Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2001-09-12
2003-07-08
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S172000, C522S031000, C525S100000, C525S101000, C525S474000, C525S472000, C525S479000, C525S477000, C525S476000, C525S478000, C524S861000, C524S862000, C526S279000, C526S280000, C526S281000, C526S282000, C526S284000, C427S508000, C427S510000, C427S515000, C427S541000
Reexamination Certificate
active
06590010
ABSTRACT:
This invention relates to organosiloxane polymers, photo-curable resin compositions comprising the same, patterning process, and substrate protective coatings.
BACKGROUND OF THE INVENTION
Organosiloxane base photo-curable resin compositions find routine use as protective coatings, insulating coatings and strippable coatings and are also used as photoresist materials for micropatterning.
Organosiloxane base photo-curable resin compositions known in the art include such compositions using photoacid generators. For example, epoxy group-containing organosiloxane base resin compositions using diaryl iodonium salts as the photoacid generator are known from JP-A 55-105627, and vinyl ether group-containing organosiloxane base resin compositions using onium salts as the photoacid generator are disclosed in JP-A 59-500522.
In these resin compositions, however, the type of photoacid generator which can be used is limited because of the poor compatibility of the resin with the photoacid generator, giving rise to the problem that the composition can be utilized with only a light source of limited wavelength. When the resin compositions are used as resist material for micropatterning, the resin is insufficiently photo-curable to form a finely defined pattern.
One known resist material for micropatterning is a resin composition comprising a cresol-novolac resin or polyhydroxystyrene resin, an alkoxymethylated amino resin and a photoacid generator (JP-A 4-136860). Regrettably, the resist formed from this resin composition has poor resistance to oxygen dry etching. Also, when such a resin composition is used as a protective insulating material for a substrate, the composition has an essential problem of poor adhesion to the substrate.
SUMMARY OF THE INVENTION
An object of the invention is to provide a novel organosiloxane polymer, a photo-curable resin composition comprising the same which can be exposed to radiation in a broad wavelength range and readily form a thin film without oxygen attack, a patterning process capable of forming a fine pattern having improved dry etching resistance, and a substrate protective coating having a high dielectric strength and improved substrate adhesion.
It has been found that a photo-curable resin composition comprising an organosiloxane polymer comprising recurring units of the general formula (1) shown below and having a weight average molecular weight of 500 to 200,000 can be exposed to radiation in a broad wavelength range and a thin film can be readily formed therefrom without oxygen attack or interference. Using the composition, a fine pattern having improved dry etching resistance can be formed by a patterning process to be described below. Additionally, a cured coating obtained from the composition by the patterning process has improved adhesion to substrates, heat resistance, and electrically insulating properties.
In a first aspect, the invention provides an organosiloxane polymer comprising recurring units of the following general formula (1) and having a weight average molecular weight of 500 to 200,000.
Herein R
1
to R
4
are independently selected from monovalent hydrocarbon groups having 1 to 8 carbon atoms, and n is an integer of 1 to 1000.
In a second aspect, the invention provides a photo-curable resin composition comprising (A) the organosiloxane polymer defined above, (B) at least one compound selected from among amino condensates modified with formalin or formalin-alcohol, phenol compounds having on the average at least two methylol or alkoxymethylol groups in a molecule, and epoxy compounds having on the average at least two epoxy groups in a molecule, and (C) a photoacid generator.
In a third aspect, the invention provides a patterning process comprising the steps of (i) applying the photo-curable resin composition defined above onto a substrate to form a coating, (ii) exposing the coating to radiation having a wavelength of 150 to 450 nm through a photomask, and (iii) developing the exposed coating with a developer.
A substrate protective coating obtained by post-curing the coating patterned by the above process is also contemplated.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention, the organosiloxane polymer or high molecular weight compound is defined as comprising recurring units of the following general formula (1) and having a weight average molecular weight of 500 to 200,000.
Herein R
1
to R
4
, which may be the same or different, each are a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. Examples include straight, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, and cyclohexyl, straight, branched or cyclic alkenyl groups such as vinyl, allyl, propenyl, butenyl, hexenyl and cyclohexenyl, aryl groups such as phenyl and tolyl, and aralkyl groups such as benzyl and phenylethyl.
The letter n is an integer of 1 to 1000 and preferably 1 to 100. With n in excess of 1000, the polymer becomes less compatible with components (B) and (C) of the composition so that the composition may become less photo-curable.
The organosiloxane polymer should have a weight average molecular weight Mw of 500 to 200,000, and preferably 1,000 to 100,000. With Mw of less than 500, the polymer is less photo-curable. With Mw in excess of 200,000, the polymer becomes less compatible with components (B) and (C) of the composition.
The organosiloxane polymer of the invention can be prepared, for example, by effecting polymerization reaction, known as “hydrosilylation,” of a specific phenol compound having allyl groups represented by the following formula (2) with an organohydrosiloxane of the following formula (3) in the presence of a catalyst.
Herein R
1
to R
4
and n are as defined above. The organohydrosiloxane of formula (3) is obtainable as a desired oligomer or prepolymer by subjecting a corresponding organohydrosiloxane monomer to condensation reaction under appropriate conditions.
It is understood that the weight average molecular weight Mw of the organosiloxane polymer comprising recurring units of formula (1) can be readily controlled by adjusting the ratio of the total number of allyl groups in the phenol compound of formula (2) to the total number of hydrosilyl groups in the organohydrosiloxane of formula (3), to be referred to as “total allyl/total hydrosilyl ratio.” Accordingly, in the above polymerization reaction, the phenol compound (2) and the organohydrosiloxane (3) may be used in such amounts as to give a sufficient total allyl/total hydrosilyl ratio to afford a desired Mw. Specifically, an appropriate total allyl/total hydrosilyl ratio to form an organosiloxane polymer with a Mw of 500 to 200,000 is between 0.5 and 2, and especially between 0.8 and 1.2. It is then recommended that the phenol compound (2) and the organohydrosiloxane (3) be used in such amounts as to give a total allyl/total hydrosilyl ratio within this range.
Examples of the catalyst used in the above polymerization reaction include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid and chloroplatinic acid salts such as H
2
PtCl
4
.nH
2
O, H
2
PtCl
6
.nH
2
O, NaHPtCl
6
.nH
2
O, KHPtCl
6
.nH
2
O, Na
2
PtCl
6
.nH
2
O, K
2
PtCl
4
.nH
2
O, PtCl
4
.nH
2
O, PtCl
2
, and Na
2
HPtCl
4
.nH
2
O wherein n is an integer of 0 to 6, especially 0 or 6; alcohol-modified chloroplatinic acid (U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid with olefins (U.S. Pat. Nos. 3,159,601, 3,159,662 and 3,775,452); platinum group metals on carriers such as platinum black and palladium on alumina, silica and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium known as Wilkinson catalyst; and complexes of platinum chloride, chloroplatinic acid or chloroplatinic acid salts with vinyl-containing siloxanes, especially vinyl-containing cyclic siloxanes.
If desired, an organic solvent is used in the above polymerization reaction. The preferred organic solvents are hydrocarbon solvents such as t
Furihata Tomoyoshi
Kato Hideto
Ueda Takafumi
McClendon Sanza L
Seidleck James J.
Shin-Etsu Chemicals Co., Ltd.
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