JP4374999B2 - Cyclic olefin compound, method for producing the same, and radiation-sensitive resin composition - Google Patents

Description

  The present invention relates to a novel cyclic olefin compound, a method for producing the same, and a radiation-sensitive resin composition containing the cyclic olefin compound.

Cyclic olefin compounds such as norbornene and derivatives thereof, tetracyclododecene and derivatives thereof can be subjected to addition polymerization or ring-opening polymerization, and addition (co) polymers and ring-openings of such cyclic olefin compounds. (Co) polymers or hydrogenated products thereof are used as transparent resin materials or elastomer materials for various applications.
Conventionally, as a cyclic olefin compound, those in which various polar groups or functional groups are introduced as substituents are known. For example, Patent Document 1 and Patent Document 2 include as substituents ester groups such as alkoxy groups, hydroxyl groups, and methoxycarbonyl groups, amide groups, imide groups, sulfonyl groups, ketone groups, amino groups, sulfide groups, ether groups, Cyclic olefin compounds into which polar groups such as thiol groups and silyl groups are introduced are described.
However, a cyclic olefin compound having a carboxylic acid silyl ester residue introduced as a substituent is not known.

JP 2003-165828 A JP 2003-183360 A

  An object of the present invention is to provide a novel cyclic olefin compound having a carboxylic acid silyl ester residue, a method for producing the same, and a radiation-sensitive resin composition containing the cyclic olefin compound.

  The cyclic olefin compound of the present invention is represented by the following general formula (1).

[In General formula (1), R < ¹ >, R < ² >, R < ³ > and R < ⁴ > show a hydrogen atom, a halogen atom, or a C1-C20 hydrocarbon group each independently. ]

In the cyclic olefin compound of the present invention, in the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. preferable.
In the general formula (1), it is preferable that at least one of R ¹ , R ² and R ³ is a hydrocarbon group having 2 to 20 carbon atoms and R ⁴ is a methyl group.
In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are preferably methyl groups.

  The method for producing a cyclic olefin compound of the present invention comprises reacting a cyclic olefin compound represented by the following general formula (2) with a chlorosilane represented by the following general formula (3) to thereby produce the above general formula (1). It has the process of obtaining the cyclic olefin compound represented by these.

In [general formula (2), R ⁵ represents a periodic table Group 1 atom, R ⁴ represents a water atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]

[In General formula (3), R < ¹ >, R < ² > and R < ³ > show a hydrogen atom, a halogen atom, or a C1-C20 hydrocarbon group each independently. ]

  Moreover, the manufacturing method of the cyclic olefin compound of this invention makes the said general formula react by reacting the cyclic olefin compound represented by the said General formula (2), and the silylamine represented by following General formula (4). It has the process of obtaining the cyclic olefin compound represented by (1), It is characterized by the above-mentioned.

[In General Formula (4), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by the following General Formula (5); At least one of R ^{6 to} R ⁸ is a group represented by the following general formula (5). ]

[In General formula (5), R < ¹ >, R < ² > and R < ³ > show a hydrogen atom, a halogen atom, or a C1-C20 hydrocarbon group each independently. ]

  The radiation sensitive resin composition of this invention is characterized by containing said cyclic olefin compound.

ADVANTAGE OF THE INVENTION According to this invention, the novel cyclic olefin compound which has a carboxylic acid silyl ester residue , and its manufacturing method can be provided.
The cyclic olefin compound of the present invention is useful as an additive contained in the radiation-sensitive resin composition, and the cyclic olefin compound of the present invention is added (co) polymerized, ring-opened (co) polymerized, or ring-opened ( The (co) polymer obtained by hydrogenation after co) polymerization is useful as a resin material or an elastomer material for various applications, and further, the cyclic olefin compound of the present invention is reacted with a silane compound for silylation. The cyclic compound obtained by doing so is useful as a raw material for polysiloxane resins used for chemically amplified resists.

Hereinafter, embodiments of the present invention will be described in detail.
The cyclic olefin compound of the present invention is represented by the above general formula (1).
In the general formula (1) showing the structure of the cyclic olefin compound of the present invention, R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, preferably a hydrogen atom or a carbon number. Is a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms.
Here, specific examples of the halogen atom include chlorine, bromine and the like.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include aliphatic saturated hydrocarbon groups such as methyl group, ethyl group, and butyl group, alicyclic hydrocarbon groups such as cyclohexyl group, and vinyl groups. An aromatic hydrocarbon group such as an aliphatic unsaturated hydrocarbon group, a phenyl group, and a benzyl group can be exemplified.

As a specific example of the cyclic olefin compound of the present invention,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate t-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] n-butyldimethylsilyl dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid allyldichlorosilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid diallylchlorosilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate vinyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid chloromethyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid t-butylphenylchlorosilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate tribenzylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate dimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate t-butyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] n-butyldimethylsilyl dodeca-9-ene-4-carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid allyldichlorosilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid diallylchlorosilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate vinyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid chloromethyldimethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid t-butylphenylchlorosilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate tribenzylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate dimethylsilyl,
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate t-butyldimethylsilyl,
4-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid t-butyldimethylsilyl, 4-methoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-methoxytetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodec-9-ene-4-carboxylic acid t-butyldimethylsilyl.

As the cyclic olefin compound of the present invention, in the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. preferable.
In the general formula (1), it is preferable that at least one of R ¹ , R ² and R ³ is a hydrocarbon group having 2 to 20 carbon atoms and R ⁴ is a methyl group.
In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are preferably methyl groups.

As a specific example of a preferable cyclic olefin compound,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate t-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] n-butyldimethylsilyl dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate tribenzylsilyl,
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-ethyltetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodec-9-ene-4-carboxylic acid t-butyldimethylsilyl.
Among these, more preferred are
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate trimethylsilyl;
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate t-butyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] n-butyldimethylsilyl dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid cyclohexyldimethylsilyl,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate tribenzylsilyl;
Particularly preferred is 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate trimethylsilyl.

  The cyclic olefin compound of the present invention includes, for example, a cyclic olefin compound represented by the general formula (2), a chlorosilane represented by the general formula (3) and / or a silylamine represented by the general formula (4). Can be obtained by reacting in a suitable reaction solvent.

In general formula (2), R ⁴ is the same as R ⁴ in formula (1). R ⁵ represents an atom of Group 1 of the periodic table, and specific examples thereof include a hydrogen atom, a lithium atom, a sodium atom, and a potassium atom.

As a specific example of the cyclic olefin compound represented by the general formula (2),
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid,
4-methyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] lithium dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] sodium dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] potassium dodeca-9-ene-4-carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid,
Tetracyclo [6.2.1.1 ^3,6 . ^02,7 ] lithium dodeca-9-ene-4-carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] sodium dodeca-9-ene-4-carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] potassium dodeca-9-ene-4-carboxylate,
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid,
4-ethyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] lithium dodeca-9-ene-4-carboxylate,
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] sodium dodeca-9-ene-4-carboxylate,
4-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid,
4-chlorotetracyclo [6.2.1.1 ^3,6 . ^02,7 ] lithium dodeca-9-ene-4-carboxylate,
4-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] sodium dodeca-9-ene-4-carboxylate,
4-methoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid,
4-methoxytetracyclo [6.2.1.1 ^3,6 . ^02,7 ] lithium dodeca-9-ene-4-carboxylate,
4-methoxytetracyclo [6.2.1.1 ^3,6 . ^0,7 ] sodium dodeca-9-ene-4-carboxylate.

In the general formula (3), R ^1, R ² and R ³ are the same as R ^1, R ² and R ³ in the general formula (1).
Specific examples of the chlorosilanes represented by the general formula (3) include trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, n-butyldimethylchlorosilane, t-butyldiphenylchlorosilane, t-butylphenyldichlorosilane, dimethylchlorosilane. Dimethyldichlorosilane, diallyldichlorosilane, allyltrichlorosilane, vinyldimethylchlorosilane, tribenzylchlorosilane, hexyldimethylchlorosilane, tri-n-butylchlorosilane and the like.

In the general formula (4), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a group represented by the above general formula (5), At least one of R ⁶ , R ⁷ and R ⁸ is a group represented by the general formula (5). In the general formula (5), R ^1, R ² and R ³ are the same as R ^1, R ² and R ³ in the general formula (1).
Specific examples of the silylamines represented by the general formula (4) include hexamethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, N, N-dimethylaminotrimethylsilane, N, N-diethylamino. Examples thereof include trimethylsilane, nonamethyltrisilazane, 1,1,3,3-tetramethyldisilazane, and the like.

Specific examples of the reaction solvent include acetonitrile, N, N-dimethylformamide, hexane, tetrahydrofuran, toluene, pyridine, triethylamine and the like. These compounds can be used alone or in combination of two or more. Moreover, as a solvent, it is preferable to use what was dried by the appropriate method.
Moreover, as reaction conditions, reaction temperature is -50-150 degreeC normally, Preferably it is -10-50 degreeC, and reaction time is 0.1 to 24 hours normally.
Further, since the silyl esterification reaction is an equilibrium reaction, it is preferable to remove HCl, ammonia and the like by-produced during the reaction from the reaction system.
And after completion | finish of reaction, the cyclic olefin compound of this invention is obtained by concentrating a reaction liquid and refine | purifying by vacuum distillation etc.

The cyclic olefin compound of the present invention is a novel cyclic olefin compound having a carboxylic acid silyl ester residue, and the ester moiety in the carboxylic acid silyl ester residue is easily hydrolyzed with water or the like to be converted into a carboxyl group. This increases the affinity for the aqueous alkali solution. Various functional groups can be introduced into the olefin moiety in the cyclic olefin skeleton. For example, a cyclic compound having a silyl group can be obtained by reacting the cyclic olefin compound of the present invention with a silane compound for silylation, and such a cyclic compound is used in a chemically amplified resist. It is useful as a raw material for polysiloxane resins. Here, as a method for silylating a cyclic olefin compound, a method described in JP-A-2002-105086 can be used. Moreover, the cyclic olefin compound of this invention is useful as an additive contained in a radiation sensitive resin composition so that it may mention later.
The (co) polymer obtained by hydrogenating the cyclic olefin compound of the present invention after addition (co) polymerization, ring-opening (co) polymerization, or ring-opening (co) polymerization is a resin for various uses. Useful as a material or elastomeric material.

The radiation sensitive resin composition of this invention contains the cyclic olefin compound represented by the said General formula (1), and components other than the cyclic olefin compound represented by the said General formula (1) are contained. However, it is not particularly limited, and components in a conventionally known radiation-sensitive resin composition can be used.
As an example of this radiation-sensitive resin composition, component A: an alkali-insoluble or hardly alkali-soluble resin that becomes alkali-soluble by the action of an acid, and component B: an acid generator that generates an acid upon receiving radiation, C component: Cyclic olefin compound represented by the general formula (1) and D component: solvent are included, and a chemically amplified radiation sensitive resin composition can be exemplified.

In such a radiation sensitive resin composition, the resin used for the component A includes a structural unit represented by the following general formula (i), a structural unit represented by the following general formula (ii), and the following general Examples thereof include a copolymer resin containing a structural unit represented by the formula (iii).
Moreover, as an acid generator used for B component, the compound represented by the following general formula (iv) can be mentioned.

[In the general formula (i) ~ formula (iii), R ¹¹ ~R ¹³ independently of one another, a hydrogen atom or a methyl group, R ¹⁴ is a straight-chain or branched having 1 to 6 carbon atoms -Like alkyl group. ]

[In the general formula (iv), R ¹⁵ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkoxyl group having 1 to 10 carbon atoms. Or a C2-C11 linear or branched alkoxycarbonyl group is shown. R ¹⁶ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and j is an integer of 0 to 3. Each R ¹⁷ independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group. Two R ^{17 's} may be bonded to each other to form a substituted or unsubstituted divalent group having 2 to 10 carbon atoms. k shows the integer of 0-2. X ⁻ represents an anion having a structure of C _n F _{2n + 1} SO ₃ ^— . ]

Specific examples of the alkyl group represented by R ¹⁴ in the structural unit represented by the general formula (i) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group and the like. Among these, a methyl group, an ethyl group and the like are preferable.

Such a copolymer resin preferably has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of 3,000 to 30,000, more preferably 5,000 to 30,000, Preferably it is 5,000-20,000. When this weight average molecular weight (Mw) is less than 3,000, the resulting resist film tends to have low heat resistance. On the other hand, when this weight average molecular weight (Mw) exceeds 30,000, the developability of the resulting resist film tends to be low.
Moreover, the ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) to the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is usually 1 to 5, preferably 1 to 3.

Preferred specific examples of the compound represented by the general formula (iv) used for the component B include triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, 1- (3,5 -Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4 -N-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate It is done.
From the viewpoint of sensitivity and developability of the resulting radiation-sensitive resin composition, the proportion of component B used is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts by weight of component A. Part. When this ratio is less than 0.1 part by weight, the sensitivity and developability of the radiation sensitive resin composition may be low. On the other hand, when this ratio exceeds 20 parts by weight, the radiation-sensitive resin composition has low permeability to radiation, and thus it may be difficult to obtain a rectangular resist pattern.

The cyclic olefin compound represented by the general formula (1), which is a component C, is contained to improve resistance to dry etching, the shape of a resist pattern, adhesion to a substrate, and the like.
The proportion of component C used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of component A.

The solvent used for component D is preferably one containing at least one compound selected from the group of propylene glycol monomethyl ether acetate, 2-heptanone and cyclohexanone.
The amount of the solvent used as component D is such that the total solid content in the composition is usually 5 to 50% by weight, preferably 10 to 25% by weight, more preferably 10 to 20% by weight. Is the amount.

In such a radiation sensitive resin composition, in addition to the above A component, B component, C component and D component, if necessary, an acid diffusion controller, an alicyclic additive having an acid dissociable group, Various additives such as a surfactant and a sensitizer can be contained.
The acid diffusion controlling agent is a component having an action of suppressing an acid generated from the acid generator by radiation from diffusing into the resist film and suppressing an undesirable chemical reaction in a non-exposed region of the resist film. By containing such an acid diffusion control agent, the storage stability of the resulting radiation-sensitive resin composition is improved, the resolution as a resist is further improved, and after the exposure process after the exposure process is completed. Changes in the line width of the resist pattern due to fluctuations in the holding time (PED) until the heat treatment to be performed can be suppressed, and a composition having excellent process stability can be obtained.
As the acid diffusion control agent, it is preferable to use a nitrogen-containing organic compound from the viewpoint that the basicity does not change by exposure treatment or heat treatment.
Examples of such nitrogen-containing organic compounds include amines, diamines, polyamino compounds or polymers having 3 or more nitrogen atoms, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like. Then, amines, amide group-containing compounds, nitrogen-containing heterocyclic compounds and the like are preferable.

In such a radiation sensitive resin composition, the acid dissociable group in the resin is dissociated to generate a carboxyl group by the action of the acid generated from the acid generator by receiving the radiation, so that the exposed region of the resist film The solubility in an alkaline developer becomes higher, and the exposed area is dissolved and removed by the alkaline developer, whereby a positive resist pattern is obtained.
An example of a resist pattern forming method is as follows.
A radiation-sensitive resin composition is applied on a substrate on which a resist pattern is to be formed by an appropriate application method such as a spin coating method, a casting coating method, or a roll coating method, and is necessary for the resulting resist film. In response to the heat treatment, an exposure treatment is performed. Here, the radiation used for the exposure process is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, etc., depending on the type of acid generator used. ArF excimer laser Far ultraviolet rays with a wavelength of 193 nm or a KrF excimer laser (wavelength of 248 nm) are preferably used.
Next, the exposed resist film is heated and then developed to form a positive resist pattern. Here, as the developer used for the development processing, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n- Propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An alkaline aqueous solution in which at least one alkaline compound such as diazabicyclo- [4.3.0] -5-nonene is dissolved can be preferably used.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
<Example 1>
In a 300 mL three-necked flask thoroughly purged with nitrogen, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid (15.0 g, 68.7 mmol), dry tetrahydrofuran (100 mL) and dry pyridine (5.98 g, 75.6 mmol) were added to the reaction system. Then, 8.21 g (75.6 mmol) of trimethylchlorosilane was slowly added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 5 hours. Next, the reaction solution was filtered, and the filtrate was concentrated. Then, 50 mL of n-hexane was added and stirred for 1 hour, and then the solution was filtered. Next, the filtrate was concentrated and purified by distillation under reduced pressure at 129 to 132 ° C. and 3 mmHg to obtain 7.2 g of a colorless liquid compound. This compound became a white solid at room temperature. When the obtained compound was analyzed, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl.
FIG. 1 shows an infrared absorption spectrum of the obtained compound, and FIG. 2 shows a ¹ H-NMR spectrum of the obtained compound.

<Example 2>
In a 300 mL three-necked flask thoroughly purged with nitrogen, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-9-ene-4-carboxylic acid lithium 15.4 g (68.7 mmol) and placed in dry tetrahydrofuran 150 mL, to the reaction system, trimethylchlorosilane 8.21g at 0 ° C. (75.6 mmol) Was slowly added dropwise, and the mixture was stirred at room temperature for 5 hours after completion of the addition. Then, after concentrating the reaction solution, 100 mL of n-hexane was added and filtered. Next, the filtrate was concentrated and purified by distillation under reduced pressure at 129 to 132 ° C. and 3 mmHg to obtain 6.8 g of a colorless liquid compound. This compound became a white solid at room temperature. When the obtained compound was analyzed, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl.

<Example 3>
In a 300 mL three-necked flask thoroughly purged with nitrogen, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-9-ene-4-carboxylic acid 32.8 g (150 mmol), placed in dry tetrahydrofuran 200mL and dry pyridine 13.1 g (165 mmol), to the reaction system, triethylchlorosilane 24 at a temperature 0 ℃ .9 g (165 mmol) was slowly added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 5 hours. Next, the reaction solution was filtered, and the filtrate was concentrated. Then, 50 mL of n-hexane was added and stirred for 1 hour, and then the solution was filtered. Next, the filtrate was concentrated and purified by distillation under reduced pressure under conditions of 143 to 147 ° C. and 1.5 mmHg to obtain 22.1 g of a colorless liquid compound. When the obtained compound was analyzed, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate triethylsilyl.
FIG. 3 shows an infrared absorption spectrum of the obtained compound.

<Example 4>
In a 300 mL three-necked flask thoroughly purged with nitrogen, 4-methyltetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] 30.6 g (140 mmol) of dodeca-9-ene-4-carboxylic acid and 180 mL of dry tetrahydrofuran were added to this reaction system, and t-butyldimethyl having a concentration of 1.44 mol / L at a temperature of 0 ° C. A tetrahydrofuran solution of 100 mL of chlorosilane (144 mmol of t-butyldimethylchlorosilane) was slowly added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 5 hours. Next, the reaction solution was filtered, and the filtrate was concentrated. Then, 50 mL of n-hexane was added and stirred for 1 hour, and then the solution was filtered. Next, the filtrate was concentrated and purified by distillation under reduced pressure at 145 to 149 ° C. and 2.5 mmHg to obtain 31.2 g of a colorless liquid compound. This compound became a white solid at room temperature. When the obtained compound was analyzed, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid t-butyldimethylsilyl.
FIG. 4 shows an infrared absorption spectrum of the obtained compound, and FIG. 5 shows a ¹ H-NMR spectrum of the obtained compound.

<Example 5>
In a 300 mL three-necked flask thoroughly purged with nitrogen, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid 15.0 g (68.7 mmol), dry tetrahydrofuran 100 mL and dry pyridine 50 mL were added to the reaction system, and hexamethyldisilazane 6. 13 g (38.0 mmol) and trimethylchlorosilane 0.82 g (7.6 mmol) were slowly added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 1 hour. Subsequently, after concentrating the reaction liquid, it was further purified by distillation under reduced pressure at 129 to 132 ° C. and 3 mmHg to obtain 4.3 g of a colorless liquid compound. This compound became a white solid at room temperature. When the obtained compound was analyzed, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylate trimethylsilyl.

<Example 6>
As component A, 45.3 mol% of structural units derived from 2-methyl-2-adamantyl methacrylate, 25.1 mol% of structural units derived from 3-hydroxy-1-adamantyl methacrylate, and the following structural formula (I) 100 parts of a copolymer having a polystyrene-equivalent weight average molecular weight of 10,000 measured by a gel permeation chromatograph method, and a B component, 2 parts of phenylsulfonium nonafluoro-n-butanesulfonate, 0.22 part of 2-phenylbenzimidazole as an acid diffusion controller, and 4-methyltetracyclo [6.2 as obtained in Example 4 as a C component 1.1 ^3,6 . [0 ^2,7 ] 5 parts of t-butyldimethylsilyl dodeca-9-ene-4-carboxylate and 600 parts of 2-heptanone as D component, the above A component, B component, C component and acid diffusion The radiation sensitive resin composition of the present invention was prepared by dissolving the control agent in the component D.

<Application example 1>
As a substrate on which a resist film is to be formed, an antireflection film having a thickness of 82 nm is formed on the surface of a silicone wafer by an antireflection coating agent (trade name “ARC25”, manufactured by Brewer Science). The radiation-sensitive resin composition obtained in Example 6 was applied onto this substrate by spin coating, and heat-treated for 90 seconds on a 130 ° C. hot plate, resulting in a thickness of 0. A 4 μm resist film was formed. The resist film was subjected to an exposure process through a mask pattern by an ArF excimer laser exposure apparatus (lens numerical aperture 0.55, exposure wavelength 193 nm) manufactured by Nikon Corporation, and then on a 130 ° C. hot plate By using a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developer, developing at 23 ° C. for 1 minute, washing with water and drying, A positive resist pattern was formed on the substrate.

The cyclic olefin compound of the present invention is useful as an additive contained in the radiation-sensitive resin composition.
The (co) polymer obtained by hydrogenating the cyclic olefin compound of the present invention after addition (co) polymerization, ring-opening (co) polymerization, or ring-opening (co) polymerization is a resin for various uses. Useful as a material or elastomeric material.
The cyclic compound obtained by reacting the cyclic olefin compound of the present invention with a silane compound and silylating it is useful as a raw material for polysiloxane resins used for chemically amplified resists.

2 is a graph showing an infrared absorption spectrum of the compound obtained in Example 1. FIG. 1 is a diagram showing a ¹ H-NMR spectrum of a compound obtained in Example 1. FIG. 2 is a graph showing an infrared absorption spectrum of the compound obtained in Example 3. FIG. 6 is a graph showing an infrared absorption spectrum of the compound obtained in Example 4. FIG. 4 is a diagram showing a ¹ H-NMR spectrum of a compound obtained in Example 4. FIG.

Claims (7)

The cyclic olefin compound represented by following General formula (1).

[In General formula (1), R < ¹ >, R < ² >, R < ³ > and R < ⁴ > show a hydrogen atom, a halogen atom, or a C1-C20 hydrocarbon group each independently. However, compounds in which R ¹ , R ² and R ³ are methyl groups and R ⁴ is a hydrogen atom are excluded. ] In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Olefin compound. The general formula (1), wherein at least one of R ¹ , R ² and R ³ is a hydrocarbon group having 2 to 20 carbon atoms, and R ⁴ is a methyl group. The cyclic olefin compound described. The cyclic olefin compound according to claim ¹ , wherein in the general formula (1), R ¹ , R ² , R ³ and R ⁴ are methyl groups. It has the process of obtaining the cyclic olefin compound of Claim 1 by making the cyclic olefin compound shown by following General formula (2), and the chlorosilane represented by following General formula (3) react. A method for producing a cyclic olefin compound.

In [general formula (2), R ⁵ represents a periodic table Group 1 atom, R ⁴ represents a water atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]

[In General formula (3), R < ¹ >, R < ² > and R < ³ > show a hydrogen atom, a halogen atom, or a C1-C20 hydrocarbon group each independently. ] The cyclic olefin compound according to claim 1 is obtained by reacting the cyclic olefin compound represented by general formula (2) according to claim 5 with a silylamine represented by general formula (4) below. The manufacturing method of the cyclic olefin compound characterized by having a process.

[In General Formula (4), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by the following General Formula (5); At least one of R ^{6 to} R ⁸ is a group represented by the following general formula (5). ]

[In General formula (5), R < ¹ >, R < ² > and R < ³ > show a hydrogen atom, a halogen atom, or a C1-C20 hydrocarbon group each independently. ] A radiation-sensitive resin composition comprising the cyclic olefin compound according to any one of claims 1 to 4.