TW200910003A - Resist composition, resist protective film composition, and method for forming resist pattern - Google Patents

Abstract

Disclosed is a resist composition. Specifically disclosed is a resist composition containing a polymer (PA) having a repeating unit (A) which is formed by polymerizing a compound represented by the following formula: CF2=CFCF2C(X<A>)(C(O)OZ<A>)(CH2)naCR<A>=CHR<A>. (In the formula, X<A> represents a hydrogen atom, a cyano group or a group represented by the following formula: -C(O)OZ<A>; Z<A> represents a hydrogen atom or a monovalent organic group having 1-20 carbon atoms; na represents 0, 1 or 2; and R<A> represents a hydrogen atom or a monovalent organic group having 1-20 carbon atoms, and two R<A>'s may be the same as or different from each other.)

Description

200910003 IX. Description of the Invention [Technical Field] The present invention relates to a photoresist composition, a photoresist protective film composition, and a photoresist pattern forming method. [Prior Art] In the manufacture of an integrated circuit such as a semiconductor, a photosensitive photoresist layer that projects an exposure light source onto a mask to form a mask pattern onto a substrate is used to transfer the pattern to Photolithographic method of photosensitive photoresist layer. Usually, the projection of the image is performed by scanning. That is, the projection of the pattern image is performed by relatively moving the projection lens on the photosensitive resist layer to project the pattern image onto the photosensitive photoresist layer. The Applicant has proposed a cyclized polymer of a fluorodiene having a functional group as a polymer for photoresist. For example, the Applicant has proposed that 1,1,2-diox-4-indolyl-1,6-glyb as the aforementioned gas (cf2 = cfcf2ch(c(o)oc(ch3)3) ) ch2ch = ch2), etc. (refer to Patent Document 1). However, in recent years, the 'immersion lithography method' means that a high-refractive-index liquid medium (liquid medium such as ultrapure water) is filled between the lower portion of the projection lens and the upper portion of the photosensitive photoresist layer (hereinafter also referred to as liquid medium). The method of projecting the pattern image of the mask to the photosensitive photoresist layer through the projection lens for the immersion liquid is under investigation. In the immersion lithography method, since the immersion liquid is filled between the projection lens and the photosensitive photoresist layer, the components of the photosensitive photoresist layer (photoacid production-5-200910003, etc.) are eluted to the immersion. The photosensitive photoresist layer caused by the liquid is swollen by the immersion liquid. In order to solve this problem, there is a discussion on photoresist materials for immersion lithography. The photosensitive resist material for the immersion lithography method is a photoresist composition containing a copolymer of three kinds of compounds represented by the following formula and a fluorine-based surfactant (see Patent Document 2).

Ch2=c ^ch3 , c=o

Further, in the immersion lithography method, there is an attempt to suppress the dissolution and swelling of the photosensitive photoresist layer by providing a photoresist protective film layer on the photosensitive photoresist layer. As a material for a photoresist film for immersion lithography, there is a composition of an alkali-soluble polymer containing a repeating unit of a polymerizable compound having a polar group such as the following compound, and a composition of a fluorosurfactant. (refer to Patent Document 3). [Chemical 2] CH2=CHC(0)〇 c(cf3)2oh

C(CF3)2OH Further, as a photoresist film for immersion lithography, the polymer described in Patent No. 6-200910003 is: containing CF2 = CFCF2C(CF3)(ORg)CH2CH = a polymer of the following repeating unit (P 1 ) formed by cyclization polymerization of CH 2 (Rg is a hydrogen atom or an alkoxy group having 1 to 15 carbon atoms or an alkoxyalkyl group); and described in Patent Document 5 The polymer is a polymer having the following repeating unit (pi) formed by cyclization polymerization of cfch2chc(cf3)(oh)ch2ch = ch2. [Chemical 3]

Cf2 Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2005-234178. [Claim 4] Japanese Laid-Open Patent Publication No. 2007-072336. SUMMARY OF THE INVENTION The cyclized polymerizable fluorodiene having a functional group has been studied for various properties in order to improve the properties of the polymer. However, in practice, in order to make such a discussion practical, it is difficult to obtain raw material compounds, and thus it is difficult to perform. Regarding the fluorodiene having a carboxyl group-like rim group, the conventional ones are only 1,1,2-trifluoro-4-enoxycarbonyl-;,6-heptadiene described in Patent Document 200910003. Other compounds are not known. On the other hand, the photosensitive photoresist material for immersion lithography has a good followability of the immersion liquid for the projection lens moving over the photosensitive resist layer, and it is desired to have excellent dynamic liquid repellency. For example, in the case where the immersion liquid is water, the photosensitive photoresist material for lithography is immersed, and it is desired to have excellent dynamic water repellency. However, such photoresist materials are still not known. For example, the fluorine-based surfactant described in Patent Document 2 is only a polymer of a non-polymeric fluorine-containing compound and an acyclic fluorinated (meth)acrylic acid alkyl ester. Very low water. Therefore, in the immersion lithography method using the photosensitive photoresist material prepared by the above-mentioned photoresist composition, the immersion liquid sometimes has difficulty in following the projection lens which moves at a high speed. The photoresist film provided in the immersion lithography method is also expected to have excellent dynamic liquid repellency. However, such photoresist films are still not known. For example, the fluorine-based surfactant described in Patent Document 3 is only a polymer of a non-polymeric fluorine-containing compound and an acyclic fluorinated (meth)acrylic acid alkyl ester, and the photoresist film composition of Patent Document 3 The dynamic water repellency is very low. Further, the polymer 'described in Patent Document 4 or 5 does not have sufficient dynamic water repellency and developer solubility. Therefore, in the immersion lithography method using such a photoresist film material, it is sometimes difficult for the immersion liquid to follow the projection lens which is moved at a high speed through the photoresist film layer. 200910003 (Means for Solving the Problem) The present invention is proposed to provide a photoresist material which is excellent in characteristics of a photosensitive photoresist material or a photoresist film material and dynamic liquid repellency (especially dynamic water repellency). invention. That is, the present invention provides the following invention. &lt;1&gt; A photoresist composition containing a polymer (PA) having a repeating unit (A) formed of a polymer of a compound represented by the following formula (a), CF2 = CFCF2C (XA)(C(0)0ZA)(CH2)naCRA = CHRA (a) The symbol in the formula does not have the following meaning, xA: hydrogen atom 'cyano group or a group represented by formula c(o)ozA, ZA: hydrogen atom or carbon A monovalent organic group having an atomic number of 1 to 20, na: 0, 1 or 2, RA: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms' 2 RAs may be the same or different. &lt;2&gt; The photoresist composition of &lt;1&gt;, wherein the compound represented by the formula (a) is a compound represented by the following formula (al) or the following formula (a2), CF2 = CFCF2CH (C(0) 0ZA1)CH2CH = CH2 (") cf2 = cfcf2c(c(o)oza1)2ch2ch = ch2 (a2) 200910003 The symbol in the formula shows the following meaning, the base, the formula -CH2OZa

Z A 1 : a hydrogen atom, a group of the formula -c (z A I 1J or a group represented by the following formula).

a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 19 1 to 1 6 carbon atoms, a carbon atom of a divalent cyclic hydrocarbon group ZA11 and zA12: each independently a monovalent saturated hydrocarbon group, zA13: a hydrogen atom or a carbon atom QA13: a group having a number of 3 to 19 in common with carbon atoms in the formula. Wherein, ZAH, ZA12 or ZA13 which is a monovalent saturated hydrocarbon group, and a group which can be inserted between carbon atoms of carbon atoms in QA13, a group represented by the formula _c(〇)_ or a formula - c(0)0 - Further, the carbon atom in zA11, zA12, ZA13 or QA13 may be bonded to a fluorine atom, a trans group or a mercapto group. &lt;3&gt; The photoresist composition of &lt;1&gt; or &lt;2&gt;, which contains a polymer (pB) having: other than the repeating unit (A), by acid A repeating unit (B) that acts to increase alkali solubility. &lt;4&gt; The photoresist composition of &lt;3&gt;, wherein the polymer (PB) system has the following formula (kbl), the following formula (kb2), the following formula (kb3) or the following formula (kb4) The polymer (b) of the group shown is polymerized to obtain a polymer' -10- 200910003

!b2 (kb2) [C5], C=0 ΧΌ (kb1) xB2-c-ΧΒ2 -CiCFaJaiOz®) (kb3) —C(CF3)(OZb)—(kb4) where the symbol indicates the following meaning, XB1 : an alkyl group having 1 to 6 carbon atoms, QB1: a valence group having 3 to 18 carbon atoms and a carbon atom having 1 to 17 carbon atoms together with a carbon atom in the formula; Wherein 3 XB2 may be the same or different, and zB: each independently 'alkyl, alkoxyalkyl, alkoxycarbonyl or alkylcarbonyl or a hydrogen atom' wherein the above group is a group having 1 to 20 carbon atoms or hydrogen atom. Further, a group represented by the formula may be inserted between XB1, QB1, XB2 or a carbon atom-carbon atom, a group represented by the formula -c(0)0- or a group represented by the formula -c(0)-, at χΒ1, QB1 The carbon atom in XB2 or zB may bond a fluorine atom, a hydroxyl group or a carboxyl group. A photoresist composition according to <3> or <4>, wherein the polymerizable compound (b) is a compound represented by the following formula (bl), the following formula (b2) or the following formula (b3), -11 - 200910003

Ch2=c, , c=o cf2=cf—qB3-ch=ch2

XB2_C—X82 XM (b2) (b3) The symbol in the formula indicates the following meaning, RB: hydrogen atom, fluorine atom, alkyl group having 1 to 3 carbon atoms or fluoroalkyl group having 1 to 3 carbon atoms, XB1: carbon An alkyl group having an atomic number of 1 to 6, QB1: a valence group having 3 to 18 carbon atoms and a carbon atom number of 1 to 17 together with a carbon atom of the formula, XB2: an alkyl group having 1 to 17 carbon atoms, and 3 XB groups 2 may be the same or different, QB3: with the formula -CF2C(CF3)(OZB)(CH2)nb-, or the formula -CH2CH((CH2)mbC(CF3)2(〇ZB))(CH2)nb- An alkyl group, an alkyloxyalkyl group, an alkoxycarbonyl group or an alkylcarbonyl group or a hydrogen atom, wherein the above group is a group having 1 to 2 carbon atoms or a hydrogen atom, and mb and nb are each independently represented. , 1 or 2, wherein a carbon atom-carbon atom of XB1, QB1, χΒ2 or ZB may be inserted between -0-, -C(0)〇- or -C(O)-, and further, at XB1, QB1 The carbon atom of XB2 or ZB may bond a fluorine atom, a hydroxyl group or a carboxyl group. The photoresist composition according to any one of <3> to <5>, wherein the polymer (ρΑ) 〇.1 to 30 mass is contained with respect to 100 parts by mass of the layered material (PB). </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Repeat unit (F) 'The repeat unit (F) is a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. &lt;8&gt; The photoresist composition of <7>, wherein the polymerizable compound (1) is represented by the following formula (Π), the following formula (f2), the following formula (f3), the following formula (f4) or the following formula (f5) Compound shown, [Chem. 7]

The symbol in the formula indicates the following meaning, RF: a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms, and a fluorine atom in the compound (Π) to (f5). It may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. The photoresist composition according to any one of <1> to <8>, which comprises a photoacid generator and an organic solvent. &lt; 1 0&gt; - a method for forming a photoresist pattern, which is a method for forming a photoresist pattern caused by immersion lithography, which is carried out in order, and is resistant to light-13-200910003 as in &lt;9&gt; The composition is coated on the substrate to form a photoresist film on the substrate, and the lithography step and the development step are immersed to form a photoresist pattern on the substrate. &lt;1 1&gt; A photoresist protective film composition containing a polymer (PA) having a repeating unit (A) formed by polymerization of a compound represented by the following formula (a), CF2 = CFCF2C(XA)(C(0)0ZA)(CH2)naCRA = CHRA (a) The symbol in the formula indicates the following meaning, xA: hydrogen atom, cyano group or group represented by formula -c(〇)ozA, ZA: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, na: 0, 1 or 2,

RA: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the two RAs may be the same or different. <12> The photoresist protective film composition according to <11>, wherein the compound represented by the formula (A) is a compound represented by the following (a 1) or (a 2), CF2 = CFCF2CH (C (0) ) 0Za1)CH2CH = CH2 (al) CF2 = CFCF2C(C(0)0ZA1)2CH2CH = CH2 (a2) The symbol in the formula indicates the following meaning, ZA1: hydrogen atom, formula -C (base group of ZA11h, formula - The base shown by CH20Za12, or the base shown by the following formula, -14- 200910003 [Chem. 8]

And each of them is independently a hydrogen atom or a carbon atom, and a monovalent saturated hydrocarbon group of 19, a chlorine atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms, Q, and a carbon atom in the formula form a divalent ring type. a hydrocarbon group having a carbon atom number of 3 to 19, wherein 'is a monovalent saturated hydrocarbon group of zA11, zA12s zA13, and a carbon atom in Q 13 may be inserted between the carbon atoms and the formula _c(0) Further, the carbon atom in zA11, ZA12, ZA13 or Qa13 may have a fluorine atom, a hydroxyl group or a carboxyl group. &lt;13&gt; The photoresist protective film composition of &lt;11&gt; or &lt;12&gt;, wherein the polymer (PA) further has a polymer (paF) having a repeating unit (F) The repeating unit (F) is a repeating unit (F) formed by polymerization of a polymerizable compound (1) having a fluorine-containing ring structure. &lt;14&gt; The photoresist protective film composition according to <13>, wherein the polymerizable compound (f) is represented by the following formula (Π), the following formula (f2), the following formula (f3), the following formula (f4) or Compound of the following formula (f5), -15- 200910003

Ch2: ,CH cf2 ;cf I .CF2| CF,,CF2 CF2 (f3) =cv o&gt;=〇ch2=c ,rf &gt;=〇CH2=C; ,rf ch2 CF2 )CF I .CF2 I CF, /CF2, cf2 (M) ϋ I /CH CF2, ?F2 cf2 .cf2 , cf2 (f5) where the symbol indicates the following meaning, RF: hydrogen atom, fluorine atom, alkyl number of carbon atoms or number of carbon atoms The fluoroalkyl group of ~3, and the fluorine atom in the compound (fl) to (f5) may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. &lt; 1 5 &gt; The photoresist protective film composition of &lt; 1 3 &gt;&lt; 1 4 &gt; wherein the polymer (PAF) contains a repeating unit (F) of 1 to 50 mol%. The photoresist protective film composition according to any one of <11> to <15>, which contains an organic solvent. &lt; 1 7 &gt; - A method for forming a photoresist pattern, which is carried out in the order of applying a photosensitive photoresist material on a substrate to form a photoresist film on the substrate, and &lt;1 6 &gt; The photoresist film composition is coated on the photoresist film to form a photoresist film on the photoresist film, and the lithography step and the development step are performed to form a photoresist pattern on the substrate. (Effects of the Invention) According to the present invention, it is possible to provide photoresist characteristics (transparency to short-wavelength light, etching resistance, etc.), photoresist film properties (swelling of photosensitive photoresist, and suppression of dissolution of -16 - 200910003, etc.) ), a photoresist composition excellent in dynamic liquid repellency (especially dynamic water repellency). By using the photoresist composition of the present invention, the immersion lithography method capable of high-resolution transfer mask pattern image can be stably and rapidly performed. [Embodiment] In the present specification, "the compound represented by the formula (a)" is also referred to as "compound (a)", and "the base represented by the formula -C(0) 〇 ZA" is also referred to as -C(0). 0ZA. Other compounds are the same as other bases. Further, unless otherwise stated, the symbols in the base are synonymous with the above. The present invention provides a photoresist composition containing a polymer (PA) having a repeating unit (A) formed of a polymer of a compound represented by the following formula (a), CF2 = CFCF2C (XA) (C(0)0ZA)(CH2)naCRA = CHRA (a) xA: a hydrogen atom, a cyano group or a formula -C(〇)〇ZA ' wherein a hydrogen atom or -c(o)ozA is preferred, na : 0 1 or 2, preferably 1 or less, RA: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the two RAs may be the same or different. Preferably, both of the two RAs are hydrogen atoms. ZA: preferably a hydrogen atom, a group represented by the formula -C(ZA11)3 (hereinafter also referred to as "base (G1)"), and a group represented by the formula -CH2〇ZA12 (hereinafter also referred to as "base-17-200910003 ( G2)" or the base shown in the following formula (hereinafter also referred to as base (G3)"), [10]

Z and ZA12 are each independently represented, and a hydrogen atom or a monovalent saturated radial group having a carbon number of 1 to 19 'ZA! 3 indicates a hydrogen atom or a monovalent saturated nicotinyl group of carbon atoms' QM3 is formed together with a carbon atom in the formula 2 The valent cyclic hydrocarbon group has a carbon atom number of from 3 to 19. Wherein 'is a monovalent saturated hydrocarbon group ι, i, zA12 or ZA13, and a carbon atom-carbon atom in qA13 can be inserted into the formula - 〇-, a formula _c(0)_m or a formula -C(〇 ) 〇- shown, in addition, the carbon atom in ZA11, zA12, ZA13 or qa&quot; may also bond a fluorine atom, a hydroxyl group or a carboxyl group. In the case where ZA11 in the group (G1) is a monovalent saturated hydrocarbon group having 1 to 19 carbon atoms, ZA11 may be an acyclic group or a group having a ring group. The acyclic group may be a linear group or a divergent group. The group having a cyclic group may be a group having a polycyclic group or a group having a monocyclic group. The group having a polycyclic group may be a group containing a crosslinked cyclic group or may be a group having a fused cyclic group. Specific examples of the group containing a cyclic group include a group containing a group represented by the following formula and a group containing a hydrogen atom in the above substituted with a fluorine atom. -18- 200910003 [化11] -0^3-0 XX)-&lt;X3^

The following examples of the group in which the hydrogen atom in the group containing a ring group is substituted with a fluorine atom may be exemplified below. [化 12]

The three ZA11's in the group (G1) may be the same or different. 3 ZA11 in the group (G1), preferably a combination of 2 carbonic acid monovalent saturated hydrocarbon groups having 1 to 6 carbon atoms, 1 monovalent cyclic saturated hydrocarbon group having 1 to 12 carbon atoms, or 2 A combination of a hydrogen atom, a polyfluoroalkyl group having a carbon number of 12, or a combination of three monovalent saturated hydrocarbon groups each having a carbon number of 1 to 6. Particularly preferred are two monovalent alkyl groups having a carbon number of 1 to 6 (preferably methyl), one combination of adamantyl groups, or two hospitals having a carbon number of 1 to 6 A combination of a polyfluoroalkyl group represented by the formula -ch2rfz (wherein "RFZ represents a perfluoroalkyl group having a carbon number of 1 to 10" or a carbon number of 1 is preferred. A combination of 6 alkyl groups (preferably methyl groups). -19- 200910003 As a specific example of the base (G1), a base represented by the following formula can be cited.

I

C(CH3)3 CH3-C-CH3 ch2cf2cf3 ZA12 in the group (G2), preferably a saturated hydrocarbon group having 1 to 12 carbon atoms, a saturated hydrocarbon group having 0 to 12 carbon atoms, and a carbon number of 1 a fluorine-containing saturated hydrocarbon group of ～12 or a fluorine-containing saturated hydrocarbon group having a carbon number of 1 to 12 and containing -0. Specific examples of the group (G2) include any of the groups shown by the following formula. [化14] —ch2o—ch3 -ch2o—ch2ch3 -ch2o -ch2o

—ch2o -ch2o —ch2o fir2 CF.I P---CF 4-3⁄4 —Cn2〇一〇Π2〇Π2〇〇Π3 —ch20-/?&gt; ΪΘ -ch2o CFr^CFa II CF2 /CF2 , cf2 icH f3cF ?rCF, eCF2 - CH2〇

The preferred one of ZA13 is a saturated hydrocarbon group having a carbon number of -O-. Preferably, QA13 is a saturated hydrocarbon group having 1 to 6 carbon atoms or a saturated hydrocarbon group having 1 to 6 carbon atoms of 1 to 6 and intercalated between carbon atoms of -20-200910003 carbon atoms, _-, _c(〇)_ Or - c(〇)〇- a saturated hydrocarbon group having 4 to 12 carbon atoms, a fluorine-containing saturated hydrocarbon group having 4 to 12 carbon atoms, or -0-, -C(O)- or - between carbon atoms and carbon atoms. C(0)0 - a fluorine-containing saturated hydrocarbon group having 4 to 12 carbon atoms. Specific examples of the group (G3) include any of the groups shown by the following formula. [it 15]

As the compound (a), the following compound (a 1) or (a2) is preferred. CF2 = CFCF2-CH(C(0)0ZA1)CH2CH = CH2 (al) CF2 = CFCF2-C(C(0)0ZA1)2CH2CH = CH2 (a2) zA1 : hydrogen atom, formula -C(ZA11)3 The base represented by the formula, the formula -ch2ozA12, or the group represented by the following formula, [Chem. 16]

2 and ZA12: each is a hydrogen atom or a carbon atom, a monovalent saturated hydrocarbon group of 19-21-200910003, ZA13: a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms, QA13: a carbon atom in the formula a group having a carbon number of 3 to 19 in which a divalent cyclic hydrocarbon group is formed, wherein ZA11, ZA12 or ZA13 which is a monovalent saturated hydrocarbon group, and a group which can be inserted into a -a-carbon group between carbon atoms and carbon atoms in QA13, A group represented by the formula -c(o)- or a group of the formula -C(0)0-, and a fluorine atom, a hydroxyl group or a thiol group may be bonded to a carbon atom in the 'ZA11, ZA12, ZA13 or QA13. Specific examples of the compound (a) include the following compounds. -22- 200910003 [it 17] Specific example of compound (a) in which z A is a hydrogen atom CF2=CFCF2CH(C{0)0H)CH2CH=CH2 CF2sCFCF2C(C(0)0H)2CH2CH=CH2 CF2sCFCF2C(CN)( C(0)0H)CH2CH=CH2 ZA is a specific example of the compound (a) of the group (G1). CP2=CFCF2CH(C(0)0C&lt;CH3)3}CH2CH:CH2CF2=CFCF2C(C(0)0C( CH3)3&gt;2CH2CH=CH2 CF2=CFCF2C(CN)(C(0)0C(CH3)3)CH2CH»CH2 CF2=CFCF2CH(C{0)0CH2CF2CF3)CH2CH=CH2 ZA is a compound of the group (G2) (a Specific example CF2=CFCF2CH(C{〇K)CH2OCH3)CH2CH=CH2CF2*CFCF2CH(C{0}OCH2OCH2CH3)CH2CH=CH2 cF2sCFCF2C(C(0&gt;OCH2〇CH3)2CH2CH=CH2 cf2=cfcf2c(cn&gt;( c(〇}〇ch2och3)ch2ch=ch2 CF2*CFCF2CH(C(0}OCH2OCH2CH2OCH3)CH2CH=CH2

The compound (a) is preferably produced by reacting cH2 = c(c(〇)ozP)2 with CH2 = CH(CH2)naBr in the presence of a basic compound to obtain CH(C(0)0ZP)2 ( (CH2)naCH = CH2). Secondly, CH(C(〇)〇Zp)2((CH2)naCH=CH2) is reacted with CF2=CFCF2〇S02F in the presence of a basic compound to obtain CF2=CFCF2C(C(0)0Zp)2(CH2)naCH =CH2 (hereinafter also referred to as compound (pi)), which is used to produce compound (a) (wherein Zp represents a monovalent organic group having 1 to 20 carbon atoms. zp is preferably the same as ZA). For example, CF2 = CFCF2C(C(0)0H)2(CH2)naCH = CH2' is preferably produced by hydrolyzing the compound -23-200910003 (P1). CF2 = CFCF2C(C(0)0H)(CH2)naCH = CH2 is preferably produced by removing carbon dioxide from the compound (P1). The polymer (PA) of the present invention preferably has a weight average molecular weight of 1,000 to 1,000,000, particularly preferably 1, 〇〇〇 to 50,000. The polymer (PA) of the present invention has excellent dynamic liquid repellency, especially dynamic water repellency. Although the reason is not clear, 'we think that the compound (a) is a compound having a cyclization property' can usually form any of the following repetitive units (A) which are formed by the cyclization polymerization of the compound (a). polymer.

[ratio 18] ra rA I , cf2 ? ch, ^CF-C CF2 (C«2)na χΑ/, c(〇)〇ZA

The polymer is a polymer containing a repeating unit having a fluffy fluorine-containing ring structure in the main chain. Compared with a polymer having a repeating unit formed by cyclization polymerization of a conventionally known compound (1,1,2-trifluoro-4-alkoxycarbonyl-1,6-heptadiene), due to fluorine content High, so the dynamic liquid repellency (especially dynamic water repellency) is excellent. Therefore, the photoresist composition of the present invention can suppress the intrusion of the immersion liquid by containing the polymer (PA). Further, since the immersion liquid easily slides over the surface of the photoresist layer, it is possible to suppress the occurrence of defects caused by the immersion liquid droplets remaining on the surface of the photoresist. -24- 200910003 The photoresist composition of the present invention contains a polymer (PA). The polymer (PA)' acts as a carboxylic acid ester moiety (-C(0)0ZA) which acts as a carboxylic acid. Therefore, the alkali solubility increases. The photoresist of the present invention has excellent dynamic water repellency, which is suitable as a photoresist composition for immersion lithography. In the immersion lithography method using the photoresist composition of the present invention, the immersion liquid satisfactorily follows the projection lens which is moved at a high speed through the photoresist layer. Further, the photoresist composition of the present invention contains a polymer (PA), and the solubility of the alkali can be increased by the action of an acid. The exposed portion of the photoresist layer obtained from the photoresist composition of the present invention can be easily removed by an alkali solution. Therefore, the immersion lithography method capable of high-resolution transfer mask pattern images can be applied at a high speed by the photoresist composition of the present invention. In the polymer (PA) of the present invention, the repeating unit (A) may be composed of only one type or may be composed of two or more kinds. The photoresist composition of the present invention preferably contains a polymer (PB) having a repeating unit other than the repeating unit (A) which can increase the alkali solubility by the action of an acid (B) ) of the polymer. The photoresist composition of the present invention may have both the repeating unit (A) and the repeating unit (B) of the polymer (PA). This is a polymer (PAB). In the photoresist composition of the present invention, it is also possible to mix a polymer (PA*) having a repeating unit (A) without a repeating unit (B), and having a repeating unit (B) without repeating The polymer (PB*) of the unit (A) serves as a photoresist composition. In the following description, the polymer (PAB) is in principle a polymer (PA). Further, the polymer (PB) is in principle a polymer (P B *). The polymer (PB) is preferably a polymerizable compound (b) having a group represented by the following formula (kbl), the following formula-25-200910003 (kb2), the following formula (kb3) or the following formula (kb4); The polymer obtained by polymerization. The polymer compound (b) is particularly preferably the following compound (b1), (b2) or (b3). [Chem. 19]

XB1 is an alkyl group having 1 to 6 carbon atoms. QB1 is a divalent group having 3 to 18 carbon atoms which forms a divalent cyclic hydrocarbon group together with a carbon atom in the formula. XB2 is a monovalent hydrocarbon group having 1 to 17 carbon atoms, and 3 XB2s may be the same or different. ZB is a respective alkyl group, alkoxyalkyl group, alkoxycarbonyl group or an alkylcarbonyl group or a hydrogen atom, wherein the above group is a group having 1 to 20 carbon atoms or a hydrogen atom. Wherein 'in the XB1, QB1, χΒ2 or ZB* carbon atom-carbon atom can be inserted into the formula - 〇-, the group represented by the formula -C(0)0- or the formula -C(O)-, The carbon atom in XB1, QB1, XB2 or ZB may also bond a fluorine atom, a hydroxyl group or a carboxyl group. XB1 is preferably an alkyl group having 1 to 6 carbon atoms or a group having 1 to 6 carbon atoms having an etheric oxygen atom. The methyl group or the ethyl group is particularly preferred. -26 - 200910003 The divalent group formed by QB1 and the carbon atom in the formula is preferably an aliphatic group, and particularly preferably a saturated aliphatic group. The above divalent group may be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group. The above-mentioned divalent group is preferably a polycyclic hydrocarbon group, and particularly preferably a crosslinked cyclic hydrocarbon group. In the case where the carbon atom-carbon atom in QB1 can be inserted - 〇-, -c(o)o- or -C(O)-, it is preferred to insert -C(0)0-. In the case where a carbon atom is bonded to a fluorine atom, a hydroxyl group or a carboxyl group in QB1, it is preferred to bond a hydroxyl group or a carboxyl group. Preferably, XB2 is a combination of three alkyl groups having a carbon number of 1 to 3, two alkyl groups having 1 to 3 carbon atoms, and 1 monovalent cyclic hydrocarbon group having 4 to 17 carbon atoms (1). - The combination of King Kong Foundation, etc.). ZB is preferably -C(ZB11h (wherein ZB11 represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 12, the same applies hereinafter) or - ch2ozbm, and -C(CH3)3, -CH2OCH3, -CH2OCH2CH3, -CH2OC (CH3) ) 3 or the following - the base is particularly good. [Chem. 20]

RB is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms. QB3 is a group of the formula -CF2C(CF3)(OZB)(CH2)nb- or the formula CH2CH((CH2)mbC(CF3)2(OZB))(CH2)nb•. zB is a group, alkoxyalkyl group, alkoxycarbonyl group or alkylcarbonyl group, and is a group having 1 to 20 carbon atoms or a hydrogen atom. Mb and nb are independent 0, 1, or 2. -27- 200910003 RB is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and is preferably a hydrogen atom or a methyl group. The nb in QB3 is preferably 1. The mb in QB3 is preferably 0. QB3 is -CF2C(CF3)(OC(ZB1 hOCHr, -CF2C(CF3)(OCH2OZB11)CH2-, -CH2CH(C(CF3)2(OCH2OZBn))CH2- or -CH2CH(C(CF3)2(OC( Zb &quot;) 3)) CH2- is preferable. Specific examples of the base (kbl) include any of the groups shown below.

Specific examples of the radical (kb2) include any of the groups shown below. [Chem. 22] CH3-C-CH3 CH3-C-CH3

The compound (b1) of ch3 is preferably the following compound (bll), (bl2), (bl3), (bl4) or (b1 5 ), and particularly preferably the compound (b 1 1). -28- 200910003 [Chemical 23] CH2=CC=0 CHz=c^c=o CHa=ci (!) XB1—XB1 ο ο ο jg xBiiD xBiiro χΒΌ χΒ1~ο (bn) (b!2) (b13) (b14) (b15) The compound (b2) is preferably the following compound (b2l) or (b22)

c H H2 c CH3_C-CH3 H3 c

BMR CIOICIC 〆 / I ο H3 c H3 (b21) (b22) Compound (b3) is -CF2=CFCF2C(CF3)(OC(ZB11)3)CH2CH=CH2-, -CF2 = CFCF2C(CF3)(OCH2OZB11)CH2CH = CH2-, -CF2 = CFCH2CH(C(CF3)2(OCH2〇Zb11))CH2CH = CH2- or -CF2 = CFCH2CH(C(CF3)2(OC(ZB1 = is preferred. As compound (b 1)) Specific examples thereof include the following compounds: [ 2 S/ c = Hi c

RB o c CH3 cp o B If R cio&lt; h22=CH £H3 p

w H9 CH o B= R cl

-29-200910003 Specific examples of the compound (b2) include the following compounds.

Specific examples of the compound (b3) include the following compounds. CF2-CFCF2C(CF3}(OCH2OCH3)CH2CH=CH2 CF2=CFCF2C(CF3)(OCH2OCH2CH3)CH2CH=CH2 cf2=cfcf2c(cf3)(och2oc(ch3)3)ch2ch=ch2

CF2=CFCF2CCH2CH-CH2 cf2=cfcf2cch2ch=ch2

CF2-CFCH2CH(C(CF3&gt;2〇CH2OCH3)CH2CH=CH2 CF2=CFCH2CH&lt;C(CF3)2OCH2〇CH2CH3)CH2CH=CH2 CF2-CFCH2CH(C(CF3)2OCH2OC(CH3}3)CH2CH-CH2 is further improved The dynamic liquid repellency of the photoresist composition of the present invention is preferably such that the polymer (PA) further contains a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. In this case, it is a polymer (PAF). As the polymerizable compound (f), a compound having a monovalent polymerizable group and a monovalent fluorine-containing cyclic hydrocarbon group is preferred. -30- 200910003 The monovalent polymerizable group means ethylene. a (meth)acryloxycarbonyl group, a 2-fluoro-propenyloxy group, or a 2-fluoroalkyl-propenyloxy group is preferred, and a (meth)acryloxy group is particularly preferred. Methyl) propylene oxime refers to propylene oxime or methacryloxy (hereinafter the same). The monovalent fluorine-containing cyclic hydrocarbon group is a monovalent fluorine-containing monocyclic hydrocarbon group or a monovalent fluorine-containing polycyclic hydrocarbon group. Preferably, the monovalent fluorine-containing polycyclic hydrocarbon group may be a monovalent fluorine-containing condensed cyclic hydrocarbon group or a monovalent fluorine-containing crosslinked cyclic hydrocarbon group. A monovalent fluorine-containing cyclic hydrocarbon group, preferably a ring type saturation The compound is removed from the monovalent group of one hydrogen atom. The remaining hydrogen atom is 50% or more of the group substituted by the fluorine atom. It is more preferable to substitute the fluorine atom with more than 80% of the residual hydrogen atom. The substitution with a fluorine atom is particularly preferred. The cyclic saturated hydrocarbon compound is preferably any of the compounds shown below.

The polymerizable compound (f) is particularly preferably the following compound (π), (f2), (f3), (f4) or (f5). [化29]

-31 - 200910003. It is a hydrogen atom, a fluorine atom, an alkyl group having a carbon number or a fluoroalkyl group having a carbon number of 1 to 3. Further, the fluorine atom in the compounds (Π) to (f5) may be substituted with a perfluoroalkyl group having a carbon number of > a perfluoroalkoxy group having a carbon number of 1 to 6. Further, in the compound (f3) or the compound (f4), the arrangement of the asymmetry center may be an endo type or an ex" type. RF is preferably a hydrogen atom or a methyl group. The compound (f 2), the compound (f 3 ) and the compound (f 4 ) are novel compounds. In the production of the compound (f2), it is preferred to react the following compound (Pf2) with H-CH0 in the presence of a basic compound to obtain the following compound Uf2), and then to make the compound (qf2) and CH2 = CRFC ( 0) C1 reaction derived. ~6 -yL-. in the system

Compound f(3) is preferably produced by a series of reactions as described below. First, the following compound 〇f3 is reacted with Rf_c〇F (wherein RF is a perfluoroalkyl group having a carbon number of 1 to an etheric oxygen atom) to obtain the following compound (nf3). Then, the compound (nf3) was subjected to fluorine by a liquid phase fluorination method to give the following compound (of3). Then, the compound (of3) is decomposed in the presence of KF to give the following compound (pf3). Then, the following compound (Pf3) was subjected to the original reaction to obtain the following compound (qf). Then, the compound -32- 200910003 (qf3) is reacted with CH2 = CRFC(0)C1.

The compound (f4) is preferably produced in the same manner except that the compound (mf3) is substituted with the following compound (mf4).

[化32] CH20H

(mf4) In the polymer (PA), it is preferred to contain a repeating unit (A) of 1 to 1 mol% with respect to all the repeating units. The content of the repeating unit (A) is preferably from 1 〇 to 100 mol%, particularly preferably 100 mol%. That is, the polymer (PA) is particularly preferably composed of the repeat unit (A). Further, the repeating unit (A) may be composed of only one type or two or more types. Further, in the case where the polymer (PA) is a polymer (PAB), it is preferable to contain 10 to 60 mol% of the repeating unit (B) with respect to all the repeating units. Further, in the case where the polymer (P A) is a polymer (p A F ), it is preferably 1 to 4 5 mol% based on the total repeat unit (F). In the polymer (PAF), with respect to all the repeating units, it is preferable to contain the repeating unit (A) -33 - 200910003 80 to 99 mol%, and the repeating unit (ρμ 2 2 mol % is preferable. The weight average molecular weight of the polymer (PAF) in this case is preferably from 〇〇〇 to 30,000. The polymer (ΡΑ) may further contain other units. As other units, by having the following group (kcl) The repeating unit (c) formed by the polymerization of the polymerizable compound (c) of (kc2) is preferred. The polymer compound (c) is particularly preferably the following compound (cl) or (C2).

The symbol in the formula indicates the following meaning,

Qei is a valence group having 4 to 2 carbon atoms which form a cyclic hydrocarbon group together with a carbon atom in the formula.

Qe2 is a valence group having a carbon number of 4 to 2, which forms a crosslinked cyclic hydrocarbon group together with a carbon atom in the formula. Wherein 'in the QAI or Qe2, a carbon atom-carbon atom can be inserted between -0-, -C(0)0- or -C(O)-' and can also be bonded to a carbon atom in QC1 or qQ. The knot contains a hydroxyl group or a carboxyl group.

Rc is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms (Re is preferably a hydrogen atom or a methyl group). -34- 200910003 Base (kcl) Any of the groups shown in the following formula is preferred. [34]

The base (kc2) is preferably any of the groups shown by the following formula. [化35]

The OH Ο 化合物 compound (c2) is preferably any of the following compounds.

The compound (c 1) is preferably any one of the following compounds. -35- 200910003 [化37]

The weight average molecular weight of the polymer (PA) is preferably from 1,000 to 1,000,000, particularly preferably from 1,000 to 50,000. The photoresist composition of the present invention is usually used as a chemically amplified photosensitive resist in the immersion lithography method. The photoresist composition of the present invention is preferably formulated with a photoacid generator. Further, the photoresist composition is usually applied to a substrate and used in the immersion lithography method. Therefore, it is preferred that the photoresist composition is prepared as a liquid composition containing an organic solvent. The photoacid generator is not particularly limited as long as it has a group capable of generating phosphoric acid by irradiation with active rays ("active rays" include a broad sense of radiation). The above compound may be a non-polymeric compound or a polymer compound. Further, the photoacid generator may be used singly or in combination of two or more kinds. The photoacid generator is selected from the group consisting of a key salt, a halogen-containing compound, a bisazo ketone, a maple compound, a sulfonic acid compound, a diazo bismuth, a diazo oxan oxime, an imido sulfonate. A photoacid generator in the group consisting of an acid ester and a diterpenoid is preferred. -36- 200910003 Specific examples of the photoacid generator include ditritium difluorolate, diphenyl iodide sulfonate, diphenyl iodine hexacarboxylate, Diphenyliodododecylbenzenesulfonate, bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, bis(4-tert-butylphenyl)iodo-12-benzoic acid Ester, triphenylsulfonium trifluoromethanesulfonate, triphenyl phthalate, triphenylsulfonium perfluorooctane sulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonic acid Ester, triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorquinone, 1-(naphthylethylidenemethyl)tetrahydrothiophene salt (thioranium) trifluoromethanesulfonate, cyclohexylmethyl (2 -oxycyclohexyl)phosphonium trifluoromethanesulfonate, dicyclohexylmethyl (2-oxocyclohexyl)phosphonium trifluoromethanesulfonate, dimethyl (4-hydroxynaphthalene) anthracene tosylate, dimethyl (4-hydroxynaphthalene) oxime dodecyl benzene sulfonate, dimethyl (4-hydroxynaphthalene) fluorene naphthalene sulfonate, triphenyl camphorsulfonate, (4-hydroxyphenyl)benzylmethyl Indole tosylate, (4-methoxyphenyl)phenyliodotrifluoromethanesulfonate Acid ester, bis(tert-butylphenyl)iodotrifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, methoxyphenylbis(trichloromethyl)-s -Triazine, naphthyl = bis(trichloromethyl)-s-triazine, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 4-tribenzoic acid 4-trisphnacyl sulfone, mesytyl phenacyl sulfone, bis(phenylfluorenyl) sulfonate, benzoin tosylate, 1,8-naphthalene dicarboxylate Lithium imide trifluoromethanesulfonate. The organic solvent is not particularly limited as long as it is a solvent having high compatibility with the polymer (PA). The organic solvent may be a fluorine-based organic solvent or a non-fluorine-based organic solvent. Specific examples of the fluorine-based organic solvent include: hydrofluorocarbons such as CC12FCH3, -37-200910003 cf3cf2chci2, and ccif2cf2chcif; cf3chfcf2cf3, CF3(CF2)5H, cf3(cf2)3c2h5, cf3(cf2)5c2h5, Hydrofluorocarbons such as CF3(CF2)7C2H5; hydrofluorobenzenes such as 1,3-bis(trifluoromethyl)benzene and xylene hexafluoride: hydrofluoroketones; hydrofluorocarbons; CF3CF2CF2CF2OCH3 Hydrogenated acids such as (CF3)2CFCF(CF3)CF2OCH3, CF3CH2OCF2CHF2, etc.; hydrofluoroalcohols such as chf2cf2ch2oh. Specific examples of the non-fluorine-based organic solvent include methanol, ethanol, diacetone alcohol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-B. An alcohol such as butanol, pentanol, hexanol or heptanol; acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, N-methylpyrrolidone, r-butyrolactone, etc. Ketones; propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, carbitol acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 10,000- Ester of methyl methoxybutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, methyl lactate, ethyl lactate, etc. Aromatic hydrocarbons such as toluene, xylene, etc.; propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol a mono- or dialkyl ether of monomethyl ether or the like; N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, and the like. The photoresist composition of the present invention can be used for immersion lithography. As a immersion lithography method, the following steps are carried out in order to apply a photoresist composition to a substrate (a silicon wafer or the like) to form a photoresist film on the substrate; Shadow step; development step; etching step; and photoresist film stripping -38- 200910003. The immersion lithography step includes a pattern image of a mask obtained by irradiation with an exposure light source, and is filled with a immersion liquid between the projection lens and the photoresist film, and relatively moved through the photoresist film. The step of projecting the projection lens onto the desired position of the photoresist film. The exposure light source is preferably: g line (wavelength 43 6 nm), i line (wavelength 3 6 5 nm), K r F excimer laser light (wavelength 2 4 8 nm), A r F excimer laser light (wavelength 193 nm) ), or F2 excimer laser light (wavelength 157nm), more preferably: ArF excimer laser light, or F2 excimer laser light, with ArF excimer laser light is particularly good. The immersion liquid may be an oily liquid medium (decahydronaphthalene or the like), or an aqueous liquid medium (ultra-pure water, etc.), preferably a liquid medium containing water as a main component, especially ultrapure water. good. As the developing step, a step of removing the exposed portion of the photoresist film by an alkali solution is exemplified. The alkali solution is not particularly limited, and examples thereof include an alkali compound selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and triethylamine. Aqueous aqueous solution. The photoresist composition of the present invention preferably contains a polymer (P A ) and a polymer (P B ). Further, a polymer other than the polymer (PA) or the polymer (pb) may be contained. Since the photoresist composition of the present invention contains a polymer (P A ), it is particularly excellent in dynamic water repellency. In the immersion lithography method using the photoresist layer obtained by using the photoresist composition of the present invention, the immersion liquid has good followability to a projection lens which moves at a high speed through the photoresist layer. Further, since the photoresist composition of the present invention contains a polymer (PB), the exposed portion of the photoresist layer can be easily removed by an alkali solution. Therefore, by using the photoresist composition of the present invention, the immersion lithography method capable of high-resolution transfer mask image can be performed at high speed. In the polymer (PB), it is particularly preferable to contain 25 mol% or more of the repeating unit (B) with respect to all the repeating units. The weight average molecular weight of the polymer (?8) is preferably 1, 〇〇〇~1 〇〇, 〇〇〇, and particularly preferably 1, 0 0 0 to 5 0,0 0 0. The photoresist composition of the present invention is preferably contained in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the polymer (PB), and is contained in an amount of 0.1 to 1 part by mass. good. Further, in the photoresist composition of the present invention, the photoacid generator is contained in an amount of from 1 to 10 parts by mass based on 100 parts by weight of the total of the polymer of the polymer (polymer), the polymer (ΡΒ) and other polymers. good. Further, in the photoresist composition of the present invention, 100 parts by mass of the organic solvent is preferably contained in an amount of 100 parts by mass to 100 parts by mass based on 100 parts by mass of the total of all the polymers. In the photoresist composition of the present invention, the total of all the polymers is preferably from 1 to 50% by mass based on the total of the photoresist composition (100% by mass). The present invention provides a photoresist film composition (hereinafter also referred to as a protective film composition) containing a polymer (PA) having a repeating unit (A) formed by polymerization of the compound (a). Since the protective film composition of the present invention contains a polymer (PA), it exhibits alkali solubility. Therefore, it can be easily removed by an alkali solution. Moreover, since it is excellent in water repellency, it is suitable for use in the immersion lithography method. That is, the immersion lithography method capable of high-resolution transfer mask pattern image can be performed at a high speed by the protective film composition of the present invention. -40 - 200910003 The protective film composition of the present invention is preferably a repeating unit containing an alkali solubility. As the repeating unit, it is preferable to use a repeating unit derived from the repeating unit (A) or another repeating unit having an alkali solubility other than the unit (A). As the repeating unit derived from the repeating unit (A), a repeating unit formed by polymerization of the compound (a) in which ZA is a hydrogen atom is preferred. The other repeating unit may be a repeating unit formed by polymerization of a polymerizable compound other than the compound U) having a hydroxyl group, a carboxyl group, a maple group, a guanamine group, an amine group or a phosphoric acid group. The polymerizable compound other than the compound (a) is preferably (〇 a 1 ), ( 〇 a2 ), (oa3) or (oa4). [Chemical 3 8] CF2=CF-QOA1-CH=CH2 (〇a1) CH2=CR0A2 -C(0)0 -QOA2(-C(CF3)2OH)ab (oa2) CH2=CH-QOA3(-C( CF3)2OH)ab (〇a3)

-C(CF3)2〇H (oa4) The symbol in the formula indicates the following meaning, QOA1 is -CF2C(CF3)(OH)(CH2)- or -CH2CH(C(CF3)2(OH))(CH2)- . Qqa2 is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having a carbon number of 3. Q〇a2 and Q0A3 are independently (ab + l) valent hydrocarbon groups having a carbon number of 1 to 2 Å. Ab is 1 or 2.

Qqa4 is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms. -41 - 200910003 Also, a carbon atom in qQA2, qQA3 or qQA4 may bond to a fluorine atom. Specific examples of the polymerizable compound other than the compound (a) include the following compounds. [it 39] cf2=cfcf2c(cf3)(oh)ch2ch=ch2 cf2=cfcf2c(c(cf3)2(oh))ch2ch=ch2

CH2=CHC(0)0-^^-C(CF3)2〇H CH2=C(CH3)C(0)0-^)-C(CF3)2〇H

CH2=CHC(0}0&lt;^-CH2C(CF3)2〇H CH2=C(CH3)C(0)0&lt;^-CH2C(CF3)2〇H CH2=CHC(O)O-^^-C (CF3)20H CH2=C(CH3)C(0)0-^-C(CF3)20H

CH2 =CHC(0)0 -^^-CH2C(CF3)2〇H CH2=C(CH3)C(0)0 -^^-CH2C(CF3)2〇H c(cf3)2oh

CH2=C(CH3jCC〇)P

c(cf3)2oh C(CF3)2OH CH2C(CF3)2OH CH2C(CF3)2OH CH2=CHC(0)P-^^ CH2=CHC(0)0

(C(CF3)2〇H CH2C(CF3)20H CH2=C(CH3)C(0)0

CH2C(CF3)2〇H

CH^CH-^CiCFahOH CH2=CH-&lt;^)-CH2C(CF3)2OH 0-C(CF3)2OH 0-ch2c(cf3)2oh as a compound in the polymer (PA) used in the protective film composition (a) Preferably, the aforementioned compound (al) or (a2) is used. The repeating unit (A) in the polymer (PA) used in the protective film composition may be one type or two or more types. The polymer (PA) used in the protective film composition of the present invention is preferably contained in an amount of 50 to 100% by volume based on the total unit (A) of 50 to 100% by volume based on the total of the repeated units. Better. A preferred form of the polymer (PA) is a polymer having a weight average molecular weight of -42 to 200910003 1,000 to 30, which is composed only of the repeating unit (A). The polymer (p A) used in the protective film composition of the present invention has a dynamic liquid repellency which is further improved to have a repeating unit (F) formed by polymerization of a fluorine-containing polymerizable compound (f). ) is better. In this case, the polymer is a polymer (PAF). When a polymer (PAF) is used in the protective film composition, the immersion liquid can follow well the projection lens that has moved over the photosensitive resist layer. Further, since the protective film composition of the present invention is an alkali-soluble polymer, the photoresist protective film can be easily removed by an alkali solution. Therefore, according to the protective film composition of the present invention, the immersion lithography method capable of high-resolution transfer mask image can be performed at a high speed. The polymerizable compound (f) is preferably a compound having a monovalent polymerizable group and a monovalent fluorine-containing cyclic hydrocarbon group. Further, the polymerizable compound (f) is preferably the following compound (f 1), (f 2), (f 3 ), (F4) or (f5). [40]

〇rRF

RF is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms. Further, the fluorine atom in the compound (Π) to (f5) may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. -43- 200910003 The polymer (PA) (i.e., polymer) used in the protective film composition of the present invention in the case where the polymer (PA) used in the protective film composition of the present invention has a repeating unit (F) PAF)), preferably with a repeat unit (F) of 1 to 50 mol%, relative to the entire repeat unit. Further, in the polymer (PAF), it is more preferable to contain a repeating unit (A) of 80 to 99 mol% and a repeating unit (F) of 1 to 20 mol% with respect to the entire repeat unit. The polymer (PA) used in the protective film composition of the present invention preferably has a weight average molecular weight of 1,000 to 100,000, particularly preferably 1,000 to 50,000. The protective film composition of the present invention is usually used in the immersion lithography method because it is applied to the surface of the photosensitive resist film formed on the substrate, so that it is preferably prepared into a liquid composition. The protective film composition of the present invention preferably contains an organic solvent. The ratio of the organic solvent is preferably 55 to 9% by mass based on the total mass of the protective film composition. That is, in the protective film composition, the total ratio of all the polymers is preferably from 1 to 50% by mass. The organic solvent is not particularly limited as long as it has a high compatibility with the polymer (PA) used in the protective film composition of the present invention. Specific examples of the organic solvent include the same solvents as those of the organic solvent described in the resist composition. Among them, particularly preferred are: alcohols, ketones, esters (especially monoalkyl ether esters), fluoroethers (especially perfluoroethers), fluoroalcohols, fluorobenzenes (especially hydrofluoric) Benzene) or fluoroketone. Further, the protective film composition is usually applied by coating on a photosensitive resist layer by a spin coating method. The organic solvent is preferably a solvent which does not dissolve the photosensitive photoresist layer, and particularly preferably an alcohol, a fluoroether, a fluoroalcohol, a fluoroketone or a fluorobenzene. The alcohol is preferably isopropanol, 1-butanol, 1-hexanol, 2-methyl-1-propanol, 4-methyl-2-pentanol or 2-octanol; especially 2-A The base-1-propanol and 4-methyl-2-pentanol are particularly preferred. The fluoroalcohol is preferably C3H7CH2OH or C4H9CH2CH2〇H. Fluorobenzenes are preferably 1,3-bis(trifluoromethyl)benzene. The protective film composition may also contain a component other than the polymer (PA) and the organic solvent. Specific examples of the component include a plasticizer, a stabilizer, a coloring agent, and a halation preventing agent. The protective film composition can be used for impregnating the protective film material of the photosensitive photoresist layer in the lithography method. Examples of the immersion lithography method include a step of sequentially applying a photosensitive photoresist material onto a substrate to form a photosensitive photoresist film on a substrate, and forming a photoresist film composition. The step of forming a photoresist protective film on the photosensitive photoresist film on the photosensitive photoresist film, immersing the lithography step, and developing the step to form a photoresist pattern on the substrate. The photosensitive material to be used in the use of the protective film composition of the present invention is not particularly limited as long as it contains a polymer which can increase alkali solubility by an action of an acid and a composition of a photoacid generator. As a specific example of the photosensitive resist material, a photosensitive resist material described in JP-A-2005-234178 or the like can be mentioned. More specifically, a composition containing a triphenylsulfonium trifluoromethanesulfonate as a photoacid generator and a copolymer containing the following three compounds as the above-mentioned polymer is mentioned. -45- 200910003 [化41]

CH2^=C

,ch3 &quot;c=c I

σ Next, the embodiment of the present invention will be specifically described, but the present invention is not limited thereto. In the examples, tetrahydrofuran is referred to as THF, 1,1,2-trichloro 1,2,2-trifluoroethane is designated as R113, and dichloropentafluoropropane is designated as R225, diisopropyl peroxycarbonate. It is referred to as hydrazine, isopropyl alcohol as hydrazine, propylene glycol monomethyl ether acetate as PGMEA, weight average molecular weight as Mw, number average molecular weight as Μη, and glass transition temperature as Tg. The Mw and Μη of the polymer were measured by gel permeation chromatography (developing solvent: THF, internal standard: polystyrene, the same applies hereinafter). [Example 1] Production Example of Compound (a) [Example 1-1] cf2 = cfcf2c (c(o)oc(ch3)3) 2ch2ch = ch2 (hereinafter referred to as compound c1) Production example: NaH having a purity of 60% (2.1g) and THF (100mL) were added to the reactor, and then mixed with CH2(C(0)0C(CH3)3)2 (llg) at 2 5 °C for 2 〇 minutes. ). After the completion of the dropwise addition, the inside of the reactor was stirred at this state at 25 ° C for a minute. Further, H2 = CHCH2Br (6.0 g) was added to the reactor C over a period of 10 minutes. The reactor was stirred at 65 ° C for 5 hours. Then, 1 〇〇mL of water was added to the reactor. In the end, the solution in the reactor was extracted 3 times with 50 mL of tert-butyl methyl ether. The extract was washed with brine and dried over sodium sulfate. Further, the extract was concentrated and subjected to distillation under reduced pressure to give CH2 = CHCH2CH(C(0)0C(CH3)3)2 (9.4 g) of NMR purity of 90%. NaH (1.8 g) having a purity of 60% and THF (80 mL) were added to the reactor, followed by mixing and stirring. CH(C(0)0C(CH3)3)2(CH2CH=CH2) (9_4g) was dropped into the reactor over 15 minutes. At the time of dropping, the internal temperature of the reactor was maintained at 2 ° C or lower. In this state, the reactor is taught for 75 minutes. Then, CF2 = CFCF20S02F (8.5 g) was added to the reactor at a temperature of 〇 ° C for 25 minutes, and the solution in the reactor turned yellow to precipitate a solid (FS03Na). After stirring in the reactor for 20 hours in this state, water (150 mL) was added to the reactor to cool it. The solution in the reactor was extracted 3 times with tert-butanol (50 mL). The extract was washed with a sodium chloride aqueous solution, dried over sodium sulfate and concentrated to give a crude material. The crude product was purified by a silica gel column chromatography to give Compound Compound (?) (5.3 g). The NMR data of the compound (a2)) are as follows: iH-NMR pOOJMHz, solvent: CD C13, standard: TMS) 5 (ppm): 1·47 (18Η), 2·85 (2Η), 5_11 (1Η), 5 · 18 (1 Η), 5.90 (1 Η). 19F-NMR (282.7MHz; solvent: CDC13, standard: CFC13) (5 (ppm): -95.2 (1F), -103_2 (2F), -106_2 (1F), -181.32 (1F). -47- 200910003 [ Example 2] cf2 = cfcf2c(c(o)oh2)ch2ch = ch2 (The production example of the compound (a2H) hereinafter referred to as a mixture of 5 minutes in trifluoroacetic acid (6 〇mL) under ice-cooling stirring The compound (32^(6.48) was stirred for 2 hours in this state after completion of the dropwise addition. Then, trifluoroacetic acid was distilled off under reduced pressure at 25 ° C to give Compound a2H (4.6 g). The a2H)2 NMR data are as follows: 1H-NMR (3 00.4 MHz &gt; solvent: CDC13, standard: TMS) &lt;5 (ppm): 2·97 (2Η), 5.20 (1Η), 5.26 (1Η), 5 .89( 1 Η) &gt; 1 1.29 (2Η) 19F-NMR (282.7MHz; solvent: CD C13, benchmark: c FC 13) 5 (ppm): -92.4 (1F), -102.6 (2F), -105.1 (1F), -183.0 (1F) [Example 1-3] cf2 = cfcf2ch(c(o)oh)ch2ch = ch2 (hereinafter referred to as compound alH) Production example Compound (a2H) (2.6 g) After mixing with toluene (15 mL), the toluene was distilled off in this state, and the mixture was further heated at II 2 to 13 9 ° C for 1 hour. The compound (alH) (l.Sg) was obtained. The data of the compound (al H) is as follows: 'H-NMRiSOO^MHz &gt; Solvent: CDC13, standard: TMS) 5 (ppm): 2·55 (1Η), 2.67 (1Η), 3.28 (1Η), 5·15 (1Η), 5.20(1Η) &gt; 5.79(1Η),1 1.72(1Η)., 9F-NMR (282.7MHz; Solvent: CD C13, benchmark :CFC 13) ό (ppm) : -93.6(1F) &gt; -105.4(2F) &gt; -108.0(1F), -186.7(1F) -48- 200910003 [Example 1-4] CF2 = CFCF2CH(C (0)0C(CH3)3)CH2CH=CH2 (hereinafter referred to as the production example of the compound (al1) in the reactor, the compound (alH) (1.77 g) was dissolved in dichloromethane (10 m) Then add 3 drops of concentrated sulfuric acid (about 0 _ 0 4 g). The reactor was stirred at 25 ° C, and CH2 = C(CH3)2 (0.51 g) was added to the reactor while foaming. After the reaction was stirred for 5 hours in the reactor in this state, a 5% aqueous sodium hydrogencarbonate solution (2 mL) was added to the reactor to quench it. The solution in the reactor was extracted 4 times with tert-methylene ether (50 mL), and the obtained extract was washed with aqueous sodium chloride, dried over sodium sulfate and concentrated. The obtained concentrate was purified by silica gel permeation chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate (mixing ratio 1 〇: 1 )) to obtain a compound (al '(lJlg). Compound (a 1 1 The NMR data are as follows: iH-NMROOOjMHz, solvent: CDC13, benchmark: TMS) (5 (ppm): 1·45 (9Η), 2.47 (1Η) ' 2.62(1 Η) , 3.1 1 (1 Η) &gt; 5 . 1 0( 1 Η) - 5·16(1Η), 5·76(1Η) 19F-NMR (282.7MHz; solvent: CDC13, benchmark: CFC13) &lt;5 (ppm): -95.0 (1F) , -104.1(IF) &gt; - 107.7(1 F) &gt; -108.9(1F)--186.0(1F) o [Example 1-5] cf2 = cfcf2ch(c(o)och2och3)ch2ch = ch2 (hereinafter referred to as For the production of the compound (al2) in the reactor, the compound (alH) (2-30 g) was dissolved in tert-butyrate-49-200910003 ether (20 mL), and then diisopropylethylamine (l.29 g) was gradually added. Further, chloromethyl methyl ether (〇.79 g, 10 mmol) was added, and the reaction was stirred in the reactor for 2 hours in this state. Then, water (30 mL) was added to the reactor to quench the reaction. Methyl ether (10mL) was extracted twice from the aqueous layer, and the extract was washed with brine to sulfuric acid. The sodium is dried, and the concentrate obtained by concentrating the extract is concentrated by gelatin penetrating chromatography (developing solvent is a mixed solvent of hexane and ethyl acetate (mixing ratio 5:1)) to obtain a compound (a I2). (1.97 g) The NMR data of the compound (al2) are as follows: 'H-NMROOOjMHz, solvent: CDC13, standard: TMS) &lt;5 (ppm): 2.53 (1 Η), 2·69 (1 Η), 3.28 (1 Η) ) ' 3.47(3Η), 5 . 1 3 (1 Η) &gt; 5.19(1Η), 5·28(1Η), 5.31(1Η), 5.77(1Η) 19F-NMR(2 82.7MHz; Solvent: CDC13 , Criteria: CFC13) 6 (ppm): -93.8 (1F), -104.9 (1F), -106.0 (1F), -108.2 (1F), -186.6 (1F) [Examples 1 to 6] Compound (al3) In the solution containing the compound (alH) (2.05 g) and tert-butanol, diisopropylethylamine (1.15 g) was slowly added dropwise under ice cooling, and the following compound (w3) was added dropwise. (1. 9 1 g). The mixture was stirred for 5 hours in this state to carry out a reaction. Then, water was added to the solution to quench the reaction, and the organic layer was recovered. The organic layer was dried over magnesium sulfate and concentrated to give a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 10:1) to give the compound (al3) (2.1 g). -50- 200910003 CFa=CFCF2CHCH2CH=CH2 CH2OCH2CI C(0)0CH20CH2 [化42]

(w3)

The NMR data of (a1 ' compound (al3) are as follows: iH-NMRpOOdMHz, solvent: heavy acetone, standard: TMS) 5 (ppm): 1.51-1.97 (15H), 2.48-2.73 (2H), 3_22 (2H), 3.27 (1H), 5.13 (2Η), 5.32 (2H), 5.76 (1H). 19F-NMR (2 82.7 MHz; solvent: heavy acetone, standard: CFC13) (5 (ppm): -94.1 (1F), -105_3 (2F), -108.2 (1F), -186.4 (1F). -7] Production Example of Compound (al4) To a solution containing the compound (a 1H ) (2.35 g) and toluene, 2 drops of concentrated sulfuric acid was added, and then the following compound (w4) (2.04 g) was added dropwise under ice cooling. The reaction was carried out in a toluene solution (3 mL). After the solution was stirred for 12 hours, the aqueous sodium hydrogencarbonate solution was added to the solution to quench the reaction to recover the organic layer. The organic layer was washed with water, dried over magnesium sulfate and concentrated. The crude product was obtained, and the crude product was purified by silica gel column chromatography (developing solvent: hexane) to give the following compound (a 14) (2.1 1 g). -51 - 200910003

The NMR data of the compound (al4) are as follows: iH-NMR pOOjMHz, solvent: CDC13, standard: TMS) 5 (ppm): 1.57 (2H), 1.59 (3H), 1.6 9 - 1.9 2 (8 Η), 2·02 ( 2Η), 2.29(2Η), 2.49(1 Η), 2.66(1Η), 3.19 (1 Η), 5. 1 1 (1 Η), 5.1 8(1Η), 5.79(1Η). 19F-NMR (282.7MHz; solvent: CD C13, standard: CFC 13) 5 (ppm): -94.6 (1F), -l〇4.4 (lF), -106.2 (1F), -108.6 (1F), -185.9 (1F). [Example 1-8] Production example of the compound (al5) In a solution containing the compound (alH) (2.0 g) and tert-butyl methyl ether (20 mL), slowly, dropwise, diisopropylethylamine (1) under ice cooling .1 2 g ), the following compound (w5) (1.83 g) was further added dropwise. The solution was stirred for 5 hours in this state to carry out a reaction. Then, water was added to the solution to quench the reaction, and the organic layer was recovered. The organic layer was washed with water, dried over magnesium sulfate, and concentrated to give a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 1:1) to give the compound (a i 5) (2.7 g). -52- 200910003 [Chem. 44] CF2*CFCF2CHCH2CH«CH2 ((w5) ocH2a C(0)0CH20 te (a15) The NMR data of the compound (al5) are as follows: h-NMROOOjMHz, solvent: heavy acetone, standard: TMS) (ppm): 1.48-2.05 (1 5H), 2.4 7 - 2.7 3 (2 Η), 3 · 1 7 - 3 · 3 2 (1 Η), 5 · 0 8 - 5.2 1 (2 Η), 5 · 4 3 (2 Η), 5.6 9 - 5 . 8 3 (1 Η). 19F-NMR (282_7MHz, solvent: heavy acetone, standard: CFC13) &lt;5 (ppm): -94.1 (1 F) &gt; -105.9 (1F), -108.3 (1F), -186.4 (1F) ° [Example 1-9] The compound (a 1H) (5. Og), the compound (W6) (9.9 g), dimethylamine pyridine (〇. 2 g), and dichloromethane (30 g) were placed in a reactor. 〇°C. Then, a solution in which dicyclohexylcarbodiimide (4.7 g) was dissolved in methylene chloride (15 g) was slowly dropped into the reactor. In this state, the reaction in the reactor was stirred for 1 hour, and then the reaction was carried out by stirring at 25 ° C for 1 hour. The solution in the reactor was filtered, and the filtrate was concentrated to give a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 20:1) to give the compound (a. -53- 200910003 [化45] OH I /CH ?F, ri=,? F2 I °\\ cf2 )cf , cf2 (w6) cf2=cfcf2chch2ch-ch2 i(0)?/CP2

NMR data of ??F CF, CFrCF2 (ai6) compound (al6) are as follows: ^-NMROOO.AMHz' solvent: heavy acetone, standard (ppm) - 2.64~2.70 (2H) '3.44~3.48(lH), 5.16 ~5. 5·68~5.80 (2Η). 19F-NMR (282.7MHz; solvent: heavy acetone, basis (ppm): - 92 · 3 ( 1 F) ' -1 0 5 _ 2 (2 F), _ 1 〇7 · 2 (1 F), -123.6 (6F)' -132.6(2F), -187.3(1F), -214.7(m, -223_0(1F). Further, the compound (w6) represents that R11 is F(CF2)3〇CF according to the following synthesis sequence. (CF3) CF2〇CF(CF3)-) [Chem. 4 6]

(aw6) (bw6) (cw6) (dw6) (w6) That is, the compound (aw6) (15g) and chloroform (100g) were placed in a flask under a nitrogen atmosphere, and the flask was iced into Rn. -COF (79 g), and the inside of the flask was stirred. By :TMS) δ 21 (2Η)- '· C F C13) &lt;5 IF), into (where

NaF (7.02g): After stirring, remove the insoluble solids in the flask from -54 to 200910003, and then add a saturated aqueous solution of sodium hydrogencarbonate (1 〇 3 g) to the flask to recover the organic layer. Concentration gave compound (bw6) (74 g). R11 3 (3 1 3 g) was placed in an autoclave provided with a NaF particulate matter filling layer at the gas outlet, and the inside of the autoclave was stirred at 25 ° C, and nitrogen gas was blown into the autoclave for 1 hour, and then blown in. The fluorine gas was diluted to 20% by volume with nitrogen. In this state, while blowing the 20% fluorine gas, the solution in which the compound (bw6) (67 g) was dissolved in R 1 13 (2 99 g) was introduced into the autoclave under a pressure of 0.1 MPa. . After the completion of the introduction, the contents of the autoclave were recovered and concentrated to give a compound (cw6). The compound (cw6) (80 g) and powdery KF (0.7 g) were placed in a flask under a nitrogen atmosphere, and the mixture was heated for 6 hours, and then the contents of the flask were purified to obtain a compound (dw6) (38 g). NaBH4 (1.lg) and THF (30 g) were placed in a round bottom flask under a nitrogen atmosphere. While the flask was ice-cooled, a solution (48 g) containing 22% by mass of the compound (dw0) was dropped into the flask. After the completion of the dropwise addition, the mixture was stirred in a flask, and the solution in the flask was neutralized with a 1 N aqueous hydrochloric acid solution (15 mL), and the obtained solution was washed with water and then purified by distillation to obtain Compound (w6). The NMR data of the compound (w6) are as follows: j-NMROOOJMHz, solvent: CDCU, standard: TMS) &lt;5 (ppm): 4 · 8 9 to 4.5 7 (2 Η). 19F-NMR (282.7MHz, solvent: CDC13, reference: CFC13) &lt;5 (ppm): -105.0 (1F), -1 19.7 (1F), -124_0 (1F), -55- 200910003 -124.3 (1F) , -125.7 (1F), -126.8 (1F), -133.2 (2F), -216_6 (1F), -223_5 (1F). [Example 1 - 1 0] CF2 = CFCF2CH (C(0)0CH2CF2CF3) CH2 CH = CH2 (hereinafter referred to as compound (al7)) Production example In the reactor, compound (alH) (5.0 g), CF3CF2CH2OH ( 3.6 g), dimethylaminopyridine (0.23 g) and dichloromethane (15 mL) were cooled to EtOAc. Then, a solution in which dicyclohexylcarbodiimide (4.9 g) was dissolved in methylene chloride (35 mL) was slowly dropped into the reactor. After the reaction in the reactor was stirred for 1 hour in this state, the reaction was carried out, and the mixture was further stirred at 25 ° C for 1 hour to carry out a reaction. Water is then added to the reactor to quench the reaction and the organic layer is recovered. The organic layer was dried over magnesium sulfate and concentrated to give a crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 10:1) to afford compound (al7) (4.0 g). The NMR data of the compound (al7) are as follows: 1H-NMR (300_4 MHz, solvent: heavy acetone, standard: TMS) 5 (ppm): 2.5 1 to 2.73 (2H), 3 · 3 0 to 3.44 (1 Η), 4 · 5 0 to 4.6 9 (2 Η), 5.07 to 5.23 (2 Η), 5.66 to 5.84 (1 Η) 0 19F-NMR (282_7 MHz, solvent: heavy acetone, standard: CFC13) &lt; 5 (ppm): -84.4 (3F ), -94_2(1F), -l〇5.3(2F), -107.8(1F), -124.0(2F), -187.0(1F). [Example 1 - 1 1] Production Example of Compound (a 18) -56 - 200910003 In the reactor, the compound (alH) (7.6 g) was dissolved in toluene (1 mL), and 3 drops of concentrated sulfuric acid was added. Then, the following compound (w8) (4.1 g) was added dropwise to the solution under ice cooling to carry out a reaction. After the temperature was raised to 25 ° C, the solution was stirred for 7 hours in this state, and an aqueous solution of sodium hydrogencarbonate was added to the solution to quench the reaction to recover the organic layer. The organic layer was washed with water, dried over magnesium sulfate and concentrated to give a crude product. The crude product was purified by silica gel column chromatography (developing solvent:hexane) to give the compound (a I8) (1.78 g). [化47]

CF2=CFCF2CHCHaCH=CH2 C(0)0 CH3CH2-- The NMR data of the compound (al8) are as follows: iH-NMRpOOJMHz, solvent: CDC13 'Base: TMS) 5 (ppm): 1.57 (2Η) '1·59 (3Η) '1·69-1·92(8Η) ' 2·02(2Η) ' 2·29(2Η), 2·49(1Η) ' 2.66(1Η), 3.19(1Η) ' 5.11(1Η) ' 5· 18 (1 Η), 5.79 (1 Η). l9F-NMR (282.7MHz, solvent: CDC13, reference CFC13) 5 (ppm): -94_6(1F), -104_4(1F), -l〇6.2(lF), -l〇8.6(lF)' -185.9( 1F). [Example 2] Production Example of Polymer-57-200910003 [Example 2-1] Production Example of Polymer (A1) A compound 02(1.54) and acetic acid were added to a pressure-resistant reactor (internal volume: 30 mL, made of glass). Ethyl ester (3.41 g). Then, a R225 solution (〇.20 g) containing 50% by mass of IPP was added as a polymerization initiator to the pressure-resistant reactor. After degassing in the reactor, the reactor was maintained at 40 ° C and subjected to polymerization treatment for 18 hours. The solution in the reactor was dropped into methanol, and the solid matter produced was recovered, and vacuum-dried at 80 ° C for 20 hours, and a white powdery polymer (A^OJAg) was obtained at 25 °C. The polymer (A1) had Mw of 6,3 00 and Μη of 4,600. As a result of analyzing the polymer (Α1) by 19F-NMR and 1H-NMR, it was confirmed that the polymer (A1) was selected from the following formula (U1-A21), the following formula (U2-A21), and the following formula (U3). -A21) One or more overlapping units (A 2 1) of the group formed by the repeated units. Cf2 , ch2 / , CF-CH , cf2 , ch2 XC(C(0)0C(CH3)3)2 (U1-A21) , CF2 /C 吒 / \ /CH2 ^CF , CH , CF III CF2 /CH2 cf2 , qq〇)〇c(CH3}3)2 (U2-A21) ,ch2 CH I ', /CH2 VC(C(0)0C(CH3)3)2 (U3-A21) Polymer ( A1) is soluble in acetone, THF, ethyl acetate, methanol, 2-hexylfluoroethanol, and is insoluble in R225, perfluoro(2-butyltetrahydrofuran), perfluoro-η-octane. [Example 2-2] Production Example of Polymer (Α2) -58- 200910003 A compound 02^(1.5^) and R225 (8.56g) were added to a pressure-resistant reactor (internal volume 3 OmL, made of glass). Then, a R225 solution (0.20 g) containing 50% by mass of IPP was added as a polymerization initiator to the pressure-resistant reactor. After degassing in the reactor, the reactor was maintained at 4 ° C for 18 hours of polymerization. The solution in the reactor was dropped into methanol to recover the solid matter formed, and vacuum drying was carried out at 80 ° C for 20 hours. The polymer (A2) (0.81 g) was obtained as a white powder at 25 ° C. . The polymer (A2) had a Mw of 30,000 and a Μη of 18, 〇〇〇. Further, it was confirmed that the polymer (Α2) contained a repeating unit (Α21). [Example 2-3] Production Example of Polymer (Α3) A compound (a2H) (1.00 g) and R225 (5.41 g) and IPP (O.10 g) were added to a pressure-resistant reactor (internal volume 2 mL, made of glass). ). Then, a R225 solution (0.28 g) containing 5 〇 mass% of IPP was added as a polymerization initiator to the pressure-resistant reactor. After degassing in the reactor, the reactor was maintained at 40 ° C and subjected to polymerization treatment for 18 hours. The solvent in the reactor was changed to THF, and the mixture was added dropwise to hexane, and the resulting solid matter was collected, and vacuum-dried at 80 ° C for 20 hours to obtain a white powdery polymer at 25 ° C (A3). ) (0.82g). The polymer (A3) had an Mw of 22,000 and a Μη of 8,700. The result of analysis of the polymer (Α3) by 19F-NMR and 1H-NMR confirmed that the polymer (A2) contained a compound selected from the following formula (U1-A2H), the following formula (U2-A2H), and the following formula (U3) -A2H) One or more overlapping units (A2H) of the group consisting of the repeated units. -59- 200910003 [CF49] /CF2,ch2 / ,CF-CH , / \ CF2 /CH2 O(C(0)OH)2 (U1-A2h) .CF2 /CHn2 / ~CF CH II CF2 /CH2 Nqq 〇)〇H)2 (U2-A2h) , cf2 , CF I cf2 'CH I ,ch2 ,ch2 C(C(0)0H)2 (U3^A2h) [Example 2-4] Polymer (A4) Production Example The compound (a2H) was polymerized with the compound (f1) represented by the following formula in the presence of a polymerization initiator (R-225 solution containing 50% by mass of IPP) in a solvent of R22 5 and 2-propanol. . The solid matter obtained by dropping the reaction solution into hexane is recovered, and dried under vacuum at 1 ° C for 24 hours to obtain a formula formed by polymerization of a repeating unit (U-A2H) and a compound (f1). The polymer (A4) containing the repeating unit (F1) is shown.

[Example 2-5] Production Example of Polymer (A5) A compound (al~ (l6.0 g) and ethyl acetate (I29.8 g) was placed in a reactor (internal volume: 200 mL, made of glass), and added as a iPp (5.95 g) of a 50% by mass R225 solution of the polymerization initiator. After degassing under reduced pressure in the reactor -60-200910003, the polymerization was carried out at a reactor internal temperature of 40 t for 18 hours. The inside of the reactor was recovered. The solid fraction obtained by dropwise addition of the solution to hexane was dried at 1200 ° C. (vacuum under vacuum for 40 hours). As a result, a white powdery polymer (A5) (l 5.5 g) was obtained at 25 〇c. The polymer (A5) had a Mw of 9,700 and a Μη of 4,600, and the Tg of the polymer (Α5) determined by differential scanning calorimetry was 178. (:: Polymer by 19F-NMR and 1H-NMR (A5) As a result of the analysis, it was confirmed that the polymer (A5) contains a group consisting of repeating units represented by the following formula (U1-A1H), the following formula (U2-A1H), and the following formula (U3-A1H). One or more overlapping units (A1h).

Cf2 /ch2 XCH(C(0)OH) (U3-A1h) Polymer (A5) is soluble in acetone, THF, ethyl acetate, methanol, PGMEA, insoluble in R225, perfluoro(2-butyltetrahydrofuran) , perfluoro-n-xin hospital. [Example 2-6] Production Example of Polymer (A6) In a reactor (internal volume: 30 mL, made of glass), a compound (al1) (0.8 g) 'R225 (8.0 g) and ipA (〇.〇6g) were placed. Further, IPP (1.〇g) of a 50% by mass R225 solution as a polymerization initiator was added. After degassing under reduced pressure in the reactor, the polymerization was carried out for 18 hours at an internal temperature of the reactor. Recovery -61 - 90 200910003 The solution obtained by dropping the solution into hexane (90 g) in a reactor was vacuum dried at t for 40 hours. As a result, a white powdery polymer (A6) (0.56 g) was obtained at 25 °C. The polymer (A6) had a Mw of 16,000 and a Μη of 11, and the Tg of the polymer (?6) as determined by differential scanning calorimetry was 1 18t. It was confirmed by NMR analysis that the polymer (A6) contained one selected from the group consisting of the repeating positions represented by the formula (U1-A11), the following formula (U2-A11), and the following formula (U3-A11). More than one repeating unit (A 1 1). /CF2, CF c»rCH2, /2, /CH2, / \ Strict C, H, /, CF, CH, CF CH, CF&lt; /CH2 CF2 CF2 yCH2 CH(C(0)OC( CH)3), CH(C(0)0C(CHh) NCH(C(0)0C(CH)3) (U1-A11) (U2-A11) (U3-A11) The polymer (A6) is soluble Acetone, THF, ethyl acetate, PGMEA are insoluble in R22 5, perfluoro(2-butyltetrahydrofuran), perfluoro-n-octane. [Example 2-7] Production example of polymer (Α7) in the reactor (A: (0.8 g), R225 (4.3 g) and IPA (0.07 g) were placed in an internal volume (30 mL, glass), and IPP (0.53 g) was added as a 50% by mass solution of the initial polymerization. After the gas was degassed in the reactor, the polymerization was carried out at a temperature of 4 (TC) for 18 hours. The solid solution obtained by dropping the solution into the hexane (60 g) in the reactor, 9〇 Drying under vacuum at ° C for 40 hours. As a result, a white final polymer (A7) (0.6 g) was obtained at 25 ° C. The final micro-subject was pressed back to the powder -62-200910003 polymer (A7) Mw was 1 5,800 and Μη was 8,900. It was confirmed by NMR analysis that the polymer (Α7) contained a compound selected from the following formula (U1-A12) and the following formula (U2-A) 12) and one or more overlapping units (A 12) of the group consisting of the repeating units represented by the following formula (U3-A12). [Chem. 53] cf2 / CF2 is 〆 / , CF , CH cf2 ^. Ch2 cf2 ch2 CH(C(0)OCH2OCH3) sCH(C(0)OCH2〇CH3) xCH(C(0)OCH2〇CH3) (U1-A12) (U2-A12) (U3-A12) CF-CH ) CH2, ch2 CFa

Yc\ ^ch2 , CF , CH ' II polymer (A7) soluble in acetone, THF 'ethyl acetate, PGMEA ' insoluble in R2 25, perfluoro(2-butyltetrahydrofuran), perfluoro-n-octyl alkyl. [Example 2-8] Production Example of Polymer (Α8) A compound (al3) (2.0 g) and ethyl acetate (15.8 g) were placed in a reactor (internal volume: 30 mL, glass), and then placed as 50. % by mass of R225 solution IPP (〇.73g). The polymerization was carried out at 40 ° C for 18 hours. The solid solution obtained by dropping the solution into the hexane (60 g) in the reactor was vacuum dried at 90 ° C for 24 hours to obtain a white powdery polymer (A8) (1 - 40 g). The polymer (A8) had an Mw of 12,600 and a Μη of 6,100. The Tg of the polymer (Α8) determined by differential scanning calorimetry was 9 (rC. The polymer (α8) was selected by NMR analysis. Freedom of the following formula (U1-A13) 'The following formula (U2-A13) and the following formula (U3_A13) indicate one or more overlapping units (A丨3) of the group consisting of repeated units. -63- 200910003 [Chem. 54] CH IC(O)0CH20CH2

, cf2

.cf2 ,ch2 ^CF-CH ' cf2 'ch2 (U1-A13)

/CH2 / 'CF XCH cf2 J:h2

CH C(0)OCH2OCH2 (U2-A13)

.CF2 ^ch2 , CF 'CH , CF2 /CH2 VCH C(0)0CH20CH2 (U3-A13) The polymer (A8) is white powder at 25 ° C and soluble in acetone, THF and ethyl acetate. in. [Example 2 - 9] Production Example of Polymer (A9) A compound (al4) (2.0 g) and ethyl acetate (ll. Og) were placed in a reactor (internal volume: 30 mL, glass), and then placed as 5 〇 mass% of R225 solution IPP (〇, 53 g). The polymerization was carried out at 40 ° C for 18 hours. The solid solution obtained by dropping the solution in the reactor into hexane (60 g) was vacuum-dried at ll ° C for 24 hours to obtain a polymer (human 9) (19 〇 §). The polymer (Eight 9) had a MW of 23,500 and a Μη of 9,600, and the Tg of the polymer (Α9) as determined by differential scanning calorimetry was 1〇7t. It is confirmed by NMR analysis that the polymer (a9) contains one or more selected from the group consisting of repeating units represented by the following formula (in-Al4), the following formula (U2-A14), and the following formula (U3_Al4). Repeat unit (A丨4). -64 - 200910003 [化55]

/η2 , CF—CH , CFj ^CHz CH C(0)0 CH® (U1-A14) CF2 /CH2 /

Ύ '?H cf2 ch2

&quot;&quot;CH C(0)0 CH3i0 (U2-A14) /CF2 ,ch2 &gt;CF , CH , CF2 /CH2 nch έ(ο)ο CH3fe (U3-A14) Polymer (A9) at 25°C It is white powder and soluble in acetone, tetrahydrofuran and ethyl acetate. [Example 2-10] Production Example of Polymer (A1()) In a reactor (internal volume: 30 mL, made of glass), a compound (al5) (1.0 g) and ethyl acetate (8.8 g) were placed, and then placed. IPP (〇.4〇g) as a 50% by mass R225 solution. The polymerization was carried out at 40 ° C for 18 hours. The solid content obtained by dropping the solution in the reactor into methanol was recovered by vacuum drying at 90 ° C for 24 hours to obtain a polymer (A1()) (0.62 g). The polymer (A1G) had a Μη of 6,100 and a Mw of 10,200, and the Tg of the polymer (A 1 G) determined by differential scanning calorimetry was 107. (: NMR analysis confirmed that the polymer (Αι〇) contains one selected from the group consisting of repeating units represented by the following formula (U1-A15), the following formula (U2_A15), and the following formula (U3_Al5) More than the above repeated units (A丨5). -65- 200910003 [化56] , cf2 xch2 ^CF-CH , / \ e cf2 /CH2 \h C(0)0CH20

, cf2 /CH2 / , CF , CH I I cf2 .ch2 , CH' I C(O)OCH20 /CF2 , ch2 , CF , CH , I I cf2 ch2 , ?H' C(0)0CH20

iB © (U1-A18) (U2-A18) (U3-A1S) [Example 2-1 1] Production example of polymer (A11) A compound (al6) was placed in a reactor (internal volume: 30 mL, glass). (0.5 g) and R225 (1.93 g) were placed in an IPP (0.15 g) as a 50 mass% R225 solution. The polymerization was carried out at 40 ° C for 18 hours. The solid solution obtained by dropping the solution in the reactor into hexane was vacuum dried at 1 ° C for 24 hours to obtain a polymer (AM) (0.42 g). The polymer (A1G) had a Μη of 9,900 and a Mw of 15,1〇〇. It was confirmed by NMR analysis that the polymer (A11) contained one selected from the group consisting of the repeating units represented by the following formulas (U1-A16), (U2-A16), and the following formula (U3-A16). More than one repeating unit (A 16). 7 5 --. CH· H2 c〆 &lt;/H2

7C oiHk F2 Η H CIC HI /H(o) c PIC F&quot;F2, ^ulc F2 c

F F CIC F2 c CH—CH2

H2 C

(U1-A FF2 CIC FrCFr ~l c

Ff2 CIC F2FrCFr2C, CF/c /tt /F, · O—CIC A 2· (u FIT CIC 5 h/f, 16) O—CICA1 \H(0)U3- PIC(u -66- 200910003 Polymer ( A11) is a white powder at 25 t, and can be dissolved in acetone, THF, ethyl acetate, methanol, and R225, respectively. [Example 2-12] The production example of the polymer (A12) is in a reactor (internal volume 30 mL, The compound (a1. (0.81g) and R2 25 (7_2g) were placed in the glass), and IPP (0.81g) as a 50 mass% R225 solution was put in. The polymerization reaction was carried out for 40 hours. The solid solution obtained by dropping the solution in the reactor into methanol was recovered, and dried at 9 ° C for 24 hours to obtain a polymer (A12) (0.66 g). The η of the polymer (A12) was 4,300. Mw was 6,000. It was confirmed by NMR analysis that the polymer (A12) contained a repeating unit selected from the group consisting of the following formula (U1-A17), the following formula (U2-A17), and the following formula (U3-A17). One or more overlapping units (A17) of the group. [Chem. 58]

/ \ CF2 /CH2 ΌΗ , CH2 / , 〒F , ?H cf2 .ch2 nch

Cf2 /CH2, CH %

I I cf2 .ch2 VCH C(0)0CH2CF2CF3 C(0)0CH2CF2CF3 C(0)0CH2CF2CF3 (U1-A17) (U2-A17) (U3-A17) [Example 2 -1 3] Manufacturing Example of Polymer (A13)

The compound (al) (0.89 g) and ethyl acetate (7.8 g) were placed in a reactor (internal volume 3 mL of 'glass), and then placed in an IPP (0.35 g) as a 50 mass/R R225 solution. . The polymerization was carried out at 4 ° C for 18 hours. The solid fraction obtained by the dropwise addition of the solution in the reactor to hexane was vacuum dried at 1 °C - 67 - 200910003 for 24 hours to obtain a polymer (A13) (〇. 80 g). The polymer (A13) had a Μη of 7,500 and a Mw of 16,000. It was confirmed by NMR analysis that the polymer (A!3) contained a group selected from the group consisting of repeating units represented by the following formula (ΙΠ-Α18), the following formula (U2-A18), and the following formula (U3-A18). One or more overlapping units (A 18). [邙59] /邙2, CF-CH CF2 .ch2 pCH2 CH C(0)0 , CF2 yCH2 〆^CF nCH II cf2 ch2 XCH C(0)0 CH3CH2 t&gt; (U1-A18) CH3CH2 (U2-A18 ) \ /CF2 ,ch2 CF , CH C^2 /CH2 nch C(0)0 ch3ch2 (U3-A18) The polymer (A13) is white powder at 25 ° C and can be dissolved in tetrahydrofuran or ethyl acetate. in. [Example 2-14] Production Example of Polymer (A14) In a reactor (internal volume: 30 mL, made of glass), a compound (alH) (0.07 g), a compound 0^) (0.758), and ethyl acetate (1_) were placed. 85 g), IPP (O.Ug) of a 50 mass% R225 solution as a polymerization initiator was further added. After degassing under reduced pressure in the reactor, the polymerization was carried out at a reactor temperature of 40 ° C for 18 hours. The solid solution obtained by dropping the solution in the reactor into hexane was recovered, and dried under vacuum at 90 ° C for 24 hours to obtain a polymer (A14) (0.67 g). The polymer (A14) had an Mw of 28,000 and a Μη of 1,4,500. -68- 200910003 It was confirmed by NMR analysis that the polymer (A14) was a polymer containing a repeating unit (A1H) and a repeating unit (A11), and contained a repeating unit (A1H) with respect to the entire repeating unit. Mole%, a polymer containing 88% by mole of the repeating unit (A11). [Example 2-15] Production Example of Polymer (A15) A compound (al4) (0.75 g), a compound (al7) (〇18 g), and ethyl acetate were placed in a reactor (internal volume: 30 mL, glass). (6.7 g), IP P (0.3 1 g) of a 50 mass% R 2 2 5 solution as a polymerization initiator was further added. After degassing under reduced pressure in the reactor, the polymerization was carried out at a reactor temperature of 40 ° C for 18 hours. The solid portion obtained by dripping the solution into the hexane in the recovery reactor was vacuum dried for 24 hours at TC to obtain a polymer (A15) (0·61 g). The Mw of the polymer (A15) was 18,900, and Μη was 10,600. By NMR analysis, it was confirmed that the polymer (Αΐ5) was a polymer containing a repeating unit (Α14) and a repeating unit (Α17), and contained a repeating unit (Al4) 77 mol with respect to the entire repeating unit. %, a polymer containing 23 mol% of a repeating unit (αΓ). [Example 2-16] Production example of a polymer (Α16) A compound (alH) was placed in a reactor (internal volume: 3 mL, made of glass). (0.02 g), compound (al6) (〇.41 g) and ethyl acetate (3,8 g)' were further added as a polymerization initiator in a 50 mass% R225 solution (〇·1 7 g). After degassing under reduced pressure in the reactor, the polymerization was carried out at a temperature of 40 ° C in the reactor at -40 - 200910003 for 18 hours. The solid content obtained by dropping the solution in the reactor into hexane was recovered at 100 °. The polymer was dried under vacuum for 24 hours to obtain a polymer (A16) (0.29 g). The Mw of the polymer (A16) was 8,700, and Μη was 6,300. It was confirmed by NMR analysis. The compound (Α16) is a polymer containing a repeating unit (Α1Η) and a repeating unit (Α16), and contains 10 mol% of a repeating unit (Α1Η) with respect to the entire repeating unit, and contains a repeating unit (Al6). 90 mol% of the polymer. Further, the polymer (Α16) was dissolved in acetone, THF, ethyl acetate, and methanol, respectively. [Example 2-17] Production example of the polymer (Α17) in the reactor (internal volume 30 mL) 0.5 g of CF2 = CFCH2 (C(CF3)2(OH))CH2CH = CH2, compound (al6) (0.15g), and R225 (2.5 g) were added to the glass) and added as a polymerization initiator. 50% by mass of R22 5 solution of IPP (0.10 g). After degassing under reduced pressure in the reactor, the polymerization reaction was carried out at a temperature of 40 ° C for 18 hours in the reactor. The solution in the reactor was recovered. The solid fraction obtained in hexane was dried under vacuum at 90 ° C for 24 hours to obtain a polymer (A 17) (0.5 7 g). The polymer (A17) had a Μη of 9,200 and a Mw of 14,200. The result of NMR analysis of the polymer (A17) confirmed that the polymer (A17) was the following repeating unit (OA1) formed by polymerization of cf2 = cfch2(c(cf3)2(〇h))ch2ch = ch2. )versus The polymer of the repeat unit (Ai6) is a polymer containing 87 mol% of the overcoat unit (OAi) and 13 mol% of the repeat unit (Al6) with respect to the entire repeat unit. Further, the polymer -70-200910003 (A17) was dissolved in acetone, THF, ethyl acetate and methanol, respectively. [Chem. 60] /CF2 /CH2 / ^CF-CH , CHz JcH2 {0Α1)

, CH

C(CF3)2〇H The physical properties of the polymer (A) produced in the second embodiment are shown in Table 1. In addition, the number in parentheses in the column of "Type of repeating unit" in Table 1 indicates the proportion of the repeating unit in all repeating units (% by mole). [Table 1] Polymer No. Repetitive unit type Mw Mn Polymer (A1) (8 亇1〇〇1 6300 4600 Polymer (A2) (ΑΙ^ΓΙΟΟΙ 30000 18000 Polymer (A3) (A2h)『10 〇1 22100 8700 Polymer (A5) (A1h) [10〇1 9700 4600 Polymer (A6) (Al^flOOl 16000 11000 Polymer (A7) (Al2) flO〇l 15800 8900 Polymer (A8) (Al3) [10〇l 12600 6100 polymer (A9) (Al4) [10〇l 23500 9600 polymer (A, (Al5) [10〇l 10200 6100 polymer (A11) (ai6) "io〇i 15100 9900 polymer (A12) (Al7) [10〇l 6000 4300 Polymer (A13) (Al8) [10〇l 16000 7500 Polymer (A14) (Al^rnKAl^iSSl 28000 14500 Polymer (A15) (A14) [771 ( A17) [231 18900 10600 Polymer (A16) (A1h) [1〇1 (A16) [9〇1 8700 6300 Polymer (A17) (ΟΑ^ίΒΤΚΑΙ^ΓΠΙ 14200 9200 -71 - 200910003 [Example 3] Other polymerization Production Example [Example 3-1] Production Example of Polymer (B1) The following compound (b^10jg) and the following compound (¢2^(8) were placed in a reactor (internal volume 200 mL, glass). (^), the following compound (cl1) (3.7g) and methyl ethyl ketone (76.5g) were added as a chain shifting agent. Isopropanol (6.3 g) and R225 solution (1 l.Og) containing 50 parts by mass of IPP as a polymerization initiator, after degassing under reduced pressure in the reactor, at a reactor internal temperature of 40 ° C The polymerization was carried out for 18 hours. [Chem. 61]

Then, the solid solution obtained by dropping the solution in the reactor into the hospital was recovered, and the solid portion was vacuum dried at 901 for 24 hours at 25. (: A white powdery polymer (84 (15.9 g) was obtained. The polymer (B. Mn was 2,8 70, Mw was 6,600. The polymer (βΐ) was analyzed by the 13c-nmr method. a repeating unit containing 40 mol% of the compound (b 1), 40 mol% of the compound (c2 1 ), and a repeating unit of the compound (cl1) 2 mol% of the polymer in the entire repeat unit Further, the polymer (B1) is soluble in THF, PGMEA, and cyclopentanone, respectively. -72-200910003 [Example 4] Production Example of Composition [Example 4-1] Production Example of Composition (1) Polymerization The substance (AMCOJg) was dissolved in PGMEA (3.74 g) to obtain a uniform solution. The solution was filtered with a filter to obtain a composition (1) containing the polymer (A1). [Example 4-2] Composition (2) In the production example, the polymer (A2) (〇3 g) was dissolved in PGMEA (3.74 g) to obtain a uniform solution, and the solution was filtered with a filter to obtain a composition (2) containing the polymer (A2). Example 4-3] Production Example of Composition (3) The polymer (B1) was dissolved in a mixed solvent of PGMEA (90% by mass) and cyclopentanone (1% by mass) to prepare a polymer (Βι) 7 ·63 Amount of the solution (4.46 g). Add the polymer (A, (0.017 g) to the solution to make it a solution of the solution. The solution was filtered through a filter to obtain a polymer containing (B 4 and The composition (3) of the polymer (A1) [Example 4_4] The production example of the composition (4) was obtained by the same procedure as in Example 4-3 except that the polymer (A2) was used instead of the polymer (Al). Composition (4) of the compound (Βι) and the polymer (A2) [Example 4 - 5] Production example of the composition (5) - 73 - 200910003 Dissolving the polymer (A3) in 2-methyl-1- The homogeneous solution obtained in the propane was filtered through a filter to obtain a composition (5) containing the polymer (A3). [Example 4-6] Production Example of the Composition (6) The polymer (A4) was dissolved in 2- A homogeneous solution obtained in methyl-1-propanol was filtered through a filter to obtain a composition (6) containing the polymer (A4). [Example 4-7] Production Example of the Composition (7) A polymer ( A3) A solution obtained by dissolving the polymer (A4) in 4-methyl-2-pentanol is filtered with a filter to obtain a polymer containing 50% by mass based on the total mass of the polymer (A3) ( A4) Composition (7) [Example 4 - 8] Production Example of Composition (C) A polymer (ByiOJg) was dissolved in PGMEA (3.74 g) to obtain a uniform solution. The solution was passed through a filter. The composition (C) was obtained. Hereinafter, the polymer and the solvent produced in Example 2 or 3 were appropriately selected in the same manner to prepare a composition. The composition of each of the modulations and the composition thereof are shown in Table 2. Further, the number 値 in the parentheses in Table 2 indicates the mixing ratio (mass ratio) of the polymer when a plurality of polymers are contained. -74- 200910003 [Table 2]

Composition No. Polymer Type Solvent Type (1) Polymer (A1) PGMEA (2) Polymer (A2) PGMEA (3) Polymer (^) + Polymer (B1; ^)] Mixed Solubility i ( PGMEA+CP) (4) Polymer (A2) + polymer mixed solution IKPGMEA + CP) (5) Polymer (A3) 2-methyl-1-propanol (6) Polymer (A4) 2-A 1-propanol (7) polymer (A3) + polymer (A4) [2: 1] 4-methyl-2-pentanol (8) polymer (A6) PGMEA (9) polymer (A7) PGMEA (1〇) Polymer (A8) PGMEA (11) Polymer (A9) PGMEA (12) Polymer (A10) PGMEA (13) Polymer (A11) PGMEA (14) Polymer (A12) PGMEA (15) Polymerization (A13) PGMEA (16) Polymer (A14) PGMEA 07) Polymer (A15) PGMEA (18) Polymer (A5) 4-methyl-2-pentanol 09) Polymer (Ai) + Polymer ( B1) [5:95] PGMEA (20) Polymer (A6) + Polymer (B1) [5:95] PGMEA (21) Polymer (A8) + Polymer (B1) [5:95] Mixed Solvent !I(PGMEA+CP) (22) Polymer (A8)+Polymer (B1) [5:95] PGMEA (23) Polymer (A9)+Polymer (B1) [5:95] PGMEA (24) Polymer (A5) + Polymer (A17) [80:20] 4-Methyl-2-pentanol (25) Polymer (A15) + Polymer (B1) [ 5:95] PGMEA (26) Polymer (A16) + Polymer (B1) [5:95] PGMEA (27) Polymer (A16) 4-Methyl-2-pentanol (28) Polymer (A17) 4-methyl-2-pentanol (6) polymer (B1) PGMEA

[Example 5] Production Example of Photoresist Composition - 75 - 200910003 [Example 5 - 1] Production Example of Photoresist Composition (丨) Triphenylsulfonium trifluoride in which photoacid generator was dissolved in the composition (1) A transparent and uniform solution of methanesulfonate (0.01 3 g) was filtered through a filter to obtain a photoresist composition (1). [Example 5-2] Production Example of Photoresist Composition (2) A transparent and uniform solution obtained by dissolving triphenylsulfonium trifluoromethanesulfonate (O.OMg) in the composition (2) was filtered. The filter was filtered to obtain a photoresist composition (2). [Example 5-3] Production Example of Photoresist Composition (3) A transparent and uniform solution obtained by dissolving triphenylsulfonium trifluoromethanesulfonate (0.014 g) in the composition (3) was used as a filter. Filtering 'to obtain a photoresist composition (3). [Example 5-4] Production Example of Photoresist Composition (4) A transparent and uniform solution obtained by dissolving a tribasic quinone nonafluorobutane sulfonate (0.01 4 g) of a photoacid generator in the composition (3) It was filtered with a filter to obtain a photoresist composition (4). [Example 5-5] Production Example of Photoresist Composition (5) A transparent and uniform solution obtained by dissolving triphenylsulfonium nonafluorobutanesulfonate (〇.〇i4g) in the composition (4) was used to make it The photoresist composition was obtained by the filter "(5) ° -76- 200910003 [Example 5-7 (Comparative Example)] Production Example of Photoresist Composition (C) Polymer (84 (0.3 g) and three Phenylfluorene trifluoromethanesulfonate (0.014 g) was dissolved in PGMEA (3.74 g) to obtain a homogeneous solution. The solution was filtered through a filter to obtain a photoresist composition (C). (Comparative Example)] Production Example of Photoresist Composition (D) A polymer and triphenylsulfonium nonafluorobutanesulfonate (0.014 g) were dissolved in PGMEA (3.74 g) to obtain a uniform solution. This solution was filtered with a filter to obtain a photoresist composition (D). Hereinafter, the composition prepared in Example 4 and the photoacid generator were appropriately selected to modulate the photoresist composition in the same manner. The components contained in the composition are shown in Table 3. Further, the triphenylsulfonium trifluoromethanesulfonate of the photoacid generator is referred to as TPS, and the triphenylsulfonium nonafluorobutanesulfonate is referred to as TPSF. -77-200910003 [Table 3]

Photoresist composition No. Polymer type Photoacid generator type (1) Polymer (A1) TPS (2) Polymer (A2) TPS (3) Polymer (A1) - Polymer (B1) TPS (4) Polymerization (A1). Polymer (B1) TPSF (5) Polymer (A2) + Polymer (B1) TPSF (6) Polymer (A5) TPSF (7) Polymer (A7) TPSF (8) Polymer (A8) TPSF (9) Polymer (A9) TPSF (10) Polymer (A10) TPSF (11) Polymer (A8) + Polymer (B1) TPSF (12) Polymer (A10) TPSF (C) Polymer (B1) TPS (D) Polymer ( B1) TPSF

[Example 6] Evaluation example of the water repellency of the composition or the photoresist composition The composition (2) was spin-coated on a sand substrate having an antireflection film (ROHM AHD HAAS Electronic Materials trade name AR26, the same applies hereinafter) formed on the surface. Then, the tantalum substrate was heat-treated at 100 ° C for 90 seconds to form a resin film (film thickness 5 Onm) composed of the polymer (A2) on the tantalum substrate. Next, the static contact angle, the falling angle, the advancing angle, and the receding angle of the resin film against water were measured. The falling angle measured by the sliding method is referred to as "turning angle". The forward contact angle is referred to as "forward angle" and the backward contact angle is "retracted angle". The units of the static contact angle, the falling angle, the advancing angle, and the receding angle are all angles (degrees) (the same applies hereinafter). The measurement system was made using the Concord Interface Scientific Contact Angle Meter DM-700. Further, the volume of the water droplets used was 2#L' at the contact angle, and the turning angle, the advancing angle, and the receding angle were 5 〇 #1. -78- 200910003 A resin film was formed on a tantalum substrate in the same manner as in the case of using the composition produced in Example 4 and the photoresist composition produced in Example 5 instead of the composition (2). Static contact angle, falling angle, advancing angle, and receding angle. The results are shown in Table 4. [Table 4] Material Forming Resin Film Static Contact Angle Drop Angle Advance Angle Backward Angle Advance Angle and Retreat Angle Difference Composition (2) 88 8 92 85 7 Composition (8) 88 8 91 83 8 Composition (10 86 14 89 75 4 Composition (11) 87 8 87 80 7 Composition (12) 82 14 86 73 13 Composition (13) 103 12 105 92 13 Composition (14) 98 15 86 73 13 Composition (15 86 9 90 80 10 Composition (16) 86 14 89 75 14 Composition (Π) 89 12 92 80 12 Composition (19) 87 8 90 81 9 Composition (20) 87 10 91 81 10 Composition (24 98 17 104 84 20 Composition (25) 85 14 89 76 13 Composition (26) 84 12 86 75 11 Composition (27) 82 22 87 64 23 Composition (C) 69 25 74 50 24 Photoresist composition (1) 86 9 90 81 9 Photoresist composition (2) 88 8 92 84 8 Photoresist composition (C) 69 25 74 50 24 From the above results, it can be known that the polymer containing the repeat unit (A) Excellent water repellency (especially dynamic water repellency). Thus, in the immersion lithography method -79-200910003, the immersion liquid can easily follow the projection lens moving over the photosensitive photoresist layer. [Example 7] Evaluation of the liquid repellency of the developer of the photoresist composition The composition (1) was spin-coated on a substrate on which a reflection preventing film was formed on the surface. Then, the tantalum substrate was heat-treated at 1 〇 ° C for 9 sec seconds to form a resin film (film thickness: 50 nm) composed of the polymer (A1) on the ruthenium substrate. Then, the germanium wafer was exposed to an ArF excimer laser (intensity of 50 rnJ/cm 2 ) to expose the germanium wafer. The wafer is then heat treated with a hot plate at 60 ° C for 60 seconds. After the formation of the film, after the exposure, and after the heat treatment, the static contact angle was measured for the aqueous test solution of the film of each of the twin crystals (trade name "D D _ 1 0" by Tama Chemical Co., Ltd.). Further, the other photoresist compositions produced in Example 5 were also measured in the same manner, and the results are shown in Table 5. [Table 5] The film of the material forming the resin film is formed after exposure, and the photoresist composition after heat treatment (1) 81 79 36 Photoresist composition (8) 74 73 27 Photoresist composition (9) 72 72 28 Photoresist composition (10) 71 70 28 Photoresist composition (C) 69 70 43 It can be seen from the above results that the photoresist composition containing the repetitive unit (A) increases the affinity for the aqueous alkali solution after the immersion lithography method. Material -80- 200910003 material. [Example 8] Evaluation Example of PAG Dissolution Amount of Photoresist Composition The composition (4) was spin-coated on a crucible substrate having an antireflection film formed on its surface. Then, the sand substrate was heat-treated at 10 ° C for 90 seconds to form a resin film (having a film thickness of 150 nm) composed of the polymer (A 1) and the polymer (B 1 ) on the substrate. Then, the germanium substrate is mounted on a double-beam interference exposure device using ArF laser light (wavelength 193 nm) as a light source, and ultrapure water (45 0 // L) is sealed between the cover glass (made of synthetic quartz) and the germanium substrate. After that, leave it for 60 seconds. Further, the area of the resin film on the crucible substrate and the ultrapure water was 7 cm 2 °, and then ultrapure water was recovered, and LC/MS/MS (Quarttro micro API, manufactured by Waters) was used (measurement limit: 7.0) Xl (T15mol/cm2), which is determined from the photoresist composition contained in ultrapure water (4) The photoacid generator (PAG) eluted from the cation (triphenylphosphonium cation) and the anion (nonafluorofluoride) The amount of dissolved butanesulfonate anion) (unit of elution amount: mol/cm 2 / 60 seconds). The other photoresist compositions were also measured in the same manner. The results are shown in Table 6. [Table 6] Formation of a resin film Material anion elution amount cation elution amount photoresist composition (4) 4.8xl〇·13 1.8xl〇·13 Photoresist composition (5) Below the detection limit, the photoresist composition below the limit (6) 1·13χ10· 14 The photoresist composition below the measured limit (D) 1.5Χ10·11 1.4χ1〇·π -81 - 200910003 [Example 9] The sensitivity evaluation example of the photoresist composition is formed on a sand substrate having an antireflection film formed on the surface. Rotating the composition (3). Then, the crucible substrate was heat-treated at 100 ° C for 90 seconds. A resin film (film thickness: 200 nm) composed of a polymer (A1) and a polymer (b1) was formed on the plate. The substrate was exposed to ArF excimer laser irradiation to expose the ruthenium substrate. Then, the exposure amount was changed by controlling the number of times of irradiation. Then, the wafer was heat-treated at 130 ° C for 60 seconds by a hot plate, and then developed, and the film thickness (unit: nm) of the resin film was measured. The thickness of the film according to the exposure amount is shown in Fig. 1. The resin film when the photoresist composition (6) to (9) is used instead of the photoresist composition (3) is also measured in the same manner. The film thickness is shown in Fig. 2. [Example 1] A formation example of a photoresist pattern of a photoresist composition is formed by spin coating a composition (1) on a substrate on which a reflection preventing film is formed on a surface. The ruthenium substrate was heat-treated at 100 Torr for 90 seconds to obtain a ruthenium substrate on which a resin film (150 nm) formed of the photoresist composition (1) was formed. The ArF excimer laser was used as a light source. The beam interference exposure device is used before the liquid immersion exposure method and the dry method using ultrapure water as the liquid immersion medium. The exposure test of the substrate was performed at 90 nm/S. It was confirmed by SEM image that 'in either case' formed a good pattern on the resin film of the ruthenium substrate. Also, the photoresist composition (6) was used instead. In the case of the photoresist composition (1), -82-200910003 was also confirmed by SEM image, and a good pattern was formed on the resin film of the ruthenium substrate. [Example 11] The alkali solubility evaluation example of the composition was made up. After the object (5) was spin-coated on a crystal oscillator, heat treatment was performed at 130 ° C for 90 seconds, and a film formed of the polymer (A3) was formed on a crystal oscillator. Then, the crystal oscillator was immersed in an aqueous solution containing 2.3% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMA Η), and crystal oscillator microbalance (Q CM) method was used to reduce the film. The film speed (unit: nm/s) was measured as the development speed (unit: nm/s) of the film. The measurement was carried out in the same manner as the composition (18). The results are summarized in Table 4. Further, the refractive index of the resin film formed of the composition (18) was 1.575. [Table 7] Material developing speed composition of film (5) 490 Composition (18) 440 [Example 1 2] Evaluation of characteristics of photoresist film of composition (Part 1) Formation of anti-reflection film on the surface On the substrate, the composition (C) was spin-coated. Then, the crucible substrate was heat-treated at 100 ° C for 90 seconds to obtain a sand substrate (A) which forms a photoresist film containing the polymer (B 1). Then, the composition (7) is spin-coated on the photoresist film of the sand substrate (A), and the ruthenium substrate is heat-treated at 1 〇〇I for 90 seconds to obtain a polymer formed on the photoresist film. (A3) A substrate (B) of a resin film composed of a polymer (A4). -83- 200910003 Mounting the ruthenium substrates (A) and (B) on a double-beam interference exposure device using ArF laser light as a light source, and encapsulating ultrapure water between the cover glass (made of synthetic quartz) and the ruthenium substrate (450 / / L), placed for 60 seconds. Further, the liquid contact area of the resin film on the base plate and the ultrapure water was 7 cm 2 . Then, ultrapure water was recovered, and the amount of the photoacid generator (PAG) eluted from the photoresist composition (C) contained in the ultrapure water was measured in the same manner as in Example 7 with the ruthenium substrate ( A) Comparison shows that the photoacid generator of the ruthenium substrate (B) is inhibited from elution by the material. [Example 13] Photosensitivity evaluation of composition The double-beam interference exposure apparatus using ArF laser light as a light source was used to perform 90 ninL/S of the above-mentioned ruthenium substrate by liquid immersion exposure method and dry method using ultrapure water as a liquid immersion medium. In the exposure test, it was confirmed by SEM image that a good pattern was formed on the resin film of the substrate (B). [Example 14] Evaluation Example of Photoresist Protective Film Characteristics of Composition (Part 2) The composition (C) was spin-coated on a substrate on which a reflection preventing film was formed on the surface. Then, the tantalum substrate was heat-treated at 100 ° C for 90 seconds to obtain a tantalum substrate (A) which forms a photoresist film containing the polymer (B1). Then, the composition (24) is spin-coated on the photoresist film of the ruthenium substrate (A), and the ruthenium substrate is heat-treated at 10 ° C for 90 seconds to obtain a polymer formed on the photoresist film. (A5) A substrate (C) of a resin film (10 nm) composed of a polymer (A17). Then, using a double-light-84-200910003 beam interference exposure apparatus using ArF laser light (wavelength 193 nm) as a light source, an immersion exposure test of 90 nm/mL of the ruthenium substrate (c) was performed (impregnation liquid: ultrapure water, developer: Tetramethylammonium hydroxide aqueous solution), the result. It was confirmed by SEM image that a good pattern was formed on the resin film of the substrate (C). It can be known from the above results that the polymer (PA) is suitable as a photoresist composition for increasing the alkali solubility by the action of an acid used in the immersion lithography method, or as a immersion lithography method. An alkali-soluble photoresist protective film composition. Therefore, by using the polymer (PA), the immersion lithography method can be carried out stably and at high speed. (Industrial Applicability) According to the present invention, it is possible to provide photoresist characteristics (transparency to short-wavelength light, etching resistance, etc.) or characteristics of a photoresist film for immersion lithography (due to intrusion of an immersion liquid) A photoresist which is excellent in dynamic liquid repellency (especially dynamic water repellency) and which can smoothly slide in an immersion liquid, which is suppressed by swelling of a photosensitive photoresist, suppression of elution of a photosensitive photoresist component into an immersion liquid, and the like. By using the photoresist material of the present invention, the immersion lithography method capable of high-resolution transfer mask image pattern can be stably and rapidly performed. The specification of the present invention is directed to the specification, application of Japanese Patent Application No. 2007-093222, filed on March 30, 2007, and Japanese Patent Application No. 2007-26 1 1 86, filed on Oct. 4, 2007. The entire contents of the patent, the drawings and the abstract are hereby incorporated by reference. -85- 200910003 [Scheme 1] Thickness (Unit: The light obtained in Figure 2 shows the exposure amount of each tree. The single explanation is a curve indicating the film nm of the resin film after development processing according to the exposure amount). A graph showing the results of photosensitivity evaluation using the photoresist compositions (6) to (9) in place of the photoresist composition (3). Vertical film The film thickness of the resin film formed by the fat composition, and the abscissa indicates -86-

Claims (1)

200910003 X. Patent Application No. 1 - A photoresist composition characterized by containing a polymer (PA) having a repeating unit formed by polymerization of a compound represented by the following formula (a) ( A), CF2 = CFCF2C(XA)(C(〇)〇zA)(CH2)naCRA = CHRA (a) where the symbol indicates the following meaning, xA: hydrogen atom, cyano group or formula - C(0)0ZA Illustrative, ZA: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, na: 0, 1 or 2, RA: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, 2 of which can be Same or different. 2. The photoresist composition according to claim 1, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1) or the following formula (a2), CF2 = CFCF2CH (C(0) ) 0Zai)CH2CH = CH2 (al) CF2 = CFCF2C(C(0)0ZA1)2CH2CH = CH2 (a2) The symbol in the formula indicates the following meaning, ZA1: hydrogen atom, formula -C (base shown in ZA11h, formula - a group represented by CH2OZa or a group of the following formula; -87- 200910003 [Chemical 1] ζΑ1ι and ZA12: a monovalent saturated hydrocarbon group each independently representing a hydrogen atom or a carbon atom, ZA13: a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms, QA13: forming a divalent bond with a carbon atom in the formula The cyclic hydrocarbon group has a carbon atom number of 3 to 19, , but 'Za, ZA12 or ZAI3 which is a monovalent saturated hydrocarbon group, and a carbon atom-carbon atom intercalable between QA13 and a group of the formula - The group represented by c(o)- or the group of the formula -C(0)0-, and the carbon atom of ZAH, ZA12, ZA13 or may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group. 3. The photoresist composition of claim 2 or 2, which contains a compound (PB) having a substance other than the repeating unit (A) which is dissolved by an acid Repeated unit of increased sex (B). 4. The photoresist composition according to claim 3, wherein the polymer (PB) system has the following formula (kbl), the following formula (kb2), the following formula (kb3) or the following formula (kb4) Polymer obtained by polymerizing the polymerizable compound (b) shown, -88- 200910003 [Chemical 2] Χ8,0 (kb1) xB2-c-xB2 j[b2 (kb2) -C(CF3)2(OZB) (kb3) - C(CF3)(0Ze) — (kb4) The symbol in the formula indicates the following meaning, XB1: number of carbon atoms 1~ 6 alkyl, QB1: together with the carbon atom of the formula to form a cyclic hydrocarbon group, the number of carbon atoms of 3 to 18, XB2: a monovalent hydrocarbon group having 1 to 17 carbon atoms, of which 3 Is the same or different, ZB: each independently represents an alkyl group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkylcarbonyl group or a hydrogen atom 'where the number of carbon atoms of the above group is 1 to 2 0; and 'in XB1, Qbi, χΒ2 Or the carbon atom-carbon atom in zB can be inserted into the formula - 〇-, the formula (((〇)〇_) or the formula _C(0)_, in XB1 'QB1 ' XB2 or The carbon atom in Ζβ may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group. 5 The photoresist composition according to claim 3 or 4, wherein the polymerizable compound (b) is a formula (b1) or a formula (b2) Or a compound of the following formula (b3), -89- 200910003, rL H2 c 1VCIO 3=c B ο ο B II Rwi ο C II H2 C XB1—C) I/ C—, a 2 (b1) (b2 (b3) The symbol in the formula indicates the following meaning, RB: hydrogen atom, fluorine atom, number of carbon atoms i~3 Alkyl or a fluorine atom having 1 to 3 carbon atoms; a group of XB1: an alkyl group having 1 to 6 carbon atoms, QB1: a carbon number of 3 to 18 in combination with a carbon atom in the formula Base, Xs. is 5 ash groups with 1 to 17 ash groups. 3 XB2 can be the same or different, QB3: with the formula -CF2C(CF3)(OZB)(CH2)nb-, or the formula -CH2CH(( CH2) mbC(CF3)2(OZB)) (CH2)nb represents a group, ZB: alkyl group, alkoxyalkyl group, alkoxycarbonyl group or alkylcarbonyl group or a hydrogen atom, wherein the above group has 1 to 20 carbon atoms , mb and nb: each independently represents 0, 1 or 2, but a carbon-carbon atom of XB1, QB1, XB2 or ZB can be inserted between -0·, -C(〇)〇- or -C(O) ) - Further, a carbon atom in XB1' QB1' xB2 or zB may bond a fluorine atom, a hydroxyl group or a carboxyl group. 6) The photoresist composition of any one of the claims 3 to 5, wherein the polymer-90 - 200910003 (PA) Ol~ 30 parts by mass relative to 100 parts by mass of the polymer (PB) . 7. The photoresist composition according to any one of claims 1 to 6, wherein the polymer (PA) is a polymer (PAF), the polymer (PAF) further having a repeating unit (F), The repeating unit (F) is a repeating unit (F) formed by polymerization of a polymerizable compound (f) having a fluorine-containing ring structure. 8. The photoresist composition according to claim 7, wherein the polymerizable compound (f) is the following formula (Π), the following formula (f2), the following formula (f3), the following formula (f4) or the following formula ( F5) the compound shown, χ ch2=c o&gt;=〇,0H, cf2 ;CF le/CF21 V (f3) ch2=c ,rf &gt;=〇CH2=CI ch2 I .CF ,rf &gt;=〇I CH CF2 , CF2 / CF2 , cf2 (M) cf2 (f5) where the symbol does not have the following meaning, RF: hydrogen atom, fluorine atom, alkyl group having 1 to 3 carbon atoms or fluoroalkyl group having 1 to 3 carbon atoms, and compound (Π) The fluorine atom in the ~(f5) may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. 9. The photoresist composition according to any one of claims 1 to 8, which comprises a photoacid generator and an organic solvent. 1 〇. A method for forming a photoresist pattern, which is a method for forming a photoresist pattern by immersion lithography, which is characterized in that it is carried out in order, and will be ninth in the scope of patent application as in -91 - 200910003 The photoresist composition is coated on the substrate to form a photoresist film on the substrate, the immersion lithography step and the development step to form a photoresist pattern on the substrate. 1 1 A photoresist protective film composition characterized by containing a polymer (PA) 'The polymer (PA) has a repeating unit (A) formed by polymerization of a compound represented by the following formula (a), CF2 = CFCF2C(XA)(C(〇)〇ZA)(CH2)naCRA = CHRA (a) The symbol in the formula indicates the following meaning: 氢: hydrogen atom 'cyano or formula - c(〇)〇zAm, ZA: A hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, na: 0, 1 or 2, RA: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and 2 Ra groups may be the same or different. 1 2 The photoresist protective film composition of claim 11, wherein the compound represented by the formula (a) is a compound represented by the following formula (a 1) or (a2), and CF2 = CFCF2CH (C ( 0)0ZA1)CH2CH = CH2 (al) CF2 = CFCF2C(C(0)0ZA1)2CH2CH = CH2 (a2) The symbol in the formula shows the following meaning, zA1: shows the hydrogen atom as the formula -c(zA11)3 a group of the formula -CH2OZa, or a radical of the formula -92-200910003, ZA11 and ZA12: each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group of carbon I, ZA13: a hydrogen atom or a monovalent saturated carbon number of 1 to 16 QA13: together with a carbon atom of the formula, a divalent cyclic hydrocarbon number 3~ a group of 19, but a carbon atom-carbon atom in the ZA 1 1 , ZA 1 2 or qa13 which is a monovalent saturated hydrocarbon group may be inserted into a group represented by the formula -0, an alkyl group or a formula - c(o)o- In addition, the carbon atoms in ζΑ11, ζΑ12, ζ may be bonded to a fluorine atom, a hydroxyl group or a carboxyl group. 1 3 . The photoresist of claim 1 or 2, wherein the polymer (ΡΑ) is a polymer (PAF), and the polymerization unit has a repeating unit (F) in one step, and the repeating unit (F) The repeating unit formed by the polymerization of the polymerizable compound (f) is formed. The polymerizable compound (f) is the following formula (Π), under the photoresist film of the third aspect of the patent application. Formula (f2) 'The compound of the following formula (f4) or the following formula (f5), the number of the genus 1 to 19 hydrocarbon group, the carbon atom of the group ZA13, and the formula -C(o)-A&quot; or qA13 protective film The material (PAF) has a fluorine-containing ring structure (F). Composition, which is as follows (f3), -93- 200910003 The symbol in the formula indicates the following meaning, RF: hydrogen atom, fluorine atom, alkyl group having 1 to 3 carbon atoms or fluoroalkyl group having 1 to 3 carbon atoms, and fluorine atom in 'compound (Π)~(f5) It may be substituted by a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxy group having 1 to 6 carbon atoms. The photoresist protective film composition of claim 13 or claim 14, wherein the polymer (PAF) contains a repeating unit (F) of 1 to 50 moles. /. . The photoresist protective film composition according to any one of claims 1 to 5, which contains an organic solvent. A method for forming a photoresist pattern, wherein the step of forming a photoresist film on a substrate by applying a photosensitive photoresist material to a substrate in accordance with the procedure is as described in claim 1 The photoresist resistive film composition is coated on the photoresist film to form a photoresist protective film on the photoresist film, the immersion lithography step and the developing step 'to form a photoresist pattern on the substrate. -94 -