JP2003322969A - Solvent-free one-liquid active energy beam-curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solvent-free one-liquid active energy beam-curable resin composition which is subjected to water development and peeling of a cured body with water after curing with an active energy beam. <P>SOLUTION: The solvent-free one-liquid active energy beam-curable resin composition contains (C) 0.1-10 pts.wt. photoacid generator based on 100 pts.wt. base components including 100 wt.%, in total, of (A) 50-95 wt.% water-soluble photo-cationic polymerizable resin having oxirane rings and (B) 5-50 wt.% water-insoluble photo-cationic polymerizable resin having oxirane rings. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to acid etching treatment as an anticorrosive agent for protecting non-etched portions when chemical etching processing is performed on a printed wiring board, a lead frame, and a metal substrate with a shadow mask by a lithographic method. After etching,
The present invention relates to an imageable photosensitive resin composition that can be easily peeled off with water. More specifically, the present invention provides a solvent-free one-pack type active energy ray-curable resin composition, which is characterized by being capable of developing with water and peeling a cured product with water after curing with active energy rays.

[0002]

2. Description of the Related Art In recent years, energy saving and environmental friendly
With the keyword of improving productivity, the UV / EB curing technology for rapidly solidifying a liquid material by ultraviolet rays or electron beams has been applied to various fields. In the field of printed wiring board processing, various inks such as solder resist inks and etching resist inks are shifting from conventional thermosetting compositions to photocuring compositions for the same reason.

A typical method for forming a conductor circuit of a printed wiring board comprises the following steps. That is, a step of forming a through hole in a conductor circuit forming position in a copper clad laminate, a step of electroless plating the inner wall of the through hole and further thickening by electrolytic plating to make a through hole, a copper having a through hole thus created These are a step of forming an image circuit of an etching resist coating on the laminated laminate, a step of removing the copper foil in the non-circuit portion by etching, and a step of removing the remaining etching resist coating on the copper foil circuit.

When a fine circuit pattern is required, an etching resist image is formed by using a photographic method. This method goes through the steps outlined below. That is, a thin film layer of a photosensitive resin composition is formed on a copper foil on a copper-clad laminate, a master film on which an image is drawn is placed on this thin film layer, and an active energy ray is exposed. The exposed portion where the active energy rays have transmitted from the master film is cured, and the unexposed portion that is blocked is uncured to form a latent image in which the image is reversed from that of the master film. An image pattern of the etching resist is formed on the unexposed portion through a developing step of dissolving and removing it with an organic solvent or a dilute alkaline aqueous solution.

The liquid etching resist is applied by a roll coater, a dip coater or a spray coater and dried by hot air or far infrared rays, which is a relatively simple apparatus. There are many cases.

[0006]

The above-mentioned resist ink contains a resin as a main component and a photopolymerization initiator, but the main component resin used is often a radical polymerization type such as acrylate or unsaturated polyester. Development process,
In the residual etching resist film removing step, it is common to use an organic solvent or an alkaline aqueous solution.

However, the use of the organic solvent tends to gradually become unusable due to the deterioration of the work environment and eventually the global environment and economic problems. Further, when an alkaline aqueous solution is used, the pH tends to change with time, so that it becomes difficult to keep the conditions such as the developing time constant, and it cannot be said that work safety is good at all. Japanese Patent Laid-Open No. 2001-206922 is known as a water-developable photosensitive material, but since the composition contains an organic solvent, a step of evaporating the organic solvent is required, which is not preferable in the working environment and eventually the global environment. Further, nothing is mentioned about the etching solution resistance of the cured coating film as the etching resist and the water peeling property of the residual etching resist film.

Further, in the case of curing by radical photopolymerization,
Since oxygen inhibits curing, it must be cured in a vacuum or in the presence of an inert gas, and the active energy ray irradiation apparatus requires a corresponding facility. In addition, a compounded resin containing a radical polymerization initiator has drawbacks such that the viscosity of the resin is likely to increase and storage stability is poor.

[0009]

In order to solve the above-mentioned problems, the present inventors have found that the solvent-free one-pack type active energy ray-curable resin excellent in storage stability, which does not inhibit curing even in air, and its water solubility. We have developed a cured product. That is, the present invention contains (A) a water-soluble photocationic polymerizable resin having an oxirane ring, (B) an insoluble photocationic polymerizable resin having an oxirane ring, and (C) a photoacid generator as essential components. And a solvent-free one-component active energy ray curable resin composition characterized in that both the composition and its cured product are water-soluble.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The water-soluble photocationic polymerizable resin having an oxirane ring <component (A)> of the present invention causes a polymerization reaction or a crosslinking reaction by being irradiated with light in the presence of a photoacid generator. It is a water-soluble organic compound having an oxirane ring.

Examples of the resin that can be used as the component (A) include polyglycidyl ethers such as glycerin, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol and sorbitol, and glycerin, diglycerin, polyglycerin, diethylene glycol and polyethylene. Examples thereof include polyglycidyl ethers of alkylene oxide adducts such as glycol and sorbitol, and polyglycerin polyglycidyl ether is preferably used. Also, 3-ethyl-3-hydroxymethyleoxetane having an oxetanyl group may be used.

The above compound is not limited to a monomer, and may be an oligomerized product, and the component (A) can be composed of one type alone or a combination of two or more types. In the active energy ray-curable resin composition of the present invention, the ratio of the component (A) contained in the cationically polymerizable resin (hereinafter abbreviated as the main component) which is a combination of (A) and (B) is usually 50.
To 95% by weight, preferably 60 to 90% by weight. When the amount of the component (A) is less than 50% by weight, the cured film obtained cannot be peeled off with water. Also,
When the amount of the component (A) is more than 95% by weight, the curing rate is slow and the developability and resolution are poor.

The water-insoluble photocationic polymerizable resin having an oxirane ring <component (B)> of the present invention means an oxirane ring which causes a polymerization reaction or a crosslinking reaction by being irradiated with light in the presence of a photoacid generator. Is a water-insoluble organic compound having

The resin which can be used as the component (B) is a glycidyl ether type epoxy resin having at least one, preferably two or more oxirane rings, and an alicyclic epoxy resin. Further, an oxetane compound or a vinyl ether compound may be used.

The water-insoluble glycidyl ether type epoxy resin is not particularly limited, but butyl glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether. Ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether,
Hydrogenated bisphenol A diglycidyl ether, phenyl glycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol type epoxy resin, cresol novolac type epoxy resin, halogenated cresol novolac type epoxy resin , Phenol novolac type epoxy resin and the like, and hydrogenated bisphenol A diglycidyl ether is preferably used.

The alicyclic epoxy resin is not particularly limited, but 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, Examples thereof include epoxidized polybutadiene.

The oxetane compound is not particularly limited, but is 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-
3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-
3- (2-ethylhexyloxymethyl) oxetane and the like can be mentioned.

The vinyl ether compound is not particularly limited, and examples thereof include vinyl methyl ether, divinyl ether, vinyl ethyl ether, vinyl isopropyl ether and vinyl isoamyl ether.

The above compound is not limited to a monomer, and may be an oligomer compound, and the component (B) can be composed of one type alone or a combination of two or more types. The proportion of the component (B) in the main component of the present invention is usually 5 to
It is 50% by weight, preferably 10-40% by weight. When the amount of the component (B) is less than 5% by weight, the curing rate is slow and the developability and resolution are poor. Also, (B)
When the content of the component is more than 50% by weight, the resulting cured film cannot be peeled off by water.

Photoacid generator used in the present invention <(C) component>
Is activated by irradiating with active energy rays.
To generate cation species and generate the components (A) and (B).
It is a compound that cationically polymerizes the component, and is not particularly limited.
Aromatic iodonium salts, aromatic sulfo
Onium salts, such as aluminum salts and diazonium salts, and iron
Examples thereof include organic metal complexes such as benzene complex. Photo acid generator
Is generally (R¹ _aR^Two _bR^Three _cR^Four _dZ)^{+ M}(MX
_nm)^-M[Wherein the cation is an onium salt, and Z
Is S, Se, Te, P, As, Sb, Bi, O, I, B
r, Cl or N≡N, and R¹, R^Two, R^Threeand
R^FourAre the same or different organic groups. a, b, c, d
Are integers of 0 to 3 respectively, (a + b + c + d)
Is equal to the valence of Z. M is the central atom of the halide complex
Is a metal or metalloid that constitutes, for example, B,
P, As, Sb, Fe, Sn, Bi, Al, Ca, I
n, Ti, Zn, Sc, V, Cr, Mn, Co, etc.
It X is a halogen atom. m is a halide complex a
Is the net charge on and n is a halide complex ion
The number of atoms inside. ]] Is represented.

The cation (R ¹ _a R ² in the above general formula
Specific examples of _b R ³ _c R ⁴ _d Z) include aromatic sulfonium, aromatic diazonium, aromatic iodonium, aromatic ammonium, and [(1-methylethyl) benzene] -iron cation. Specific examples of the anion (MX _n-m ) include tetrafluoroborate (BF ₄ ), hexafluoroantimonate (SbF ₆ ), hexafluorophosphate (PF ₆ ), hexafluoroarsenate (AsF ₆ ), hexachloroantimonate. (Sb
Cl ₆ ) and the like.

It is also possible to use an onium salt having an anion represented by the general formula [MX _n (OH) ⁻ ]. Further, tetrakis pentafluorophenyl borate _{[B (C 6 F 5)} 4 -], perchlorate ion (ClO ₄
^-), trifluoromethanesulfonate ion _(CF 3 S
O ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ),
It is also possible to use onium salts with other anions such as toluene sulphonate.

Of these onium salts, the onium salts useful as the component (C) are as follows. That is, the aromatic sulfonium salt includes bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate and bis [4- (diphenylsulfonio).
Phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4
-(Phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (penta Fluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- <di (4- (2 -Hydroxyethoxy)) phenylsulfonio> phenyl] sulfide bishexafluorophosphate, The [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bis hexafluoroantimonate, bis [4-
(Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (penta Aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate and bis (dodecylphenyl) iodonium. Oxafluorophosphate,
Bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl)
Iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, Four
-Methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, etc .; aromatic diazonium salts include phenyl Diazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate, etc .; aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate , 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzil-2 -Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl)- 2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate and the like;
(2,4-Cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe salt includes (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene]- Fe (II) hexafluorophosphate,
(2,4-Cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1-yl) [(1-methylethyl ) Benzene] -Fe (II) tetrafluoroborate, (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe
(II) tetrakis (pentafluorophenyl) borate and the like.

The above compounds may be used either individually or in combination of two or more as the component (C). The ratio of the component (C) to 100 parts by weight of the main component of the present invention is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight.

If necessary, the component (D) may be used as a colorant in the composition containing the above components (A), (B) and (C) as essential components. This colorant is usually used in the paint and printing fields, and is used for coloring the resin composition, and it can be colored in any color.

The colorant which can be used as the component (D) includes white pigments such as titanium white and zinc white; blue pigments such as cyanine blue and indanthrene blue; green pigments such as cyanine green and patina; Organic red pigments such as quinacridone type; Inorganic red pigments such as red iron oxide; Organic yellow pigments such as benzimidazoline type, isoindolinone type and quinophthalone type; Inorganic yellow pigments such as titanium yellow and yellow lead; Carbon black, graphite, pine smoke Black pigments such as; aluminum powder, copper powder, nickel powder, titanium oxide-coated mica powder, iron oxide-coated mica powder, and bright pigments such as bright graphite. Further, not only a pigment but also a dye can be used as the colorant.

The component (D) can be composed of one type of the above compounds or a combination of two or more types.

<Optional Components> The active energy ray-curable resin composition of the present invention contains components other than the essential components (A) to (C) and the component (D) as long as the photocurability is not impaired. Can be included. Such optional components include photosensitizers composed of amines, thioxanthones, anthracenes, and phenothiazines, acid proliferating agents that decompose to generate acids such as p-toluenesulfonic acid, alkali metal hydroxides and alkaline earth carbonates. Acid scavengers for metals and alkaline earth metal phosphates, anti-aging agents, leveling agents,
Examples thereof include surfactants, ultraviolet absorbers, silane coupling agents, inorganic fillers, resin particles, and wettability improvers.

The active energy ray in the present invention is not particularly limited, but examples thereof include microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ-rays, electron rays, etc., and among them, simple and easy are preferable. Ultraviolet rays that can be used and have relatively large energy are used.

The above-mentioned ultraviolet rays are not particularly limited, and a mercury lamp, a xenon lamp, a metal halide lamp, a solid laser, etc. can be used as a light source, but a mercury lamp is preferably used.

The details of the present invention will be specifically described below with reference to synthesis examples and examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[0032]

EXAMPLE <Example 1> According to the formulation shown in Table 1,
Polyglycerin Polyglycidyl ether "SR-4G
L "(manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) 85 parts by weight, hydrogenated bisphenol A diglycidyl ether" SR-HBA "(manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) 15 parts by weight, triarylsulfonium hexafluorophosphate salt mixture" UVI " -6
990 "(manufactured by Union Carbide Japan Co., Ltd.) 2.0 parts by weight and diethylthioxanthone" DETX-S "(manufactured by Nippon Kayaku Co., Ltd.) 0.5 parts by weight were charged in a stirring container, and 50
A colorless transparent liquid composition (resin composition of the present invention) was obtained by stirring at 0 ° C. for 1 hour. The obtained resin composition was applied on a glass epoxy copper-clad laminate with a bar coater for about 20 minutes.
It was applied so as to have a film thickness of μm. Use a negative mask to partially shield the light if necessary, and use a high pressure mercury lamp to
It was irradiated with 00 mJ / cm ² and then left to stand for 30 minutes in a hot air dryer set at 150 ° C. The physical properties of the obtained cured film were evaluated by the following evaluation methods. The results are shown in Table 1.

<Examples 2 to 4> Liquid compositions (the present invention) were prepared in the same manner as in Example 1 except that the components (A) to (D) and optional components were stirred and mixed according to the formulation shown in Table 1. After obtaining (resin composition), a cured film was prepared and the physical properties were evaluated. The results are shown in Table 1.

<Comparative Examples 1 to 3> According to the formulation shown in Table 1, a liquid composition was obtained in the same manner as in Example 1 except that the respective constituents were stirred and mixed, and then a cured film was prepared to have physical properties. An evaluation was made. The results are shown in Table 1.

The evaluation method in the above-mentioned examples and the like will be described below. (Water developability) The cured substrate was allowed to stand in pure water at 25 ° C., the coating film was developed with water, and evaluated according to the following criteria. ◯: Development is completed in less than 2 minutes. Δ: Development is completed in 2 minutes or more and less than 10 minutes. X: Development is not possible because the resin remains even after development for 10 minutes or more. (Resolution) Using KODAK Contact Control Guide, C-3 (manufactured by Kodak), the resolution after water development was observed and evaluated according to the following criteria. Good: An image can be drawn with a pattern of line / space = 250 μm / 250 μm or less. Δ: An image can be drawn with a pattern larger than line / space = 250 μm / 250 μm. X: No image can be drawn. (Etching resistance) After development, the substrate was etched with a ferric chloride aqueous solution at 40 ° C. for 60 seconds, and the resist after completion was observed and evaluated according to the following criteria. ◯: The resist has no whitening, peeling, or blistering. Δ: The resist has any of whitening, peeling and swelling. X: The resist was completely peeled off. (Water-Removability) Pure water at 25 ° C. was added to absorbent cotton and the water-removability was observed by rubbing, and evaluated according to the following criteria. ◯: The cured product could be removed by rubbing less than 20 times. B: The cured product could be removed by rubbing 20 times or more and less than 100 times. X: No removal was possible even after rubbing 100 times or more. (Storage Stability) The viscosity after blending and the viscosity after storage at 50 ° C. for 20 days were measured, and the storage stability was evaluated based on the increase in viscosity according to the following criteria. ◯: Viscosity increase is less than 5% Δ: Viscosity increase is 5% or more and less than 20% X: Viscosity increase is 20% or more

[0036]

[Table 1]

As shown in Table 1 above, it was found that the resin compositions shown in the examples can be developed with water, have excellent etching resistance, and can be peeled off with water.

[0038]

EFFECT OF THE INVENTION The active energy ray-curable resin composition of the present invention can be cured in air, has good storage stability, is solvent-free and is a one-part type, and therefore is easy to handle in a work environment and has a developed / cured film. Since it can be stripped only with water, it can be used as a resist material for photolithography, particularly as an etching resist.

Continued front page    F-term (reference) 2H025 AA04 AA16 AB15 AB17 AC01                       AD01 BD03 BD23 BE07 CA32                       CA48 CC11 FA17

Claims (2)

[Claims] 1. A water-soluble photocationic polymerizable resin having (A) an oxirane ring in an amount of 50 to 95% by weight, and a non-water-soluble photocationic polymerizable resin having an (O) oxirane ring in an amount of 5 to 5% by weight.
0.1 to 10 parts by weight of the photoacid generator (C) based on 100 parts by weight of the main agent component containing 0% by weight (however, the components (A) and (B) are combined to make up 100% by weight). Part-containing solvent-free one-component active energy ray curable resin composition. 2. The active energy ray-curable resin composition according to claim 1, which contains (D) a colorant.