … … … 0.5 parts by weight,

Loikaw Crystal Violet… … … … … … … … … … … … … … … … 1.0 parts by weight,

2, 4-diethyl thioxanthone... … … … … … … … … … … … … … … … … 1.0 parts by weight,

p-toluenesulfonic acid monohydrate... … … … … … … … … … … … … … … 2.0 parts by weight,

Diamond Green GH… … … … … … … … … … … … … … … … … … 0.2 parts by weight,

Methyl ethyl ketone … … … … The total resin composition was added to 200 parts by weight.

Poly (methyl acrylate / acrylic acid / glycidyl acrylate) used in preparing the photosensitive resin composition of the present comparative example was prepared using 0.4 mole fraction of methyl acrylate, 0.4 mole fraction of acrylic acid, and 0.2 mole fraction of glycidyl acrylate. Used.

(Resolution test)

Examples 1 to 7 and the above-described photosensitive resin composition prepared in 1 to 5 were applied on a transparent polyester support film having a thickness of about 25 μm, respectively, at a coating amount of 40 μm, and dried at a temperature of 70 to 75 ° C. To obtain a photopolymerizable film.

The photopolymerizable film thus obtained is bonded onto a copper substrate, and then negative type having a line width of 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130 µm, respectively. A photomask was installed and exposed at an exposure dose of about 40 to 50 mJ / cm 2 using a 3KW ultra-high pressure mercury lamp, and then developed for 60 seconds at a temperature of 30 ° C. with a 1.5% Na ₂ CO ₃ aqueous solution to resolve these photosensitive resin compositions. Was tested.

Tensile Test

인 구멍이 10개씩 형성되어 있는 구리 기판상에 라미네이팅 시킨후, 3KW의 초고압 수은등을 이용하여 40~50mJ/㎠정도의 노광량으로 노광시킨 다음, 1.5% Na₂CO₃수용액으로 30℃의 온도에서 60초동안 현상시켜, 이들 감광성 수지 조성물의 텐팅성을 시험하였다.In addition, the diameter of the photopolymerizable film obtained by performing as above is 1, 2, 3, 4, 5, mm, respectively.

After laminating on a copper substrate having 10 phosphorus holes formed thereon, using a high-pressure mercury lamp of 3KW and exposing at an exposure dose of about 40 to 50 mJ / cm ₂ , 60% at 30 ° C. with 1.5% Na ₂ CO ₃ aqueous solution. It was developed for a second to test the tentability of these photosensitive resin compositions.

Resolution and tentability test results as described above are shown in Table 1 below:

TABLE 1

Claims (5)

In the photosensitive resin composition which consists of a binder polymer, a photoinitiator, and a polyfunctional monomer as a main component, the photosensitive resin characterized by using the acryl-type copolymer represented by following General formula (I) as said binder polymer and a polyfunctional monomer. Resin composition:

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₈ are each a hydrogen atom or a methyl group, and R ₆ and R ₇ are

(Wherein Z is an alkyl group having ₁ to ₄ carbon atoms) and X is

Y is formed by bonding a glycidyl group and acrylic acid

Qi, n is a natural number selected from 100 to 2,000, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , X, and Y may be mutually changed. The photosensitive resin composition according to claim 1, wherein the acrylic copolymer represented by general formula (I) is added in an amount of 40 to 90% by weight based on the total amount of the photosensitive resin composition. The acrylic copolymer represented by the above-mentioned general formula (I) is an acrylic acid component of acrylic acid, methacrylic acid or a mixture thereof, glycidyl acrylate and glycidyl methacrylate. Or it is obtained by copolymerizing the glycidyl acrylate component which is a mixture of these, The photosensitive resin composition characterized by the above-mentioned. The photosensitive resin composition according to claim 3, wherein the acrylic acid component is added in an amount of 0.1 to 0.7 mole fraction based on the total amount of monomers, and the glycidyl acrylate components are added in an amount of 0.2 to 0.9 mole fraction based on the total amount of monomers. . The acrylic copolymer according to claim 3, wherein the acrylic copolymer represented by general formula (I) is any one of methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate in the acrylic acid component and glycidyl acrylate component. The photosensitive resin composition which is obtained by further copolymerizing the alkyl acrylate component which is a mixture of two or more types.