JP3169308B2 - Developer for composite resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing solution for a composite resin, and more particularly, to a developing solution for a composite resin which has no development residue and is excellent in resolution with respect to a composite resin comprising a mixed system with PES. .

[0002]

2. Description of the Related Art A typical composite resin is a resin obtained by mixing a thermoplastic resin with a thermosetting resin to form a composite, thereby mainly improving the physical properties of the thermosetting resin. For example, epoxy resin and polyether sulfone (hereinafter, “PES”)
Is a composite resin in which the toughness of the epoxy resin is improved due to the co-continuous structure formed by the epoxy resin and the PES (Keizo Yamanaka and Takashi Inoue, Polymer, vol.3).
0, p. 662 (1989)). Here, epoxy resin and PES
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 high temperature, the epoxy resin and PES do not completely melt (compatibility state), but spinodal decomposition occurs and the thermosetting resin and 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 study of the inventors, the above-mentioned co-continuous structure has 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 denaturation). Acrylic resin) had the same structure.

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

The above-mentioned resin composites proposed by the inventors have been 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. A composite resin characterized in that a curable resin and a thermoplastic resin form a pseudo-homogeneous compatible structure. The quasi-homogeneous compatible structure is obtained by measuring the particle diameter of the constituent resin particles by observation with a transmission electron microscope (hereinafter, referred to as “TEM”).
0.1 μm or less, and the resin has one glass transition temperature peak value by dynamic viscoelasticity measurement. The conditions for the dynamic viscoelasticity measurement were as follows: vibration frequency 6.28ra
d / sec, and the rate of temperature rise is 5 ° C./min.

[0006] Among the various types of composite resins described above, the composite resin having a photosensitive group is used for various applications such as an adhesive for electroless plating and a photosensitive resist material used for a printed wiring board and the like. be able to. In this case, the composite resin needs to be exposed and developed, and as a developing solution therefor, a chlorine-based developing solution such as chlorocene is mainly used.

[0007]

SUMMARY OF THE INVENTION However, PES
The composite resin having a photosensitive group composed of a mixture of the above has a problem that a development residue is generated during the development treatment with chlorocene or the like. Accordingly, an object of the present invention is to provide a developer for a composite resin that has no development residue and can achieve development with excellent resolution with respect to a composite resin having a photosensitive group composed of a mixed system with PES. is there.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, the development residue is PES, and the development residue is generated due to low solubility of the PES in a developer. I newly found the fact that. Therefore, focusing on the solubility of PES constituting the composite resin, and as a result of further intensive research, a composite resin developing solution having the following contents as a summary configuration has been developed.

That is, the present invention provides: (1) a composite resin comprising a thermosetting resin in which a part of the functional groups is substituted by a photosensitive group and polyethersulfone (PES), and a photosensitive resin and polyethersulfone (PES). A composite resin, or a mixture of a thermosetting resin and a photosensitive resin in which a part of the functional group is substituted with a photosensitive group and polyether sulfone (PES)
A developing solution for developing any of the composite resins consisting of CH ₃ O- (CH ₂ CH ₂ O) _n -CH
₃ (n = 1 to 5), which is a developer for a composite resin. (2) The developer of the above (1) is represented by the general formula CH ₃ O- (CH ₂ CH
₂ O) includes _n -CH _{3 (n} = _1~5) compounds represented by 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 represents 2 or 3, m is 1-5, provided that (1) at least one selected from among the exception) are compounds described in A developer for a composite resin characterized by containing at least one species. Hereinafter, "a thermosetting resin in which a part of a functional group is substituted with a photosensitive group", "a photosensitive resin", or "a mixture of a thermosetting resin and a photosensitive resin in which a part of a functional group is substituted with a photosensitive group" Are collectively referred to as “resin having a photosensitive group”.

[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
It is characterized by containing a compound represented by the general formula CH ₃ O— (CH ₂ CH ₂ O) _n —CH ₃ (n = 1 to 5) as a solvent having excellent solubility in any of ES. . Thereby, PE
It is possible to provide a developer for a composite resin which has no development residue and can achieve development excellent in resolution with respect to a composite resin having a photosensitive group composed of 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 the formula (5) is used as a main component of the developer of the present invention will be described below. As a developer for a resin composition comprising a resin having a photosensitive group and polyethersulfone (PES), a good solvent is required for both the resin having a photosensitive group such as epoxy acrylate and PES. There is a need for one that has a low erosion property with respect to the exposed portion. Even if the developer penetrates into the exposed portion, it is necessary that the developer can be easily dried and removed. In this regard, the above general formula CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₃ (n
= 1 to 5) are compounds in which hydrogen at both ends of polyethylene glycol has been substituted with methyl groups, and have a plurality of ether groups in the molecule. Therefore, although this compound is an organic solvent having a relatively small polarity, it can be dissolved in an arbitrary ratio at normal temperature with a polar / non-polar organic solvent, and both a resin having a photosensitive group such as epoxy acrylate and PES. Can be a good solvent. 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 mixture with PES. It is possible to dissolve and remove only the unexposed portions of the composite resin composition without generating a development residue. In addition, since the compound has a small polarity, even if the developer penetrates into the exposed portion, the developer is easily removed by drying, and a decrease in physical properties due to the residual developer can be minimized. further,
Since the compound is dissolved in a polar / non-polar organic solvent and an arbitrary ratio at normal temperature, the solubility of the developer of the present invention in the composite resin composition can be controlled and adjusted by mixing with the other organic solvent. . For example, when the solubility is insufficient (when the molecular weight of the epoxy acrylate becomes large), it is effective to mix DMF, NMP, or the like having high solubility. On the other hand, when the solubility is too strong (mixing 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
, N is 2 or 3, m is 1 to 5, provided that the compound described in claim 1 is not included), water and the like are effective.

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 polymerization degree n of polyethylene glycol to 1 to 5 is that n = 0 has no polarity (because it becomes dimethyl ether), so that PES does not dissolve. If n exceeds 5, the molecular weight increases, the volatility decreases, and drying becomes difficult.

In the present invention, the general formula CH ₃ O— (CH ₂ CH _{2
O) n -CH 3 (n =} 1~5) compound represented by the desirably contains 50% or more in the composite resin for the developer of the present invention. The reason for this is that if it is less than 50%, the influence of the sub-components increases, making it difficult to control the developing power of the developer. The developer for a composite resin of the present invention has the general formula CH ₃ O
- (CH ₂ CH ₂ O) in addition to containing as a main component a compound represented by _{n -CH 3 (n = 1~5)} , further, n-methyl pyrrolidone (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
) May be included. Further, an additive, a stabilizer and the like for preventing generation of peroxide may be appropriately compounded. 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 resins, amino resins such as melamine resins and urea resins, epoxy resins, phenoxy resins, epoxy-modified polyimide resins, unsaturated polyester resins, and polyimide resins. And a resin in which a part of the functional groups of the urethane resin and the diallyl phthalate resin are substituted with a photosensitive group.

As the photosensitive resin constituting the composite resin according to the present invention, there is an acrylic resin such as polymethyl methacrylate or a resin in which the functional group of a thermosetting resin is acrylated 100%. Here, as the photoinitiator of the photosensitive resin, intramolecular bond cleavage type such as benzoisobutyl ether, benzyldimethyl ketal, diethoxyacetophenone, acyloxymester, chlorinated acetophenone, hydroxyacetophenone, benzophenone, Michler's ketone, dibenzos Veron, 2-ethylanthraquinone,
Any one or more of intramolecular hydrogen abstraction types such as isobutylthioxanson are preferably used. Examples of photoinitiator include triethanolamine, Michler's ketone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy) ethyl, Any one or more of isoamyl-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and polymerizable tertiary amine are used. Suitable sensitizers include Michler's ketone, Irgacure 651, isopropylthioxanthone, and the like. Some of the above photoinitiators act as sensitizers. The composition ratio of the photoinitiator and the sensitizer is, for example, benzophenone / Michler's ketone = 5 parts by weight / 0.5 parts by weight based on 100 parts by weight of the photosensitive resin. Irgacure 184 / Irgacure 651 = 5 parts by weight / 0.5.
Parts by weight Irgacure 907 / isopropyl thioxanson = 5 parts by weight / 0.5 parts by weight is preferred. Further, as a photosensitive monomer or a photosensitive oligomer constituting the photosensitive resin, epoxy acrylate, epoxy methacrylate, urethane acrylate, polyester acrylate, polystyryl methacrylate and the like are preferably used.

In the present invention, as the curing agent when an epoxy resin is used as the thermosetting resin, an imidazole-based curing agent, diamine, polyamine, polyamide, organic acid anhydride, vinyl phenol, and 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) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper-clad laminate (manufactured by Toshiba Chemical),
The 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 developing with 1-trichloroethane and removing copper in the non-conductive portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. As a result, a wiring board having a first-layer conductive circuit including a plurality of conductive patterns on the substrate was prepared. (2) Epoxy resin particles (Toray, average particle size 3.9 μm) 20
In an epoxy resin particle suspension obtained by dispersing 0 g in 5 l of acetone, 30 g of epoxy resin (manufactured by Mitsui Petrochemical) was dissolved in 1 l of acetone while stirring in a Henschel mixer. A suspension obtained by dispersing 300 g of an epoxy resin powder (manufactured by Toray, average particle size 0.5 μm) in an acetone solution was dropped, and the epoxy resin powder was allowed to adhere to the surface of the epoxy resin particles. The acetone was removed and then heated to 150 ° C. to produce pseudo particles. These pseudo particles have an average particle size of about 4.3 μm
And about 75% by weight is ± 2 μm around the average particle size.
Existed in the range. (3) 25% acrylated cresol novolak type epoxy resin (Nippon Kayaku, molecular weight 4000) dissolved in DMDG
70 parts by weight, 30 parts by weight of polyether sulfone (PES),
Caprolactone-modified tris (acryloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., trade name; ARONIX M325) as a photosensitive monomer, 10 parts by weight, benzophenone as a photoinitiator, 5 parts by weight, photosensitizer Michler's ketone
After mixing 0.5 parts by weight, 5 parts by weight of an imidazole-based curing agent (trade name: 2E4MZ-CN, manufactured by Shikoku Chemicals), and 40 parts by weight of the pseudo particles prepared in the above (2), while adding NMP,
Adjust the viscosity to 250 cps with a homodisper stirrer, then
The mixture was kneaded with three rolls to prepare a solution of the photosensitive resin composition. (4) The solution of the photosensitive resin composition is applied to the wiring board prepared in the above (1) using a knife coater, left in a horizontal state for 20 minutes, and dried at 60 ° C. 50 μm
Was formed. (5) A photomask film on which a black circle of 100 μmφ was printed was brought into close contact with the wiring board subjected to the treatment of (4), and was exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . This was subjected to ultrasonic development with developing solutions of various compositions shown in Table 1 to form openings serving as 100 μmφ via holes on the wiring board. Further, the wiring board is about 3000 mj by an ultra-high pressure mercury lamp.
/ Cm ² and a heat treatment at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours to form a resin interlayer having openings having excellent dimensional accuracy corresponding to a photomask film. (6) The wiring board subjected to the treatment of (5) is immersed in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the interlayer resin insulating layer. After being immersed in a Japanese solution (made by Shipley), it was washed with water. (7) A palladium catalyst (manufactured by Shipley) is applied to the substrate having the surface of the resin insulating layer roughened to activate the surface of the insulating 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 with a plating film thickness of 25 μm. (8) After repeating the steps (4) to (7) twice,
Further, by performing 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 the present embodiment was exposed and developed under the above conditions, it showed a resolution of up to 50/50 (μm / μm) between lines / line width. It was found that there was no development residue and no peeling due to excessive development was observed, indicating excellent developability. That is, according to the developing solution of the present invention, it can be seen that, with respect to a composite resin having a photosensitive group composed of a mixed system with PES, development having no development residue, no excessive development, and excellent resolution can be achieved.

(Example 2, Comparative Example) Using the various developing solutions shown in Table 1, a test was conducted to expose and develop a composite resin having the following compositions 1 to 3 under the same conditions as in Example 1. [Composition 1] 25% acrylate of cresol novolak 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 [Composition 2] Cresol novolak 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; 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 part by weight 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1; 5 The amount part

As a result, as apparent from the results shown in Table 1, in the comparative examples using the developing solutions other than the present invention, the resolution was up to the line interval / line width = 50/50 (μm / μm). However, the developability is poor due to severe development residue and pattern peeling due to excessive development. In this respect, it is understood that in the case of using the developing solution of the present invention, there is almost no development residue, and it is possible to achieve development excellent in developability and resolution.

[0021]

[Table 1]

[0022]

As described above, according to the present invention, P
It is possible to provide a developer for a composite resin that has no development residue and can achieve development excellent in resolution with respect to a composite resin having a photosensitive group composed of a mixed system with ES.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03F 7/32 C08L 81/06 G03F 7/039

Claims (2)

(57) [Claims] 1. A thermosetting method in which a part of a functional group is replaced by a photosensitive group.
Composite tree composed of conductive resin and polyether sulfone (PES)
Fat, photosensitive resin and polyethersulfone (PES)
Composite resin, or thermosetting with a part of the functional group replaced by a photosensitive group
Of Photocurable Resin and Polyethersulfone
(PES)
An image liquid , wherein a main component of the developer is represented by a general formula of CH ₃ O— (CH ₂ CH ₂ O) _n —CH ₃ (n = 1 to 5). Developer. 2. A thermosetting method in which a part of a functional group is replaced by a photosensitive group.
Composite tree composed of conductive resin and polyether sulfone (PES)
Fat, photosensitive resin and polyethersulfone (PES)
Composite resin, or thermosetting with a part of the functional group replaced by a photosensitive group
Of Photocurable Resin and Polyethersulfone
(PES)
An image liquid , and this developer is represented by the general formula CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₃ (n = 1 to 5).
A compound represented by the formula
Methylpyrrolidone (NMP), N, N-dimethylformamide (DM
F), _{water, RO- (C n H 2n O} ) m R (R is an alkyl of 1 to 4 carbon atoms
Group, n is 2 or 3, m is 1 to 5, provided that
At least one selected from
A developer for a composite resin, comprising: