JP2001516804A - Photoresist composition comprising polycyclic polymer having pendant acid labile group - Google Patents

Abstract

  (57) [Summary] The present invention relates to a radiation-sensitive photoresist composition comprising a photoacid initiator and a polycyclic polymer comprising a repeating unit containing an acid-labile pendant group. Upon exposure to an imaging radiation source, the photoacid initiator generates an acid that cleaves the acid labile pendant groups, causing a polarity change in the polymer. The polymer becomes soluble in aqueous base when exposed to the imaging radiation source.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polycyclic polymers and their use as photoresists in the manufacture of integrated circuits. More specifically, the present invention is directed to a photoresist composition comprising a polycyclic polymer and a cationic photoinitiator. The polycyclic polymer is
It has a repeating acid labile group hanging from the polymer backbone. By selectively cleaving the acid labile groups, repetitive polar groups can be formed along the main chain of the polymer. The polymer is transparent to short wavelengths of imaging radiation and exhibits resistance to reactive ion etching.

BACKGROUND integrated circuit of the present invention (IC's) is the most important presence in the production of various electronic devices. The integrated circuit is selectively patterned on a suitable substrate (for example, a silicon wafer) to form a circuit or a system interconnection, thereby exhibiting a specific electrical effect. It is manufactured by continuously forming the alternating zones and the linked zones of the conductive layer. Patterning of integrated circuits is performed according to various lithographic techniques that are well known in the art. Photolithography using ultraviolet (UV) light, deep ultraviolet and other radiation is a fundamental and important technique used in the manufacture of integrated circuit devices. A photosensitive polymer film (photoresist) is applied to the surface of the wafer and dried. Next, a photomask having desired pattern formation information is brought into close contact with the photoresist film. The photoresist is exposed through the photomask to one of various types of imaging radiation, including ultraviolet light, electron beams, x-rays, or ion beams. Immediately after the irradiation, a chemical change occurs in the photoresist, and at the same time, a change in solubility is observed. After irradiation, the wafer is immersed in a solution and developed (eg, selectively removes either exposed or unexposed areas) to create a patterned image in the photopolymer film. Depending on the type of polymer used or the polarity of the developer solution, either the exposed or unexposed portions of the film are removed during the development process, exposing the coated substrate and leaving a patterned exposed or unnecessary The desired pattern is left in the functional layer of the wafer by removing or changing the appropriate substrate material by the etching process. Etching is performed by plasma etching, sputter etching, and reactive ion etching (RIE). The remaining photoresist material functions as a protective layer for the etching process. Removing the remaining photoresist material results in a patterned circuit.

In the manufacture of patterned IC equipment, a method of etching a plurality of different layers on the wafer is among the most important steps involved. One method is to immerse the substrate and the patterned resist in a chemical bath, and corrode only the exposed surface of the substrate without affecting the resist itself. The problem with this "wet" chemical process is that it is difficult to create well-defined edges on the etched surface. This is due to the chemical undercutting of the resist material and the formation of an isotropic image. In other words, conventional chemical processing methods do not provide the direction selectivity (anisotropic) that is deemed necessary to obtain optimal dimensional specifications that meet current processing requirements. In addition, the wet process is associated with undesirable environmental and safety ramifications.

[0004] Various "dry" methods have been developed to overcome the disadvantages of the wet chemistry methods described above. Such a dry process generally involves passing a gas through a chamber and ionizing the gas by applying a specific potential between two electrodes in the presence of the gas. The plasma containing the ion species generated by the potential is used to etch a substrate installed in the chamber. The ionic species generated in the plasma are directed to an exposed substrate that interacts with a surface material that forms volatile products from which the ionic species are removed from the surface. Typical examples of dry etching are plasma etching, sputter etching and reactive ion etching. Reactive ion etching provides etching consistency between substrates as well as well-defined vertical wall cross-sections within the substrates. These advantages have made reactive ion etching technology the standard in IC manufacturing.

[0005] Two types of photoresists are used in the industry, negative and positive photoresists. When irradiated with imaging radiation, the negative photoresist changes its solubility properties such that it undergoes polymerization or crosslinking, or that the exposed areas become insoluble in the developer. The unexposed areas remain soluble and are washed away. Positive resists work in the opposite direction and become soluble in developing solutions when exposed to imaging radiation.

[0006] One of the positive photoresist materials is based on a phenol-formaldehyde novolak polymer. A specific example is a commercially available Shipley consisting of a m-cresol formaldehyde novolak polymer composition and a diazoketone (2-diazo-1-naphthol-5-sulfonic acid ester).
AZ1350 material. Upon exposure to imaging radiation, the diazoketone converts to a carboxylic acid, which in turn converts the phenolic polymer to a substance that readily dissolves in a weak aqueous base developer.

US Pat. No. 4,491,628 to Ito et al. Discloses positive and negative photoresist compositions having an acid generating photoinitiator and a polymer having acid labile pendant groups. . This method is known as chemical amplification, which plays a role in increasing the quantum yield of all-photochemical methods, since each of the generated acids causes deprotection of multiple acid labile groups. Disclosed polymers include vinyl polymers, such as polystyrene, polyvinyl benzoate and polyacrylate, which are substituted with repeating pendant groups that undergo a product which undergoes acid degradation to produce a different solubility from their precursors. . Preferred acid labile pendant groups include t-butyl esters of carboxylic acids and t-butyl carbonate of phenol. Depending on the nature of the developing solution used, the photoresist can be either positive-acting or negative-acting.

[0008] The trend in the electronics industry is constantly seeking faster and less power consuming ICs. To meet this criterion, the IC must be smaller. Conductive paths (eg, lines) must be thinner and the paths must be closer together. Significant reductions in transistor and line dimensions to be fabricated are expected to improve IC efficiency, for example, increase the amount of information stored on computer chips and improve processing. To reduce the line width, it is necessary to increase the resolution of optical imaging. Resolution can be increased by shortening the wavelength of the exposure source used to irradiate the photoresist material. However, conventional photoresists, such as phenol-formaldehyde novolak polymers and substituted styrene polymers, contain aromatic groups, and these aromatic groups have essentially higher absorptivity at light wavelengths below about 300 nm. (ACS Symposium Series 537, Polymers for Microelectronics, Resists and Dielectrics,
The 203rd International Conference of the American Chemical Society, April 5-10, 1992, 2-2
Page 4, polymers for electronic and photonic applications, C.P.Wong (C
P. Wong), Academic Press, pp. 67-118). Shorter wavelength sources typically have lower brightness than conventional sources that require chemical amplification using photoacids. The opacity of these aromatic polymers to short-wavelength light is considered a drawback in that the photoacids under the polymer surface are not uniformly exposed to the light source and cannot be developed because the polymers cannot be developed. To overcome the lack of transparency of these polymers, the aromatic content of the photoresist polymer must be reduced. If deep UV transmission is desired (eg, for exposure at a wavelength of 248 nm, especially 193 nm), the polymer must have minimal aromatic character.

[0009] US Pat. No. 5,372,912 relates to a photoresist composition containing an acrylate-based copolymer, a phenolic binder, and a photosensitive acid generator. The acrylate copolymer is polymerized from acrylic acid, alkyl acrylate or methacrylate and a monomer having an acid labile pendant group. Whereas this composition exhibits sufficient transparency to ultraviolet radiation at a wavelength of about 240 nm, the use of aromatic binders limits the use of shorter wavelength radiation sources. As is common in the polymer arts, an improvement in one property is achieved at the expense of another. When using acrylate-based copolymers, increased transparency to shorter wavelength ultraviolet radiation is achieved by sacrificing the resist's resistance to reactive ion etch processing.

In many cases, increasing the transparency to short wavelength imaging radiation will erode the resist material during the subsequent dry etching process. Because photoresist materials are usually organic in nature and the substrates used in the manufacture of ICs are usually inorganic, the photoresist materials have an inherently higher etch rate than the substrate materials when utilized in RIE technology. Have. This requires that the thickness of the photoresist material be much greater than the thickness of the underlying substrate. Otherwise, the photoresist material will erode before the underlying substrate is sufficiently etched. Thus, resist materials with lower etch rates can be used in thinner layers on the substrate being etched. The thinner layer of resist material increases resolution, thereby ultimately reducing the distance between conductive lines, allowing for smaller transistors.

[0011] JV Crivello et al. (Chemically amplified electron beam photoresist, chemical materials, 1996, 8, 376-3).
81) is a free radical polymerization homopolymer of norbornene monomer having an acid labile group used in an electron beam photoresist, and 20% by weight of a homopolymer of 4-hydroxy-α-methylstyrene having an acid labile group. Discloses a polymer blend consisting of: As mentioned above, increasing the absorption of aromatic groups (especially at high concentrations) makes these compositions opaque and unusable for short wavelength imaging radiation less than 200 nm. The disclosed compositions are only suitable for e-beam photoresists and are suitable for deep ultraviolet imaging (especially 193
nm resist) is not possible.

[0012] Crivello et al. Investigated the blend compositions because they found that the oxygen plasma etch rate for free radical polymerized homopolymers of norbornene monomers having acid labile groups was unreasonably high.

[0013] Thus, a photoresist composition that is compatible with conventional chemical amplification methods and that is sufficiently resistant to reactive ion etching processing environments while providing transparency to short wavelength imaging radiation is provided. is needed.

SUMMARY OF THE INVENTION It is a general object of the present invention to provide a photoresist composition comprising a polycyclic polymer backbone having pendant acid labile groups and a photoinitiator.

Another object of the present invention is to provide a polycyclic polymer having repeating acid labile pendant groups that can be cleaved to form polar groups.

[0016] Another object of the present invention is to provide a polymer composition that is transparent to short wavelength imaging radiation.

It is a further object of the present invention to provide a polymer composition that is resistant to a dry etching process.

It is a further object of the present invention to provide a polymer composition that is transparent to short wavelength imaging radiation and resistant to dry etching processes.

A further object of the present invention is to provide polycyclic monomers having pendant acid labile groups that can be polymerized to form a polymer suitable for aqueous basic development.

The above and other objects of the present invention comprise a polycycloolefin monomer functionalized with an acid labile group, a solvent, a single or multi-component catalyst system each containing a source of Group VIII metal ions. This is achieved by polymerizing the reaction mixture. In the multi-component catalyst system of the present invention, the Group VIII ion source is used in combination with the organometallic cocatalyst and / or the third component. The single or multi-component catalyst system can be used with any chain transfer agent (CTA) selected from compounds having a terminal olefinic double bond between two adjacent carbon atoms; At least one of two adjacent carbon atoms has two hydrogen atoms bonded thereto. The CT
A is usually cationically non-polymerizable and is therefore selected from unsaturated compounds except styrene, vinyl ether and conjugated dienes.

The resulting polymer is useful in photoresist compositions containing a radiation-sensitive acid generator.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a radiation-sensitive resist composition comprising an acid generating initiator and a polycyclic polymer having repeating acid labile pendant groups along the polymer backbone. The initiator-containing polymer is applied as a thin film on a substrate, fired under controlled conditions, exposed to radiation in a patterned configuration, and optionally post-fired under controlled conditions. To further promote deprotection. Where the film is exposed to radiation, the repeating acid labile pendant groups on the polymer backbone are cleaved to form polar repeating groups. The exposed portion thus treated is selectively removed with an alkaline developer. Alternatively, the non-exposed portions of the polymer remain non-polar and can be selectively removed by treatment with a suitable non-polar solvent for negative tone development. Image reversal can be easily achieved by appropriate selection of the developer, due to the difference in solubility properties between the exposed and unfiltered portions of the polymer.

The polymers of the present invention consist of polycyclic repeating units, some of which are substituted by acid labile groups. These polymers are prepared by polymerizing the polycyclic monomers of the present invention. The meaning of the term "polycyclic" (norbornene type or norbornene functionality) is that the monomer contains at least one norbornene moiety as shown below.

[0024]

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The simplest polycyclic monomers of the present invention are bicyclic monomers and bicyclo [2.2.1] hept-2-ene, commonly referred to as norbornene. In one embodiment of the present invention, one or more acid labile substituted polycyclic monomers represented by Formula I below are optionally combined with Formulas II, III, IV, and V below. The acid labile functional groups are introduced into the polymer chain by polymerizing a reaction medium containing one or more polycyclic monomers in the presence of a Group VIII metal catalyst system.

In another embodiment of the present invention, one or more acid labile substituted polycyclic monomers of Formula I are copolymerized with one or more polycyclic monomers of Formula II.

The acid labile polycyclic monomers useful in the practice of the present invention are selected from monomers represented by the following formula:

[0028]

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Here, each of R ¹ to R ⁴ is-(A) _n C (O) OR ^* ,-(A) _n C (O) O
R,-(A) _n -OR,-(A) _n -OC (O) R,-(A) _n -C (O) R,-(A) _n-
OC (O) OR,-(A) _n -OCH ₂ C (O) OR ^* ,-(A) _n -C (O) OA ′
^{_{-OCH 2 C (O) OR *}} , - (A) n -OC (O) -A'-C (O) OR *, - (A) n -C (R) 2 CH (R) (C (O ) OR ^** ), ^and- (A) _n -C (R) ₂ CH
And represents a substituent selected from the group consisting of (C (O) OR ^** ) _{2, wherein} at least one of R ¹ to R ⁴ represents an acid labile group — (A) _n C (O) OR ^* Selected. A and A ′ are each a divalent hydrocarbon radical, a divalent cyclic hydrocarbon radical, a divalent oxygen-containing radical, and a divalent bridging property selected from divalent cyclic ethers and cyclic diethers. That is, it represents a spacer radical, and n is an integer of 0 or 1. It is clear that when n is 0, A and A 'represent one covalent bond. "Divalent" means that the free valence at each end of the radical is attached to two distinct groups. A divalent hydrocarbon radical can be represented by the formula — (C _d H _2d ) —, where d represents the number of carbon atoms in the alkylene chain and is an integer between 1 and 10. Divalent hydrocarbon radicals are methylene,
It is preferably selected from linear and branched (C ₁ -C ₁₀ ) alkylenes such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. When considering branched chain alkylene radical, it should be hydrogen atoms in the alkylene straight is replaced by a linear or branched chain (C ₁ ~C ₅₎ alkyl group is understood.

The divalent cyclic hydrocarbon radical includes substituted and unsubstituted (C ₃ -C ₈ ) alicyclic moieties represented by the following formula:

[0031]

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Where a is an integer between 2 and 7 and R ^q , when present, represents straight and branched chain (C ₁ -C ₁₀ ) alkyl groups. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represented by the structure:

[0033]

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Here, R ^q has the same definition as above. As described throughout this specification as well as throughout this specification, the bond lines projecting from the cyclic structures and / or formulas represent the divalent nature of the moiety, with the carbocyclic atom being in each formula It should be understood that they indicate points of attachment to adjacent defined molecular moieties. As is conventional in the art, an oblique bond line projecting from the center of the cyclic structure indicates that the bond is optionally connected to any of the carbocyclic atoms in the ring.
It should further be understood that the carbocyclic atom to which the bond is connected satisfies the valency of carbon by having one less corresponding hydrogen atom.

Preferred divalent cyclic ethers and diethers are represented by the following structures:

[0036]

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The radical-containing divalent oxygen includes (C ₂ -C ₁₀ ) alkylene ethers and polyethers. (C ₂ -C ₁₀ ) alkylene ether means that the total number of carbon atoms in the divalent ether moiety is at least 2 and must not be greater than 10. The divalent alkylene ether is represented by the formula -alkylene-O-alkylene-, wherein each of the alkylene groups bonded to the oxygen atom may be the same or different, and methylene, ethylene, propylene, butylene, pentylene, It is selected from hexylene, heptylene, octylene, and nonylene. The simplest of this series of divalent alkylene ethers is -C
It is a radical represented by H ₂ —O—CH ₂ —. Preferred polyether moieties include
The divalent radical of the following formula is included.

[0038]

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Here, x is an integer between 0 and 5, and y is an integer between 2 and 50. However, it is assumed that a terminal oxygen atom of the spacer portion of the polyether cannot be directly bonded to a terminal oxygen atom of an adjacent group to form a peroxide bond. In other words, peroxide when the spacer of the polyether is bonded to any terminal oxygen containing substituent groups described under R ⁴ from the R ¹ bonds (i.e., -O-O-) are not taken into account .

In the above formula, R represents hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, and m represents an integer between 0 and 5. R ^* _{is, -C (CH 3) 3,} -Si (CH 3) 3, -CH (R p) OCH 2 CH 3, -CH (R p) OC (CH 3) 3, or the following cyclic groups Represents a moiety (eg, a blocking group or a protecting group) that can be cleaved by a photoacidic initiator selected from:

[0041]

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Here, R ^p represents a hydrogen atom or a linear or branched (C ₁ -C ₅ ) alkyl group. The alkyl substituent includes methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, t-pentyl and neopentyl. In the above structure, a single bond line protruding from the cyclic group indicates the position on the carbon atom ring where the protecting group is bonded to each substituent. Examples of acid labile groups include 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, and 3-oxo. Examples thereof include a cyclohexanonyl group, a mevalonic lactonyl group, a 1-ethoxyethyl group, a 1-tert-butoxyethyl group, a dicyclopropylmethyl (Dcpm) group, and a dimethylcyclopropylmethyl (Dmcp) group. Alkyl substituents in the above protecting groups are selected from linear and branched chain (C ₁ ~C ₅₎ alkyl group. R ^** independently represents R and R ^* as defined above. The Dcpm group and the Dmcp group are represented by the following structures, respectively.

[0043]

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A — (CH ₂ ) _n C (R) ₂ CH (R) (C (O) OR ^** ) group or — (CH ₂ ) _n C (R) ₂ CH (C (O) OR ^** ) _The polycyclic monomer of the above formula having a substituent selected from _two groups can be represented by the following formula.

[0045]

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Here, m is the same as defined above, and n ′ is an integer between 0 and 10.

In the above formula, m is preferably 0 or 1, and more preferably 0. When m is 0, a preferred structure is represented by the following structural formula.

[0048]

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Here, R ¹ to R ⁴ are the same as defined above.

It should be apparent to those skilled in the art that any photoacid cleavable moiety is suitable in the practice of the present invention, unless the polymerization reaction is substantially inhibited by the photoacid cleavable moiety.

Preferred acid labile groups are protected organic ester groups, in which the protecting or blocking groups undergo a cleavage reaction in the presence of an acid. Tertiary butyl esters of carboxylic acids are particularly preferred.

The monomers described under formula I, when polymerized into the polymer backbone, have a repeating acidic pendant group that is subsequently cleaved to impart polarity or solubility to the polymer. give.

The optional second monomer is represented by the structure set forth below in Formula II.

[0054]

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Here, R ⁵ to R ⁸ are independently a — (A) _n C (O) OR ″ group, — (A) _n —OR
A '' group, a-(A) _n -OC (O) R '' group, a-(A) _n -OC (O) OR '' group,
-(A) _n -C (O) R "group,-(A) _n -OC (O) C (O) OR" group,-
(A) _n -OA'-C (O) OR "group,-(A) _n- OC (O) -A'-C (
O) OR '' _{group, - (A) n -C (} O) O-A'-C (O) OR '' _{group, - (A) n -C (} O) -A'-OR '' group, -(A) _n -C (O) OA'-OC (O)
OR ″ group, — (A) _n —C (O) OA ′ ′-OA′-C (O) OR ″ group, — (A) _n —C (O) OA′-OC (O) C (O) OR '' group,-(A) _n -C
A (R ″) ₂ CH (R ″) (C (O) OR ″) group, and — (A) _n —C (R
'') ₂ CH (C (O) OR '') represents a neutral or polar substituent selected from ₂ groups. The moieties A and A 'are each independently selected from divalent hydrocarbon radicals, divalent cyclic hydrocarbon radicals, divalent oxygen-containing radicals, and divalent cyclic ethers and cyclic diethers. Represents a bridging property or a spacer radical, and n is an integer of 0 or 1. It is clear that when n is 0, A and A 'represent one covalent bond. "Divalent" means that the free valency at each end of the radical is attached to two distinct groups. Divalent hydrocarbon radical of the formula - (C _d H _2d) - can be represented by, where d represents the number of carbon atoms in the alkylene chain and is an integer between 1 and 10. Divalent hydrocarbon radicals can be linear or branched (such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene).
It is preferably selected from C ₁ -C ₁₀ ) alkylene. When considering branched alkylene radicals, it should be understood that the hydrogen atoms in the alkylene chain are replaced by a straight or branched (C ₁ -C ₅ ) alkyl group.

The divalent cyclic hydrocarbon radical includes substituted and unsubstituted (C ₃ -C ₈ ) alicyclic moieties represented by the following formula:

[0057]

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Where a is an integer between 2 and 7, and R ^q , when present, represents straight and branched chain (C ₁ -C ₁₀ ) alkyl groups. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represented by the structure:

[0059]

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Here, R ^q has the same definition as above. As described throughout this specification as well as throughout this specification, the bond lines projecting from the cyclic structures and / or formulas represent the divalent nature of the moiety, with the carbocyclic atom being in each formula It should be understood that this indicates a point of attachment to the adjacent molecular moiety being defined. As is conventional in the art, the diagonal bond lines protruding from the center of the cyclic structure are:
Indicates that the bond is optionally connected to any of the carbocyclic atoms in the ring.
It should further be understood that the carbocyclic atom to which the bond is connected satisfies the valency of carbon by having one less corresponding hydrogen atom.

[0061] Preferred divalent cyclic ethers and diethers are represented by the structure:

[0062]

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The divalent oxygen containing radicals includes (C ₂ -C ₁₀ ) alkylene ethers and polyethers. (C ₂ -C ₁₀ ) alkylene ether means that the total number of carbon atoms in the divalent ether moiety is at least 2 and must not be greater than 10. The divalent alkylene ether is represented by the formula -alkylene-O-alkylene-, wherein each of the alkylene groups bonded to the oxygen atom may be the same or different, and methylene, ethylene, propylene, butylene, pentylene, It is selected from hexylene, heptylene, octylene, and nonylene. The simplest of this series of divalent alkylene ethers is -C
It is a radical represented by H ₂ —O—CH ₂ —. Preferred polyether moieties include
The divalent radical of the following formula is included.

[0064]

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Here, x is an integer between 0 and 5, and y is an integer between 2 and 50. However, the terminal oxygen atom of the spacer portion of the polyether cannot directly bond to the terminal oxygen atom of an adjacent group to form a peroxide bond. In other words, peroxide when the spacer of the polyether is bonded to any terminal oxygen containing substituent groups described under R ⁸ from the R ⁵ bond (e.g., -O-O-) are not taken into account .

Each of R ⁵ to R ⁸ can be hydrogen, linear or branched (R) as long as at least one of the remaining substituents is selected from one of the above neutral or polar groups. It can also represent C ₁ -C ₁₀ ) alkyl. In the above formula, p is an integer between 0 and 5 (preferably 0 or 1, more preferably 0). R ″ is independently hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, linear and branched (C ₁ -C ₁₀ ) alkoxyalkylene, polyether, monocyclic and polycyclic (C ₄ -C ₂₀₎ cycloaliphatic moieties, represent a cyclic ethers, cyclic ketones, and cyclic ethers (lactone). (C ₁ -C ₁₀ ) alkoxyalkylene means that the terminal alkyl group is attached to the alkylene moiety through an ether oxygen atom. The radical is a hydrocarbon-based ether moiety, which can usually be represented as -alkylene-O-alkyl, wherein the alkylene and alkyl groups are each independently 1
From 10 to 10 carbon atoms, and each may be linear or branched. The polyether radical is represented by the following formula.

[0067]

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Where x is an integer between 0 and 5, y is an integer between 2 and 50, and ^Ra is hydrogen or linear and branched (C ₁ -C ₁₀ ) alkyl. Represent. Preferred polyether radicals include poly (ethylene oxide) and poly (propylene oxide)
Is included. Examples of alicyclic monocyclic moieties include cyclopropyl, cyclobutyl,
Cyclopentyl, cyclohexyl and the like can be mentioned. Examples of cycloaliphatic polycyclic moieties, norbornyl, adamantyl, tetrahydronaphthyl dicyclopentadienyl (tricyclo [5.2.1.0 ^2.6] decanyl), and the like. Examples of cyclic ethers include a tetrahydrofuranyl moiety and a terahydropyranyl moiety. Examples of cyclic ketones include a 3-oxocyclohexanoyl moiety. Examples of cyclic esters or lactones include a mevalonic lactonyl moiety.

As long as the substituents described for R ″ in Formula II overlap the acid unstable or protecting groups described under R ^* in Formula I, R ″ in Formula II It should be understood that an ester moiety containing For example, when R ″ is norbornyl, adamantyl, tetrahydrodicyclopentadienyl (tricyclo [
5.2.1.0 ^2.6 ] decanyl), tetrahydrofuranyl, terahydropyranyl, 3
-Oxocyclohexanonyl or a mevalonic lactonyl moiety, R
'' Cannot be directly bonded to an oxygen atom in the ester moiety (-C (O) O).

Preferred neutral or polar substituents include alkyl esters of carboxylic acids as defined above, oxalate-containing moieties (eg,-(A) _n -OC (O) -A'-C (O) OR ''), and an oxalate-containing moiety (eg,-(
A) _n -OC (O) C (O) OR ''). Esters, spaced oxalates, and oxalate-containing functional groups provide very high hydrophilicity, promote good wetting of the developer, and improve the mechanical properties of the film without the problems associated with excess carboxylic acid functional groups. Improve.

The optional third monomer component is represented by the structure of Formula III below.

[0072]

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Where R⁹To R¹²Are each independently-(CH_Two)_nC (O) OH,-(CH_Two) _n SO_ThreeH,-(CH_Two)_nC (O) O^-X⁺,-(CH_Two)_nSO_Three ^-X⁺A carboxylic acid substituent, a sulfonic acid substituent or a salt thereof selected from the formula:
Represents a tetraalkylammonium cation, wherein the alkyl substituent is linear or
And branched (C₁~ C_TenA) each independently from an alkyl, a bond to a selected nitrogen atom; and q is an integer between 0 and 5 (preferably 0 or 1, more preferably 0).
, N is an integer between 0 and 10 (preferably 0). R⁹~ R¹²Each have their R⁹~ R¹²Hydrogen, straight-chain and branched-chain (C) as long as at least one of the remaining substituents is selected from the above acids or salts of acids.₁~ C_Ten) Can represent alkyl.

The monomers containing the carboxylic acid function contribute to the hydrophilicity of the polymer and, as a result, greatly assist the developability of the polymer in aqueous base systems.

Any monomer of formula IV is represented by the structure:

[0076]

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Here, R ¹³ to R ¹⁶ each represent a linear or branched (C ₁ -C ₁₀ ) alkyl, and r is an integer between 0 and 5 (preferably 0 or 1, more preferably 0).
Any of R ¹³ to R ¹⁶ is, as long as at least one but remaining in the substituents of their R ¹³ to R ¹⁶ is selected from an alkyl group as defined above, can represent hydrogen. Among the above alkyl substituents, decyl is particularly preferred.

The alkyl-substituted monomer is polymerized into the polymer backbone by the method of controlling the Tg of a polymer disclosed in US Pat. No. 5,468,819 to Goodall et al.

An economical means for preparing the functionalized or hydrocarbyl-substituted polycyclic monomers of the present invention relies on the Diels-Alder reaction, in which cyclopentadiene (CPD) or substituted CPD is enhanced. Reacting with an appropriately substituted dienophile at a temperature usually results in the formation of a substituted polycyclic adduct represented by the following reaction scheme.

[0080]

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Other polycyclic adducts can be prepared by adding dicyclopentadiene (in the presence of a suitable dienophile)
DCPD) can be prepared by pyrolysis. The reaction converts DCPD to C
There is an initial pyrolysis to PD followed by a Diels-Alder addition reaction of CPD and dienophile to produce the adduct shown below.

[0082]

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Here, R ′ and R ″ ″ each independently represent a substituent defined for R ¹ to R ¹⁶ in the above formulas I, II, III and IV.

For example, 2-norbornene-5-carboxylic acid (bicyclo [2.2.1] hept-
5-ene-2-carboxylic acid) can be prepared by a Diels-Alder reaction between cyclopentadiene and acrylic acid according to the following reaction formula.

[0085]

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The corresponding tert-butyl ester of carboxylic acid can be prepared at reduced temperature (eg, from −30 ° C. to −2 ° C.)
(0 ° C.) by reacting the carboxylic acid function with isobutylene.

[0087]

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Another more preferred approach to the t-butyl ester of norbornene carboxylic acid involves the Diels-Alder reaction of cyclopentadiene with t-butyl acrylate.

Another synthetic means for the acid and ester substituted monomers of the present invention is to carry out subsequent hydrolysis to carboxylic acid functionality or partial hydrolysis to ester functionality via orthoester substituted polycyclic monomers. It is. The carboxylic acid functionality is esterified to the desired ester. The orthoester substituted monomer of the present invention is represented by Formula V below.

[0090]

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Here, R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a linear or branched (C ₁ -C ₅ ) alkyl group, or any of R ¹⁷ , R ¹⁸ and R ¹⁹ represents Together with the oxygen atom to which they are attached, can form a substituted or unsubstituted 5 to 10 membered cyclic or bicyclic ring having 3 to 8 carbon atoms (excluding substituents); Is an integer between 0 and 5 (preferably 0) and t is an integer between 1 and 5 (preferably 1). Representative structures where s is 0, t is 1, and R ¹⁷ , R ¹⁸ and R ¹⁹ together with the oxygen atom to which they are attached form a cyclic or bicyclic ring are shown below.

[0092]

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Here, R ^{17 ′} , R ^{18 ′} and R ^{19 ′} each independently represent hydrogen and straight-chain and branched (C ₁ -C ₅ ) alkyl. The orthoester of the present invention is a so-called piner (P
Inner) (A. Pinner, Chem. Ber., 16 , 1643 (1883)) and according to S. M. McElvain and J. T. Venerable (J. T. Venable), J. Am. Chem. Soc., 72 , 1661 (1950);
Synthesized via the procedure described by SM McElvain and JT Venerable, J. Am. Chem. Soc., 75 , 3987 (1953). be able to. A representative synthesis is shown in the following reaction scheme.

[0094]

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In another synthetic route, the alkyl acrylate is first treated with a trialkyl oxonium tetrafluoroborate salt, and then with an alkali metal (sodium alcoholate) to produce a trialkoxymethyl orthoester (etch. Mail wine [H. Meerwein], P. Borner [P. Borner], O. Fuchs [O. Fuchs], H. J. Sasse [H. J. Sasse]
H. Schrodt and J. Spill [J. Spi.
lle], Chem. Ber., 89 , 2060 (1956)).

As mentioned above, orthoesters can undergo a hydrolysis reaction in the presence of dilute acid catalysts such as hydrobromic acid, hydroiodic acid, and acetic acid to produce carboxylic acids.
The carboxylic acid can then be esterified in the presence of an aliphatic alcohol and an acidic catalyst to form the respective ester. In the case of a polycyclic monomer di- or poly-substituted with an orthoester group, the orthoester moiety is partially hydrolyzed to form a conventional ester with an acid on the same monomer as shown below. It should be understood that.

[0097]

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Another more preferred route to bifunctional polycyclic monomers is through the hydrolysis and partial hydrolysis of nadic anhydride (endo-5-norbornene-2,3-dicarboxylic anhydride). is there. As shown below, nadic anhydride can be completely hydrolyzed to a dicarboxylic acid or can be partially hydrolyzed to an acid and ester or diester function.

[0099]

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Here, R ¹⁷ independently represents a linear or branched (C ₁ -C ₅ ) alkyl. Preferably, R ¹⁷ is methyl, ethyl, or t-butyl. The nadic anhydride starting material in the preferred synthesis is the exo isomer. The exo isomer is
It is prepared simply by heating the endo isomer at 190 ° C. followed by recrystallization from a suitable solvent (toluene). To obtain the diacid under Reaction Scheme 1, nadic anhydride may be simply hydrolyzed in boiling water to obtain a nearly quantitative yield of the diacid product. Mixed carboxylic acid functionality and an alkyl ester represented by formula 3 in the presence of Nadiku anhydride suitable fatty alcohols (R ¹⁷ OH), obtained by heating for 3-4 hours at reflux. Alternatively, the product can be prepared by first reacting the nadic anhydride anhydride with an aliphatic alcohol and a trialkylamine and then treating with dilute hydrochloric acid. Identical alkyl (R ¹⁷⁾ diester product substituted with a group, the presence of diisopropylethylamine diacid trialkyl oxo tetrafluoroborate, for example _{^{R 17 3 O [BF 4]}} , at ambient temperature in methylene chloride It can be prepared from the diacid by reacting below. In order to obtain esters having different R ¹⁷ alkyl groups, the mixed product of acid and ester obtained in Formula 3 may be used as a starting material. In this embodiment, the acid groups are esterified as described in Scheme 2. However, a trialkyloxonium tetrafluoroborate having an alkyl group different from the alkyl group already present in the ester function is used.

The aforementioned monomers having a precursor functional group can be converted to the desired functional groups before being polymerized, or each having a precursor functional substituent after polymerizing the monomer first. It should be noted that the polymer can be post-reacted to obtain the desired functional groups.

It has been found that the 7-oxo-norbornene derivative can be obtained by substituting the methylene bridge unit with oxygen in the monomers described below under formulas I to V where m, p, q, r and s are 0. It is considered within the scope of the invention.

It is likewise considered that for applications at a wavelength of 248 nm, R ⁵ to R ¹⁶ and R ¹¹ in the above formulas II, III and IV can be aromatic, such as phenyl.

Polymer One or more acid labile substituted polycyclic monomers described under Formula I may be copolymerized alone or may be one or more polycyclic monomers described under Formula II And optionally in combination with one or more of the polycyclic monomers described below under Formulas III, IV and V. The polycyclic monomer of Formulas I through V can be copolymerized with carbon monoxide to provide an alternating copolymer of the polycyclic monomer and the carbon monoxide. Copolymers of norbornene with pendant carboxylic acid groups and carbon monoxide are described in U.S. Pat. No. 4,960,857, which is incorporated herein by reference. The monomers of formulas I to V and carbon monoxide are described in Chem. Rev. 1996.
, 96 , 663-681, in the presence of a palladium-containing catalyst system. It should be readily understood by those skilled in the art that alternating copolymers of polycyclic monomers and carbon monoxide exist in either isomeric form, keto or spiroketal. Accordingly, the present invention contemplates copolymers containing random repeat units derived (polymerized) from monomers of Formulas I and II, optionally in combination with any of the monomers of Formulas II and V. .
Further, the present invention contemplates alternating copolymers containing repeating units derived (polymerized) from carbon monoxide and monomers of Formulas I and V.

The pendant carboxylic acid functional groups are important from the viewpoint of imparting hydrophilicity, adhesiveness and clean dissolution (development) to the polymer main chain. However, in certain applications of photoresists, polymers having excess carboxylic acid functionality are undesirable. Such polymers do not work well in industry standard developers (0.26N, tetramethylammonium hydroxide, TMAH). Swelling of the polymer in the unexposed areas, uncontrolled thickness reduction during application, and swelling of the polymer upon exposure dissolution are essential problems with these highly acidic polymers.
Thus, in situations where excess carboxylic acid functionality is undesirable while hydrophilicity and good wettability are essential, Formula I requires a combination with a monomer of Formula II
The copolymer which is polymerized from the above monomer is preferable. Particularly preferred are each-
_{(A) n -C (O)} OR '', - (A) n -OC (O) OR '', - (A) n -O C (O) -A'-C (O) OR '', And-(A) _n -OC (O) C (O) OR ", an alkyl ester substituent, an alkyl carbonate, a spaced alkyl oxalate substituent, and an alkyl oxalate substituent. Is a monomer of formula II, wherein A, A ', n, and R "are the same as defined above.

The polymers of the present invention are a major component of the composition. The polymer usually consists of monomers (repeat units) containing from about 5 to 100 mol% of the acid labile group component. Preferably, the polymer contains about 20 to 90 mole% of a monomer containing an acid labile group. More preferably, the polymer contains about 30 to 70 mole% of monomer units containing acid labile functional groups. The remainder of the polymer composition is represented by Formula II above
Consists of repeating units polymerized from any of the monomers described below under IV. The choice and amount of the particular monomer used in the polymer will vary depending on the properties desired. For example, by varying the amount of carboxylic acid functional groups in the polymer backbone, the solubility of the polymer in various developing solutions can be adjusted as desired. The monomer having an ester function can be varied to enhance the mechanical properties of the polymer and the radiation sensitivity of the system. Finally, the glass transition temperature characteristics of the polymer can be adjusted by incorporating a cyclic repeating unit containing a long chain alkyl group such as decyl.

There are several routes for polymerizing cyclic olefin monomers such as norbornene and higher cyclic (polycyclic) monomers containing the norbornene moiety. These include (1) ring opening metathesis (metathesis) polymerization (ROMP), (2) hydrogenation after ROMP, and (3) addition polymerization. Each of the above pathways produces a polymer having a particular structure as shown in Formula 1 below.

[0108]

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[0109] ROMP polymers have a different structure than addition-polymerized polymers. ROMP polymers have repeating units with one less cyclic unit than the starting monomer.
The repeating units are bonded to each other in the unsaturated main chain as shown above. Because of this unsaturation, the polymer is preferably subsequently hydrogenated to provide oxidative stability to the backbone. On the other hand, the addition polymer has no C ＝ C unsaturated bond in the polymer main chain, even though it is formed from the same monomer.

The monomers of the present invention may be obtained by addition polymerization or ring-opening metathesis polymerization (ROMP).
After that, polymerization can be carried out preferably by hydrogenation. The cyclic polymer of the present invention is represented by the following structure.

[0111]

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Here, R ′ to R ″ ″ represent R ¹ to R ¹⁹ defined by the above formulas I to V, m is an integer between 0 and 5, and a is the polymer main chain. Indicates the number of repeating units in.

[0113] The ROMP polymer of the present invention is polymerized in a suitable solvent in the presence of a ring-opening metathesis polymerization catalyst. Polymerization processes via RMOP and subsequent hydrogenation of the resulting ring-opened polymer are described in US Pat. Nos. 5,053,471 and 5,202,88, which are incorporated herein. .

[0114] In one ROMP embodiment, the polycyclic monomers of the present invention are WO95-
It can be polymerized in the presence of a single component ruthenium or osmium metal carbene composite catalyst such as those described in US9655. The employed ratio of monomer to catalyst should be in the range of about 100: 1 to about 2,000: 1, with a ratio of about 500: 1 being preferred. The reaction can be carried out in a halohydrocarbon solvent such as dichloroethane, dichloromethane, chlorobenzene or the like, or in a hydrocarbon solvent such as toluene. The amount of solvent used in the reaction medium is about 5 to solvent.
To about 40% by weight of solids, preferably about 6 to about 25% by weight, should be sufficient. The reaction is carried out at about 0 ° C to about 60 ° C, preferably about 2 ° C.
It can be carried out at a temperature ranging from 0 ° C to 50 ° C.

The preferred metal carbene catalyst is bis (tricyclohexylphosphine) benzylidene ruthenium. Surprisingly and advantageously, this catalyst has an initial ROMP
By using it as a reaction catalyst and an efficient hydrogenation catalyst, an essentially saturated ROMP polymer can be obtained. It is not necessary to use another hydrogenation catalyst. All that is required to achieve hydrogenation of the polymer backbone after the initial ROMP reaction is to increase the hydrogen pressure over the reaction solvent to a temperature greater than about 100 ° C and less than about 220 ° C, preferably from about 150 to about 200 ° C. To maintain the temperature between ° C.

The addition polymers of the present invention can be prepared by standard free radical solution polymerization methods known to those skilled in the art. The monomers of formulas I to V can be homopolymerized or copolymerized in the presence of maleic anhydride. The technology of free radical polymerization is
"Encyclopedia of Polymer"
Science), John Wiley and Sands (John Wiley)
& Sons), 13 , 708 (1988).

Alternatively, the monomers of the present invention are preferably polymerized in the presence of a single or multi-component catalyst system comprising a Group VIII metal ion source, preferably palladium or nickel. Surprisingly, the addition polymer thus produced not only has excellent transparency to deep ultraviolet light (193 nm), but also has excellent reactive ion etching resistance.

A preferred polymer of the present invention comprises at least one polycyclic monomer selected from Formulas I and II, a solvent, a catalyst system having a Group VIII metal ion source, and an optional chain transfer agent. Polymerized from the reaction mixture. The catalyst system may be a preformed single component Group VIII metal catalyst or a multiple component Group VIII metal catalyst.

Single Component Systems In certain embodiments, the single component catalyst systems of the present invention comprise a Group VIII metal cation complex as represented by the following formula and a weakly coordinating counter anion.

[0120]

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Here, L represents a ligand having 1, 2 or 3 π bonds, M represents a transition metal of Group VIII, and X represents a ligand having one σ bond and up to three π bonds. Represents a ligand, y
Is 0, 1 or 2, z is 0 or 1, and both y and z cannot be 0 at the same time, a is 2 when y is 0 and a when y is 1. Is 1 and CA is a weakly coordinating counter anion.

The phrase “weakly coordinating counter anion” refers to a ligand that is only weakly coordinated to a cation, but remains unstable enough to be displaced by a neutral Lewis base. It means a certain anion. For more information,
This phrase refers to an anion that, when functioning as a stabilizing anion in the catalyst system of the present invention, does not provide anionic substituents or fragments thereof to the cation.
The counter anion is non-oxidative, non-reducing, non-nucleophilic, and relatively inert.

L is a neutral ligand weakly coordinated with the Group VIII metal cation complex. Toes
The ligands are relatively inert and retain monomers in the growing polymer backbone.
The insertion easily displaces the metal cation complex. Ligand
Suitable π bonds with (C_Two~ C₁₂) Monoolefinic moieties (eg 2,3-
Dimethyl-2-butene), diolefinic (C_Four~ C₁₂) Moieties (eg, norbornadiene) and (C₆~ C₁₂) Aromatic moieties are included. Examples of the ligand L include chelating bidentate cyclo (C) such as cyclooctadiene (COD) and dibenzoCOD. ₆ ~ C₁₂) Preference is given to olefins or aromatic compounds such as benzene, toluene or mesitylene.

The Group VIII metal M is selected from metals of Group VIII of the Periodic Table of the Elements. Preferably, M is selected from the group consisting of nickel, palladium, cobalt, platinum, iron, and ruthenium. Among them, nickel and palladium are most preferred.

The ligand X can be (i) a moiety that supplies a single metal carbon σ bond (not a π bond) to a metal in the cation complex, or (ii) a single metal carbon σ bond and one to three One π
It is selected from moieties that provide the bond to the metal in the cation complex. In embodiment (i), the moiety is a single metal carbon σ bond and not a π bond but a
Bonds to Group VIII metals. Representative ligands defined in this embodiment include propyl, butyl, pentyl, neopentyl, hexyl, heptyl,
Linear and branched moieties such as octyl, nonyl and decyl (C ₁ -C ₁₀ ) alkyl moieties selected from methyl, ethyl, and (C ₇ -C ₁₅ ) such as benzyl
Aralkyl. In embodiment (ii), as defined generally above, the cation comprises a hydrocarbyl group directly attached to the metal by one single metal carbon σ bond and one or more and no more than three π bonds. Have. Hydrocarbyl refers to a group capable of stabilizing a Group VIII metal cation complex by providing one single metal carbon σ bond and one to three olefinic π bonds, which may be conjugated or non-conjugated. . Hydrocarbyl group representative of a non-cyclic, monocyclic, or polycyclic may be either, and linear and branched chain (C ₁ ~C ₂₀₎ an alkoxy, (C ₆ -C ₁₅ ) can be substituted with aryloxy or halo groups, (e.g. chlorine or fluorine) (C ₃ -C ₂₀₎ alkenyl.

X is a single allylic ligand or a canonical form thereof that provides a σ bond and a π bond, or provides at least one olefinic π bond to the metal and is derived from either olefinic carbon atom Preferably, the compound provides a σ bond to a metal from a distal carbon atom separated by at least two carbon-carbon single bonds (
Embodiment iii).

In the absence of ligand L or X (eg, when y or z is 0), the metal cation complex is weakly coordinated by the solvent in which the reaction is performed. Representative examples of such solvents include, but are not limited to, carbon tetrachloride, chloroform, dichloromethane, halogenated hydrocarbons such as 1,2-dichloroethane, and benzene, toluene, mesitylene, chlorobenzene, and nitrobenzene. And aromatic solvents such as Suitable solvents are described in more detail below.

Selected embodiments of the single component catalyst system Group VIII metal cation complexes of the present invention are set forth below.

Structural Formula VII illustrates embodiment (i), wherein ligand X is a methyl group bonded to the metal via a single metal-carbon σ bond, and ligand L is COD which is weakly coordinated to palladium metal via two olefinic π bonds. In the following structural formula, M is preferably palladium or nickel.

[0130]

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Structural formulas VIII, IX, and X illustrate various examples of embodiment (ii), wherein X represents a single metal-carbon σ bond and one or more and three or less π bonds. Through the metal (
Palladium is an allyl group attached only to those shown for illustrative purposes).

In Structural Formula VIII, L is absent, but an aromatic group supplying three π bonds is weakly coordinated to the palladium metal, and X represents a single metal-carbon σ bond and an olefinic π bond. Allyl group supplied to palladium.

In structural formula IX, L is COD and X is an allyl group that supplies a metal-carbon σ bond and an olefinic π bond to palladium.

Structural Formula X represents an embodiment wherein the ligand X is an unsaturated hydrocarbon group that supplies a metal-carbon σ bond, a conjugated π bond, and two more π bonds to palladium, and L is absent. ing.

[0135]

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The substituents R ²⁰ , R ²¹ and R ²² will be described in detail below.

Structural formulas XI and XII represent examples of embodiment (iii), wherein L is COD, and X supplies at least one olefinic π bond to a Group VIII metal or either A ligand that provides a sigma bond to a metal from a distal carbon atom that is separated from the olefinic carbon atom by at least two carbon-carbon single bonds.

[0138]

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The Group VIII cation complexes described above are relatively inert, poorly nucleophilic, and weakly coordinating or non-coordinating to provide cation complexes with essential solubility in the reaction solvent. sex counter anion, CA ^-, it related to. An important point for proper anion design is that the anion is unstable and stable and inert to the reaction with the cationic Group VIII metal complex in the final catalyst species, and that That is, the single-component catalyst becomes soluble in the solvent of the present invention. Anions that are stable to reaction with water or Bronsted acids and have no acidic protons outside the anion (eg, anion complexes that do not react with strong acids or strong bases) are stable anions to the catalyst system. To have the necessary stability. Important anionic properties for maximum instability include overall size, shape (eg, major radius of curvature), and nucleophilicity.

In general, a suitable anion is one that is capable of dissolving the catalyst in the solvent of choice and has the following attributes: (1) the anion can be a Lewis acid, a Bronsted acid, a reducing Lewis acid, a protonated (2) the negative charge of the anion is delocalized to the structure of the anion and internal to the core of the anion. Should be localized,
(3) Any stable anion with the attribute that the anion should be relatively poorly nucleophilic and (4) the anion should not be a strong reducing or oxidizing agent. .

Anions meeting the above criteria are Ga, Al or B tetrafluoride,
Hexafluoride, perfluoroacetate, propio of P, Sb or As
And butyrate, hydrated perchlorate, toluene sulfonate, trif
Fluoromethylsulfonate, and the phenyl ring is fluorine or trifluoromethyl
Selected from the group consisting of substituted tetraphenyl borates
Can be. Selected examples of counter anions include BF_Four-, PF₆-, AlF _Three O_ThreeSCF_Three ^-, SbF₆ ^-, SbF_FiveSO_ThreeF^-, AsF₆ ^-, Trifluoroacetate (CF_ThreeCO_Two ^-), Pentafluoropropionate (C_TwoF_FiveCO_Two ^-), Heptafluorobutyrate (CF_ThreeCF_TwoCF_TwoCO_Two ^-), Perchlorate (ClO)_Four ^-・ H_TwoO), p-toluene-sulfonate (p-CH_ThreeC₆H_FourSO_Three ^-) And below
Tetraphenyl borate represented by the formula is mentioned.

[0142]

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Here, R ″ independently represents hydrogen, fluorine and trifluoromethyl, and n is 1 to 5.

A preferred single component catalyst of the above embodiment is represented by the following formula:

[0145]

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The catalyst comprises a π-allyl Group VIII metal complex having a weakly coordinating counter anion. The allyl group of the metal cation complex is provided by a compound containing allylic functionality attached to the M by a single carbon-metal σ bond and an olefinic π bond. The Group VIII metal M is preferably selected from nickel and palladium, of which palladium is most preferred. Surprisingly, M is palladium and the cation complex has no ligand other than the allylic function (eg,
It has been found that these single component catalysts (L _y = 0) exert excellent effects on the polymerization of functional polycyclic monomers such as the silyl-containing monomers of the present invention. As mentioned above, it is understood that the catalyst is solvated by a reaction diluent which is considered to be a very weak ligand for the Group VIII metal in the cationic complex.

The substituents R ²⁰ , R ²¹ , and R ²² of the allyl group in Structural Formulas VIII, IX, and XIII are each independently a branched chain such as hydrogen, methyl, ethyl, n-propyl, isopropyl, and t-butyl. Jo or unbranched chain (C ₁ ~C ₅₎ alkyl, such as phenyl and naphthyl (C ₆ ~C ₁₄₎ aryl, such as benzyl (C ₇ ~C _{10) ^{aralkyl, -COOR 16, - (CH 2}} ) _n oR ^16, Cl and (C ₅ ~C ₆₎ an alicyclic group, wherein R ¹⁶ is such as methyl, ethyl, n- propyl, isopropyl, the n- butyl and i- butyl (C ₁ -C ₅ A) alkyl, wherein n is 1-5.

Optionally, any two of R ²⁰ , R ²¹ , and R ²² may be joined to form a monocyclic or polycyclic ring structure. The cyclic ring structure may be carbocyclic or heterocyclic. Preferably, any two of R ²⁰ , R ²¹ and R ²² together with the carbon atom to which they are attached form a ring having 5 to 20 atoms. Representatives of heteroatoms include nitrogen, sulfur and carbonyl. Examples of the cyclic group having an allyl-type functional group include the following structures.

[0149]

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Here, R^{twenty three}Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl
Linear or branched (C) such as, isobutyl, and pentyl₁~ C_Five) Alkyl
And R^{twenty four}Is methylcarbonyl and R^{twenty five}Is linear or branched (C ₁ ~ C₂₀) Alkyl. Counter anion CA^-Is defined as above
Is the same.

Other examples of π-allyl metal complexes are RG Guy and BL Shaw, published by Academic Press, New York in 1962. ) Advances in Inorganic Chemistry and Radiation Science (Advanceds)
in Inorganic Chemistry and Radiochem
J. Birmingham, E. de Boer, M.L.H. Green (ML), published by Academic Press, New York in 1964. H. Green), RB King, R. Koest
er), PLI Nagy, GN Schrauzer, et al., Advances in Organometallic Chemistry (Advanc).
es in Organometallic Chemistry, Volume 2; WT Dent, R. Long, and A. J. Wilkinson, J. Chem.
Soc., (1964) 1585; and H. C. Wolger, Rec. Trav. Chim. Pay Bas, 88 (1969) 225, all of which are herein incorporated by reference. Combined into a book.

The single component catalyst of the above embodiment is prepared by combining the ligated Group VIII metal halide component with a salt that provides a counter anion for the subsequently formed metal cation complex. be able to. Combine the ligated Group VIII metal halide component, the counter anion providing salt, and any π-bond containing components, such as COD, in a solvent capable of solvating the formed single component catalyst . The solvent used is preferably the same as the solvent selected for the reaction medium. The catalyst can be preformed in a solvent or formed in situ in the reaction medium.

Suitable counter anion supply salts can supply the above counter anions
Any salt can be used. For example, sodium, lithium, potassium, silver, tali
And ammonium salts, wherein the anion is a salt as defined above.
Interanion (CA^-). Examples of counter anion supply salts include TlPF₆, AgPF₆, AgSbF₆, LiBF_Four, NH_FourPF₆, KAsF₆ , AgC_TwoF_FiveCO_Two, AgBF_Four, AgCF_ThreeCO_Two, AgCLO_Four・ H_TwoO, AgA
sF₆, AgCF_ThreeCF_TwoCF_TwoCO_Two, AgC_TwoF_FiveCO_Two, (C_FourH₉)_FourNB (C₆F _Five )_FourAnd salts represented by the following formulae.

[0154]

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[0155] [allyl -Pd-COD] ⁺ PF ₆ ^- specific catalyst represented by the bis (bromide ants Le palladium) such ligated palladium halide component, or bis (
After forming the allyl Pd bromide), it is preformed by cutting with the components in the presence of COD halide extractant in the form of a counter anion supply salts such as TlPF _6. The reaction flow is as described below.

[0156]

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When split, only one COD ligand remains, which is bound to palladium by two π bonds. The allyl functionality is linked to palladium by one metal-carbon σ bond and one π bond.

To prepare the preferred π-allyl group VIII metal / counter anion single component catalyst system shown in Structural Formula XIII above, for example, where M is palladium, allyl palladium chloride and the desired counter anion supply A salt, preferably a silver salt of a counter anion, may be combined in a suitable solvent. The chloride ligand is
It is separated from the allylpalladium complex as a precipitate of silver chloride (AgCl) that can be filtered off from the solution. The allyl palladium cation complex / counter anion single component catalyst remains in solution. The palladium metal has no ligand separated from the allylic functional group.

Another single component catalyst useful in the present invention is represented by the following formula:

Pd [R ²⁷ CN] ₄ [CA ⁻ ] ₂ where R ²⁷ represents linear and branched (C ₁ -C ₁₀ ) alkyl, respectively, and CA ⁻ is a counter anion as defined above. is there.

Another single component catalyst system useful in using the polymer in the present invention is represented by the formula:

EnNi (C ₆ F ₅ ) ₂ where n is 1 or 2, and E represents a neutral two-electron donor ligand. When n is 1,
E is preferably a π-arene ligand such as toluene, benzene, and mesitylene. When n is 2, E is diethyl ether, tetrahydrofuran (TH
F) and dioxane. The ratio of monomer to catalyst in the reaction medium ranges from about 2,000: 1 to about 100: 1. The reaction is carried out in a hydrocarbon solvent such as cyclohexane or toluene at about 0 ° C. to about 70 ° C.
Preferably it can be carried out at a temperature in the range from about 10 ° C to about 50 ° C, more preferably from about 20 ° C to about 40 ° C. Preferred examples of the catalyst of the above formula include (toluene) bis (perfluorophenyl) nickel, (mesitylene) bis (perfluorophenyl) nickel, (benzene) bis (perfluorophenyl) nickel, and bis (tetrahydrofuran) bis (perfluorophenyl) nickel. Phenyl) nickel and bis (dioxane) bis (perfluorophenyl) nickel.

Multicomponent Systems [0163] Embodiments of the multicomponent catalyst systems of the present invention comprise a Group VIII metal ion source in combination with one or both of an organometallic cocatalyst and a third component. The cocatalyst is selected from organoaluminum compounds, dialkylaluminum hydrides, dialkylzinc compounds, dialkylmagnesium compounds, and alkyllithium compounds.

The Group VIII metal ion source is preferably selected from compounds containing nickel, palladium, cobalt, iron and ruthenium, most preferably compounds containing nickel or palladium. As long as the Group VIII metal compound provides a catalytically active source of Group VIII metal ions, there are no restrictions on the compound. Preferably, the Group VIII metal compound is soluble or can be made soluble in the reaction medium.

The Group VIII metal compound comprises an ionic and / or neutral ligand bound to the Group VIII metal. The ionic and neutral ligands can be selected from various monodentate, bidentate, or multidentate portions, and combinations thereof.

Representative ionic ligands that can combine with the metal to form a Group VIII compound include halides such as chloride, bromide, iodide or fluoride ions; cyanides, cyanates, thiocyanates , Pseudohalides such as hydrides; branched and unbranched (C ₁ -C ₄₀ ) alkyl anions, carbanions such as phenyl anions; cyclopentadienylide anions; π-allyl groups; acetylacetonate ( 4-Pentandionate), an enolate of a β-dicarbonyl compound such as 2,2,6,6-tetramethyl-3,5-heptanedionate and 1,1,1,5,5
, 5-Hexafluoro-2,4-pentanedionate, 1,1,1-trifluoro-
Halogenated acetylacetonates such as 2,4, pentanedionate; acidic oxides of carbon such as carboxylate and halogenated carboxylate (eg, acetate, 2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.); Nitrogen oxides (e.g., nitrate, nitrite, etc.), bismuth oxides (e.g., bismutate, etc.), aluminum oxides (e.g., aluminate, etc.), silicon oxides (e.g., silicates, etc.), and phosphoric oxides (e.g., phosphates, phosphites, etc.) Phosphines, etc.), anions of sulfur oxides (e.g., triflate, p-toluenesulfonate, sulfates such as sulfite); ylides;
Amides; imides; oxides; phosphides; sulfide; (C ₆ ~C ₂₄₎ aryloxides, (C ₁ ~C ₂₀₎ alkoxides, hydroxide, hydroxy (C ₁ ~C ₂₀₎ alkyl; catechol; oxalate; chelate There are anionic ligands selected from functional alkoxides and chelating aryl oxides. Further palladium ^{_{compound, PF - 6, AlF 3 O}} 3 SCF - 3, SbF - may contain ₆ compound such as represented by complex anions and the following formula.

[0167] ^{Al (R ''') -} 4, B (X) - 4 wherein R''' and X each Cl, F, halogen atoms selected from I, and Br, or a substituted or unsubstituted hydrocarbyl, Represents a group. Representative examples of hydrocarbyl include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, (C ₁ -C ₂₅ ) alkyl such as docosyl, tricosyl, tetracosyl, pentacosyl, and their isomeric forms; vinyl, allyl, crotyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl (C ₂ -C ₂₅ ) alkenyl such as, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, pentacosenyl, and isomeric forms thereof; Phenyl, tolyl, xylyl, such as naphthyl (C ₆ ~C ₂₅₎ aryl; benzyl, phenethyl, phenpropyl, phenbutyl, Fen hexyl, such as such as Nafutookuchiru (C ₇ ~C ₂₅₎ aralkyl; cyclopropyl, cyclobutyl, (C ₃ -C ₈ ) cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbornyl, 2-norbornenyl and the like. In addition to the above definitions, X represents the following radical.

[0168]

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The term “substituted hydrocarbyl” means a hydrocarbyl group as defined above in which one or more hydrogen atoms are Cl, F, Br (eg, as in a perfluorophenyl radical). And hydroxyl; amino; alkyl; nitro; mercapto and the like.

The Group VIII metal compound may further contain a cation such as organic ammonium, organic arsonium, or organic phosphonium, and a pyridinium compound represented by the following formula.

[0171]

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Here, A represents nitrogen, arsenic, and phosphorus;²⁸The radicals represented by
In addition, hydrogen, branched or unbranched (C₁~ C₂₀) Alkyl, branched or unbranched (C_Two~ C₂₀) Alkenyl and (C) such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooptyl_Five~ C₁₆) Can be selected from cycloalkyl and the like. R²⁹And R³⁰Are each independently hydrogen, branched or undivided
Chain (C₁~ C₅₀) Alkyl, linear and branched (C_Two~ C₅₀) Alkenyl,
And (C_Five~ C₁₆) Selected from cycloalkyl and the like. n is 1 to 5, preferably 1, 2 or 3, and most preferably 1. R ³⁰ The radical represented by is preferably bonded to the 3, 4 and 5 positions of the pyridine ring.

It should be noted that increasing the total number of carbon atoms in the radical group represented by R ²⁸ increases the solubility of the transition metal compound in organic media, such as organic solvents and polycyclic monomers. Is preferably R ²⁸ radical group is selected from (C ₁ ~C ₁₈₎ alkyl group, wherein all R ²⁸ radicals the total number of carbon atoms to groups 15 to 72, preferably from 25 48, more preferably 21 To 42.
Preferably, the R ²¹ radical is selected from linear and branched (C ₁ -C ₅₀ ) alkyl, more preferably (C ₁₀ -C ₄₀ ) alkyl. R ³⁰ is preferably selected from linear and branched (C ₁ -C ₄₀ ) alkyl, more preferably (C ₂ -C ₃₀ ) alkyl.

Specific examples of the organic ammonium cation include tridodecylammonium, methyltricaprylammonium, tris (tridecyl) ammonium and trioctylammonium. Specific examples of organic arsonium and organic phosphonium cations include tridodecylarsonium and phosphonium, methyltricaprylarsonium and phosphonium, tris (tridecyl) arsonium and phosphonium, and trioctylarsonium and phosphonium. Specific examples of the pyridinium cation include eicosyl-4-
(1-butylpentyl) pyridinium, docosyl-4- (13-pentacosyl)
Pyridinium, and eicosyl-4- (1-butylpentyl) pyridinium.

Suitable neutral ligands that can bind to the palladium transition metal include olefins; acetylene; carbon monoxide; nitrogen compounds such as nitric oxide, ammonia, alkyl isocyanides, alkyl isocyanates, alkyl isothiocyanates; pyridine and pyridine derivatives (Eg, 1,10-phenanthroline, 2,2′-dipyridyl)
1,1,4-dialkyl-1,3-diazabutadiene, 1,4-diaryl-1,3-
Diazabutadiene and amines of the formula:

[0176]

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Wherein each R ³¹ is independently hydrocarbyl or substituted hydrocarbyl as defined above, and n is 2 to 10; urea; nitriles such as acetonitrile, benzonitrile and halogenated derivatives thereof; diethylene glycol Organic ethers such as dimethyl ether, dioxane, tetrahydrofuran, furandaryl ether, diethyl ether, and cyclic ethers such as diethylene glycol cyclic oligomer; organic sulfides such as thioether (diethyl sulfide); arsine; stibine; Phosphines), trialkylphosphines (eg, trimethyl, triethyl, tripropyl, tripentacosyl, and halogenated derivatives thereof), bis (di Phenylphosphino) ethane, bis (diphenylphosphino) propane,
Bis (dimethylphosphino) propane, bis (diphenylphosphino) butane,
(S)-(-) 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, (R)-(+)-2,2'-bis (diphenylphosphino) -1,1 ' Phosphines such as binaphthyl and bis (2-diphenylphosphinoethyl) phenylphosphine; phosphine oxides, phosphorus halides; phosphites of the formula: P (OR ³¹ ) ₃ where R ³¹ is each independently represents such hydrocarbyl or substituted hydrocarbyl as defined in the above; phosphorus oxyhalides; phosphonates; phosphonites, phosphinites, ketones; (C ₁ ~C ₂₀₎ alkyl sulfoxide such as scan sulfoxide; (C ₆ ~C ₂₀₎ aryl sulfoxide , there is a (C ₇ ~C ₄₀₎ alkaryl sulfoxide. It should be understood that the neutral ligands described above can be used as an optional third component as described below.

Examples of suitable Group VIII transition metal compounds as a Group VIII metal ion source include:
Palladium ethyl hexanoate, trans-PdCl ₂ (PPh ₃ ) ₂ , palladium (II) bis (trifluoroacetate), palladium (II) bis (acetylacetonate), palladium (II) 2-ethylhexanoate, Pd (acetate) ₂ (PPh ₃ ) ₂ , palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitritol tris (triphenylphosphine) palladium (II) tetrafluoroborate Rat,
Tetrakis (acetonitrile) palladium (II) tetrafluoroborate, dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (benzonitrile) palladium (II)
), Palladium acetylacetonate, palladium bis (acetonitrile) dichloride, palladium bis (dimethylsulfoxide) dichloride, nickel acetylacetonate, nickel carboxylate, nickel dimethylglyoxime, nickel ethyl hexanoate, NiCl ₂ (PPh ₃ ) ₂ , NiCl ₂ (PP
_{h 2 CH 2) 2, (} P ( _{cyclohexyl) 3) HNi (Ph 2 P} (C 6 H 4) CO 2),
_{(PPh 3) (C 6 H} 5) Ni (Ph 2 PCH = C (O) Ph), bis (2,2,6, 6-tetramethyl-3,5-heptanedionate) nickel (II), nickel (I
I) Hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichloro Hexyl nickel acetate,
Nickel lactate, nickel oxide, nickel tetrafluoroborate, bis (allyl) nickel, bis (cyclopentadienyl) nickel, cobalt neodecanoate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) ) Acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexylcobalt acetate,
Cobalt (II) stearate, cobalt (II) tetrafluoroborate, iron naphthenate, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (III) acetate Iron (III) acetylacetonate, ferrocene, ruthenium tris (triphenylphosphine) dichloride, ruthenium tris (triphenylphosphine) hydride chloride, ruthenium trichloride, ruthenium tetrakis (acetonitrile) dichloride, ruthenium tetrakis (dimethylsulfoxide) dichloride, rhodium Chloride and rhodium tris (triphenylphosphine) trichloride.

The organoaluminum component of the multi-component catalyst system of the present invention is represented by the following formula.

AlR ³² _3-X Q _X wherein R ³² is each independently a linear or branched (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₂₄ ) aryl, (C ₇ -C ₂₀₎ ) Aralkyl, (C ₃ -C ₁₀ ) cycloalkyl, Q represents chlorine, fluorine, bromine, iodine, linear and branched (C ₁ -C ₂₀ ) alkoxy, (C ₆ -C ₂₄ ) aryloxy And x is 0 to 2.5, preferably 0 to 2.

Representative examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, and tri-2aluminum. -Methylpentyl aluminum,
Trialkyl aluminums such as tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-2-methylhexyl aluminum, tri-3-methylhexyl aluminum, trioctyl aluminum, tris-2-norbornyl aluminum A dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, etc .; methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum iodide, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, isobutyl Such as aluminum dichloride Can monoalkyl aluminum dihalide; and, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, propyl aluminum sesquichloride, isobutyl aluminum sesquichloride alkyl Au mini um sesqui halides such as such.

The dialkylaluminum hydride is selected from linear and branched (C ₁ -C ₁₀ ) dialkylaluminum hydrides, with diisobutylaluminum hydride being the preferred dialkylaluminum hydride compound.

The dialkyl zinc compound is selected from linear and branched (C ₁ -C ₁₀ ) dialkyl zinc compounds, with diethyl zinc being preferred. Dialkylmagnesium compounds are selected from linear and branched chain (C ₁ ~C ₁₀₎ dialkyl magnesium, among others dibutylmagnesium being the most preferred. The alkyl lithium is selected from linear and branched (C ₁ -C ₁₀ ) alkyl lithium compounds. Butyl lithium is the preferred alkyl lithium.

In practicing the present invention, the catalyst system obtained from the Group VIII metal ion source is used in combination with one or both of a component selected from the group of cocatalyst compounds and a third component compound. .

As an example of the third component, BF_Three・ Etherato, TiCl_Four, SbF_Five, Tris (perfluorophenyl) boron, BCl_Three, B (OCH_TwoCH_Three)_ThreeLewis like
Acid; hexafluoroantimonic acid (HSbF₆), HPF₆Hydrate, trifluoro
Acetic acid (CF_ThreeCO_TwoH), and FSO_ThreeH ・ SbF_Five, H_TwoC (SO_TwoCF_Three)_TwoCF _Three SO_ThreeH, and strong Bronsted acids such as paratoluenesulfonic acid;
Loroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pen
Tachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisop
Halogenated compounds such as lopanol, and chloranil,

[0186]

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For example, they are selected from electron donors such as phosphines and phosphites, and (C ₄ -C ₁₂ ) aliphatic and (C ₆ -C ₁₂ ) alicyclic diolefins such as butadiene, cyclooctadiene and norbornadiene. Olefinic electron donors are mentioned.

The acidity of strong Bronsted acids is accurately measured by determining their Hammett acidity function H ₀ . A definition of Hammett's acidity function is given on page 107 of Advanced Inorganic Chemistry by Willie-Interscience, FA Cotton and G. Wilkinson, published in 1988. .

As described above, the neutral ligand can be used as an optional third component having an electron donating property. In one embodiment of the present invention, the multi-component catalyst system comprises a catalyst component such as a Group VIII metal compound, a co-catalyst compound, and a third component (if used) in a hydrocarbon or halohydrocarbon solvent. After being combined together, they can be prepared by mixing the premixed catalyst system in a reaction medium consisting of at least one silyl-functional polycyclic monomer. Alternatively, (assuming the optional third component was used), any two catalyst system components are premixed in a hydrocarbon or halohydrocarbon solvent and then charged into the reaction medium. The remaining catalyst components can be added to the reaction medium before or after adding the premix components. In another embodiment, the multi-component catalyst system can be prepared in situ by combining all catalyst components in a reaction medium. The order of addition is not important.

In one embodiment of the multi-component catalyst system of the present invention, an exemplary catalyst system comprises a salt of a Group VIII transition metal such as nickel ethylhexanoate, an organoaluminum compound such as triethylaluminum, and BF ₃ · etherate and mixtures such as third component Hekisafuru Oro antimonate (HSbF _6), the preferred molar ratio of aluminum / B F ₃ · etherate / Ni / acid molar ratio of 10/9/1 / 0.5-2 It is contained at a certain ratio. The reaction formula is shown below.

1. Nickel ethylhexanoate + HSbF ₆ + 9BF ₃ .etherate + 10 triethylaluminum → activated catalyst In another embodiment of the multi-component catalyst system of the present invention, the catalyst system comprises nickel as shown in the following reaction formula: Nickel salts such as ethylhexanoate, organoaluminum compounds such as triethylaluminum, and tris (perfluorophenyl)
Consists of a third component, a Lewis acid, such as boron. 2. Nickel ethyl hexanoate + tris (perfluorophenyl) boron + triethyl aluminum → active catalyst In another embodiment of the multi-component catalyst system of the present invention, the third component is a halogen selected from various halogenated activators. Compound. A typical catalyst system consists of a salt of a Group VIII transition metal, an organoaluminum, and a third component, a halogenated compound, as shown below. 3. Nickel ethyl hexanoate + triethyl aluminum + chloranil → active catalyst In yet another embodiment of the multi-component catalyst system of the present invention, there is no cocatalyst.
The catalyst system consists of a salt of a Group VIII transition metal (eg, 3-allyl nickel bromide dimer) and a Lewis acid (eg, tris (perfluorophenyl) boron), as shown below. 4. η ³ -allyl nickel chloride + tris (perfluorophenyl) boron → active catalyst

The first and second metal catalyst complexes of the present invention in both single and multi-component catalyst systems are
Find out that the choice of Group VIII metal affects the microstructure and properties of the resulting polymer
Was. For example, palladium catalysts are usually chained only at the 2- and 3-positions, usually giving norbornene units that exhibit some degree of stereoregularity. The second catalyst system and the above formula E _n Ni (C₆F_Five)_TwoThe polymer catalyzed by the single component catalyst system of
-Has a perfluorophenyl group on at least one of the two terminal groups of the main chain
. That is, the perfluorophenyl moiety can be at one of the two end groups of the polymer or
Can exist in both. In either case, the perfluorophenyl group is a polymer
Covalently attached to and pendant from a terminal polycyclic repeating unit of the main chain.

The reaction using the single-component catalyst and the multi-component catalyst of the present invention is carried out in an organic solvent which does not adversely affect the catalyst system and is a solvent for the monomer. Examples of organic solvents include aliphatic (non-polar) hydrocarbons such as pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; benzene, chlorobenzene, o-dichlorobenzene, toluene, and Aromatic hydrocarbons such as xylene; methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 2-chloropropane, 1-chlorobutane, Halogenated (polar) hydrocarbons such as 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane.

The choice of reaction solvent is based on a number of factors, including the choice of catalyst and whether it is desirable to carry out the polymerization as a slurry or solution method. Preferred solvents for most of the catalysts described in the present invention include methylene chloride and 1
Chlorinated hydrocarbons such as 1,2-dichloroethane, and aromatic hydrocarbons such as chlorobenzene and nitrobenzene. The conversion of a functional NB-type monomer is low with simple hydrocarbons. Less preferred than hydrogen. Surprisingly, a specific catalyst system, most notably a multicomponent catalyst based on a Group VIII metal compound and an alkylaluminum halide, especially a monoalkylaluminum dihalide (eg ethylaluminum dichloride), and said second catalyst Have been found to leave good results (and high monomer conversion) when used in simple hydrocarbons such as heptane, cyclohexane, and toluene.

The molar ratio of total monomer to Group VIII metal for single and multi-component catalysts is from 20: 1 to 100,000: 1, preferably from 50: 1 to 20,000: 1,
More preferably, it may range from 100: 1 to 10,000: 1.

In a multi-component catalyst system, the molar ratio of promoter metal (eg, aluminum, zinc, magnesium, and lithium) to Group VIII metal is less than 100: 1, preferably less than 30: 1, and most preferably less than 20: 1. 1 or less.

The third component is used in a molar ratio ranging from 0.25: 1 to 20: 1 with respect to the Group VIII metal. When an acid is used as the third component, the molar ratio of the acid to the Group VIII metal ranges from 4: 1 or less, preferably 2: 1 or less.

The temperature at which the polymerization reaction of the present invention is carried out is usually in the range from -100 ° C to 120 ° C, preferably from -60 ° C to 90 ° C, and most preferably from -10 ° C to 80 ° C.

The optimum temperature for the present invention depends on a number of variables, mainly the choice of catalyst and the choice of reaction diluent. Thus, for any given polymerization, the optimal temperature will be determined empirically taking into account these variables.

In the course of constructing these catalysts and the polymer system, it was confirmed that the palladium-carbon bond connecting the palladium catalyst to the polymer main chain in the growing process was particularly stable. This is a major benefit when polymerizing polycyclic monomers containing acid labile groups, ester and carboxylic acid functionalities, since palladium catalysts are very resistant to these functional groups Because. However, this stability also makes it difficult to remove palladium catalyst residues from the resulting polymer. During the development of these compositions, the palladium-carbon bond is conveniently cleaved with carbon monoxide, preferably in the presence of a protic solvent such as an alcohol, moisture, or carboxylic acid (filtration or centrifugation). Can result in a precipitate of palladium metal that can be removed).

The polymer obtained by the process of the present invention has a molecular weight of from about 1,000 to about 1,000,000, preferably from about 2,000 to about 700,000, more preferably from about 5,000 to about 500,000. , And most preferably, with a molecular weight ( _Mn ) in the range of about 10,000 to about 50,000.

The molecular weight can be controlled by varying the catalyst to monomer ratio, for example, the initiator to monomer ratio. Low molecular weight polymers and oligomers can also be formed in the range from about 500 to about 500,000 by conducting the polymerization in the presence of a chain transfer agent. The macromonomer or oligomer having 4 to 50 repeating units is a CTA selected from compounds having a terminal olefinic double bond between adjacent carbon atoms (
A chain transfer agent), wherein at least one of the two adjacent carbon atoms has two hydrogen atoms bonded thereto. The chain transfer agent is only a styrene type (non-styrene type), a vinyl ether type (non-vinyl ether type) and a conjugated diene type. The non-styrene type and non-vinyl ether type mean that compounds having the following structures are excluded from the chain transfer agent of the present invention.

[0203]

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Where A is an aromatic substituent and R is hydrocarbyl.

The preferred chain transfer agent of the present invention is represented by the following formula.

[0206]

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Wherein R, and R ,, are each hydrogen, branched or unbranched (C ₁ -C ₄₀ ) alkyl, branched or unbranched (C ₂ -C ₄₀ ) alkenyl, and Represents halogen.

Among the above chain transfer agents, carbon numbers such as ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1,7-octadiene, and 1,6-octadiene, and isobutylene Is preferably 2 to 10.

The optimal conditions for any given result should be determined experimentally by a skilled technician, taking into account all of the above factors, but there are general guidelines that can be conveniently used where appropriate. There are many. Generally, α-olefins (eg, ethylene, propylene, 1-hexene, 1-decene, 4-methyl-1-pentene) are the most effective chain transfer agents and 1,1-disubstituted olefins (eg, , Isobutylene) is less effective than α-olefins. That is, all other conditions being the same, the concentration of isobutylene required to achieve a given molecular weight will be higher than if ethylene were used. Styrenic olefins, conjugated dienes, and vinyl ethers are not effective as chain transfer agents because of the catalyst polymerization properties described herein.

The CTA can be used in an amount ranging from about 0.10 mol% to 50 mol% or more, based on the total molar amount of NB type monomer. The CTA is preferably used in a range of 0.10 to 10 mol%, more preferably in a range of 0.10 to 5.0 mol%. As mentioned above, depending on the type and sensitivity of the catalyst, the efficiency of the CTA and the desired end groups, the concentration of the CTA can be greater than 50 mol% (based on the total amount of NB-functional monomer present), for example 60 mol%. To 80 mol%. In order to realize the low molecular weight embodiment of the present invention in an oligomer or macromonomer application or the like, C
Higher concentrations of TA (eg, greater than 100 mole%) may need to be used. It is important to note that even with such high concentrations, CTA (with the exception of isobutylene) does not copolymerize into the polymer backbone, but rather is inserted as a terminal group for each polymer chain. Yes and surprising. In addition to chain transfer, the method of the present invention provides a means by which terminal α-olefinic end groups can be placed at the ends of the polymer chain.

[0211] The polymers of the present invention prepared in the presence of the CTA can be from about 1,000 to about 500,
000, preferably from about 2,000 to about 300,000, and most preferably has a molecular weight in the range of about 5,0 00 to about 200,000 (M _n).

[0212] The photoresist composition of the present invention comprises the above-described polycyclic composition, a solvent, and a photosensitive acid generator (photoinitiator). Optionally, a dissolution inhibitor can be added in amounts up to about 20% by weight of the composition. A suitable dissolution inhibitor is t-butyl cholate (JV Crivello et al.),
Chemically amplified electron beam photoresist, Chem. Mater., 1996,
8, 376-381).

When irradiated with radiation, the radiation-sensitive acid generator generates a strong acid. Suitable photoinitiators include triflates (eg, triphenylsulfonium triflate), pyrogallol (eg, trimesylate of pyrogallol); triarylsulfonium and diaryliodium hexafluoroantimonates, hexafluoroarsenates, Onium salts such as trifluoromethanesulfonate; esters of hydroxyimide, α, α'-bis-sulfonyl-diazomethane, sulfonic acid esters of nitro-substituted benzyl alcohol and naphthoquinone-4-diazide. Other suitable photoacid initiators are described by Lake Maris et al.
chmanis et al.), Chem. Mater. 3 , 395, (1991). Compositions containing triarylsulfonium or diaryliodonium salts are preferred in that they are sensitive to deep ultraviolet light (193 to 300 nm) and give very high resolution images. Most preferably,
Unsubstituted and symmetric or unsymmetrically substituted diaryliodonium or triarylsulfonium salts. The photoacid initiator component comprises 1 to 100% w / w of the polymer
Occupy. A preferred concentration range is 5 to 50% w / w.

The photoresist compositions of the present invention optionally contain a sensitizer that can sensitize the photoacid initiator to longer wavelengths from mid-ultraviolet to visible light. Depending on the intended use, such sensitizers include polycyclic aromatics such as pyrene and perylene. Sensitization of the photoacid initiator component is well known and is described in U.S. Patent Nos. 4,250,053, 4,371,605, and 4,491,628, which are incorporated herein. I have. The present invention is not limited to a particular type of sensitizer or photoacid initiator.

The present invention further relates to a method of forming a positive tone resist image on a substrate, comprising: (a) coating the substrate with a film comprising the positive tone resist composition of the present invention; (B) exposing the film to radiation in the form of an image, and (c) developing the image.

In the first step, the substrate is covered with a film made of a positive gradation resist composition dissolved in an appropriate solvent. Suitable substrates are comprised of silicon, ceramic, polymer, and the like. Suitable solvents include propylene glycol methyl ether acetate (P
GMEA), cyclohexanone, butyrolactate, ethyl lactate and the like. The film can be coated on a substrate using conventionally known techniques such as spin coating, spray coating, or doctor blade. Before exposing the film to radiation, the film is exposed to the
It is preferred to heat to an elevated temperature from 0 ° C to 150 ° C. In the second step of the present invention, the film is exposed to radiation in the form of an image, the radiation being suitably an electron beam, ultraviolet or X-ray, preferably from about 193 nm to 5 nm.
Electromagnetic radiation, such as ultraviolet radiation, where a wavelength of 14 nm, preferably about 193 nm to 248 nm, is suitable. Suitable radiation sources include mercury, mercury / xenon, and xenon lamps, x-rays or electron beams. The radiation is absorbed by the radiation-sensitive acid generator to produce a free acid in the exposed areas. The free acid catalyzes the cleavage of the acid labile pendant group of the copolymer, which causes the copolymer to change from a dissolution inhibitor to a dissolution enhancer, thereby providing an aqueous base of the exposed resist composition. Solubility in Surprisingly, the exposed resist composition readily dissolves in aqueous base. This solubility is surprising and unexpected given the complex nature of the cycloaliphatic backbone and the high molecular weight of the norbornene monomer units having carboxylic acid functionality. After exposing the film to the radiation, it is preferable to reheat the film at elevated temperatures of about 90 ° C. to 150 ° C. for a short period of about 1 minute.

In the third step, a positive tone image is developed using an appropriate solvent. Suitable solvents include aqueous bases, preferably those that do not contain metal ions, such as tetramethylammonium hydroxide and choline. The composition of the present invention provides a positive image having high contrast and straight walls. Uniquely, the solubility of the composition of the invention is
It can be changed simply by changing the composition of the copolymer.

The present invention further relates to an integrated circuit assembly, such as an integrated circuit chip, a multi-chip module, or a circuit board manufactured by the method of the present invention. The integrated circuit assembly comprises: (a) coating the substrate with a film comprising the positive tone resist composition of the present invention; (b) exposing the film to radiation in the form of an image;
Developing the image to expose the substrate and (d) forming circuits on the substrate by forming circuits in the developed film on the substrate by techniques known in the art.

After exposing the substrate, the circuit pattern is formed by coating the substrate with a conductive material such as a conductive metal by a conventionally known technique such as vapor deposition, sputtering, plating, chemical vapor deposition, or laser excitation vapor deposition. Can be formed in the exposed region. Excessive conductive material can be removed by shaving the surface of the film. The dielectric material can be deposited by similar means during the manufacture of the circuit. Inorganic ions, such as boron, phosphorus, or arsenic, can be implanted into the substrate during the manufacture of p- or n-type doped circuit transistors. Other ways of forming circuits are known to those skilled in the art.

The following examples illustrate in detail the preparation and use of certain compositions of the present invention. Detailed preparation methods are within the scope of more generally described preparation methods described above and serve to illustrate them. The examples are provided for illustrative purposes only and are not intended to limit the scope of the invention. As described above, photoresist is used to create and replicate patterns from a photomask to a substrate. The effect of this transfer is determined by the wavelength of the imaging radiation, the sensitivity of the photoresist, and the resistance of the photoresist to the etching conditions that pattern the substrate at the exposed portions. Photoresist is most often used in a consumable fashion, in which photoresist is etched in unexposed areas (for positive tone photoresist) and the substrate is etched in exposed areas. Because the photoresist is organic while the substrate is usually inorganic, the photoresist has an inherently higher etch rate in a reactive ion etching (RIE) process, thereby reducing the thickness of the photoresist on the substrate. It is necessary that it be greater than the thickness of the material. The lower the etch rate of the photoresist material, the smaller the thickness of the photoresist layer must be. As a result, a higher resolution is obtained. Thus, the lower the RIE rate of the photoresist, the more attractive from a processing point of view. The etching rate is mainly determined by the polymer main chain, and this will be described below in the case of the chlorine plasma etching method, which is an RIE technique commonly used in semiconductor manufacturing. As used throughout the specification, as well as in the examples, monomer to catalyst ratios are on a mole to mole basis.

No. Polymer Normalized RIE Rate (μm / min) 1 Novolak Resist 1.0 2 Polyhydroxystyrene Resist 0.98 3 248 nm (Deep UV) 1.14 (Acrylate Terpolymer / Novolak Mixture, US Pat. No. 5, No. 372,912) 4 193 nm (polyacrylate terpolymer, 1.96 Allen et al. [Allen et al.], Bulletin SPIE, 2438 (1) , 474 (1995)) 5 Homopolynorbornene 0.83

While polymers 1 and 2 are predominantly aromatic, polymer 3 is copolymerized with a small amount of acrylate which increases its etch rate. Polymer 4 is 1
Completely based on acrylates that achieve transparency at 93 nm (
There are no conventional novolaks or p-hydroxystyrene based 193 nm viable resist candidates as aromatic rings render the material opaque in this region). The etch rate approximately doubles for this polymer. Polymer 5 not only provided transparency at 193 nm, but also had a lower etch rate than that of standard photoresist materials (1 and 2). Thus, the backbone of Polymer 5 (addition cycloolefin) prepared using the nickel multi-component catalyst of the present invention functions at 193 nm, which has RIE properties comparable to commercial materials exposed at longer wavelengths. It is an improvement over all previous attempts to supply resist in the literature. In fact, cycloaddition olefin polymers can also offer some advantages in terms of etch resistance at longer wavelengths. It has been reported in the literature (H. Gokan, S. Esho, and Y. Ohnishi, H. Gokan, H. Gokan, that the etch rate of polymeric materials decreases with increasing C / H ratio.
J. Electrochem. Soc, 130 (1), 143 (1983)). Based on this assumption, the etch rate of polymer 5 should be between aromatic and acrylate based. It is surprising that cycloaliphatic olefins exhibit better etch resistance than aromatics.

Example 1 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, 5-
Norbornene-carboxylic acid t-butyl ester (carbo-t-butoxynorbornene) (2.0 g, 10.3 mmol, exo, endo ratio = 44: 56) was charged. To this stirred monomer was added η ³ -allyl palladium chloride dimer (38 mg, 103 μmol) in chlorobenzene (5 ml) to chlorobenzene (
5 ml) in silver hexafluoroantimonate (99 mg, 290 μmol).
The catalyst solution, which was added over 0 minutes and prepared by filtration through a micropore filter (to remove precipitated silver chloride), was added at ambient temperature. Thereafter, the resulting mixture was reacted and gelled for 36 hours to obtain a transparent yellow gel. Upon addition of the resulting gel to excess methanol, a white powdery polymer precipitated. The polymer was washed with excess methanol and dried. The yield of the polymer was 1.5 g (75%). The presence of the ester-containing monomer in the polymer indicates strong bands at 1728 cm ^-1 (C = O stretch), 1251 cm ^-1 (COC stretch) and 1369 and 1392 cm ^-1 (characteristic of t-butyl group). Proven by infrared analysis showing the absence of unconverted monomer (proton NMR). The molecular weight (Mw) of the polymer was found to be 22,500. Thermogravimetric analysis (TGA) under nitrogen (heated at a heating rate of 10 ° C./min)
The polymer is thermally stable up to about 210 ° C. and the weight loss up to 260 ° C. is approximately 28% (this is due to the complete disappearance of the isobutene t-butyl group and the 5-norbornene-carboxylic acid). (Showing that a homopolymer of the acid is obtained), and it was found that the polymer degraded at about 400 ° C. (90% of total weight loss).

Example 2 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, norbornene (0.8 g, 8.6 mmol), 1,2-dichloroethane (8 ml), and 5-norbornene- Carboxylic acid t-butyl ester (carbo-t-butoxynorbornene) (0.2 g, 1 mmol, exo, endo ratio = 44: 56) was charged. Nickel ethyl hexanoate (3 μmol) was added to the stirred solution.
), Trisperfluorophenylboron (23 μmol) and triethylaluminum (27 μmol) were added at ambient temperature. The reaction occurs immediately after the addition,
By the time 0 seconds had elapsed, a white polymer began to precipitate out of solution. The reaction was carried out for 60 minutes, after which the contents of the reactor were dissolved in cyclohexane and poured into excess methanol. The polymer was washed with excess methanol and dried in a vacuum oven at 80 ° C. overnight. The yield of the copolymer was 0.9 g (90%). The molecular weight of the copolymer was determined using the GPC method and was found to have a molecular weight of 535,000 (Mw) and a polydispersity of 4.7.

Example 3 A 5-ml glass bottle equipped with a Teflon-coated stir bar was charged with 5-
Norbornene-carboxylic acid t-butyl ester (carbo-t-butoxynorbornene) (2.2 g, 11.3 mmol, exo, endo ratio = 44: 56) was charged. To this stirred monomer was added η ³ -allyl palladium chloride dimer (29 mg, 74 μmol) in dichloroethane (6 ml) to dichloroethane (6 ml).
The catalyst solution prepared by adding over 30 minutes to silver tetrafluoroborate (61 mg, 311 μmol) and filtering through a micropore filter (to remove precipitated silver chloride) was heated to ambient temperature. Was added. Thereafter, the resulting mixture was reacted and gelled for 36 hours to obtain a transparent yellow gel. Upon addition of the resulting gel to excess methanol, a white powdery polymer precipitated. The polymer was washed with excess methanol and dried. The yield of the polymer is 1
0.4 g (64%). The presence of the ester-containing monomer in the polymer was 1728 cm ^-1 (C = O stretch), 1251 cm ^-1 (COC stretch) and 136 cm ^-1.
Strong bands at 9 and 1392 cm ^-1 (characteristic of t-butyl group) and evidenced by infrared analysis indicating the absence of unconverted monomer or carboxylic acid functionality (proton NMR and IR). The molecular weight (Mw) of the polymer was found to be 54,100. By thermogravimetric analysis (TGA) under nitrogen (heated at a heating rate of 10 ° C./min), the polymer is thermally stable up to about 210 ° C., with a weight loss up to 250 ° C. of approximately 29%. (Indicating that the iso-butene t-butyl group has completely disappeared to give a homopolymer of 5-norbornene-carboxylic acid), and the polymer is heated to about 400 ° C.
, The total weight loss was 80%.

Example 4 In a 100 ml glass bottle equipped with a Teflon-coated stir bar, norbornene (1.16 g, 12.3 mmol), 1,2-dichloroethane (50 ml) and 5-norbornene-carbone T-butyl ester of acid (carbo-t-
Butoxynorbornene) (0.6 g, 3.1 mmol, exo, endo ratio = 44:
56). To this stirred solution was added palladium bis (2,2,6,6-tetramethyl-3,5-pentanedionate) (31 μmol) and trisperfluorophenylboron (279 μmol) at ambient temperature. The reaction was carried out for 16 hours, after which the contents of the reactor were poured into excess methanol. The polymer was washed with excess methanol and dried in a vacuum oven at 80 ° C. overnight. The yield of the copolymer was 0.54 g (31%).

Example 5 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, 5-
Norbornene-carboxylic acid t-butyl ester (carbo-t-butoxynorbornene) (4.4 g, 22.7 mmol, exo, endo ratio = 44: 56) was charged. To this stirred solution was added η ³ -allylparadium chloride dimer (41.5 mg, 113 μmol) in dichloroethane (7 ml) to silver tetrafluoroborate (42 mg, 215 μmol) in dichloroethane (7 ml) over 30 minutes. The catalyst solution added and prepared by filtering through a micropore filter (to remove precipitated silver chloride) was added at ambient temperature. The resulting reaction mixture was warmed to 75 C in an oil bath. After 90 minutes, it was confirmed that the mixture solidified to obtain a gray polymer material. The material was dissolved in acetone to give a dark solution. Bubbling gaseous carbon monoxide in the solution for 30 minutes resulted in a large amount of finely divided black precipitate (metal palladium and possibly other catalyst residues). The precipitate was removed by centrifugation and the process was repeated twice.
Finally, the resulting colorless solution was filtered through a 45 micron microdisk and the polymer was precipitated by adding the acetone solution to excess hexane. The obtained white polymer was separated by a centrifuge and dried overnight to obtain a white powdery copolymer (2.21 g, 50%). By thermogravimetric analysis (TGA) under nitrogen (heated at a heating rate of 10 ° C./min), the polymer is thermally stable up to about 210 ° C., with a weight loss up to 260 ° C. of approximately 28%. (Indicating that the isobutene t-butyl group has completely disappeared to give a homopolymer of 5-norbornene-carboxylic acid), and that the polymer degrades at about 400 ° C. ( (Total weight loss of 90%). The molecular weight of the polymer was Mn = 3,300 g / mol, Mw = 6,900 g / mol (
GPC in THF, based on polystyrene).

Example 6 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, 5-
The pure exo isomer of the t-butyl ester of norbornene-carboxylic acid (carbo-t-butoxynorbornene) (0.6 g) was charged. To this stirred monomer over, dichloroethane eta ³ in (10 ml) - was added over 30 minutes allyl palladium chloride dimer (30 mg) of silver hexafluoroantimonate in dichloroethane (20 ml) (50 mg) and ( A catalyst solution prepared by filtration through a micropore filter (to remove precipitated silver chloride) was added at ambient temperature. Thereafter, the mixture obtained was added to excess methanol while the reaction was carried out for 15 hours to precipitate a white powdery polymer. The polymer was washed with excess methanol and dried. The yield of the polymer was 0.5 g (85%). The molecular weight (Mw) of the polymer was found to be 46,900 and the polydispersity was 2.4.

Example 7 In a 100 ml glass bottle equipped with a Teflon-coated stir bar, norbornene (4.01 g, 42.6 mmol), 1,2-dichloroethane (50 ml) and 5-norbornene-carbone T-butyl ester of acid (carbo-t-
Butoxynorbornene) (2 g, 10.3 mmol, exo, endo mixture) was charged. This stirred solution was added to η ³ − in 1,2-dichloroethane (3 ml).
The catalyst solution prepared by reacting allyl palladium chloride dimer (10 mg, 27.3 μmol) with silver hexafluoroantimonate (19.6 mg, 57 μmol) for 30 minutes and filtering through a micropore filter was used to prepare the surrounding catalyst solution. Added at temperature. The reaction was carried out for 20 hours, after which the contents of the reactor were poured into excess methanol. The polymer was washed with excess methanol and dried. The yield of the copolymer was 4.15 g. The molecular weight of the copolymer was determined using the GPC method and was found to have a molecular weight of 618,000 (Mw) and a polydispersity of 7.1.

Example 8 In a 100 ml glass bottle equipped with a Teflon-coated stir bar, norbornene (3.75 g, 39.8 mmol), 1,2-dichloroethane (50 ml) and 5-norbornene-carbone T-butyl ester of acid (carbo-t-
Butoxynorbornene) (2 g, 10.3 mmol, exo, endo mixture) was charged. Palladium ethyl hexanoate (12 μm
ol, tris (perfluorophenylboron) (108 μmol) and triethylaluminum (120 μmol) were added at ambient temperature. The reaction was carried out for 72 hours, after which the contents of the reactor were poured into excess methanol. The polymer was washed with excess methanol, dried, then redissolved in chlorobenzene, reprecipitated with excess methanol, filtered, washed with methanol and dried in a vacuum oven at 80 ° C. overnight. The yield of the copolymer was 1.66 g. The molecular weight of the copolymer was determined by the GPC method and was found to have a molecular weight of 194,000 (Mw) and a polydispersity of 2.3. The presence of the ester-containing monomer in the copolymer indicates the absence of bands at 1730 cm ^-1 (C = O stretch) and 1154 cm ^-1 (CO-C stretch) and unconverted monomer (proton NMR). Proven by infrared analysis.

Example 9 In a 100 ml glass bottle equipped with a Teflon-coated stir bar, 1
, 2-Dichloroethane (25 ml) and t-butyl ester of 5-norbornene-carboxylic acid (carbo-t-butoxynorbornene) (10 g, 51.5 mmol, exo, endo mixture). To this stirred solution, 1,2-dichloroethane (10 ml) eta in ³ - allyl palladium chloride dimer (82 mg, 223μmol) of silver hexafluoroantimonate (200 mg, 581
μmol) and a catalyst solution prepared by filtration through a micropore filter at ambient temperature. The reaction was carried out for 48 hours,
Thereafter, the contents of the reactor were poured into excess methanol. The polymer was washed with excess methanol and dried. The yield of the homopolymer was 4.5 g.

Example 10 In a 100 ml glass bottle equipped with a Teflon-coated stir bar, 1
, 2-Dichloroethane (50 ml), 5-norbornene-carboxylic acid t-butyl ester (carbo-t-butoxynorbornene) (5 g, 25.8 mmol, exo, endo mixture), norbornene (0.82 g, 8.7 mmol) And 5
-Triethoxysilyl norbornene (0.47 g, 1.8 mmol) was charged.
To this stirred solution, 2-dichloroethane (10ml) in at eta ³ - allyl palladium chloride dimer (47.2mg, 128μmol) and silver tetrafluoroborate (138mg, 700μmol) and micro reacted with 30 minutes The catalyst solution prepared by filtration through a pore filter was added at ambient temperature. The reaction was carried out for 48 hours, after which the contents of the reactor were poured into excess methanol. The polymer was washed with excess methanol and dried. The yield of terpolymer was 5.3 g. The molecular weight of the terpolymer was determined by the GPC method, and it was found that the molecular weight was 39,900 (Mw) and the polydispersity was 3.2.

Example 11 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, 7.25 g (37.5 mmole) of t-butyl ester of norbornene, 1.9 g (
12.5 mmole) of norbornene methyl ester and 50 ml of dichloroethane immediately after distillation were added, and the resulting solution was degassed under an argon atmosphere. Teflon glass bottle 10ml with the coated stir bar, 0.0365 g of (0.1 mmol) (the ratio of the final monomer to catalyst for obtaining 500/1) eta ³ - allyl Palladium chloride dimer and 2 ml of dichloroethane were charged. In another 10 ml glass bottle was charged 0.0344 g (0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane. The catalyst solution was prepared by mixing the allylpalladium chloride dimer solution with the silver hexafluoroantimonate solution in a dry box. Immediately after, precipitation of the silver chloride salt was observed, and the salt was filtered to obtain a clear yellow solution. The active yellow catalyst solution was added to the monomer solution using a syringe, and the resulting reaction mixture was stirred at 60 ° C. for 20 hours. No apparent increase in viscosity was observed, but solids precipitated in the solution, and the solution was cooled, concentrated in a rotovap, and precipitated in hexane to give a white polymer. The yield was 2.3 g, 26%. The obtained polymer was dried under vacuum at room temperature, and its molecular weight was analyzed using GPC. GPC was obtained in THF using polystyrene standards. The molecular weight was confirmed to be Mn = 1,950 g / mole and Mw = 3,150 g / mole. ¹ H NMR shows that both the methyl and t-butyl esters of norbornene are present and that a small amount of t
-Butyl hydrolysis product, an acid, was present.

Example 12 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, 2.42 g (12.5 mmole) of t-butyl ester of norbornene, 5.7 g (
37.5 mmole) of norbornene methyl ester and 50 ml of dichloroethane immediately after distillation were introduced, and the resulting solution was degassed under an argon atmosphere. Teflon glass bottle 10ml with the coated stir bar, the ratio of monomer to catalyst is 500/1 eta ³ - allyl palladium chloride dimer 0.0365g
(0.1 mmol) and 2 ml of dichloroethane. Another 10 ml glass bottle was charged with 0.0344 g (0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane. The catalyst solution was prepared by mixing the allylpalladium chloride dimer solution with the silver hexafluoroantimonate solution in a dry box. Immediately after, precipitation of the silver chloride salt was observed, and the salt was filtered to obtain a clear yellow solution. The active yellow catalyst solution was added to the monomer solution using a syringe, and the resulting reaction mixture was stirred at 60 ° C. for 20 hours. No apparent increase in viscosity was observed, but solids precipitated in the solution, and the solution was cooled, concentrated in a rotovap, and precipitated in hexane to give a white polymer. The yield is 2
.05 g, 25%. The obtained polymer was dried at room temperature under vacuum, and its molecular weight was analyzed using GPC. GPC was obtained in THF using polystyrene standards. The molecular weight is Mn = 1,440 g / mole, Mw = 2,000 g / m
ole was confirmed. ¹ H NMR indicated that both the methyl and t-butyl esters of norbornene were present and that a small amount of t-butyl hydrolysis product, the acid, was present.

Example 13 A 25 ml glass bottle equipped with a Teflon-coated stir bar was first charged with 2 g (7.94 mmole) of the dicarboxylic acid bicyclo [2.2.1] hept-5-en-exo. , 2-t-butyl, pure exo-3-methyl ester, then 15 ml of methylene chloride immediately after distillation and 10 ml of methanol, and the resulting solution was degassed under an argon atmosphere. . In a 10 ml glass bottle equipped with a Teflon coated stir bar, a monomer to catalyst ratio of 500/1,
η ³ - 0.00588g allyl palladium chloride dimer (0.0158mm ol) and methylene chloride were 2ml charged. Another 10 ml glass bottle was charged with 0.0108 g (0.01212 mmol) of silver hexafluoroantimonate and 2 ml of methylene chloride. The catalyst solution, eta ³ - was prepared by mixing the allylpalladium chloride two mers solution and the silver hexafluoroantimonate solution inside the dry box. Immediately after, precipitation of the silver chloride salt was observed, and the salt was filtered to obtain a clear yellow solution. The active yellow catalyst solution was added to the monomer solution using a syringe at 50 ° C., and the resulting reaction mixture was stirred at room temperature for 16 hours. No apparent increase in viscosity was seen and the solution was filtered through a 0.5μ filter and concentrated using a rotovap. The resulting concentrated solution was dissolved in methanol and precipitated in a mixture of methanol and water to obtain a white solid (65%). The molecular weight was confirmed to be Mn = 10,250 g / mole and Mw = 19,700 g / mole (GPC in THF, based on polystyrene). ¹ H NMR indicated that both methyl and t-butyl esters of norbornene were present.

Example 14 In a 25 ml glass bottle equipped with a Teflon-coated stir bar, firstly 3.06 g (12.8 mmole) of bicyclo [2.2.1] hept-5-ene-exo, Charge pure exo-2,3-dicarboxylic acid diethyl ester and 2.5 g (12.8 mmole) of norbornene t-butyl ester, then add 15 ml of distilled methylene chloride immediately after distillation and 10 ml of methanol. The resulting solution was degassed under an argon atmosphere. In a 10 ml glass bottle equipped with a Teflon-coated stir bar, add 0.0188 g (0.052 mmol) of allyl palladium chloride dimer (to obtain a monomer to catalyst ratio of 500/1) with 2 ml
Methylene chloride was charged. In another 10 ml glass bottle, 0.0357 g (0.1
04 mmol) of silver hexafluoroantimonate and 2 ml of methylene chloride. The catalyst solution was prepared by mixing the allylpalladium chloride dimer solution and the silver hexafluoroantimonate solution in a dry box. Immediately after, precipitation of the silver chloride salt was observed, and the salt was filtered to obtain a clear yellow solution. The active yellow catalyst solution was added to the monomer solution using a syringe at 50 ° C., and the resulting reaction mixture was stirred at room temperature for 16 hours. No apparent increase in viscosity was seen, and the solution was filtered through a 0.5 μ filter and concentrated using a rotovap. The resulting concentrated solution was dissolved in methanol and precipitated in a mixture of methanol and water to give a white solid (
23%). The molecular weight was Mn = 15,700 g / mole, Mw = 32,1
It was confirmed to be 00 g / mole (GPC in THF, based on polystyrene). ¹ H NMR indicated that both the methyl ester of norbornene and t-butyl ester were present. By thermogravimetric analysis (TGA) under nitrogen (heated at a heating rate of 10 ° C./min), the polymer is thermally stable up to about 155 ° C., with a weight loss up to 290 ° C. of approximately 20 wt%. (Indicating that the isobutene t-butyl group is completely eliminated to give a homopolymer of 5-norbornene-carboxylic acid), and the polymer degrades at about 450 ° C. It became clear.

Example 15 Synthesis of Bicyclo [2.2.1] hept-5-ene-exo, exo-2,3-dicarboxylic acid diethyl ester: Exo of norbornene and exo diethyl ester are exo-5-norbornene Synthesized from 2,3-dicarboxylic acid. The exo isomer is purified by several recrystallizations from toluene as described in reference 1 after thermal conversion of endo-5-norbornene-2,3-dicarboxylic anhydride at 190 ° C. Exo-5
Prepared by obtaining norbornene-2,3-dicarboxylic anhydride. A portion of the exoanhydride was hydrolyzed in boiling water and the resulting solution was cooled to give pure diacid in almost quantitative yield. The diacid is converted to a diethyl ester using a triethyloxonium salt as shown below.

In a 250 ml three-necked round bottom flask equipped with a magnetic stir bar, 16.0 g (0.082 g) was added.
4 moles) of pure exonorbornene dicarboxylic acid and 35 g (0.1846 moles) of triethyloxonium tetrafluoroborate were charged. After stoppering the flask, 300 ml of dichloromethane was added via cannula under an argon atmosphere. The rubber stopper was replaced with a condenser under an argon atmosphere, and the other end was fitted with a funnel. 35 ml of ethyldiisopropylamine was added to the funnel and allowed to slowly drip into the reaction vessel. A small exotherm was observed and the resulting solution was lightly refluxed. After the addition of the amine was completed, the resulting solution was left at room temperature for 15 hours. The reaction mixture obtained is diluted with 50 ml of hydrogen chloride solution.
Work-up was carried out by extracting twice, after which it was extracted three times with 50 ml of sodium bicarbonate and finally washed twice with water. The resulting organic solution was dried over magnesium sulfate, treated with carbon black, filtered and concentrated on a rotary evaporator. By purifying the residue by distillation at 110 ° C., 15 g (7 g) of pure exo-diethyl ester of norbornene, a colorless, viscous and fruity scented liquid, are obtained.
5%). ¹ H NMR (CDCl ₃ ): d = 1.22 (3H; t, CH ₃ ), d = 1.47 (1H), d = 2.15 (1H), d = 2.58 (2H; s, C H COO), d = 3
.07 (2H; s, bridge head), d = 4.10 (2H; m, CH 2), d = 6.19 (2H; s, C = C), FI-MS (DIP) = M +. (238)

Example 16 Bicyclo [2.2.1] hept-5-ene-exo-2-t-butyl ester,
Synthesis of exo-3-carboxylic acid: 1.5 g (9.15 mmole) of pure exo-nadic anhydride, 10 ml, in a 50 ml one-necked round bottom flask equipped with a Teflon-coated stir bar
Methylene chloride immediately after the distillation, 20 ml (0.209 mole) of t-butanol was added. To this solution was added 7.5 g (0.061 moles) of dimethylaminopyridine and the resulting solution was refluxed at 75 ° C. for 8 hours. The anhydride did not initially dissolve, but dissolved over time to form a brown solution. The reaction solution was cooled, concentrated in a rotovap to remove methylene chloride, and the resulting concentrated solution was slowly added to acidic water (hydrogen chloride). The precipitated solid was filtered, washed with water, further dissolved in MgSO ₄ followed by ether treated with carbon black, and the resulting solution was filtered over celite. The ether was removed on a rotovap to give a white solid (8.5 g, 60%). ¹ H NMR (CDCl ₃ ): d = 1.47 (9H; s, t-butyl), d = 1.6
0 (1H), d = 2.15 (1H), d = 2.58 (2H; m, C H COO), d
= 3.07 (2H; s, bridgehead), d = 6.19 (2H; s, C = C),
d = 10.31 (1H; broad, COOH)

Example 17 Synthesis of bicyclo [2.2.1] hept-5-ene-exo-2-t-butyl, exo-3-methyl ester of dicarboxylic acid: 100 ml three with magnetic stir bar In a round bottom flask, 9.7 g (0.0408 mole) of pure exo-t-butyl half ester of norbornene dicarboxylic acid was added.
, 6.05 g (0.0408 mol) of trimethyloxonium tetrafluoroborate
e) It was thrown. After stoppering the flask, 100 ml of dichloromethane was added via cannula under an argon atmosphere. The rubber stopper was replaced with a condenser under an argon atmosphere, and the other end was fitted with a funnel. 7.3 ml of ethyldiisopropylamine was added to the funnel and allowed to slowly drip into the reaction vessel. A small exotherm was observed and the resulting solution was lightly refluxed. After the addition of the amine was completed, the resulting solution was left at room temperature for 15 hours. The resulting reaction mixture is
The work-up is carried out by extracting three times with 0 ml of hydrogen chloride solution and then 50 ml
Extracted three times with sodium bicarbonate and finally washed twice with water. The resulting organic solution was dried over magnesium sulfate, treated with carbon black, filtered and concentrated on a rotary evaporator. A colorless liquid was obtained, which began to crystallize. The resulting solid was washed with cold pentane and the resulting pentane solution was concentrated in a rotovap to give a colorless liquid which crystallized on cooling. The yield was 5.1 g. ¹ H NMR (CDCl ₃ ): d = 1.45 (9H; s, t-butyl), d = 1.4
7 (1H), d = 2.15 (1H), d = 2.54 (2H; m, C H COO), d
= 3.07 (2H; s, bridge head), d = 3.65 (3H; s, CH 3), d = 6.19 (2H; s, C = C)

Example 18 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, 5-
Norbornene-carboxylic acid (2.0 g, 14.5 mmol, exo, endo mixture) and dichloroethane (20 ml) were charged. To this stirred mixture was added η ³ -allyl palladium chloride dimer (6 mg, 16 μmol) in dichloroethane (5 ml) to silver hexafluoroantimonate (5 ml) in dichloroethane (5 ml).
(50 mg, 146 μmol) over 30 minutes and a catalyst solution prepared by filtration through a micropore filter (to remove precipitated silver chloride) was added at ambient temperature. Thereafter, the obtained mixture was reacted and gelled for 18 hours to obtain a transparent yellow gel. Upon addition of the resulting gel to excess hexane, a white powdery polymer precipitated. The polymer was washed with excess hexane and dried. The yield of the polymer was 1.2 g (60%). The molecular weight (Mw) of the polymer was found to be 22,000 and the polydispersity was 2.3.

When a portion (0.5 g) of this polymer was added to a stirred 0.1 N aqueous solution of KOH (10 ml), the polymer immediately dissolved and a viscous colorless solution was obtained. This demonstrates the base developability of these materials since homopolymers of the t-butyl ester of 5-norbornenecarboxylic acid do not tend to dissolve under the same conditions.

Example 19 The Pinner synthesis of the orthoester is a two-step synthesis. Step 1. Synthesis of imidized ester hydrochloric acid The reaction was carried out in a 1 L two-necked round bottom flask equipped with a stirrer, oil jetting device, and a tube containing anhydrous calcium chloride. 100 g (0.84 mol) of norbornene carbonitrile (NB-CN), 37 ml (0.91 mol) of anhydrous methanol, and 200 ml of anhydrous diethyl ether were placed in the flask. The flask was placed in an ice-water bath and 61 g (1.67 mol) of dry hydrogen chloride was bubbled through the mixture for 1.5 hours while stirring the mixture. The flask was placed in a refrigerator kept at 0 ° C. overnight. The next morning, the mixture had solidified into a "cake". It was broken into small pieces and an additional 200 ml of diethyl ether was added. The flask was stored in the refrigerator for another 10 days with occasional stirring. After 10 days, the precipitated imidoester hydrochloride was filtered off with suction and washed 5 times with 〜300 ml of diethyl ether. 20 g of unreacted NB-CN was recovered from the filtrate.

The yield of the imidoester hydrochloric acid was 76% (120 g, 0.64 mol). The structure of the product obtained was confirmed by ¹ H NMR spectroscopy. Step 2. Synthesis of orthoester A 0.5 L flask was charged with 56.7 g (0.30 mol) of the imidoester hydrochloride, 37 ml (0.91 mol) of anhydrous methanol, and 250 ml of anhydrous petroleum ether. The resulting reaction mixture was stored at room temperature for 5 days with occasional stirring. The precipitated ammonium chloride was filtered off and washed three times with petroleum ether. The filtrate and the wash water were combined, petroleum ether was distilled off, and the resulting product was fractionally distilled under vacuum. A fraction having a boiling point of 68-69 ° C./3 mmHg was collected. The yield was 50% (30 g, 0.15 mol). According to ¹ H NMR spectroscopy, the product obtained was 97 +% of 5-norbornene-2-trimethoxymethane (orthoester).

Example 20 2.16 g (10.9 mmol) of C in 16 ml of 1,2-dichloroethane₇H ₉ C (OCH_Three)_Three(Norbornene trimethyl orthoester) solution in dichloroethane with 1 mole of allyl palladium chloride dimer and 2 moles of hexamer
Mix with silver safluoroantimonate and filter off the resulting silver chloride precipitate
A solution of the reaction product thus obtained was added. 2 ml of catalyst added
Corresponded to 0.08 mmol of palladium dissolved in dichloroethane. The stirred reaction mixture was placed in a 70 ° C. oil bath and reacted for 20 hours.

At the end of the reaction, 2 ml of methanol were added, the solvent was removed using a rotary evaporator and the polymer was dried under vacuum to constant weight.

The yield was 1.28 g (60%).

Example 21 Bicyclo [2.2.1] hept-5-en-2-methylacetate (18.44 g, 0.5 g) was placed in a 50 ml glass bottle equipped with a Teflon-coated stir bar.
1109 mol), norbornene t-butyl ester (21.55 g, 0.11
09 mol) and 75 ml of toluene. A solution of a nickel catalyst [toluene complex of bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] was 0.5673 g (1.109 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 15 ml. Prepared in a dry box by dissolving in toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The reaction was carried out at room temperature under stirring for 6 hours. The resulting solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone, and dried under vacuum overnight. The isolated yield of the polymer was 24.9 g (63%). The molecular weight of the polymer was characterized using GPC. Mn = 21,000 and Mw = 52,000. NMR analysis of the copolymer indicated that 51 mol% of t-butyl ester groups were present. IR analysis of the copolymer indicated that no acid groups were present.

Example 22 In a 50 ml glass bottle equipped with a Teflon-coated stir bar, bicyclo [2.2.1] hept-5-en-2-methylethyl carbonate (4.03 g, 0 0.0205 mol), norbornene t-butyl ester (3.98 g, 0
0.0205 mol) and 50 ml of toluene. A solution of a nickel catalyst [toluene complex of bis-perfluorophenylnickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] was added to 0.0991 g (0.249 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 15 ml. Prepared in a dry box by dissolving in toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The reaction was carried out at room temperature under stirring for 6 hours. The resulting solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone, and dried under vacuum overnight. The isolated yield of the polymer was 4.16 g (52%). The molecular weight of the polymer was characterized using GPC. Mn = 22,000 and Mw = 58,000. NMR analysis of the copolymer indicated that t-butyl ester groups were present at 50 mol%. Copolymer I
R analysis indicated that no acid groups were present.

Example 23 In a 50 ml glass bottle equipped with a Teflon-coated stir bar,
Chromo [2.2.1] hept-5-ene-2-methylbutyl carbonate (17.15 g, 0.0764 mol), t-butyl ester of norbornene (14.85 g)
, 0.0764 mol) and 72 ml of toluene. Nickel catalyst [Toluene complex of bisperfluorophenyl nickel, (Tol) Ni (C₆F_Five) _Two ] With 0.3699 g (0.7644 mmol) of (Tol) Ni (C₆F_Five )_TwoWas prepared in a dry box by dissolving in 15 ml of toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The anti
The reaction was carried out at room temperature under stirring for 6 hours. Dilute the resulting solution with toluene
The polymer was precipitated in excess methanol. The precipitated polymer is filtered and
After washing with water, it was dried under vacuum overnight. The isolated yield of the polymer was 17.53 g (54%). The molecular weight of the polymer was characterized using GPC. Mn = 2
2,000 and Mw = 58,000. By NMR analysis of the copolymer
, T-butyl ester group was found to be present at 54 mol%. Copolymer
IR analysis indicated that no acid groups were present.

Example 24 A 50 ml glass bottle equipped with a Teflon-coated stir bar was first charged with t-butyl ester of norbornene (29.92 g, 0.154 mol) and then dried with maleic anhydride. (15.10 g, 0.154 mol) and 90 ml of chlorobenzene were charged. The mixture was degassed three times to remove all oxygen. Next, the resulting reaction mixture was heated to 80 ° C. A degassed benzoyl peroxide solution consisting of 0.9948 g (0.04 mol) of benzoyl peroxide free radical initiator in 10 ml of chlorobenzene was added to the reaction mixture using a dry syringe. The reaction was carried out under stirring for 19 hours. After the reaction, the obtained polymer solution was directly poured into hexane to precipitate the polymer. A white precipitate was obtained. Next, any unreacted maleic anhydride that may have been present was removed from the precipitated polymer. The resulting polymer was dried in a vacuum oven at room temperature overnight. The weight of the obtained dry polymer was 20.62 g and the yield was 45.
8%. The molecular weight of the polymer was characterized using GPC. Mn = 4,200 and Mw = 8,800. NMR analysis of the copolymer indicated that t-butyl groups were present. IR analysis of the copolymer indicated that both t-butyl and maleic anhydride groups were present.

Example 25 In a 50 ml glass bottle equipped with a Teflon-coated stir bar was first placed bicyclo [2.2.1] hept-5-en-2-methylacetate (13.3 g, 0.3 g). 0799 mol), t-butyl ester of norbornene (15.70 g, 0.0808 mol), and then dry maleic anhydride (15.85 g, 0.162).
mol) and 90 ml of chlorobenzene. The mixture was degassed three times to remove all oxygen. Next, the resulting reaction mixture was heated to 80 ° C. 10
A degassed benzoyl peroxide solution consisting of 1.0438 g (0.041 mol) of benzoyl peroxide free radical initiator in ml of chlorobenzene was added to the reaction mixture using a dry syringe. The reaction was carried out under stirring for 19 hours. After the reaction, the obtained polymer solution was directly poured into hexane to precipitate the polymer. A white precipitate was obtained. Next, any unreacted maleic anhydride that may have been present was removed from the precipitated polymer. The resulting polymer was dried in a vacuum oven at room temperature overnight. The weight of the dry polymer obtained is 21
It was .89 g, and the yield was 48.7%. The molecular weight of the polymer was characterized using GPC. Mn = 3,000 and Mw = 6,600. NMR analysis of the copolymer indicated the presence of acetate and t-butyl groups. IR analysis of the copolymer indicated the presence of acetate, t-butyl and maleic anhydride groups.

Example 26 t-BuNB Ester / NB-COOH 50:50 Copolymer In a 50 ml glass bottle equipped with a magnetic stir bar and under a nitrogen atmosphere, t-butyl ester of norbornene carboxylic acid (2 g, 10 mmol) and norbornene carboxylic acid The acid (1.38 g, 10 mmol) was charged. To the stirred mixture at ambient temperature was added initiator (t-butyl peroxide) (2.9 g) and the resulting mixture was heated to 130 ° C. and stirring was continued for 16 hours. The obtained polymer (soluble in both THF and toluene) was precipitated in hexane, filtered, and dried to obtain a product having a weight of 2.91 g (86% conversion). The Mw of the obtained solid polymer is 20
And Mn was 3,000. IR, NMR and T of the copolymer
GA analysis demonstrated that the composition of the copolymers was a random addition copolymer of two monomers.

Example 27 50:50 Copolymer of t-BuNB Ester / NB-MeNB Ester In a 50 ml glass bottle equipped with a magnetic stir bar and under a nitrogen atmosphere, t-butyl ester of norbornene carboxylic acid (2 g, 10 mmol) and norbornene The carboxylic acid methyl ester (1.5 g, 10 mmol) was charged. To this stirred mixture at ambient temperature was added initiator (t-butyl peroxide) (2.9 g) and the resulting mixture was heated to 130 ° C. and stirring was continued for 16 hours. The obtained polymer (soluble in toluene) was precipitated in methanol, filtered, and a product having a weight after drying of 0.82 g (conversion rate: 23%) was obtained. The Mw of the obtained solid polymer is 3
It was 5,000 and Mn was 6,000. IR, NMR and TGA analyzes of the copolymers demonstrated that the composition of the copolymers was a random addition copolymer of two monomers.

Example 28 50:50 Copolymer of t-BuNB Ester / EtTD Ester A 100 ml glass bottle equipped with a magnetic stir bar and under a nitrogen atmosphere was charged with toluene (4
0 ml), t-butyl ester of norbornenecarboxylic acid (1.94 g, 10 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (2.32 g, 10 mmol). To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) -benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 1 hour, ethyl vinyl ether (0.015 ml, 0.156 mmol) was added and stirred for 1 hour.
The resulting polymer solution was added to excess MeOH to precipitate, collected by filtration and dried under vacuum. 3.46 g (81% yield) of copolymer (Mw = 221,000,
(Mn = 133,000) was recovered.

The resulting copolymer was redissolved in toluene and passed through a silica gel column to remove any discernable color (Ru). The resulting polymer was precipitated again in excess MeOH to give a pure white copolymer.

Example 29 50:50 Copolymer of t-BuNB Ester / EtTD Ester Toluene (8
0 ml), norbornene carboxylic acid t-butyl ester (3.9 g, 20 mmol) and tetracyclododecene carboxylic acid ethyl ester (4.64 g, 20 mmol). To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours, ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and stirred for 2 hours.

The resulting orange-amber solution was passed through a silica gel column to give a clear, colorless solution. The resulting solution was precipitated by adding excess MeOH, collected by filtration and dried under vacuum. 6.54 g (77% yield) of copolymer (Mw = 244,000, Mn =
182,000) were recovered. Glass transition temperature was measured using DSC and was determined to be 220 ° C.

Example 30 50:50 Copolymer of t-BuNB Ester / EtTD Ester In a 300 ml stainless steel reactor equipped with a mechanical stir bar and containing nitrogen, toluene (90 ml), t- of norbornene carboxylic acid Butyl ester (3
.9 g, 20 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (4.64 g, 20 mmol). To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours, ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and stirred for 16 hours. Hydrogen (350 psig) was added to the reactor and the temperature was maintained at 175 ° C. for 7 hours. After the reaction, the obtained solution was passed through a silica gel column to isolate a hydrogenated copolymer. NMR showed that the copolymer was 95% hydrogenated (Mw = 237,000, Mn = 163,000).

Example 31 50:50 Copolymer of t-BuNB Ester / EtTD Ester In a 300 ml stainless steel reactor equipped with a mechanical stir bar and containing nitrogen, toluene (90 ml), t- of norbornene carboxylic acid Butyl ester (2
.9 g, 15 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (3.5 g, 15 mmol). To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (50 mg, 0.060 mmol) in 5 ml of toluene. After 2 hours, hydrogen (800 psig) was added to the reactor and the temperature was maintained at 175 ° C for 7 hours.
After the reaction, the obtained solution was passed through a silica gel column to isolate a hydrogenated copolymer. NMR revealed that the copolymer was 96% hydrogenated (Mw = 278,000, Mn = 172,000).

Example 32 50:50 Copolymer of t-BuNB Ester / EtTD Ester In a 100 ml glass bottle equipped with a magnetic stir bar and containing nitrogen, toluene (4
0 ml), t-butyl ester of norbornene carboxylic acid (1.94 g, 10 mmol), ethyl ester of tetracyclododecene carboxylic acid (2.32 g, 10 mmol) and 1-hexene (0.050 ml, 0.4 mmol) Was introduced. To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 2 hours, the resulting polymer solution was added to excess MeOH, collected by filtration and dried under vacuum. 3.1 g (73% yield) of polymer (Mw = 35,000, Mn = 22,000) was recovered.

Example 33 50:50 Copolymer of t-BuNB Ester / EtTD Ester A 100 ml glass bottle equipped with a magnetic stir bar and containing nitrogen was charged with toluene (4
0 ml), t-butyl ester of norbornenecarboxylic acid (1.94 g, 10 mmol), ethyl ester of tetracyclododecenecarboxylic acid (2.32 g, 10 mmol) and 1-hexene (0.275 ml, 2.2 mmol) Was introduced. To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 2 hours, the resulting polymer solution was added to excess MeOH, collected by filtration and dried under vacuum. 3.45 g (81% yield) of polymer (Mw = 8,000, Mn = 6,000) was recovered.

Example 34 50:50 Copolymer of t-BuNB Ester / EtTD Ester In a 100 ml glass bottle equipped with a magnetic stir bar and containing nitrogen, toluene (4
0 ml), t-butyl ester of norbornenecarboxylic acid (1.94 g, 10 mmol), ethyl ester of tetracyclododecenecarboxylic acid (2.32 g, 10 mmol) and 1-hexene (0.62 ml, 5.0 mmol) Was introduced.
To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 2 hours, the resulting polymer solution was added to excess MeOH, collected by filtration and dried under vacuum. 2.75 g (65% yield) of polymer was recovered.

Example 35 50:50 Copolymer of t-BuNB Ester / EtTD Ester A 100 ml glass bottle equipped with a magnetic stir bar and containing nitrogen was charged with toluene (8
0 ml), t-butyl ester of norbornenecarboxylic acid (3.9 g, 20 mmol), ethyl ester of tetracyclododecenecarboxylic acid (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol) Was introduced.
To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours, ethyl vinyl ether (0.030 ml, 0.
31 mmol) and stirred for 2 hours.

The resulting orange-amber polymer solution was passed through a silica gel column to remove dark (Ru). The resulting solution was precipitated by addition to excess MeOH, collected by filtration and dried under vacuum at 80 ° C. overnight. 2.6 g (30% yield) of polymer (Mw = 4,000
0, Mn = 3,000).

Example 36 50:50 Copolymer of t-BuNB Ester / EtTD Ester To a 300 ml stainless steel reactor equipped with a mechanical stir bar and containing nitrogen, toluene (80 ml), t- of norbornene carboxylic acid Butyl ester (3
.9 g, 20 mmol), ethyl ester of tetracyclododecenecarboxylic acid (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). This stirred solution is added at ambient temperature to bis (5 ml) in toluene.
Tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg
, 0.042 mmol). After 2 hours, hydrogen (750 psig) was added to the reactor and the temperature was maintained at 175 ° C for 20 hours.

The resulting solution was precipitated by addition to excess MeOH, collected by filtration and 80 ° C. under vacuum
For overnight. About 5 g (59% yield) of polymer (Mw = 30,000, Mn = 20,000) was recovered. NMR indicated that the copolymer was 99% or more hydrogenated.

Example 37 t-BuNB Ester / EtTD Ester 65:35 Copolymer In a 250 ml round bottom flask equipped with a magnetic stir bar and containing nitrogen, toluene (160 ml), t-butyl ester of norbornene carboxylic acid (10 .1 g, 52 mmol), ethyl ester of tetracyclododecenecarboxylic acid (6.5 g, 28 mmol) and 1-hexene (0.176 ml, 1.4 mmol). To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (131 mg, 0.160 mmol) in 5 ml of toluene. After 16 hours, ethyl vinyl ether (0.060 ml, 0.62 mmol) was added and stirred for 1.5 hours. The obtained polymer solution was passed through a silica gel column to remove Ru. The resulting solution was added to excess methanol, collected by filtration and dried under vacuum. 9.69 g (58% yield) of polymer (Mw = 42,000, Mn = 31,000) was recovered. The glass transition temperature (110 ° C.) was measured using the DSC method.

Example 38 In a 100 ml glass bottle containing nitrogen, 5.0 g of the polymer of Example 37 was dissolved in THF (80 ml). The resulting solution was transferred to a 300 ml stainless steel reactor. 2.25 g of 5 wt% palladium on alumina catalyst (purchased from Aldrich) was charged to the reactor. The reactor was then heated to 175 ° C. and pressurized with 800 psig of hydrogen. The temperature and pressure were maintained for 9.5 hours. The resulting polymer solution was centrifuged to separate a colorless liquid, and the polymer was precipitated in excess methanol. NMR showed that the resulting copolymer was 99% or more hydrogenated.

Example 39 50:50 Copolymer of t-BuNB Ester / EtTD Ester In a 100 ml glass bottle equipped with a magnetic stir bar and containing nitrogen, toluene (8
0 ml), t-butyl ester of norbornenecarboxylic acid (3.9 g, 20 mmol), ethyl ester of tetracyclododecenecarboxylic acid (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol) Was introduced.
To this stirred solution at ambient temperature was added a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.084 mmol) in 5 ml of toluene. After 2 hours, the reaction was short-stopped by adding ethyl vinyl ether (30 μl) and the resulting mixture was stirred for 1.5 hours. The resulting polymer solution was passed through a silica gel column to remove Ru residues, and precipitated in methanol to recover a clean white solid polymer. The Mw of the obtained polymer was 46,600 (Mn was 33,700), and IR, NMR and TG
Completely characterized by Method A.

Example 40 Ethyl 2-methyl-4 in a 300 ml internal volume stainless steel autoclave
Pentanoate (99 g, 0.7 mole) and freshly pyrolyzed cyclopentadiene (46.4 g, 0.7 mole) were charged. This stirred mixture is mixed with 2
Heated to 00 ° C. and left overnight. The reactor was then cooled and its contents were removed. The resulting functionalized norbornene _{(NB-CH 2 CH (CH} 3) C (O) O
CH ₂ H ₅ ) was purified by vacuum distillation and found to have a boiling point of about 46-47 ° C. at 0.02 mmHg. The material was analyzed by GC and found to be between 98.4 and 99.3% pure (different fractions). The isolation yield of the high purity product was 33 g.

Example 41 40 of the t-BuNB ester (NB-CH ₂ CH (CH ₃ ) C (O) OC ₂ H ₅ )
: 60 copolymer In a 100 ml glass bottle equipped with a magnetic stir bar and under a nitrogen atmosphere, toluene (50 ml), t-butyl ester of norbornene carboxylic acid (2.7 g, 14 mmol) and the ester of Example 40 (NB-CH ₂ CH (CH ₃ ) C (O) O
_{C 2 H 5) (4.4g,} 21mmol) was charged. A (toluene) Ni (C ₆ F ₅ ) ₂ solution in toluene (1 ml) was added to the stirred solution at ambient temperature, the resulting solution was heated to 50 ° C. and stirring was continued for 3 hours. . The polymer was precipitated in methanol and then filtered. The solid obtained was redissolved in THF, filtered, precipitated again in methanol and filtered. When the obtained white solid polymer was dried, it was found that its weight was 2.66 g (Mw = 70,000, Mn = 39,800). When the obtained supernatant was evaporated to dryness, a new product was obtained. A white polymer was obtained, which was found to be 1.52 g (Mw = 60,650, Mn = 31,000) by drying. Total yield of the copolymer indicated that the conversion of the monomer was 59%. IR, NMR and TGA analyzes of the copolymers demonstrated that the composition of the copolymers was a random addition copolymer of two monomers.

Example 42 40 of t-BuNB ester (NB-CH ₂ CH (CH ₃ ) C (O) OC ₂ H ₅ )
: 60 copolymer In a 250 ml glass bottle equipped with a magnetic stir bar and under a nitrogen atmosphere, dichloroethane (200 ml), t-butyl ester of norbornene carboxylic acid (7.76 g, 40 mmol) and the ester of Example 40 (NB-CH) ₂ CH (CH ₃ )
_{C (O) OC 2 H 5} ) (12.5g, 60mmol) and 2,6-di -t- butyl-pyridine (28.8 g, 0.26 mmol) was charged. To this stirred solution at ambient temperature, allyl palladium chloride dimer (0.183 g, 0.5 mmol)
And silver hexafluoroantimonate (equivalent) in dichloroethane (3 ml) and then a solution of the catalyst obtained by filtering and removing the silver chloride precipitate was added. The resulting solution was heated to 50 ° C. and kept stirring for 16 hours. The resulting polymer solution was treated with carbon monoxide (4 psi pressure) for 48 hours to precipitate the palladium residue, filtered through a 0.45μ filter, reduced in volume, precipitated with excess methanol and weighing 7.9 g. , Mw = 11,600 and Mn = 7,000 (conversion 39%). The resulting copolymer has IR, NMR and TGA
It was fully characterized using the method.

Example 43 Copolymerization of CO and Norbornene-5-t-butyl Ester A deoxygenated methanol solution of bipyridine (0.025 g, 0.16 mmol) was
Added to palladium (II) acetate (0.012 g, 0.053 mmol) dissolved in deoxygenated methanol. To this solution was added p-toluenesulfonic acid (0.045 g, 0.27 mmol) dissolved in deoxygenated methanol. To the resulting brown solution was added a solution of benzoquinone (1.72 g, 1.59 mmol) in methanol (deoxygenated). This was charged into a stainless steel reactor preheated to 50 ° C. The reactor was charged with norbornene-5-tert-butyl ester (5.14 g, 0.027 mol) in 100 ml (argon deoxygenated) MeOH. The reactor was pressurized to 600 psig with carbon monoxide and warmed to 65 ° C.
After 4.5 hours, the carbon monoxide was withdrawn and the reactor was cooled. The pink solution from the reactor was filtered to remove palladium residues and evaporated. The resulting mixture was dissolved in a minimum amount of THF and slowly poured into a 25:75 mixture of water and methanol to precipitate the polymer. This process was repeated twice. The resulting white polymer was filtered and dried under vacuum at room temperature. The yield was 2.9 g.

Example 44 Benzoquinone (0.43 g, 0.40 mmol), bipyridine (0.0062 g, 0.0040 mmol), and Pd (MeCN) ₂ (p-toluenesulfonate) ₂ (0.0070 g, 0.40 mmol). 0013 mmol) of deoxygenated dry THF / methanol (35 ml / 15 ml) solution was charged to a 500 ml dry stainless steel reactor warmed to 50 ° C. The reactor was charged with norbornene-5-t-butyl ester (5.14 g, 0.027 mol) in 100 ml (deoxygenated and dried) of THF. The reactor was pressurized with carbon monoxide to 600 psig and warmed to 65 ° C. After 12.5 hours, the reactor was brought to 90 ° C for 1.5 hours.
Heated for hours. Thereafter, carbon monoxide was removed and the reactor was cooled. The purple solution from the reactor was filtered to remove the palladium residue and evaporated. The resulting mixture was dissolved in a minimum amount of THF and slowly poured into a 25:75 mixture of water and methanol to precipitate the polymer. This process was repeated twice. The resulting white polymer was filtered and dried under vacuum at room temperature. The yield was 2.9 g.

Examples 45-51 Optical Density Measurements at 193 nm for Cyclic Olefin Based Homopolymers and Copolymers Since optical density determines the uniformity of energy across the thickness of the film,
An important characteristic of an effective photoresist. Typical lithographically useful polymer backbones have an optical density of less than 0.2 absorbance units / micron before adding the photoacid generator. (T. Neenan, E. Chandros, J. Kometani [J. Komet]
ani] and O. Nalamasu, "Styrylmethylsulfonamide: Versatile base soluble component of photoresist resin", Microelectronics Technology [Microelectronics Technology].
y], page 199, Polymers for Advanced Imaging and Packaging, ACS
Symposium Series No. 614, Editor: E. Lake Manis [E. Reichm
anis], C. Ober, C. Ober, S. McDonald [S. MacDo
nald], T. Iwayanagi and T. Nishikubo, April 1995). Polyhydroxystyrene, the major component of a typical 248 nm DUV photoresist, has an optical density of 2.8 absorbance units / micron at 193 nm and cannot be used as a resist backbone at this wavelength. Preparation of Sample Solutions Samples of the various polymers described in the above examples (0.016 ± 0.001 g of polymer) were weighed and dissolved in 4 ml of chloroform. The solution of polymer was pipetted off and a thin film was placed on a clean uniform quartz slide. The film was dried overnight. The resulting circular film on the quartz slide was further dried in a 70 ° C. oven for 10 minutes under a nitrogen purge.

The UV spectrum of the film was measured using a Perkin-Elmer Lambda 9 UV / VIS
/ IR spectrophotometer was used at a scan rate of 120 nm / min. The range of the spectrum was set from 300 nm to 180 nm. The absorbance at 193 nm of the film was measured and normalized to the film thickness to give
The optical density at 93 nm was measured. The results are shown in the table below.

[0278]

[Table 1]

Preparation of Resist Solution, Exposure and Development: The polymer obtained in the above example was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 15 w / v%, which was described in the above example. The onium salt was added at 5 or 10% w / w solids based on the polymer.

The solution obtained was filtered through a 0.2 μ Teflon® filter. Each of these solutions was spin-coated on a silicon wafer primed with hexamethyldisilazane (HMDS) to form a resist layer. The coating was baked at 95 ° C. for 1 minute. Next, the film was subjected to Karl Suss MJB3UV.
The device was exposed to ultraviolet radiation having a wavelength of 230 to 250 nm from a 250 device through a quartz mask. The exposed film was heated at 125 ° C to 150 ° C for 1 minute. The exposed and heated film was developed in an aqueous base to obtain a high resolution positive tone image without loss of film thickness in unexposed areas.

The system is easily rendered negative by developing in a non-polar solvent. These materials can be made sensitive to longer wavelengths (365 nm) by the addition of small amounts of sensitizers such as pyrene, perylene, or thioxanthone, or (as described above) these materials can be very poor at 193 nm. Since it has been confirmed that it has a low optical density, it can be made to respond to even shorter wavelengths (193 nm).

Example 52 Copolymer of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylacetate / norbornene (polymer of Example 21) (number average molecular weight: 21,000) It was dissolved in propylene glycol monomethyl ether acetate (PG MEA) at a solid content of 10% w / v. Triphenylsulfonium hexafluoroarsenate was added in an amount of 10% w / w to the polymer.
The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer primed with hexamethyldisilazane for 500 hours.
Spin coating was performed for 30 seconds at rpm and then for 25 seconds at 2,000 rpm. This resulted in a 0.7 μ thick layer. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) through a quartz mask at a radiation dose of 50 mJ / cm ² . After post-baking at 125 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 53 Bicyclo [2.2.1] hept-5-ene-2-methylethyloxalate / Copolymerization of t-butyl norbornene with NiArf catalyst Teflon-coated In a 50 ml glass bottle equipped with a stir bar, bicyclo [2.2.1] hept-5-ene-2-methylethyl oxalate (8.57 g, 0.0382 mol), t-butyl ester of norbornene (7. .42g, 0
.0392 mol) and 38 ml of toluene. A solution of a nickel catalyst [toluene complex of bis-perfluorophenylnickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] was prepared using 0.1854 g (0.382 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 5 ml. Prepared in a dry box by dissolving in toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The reaction was carried out at room temperature under stirring for 5 hours. The resulting solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone, and dried under vacuum overnight. The isolated yield of the polymer was 7.62 g (48%). The molecular weight of the polymer was characterized using GPC. Mn = 28,000 and Mw = 56,000. NMR analysis of the copolymer indicated that the composition of the copolymer was very close to the charge ratio. IR analysis of the copolymer indicated that no acid groups were present.

Example 54 Bicyclo [2.2.1] hept-5-ene-2-methylacetate / norbornene
T-butyl ester copolymer (polymer of Example 21) (number average molecular weight
: 21,000) was dissolved in propylene glycol monomethyl ether acetate (PG MEA) at a solid content of 10 w / v%. Diaryliodonium hexaf
Luoroantimonate (Sartomer 1012) was added to the polymer.
The amount was added at 10 w / w% based on the total amount. The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was treated with hexamethyldisilaza.
The substrate was spin-coated at 500 rpm for 30 seconds and then at 2,000 rpm for 25 seconds on a silicon wafer undercoated with a coating. As a result, a layer having a thickness of 0.7 μ was obtained. After baking the coating on a hot plate at 95 ° C for 1 minute, ^Two UV radiation (240 nm) was exposed through a quartz mask at a radiation dose of. After post-baking at 125 ° C for 1 minute, develop in aqueous base for 60 seconds.
As a result, a high-resolution positive image was obtained.

Example 55 Copolymer of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylacetate / norbornene (polymer of Example 21) (number average molecular weight: 21,000) It was dissolved in propylene glycol monomethyl ether acetate (PG MEA) at a solid content of 10% w / v. Diaryliodonium hexafluoroantimonate (Sartomer 1012) was added at 10 w / w% to the polymer. The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was spin-coated on a silicon wafer primed with hexamethyldisilazane at 500 rpm for 30 seconds, and then at 2,000 rpm for 25 seconds. did. As a result, a layer having a thickness of 0.7 μ was obtained. After baking the coating on a hot plate at 95 ° C. for 1 minute, 100 mJ /
Ultraviolet radiation (240 nm) was exposed through a quartz mask at a radiation dose of cm ² . After post-baking at 125 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 56 Copolymerization of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylethyloxalate / norbornene (molar ratio: 70/30) using a NiArf catalyst In a 50 ml glass bottle equipped with a Teflon-coated stir bar, bicyclo [2.2.1] hept-5-en-2-methylethyloxalate (14.8 g, 0.0663 mol), Norbornene t-butyl ester (5.52 g, 0
.0284 mol) and 113 ml of toluene. A solution of a nickel catalyst [toluene complex of bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] was added to 0.2296 g (0.474 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 5 ml. Prepared in a dry box by dissolving in toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The reaction was carried out at room temperature under stirring for 5 hours. The resulting solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone, and dried under vacuum overnight. The isolated yield of the polymer was 10.15 g (50%). The molecular weight of the polymer was characterized using GPC. Mn = 35,000 and Mw = 98,000. NMR analysis of the copolymer indicated that the composition of the copolymer was very close to the charge ratio. IR analysis of the copolymer indicated that no acid groups were present.

Example 57 Bicyclo [2.2.1] hept-5-ene-2-methylacetate / norbornene t-butyl ester copolymer (polymer of Example 21) (number average molecular weight: 21,000) It was dissolved in propylene glycol monomethyl ether acetate (PG MEA) at a solid content of 10% w / v. Triphenylsulfonium hexafluoroarsenate was added in an amount of 10% w / w to the polymer.
The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer primed with hexamethyldisilazane for 500 hours.
Spin coating was performed for 30 seconds at rpm and then for 25 seconds at 2,000 rpm. This resulted in a 0.7 μ thick layer. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) at a radiation dose of 10 mJ / cm ² through a quartz mask. After post-baking at 125 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 58 A copolymer of t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methylacetate / norbornene (polymer of Example 21) (number average molecular weight: 21,000) was prepared. It was dissolved in propylene glycol monomethyl ether acetate (PG MEA) at a solid content of 10% w / v. Triphenylsulfonium hexafluoroarsenate was added in an amount of 10% w / w to the polymer.
The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer primed with hexamethyldisilazane for 500 hours.
Spin coating was performed for 30 seconds at rpm and then for 25 seconds at 2,000 rpm. This resulted in a 0.7 μ thick layer. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) through a quartz mask at a radiation dose of 30 mJ / cm ² . After post-baking at 125 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 59 Bicyclo [2.2.1] hept-5-ene-2-methylethyloxalate / 1
-Copolymerization of (1-ethoxy) ethyl-5-norbornene-2-carboxylate (molar ratio: 50/50) with NiArf catalyst In a 50 ml glass bottle equipped with a Teflon-coated stir bar, Bicyclo [2.2.1] hept-5-ene-2-methylethyl oxalate (0.5166 g, 2.304 mmol), 1- (1-ethoxy) ethyl-5-norbornene-2-carboxylate (0.4885 g, 2.304 mol) and 2.25 ml of cyclohexane. 0.0112 g of a solution of a nickel catalyst [toluene complex of bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] was used.
It was prepared in a dry box by dissolving 0.023 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 0.65 ml of ethyl acetate. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The reaction was carried out at room temperature under stirring for 5 hours. The resulting solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone, and dried under vacuum overnight. The isolated yield of the polymer was 0.0315 g (3%). The molecular weight of the polymer was characterized using GPC. Mn = 52,000 and Mw = 100,000.

Example 60 A maleic anhydride / norbornene t-butyl ester copolymer obtained via free radical polymerization (polymer of Example 24) (number average molecular weight: 4,000) was treated with propylene glycol monomethyl ether acetate ( PGMEA) 15
Dissolved at w / v% solids. Triarylsulfonium hexafluoroantimonate (Saltomer CD1010, 50% solution in propylene carbonate)
Was added in an amount of 5% w / w based on the polymer. The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was spin-coated on a silicon wafer undercoated with hexamethyldisilazane at 500 rpm for 30 seconds and then at 2,000 rpm for 25 seconds. This resulted in a layer having a thickness of 0.6μ. After baking the coating on a hot plate at 95 ° C. for 1 minute, 30 m
Ultraviolet radiation (240 nm) was exposed through a quartz mask at a radiation dose of J / cm ² . After post-baking at 125 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 61 Maleic anhydride / norbornene t-butyl ester copolymer obtained via free radical polymerization (polymer of Example 24) (number average molecular weight: 4,000) was treated with propylene glycol monomethyl ether acetate ( PGMEA) 15
Dissolved at w / v% solids. Triarylsulfonium hexafluoroantimonate (Saltomer CD1010, 50% solution in propylene carbonate)
Was added in an amount of 5% w / w based on the polymer. The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was spin-coated on a silicon wafer undercoated with hexamethyldisilazane at 500 rpm for 30 seconds and then at 2,000 rpm for 25 seconds. This resulted in a layer having a thickness of 0.6μ. After baking the coating on a hot plate at 95 ° C. for 1 minute, 30 m
Ultraviolet radiation (240 nm) was exposed through a quartz mask at a radiation dose of J / cm ² . After post-baking at 95 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 62 Copolymerization of tricyclosilyl ester of bicyclo [2.2.1] hept-5-en-2-methylethyloxalate / norbornene (molar ratio: 50/50) using NiArf catalyst Teflon ( In a 50 ml glass bottle equipped with a stir bar coated with Bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate (1.584 g, 6.904 mmol), norbornene Trimethylsilyl ester (1.
4523 g, 6.905 mol) and 6.75 ml of cyclohexane. Nickel catalyst [toluene complex of bisperfluorophenyl nickel, (Tol
) Ni (C ₆ F ₅ ) ₂ ] in a dry box by dissolving 0.0335 g (0.0691 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 1.95 ml of ethyl acetate Prepared. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The reaction was carried out at room temperature under stirring for 5 hours. The resulting polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone, and dried under vacuum overnight. The isolated yield of the polymer was 0.2675 g (9%). The presence of an acid function resulting from the deprotection of the trimethylsilyl group was indicated.

Example 63 Terpolymer of maleic anhydride / bicyclo [2.2.1] hept-5-en-2-methylacetate / t-butyl ester of norbornene obtained via free radical polymerization (Example Polymer 25 (number average molecular weight: 3,000) was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 10 w / v%. Diaryliodonium hexafluoroantimonate (Saltomer 1012) was added at 10 w / w% to the polymer. The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer undercoated with hexamethyldisilazane for 500 r.
Spin coating was performed at pm for 30 seconds and then at 2,000 rpm for 25 seconds. As a result, a layer having a thickness of 0.5 μ was obtained. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) through a quartz mask at a radiation dose of 50 mJ / cm ² . After post-baking at 125 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 64 Copolymer of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylethyl carbonate / norbornene (polymer of Example 22) (number average molecular weight: 22,000) Was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 15 w / v%. Triarylsulfonium hexafluoroantimonate (Saltomer CD1010, a 50% solution in propylene carbonate) was added at a loading of 5% w / w based on the polymer.
The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer primed with hexamethyldisilazane for 500 hours.
Spin coating was performed for 30 seconds at rpm and then for 25 seconds at 2,000 rpm. As a result, a layer having a thickness of 1.1 μ was obtained. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) through a quartz mask at a radiation dose of 30 mJ / cm ² . After post-baking at 95 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 65 Copolymerization of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylethyloxalate / norbornene Equipped with a Teflon coated stir bar In a 50 ml glass bottle, 2.42 g (12.5 mmole) of norbornene t-butyl ester, 8.57 g
(38.2 mmole) of bicyclo [2.2.1] hept-5-en-2-methylethyloxalate and 50 ml of dichloroethane immediately after distillation were added, and the resulting solution was degassed under an argon atmosphere. . In a 10 ml glass bottle equipped with a Teflon coated stir bar, 0.0365 g (0.1 mmol) of allyl palladium chloride dimer and 2 ml of dichloroethane at a monomer / catalyst ratio of 500/1. Was introduced. In another 10 ml glass bottle, 0.0344 g (0.1 mmo
1) Silver hexafluoroantimonate and 2 ml of dichloroethane were charged. The catalyst solution was prepared by mixing the allylpalladium chloride dimer solution and the silver hexafluoroantimonate solution in a dry box. Immediately after, precipitation of a silver chloride salt was observed, and the salt was filtered to obtain an active catalyst solution. Next, the active catalyst solution was added to the monomer solution using a syringe, and the resulting reaction mixture was heated at 60 ° C. for 2 hours.
Stirred for 0 hours. The resulting polymer solution was cooled, concentrated in a rotovap and precipitated in methanol.

Example 66 Copolymer of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylethyl carbonate / norbornene (polymer of Example 22) (number average molecular weight: 22,000) Was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 15 w / v%. Triphenylsulfonium hexafluoroantimonate (Saltomer CD1010, a 50% solution in propylene carbonate) was added at 5 w / w% to the polymer.
The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer primed with hexamethyldisilazane for 500 hours.
Spin coating was performed for 30 seconds at rpm and then for 25 seconds at 2,000 rpm. As a result, a layer having a thickness of 1.1 μ was obtained. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) through a quartz mask at a radiation dose of 15 mJ / cm ² . After post-baking at 95 ° C. for 1 minute, development in an aqueous base for 60 seconds gave a high-resolution positive-working image.

Example 67 Copolymer of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylbutyl carbonate / norbornene (polymer of Example 23) (number average molecular weight: 22,000) Was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 15 w / v%. Triarylsulfonium hexafluoroantimonate (Saltomer CD1010, a 50% solution in propylene carbonate) was added at a loading of 5% w / w based on the polymer.
The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer primed with hexamethyldisilazane for 500 hours.
Spin coating was performed for 30 seconds at rpm and then for 25 seconds at 2,000 rpm. As a result, a layer having a thickness of 1.0 μ was obtained. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) through a quartz mask at a radiation dose of 30 mJ / cm ² . After post-baking at 125 ° C. for 0.5 minutes, a high-resolution positive-working image was obtained by developing in an aqueous base for 60 seconds.

Example 68 Co-polymer of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylbutyl carbonate / norbornene (polymer of Example 23) (number average molecular weight: 22,000) Was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 15 w / v%. Triarylsulfonium hexafluoroantimonate (Saltomer CD1010, a 50% solution in propylene carbonate) was added at a loading of 5% w / w based on the polymer.
The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was placed on a silicon wafer primed with hexamethyldisilazane for 500 hours.
Spin coating was performed for 30 seconds at rpm and then for 25 seconds at 2,000 rpm. As a result, a layer having a thickness of 1.0 μ was obtained. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) through a quartz mask at a radiation dose of 30 mJ / cm ² . After post-baking at 150 ° C. for 0.5 minutes, a high-resolution positive image was obtained by developing in an aqueous base for 60 seconds.

Example 69 35/65 mol% hydrogenated copolymer of ethyl ester of tetracyclodecene / t-butyl ester of norbornene obtained via ring-opening metathesis polymerization (Example 3
Polymer 7) (number average molecular weight: 23,000) was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 15 w / v%. Triarylsulfonium hexafluoroantimonate (Saltomer CD101
0, 50% solution in propylene carbonate) with 5% w / w based on the polymer
Was added in the amount added. The obtained resist film was filtered through a 0.2 μm Teflon (registered trademark) filter, and the filtrate was spin-coated on a silicon wafer primed with hexamethyldisilazane at 500 rpm for 30 seconds and then at 2,000 rpm for 25 seconds. did. This resulted in a 1.1 μ thick layer. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) at a radiation dose of 30 mJ / cm ² through a quartz mask. After post-baking at 125 ° C. for 1.0 minute, development in an aqueous base for 30 seconds gave a high-resolution positive-working image.

Example 70 50/50 mol% non-hydrogenated copolymer of ethyl ester of tetracyclodecene / t-butyl ester of norbornene obtained via ring-opening metathesis polymerization (polymer of Example 39) (number average molecular weight : 34,000) was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 15 w / v%.
Triarylsulfonium hexafluoroantimonate (Saltomer CD10
10, 50% solution in propylene carbonate) to the polymer at 5 w / w
%. The obtained resist film was filtered with a 0.2 μm Teflon (registered trademark) filter, and the filtrate was spin-coated on a silicon wafer primed with hexamethyldisilazane at 500 rpm for 30 seconds and then at 2,000 rpm for 25 seconds. . This resulted in a 1.25 μ thick layer. After baking the coating on a hot plate at 95 ° C. for 1 minute, it was exposed to ultraviolet radiation (240 nm) at a radiation dose of 50 mJ / cm ² through a quartz mask. After post-baking at 150 ° C. for 30 seconds, development was carried out in an aqueous base for 60 seconds to obtain a high-resolution positive-working image.

Example 71 Bicyclo [2.2.1] hept-5-en-2-methylethyloxalate (8.57 g) was placed in a 50 ml glass bottle equipped with a Teflon-coated stir bar. , 0.0382 mol), t-butyl ester of norbornene (7.42 g, 0
.0392 mol) and 38 ml of toluene. A solution of a nickel catalyst [toluene complex of bis-perfluorophenylnickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] was prepared using 0.1854 g (0.382 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 5 ml. Prepared in a dry box by dissolving in toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature. The reaction was carried out at room temperature under stirring for 5 hours. The resulting solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone, and dried under vacuum overnight. The isolated yield of the polymer was 7.62 g (48%). The molecular weight of the polymer was characterized using GPC. Mn = 28,000 and Mw = 56,000. NMR analysis of the copolymer indicated that the composition of the copolymer was very close to the charge ratio. IR analysis of the copolymer indicated that no acid groups were present.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AU, AZ, BA, BB, BG, BR, BY, CA, CN, CZ, EE, GE, HU, ID, IL, IS, JP, KE, KG, KR, KZ, LC, LK, LR, LS, LT, LV, MD, MG, MK, MN , MW, MX, NO, NZ, PL, RO, RU, SD, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW Cycmar Jayalaman United States 44087 Two Ingsberg, Darrow Park Drive 9931, Apartment 211 M (72) Inventor Robert A. Chic United States 44136 Ohio Strongsville, Pamela Drive 10375 (72) Inventor Larry F. Rhodes United States 44224 Ohio Silva Lake, Vincent Road 3036 (72) Inventor Robert David Allen United States 95120 San Jose, California Calle del Connejo 6186 (72) Inventor Richard Anthony di Pietro United States of America California 95120 San Jose , Mount Holly Drive 6682 (72) Inventor Thomas Warrow United States 94587 California, Union City, Royal Anne Drive 2656 F-term (reference) 2H025 AA02 AA09 AB16 AC08 AD01 AD03 AD07 BE00 BE10 BG00 BJ10 CB08 CB41 CC20 4J011 QA03 QA34 RA10 RA11 SA84 SA87 TA07 UA01 UA04 WA01 4J032 CA34 CA43 CA45 CC03 CD02 CD08 4J100 AK32Q AK32R AR09P AR09Q BA04P BA04Q BA10P BA10Q BA12P BA12Q BA16P BA16Q BA20P BA20P CA03 BC03 BC03 BC03 BC03 BC03 BC03 BC03 BC03

Claims (30)

[Claims] 1. A photoacid initiator, an optional dissolution inhibitor, and at least two types of polycyclic repeating units, wherein one of the repeating units has an acid labile pendant group and the other is a pendant polar functional group. A photoresist composition comprising a copolymer having a group, wherein the repeating unit having the polar functional group has the following structure: Here, R ⁵ to R ⁸ are each independently hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, and a — (A) _n —C (O) OR ″ group, — (A) _n -OR '' group,-
(A) _n- OC (O) R "group,-(A) _n- OC (O) OR" group,-(A) _n- C (O) R "group,-(A) _n- An OC (O) C (O) OR ″ group, — (A) _n −
OA'-C (O) OR "group,-(A) _n- OC (O) -A'-C (O) OR" group,-(A) _n -C (O) OA A '-C (O) OR''group,-(A) _n -C (
O) -A'-OR "group,-(A) _n- C (O) O-A'-OC (O) OR" group,-(A) _n- C (O) OA'- OA'-C (O) OR "group,-(A) _n- C (O) OA'-OC (O) C (O) OR" group,-(A) _n- C ( R ″) ₂ CH (R ″) (C (O) OR ″) group and — (A) _n —C (R ″) ₂ CH (C (O) OR ″) ₂ group Represents a substituent selected from the group consisting of polar substituents, wherein n is 0 or 1, p is an integer between 0 and 5, and -A- and -A'- are each Linear and branched (C ₁ -C ₁₀ ) alkylene, (C ₂ -C ₁₀ ) alkylene ether, polyether, cyclic ether, cyclic diether or cyclic group represented by the following formula: ] Where a is an integer between 2 and 7 and R ″ is hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, linear and branched (C ₁ -C ₁₀₎ ) alkoxyalkylene, polyethers, monocyclic and polycyclic (C ₄ -C ₂₀₎ cycloaliphatic moieties, cyclic ether, cyclic diethers, cyclic ketones, and from the group consisting of cyclic esters (lactones) Represents a divalent radical selected, wherein R '' is alkyl, lactone,
When a cycloaliphatic or cyclic ketone, the -A- group must be present and cannot represent an alkylene radical, and is polymerized from a monomer represented by Resist composition. 2. The polymer has the following structure:Where R¹To R^FourIs independently hydrogen, linear or branched (C₁~ C_Ten) Alkyl,-(A)_nC (O) OR^*,-(A)_nC (O) OR,-(A)_n-OR,-(A)_n-OC (O) R,-(A)_n-C (O) R,-(A)_n-OC (O) OR,-(A)_n-OCH_TwoC (O) OR^*,-(A)_n-C (O) O-A'-OCH_TwoC (O) O
R^*,-(A)_n-OC (O) -A'-C (O) OR^*,-(A)_n-C (R)_TwoCH (R) (C (O) OR^**), And-(A)_n-C (R)_TwoCH (C (O) OR^**)_Two Represents a substituent selected from the group consisting of: wherein n is 0 or 1, and m is 0 to 5.
And -A- and -A'- are each independently a linear or branched (C₁~ C_Ten) Alkylene, (C_Two~ C_Ten) Alkylene ethers, polyethers, or cyclic groups represented by the following formula:Where a is an integer between 2 and 7 and R is hydrogen or linear and branched (C ₁ ~ C_Ten) Alkyl, and R^*Is cleavable by a photoacid initiator and -C (CH _Three )_Three, -Si (CH_Three)_Three, -CH (R^p) OCH_TwoCH_Three, -CH (R^p) OC (C
H_Three)_ThreeOr the following cyclic group:Where R^pIs hydrogen or linear or branched (C₁~ C_Five) Represents an alkyl group,^{* *} Is independently R and R^*And R¹To R^FourAt least one of the acids is
Acid labile selected from the group consisting of substituents containing labile groups
Represents a group polymerized from at least one acid labile group-substituted polycyclic monomer represented by
The composition of claim 1, wherein 3. The polycyclic polymer has the following structural formula:Where R⁹To R¹⁶Is independently hydrogen and linear and branched (C₁~ C _Ten ) Represents alkyl, provided that R⁹To R¹²At least one of the structural formulas:-(CH_Two) _n Shall represent a carboxylic acid substituent represented by C (O) OH, wherein n is an integer between 0 and 10 and q and r are integers between 0 and 5;
3. The composition of claim 2, comprising a repeating unit polymerized from one or more monomers represented.
Composition. 4. The monomer is polymerized by ring-opening polymerization to obtain a ring-opened polymer.
A composition according to claim 1, 2 or 3. 5. The composition of claim 4, wherein said ring-opening polymer is hydrogenated. 6. The method of claim 2, wherein said monomer is polymerized by free radical polymerization.
Composition. 7. The polymer of the following formula: The composition according to claim 1, 2 or 3, wherein the definitions of R ¹ to R ⁸ , m and p are as described above. 8. The polymer of the following formula: Defined here from R ⁹ in R ¹⁶ are as defined above, further comprising at least one repeating unit selected from groups represented by the composition of claim 7. 9. The polymer of claim 1, wherein the polymer has the following structural formula: Here, R ¹ to R ⁴ are each independently hydrogen, linear or branched (C ₁ -C ₁₀ ) alkyl,-(A) _n C (O) OR ^* ,-(A) _n C (O ) OR,-(A) _n -OR,-(A) _n -OC (O) R,-(A) _n -C (O) R,-(A) _n -OC (O) OR,-(A ) _N -OCH ₂ C (O) OR ^* ,-(A) _n -C (O) OA-OCH ₂ C (O) O
_{^{R *, - (A) n}} -OC (O) -A'-C (O) OR *, - (A) n -C (R) 2 CH (R) (C (O) OR **), and -(A) _n -C (R) ₂ CH (C (O) OR ^** ) ₂ represents a substituent selected from the group consisting of: and R ⁵ to R ⁸ are each independently:
Represents a substituent selected from the group consisting of hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, and wherein at least one of R ⁵ to R ⁸ is — (A) _n —C (O ) OR "" group,-(A) _n- OR "group,-(A) _n- OC (O) R" group,-(A) _n -OC (O) OR "group,-(A ) _N —C (O) R ″ group, — (A) _n —OC (O)
C (O) OR "group,-(A) _n -OA'-C (O) OR" group,-(A) _n-
OC (O) -A'-C ( O) OR '' _{group, - (A) n -C (} O) O-A'-C (O) OR '' _{group, - (A) n -C (} O ) -A′-OR ″ group, — (A) _n —C (O
) OA'-OC (O) OR "group,-(A) _n- C (O) OA'-OA'-C (O) OR" group,-(A) _n- C (O) O-A'- OC (O) C (O) O R '' _{groups, - (A) n -C (} R '') 2 CH (R '') (C (O) OR '' ) Group,
And _{- (A) n -C (R} '') 2 CH (C (O) OR '') must be represented Ru polar substituent by ₂ group; each -A- and -A'- is a straight Linear and branched (C ₁ -C ₁₀ ) alkylene, (C ₂ -C ₁₀ ) alkylene ethers, polyethers, cyclic ethers, cyclic diethers or the following formulas: Wherein a is an integer between 2 and 7, n is each 0 or 1, m and p are each independently an integer between 0 and 5, and R is hydrogen or linear or A chain (C ₁ -C ₁₀ ) alkyl, wherein R ^* is —C (CH ₃ ) ₃ , —Si (CH ₃ ) ₃ , —C
H (R ^p ) OCH ₂ CH ₃ , —CH (R ^p ) OC (CH ₃ ) ₃ , or the following cyclic group: Wherein at least one of the R ^p represents hydrogen or a linear or branched chain (C ₁ ~C ₅₎ alkyl group, R ^{* *} each represents R and R ^*, and among the R ¹ of R ⁴ Is essential to be selected from substituents containing the acid labile group, and R ″ is hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, linear and branched (C ₁ -C ₁₀ ) alkoxyalkylenes, selected from polyethers, monocyclic and polycyclic (C ₄ -C ₂₀ ) alicyclic moieties, cyclic ethers, cyclic ketones, and cyclic esters (lactones) Where R '' is an alkyl, lactone, cycloaliphatic or cyclic ketone, the --A-- group must be present and cannot represent an alkylene radical; Acid cleavable by a photoacid initiator selected from the group consisting of Represents a stable group, a ring-opening polymer comprising repeating units represented by represents a divalent radical selected from the group consisting of The composition of claim 1 10. The ring-opened polymer has the following structural formula:Where R⁹To R¹⁶Is independently hydrogen and linear and branched (C₁~ C _Ten ) Represents alkyl, provided that R⁹To R¹²At least one of the structural formulas:-(CH_Two) _n Shall represent a carboxylic acid substituent represented by C (O) OH, wherein n is an integer between 0 and 10, and q and r are independently integers between 0 and 5,
Further contains at least one repeating unit selected from the groups represented by
The composition of claim 9. 11. The copolymer of claim 1, wherein the copolymer has the following structural formula: Wherein R ^* is _{-C (CH 3) 3, -Si} (CH 3) 3, 1- methyl-1 key sill cyclohexane, isobornyl, 2-methyl-2-methyl-2-adamantyl, Group consisting of tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanonyl, lactonyl mevalonate, 1-ethoxyethyl, 1-tert-butoxyethyl, dicyclopropylmethyl (Dcpm) group and dimethylcyclopropylmethyl (Dmcp) group And R '' is selected from linear and branched (C ₁ -C ₁₀ ) alkyl, consisting of a repeating unit represented by: The composition of claim 9. 12. R ¹ to R ³ and R ⁵ to R ⁷ are hydrogen or linear or branched (C ₁ -C ₁₀ ) alkyl, and R ″ is linear or branched ( C _1-
C ₁₀₎ alkyl The composition of claim 11. 13. The ring-opened polymer has the following structural formula: Wherein m and p are each independently 0 or 1, n is 1, and A is an alkylene group having 1 to 10 carbon atoms. Composition. 14. The method of claim 13, wherein R ^* is t-butyl, A is a methylene group, and R ″ is selected from linear or branched (C ₁ -C ₅ ) alkyl.
Composition. 15. The polymer of claim 9, 10, 11, 12, 13, or 14, wherein the unsaturation in the backbone of the ring-opened polymer is hydrogenated. 16. The polymer of claim 15, wherein at least 90% of the unsaturation in the backbone of the ring-opened polymer is hydrogenated. 17. The polymer of claim 16, wherein substantially 100% of the unsaturation in the backbone of the ring-opened polymer is hydrogenated. 18. A photoacid initiator, an optional dissolution inhibitor, and the following structural formula: Here, R ¹ to R ⁴ are each independently hydrogen, linear or branched (C ₁ -C ₁₀ ) alkyl,-(A) _n C (O) OR ^* ,-(A) _n C (O ) OR,-(A) _n -OR,-(A) _n -OC (O) R,-(A) _n -C (O) R,-(A) _n -OC (O) OR,-(A ) _N -OCH ₂ C (O) OR ^* ,-(A) _n -C (O) OA-OCH ₂ C (O) O
_{^{R *, - (A) n}} -OC (O) -A'-C (O) OR *, - (A) n -C (R) 2 CH (R) (C (O) OR **), and -(A) _n -C (R) ₂ CH (C (O) OR ^** ) ₂ represents a substituent selected from the group consisting of: and R ⁵ to R ⁸ are each independently:
Represents a substituent selected from the group consisting of hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, and wherein at least one of R ⁵ to R ⁸ is — (A) _n —C (O ) OR "" group,-(A) _n- OR "group,-(A) _n- OC (O) R" group,-(A) _n -OC (O) OR "group,-(A ) _N —C (O) R ″ group, — (A) _n —OC (O)
C (O) OR "group,-(A) _n -OA'-C (O) OR" group,-(A) _n-
OC (O) -A'-C ( O) OR '' _{group, - (A) n -C (} O) O-A'-C (O) OR '' _{group, - (A) n -C (} O ) -A′-OR ″ group, — (A) _n —C (O
) OA'-OC (O) OR "group,-(A) _n- C (O) OA'-OA'-C (O) OR" group,-(A) _n- C (O) O-A'- OC (O) C (O) O R '' _{groups, - (A) n -C (} R '') 2 CH (R '') (C (O) OR '' ) Group,
And _{- (A) n -C (R} '') 2 CH (C (O) OR '') is selected from a polar substituent you express by ₂ group it is essential; -A- and -A ' Each independently represents a linear or branched (C ₁ -C ₁₀ ) alkylene, (C ₂ -C ₁₀ ) alkylene ether, polyether, cyclic ether, cyclic diether or a ring represented by the following formula: Formula group: Here, a is an integer between 2 and 7, n is independently 0 or 1, and m
And p are each independently an integer between 0 and 5, R represents hydrogen or linear and branched (C ₁ -C ₁₀ ) alkyl, R ^* represents —C (CH ₃ ) ₃ , -Si (C
H ₃ ) ₃ , —CH (R ^p ) OCH ₂ CH ₃ , —CH (R ^p ) OC (CH ₃ ) ₃ , or the following cyclic group: Wherein R ^p represents hydrogen or a linear or branched chain (C ₁ ~C ₅₎ alkyl group, R ^{* *} are independently represents R and R ^*, and of from R ¹ to R ⁴ At least one must be selected from substituents containing the acid labile group, and R '
'Is hydrogen, linear and branched (C ₁ -C ₁₀ ) alkyl, linear and branched (C ₁ -C ₁₀ ) alkoxyalkylene, polyether, monocyclic and polycyclic (C ₄ ~
C ₂₀ ) represents a substituent selected from an alicyclic moiety, a cyclic ether, a cyclic ketone, and a cyclic ester (lactone), wherein R ″ is an alkyl, lactone, alicyclic or cyclic ketone Wherein the -A- group must be present and cannot represent an alkylene radical; represents an acid labile group cleavable by a photoacid initiator selected from the group consisting of: A copolymer comprising a polycyclic repeating unit represented by the following formula: wherein the divalent radical is selected from the group consisting of: 19. The copolymer has the following structural formula: Here, R ⁹ to R ¹⁶ represent hydrogen and linear and branched (C ₁ -C ₁₀ ) alkyl, respectively, provided that at least one of R ⁹ to R ¹² has the structural formula: — (CH ₂ ) _n C ( O 2) shall represent the carboxylic acid substituent represented by OH, wherein n is an integer between 0 and 10 and q and r are independently integers between 0 and 5 20. The composition of claim 18, further comprising at least one repeating unit selected from the group consisting of: 20. The copolymer of claim 1, wherein the copolymer has the following structural formula: Wherein R ^* is _{-C (CH 3) 3, -Si} (CH 3) 3, 1- methyl-1 key sill cyclohexane, isobornyl, 2-methyl-2-methyl-2-adamantyl, Group consisting of tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanonyl, lactonyl mevalonate, 1-ethoxyethyl, 1-tert-butoxyethyl, dicyclopropylmethyl (Dcpm) group and dimethylcyclopropylmethyl (Dmcp) group And R '' is selected from linear and branched (C ₁ -C ₁₀ ) alkyl, consisting of a repeating unit represented by: 19. The composition of claim 18. 21. R ¹ to R ³ and R ⁵ to R ⁷ are hydrogen or linear or branched (C ₁ -C ₁₀ ) alkyl and R ″ is linear or branched (C ₁ -C ₁₀ ) alkyl. C _1-
C ₁₀₎ alkyl The composition of claim 20. 22. The copolymer of claim 1, wherein the copolymer has the following structural formula: Wherein m and p are each independently 0 or 1, n is 1, and A is an alkylene group having 1 to 10 carbon atoms. Composition. 23. The method of claim 22, wherein R ^* is t-butyl, A is a methylene group, and R ″ is selected from linear or branched (C ₁ -C ₅ ) alkyl.
Composition. 24. The polymer according to claim 1, wherein the polymer contains 5 to 1 repeating units containing the acid labile group.
1, 2, 3, 5, 11, 12, 13, 14,
15. The composition of 15, 16, 17, 18, 19, 20 or 21. 25. The polymer according to claim 20, wherein the repeating unit containing the acid labile group is 20 to 20.
25. The composition of claim 24, containing in an amount of 90 mol%. 26. The polymer, wherein the repeating unit containing the acid labile group is 30 to
26. The composition of claim 25, containing in an amount of 70 mol%. 27. The polymer comprises 5 to 1 repeating units containing the acid labile group.
26. The composition of claim 25, containing in an amount of 00 mol%. 28. The polymer of claim 7, 8, 18, 19, 20, 2 wherein the polymer has a perfluorophenyl pendant group on at least one of its terminal groups.
1, 22, or 23 polymers. 29. The polymer of claim 1, 2, or 3, wherein said polycyclic polymer comprises repeat units polymerized from maleic anhydride. 30. The polymer of the following formula: 7, 8, 18, 19, 20, 2 comprising a repeating unit represented by
1, 22, or 23 polymers.