JPH0862858A - Developer for combined resin - Google Patents

Abstract

PURPOSE: To obtain a developer capable of attaining development to a combined resin having photosensitive groups made of a mixed system with a polyether sulfone with superior resolution without leaving residue on development. CONSTITUTION: This developer is a developer for a resin compsn. consisting of a resin having photosensitive groups and polyether sulfone and contains a compd. represented by formula CH3 O-(CH2 CH2 O)n -CH3 (where 1<=n<=5) as an essential component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite resin developer, and more particularly to a composite resin developer which has no development residue and is excellent in resolution, as compared with a composite resin composed of a mixed system with PES. .

[0002]

2. Description of the Related Art A typical composite resin is one in which a thermosetting resin is mainly mixed with a thermoplastic resin to improve the physical properties of the thermosetting resin. For example, epoxy resin and polyether sulfone (hereinafter "PES")
In the mixed system (PES modified epoxy resin), the composite resin improved the toughness of the epoxy resin due to the co-continuous structure formed by the epoxy resin and PES (Keizo Yamanakaand Takashi Inoue, Polymer, vol.3).
0, P662 (1989)). Where epoxy resin and PES
The co-continuous structure with is a structure in which epoxy spherical domains are connected to each other and regularly dispersed in a PES matrix. This is because when the epoxy resin is cured at a high temperature, the epoxy resin and PES do not become completely melted (compatibility state) but spinodal decomposition occurs and the thermosetting resin and the thermoplastic resin are mixed in a separated state. This is because it is in a state (phase separation state).

On the other hand, according to the studies by the inventors, the above-mentioned co-continuous structure shows that a mixed system of a resin having a photosensitive group and a thermoplastic resin, for example, a mixed system of an acrylic resin and PES (PES modification). The acrylic resin) had a similar structure.

By the way, the inventors previously developed a completely new resin composite different from the known resins having the above-mentioned co-continuous structure. This resin composite has unique physical properties of a thermosetting resin such as an epoxy resin or a photosensitive resin such as an acrylic resin, for example, heat resistance and photosensitivity, and the original properties of a thermoplastic resin such as PES. It is a novel substance showing higher physical properties than the physical properties, and was proposed as Japanese Patent Application No. 5-271192.

The above-mentioned resin composite previously proposed by the inventors is a composite obtained by curing a resin having a photosensitive group and a thermoplastic resin by controlling the phase separation rate and the curing rate to form a composite. It is a composite resin in which a curable resin and a thermoplastic resin form a pseudo-homogeneous compatible structure. This quasi-homogeneous compatible structure is a value measured by observing the particle size of the constituent resin particles with a transmission electron microscope (hereinafter referred to as "TEM").
It is characterized in that it is 0.1 μm or less and that the glass transition temperature peak value of the resin measured by dynamic viscoelasticity is one. The condition for dynamic viscoelasticity measurement is a vibration frequency of 6.28ra.
d / sec, heating rate 5 ° C./min.

Among the various composite resins described above, the composite resin having a photosensitive group is used in various applications such as an adhesive for electroless plating used in printed wiring boards and photosensitive resist materials. be able to. In this case, the composite resin needs to be exposed and developed, and as a developer therefor, a chlorine-based developer such as chlorocene has been mainly used.

[0007]

[Problems to be Solved by the Invention] However, PES
The composite resin having a photosensitive group composed of a mixed system of and had a problem that a development residue was generated during the development treatment with chlorocene or the like. Therefore, an object of the present invention is to provide a developer for a composite resin, which is capable of achieving development with no development residue and excellent resolution for a composite resin having a photosensitive group which is a mixed system with PES. is there.

[0008]

DISCLOSURE OF THE INVENTION As a result of intensive studies aimed at achieving the above-mentioned object, the inventors have found that the development residue is PES, and the development residue occurs because the solubility of this PES in a developing solution is low. I newly discovered the fact. Therefore, as a result of further intensive research focusing on the solubility of PES constituting the composite resin, a developer for a composite resin having the following contents as a gist constitution was developed.

That is, the present invention is as follows. Resin having photosensitive group and polyether sulfone (PE
S) is a developer of a resin composition, the main component of which is represented by the general formula of CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₃ (n = 1 to 5). A developer for a composite resin, characterized in that ． A compound represented by the general formula CH ₃ O— (CH ₂ CH ₂ O) _n —CH ₃ (n = 1 to 5) is contained as a main component, and further normal methylpyrrolidone (NMP) and N, N-dimethylformamide are included. (DMF), _{water, RO- (C n H 2n O} ) m R (R is an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, m is 1-5, provided that the compound according to claim 1, Except for at least one selected from the group consisting of
The developer for a composite resin as described in 1. ． The resin having a photosensitive group is a thermosetting resin having a functional group partially substituted with a photosensitive group, a photosensitive resin, or a mixture of a thermosetting resin and a photosensitive resin having a functional group partially substituted with a photosensitive group. The developer for composite resin as described above, which is any one of the above.

[0010]

The developer for a composite resin of the present invention comprises a resin having a photosensitive group in a dry state (unexposed and B-stage state) and P.
As a solvent excellent in solubility for any ES, is characterized in that it contains a compound represented by the general formula _{CH 3 O- (CH 2 CH 2} O) n -CH 3 (n = 1~5) . This allows PE
It is possible to provide a developing solution for a composite resin which does not have a development residue and can achieve development with excellent resolution for a composite resin having a photosensitive group which is a mixed system with S.

The general formula CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₃ (n = 1 to 1
The reason why the compound represented by 5) is used as the main component of the developer of the present invention will be described below. Now, a developing solution of a resin composition comprising a resin having a photosensitive group and polyether sulfone (PES) needs to be a good solvent for both the resin having a photosensitive group such as epoxy acrylate and PES. In addition, it is desired that the exposed portion is less corrosive. If the developer penetrates into the exposed area, it is necessary that the developer can be easily dried and removed. In this respect, the above general formula CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₃ (n
= 1 to 5) is a compound in which hydrogen at both ends of polyethylene glycol is replaced with a methyl group and has a plurality of ether groups in the molecule. Therefore, even though this compound is an organic solvent having a relatively small polarity, it can be dissolved with polar / non-polar organic solvents in any proportion at room temperature and has both a resin having a photosensitive group such as epoxy acrylate and PES. Can be a good solvent for as a result,
The developer containing a compound represented by the above general formula CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₃ (n = 1 to 5) as a main component has a photosensitive group composed of a mixed system with PES. It is possible to dissolve and remove only the unexposed portion of the composite resin composition without generating a development residue. Moreover, since the compound has a low polarity, even if the developing solution penetrates into the exposed portion, the developing solution is easily removed by drying and the deterioration of the physical properties due to the residual developing solution can be minimized. further,
Since the above compounds dissolve in polar / nonpolar organic solvents at any ratio at room temperature, the solubility of the developer of the present invention in the above composite resin composition can be controlled and adjusted by mixing with other organic solvents. . For example, when the solubility is insufficient (when the molecular weight of the epoxy acrylate becomes large), it is effective to blend DMF, NMP, etc. having a large solubility, while when the solubility is too strong (the blending amount of PES). the etc.) is small, the molecular weight of greater general formula _{RO- (C n H 2n O)} m R (R is 1 to 4 carbon atoms
It is effective to add a compound represented by the above alkyl group, n is 2 or 3, m is 1 to 5 (excluding the compound described in claim 1), water and the like.

Here, the above general formula CH ₃ O- (CH ₂ CH ₂ O) _n -C
In H ₃ (n = 1 to 5), the reason for limiting the degree of polymerization n of polyethylene glycol to 1 to 5 is that when n = 0, there is no polarity (because it becomes dimethyl ether), so PES does not dissolve, and , N exceeds 5, the molecular weight becomes large, the volatility is lowered, and it becomes difficult to dry.

In the present invention, the general formula CH ₃ O- (CH ₂ CH ₂
The compound represented by O) _n —CH ₃ (n = 1 to 5) is preferably contained in the developer for composite resin of the present invention in an amount of 50% or more. The reason is that if it is less than 50%, the influence of the subcomponents becomes large, and it becomes difficult to control the developing power of the developing solution. The developer for composite resin of the present invention has the above general formula CH ₃ O.
-(CH ₂ CH ₂ O) _n -CH ₃ (n = 1 to 5) as a main component, in addition to normal methylpyrrolidone (NMP), N, N-dimethylformamide (DM
F), _{water, RO- (C n H 2 n} O) m R (R is an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, m is 1-5, provided that claim 1
(Excluding the compounds described in 1.) may be included. Further, additives, stabilizers, etc. for preventing the generation of peroxide may be appropriately mixed. Further, a low molecular weight alcohol may be appropriately blended for the purpose of lowering the surface tension.

The thermosetting resin constituting the composite resin according to the present invention includes phenol resin, amino resin such as melamine resin and urea resin, epoxy resin, phenoxy resin, epoxy modified polyimide resin, unsaturated polyester resin, polyimide resin. , Urethane resins and diallyl phthalate resins have some of the functional groups substituted with photosensitive groups.

As the photosensitive resin constituting the composite resin according to the present invention, there is an acrylic resin such as polymethylmethacrylate or a thermosetting resin in which the functional groups are 100% acrylated. Here, as the photoinitiator for this photosensitive resin, benzoisobutyl ether, benzyl dimethyl ketal, diethoxyacetophenone, acyloxime ester, chlorinated acetophenone, hydroxyacetophenone, etc. intramolecular bond cleavage type, benzophenone, Michler's ketone, dibenzos Bellon, 2-ethylanthraquinone,
Any one or more intramolecular hydrogen abstraction type such as isobutylthioxanthone is preferably used. Examples of photoinitiator aids are triethanolamine, Michler's ketone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, 4 Any one or more of isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, polymerizable tertiary amine and the like are used. As the sensitizer, Michler's ketone, Irgacure 651, isopropylthioxanthone, etc. are suitable, and among the above photoinitiators, some act as a sensitizer. The composition ratio of the photoinitiator to the sensitizer is, for example, benzophenone / Michler's ketone = 5 parts by weight / 0.5 parts by weight Irgacure 184 / Irgacure 651 = 5 parts by weight / 100 parts by weight of the photosensitive resin.
Weight parts Irgacure 907 / isopropyl thioxanthone = 5 weight parts / 0.5 weight parts are preferred. Further, as the photosensitive monomer or photosensitive oligomer constituting the photosensitive resin, epoxy acrylate, epoxy methacrylate, urethane acrylate, polyester acrylate, polystyryl methacrylate, etc. are preferably used.

In the present invention, as the curing agent when the epoxy resin is used as the thermosetting resin, an imidazole type curing agent, diamine, polyamine, polyamide, organic acid anhydride, vinylphenol or the like can be used. On the other hand, when a thermosetting resin other than the epoxy resin is used, a known curing agent can be used.

[0017]

【Example】

(Example 1) (1) Laminate a photosensitive dry film (manufactured by DuPont) on a glass epoxy copper clad laminate (manufactured by Toshiba Chemical),
An image was printed by exposing it to ultraviolet light through a mask film on which a desired conductor circuit pattern was drawn. Then 1,1,
After development with 1-trichloroethane and removal of copper in the non-conductor portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. Thus, a wiring board having a first-layer conductor circuit composed of a plurality of conductor patterns on the substrate was prepared. (2) Epoxy resin particles (Toray, average particle size 3.9 μm) 20
0 g of epoxy resin was dispersed in 5 liters of acetone, and the epoxy resin (manufactured by Mitsui Petrochemical Co., Ltd.) was dissolved in 1 liter of acetone at a ratio of 30 g into an epoxy resin particle suspension obtained by stirring in a Henschel mixer. After 300 g of epoxy resin powder (manufactured by Toray, average particle size 0.5 μm) is dispersed in an acetone solution, a suspension obtained by dropping the epoxy resin powder on the surface of the epoxy resin particles is added. Acetone was removed and then heated to 150 ° C. to create pseudo particles. This pseudo particle has an average particle size of about 4.3 μm.
And about 75% by weight is ± 2 μm centered on the average particle size.
Existed in the range. (3) A 25% acrylate of cresol novolac type epoxy resin (Nippon Kayaku, molecular weight 4000) dissolved in DMDG
70 parts by weight, 30 parts by weight of polyether sulfone (PES),
10 parts by weight of caprolactone-modified tris (acryloxyethyl) isocyanurate (manufactured by Toagosei, trade name; Aronix M325) as a photosensitive monomer, 5 parts by weight of benzophenone as a photoinitiator, Michler's ketone as a photosensitizer
After mixing 0.5 parts by weight, 5 parts by weight of an imidazole type curing agent (manufactured by Shikoku Kasei, trade name: 2E4MZ-CN), and 40 parts by weight of the pseudo particles prepared in (2) above, while adding NMP,
Adjust the viscosity to 250 cps with a homodisper stirrer, then
A three-roll mill was kneaded to prepare a solution of the photosensitive resin composition. (4) Apply the solution of this photosensitive resin composition onto the wiring board prepared in (1) above using a knife coater, leave it in a horizontal state for 20 minutes, and then dry at 60 ° C to obtain a thick film. 50 μm
The photosensitive resin insulation layer of was formed. (5) A photomask film having a 100 μmφ black circle printed thereon was brought into close contact with the wiring board subjected to the treatment of (4), and exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . This was subjected to ultrasonic development treatment with developers having various compositions shown in Table 1 to form 100 μmφ via-hole openings on the wiring board. Furthermore, the wiring board was set to about 3000 mj by an ultra-high pressure mercury lamp.
/ Exposed with cm ^2, 1 hour at 100 ° C., to form a subsequent resin interlayer layer having an opening having excellent dimensional accuracy corresponding to the photomask film by heating for 5 hours at 0.99 ° C.. (6) The wiring board treated in (5) above is immersed in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C for 15 minutes to roughen the surface of the interlayer resin insulation layer, and then It was immersed in a Japanese solution (made by Shipley) and washed with water. (7) Palladium catalyst (made by Shipley) is applied to the substrate with the surface of the resin insulation layer roughened to activate the surface of the insulation layer,
Then, it was immersed in an electroless plating solution for additive having the composition shown in Table 4 for 11 hours to perform electroless copper plating having a plating film thickness of 25 μm. (8) After repeating steps (4) to (7) twice,
Further, by carrying out the step (1), a build-up multilayer wiring board having four wiring layers was manufactured.

When only the composite resin corresponding to the matrix of the adhesive used in this example was exposed and developed under the above conditions, a resolution of up to 50/50 (μm / μm) was obtained between lines / line width, and It was found that there was no development residue and no peeling due to overdevelopment was observed, indicating excellent developability. That is, according to the developer of the present invention, it can be seen that, with respect to the composite resin having a photosensitive group, which is a mixed system with PES, there is no development residue and no overdevelopment, and development with excellent resolution can be achieved.

(Examples 2 and Comparative Examples) Using each of the developers shown in Table 1, a test of exposing and developing a composite resin having the following compositions 1 to 3 under the same conditions as in Example 1 was conducted. [Composition 1] 25% acrylate of cresol novolac type epoxy resin; 70 parts by weight PES; 30 parts by weight caprolactone-modified tris isocyanurate; 30 parts by weight 2E4MZ-CN; 5 parts by weight BP / MK; 5 / 0.5 parts by weight 2] Cresol novolac type epoxy resin; 40 parts by weight EO-modified bisphenol A dimethacrylate; 40 parts by weight PES; 20 parts by weight dipentaerythritol tetraacrylate; 15 parts by weight 2E4MZ-CN; 5 parts by weight BP / MK; 5 / 0.5 parts by weight Parts [Composition 3] 15% acrylate of cresol novolac type epoxy resin; 60 parts by weight PES; 40 parts by weight bisphenol S diacrylate; 10 parts by weight trimethylolpropane triacrylate; 10 parts by weight DICY / 2PZ; 5 / 0.5 parts by weight 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1; 5 The amount part

As a result, as is clear from the results shown in Table 1, in the comparative examples using the developing solutions other than the present invention, the resolution up to the line spacing / line width = 50/50 (μm / μm) was exhibited. However, the development residue is severe, and pattern peeling occurs due to excessive development, resulting in poor developability. In this respect, it can be seen that in the compatible example using the developing solution of the present invention, there is almost no development residue, and development having excellent developability and resolution can be achieved.

[0021]

[Table 1]

[0022]

As described above, according to the present invention, P
It is possible to provide a developing solution for a composite resin which does not have a development residue and can achieve development with excellent resolution for a composite resin having a photosensitive group which is composed of a mixed system with ES.

Claims (3)

[Claims] 1. A developer of a resin composition comprising a resin having a photosensitive group and polyether sulfone (PES),
The main component of the developing _{solution, CH 3 O- (CH 2 CH} 2 O) n -CH 3 (n = 1~5) composite resin for developer characterized represented by that general formula. 2. The general formula CH ₃ O— (CH ₂ CH ₂ O) _n —CH ₃ (n = 1 to 1
Includes a compound represented by a 5) as a main component, further, normal methyl pyrrolidone (NMP), N, N-dimethylformamide (DMF), _{water, RO- (C n H 2n O} ) m R
(R is an alkyl group having 1 to 4 carbon atoms, n is 2 or 3, m is 1 to 5, but excluding the compound according to claim 1) at least one selected from the group consisting of The developer for composite resin according to claim 1. 3. The resin having a photosensitive group is a thermosetting resin having a functional group partially substituted with a photosensitive group, a photosensitive resin, or a thermosetting resin having a functional group partially substituted with a photosensitive group. The composite resin developer according to claim 1, wherein the developer is a mixture of photosensitive resins.