WO2007116614A1

WO2007116614A1 - Process for producing resin for semiconductor lithography

Info

Publication number: WO2007116614A1
Application number: PCT/JP2007/053041
Authority: WO
Inventors: Isao Hirano; Takeshi Iwai
Original assignee: Tokyo Ohka Kogyo Co., Ltd.
Priority date: 2006-03-30
Filing date: 2007-02-20
Publication date: 2007-10-18
Also published as: JP2007291335A; JP5138234B2

Abstract

This invention provides a process for producing a resin for semiconductor lithography that can suppress the occurrence of defects, particularly bridge mode defects. The process for producing a resin for semiconductor lithography comprises bringing a resin solution (R1) of a resin (A1) for semiconductor lithography, comprising constituent units (a2) containing a lactone-containing cyclic group, dissolved in an organic solvent (S1) into contact with a resin (A1’) having a solubility parameter in the range of 17 to 20 (J/cm3)1/2 and a specific surface area in the range of 0.005 to 1 m2/g.

Description

Specification

Manufacturing method of resin for semiconductor lithography

Technical field

The present invention relates to a method for producing a resin for semiconductor lithography.

This application is based on Japanese Patent Application No. 2006-095191 filed in Japan on March 30, 2006, and Japanese Patent Application No. 2007-019351 filed on January 30, 2007 in Japan. Insist and use that content here.

Background art

[0002] In recent years, in the manufacture of semiconductor elements and the like, miniaturization has rapidly progressed due to advances in lithography technology.

As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, in the past, the power used for ultraviolet rays typified by g-line and i-line Currently, KrF excimer laser (248 nm) is the center of mass production, and ArF excimer laser (193 nm) is introduced in mass production. Being started. In addition, F excimer laser (157nm) and EUV (extreme purple)

2

Research is also being conducted on lithography technology that uses external light), EB (electron beam), etc. as a light source (radiation source).

[0003] A resist material used in lithography using such a light source is required to have high sensitivity to the light source. In addition, various improvements in lithography characteristics (resolution, depth of focus characteristics, resist pattern shape, etc.) other than sensitivity are required.

As one of the resist materials that satisfy the strong demands, a chemically amplified resist composition containing a base resin and an acid generator that generates an acid upon exposure is known! /. Chemically amplified resist compositions include a positive type in which the alkali solubility in the exposed area increases and a negative type in which the alkali solubility in the exposed area decreases.

At present, as a base resin of a chemically amplified resist composition, for example, when a KrF excimer laser is used as a light source, a polyhydroxystyrene (PHS) -based resin is mainly used. When ArF excimer laser is used as the light source, (a-lower alkyl) is mainly used. ) Resins having a structural unit derived from acrylic acid in the main chain (acrylic resin) are generally used.

In the production of base resin, the so-called temperature rising batch polymerization method, in which the raw material monomer, the polymerization initiator, and, if necessary, the chain transfer agent are dissolved in a polymerization solvent and then polymerized by heating, is the most common. It is used as a target.

[0004] However, the resist materials as described above have a problem that defects (defects) are likely to occur on the surface of the resist pattern to be formed. Diffeta is a general defect detected when a developed resist pattern is observed from directly above, for example, with a surface defect observation device (trade name “KLA”) manufactured by KLA Tencor. Examples of defects include scum, bubbles, dust, bridges (bridge structures between resist patterns), uneven color, and precipitates after development.

Improvement of the differential is important as a resist pattern with high resolution is required. In particular, ArF excimer laser and later, that is, ArF excimer laser, F excimer laser, EUV, EB, etc.

2

When forming the resist pattern below, the problem of solving the differential is becoming more severe.

[0005] One possible cause of differentials is the variation in molecular weight among the molecules that make up the base resin, and the bias in polarity within the molecules.

That is, in the reaction system after the polymerization reaction, from a relatively low molecular weight such as an unreacted monomer, a by-product oligomer or a low molecular weight polymer to a polymer having a high degree of polymerization and a relatively high molecular weight. There are a wide range of molecular weights. Each of these molecules has a different solubility in a solvent or an alkaline developer, and this is considered to be one of the causes of deteriorating the diffeta.

Also, at present, in the production of base resin, two or more types of monomers are usually used as raw material monomers in order to obtain good lithographic characteristics. For example, in Patent Document 1, (meth) acrylic acid having a (meth) acrylate ester having an acid dissociable, dissolution inhibiting group in the ester moiety and a (meth) acrylic acid having a rataton skeleton such as a γ-petit-oralataton skeleton in the ester moiety. Esters have a polycyclic group containing a polar group such as a hydroxyl group A) Polymers using acrylic acid esters and the like are described. Each of these monomers has a different reactivity (polymerization rate) in the polymerization reaction.

Therefore, in the base resin obtained by polymerizing these monomers, the structural units derived from the monomer cartridges are unevenly distributed in the structure, and this also makes the defect worse. Probably one of the causes.

[0006] The variation in molecular weight can be reduced by purifying the coffin after polymerization. For example, in Patent Document 2, etc., it is described that rosin is washed with a lower alcohol such as methanol. This removes unreacted monomers, by-product oligomers, low molecular weight polymers, and the like.

Patent Document 1: Japanese Patent Laid-Open No. 2003-167347

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-231834

Disclosure of the invention

Problems to be solved by the invention

[0007] However, even if a resin manufactured using a conventional refining method is used as a base resin (a resin for semiconductor lithography), it is possible to generate enough differentials, particularly bridge-shaped differentials (bridge mode differentials). It is difficult to suppress it.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a resin for a semiconductor lithography capable of suppressing the occurrence of differentials, particularly bridge mode differentials.

Means for solving the problem

[0008] In the method for producing a resin for semiconductor lithography of the present invention that solves the above-described problem, the resin for semiconductor lithography (A1) containing the structural unit (a2) having a latathone-containing cyclic group is an organic solvent (S1). the榭脂solution (R1) dissolved in solubility parameter ^ SO CF / cm ³⁾ is in the range of ^{^1/2,} and a specific surface area in the range of 0. 005~lm ² Zg榭脂(ΑΙ ') Including contact with.

In the present specification and claims, the “structural unit” means a monomer unit constituting a polymer (wax).

“Exposure” is a concept that includes general irradiation of radiation. The invention's effect

[0010] According to the present invention, there is provided a method for producing a resin for a semiconductor lithography capable of suppressing the occurrence of a differential, particularly a bridge mode differential.

Brief Description of Drawings

FIG. 1 is a schematic diagram for explaining a method suitably used when contacting a resin solution (R1) and a resin (resin).

Explanation of symbols

[0012] 1 housing

2 Oil (Al,)

3 Huino Letter

4 Huino Letter

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The method for producing a resin for semiconductor lithography according to the present invention comprises a resin for semiconductor lithography (A1) (hereinafter simply referred to as resin (A1)) containing the structural unit (a2) having a latathone-containing cyclic group. ) is a resin solution (R1) dissolved in an organic solvent (S 1) with a solubility parameter in the range of 17-20 (jZcm ³ ) ^1/2 and a specific surface area. Including contact with rosin (A1,) in the range of 0.005 to lm ² Zg.

The resin (A1) produced according to the present invention is any resin used for semiconductor lithography as long as it contains the structural unit (a2) having a latathone-containing cyclic group. It may be. Specific examples include hydroxystyrene-based resins, acrylic resins, and the like, and preferable examples include those manufactured by radical polymerization reaction. In the present invention, it is further proposed as a base resin for a chemically amplified resist composition, which is suitable for the production of resin.

Until now, as a resin that has been proposed as a base resin for a chemically amplified resist composition, a resin whose alkali solubility is changed by the action of an acid has been used. It has soluble greaves or acid-dissociable, dissolution-inhibiting groups. A rosin that increases resolubility is used. The former is for negative resist compositions, and the latter is for positive resist compositions. In the present invention, the resin (A1) may be used for a negative resist composition or a positive resist composition.

4 When the resin (A1) is for a negative resist composition, the resin (A1) is an alkali-soluble resin. The negative resist composition containing strong rosin is blended with the resin, an acid generator component that generates an acid upon exposure, and a crosslinking agent. In such a negative resist composition, when an acid is generated from an acid generator component (hereinafter referred to as component (B)) by exposure at the time of resist pattern formation, the acid acts to form an alkali-soluble resin and a crosslinking agent. Cross-linking occurs between them, and it becomes insoluble in alkali.

As the alkali-soluble coconut resin, coconut oil having a unit that also induces at least one force selected from a- (hydroxyalkyl) acrylic acid or a lower alkyl ester of a- (hydroxyalkyl) acrylic acid is excellent in low swelling. A resist pattern can be formed, which is preferable. In addition, a (hydroxyalkyl) acrylic acid is composed of acrylic acid in which a hydrogen atom is bonded to the α-position carbon atom to which the carboxy group is bonded, and a hydroxyalkyl group (preferably a carbon atom to the α-position carbon atom). 1 to 5 hydroxyalkyl groups) are bonded to each other to represent one or both of α-hydroxyalkylacrylic acids.

When the resin (A1) is used for a positive resist composition, the resin (A1) has an acid dissociable, dissolution inhibiting group and increases alkali solubility by the action of an acid. In the positive resist composition containing such a resin, the resin and the component (Β) are blended. In such a resist composition, when an acid is generated from the component (Β) upon exposure during the formation of a resist pattern, the acid dissociates the acid dissociable, dissolution inhibiting group, whereby the resin (A1) becomes alkaline. It becomes soluble. Therefore, in the formation of the resist pattern, when the resist composition applied on the substrate is selectively exposed, the alkali solubility in the exposed portion is increased and alkali development can be performed.

Since rosin (A1) is highly transparent to exposure light sources such as ArF excimer laser and has excellent lithographic properties such as resolution, acrylic acid power is also induced in both positive and negative types. It is preferable to contain a structural unit.

Here, in the present specification and claims, “acrylic acid” means attaly in a narrow sense. Luric acid (CH = CHCOOH) and some or all of its hydrogen atoms are

2

The concept includes a derivative substituted with a child.

Examples of the acrylic acid derivative include a substituted acrylic acid in which a substituent (atom or group other than a hydrogen atom) is bonded to the α-position carbon atom of acrylic acid in a narrow sense, and a carboxyl group of these acrylic acids. And acrylic acid esters in which the hydrogen atom of the group is substituted with an organic group.

The organic group in the acrylic acid ester is not particularly limited, for example, later-described structural unit (al) ~ _(a 4) Hitoshinio Te you, the structural units mentioned Te, and the ester side chain part of the acrylic acid ester And bonded groups (acid dissociable, dissolution inhibiting group, rataton-containing cyclic group, polar group-containing aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, etc.).

Unless otherwise specified, the α-position carbon atom of acrylic acid is a carbon atom to which a carbonyl group is bonded.

Examples of the substituent of α-substituted acrylic acid include a halogen atom, a lower alkyl group, a halogenated lower alkyl group and the like.

Examples of the halogen atom as the substituent at the α-position include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

In the present specification, the lower alkyl group is an alkyl group having 1 to 5 carbon atoms.

Specific examples of the lower alkyl group as a substituent at the α-position include methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. And a lower linear or branched alkyl group such as a group.

Examples of the halogenated lower alkyl group as the substituent at the a-position include groups in which some or all of the hydrogen atoms of the lower alkyl group have been substituted with the halogen atoms.

Bonded to the α-position of acrylic acid is preferably a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, preferably a hydrogen atom, a fluorine atom, a lower alkyl group or a fluorinated lower alkyl group. The group is most preferably a hydrogen atom or a methyl group because of the ease of industrial availability, which is more preferably a group.

“Acrylic acid power-derived structural unit” means that the ethylenic double bond of acrylic acid is opened. It means a structural unit formed by splitting.

The “structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.

Examples of the structural unit derived from acrylic acid power include structural units represented by the following general formula (a ").

[0015] [Chemical 1]

[Wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and X is a hydrogen atom or a monovalent organic group]

[0016] Examples of the halogen atom, lower alkyl group or halogenated lower alkyl group for R include the same as the halogen atom, lower alkyl group or halogenated lower alkyl group as the substituent at the a position.

Examples of the organic group for X include the same as the above-mentioned “organic group in acrylic ester”.

[0017] The resin (A1) contains a structural unit derived from an acrylic acid salt in a ratio of 50 to LOO mol% with respect to the total of all the structural units constituting the resin (A1). It is more preferable to contain 70-100 mol%. In particular, since the effect of the present invention is particularly excellent, it is preferable that the resin (A1) has only a structural unit that also induces acrylic acid power.

Here, “only the structural unit (a) has a force” means that the main chain of the resin (A1) is composed only of the structural unit derived from acrylic acid and does not contain other structural units. means.

[0018] · Unit (a2)

The resin (A1) contains the structural unit (a2) having a latathone-containing cyclic group as an essential structural unit. Here, a ratatone-containing cyclic group is a ring containing a -oc (o) structure (a rataton ring).

) -Containing cyclic group. The rataton ring is counted as the first ring, and if it is only the rataton ring, it is called a monocyclic group, and if it has another ring structure, it is called a polycyclic group regardless of the structure.

The lathetone-containing cyclic group in the structural unit (a2) is formed by increasing the adhesion of the resist film to the substrate or increasing the hydrophilicity when the resin (A1) is used for forming a resist film. It is effective in increasing the affinity with.

The ratatone-containing cyclic group may be a monocyclic group or a polycyclic group. Specifically, examples of the latatatone-containing monocyclic group include groups in which Ύ-petit-latatoton force is removed from one hydrogen atom. In addition, examples of the latathone-containing polycyclic group include groups in which a bicycloalkane, tricycloalkane, and tetracycloalkane force having a latathone ring has one hydrogen atom removed.

The ratatone-containing monocyclic group which may have a substituent on the ring includes a lower alkyl group such as a methyl group; an alkoxy group having 1 to 5 carbon atoms, and the like.

In the present invention, it is preferable that the structural unit (a2) has a monocyclic or polycyclic ratatone-containing cyclic group containing a γ-petit-mouthed rataton ring. It preferably has a cyclic or polycyclic ratatone-containing cyclic group.

Here, “including a γ-petit-mouthed rataton ring” means that the rataton-containing cyclic group includes a γ-petit-mouthed rataton ring as a rataton ring in the structure, and the rataton-containing cyclic group is It may be a monocyclic group or a polycyclic group.

y Examples of the monocyclic group containing a petit-mouthed rataton ring include the structural unit (a2-1) described later.

Examples of the polycyclic group containing a プチ -petit-mouth rataton ring include the structural units (a2-2) to (a25) described later.

[0020] The structural unit (a2) is not particularly limited as long as it has a strong rataton ring. In the base resin for a chemically amplified resist composition, the structural unit having a rataton ring is used. Any of the suggested ones can be used.

In the present invention, in particular, the structural unit (a2) force acrylate ester having a rataton ring It is preferred to be a structural unit derived from.

As an example of the powerful structural unit (a2), more specifically, the following general formula (a2)

) Represented by structural units (a2-1) to (a2-5).

[Chemical 2]

[Wherein, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, R ′ is a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is 0. Or an integer of 1. ]

[0022] R in the general formulas (a2-l) to (a2-5) is the same as the lower alkyl group for R in the formula (a ").

The lower alkyl group for R ′ is the same as the lower alkyl group for R in the above formula (a ″). In general formulas (a2−l) to (a2−5), R ′ is commercially available. In view of ease, etc., a hydrogen atom is preferable.

Specific examples of the structural units of the general formulas (a2-1) to (a2-5) are shown below.

[0023] [Chemical 3]

D / rlud

O S9l / l /.

One-e <. : -.

o 1 2¾1-]) 0

[] [G] sso § 26

-{a7a2-,

舍

twenty three,

[Z200]

ZY 99 percussion OAV

[0028] Among these, it is preferable to use at least one selected from the general formulas (& 2-1) to (& 2-3) V, and it is selected from the general formula (a2-1) It is more preferable to use at least one kind. Specifically, chemical formulas (a2-1 1), (a2-1 2), (a2-2-1), (a2-2-2), (a2-3-1), (a2-3-2) ), (A2-3-9) and (a2-3-10), it is preferable to use at least one selected from the group consisting of (a2-1-1-1) or (a2-1-2) ) Is preferred.

[0029] In the resin (A1), as the structural unit (a2), one type may be used alone, or two or more types may be used in combination.

Ratio of榭脂(A1) structural unit in (a2), relative to the combined total of all the structural units that constitute the榭脂(A1), 5 to 70 Monore ^_0/0 force S Preferably, 10 to 60 Monore ⁰ / more preferably ₀ force S, 15 to 60 Monore ^_0/0 force S more preferred. By setting it to the lower limit value or more, the effect of containing the structural unit (a2) can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to balance with other structural units. It becomes a suitable thing as rosin.

[0030] · Unit (al)

In the present invention, when the resin (A1) is for a positive resist composition, the resin (A1) Preferably has a structural unit (al) containing an acid dissociable, dissolution inhibiting group. The acid-dissociable, dissolution-inhibiting group in the structural unit (al) has an alkali dissolution-inhibiting property that makes the entire resin (A1) insoluble in alkali before dissociation, and the entire resin (A1) is alkali-soluble after dissociation. In the past, those proposed as acid dissociable, dissolution inhibiting groups for base resin for chemically amplified resists can be used. In general, a carboxy group of (meth) acrylic acid, a group forming a cyclic or chain tertiary alkyl ester, or a group forming a cyclic or chain alkoxyalkyl ester are widely known. It has been. “(Meth) acrylic acid ester” means either an acrylic acid ester having a hydrogen atom bonded to the α-position or a methacrylic acid ester having a methyl group bonded to the a-position !.

Here, the tertiary alkyl ester is an ester formed by substitution with a hydrogen atom of a carboxy group, a chain or cyclic alkyl group, and the carbo-oxy group (one C (O ) —O 2) A structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the terminal oxygen atom. In this tertiary alkyl ester, when an acid acts, a bond is broken between an oxygen atom and a tertiary carbon atom.

The chain or cyclic alkyl group may have a substituent! /. Hereinafter, a group that becomes acid dissociable by constituting a carboxy group and a tertiary alkyl ester will be referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience. In addition, a cyclic or chain alkoxyalkyl ester forms an ester by replacing a hydrogen atom of a carboxy group with an alkoxyalkyl group, and the carbonyloxy group (C (O) —O—) A structure in which the alkoxyalkyl group is bonded to the terminal oxygen atom is shown. In this alkoxyalkyl ester, when an acid acts, the bond is broken between the oxygen atom and the alkoxyalkyl group.

[0032] In the present invention, it is particularly preferred that the structural unit (al) is a structural unit derived from the allylic acid ester force having an acid dissociable, dissolution inhibiting group, in particular the following general formula (

It is preferable to use at least one selected from the group consisting of the structural unit represented by -0-1) and the structural unit represented by the following general formula (al-0-2).

[0033] [Chemical 8]

(In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X ¹ represents an acid dissociable, dissolution inhibiting group.)

[Chemical 9]

(Wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X ² represents an acid dissociable, dissolution inhibiting group; Y ² represents an alkylene group or an aliphatic cyclic group. )

In the general formula (al-0-1), the R halogen atom, lower alkyl group or halogenated lower alkyl group is bonded to the a-position of the above acrylate ester. The same as /, a nitrogen atom, a lower alkyl group or a halogenated lower alkyl group.

X ¹ is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include an alkoxyalkyl group, a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, and the like. A dissociable, dissolution inhibiting group is preferred. Examples of ^tertiary alkyl ester le type acid dissociable, dissolution inhibiting groups include aliphatic branched, acid dissociable, dissolution inhibiting group, include acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group.

The “aliphatic cyclic group” in the structural unit (al) may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, and a fluorine atom. Examples thereof include a fluorinated lower alkyl group having 1 to 5 carbon atoms and an oxygen atom (= 0), which are substituted with an elementary atom.

Except for the substituents of the “aliphatic cyclic group”, the basic ring structure is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but may be a hydrocarbon group. Favored ,. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated. A polycyclic group is preferred. The carbon number of the aliphatic cyclic group is preferably 4-20.

Specific examples of such an aliphatic cyclic group include, for example, a lower alkyl group, a fluorine atom or a fluorinated alkyl group, which may or may not be substituted, a monocycloalkane, a bicyclo Examples thereof include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as alkane, tricycloalkane, and tetracycloalkane. Specifically, monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Is mentioned.

As the aliphatic branched acid dissociable, dissolution inhibiting group, a tertiary alkyl group having 4 to 8 carbon atoms is preferred. Specific examples include a tert butyl group and a tert-amyl group. Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include a group having a tertiary carbon atom on the ring skeleton of a cyclic alkyl group. Examples include 2-adamantyl group and 2-ethyl 2-adamantyl group. Alternatively, as a structural unit represented by the following general formula, a group having an aliphatic cyclic group such as an adamantyl group and a branched alkylene group having a tertiary carbon atom bonded thereto can be used.

[Chemical 10]

[Wherein, R is the same as above, and R ¹⁵ and R ^{lb each} represent an alkyl group (both linear and branched, preferably 1 to 5 carbon atoms). ]

[0037] Further, the alkoxyalkyl group is preferably a group represented by the following general formula (pi).

[0038] [Chemical 11]

(Wherein R ¹⁷ and R ¹⁸ are each independently a linear or branched alkyl group or a hydrogen atom, and R ¹⁹ is a linear, branched or cyclic alkyl group, or R ¹⁷ And the end of R ¹⁹ may be bonded to form a ring.

In R ¹⁷ and R ¹⁸ , the alkyl group preferably has 1 to 15 carbon atoms, and is preferably a straight chain or branched chain ethyl group or a methyl group with a methyl group being preferred. . In particular, one of R ¹⁷ and R ¹⁸ is preferably a hydrogen atom and the other is a katyl group.

R ¹⁹ is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be linear, branched or cyclic.

When R ¹⁹ is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.

When R ¹⁹ is cyclic, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and further preferably 5 to carbon atoms: LO is most preferable. Specifically, a monocycloalkane or bicyclyl which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Examples thereof include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as cloalkane, tricycloalkane or tetracycloalkane. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. It is done. Among them, a group in which one or more hydrogen atoms are removed from adamantane is preferable.

In the above formula, R ¹⁷ and R ¹⁹ are each independently an alkylene group having 1 to 5 carbon atoms, and the end of R ^{19 and} the end of R ¹⁷ may be bonded together.

In this case, a cyclic group is formed by R ¹⁷ and R ¹⁹ , the oxygen atom to which R ¹⁹ is bonded, and the carbon atom to which the oxygen atom and R ¹⁷ are bonded. As the cyclic group, a 4- to 7-membered ring is preferable, and a 4- to 6-membered ring is more preferable. Specific examples of the cyclic group include a tetrahydrobiranyl group and a tetrahydrofuran group.

In the general formula (al-0-2), R is the same as described above. For X ^2, formula

Same as X ¹ in (al— 0— 1).

Y ² is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group.

In the case where Y ² is a divalent aliphatic cyclic group, the description of the “aliphatic cyclic group” in the structural unit (al) except that a group in which two or more hydrogen atoms are removed is used is used. The same thing can be used.

[0041] Specific examples of the structural unit (al) include structural units represented by the following general formulas (al-1) to (al-4).

[0042] [Chemical 12]

[In the above formula, X ′ represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, Y represents a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group; n represents 0 to 3 M represents 0 or 1; R is the same as defined above; R ¹ ′ and R ² ′ each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. ]

[0043] At least one of R ¹ 'and R ² ' is preferably a hydrogen atom, more preferably a hydrogen atom. n is preferably 0 or 1.

[0044] X is the same as the tertiary alkyl ester type acid dissociable, dissolution inhibiting group exemplified for X ¹ above.

Examples of the aliphatic cyclic group for Y include the same groups as those exemplified above in the explanation of the “aliphatic cyclic group”.

[0045] Specific examples of the structural units represented by the general formulas (al-1) to (al-4) are shown below.

[0046] [Chemical 13]

((a1-1-18)

[§] 00496

.

liloi / 2Tl:> d / 399ΪΪ O 00ZAV.

CM

¾6ΐsoo

[0053] [Chemical 20]

(a 1-3-21) (a 1-3-22) (al-3-23) (a 1-3

§ s [] 22

(丄 al ⁰ ,

() 4 top 2) al11 1-

. -.

° " ¹ Ό o〇 ο 一 = ^M |

-o-o

Li o ^ "χe τ0 s H

) (al42i.1

"

As the structural unit (al), one type may be used alone, or two or more types may be used in combination.

Of these, the structural units represented by the general formula (al-1) are specifically preferred (al-1-11) to (al-1-6) or (al-1 35) to (al-1). It is more preferable to use at least one selected from the structural units represented by —41).

Furthermore, as the structural unit (al), in particular, those represented by the following general formula (al-1 01) including structural units of the formula (al 1 1) to the formula (al 1-4), and the formula (al — The following general formula (a 1—102) including the structural units of (1 35) to (al— 1 -41) is also preferred. [0057] [Chemical 23]

He

(In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ¹¹ represents a lower alkyl group.)

[0058] [Chemical 24]

(In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, R ¹² represents a lower alkyl group, h represents an integer of 1 to 3)

[0059] In the general formula (al-1-01), R is the same as described above. The lower alkyl group for R ^{11 is the same as} the lower alkyl group for R, and is preferably a methyl group or an ethyl group! /.

In general formula (al-1-02), R is the same as described above. Lower alkyl group of R ¹² is the same as the lower alkyl group for R, and most preferably preferred instrument Echiru group is a methyl group or Echiru group. h is preferably 1 or 2, and most preferably 2.

[0061] In榭脂(A1), the proportion of the structural unit (al) is based on all the structural units that constitute the榭脂(A1), 10 to 80 Monore ^_0/0 force S Preferably, 20-70 Monore ⁰ / more preferably ₀ force S, 25 to 60 Monore ^_0/0 force S further favorable preferable. By setting it to the lower limit value or more, a pattern can be easily obtained when the resist yarn and the composition are made, and by setting it to the upper limit value or less, it is possible to balance with other structural units. [0062] · Unit (a3)

In addition to the structural unit (a2) or in addition to the structural units (al) and (a2), the rosin (Al) is a structural unit derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group ( It is preferable to have a3). By having the structural unit (a3), the hydrophilicity of the resin (A1) is increased, the affinity with the developer is increased, the alkali solubility in the exposed area is improved, and the resolution is improved. .

Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group substituted with a partial S hydrogen atom of an alkyl group, and a hydroxyl group is particularly preferred.

Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a polycyclic aliphatic hydrocarbon group (polycyclic group). . As the polycyclic group, for example, V has been proposed in a variety of resins for resist compositions for ArF excimer lasers, and can be appropriately selected from those used.

Among them, it is derived from an acrylate ester group containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, cyano group, carboxy group, or alkyl group is substituted with a fluorine atom. The structural unit is more preferable. Examples of the polycyclic group include groups in which one or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane or the like. Specific examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Among these polycyclic groups, two or more hydrogen atoms are removed from adamantane, two or more hydrogen atoms are removed from norbornane, and two or more hydrogen atoms are removed from tetracyclododecane. The industrial group is preferred.

[0063] As the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to: LO carbon atoms, the hydroxy group of acrylic acid is used. Preferred structural units derived from tilesters When the hydrocarbon group is a polycyclic group, a structural unit represented by the following formula (a3-1), a structural unit represented by (a3-2), The structural unit represented by (a3-3) is preferable.

[0064] [Chemical 25]

{a3-3}

(Wherein R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t 'is an integer of 1 to 3, and 1 is an integer of 1 to 5) And s is an integer from 1 to 3.)

In formula (a3-l), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, a hydroxyl group is preferably bonded to the 3rd position of the adamantyl group.

j is preferably 1, particularly preferably one in which the hydroxyl group is bonded to the 3-position of the adamantyl group.

In formula (a3-2), k is preferably 1. The cyan group is the 5-position of the norbornyl group or

I prefer to be in 6th place.

In formula (a3-3), t ′ is preferably 1. 1 is preferably 1. s is preferred to be 1,. These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the terminal of the carboxy group of acrylic acid. It is preferred that the fluorinated alkyl alcohol be bonded to the 5 or 6 position of the norbornyl group! /.

As the structural unit (a3), one type may be used alone, or two or more types may be used in combination.

Resin (A1), the proportion of the structural unit (a3), the polymer based on the combined total of all structural units constituting the (A2), 5 to 50 mole ^_0/0, it is preferred instrument 40 mol ⁰ / ₀ force S is more preferable, and 5 to 25 mol% is more preferable.

[0069] · Structural unit (a4)

The resin (A1) is contained in the above structural units (al) to (a3) and within the range not impairing the effects of the present invention. Including other structural units outside (a4)! /, May!

Structural unit (a4) is not classified as structural unit (al) (a3) above! However, other structural units are not particularly limited. Many of them are known to be used in resist resins such as for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). Things can be used.

As the structural unit (a4), for example, a structural unit derived from an ester acrylate ester containing an acid non-dissociable aliphatic polycyclic group is preferable. Examples of the polycyclic group include those exemplified in the case of the structural unit (al), for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser). A large number of conventionally known strengths can be used as the oil component of the resist composition.

In particular, at least one kind selected from tricyclodecanyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable in terms of industrial availability. These polycyclic groups have a linear or branched alkyl group having 15 carbon atoms as a substituent! /, Or may be! /.

Specifically, as the structural unit (a4), those having the structures of the following general formulas (a4-l) to (a4-5) can be shown in column f.

[Chemical 26]

(Wherein R is the same as defined above.)

Force a constitution unit (a4) when to be contained in榭脂(A1), relative to the combined total of all configuration units constituting the榭脂(A1), a 1 30 mol ⁰ preferably structural unit (a4) preferred 10 20 mole ^_0/0 the inclusion. [0072] In the present invention, it is preferable that the resin (Al) is a copolymer having at least the structural units (al) and (a2). ) And structural unit (a2) force copolymer, structural unit (al), (a2) and (a3) force copolymer, the above structural units (al), (a2), (a3) and ( a4) Powerful copolymers can be exemplified.

[0073] In the present invention, as the resin (A1), a copolymer containing four kinds of structural units in combination represented by the following general formula (A1-11) is particularly preferable.

[0074] [Chemical 27]

(A 1-1 1)

[0075] In the formula, R is the same as R in the formula (a ").

R ⁹ is a lower alkyl group, a lower alkyl group of R ⁹ is the same as the lower alkyl groups described above R, and most preferably preferred instrument methyl group is methyl group or Echiru group.

[0076] The mass average molecular weight (Mw; mass average molecular weight in terms of polystyrene by gel permeation chromatography) of rosin (A1) is not particularly limited, but is preferably 2000-30000 force S, more preferably from 2000 to 10,000 force Preferably, 3000-7000 force is more preferred! / ヽ. By setting it within this range, a good dissolution rate in an alkali developer can be obtained, which is preferable from the viewpoint of high resolution. Within this range, the lower the molecular weight, the better characteristics tend to be obtained.

The dispersity (MwZMn) is about 1.0 to 5.0, preferably 1.0 to 2.5.

[0077] The resin (A1) is a monomer derived from each structural unit, for example, a radiocarbon such as azobisisobutyl-tolyl (AIBN) or dimethyl-2,2, -azobis (2-methylpropionate). It can be obtained by polymerization by known radical polymerization using a polymerization initiator.

In addition, rosin (A1) can be converted into, for example, HS—CH—CH—CH—C

2 2 2

When a chain transfer agent such as F) —OH is used in combination, one terminal C (CF) — O

3 2 3 2

An H group may be introduced. In this way, copolymers in which a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms are introduced have reduced development defects and LER (Line Edge Roughness: uneven unevenness on the line sidewalls). ).

[0078] <Organic solvent (Sl)>

The organic solvent (S1) should be one that can dissolve the resin (A1) to make a uniform solution. In addition, it is preferable that the organic solvent (S 1) does not dissolve the resin (A1,)!

[0079] As the organic solvent (S1), for example, one or two or more kinds of conventionally known solvents for chemically amplified resists can be appropriately selected and used. Specifically, for example, ratatones such as γ-petit-mouth rataton; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-η-amyl ketone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, Polyhydric alcohols such as diethylene glycol, propylene glycol, and dipropylene glycol and their derivatives; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycolanol monoacetate, propylene glycolanol monoacetate, or dipropylene glycol monoacetate Monopolyethers such as the polyhydric alcohols or the compounds having an ester bond, such as monomethyl ether, monoethinoreethenore, monopropinoreethenore, monobutinoreethenore, etc. Derivatives of polyhydric alcohols such as compounds having an ether bond such as tellurium or monophenyl ether; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, pyruvin Esters such as methyl acid, ethyl pyruvate, methyl methoxypropionate, ethoxypropionate, etc .; , Phenenole, butinolevenoleethenore, ethinorebenzene, dimethylbenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene, Examples thereof include aromatic organic solvents such as styrene.

These organic solvents can be used alone or as a mixed solvent of two or more. As the organic solvent (S1), propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate (PGM EA); propylene glycol monoalkyl ether such as propylene glycol monomethyl ether (PGME); PGMEA is preferred, especially propylene glycol monoalkyl ether acetate!

A mixed solvent in which PGMEA and a polar solvent are mixed is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Preferably within range! /.

More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When PGM E is blended as a polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: Three.

In addition, as the organic solvent (S1), a mixed solvent of at least one selected from PGMEA and EL and γ-petit-mouthed rataton is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.

The amount of the organic solvent (S1) to be used is not particularly limited, and may be set appropriately in consideration of, for example, the contact method between the resin solution (R1) and the resin (ΑΙ ′). For example, when the resin solution (R1) is passed through a container filled with resin (A1 '), considering the contact efficiency, the concentration of the resin (A1) in the resin solution (R1) is 2 to 20% by mass. An amount that falls within the range of 5 to 15% by mass is more preferred.

Resin solution (Rl)>

The resin solution (R1) can be prepared by dissolving the resin (A1) in an organic solvent (S1). The resin (A1) can be dissolved in the organic solvent (S1), for example, by simply mixing and stirring the above components in the usual manner, and if necessary, one or three dissolvers, homogenizers. You may disperse and mix using dispersers, such as a roll mill. Further, after mixing, it may be filtered using a mesh, a membrane filter or the like. [0081] <Resin (Al,)>

The fat (榭 ') has a solubility parameter (hereinafter referred to as SP value) in the range of 17-20CiZcm ³ ) ^1/2 and a specific surface area in the range of 0.005 to lm ² / g. It is a rosin. In the present invention, a resin (A1 ′) having an SP value and a specific surface area within a certain specific range is brought into contact with an organic solvent (S1) solution of the specific resin (A1). Thus, the differential in forming a resist pattern using the obtained resin for semiconductor lithography is reduced.

[0082] This is due to the fact that the fat that is relatively high polarity in rosin (A1) and the high affinity with rosin (ΑΙ ') It is presumed that it is adsorbed on the surface and removed from the resin (A1).

That is, in the resin (A1) containing the structural unit (a2) having a latathone-containing cyclic group, the monomer having a latathone-containing cyclic group used in the production thereof (latathone monomer), the ratata Polymers containing a high proportion of structural units (a2) (lataton rich polymers), etc., produced by uneven polymerization of ton monomers, are included, and these contribute to the occurrence of diffetats. Conceivable. For example, since the solubility of alkali in a rataton rich polymer hardly changes before and after exposure, the part where the rataton rich polymer is present in the positive part is exposed in the exposed part, and in the negative part in the unexposed part. After development, it remains as it is without dissolving, and it is considered that it causes differentials (especially bridge mode differentials).

In contrast,榭脂used in the present invention (ΑΙ '), by SP value is in the range of ^{^{T SO Ci / cm 3) 1}} /2, these rata tons monomers, compounds such Lata tons rich polymers ( In the following, it is presumed to have a strong interaction with Rataton-rich compounds.

In addition, the specific surface area of rosin (ΑΙ ') is 0.005 m ² Zg or more, so the contact area when the rosin solution (R1) is contacted is large, and the specific surface area is lm ² Zg or less. As a result, the solution permeability when the rosin solution (R1) is supplied is also good.

Therefore, by bringing the resin solution (R1) into contact with the resin (ΑΙ ′), the Ra-rich compound contained in the resin solution (R1) is efficiently adsorbed on the resin (ΑΙ ′). Retained and oiled It is estimated that the amount of Rataton-rich compound in the solution (Rl) can be reduced to a level sufficient to improve diffetat.

[0083] [SP value]

The SP value is a parameter indicating the solubility of the compound in the solvent. The higher the SP value, the higher the polarity of the solvent in a hydrophilic solvent. The smaller the value, the higher the solubility of the compound in a low polarity solvent or a hydrophobic solvent.

In the present invention, the SP value of rosin (Al,) is a value calculated using the computational chemical software CAChe (product name) manufactured by Fujitsu. Specifically, the SP value of rosin (ΑΙ ') is determined for each constituent unit of rosin (ΑΙ'), and the atoms constituting the constituent unit and the bond type (single bond, double (Types of bonds such as bonds, triple bonds, etc.) are input as two-dimensional information, and the two-dimensional information is used to determine the atoms and bond types in three dimensions so that the potential energy between atoms is minimized by the ΡΜ5 method. Optimize the structural arrangement. Then, the SP value is calculated for each structural unit that has undergone structural optimization, and the product of the molar composition ratio of each structural unit of rosin (A1,) and the SP value of each structural unit described above is accumulated. Can be obtained by doing so.

The concrete operation method of the structure optimization of the ΡΜ5 method by Fujitsu computational chemistry software CAChe (product name) is as follows. After modeling the building blocks on the Workspace screen of Fujitsu computational chemistry software CAChe (product name), Select “New” from the “Experiment” pull-down menu, and in the newly appearing screen, “Proparty of:” item is “chemical samp lej”, “Proparty:” item is “optimized geometry”, “Using” The item of “:” is to select “Start” after selecting “P M5 geometry”, and this operation can optimize the structure.

[0084] Examples of the resin having an SP value in the range of 17 to 20 (j / cm ³ ) ^1/2 include a structural unit represented by the following formula (1-1) and formula (12) And a polymer having a structural unit represented by:

[0085] [Chemical 28]

(1—1) (1-2)

[0086] The structural unit represented by the formula (1-1) is a structural unit derived from α-methacryloyloxy γ-butyral rataton (hereinafter also referred to as GBLMA) (hereinafter also referred to as GBLMA unit). ) And the SP value of this structural unit is 18.5 (jZcm ³ ) ^1/2 .

The structural unit represented by the formula (1-2) is a structural unit (hereinafter also referred to as TMPTMA unit) derived from trimethylolpropane trimetatalylate (hereinafter also referred to as TMPTMA). The SP value of the unit is 17.2 (j / cm ³ ) ^1/2 .

Therefore, for example, the SP value of a polymer having GBLMA unit ZTMPTMA unit = 97 mono% 3 monole% is 18.5 × 0.97 + 17.2 × 0.03 = 18.5 (j / cm ³ ) ^1/2 .

Moreover, since the SP values of GBLMA units and TMPTMA units are both in the range of 17-20 (j / cm ³ ) ^1/2 , the SP value of the polymer composed of these two types of constituent units is Even in the composition ratio, it is in the range of 17 to 20 a / cm ³ ) ^1/2 .

[0087] On the other hand, when the GBLMA unit is replaced with, for example, a structural unit derived from acrylonitrile (hereinafter also referred to as AN), the SP value of the AN unit is 24.6 (J / cm ³ ) ^1/2. AN / TMPTMA = 97 mol% / 3 mol% polymer SP value is 24.6X0.97 + 1 7.2X0.03 = 24.4 (J / cm ³ ) ^1/2 , 17-20 (j / cm ³ ) Out of ^1/2 range force. Here, in a polymer comprising AN units and TMPTMA units, by increasing the SP value 17~20 (JZ cm ³⁾ composition ratio of TMPTMA unit in the ^half of the range, ΑΝΖΤΜΡΤΜΑ = 37. 8 Monore ^_0/0 When /62.2 Monore ^_0/0 thread且成it, 24.6X0.378 + 17.2X0.622 = 20 .0 (J / cm 3) 1/2 next, SP value of this polymer, 17 to 20 ( j / cm ³ ) ^1/2 .

[0088] As can be seen from the above examples, the SP values of all the structural units of the polymer are 17 to 20 (JZcm ³ )

In the range of ^1/2 , the SP value of the polymer is 17 to 20 (J Zcm ³ ) ^1/2 .

In addition, among the structural units of the polymer, if the SP value is greater than 20CF / cm ³ ) ^1/2 , other structural units (SP value is 20 a / cm ³ ) ^1/2 or less It is possible to control the SP value of the polymer within the range of 17 to 20 (jZcm ³ ) ^1/2 by increasing the composition ratio of the structural unit.

Furthermore, among the structural units of the polymer, when the structural unit with SP value smaller than 17CF / cm ³ ) ^1/2 is included, other structural units (with SP value of 17 Ci / cm ³ ) ^1/2 By increasing the composition ratio of the above structural units), the SP value of the polymer can be controlled in the range of 17 to 20 (jZcm ³ ) ^1/2 .

In this way, the SP value of the polymer is controlled within the range of 17 to 20 (j / cm ³ ) ^1/2 by controlling the composition ratio according to the SP value of each constituent unit of the polymer. In the present invention, since the SP value is easily in the range of 17-20 (jZcm ³ ) ^1/2 , the SP values of all the structural units are 17.0-20 (j / cm ³ ) ^1/2

[0089] [Specific surface area]

The specific surface area of rosin (A1,) ranges from 0.005 to lm ² Zg.

The specific surface area is the surface area per unit mass of the powder particles, and is determined by the nitrogen adsorption method.

The lower limit of the specific surface area of榭脂(ΑΙ '), the adsorption of Ratatonritchi compounds, from the viewpoint of the retention, 0 .01m ² or Zg is preferably instrument 0.03 m ² or more Zg is more preferable. In addition, the upper limit value of the specific surface area of rosin (ΑΙ ′) is preferably 0.8 mg ² Zg or less, more preferably 0.5 mg or less, from the viewpoint of solution permeability.

[0090] The method for adjusting the specific surface area of rosin (A1 ') to a range of 0.005 to lm ² Zg is not particularly limited, and a method generally used for adjusting the specific surface area of rosin is used. it can. For example, when producing rosin (ΑΙ ′), if the polymerization of the monomer is carried out by suspension polymerization or emulsion polymerization, particles of rosin (A1 ′) produced by the polymerization (there are suspended particles, May be adjusted so that the particle diameter of the emulsified particles is in the range of about 6 / ζπι to 1.2 mm. These particles In order to control the diameter, the addition amount of the surfactant may be adjusted in the case of suspension polymerization, and the addition amount of the emulsifier may be adjusted in the case of emulsion polymerization.

[0091] The resin (A1 ') is not particularly limited as long as it has the above SP value and specific surface area. In particular, since the effects of the present invention are excellent, it is preferable that the resin (ΑΙ ′) contains a structural unit (a2 ′) having a latathone-containing cyclic group. This is because rosin (A1) contains the structural unit (a2) having a latathone-containing cyclic group, so that rosin (A1 ') contains the structural unit (a2'), This is presumably due to the improved removal efficiency of the rataton-rich compound when the resin solution (R1) is contacted with the resin (Al,).

As the structural unit (a2,), for example, (meth) atallylate having a δ valerolataton ring, methylene having a δ valerolataton ring, norbornene having a δ valerolataton ring, tetracyclododecene having a δ valerolataton ring, γ - having Petit port Rataton ring (meth) Atari rate, methylene having a γ Buchirorataton ring, norbornene that having a γ Buchirorataton ring, _Y - tetracyclododecene with petit port Rataton ring, to have a cycloaliphatic Rataton ( A monomer having a cyclic group-containing cyclic group, such as (meth) acrylate, methylene having an alicyclic rataton, and derivatives having substituents on the lactone ring of these compounds, is induced. A structural unit is mentioned.

Here, “(meth) acrylate” means one or both of metatalate and attalate.

The term “alicyclic ring” means a ring that contains a bridged four-ring hydrocarbon group. The monomer having a latathone-containing cyclic group and having chain polymerizability is not particularly limited, and examples thereof include monomers represented by the following formulas (10-1) to (: L0-37). . In formulas (10-1) to (: LO-37), R represents a hydrogen atom or a methyl group.

Among them, monomers represented by the formulas (10-1) to (: LO-29) from the viewpoint of good chain polymerizability

, And these geometric and optical isomers are preferred.

[0093] [Chemical 29] § [] ^ 0095

(10-34)

In addition, as the structural unit (a2 ′), for example, a diol having a δ valerolataton ring, a dicarboxylic acid having a δ valerolataton ring, a diamine having a δ valerolataton ring, a diol having a γ-butyrolataton ring, and a γ-butyrolatatone ring Dicarboxylic acid

, Diamine having a γ-petit-mouth rataton ring, diol having alicyclic rataton, dicarboxylic acid having alicyclic rataton, diamine having alicyclic rataton, and derivatives having substituents on the lactone ring of these compounds, etc. Examples thereof include structural units derived from a monomer force having a latathone-containing cyclic group and having polycondensation properties.

[0097] The monomer having a latathone-containing cyclic group and having a polycondensation property is not particularly limited. Examples thereof include monomers represented by the following formulas (10-101) to (10-103).

[0098] [Chemical 32]

In the present invention, it is preferable that the latatone-containing cyclic group in the structural unit (a2 ′) and the latatone-containing cyclic group in the structural unit (a2) have the same structure.

[0100] In the resin (榭 '), as the structural unit (a2'), one type may be used alone, or two or more types may be used in combination.

The proportion of structural unit (a2,) in rosin (Al,) From the standpoint of adsorption and retention of the rataton-rich compound, the total amount is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more. In addition, when considering the resistance to the organic solvent (S 1) used in the resin solution (R1) to be contacted with the resin (A 1 '), 100 mol% or less is preferable 99.9 mol % Or less is more preferable 99.5 mol% or less is particularly preferable 99 mol% or less is more preferable 98 mol% or less is most preferable.

[0101] It is preferable that the resin (を ') further has a structural unit (a5') that also induces a crosslinking agent power. When the resin (ΑΙ ′) is a polymer having such a structural unit (crosslinked polymer), resistance to the organic solvent (S1) and the like are improved.

The cross-linking agent for deriving the structural unit (a5,) is not particularly limited as long as it can be copolymerized with the monomer deriving the structural unit (a2,). For example, a polyfunctional bull monomer (ml) can be mentioned. A monomer (ml) is a beer monomer containing two or more structures having radical polymerizability or ion polymerizability (for example, ethylenic carbon-carbon double bond) in one molecule.

As the polyfunctional bull monomer (ml), a known polyfunctional bull monomer (ml) that is not particularly limited can be used. For example, a polyfunctional (meth) acrylic acid ester monomer, an aromatic polyfunctional vinyl Monomers and aliphatic polyfunctional vinyl monomers can be used. Of these, a polyfunctional (meth) acrylic acid ester monomer is preferable from the viewpoint of polymerizability.

[0102] Examples of the polyfunctional (meth) acrylic acid ester monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Atylate, Polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate Alkylene glycol di (meth) acrylates such as polytetramethylene glycol di (meth) acrylate; trimethylol ethane tri (meth) acrylate, trimethylol propane tri (meth) acrylate , Tetramethylolpropane tri (meta) Atalylate, tetramethylol methane tri (meth) acrylate, tetramethyl methane methane tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, hydroxypivalic acid Neopentyl glycol di

(Meth) acrylate, 1, 3 Butylene glycol di (meth) acrylate, 1, 6 hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) Atalylate, 2-Hydroxy—1, 3 Di (meth) Atalyloxypropan, 2 Hydroxy-1-Atalyloxy-3-Methacryloxypropane, Urethane (Meth) Ditalylate, Glycerol Di (Meth) Atalylate, Glycerol Atarylate Meta Talylate, 1, 10 Di (meth) atarioxy--4,7 Dioxadecane-2,9 diol, 1,10 Di (meth) atari-oxyxy-5-methyl 4,7 Dioxadecane-1,9 diol, 1, 11—Di (meth) atalyloxy—4, 8 Dioxaoundegan—2, 6, 10 Triol, Bulle (Meta) Atarylate, Arryl (Meth) Ata Relates and so on.

Examples of the aromatic polyfunctional butyl monomer include dibutylbenzene, dibutene, divinylxylene, dibutaphthalene, and tributylbenzene. Examples of the aliphatic polyfunctional butyl monomer include 1,3 butadiene.

[0103] As the cross-linking agent for deriving the structural unit (a5 '), a compound having two or more allyloyloxy groups is particularly preferable.

Here, the “attalylooxy group” is a group represented by the general formula CH═CHR—COO.

2

And R is the same as R in the general formula (a ").

Examples of the structural unit that is derived from the compound force having two or more allyloyloxy groups include a structural unit represented by the following general formula (a5′-1).

[0104] [Chemical 33]

[Wherein R is the same as above, R ³ is a (f + 1) -valent saturated hydrocarbon group, and f is 1 to 3 It is an integer. ]

[0105] f is an integer of 1 to 3, 1 or 2 is preferred, and 2 is most preferred.

R ³ is a (f + 1) valence, that is, a divalent to tetravalent saturated hydrocarbon group, particularly preferably a divalent saturated hydrocarbon group or a trivalent saturated hydrocarbon group.

The saturated hydrocarbon group for R ³ may be either a chain (straight chain or branched chain) or cyclic (including only a ring or a chain having a saturated hydrocarbon group bonded to the ring). A straight chain or branched saturated hydrocarbon group is more preferred. The saturated hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

In the saturated hydrocarbon group for R ³ , the hydrogen atom may be substituted with an atom other than a hydrogen atom. Examples of the other atoms include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of R ^{3 also} include groups in which a part of carbon atoms of the saturated hydrocarbon group as described above is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

[0106] Examples of the trivalent linear or branched saturated hydrocarbon group include groups in which three hydrogen atoms have been removed from methane, ethane, propane, butane, pentane, hexane, heptane, octane and the like.

As the trivalent cyclic saturated hydrocarbon group, _three hydrogen atoms were removed from a saturated hydrocarbon ring such as cyclopentane, cyclohexane, cycloheptane, norbornane, isobornane, adamantane, tricyclodecane, tetracyclododecane, etc. Examples thereof include a cyclic group and a group in which a linear or branched alkylene group is bonded to the cyclic group.

Examples of the divalent linear or branched saturated hydrocarbon group include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, pentylene group, isopentylene group, neopentylene group. Groups and the like.

Divalent cyclic saturated hydrocarbon groups include cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, tetracyclododecane, and other saturated hydrocarbon ring forces. And a group in which a linear or branched alkylene group is bonded to the cyclic group. As R ³ , a trivalent linear or branched saturated hydrocarbon group is particularly preferred, except for a hydrogen atom of 3 methane power, which is particularly preferred.

[0107] In the resin (ΑΙ '), as the structural unit (a5'), one type may be used alone, or two or more types may be used in combination.

The proportion of the structural unit (a5,) in the resin (Al,) is preferably 0.1 mol% or more with respect to the total of all the structural units constituting the resin (Al,). 1 mol% or more is more preferable 1 mol% or more is more preferable 2 mol% or more is especially preferable. Also, from the viewpoint of adsorption and retention of the rataton-rich compound, 60 mol% or less is preferable, and 50 mol% or less is more preferable 40 mol.

% Or less is more preferable.

[0108] The resin (Al,) may further contain a structural unit (a6,) other than the above structural units (a2,) and (a5,).

The structural unit (a6 ′) is not particularly limited as long as it is derived from a monomer that can be copolymerized with the monomer that derives the structural unit (a2 ′).

Monomers that can be copolymerized with the monomer that derives the structural unit (a2 ′) include, for example, (meth) methyl acrylate, (meth) acrylate ethyl, (meth) acrylate 2-ethylhexyl, (meth) N-propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, methoxymethyl (meth) acrylate, n-propoxychetyl (meth) acrylate, (meth) acrylic acid iso propoxychetil, (meth) acrylic acid n-butoxy shetyl, (meth) acrylic acid iso butoxychyl, (meth) acrylic acid tert-butoxychyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 3 -Hydroxypropyl, (meth) acrylic acid 2-hydroxy- n propyl, (meth) acrylic acid 4-hydroxy- n Butyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 1 ethoxyethyl, (meth) acrylic acid 1 adamantyl, (meth) acrylic acid norbornyl, (meth) acrylic acid tricyclodehydryl, (meth ) Isobornyl acrylate, (meth) acrylic acid-1- (3-hydroxy) adamantyl, (meth) acrylic acid 2, 2, 2-trifluoroethyl, (meth) acrylic acid 2, 2, 3, 3 —Tetrafluorine n-propyl, (meth) acrylic acid 2, 2, 3, 3, 3 Pentafluoro n propyl, methyl α-trifluoromethyl acrylate, methyl α-fluoroacrylate, α-trifluoromethyl acrylate, α-fluoroethyl acrylate, a 2-Ethylhexyl trifluoromethyl acrylate, a 2-Ethylhexyl trifluoroacrylate, n-propyl α-trifluoromethyl acrylate, η-propyl α-fluoroacrylate, iso-propyl α-trifluoromethyl acrylate Α-Fluoroatalylate isopropyl, α-trifluoromethyl acrylate n-butyl, α-fluoroacrylic acid η-butyl, α-trifluoromethyl acrylate isobutyl, α-fluoroacrylic acid isobutyl, α-trifluoro Tert-Butyl acrylate, α-tert-butyl chlorofluoroacrylate, methoxymethyl α-trifluoromethyl acrylate, α-methoxymethyl chloroacrylate, ethoxyethyl α-trifluoromethyl acrylate, ethoxyethyl α-fluoroacrylate, _α —Trifluorome Ruakuriru acid _eta - Purobokishe chill, alpha Furuoroakuriru acid eta Puropokishechiru, alpha triflumizole Ruo b methyl acrylate iso Puropokishechiru, alpha Furuoroakuriru acid iso Puropokishechiru, alpha triflupromazine O b methyl acrylate _eta - Butokishechiru, _alpha - Furuoroakuriru Acids _η —Butoxychyl, α-trifluoromethyl acrylate iso-butoxetyl, α-Fluoroacrylate iso-butoxetyl, α-trifluoromethyl acrylate tert-butoxetyl, α-Fluoroacrylate tert-butoxychetyl (meth) Acrylic ester or a fluorine-substituted (meth) acrylic ester;

[0109] Styrene, α-methylstyrene, butyltoluene, ρ-hydroxystyrene, ρ-tert-butoxycarbonylhydroxystyrene, 3,5-di-tert-butyl-4-hydroxystyrene, 3,5-dimethyl-4-hydroxystyrene, p-tert Aromatic alcohol compounds such as perfluorobutylstyrene and p- (2-hydroxy-isopropyl) styrene;

[0110] Unsaturated carboxylic acids and carboxylic anhydrides such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride;

Examples thereof include ethylene, propylene, norbornene, tetrafluoroethylene, acrylamide, N-methylacrylamide, N, N dimethylacrylamide, butyl chloride, butyl fluoride, vinylidene fluoride, and bulupyrrolidone.

[0111] Here, "(meth) acrylic acid" means "methacrylic acid or acrylic acid".

“A-Fluorine-substituted (meth) acrylic acid ester” is a fluoromethyl in which a hydrogen atom of a methyl group bonded to a carbon atom at the α-position of methacrylic acid is substituted with a fluorine atom It means acrylic acid or a-fluoroacrylic acid ester in which a hydrogen atom bonded to the α-position carbon atom of acrylic acid is substituted with a fluorine atom.

In rosin (ΑΙ '), as the structural unit (a6'), one type may be used alone, or two or more types may be used in combination.

The proportion of the structural unit (a6 ′) in the resin (ΑΙ ′) is not particularly limited, but is preferably 50 mol% or less with respect to the total of all the structural units constituting the resin (ΑΙ ′).

[0112] It is preferable that the rosin used in the present invention is a solid aliphatic and does not dissolve in the organic solvent (S1)!

There is no particular limitation on the shape of the resin (wax '), but in consideration of the contact efficiency with the resin solution (R1) and the like, it is preferably granular. When it is granular, the particle diameter is preferably in the range of about 6 / ζπι to 1.2 mm in consideration of the specific surface area and the like as described above.

[0113] [Manufacture of resin (Al,)]

The production method of rosin (方法 ′) is not particularly limited, and can be obtained, for example, by polymerizing a monomer derived from each structural unit by a known polymerization method, for example, a chain polymerization method such as radical polymerization.

Specifically, for example, rosin (ΑΙ ′) can be produced by thermal polymerization or photopolymerization of a monomer that derives each of the above structural units with a radical polymerization initiator or an ionic polymerization initiator.

[0114] The method for producing the resin (A1 ') by a chain polymerization method such as radical polymerization is not particularly limited, such as Balta polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but it may form a particle shape. Suspension polymerization and emulsion polymerization are preferred from the viewpoint of ease, and suspension polymerization is more preferred from the viewpoint of good powder handleability of the resulting resin.

[0115] The dispersant used when producing the resin (ΑΙ ') by suspension polymerization is not particularly limited! /, For example, poly (meth) acrylic acid alkali metal salts, (meth) Examples thereof include alkali metal salts of copolymers of acrylic acid and methyl (meth) acrylate, polybulal alcohol having a saponification degree of 70 to 100%, and methylcellulose. One or more of these can be appropriately selected and used.

The amount of dispersant used is preferably in the range of 0.001 to 10% by weight in the aqueous suspension. Good. This is because the dispersion stability during polymerization tends to be improved by setting the amount of the dispersant to 0.001% by mass or more. More preferably, it is 0.01 mass% or more. In addition, when the content is 10% by mass or less, the dehydrating property and drying property of the rosin (ΑΙ ′) tends to be improved. More preferably, it is 1% by mass or less.

As a method for suspension polymerization in the present invention, one or more of the above-mentioned dispersants are dissolved in water, and while stirring, a monomer mixture containing a polymerization initiator is added, and 0.05 to about Lmm. It is preferable to carry out the polymerization while heating in a liquid droplet. At this time, an electrolyte or a pH adjuster can be used as needed for the purpose of improving the dispersion stability of the droplets.

[0116] In addition, the monomer mixture containing a polymerization initiator may be added to water at one time, divided into several times, or continuously. Furthermore, when a plurality of monomers are used for divided addition or continuous addition, the composition ratio of the monomers may be fixed or changed. The resin (A 1 ′) produced when the monomer composition ratio is changed forms a core-shell structure in the case of divided addition and a gradient structure in the case of continuous addition.

The polymerization temperature during suspension polymerization is not particularly limited, but is preferably in the range of 50 to 130 ° C. This is because by setting the temperature to 50 ° C. or higher, it tends to be possible to produce a polymer within a relatively short time. More preferably, it is 60 ° C or higher. In addition, the stability at the time of polymerization tends to increase when the temperature is 130 ° C or lower. More preferably, it is 100 ° C or lower.

[0117] The polymerization initiator used at the time of suspension polymerization is not particularly limited. For example, an azo initiator such as azobisisobuty-t-tolyl, or a peracid compound initiator such as benzoyl peroxide. An agent etc. can be mentioned. One or more of these can be appropriately selected and used.

In addition, a chain transfer agent can be used as necessary during suspension polymerization. The chain transfer agent that can be used is not particularly limited, and examples thereof include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, and a-methylstyrene dimer. These are selected as needed Can be used.

[0118] By filtering the polymer slurry obtained by suspension polymerization, rosin can be separated from the aqueous medium. The separated rosin (ΑΙ ') can be further washed and dried. The dried resin can be extracted with a desired particle size by sieving.

The filtration method after suspension polymerization is not particularly limited, but it is preferable to use a filter cloth having an opening of 20 to 100 / z m. This is because by setting the mesh size to 20 m or more, it is possible to discharge the emulsified fine particles and their secondary aggregates together with the filtrate. More preferably, it is 40 m or more. In addition, when the length is 100 m or less, it is possible to recover good rosin (A1 ′) with high yield. More preferably, it is 75 m or less.

[0119] The washing method after the suspension polymerization is not particularly limited, but the washing is not performed until the filtrate becomes almost transparent using a solvent or water without dissolving the resin. It is preferable to repeat.

Further, the drying method and the drying temperature are not particularly limited, but it is preferable that the drying is performed under the condition that the residual amount of water or the solvent used for washing is 2% by mass or less. This is to prevent elution of impurities when the resin (A1 ′) is dispersed in various solvents by setting it to 2% by mass or less. More preferably, it is 1% by mass or less.

[0120] The resin (A1,) obtained in the present invention contains acetone, ethyl acetate, methyl ethyl ketone, propylene glycol-monomonomethylenoateolate, propylene glycolenolemonomethinoate, lactate, y —Can be used dispersed in an organic solvent such as petit rataton.

The method for dispersing the resin (ΑΙ ') in the solvent is not particularly limited. For example, the solvent is added to a vessel equipped with a stirring blade and a cooling pipe, and the resin (ΑΙ') is gradually added while stirring. After the addition, it is preferable to maintain the state heated to about 40-80 ° C for about 2 hours.

[0121] At this time, when a monomer that induces the structural unit (a5 ') described above as a monomer, for example, a polyfunctional butyl monomer (ml), a crosslinking reaction proceeds from the polyfunctional vinyl monomer (ml) A crosslinked polymer is formed. [0122] In addition, in the production of rosin (ΑΙ '), the polymer obtained as described above is further crosslinked by the following methods (1) and Ζ or (2) to obtain a crosslinked polymer. Oh ,.

[0123] (1) Carboxylic acid is present! /, Is its anhydride and epoxy group! /, Is a method using reaction with isocyanate group

This method can be applied to the case where the polymer force carboxylic acid and Ζ or anhydride thereof obtained as described above are contained, and the case where Ζ or epoxy group and Ζ or isocyanate group are contained.

In this case, the resin (A1 ′) is prepared by mixing a polymer (pi) containing a carboxylic acid and candy or an anhydride thereof with a polymer (P2) containing an epoxy group and Z or an isocyanate group. Cross-linking these polymers,

After mixing a polymer (P1) containing a carboxylic acid and Z or an anhydride thereof with a compound (C1) containing an epoxy group and Z or an isocyanate group, the polymer and the compound can be crosslinked,

Compound (C2) containing carboxylic acid and Z or its anhydride is mixed with polymer (P2) containing epoxy group and Z or isocyanate group, and then these polymer and compound are cross-linked. Can be manufactured.

[0124] The polymer (P1) containing a carboxylic acid and Z or an anhydride thereof contains a carboxylic acid and Z or an anhydride thereof in the molecular structure (eg, main chain, side chain, terminal, etc.). For example, there is no particular limitation.

The polymer (P1) containing a carboxylic acid and Z or an anhydride thereof is at least one of a monomer having a carboxylic acid or an anhydride, an initiator having a carboxylic acid, and a chain transfer agent having a carboxylic acid. It is obtained by using.

[0125] Examples of the monomer having a carboxylic acid or its anhydride, e.g., (meth) acrylic acid, _a Echiruakuriru acid, crotonic acid, Keihi acid, Bulle acetic, isocrotonic acid, unsaturated such Cigli phosphate, and angelic acid Monocarboxylic acids; fumaric acid, maleic acid, citraconic acid, alk succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, dimethyl fumaric acid and other unsaturated dicarboxylic acids, their monoester derivatives, anhydrides and α- or Or j8-alkyl derivatives. [0126] Examples of the initiator having a carboxylic acid include 4,4'-azobis (4-cyananovaleric acid).

Examples of chain transfer agents having a carboxylic acid include mercaptoacetic acid, thiosalicylic acid, dithiodiglycolic acid, 3,3, -dithiodipropionic acid, 2,2, -dithiodibenzene acid, DL-2 mercapto. Methyl-3 guazinoethylthiopropanoic acid, 2 mercapto 4-methyl-5 thiazole acetic acid, p-mercaptophenol, 2 mercaptopropionic acid, 3 mercaptopropionic acid, thiomalic acid, (5 mercapto 1, 3, 4 thiadiazo Leu-2-ylthio) acetic acid, 2- (5-mercapto-1,3,4-thiadiazole-2-ylthio) propionic acid, 3- (5-mercapto-1,3,4-thiadiazole-2-ylthio) propionic acid, 2— (5 mercapto 1, 3, 4-thiadiazole-2 ilthio) succinic acid.

[0127] A polymer (P2) containing an epoxy group and a Z or isocyanate group has a carboxylic acid and Z or an anhydride thereof in the molecular structure (eg, main chain, side chain, terminal). There is no particular limitation.

The polymer (P2) containing an epoxy group and Z or isocyanate group can be obtained by using at least one of a monomer having an epoxy group, a monomer having an isocyanate group, and a chain transfer agent having an epoxy group.

[0128] Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, (meth) acrylic acid-methyldaricidyl, allylic glycidyl ether, allyl j8-methyldaricidyl ether, bisglycidyl (meth) acrylate. Examples include esters of glycidyl alcohol and unsaturated carboxylic acids.

Examples of the monomer having an isocyanate group include 2- (meth) ataryllooxyche.

Examples of the chain transfer agent having an epoxy group include epoxy methyl mercaptan.

[0129] The compound (C1) containing an epoxy group and Z or isocyanate group is particularly limited as long as the epoxy group and Z or isocyanate group are present in the molecular structure. However, in terms of the degree of crosslinking, epoxy groups or isocyanate groups are not present in the molecular structure.

It is preferable that there are two or more.

Examples of the compound containing two or more epoxy groups include 1,2: 8,9-diepoxy limonene, 3,4 epoxycyclohexenoremethinole 3 ', 4'-epoxycyclohexene carboxylate, and the like.

Examples of the compound containing two or more isocyanate groups include diphenylmethane diisocyanate, tonoleylene diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, trans 1,4-cyclohexane diisocyanate, 1, 3 Bis (isocyanatomethyl-benzene 4, 4'-dicyclohexylmethane diisocyanate, 1, 3-bis (isocyanatomethyl) monocyclohexane, hexamethylene diisocyanate, 3-isocyanate Natomethyl-1,3,5,5, trimethylcyclohexylisocyanate, metatetramethylxylene diisocyanate or paratetramethylxylene diisocyanate.

[0130] The compound (C2) containing a carboxylic acid and Z or an anhydride thereof is not particularly limited as long as the carboxylic acid and z or an anhydride thereof are present in the molecular structure.

From the viewpoint of the degree of crosslinking, it is preferable that the carboxylic acid is a force that exists in the molecular structure of two or more, or a cyclic carboxylic anhydride! /.

Examples of the compound containing two or more carboxylic acids in the molecular structure include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melophanoic acid, plate acid, and pyromellitic acid.

Examples of cyclic carboxylic acid anhydrides include succinic anhydride, phthalic anhydride, naphthalene-1,8: 4,5-tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid = 3, 4—anhydrides.

[0131] As a method for producing a polymer (P1) containing a carboxylic acid and Z or an anhydride thereof, and a polymer (P2) containing an epoxy group and Z or an isocyanate group, there are Barta polymerization and solution polymerization. Although not particularly limited, such as suspension polymerization and emulsion polymerization, solution polymerization and suspension polymerization are preferred from the viewpoint of easily forming a fiber shape.

When polymer (P1) or polymer (P2) is produced by solution polymerization, the solution polymerization method is used. About it, it does not restrict | limit in particular, Batch polymerization or dripping polymerization may be sufficient. Among them, a polymerization method called dropping polymerization in which a monomer is dropped into a polymerization vessel is preferable from the viewpoint that a polymer having a narrow composition distribution and Z or molecular weight distribution can be easily obtained. The monomer to be dropped may be a monomer alone or a solution in which the monomer is dissolved in an organic solvent.

[0132] In the dropping polymerization method, for example, an organic solvent is prepared and charged into a polymerization vessel (this organic solvent is also referred to as a "prepared solvent"), and heated to a predetermined polymerization temperature. A solution in which the initiator is dissolved in an organic solvent independently or in any combination (this organic solvent is also referred to as “dropping solvent”) is dropped into the charged solvent. In this case, the monomer may be added dropwise without dissolving in the dropping solvent.In this case, the polymerization initiator may be dissolved in the monomer, and a solution in which only the polymerization initiator is dissolved in the organic solvent is added to the organic solvent. May be dripped. In addition, a monomer or a polymerization initiator may be dropped into the polymerization vessel with no charged solvent in the polymerization vessel.

The monomer and the polymerization initiator may be directly dropped from an independent storage tank to a charged solvent heated to a predetermined polymerization temperature, or heated to a predetermined polymerization temperature from an independent storage tank. It may be mixed immediately before dropping into the charged solvent and dropped into the charged solvent.

[0133] Further, the timing at which the monomer or the polymerization initiator is dropped into the charged solvent may be dropped after the monomer has been dropped first, or the polymerization initiator may be dropped at a later time. Thereafter, the monomer may be dropped with a delay, or the monomer and the polymerization initiator may be dropped at the same timing. These dropping speeds may be constant until the dropping is completed, or may be changed in multiple stages according to the consumption speed of the monomer and the polymerization initiator, or intermittently. The dripping may be stopped or started.

The polymerization temperature in the drop polymerization method is not particularly limited, but it is usually preferably in the range of 50 to 150 ° C.

[0134] As the organic solvent used in the dropping polymerization method, a known solvent can be used as a polymerization solvent, and for example, a chain such as ether (jetyl ether, propylene glycol monomethyl ether (hereinafter also referred to as "PGME"). Ether, tetrahydrofuran (hereinafter also referred to as “TH F”), cyclic ethers such as 1, 4 dioxane, etc., esters (methyl acetate, vinegar, etc.) Ethyl acetate, butyl acetate, ethyl acetate, butyl lactate, propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), ketones (acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”), methyl isobutyl ketone (Hereinafter also referred to as “MIBK”), amides (N, N dimethylacetamide, N, N dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), hydrocarbons (benzene, toluene, xylene, etc.) Aliphatic hydrocarbons such as aromatic hydrocarbons, hexane, alicyclic hydrocarbons such as cyclohexane, and the like, and mixed solvents thereof.

These solvents may be used alone or in combination of two or more.

[0135] The amount of the polymerization solvent used is not particularly limited, and may be determined as appropriate. Usually, it is preferably used in the range of 30 to 700 parts by mass with respect to 100 parts by mass of the total amount of monomers used for copolymerization.

In the dropping polymerization method, when two or more polymerization solvents are used, the mixing ratio of the dropping solvent and the polymerization solvent in the charged solvent can be set at an arbitrary ratio.

The monomer concentration of the monomer solution dropped into the organic solvent is not particularly limited, but is preferably in the range of 50 to 50% by mass.

In addition, the amount of the charged solvent is not particularly limited and may be determined as appropriate. Usually, it is preferably used in the range of 30 to 700 parts by mass with respect to 100 parts by mass of the total amount of monomers used for copolymerization.

[0136] The polymer (P1) and the polymer (P2) are usually a monomer having a carboxylic acid or its anhydride in the presence of a polymerization initiator, or a monomer having an epoxy group and Z or isocyanate group. It is obtained by polymerizing each composition. The polymerization initiator is preferably one that generates radicals efficiently by heat. Examples of such a polymerization initiator include 2,2, -azobisisobutyric-tolyl (hereinafter also referred to as AIBN), dimethyl-2,2'-azobisisobutyrate (hereinafter also referred to as DAIB), and 2,2. Azo compounds such as 1,2-bis [2- (2-imidazoline-2-yl) propane]; 2,5 dimethyl-2,5-bis (tert butyl butyloxy) hexane, di (4 tert-butylcyclohexyl) per Examples include organic peroxides such as oxydicarbonate.

[0137] In consideration of safety during polymerization, the polymerization initiator has a 10-hour half-life temperature of 60 Those above ° C are preferred.

The amount of the polymerization initiator used is not particularly limited, but from the viewpoint of increasing the yield of the polymer, 0.3 mol part or more is preferred with respect to 100 mol parts of the total amount of monomers used for the polymerization. 1 mol part or more From the point of narrowing the molecular weight distribution of the more preferred copolymer, 30 mol parts or less is preferable with respect to 100 mol parts of the total amount of monomers used for the polymerization.

[0138] When the polymer (P1) or the polymer (P2) is produced, the chain transfer agent having a carboxylic acid is used in a range that does not hinder the crosslinking reaction of the polymer (P1) or the polymer (P2). Or a chain transfer agent other than a chain transfer agent having an epoxy group (hereinafter also referred to as chain transfer agent B) may be used. Examples of such chain transfer agent B include 1 butanethiol, 2-butanethiol, 1 octanethiol, 1 decanethiol, 1-tetradecanethiol, cyclohexanethiol, 2-methyl-1 propanethiol, 2-hydroxyl. Til mercaptan.

[0139] The polymer solution produced by solution polymerization can be used as a suitable solution with a good solvent such as 1, 4 dioxane, acetone, THF, MEK, MIBK, y-butylate rataton, PGMEA, PGME, etc. After diluting to viscosity, the polymer is precipitated by dripping into a large amount of poor solvent such as methanol, water, hexane, heptane and the like. This process is generally called reprecipitation and is very effective for removing unreacted monomers and polymerization initiators remaining in the polymerization solution. If these unreacted materials remain as they are, there is a possibility of adversely affecting the resist performance. Therefore, it is preferable to remove them as much as possible. The reprecipitation process may be unnecessary in some cases.

Thereafter, the precipitate is filtered off and sufficiently dried to obtain a polymer (P1) and a polymer (P2). Moreover, after filtering off, it can also be used with a wet powder, without drying.

[0140] When the polymer (P1) or the polymer (P2) is produced by suspension polymerization, the suspension polymerization method is as described above.

[0141] Using the polymer (P1) or polymer (P2) produced by the above-described method, a resin (反応 ') is obtained by reacting a carboxylic acid or its anhydride with an epoxy group or an isocyanate group. The polymer (P1) and polymer (Ρ2), the polymer (P1) and compound (C1), and the polymer (Ρ2) and compound (C2) can be combined in various solvents. After Preferred is a method in which a film forming or spinning process is performed by a known method, and the molded product is heated to advance the crosslinking reaction.

The end point of the reaction between the carboxylic acid or its anhydride and the epoxy group or isocyanate group is the cross-linking reaction point in the reaction solution using liquid chromatography (LC) or gas chromatography (GC). The end point of the reaction can be confirmed by analyzing the carboxylic acid, the epoxy group, or the isocyanate group, and not having these crosslinking reaction points. Even during the reaction, a large amount of a compound containing only one epoxy group and one Z or isocyanate group or a compound containing only one carboxylic acid and Z or its anhydride is present in the reaction solution. The reaction is terminated by injecting into the reaction site and deactivating the crosslinking reaction site.

[0142] (2) Method using reaction of hydroxyl group with isocyanate group

This method can be applied when the polymer obtained as described above contains a hydroxyl group and when it contains Z or an isocyanate group.

In this case, the resin (A1 ′) is obtained by mixing a polymer (P3) containing a hydroxyl group and a polymer (P4) containing an isocyanate group, and then crosslinking these polymers.

After mixing a polymer containing a hydroxyl group (P3) and a compound containing an isocyanate group (C3), these polymers and the compound can be crosslinked,

The compound (C4) containing a hydroxyl group and the polymer (P4) containing an isocyanate group can be mixed, and then the polymer and the compound can be crosslinked.

[0143] The polymer (P3) containing a hydroxyl group is not particularly limited as long as the hydroxyl group is present in the molecular structure (eg, main chain, side chain, terminal).

The polymer (P3) containing a hydroxyl group can be obtained by using at least one of a monomer having a hydroxyl group, an initiator having a hydroxyl group, and a chain transfer agent having a hydroxyl group.

[0144] Examples of the monomer having a hydroxyl group include bulufenol, vinyl naphthol, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate. .

Examples of the initiator having a hydroxyl group include 2, 2′-azobis (2-methyl-N— (1, 1-bis (hydroxymethyl) 2-hydroxyethyl) propionamide), 2, 2, monoazobis. (2-methyl-N- (2- (1-hydroxybutyl)) propionamide), 2,2, -azobis (2-methyl-N- (2-hydroxyethyl) propionamide) and the like.

Examples of the chain transfer agent having a hydroxyl group include 2-mercaptoethanol and thiodariserol.

[0145] The polymer (P4) containing an isocyanate group is not particularly limited as long as the isocyanate group is present in the molecular structure (eg, main chain, side chain, terminal).

The polymer (P4) containing an isocyanate group can be obtained by using a monomer having an isocyanate group.

[0146] The compound (C3) containing an isocyanate group is not particularly limited as long as the isocyanate group exists in the molecular structure. However, from the viewpoint of the degree of crosslinking, the isocyanate group is 2 in the molecular structure. It is preferable to have more than one piece.

[0147] The compound (C4) containing a hydroxyl group is not particularly limited as long as a hydroxyl group is present in the molecular structure, but from the viewpoint of the degree of crosslinking, two or more hydroxyl groups are present in the molecular structure. It is preferable to do this.

Examples of the compound containing two or more hydroxyl groups include 1,2-propanediol, 5-methyl-1,3-benzenediol, 2-hydroxybenzenemethanol, 2-((9-hydroxy-l-oxy) oxy) phenol, and the like. . [0148] The method for producing the polymer (P3) containing a hydroxyl group or the polymer (P4) containing an isocyanate group is not particularly limited, such as Balta polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. From the viewpoint of easily forming a sheet shape or fiber shape, solution polymerization or suspension polymerization is preferable.

When the polymer (P3) or polymer (P4) is produced by solution polymerization, the solution polymerization method is the same as that for the polymer (P1) and polymer (P2) described above.

When the polymer (P1) or polymer (P2) is produced by suspension polymerization, the suspension polymerization method is the same as that for the polymer (P1) or polymer (P2) described above.

Then, using the polymer (P3) or polymer (P4) produced by the above-described method, a method for producing the resin (A1 ′) of the present invention by the reaction of a hydroxyl group and an isocyanate group. Is a combination of polymer (P3) and polymer (P4), polymer (P3) and compound (C3), polymer (P4) and compound (C4), dissolved in various solvents, It is preferable to perform a crosslinking reaction by forming a film or spinning by a known method and heating the molded product.

The end point of the reaction between the hydroxyl group and the isocyanate group is determined by analyzing the hydroxyl acid or isocyanate group, which is a crosslinking reaction point in the reaction solution, using LC or GC, etc., in the reaction solution. Is not remaining, the end point of the reaction can be confirmed. Even during the reaction, a reaction containing a compound containing only one isocyanate group or a compound containing only one hydroxyl group is put into the reaction solution in a large amount to deactivate the crosslinking reaction point. Can also be terminated.

[0149] (Purification of resin (Al,))

Resin after polymerization or cross-linking (A1 ′) contains unreacted monomers, low molecular weight components such as oligomers, polymerization initiators and chain transfer agents, and unnecessary products such as reaction residues. It is preferable that (A1 ′) is subjected to purification treatment after polymerization.

[0150] In the present invention, since it is excellent in the effect of reducing differentials, particularly bridge mode differentials, the resin (榭 ') is purified by the following purification method (P1). Is preferred.

Purification method (P1): Fatty acid (Al,) with a solubility parameter of 17.0 to 20.5 CF / cm ³ ) ^1/2 A purification method comprising the step (i) of washing with an organic solvent (S 1 ′) in the range.

[0151] Resin after polymerization (A1 ') contains relatively low molecular weight compounds (unreacted monomers, by-product oligomers), low molecular weight polymers, and a high proportion of structural units (a2,) Yes Contains Rataton Rich Polymer (hereinafter these are collectively referred to as unnecessary). In the refining method (P1), it is presumed that by performing step (i), these unnecessary materials, particularly the rataton rich polymer, can be effectively removed.

That is, in a powerful purification method, in step (i), washing is performed using an organic solvent (S l,) having a solubility parameter in the range of 17.0 to 20.5 Ci / cm ³ ) ^1/2 . As a result, it is considered that impurities existing on the surface and Z or inside of the resin (ΑΙ ′) are dissolved in the organic solvent (S1 ′) to remove impurities.

[0152] · Process (i):

The organic solvent (S l,) used in step (i) is an organic solvent having a solubility parameter in the range of 17.0 to 20.5 a / cm ³ ) ^1/2 .

Since the organic solvent (S 1 ′) is used for washing the resin (A1 ′), it is preferable that the solvent does not dissolve the resin (A1 ′).

Organic solvents (S l,) include γ-petit-mouth rataton (SP value 18.4 (j / cm ³ ) ^1/2 ), propylene glycol monomethyl ether acetate (SP value 17.8 ϋ / cm ³ ) ^{1 / 2} ), tetrahydrofuran (SP value 18.6 a / cm ³ ) ^1/2 ), ethyl acetate (SP value 18.6 (j / cm ³ ) ^1/2 ), methyl ethyl ketone (SP value 19.0) (j / cm ³ ) ^1/2 ), toluene (SP value 18.2 (j / cm ³ ) ^1/2 ), and cyclohexanone (SP value 20.3 CiZcm ³ ) ^1/2 ) It is preferable to include at least one kind. Among these, γ-petit-mouth rataton is most preferable from the viewpoints of excellent effects of the present invention and availability.

In the present invention, the SP value of the organic solvent (Sl,) is a value calculated using the computational chemical software CAChe (product name) manufactured by Fujitsu.

[0153] Washing may be performed once or two or more times.

[0154] In the step (i), the washing can be performed, for example, by adding an organic solvent (S 1 ') in an amount equal to or greater than the mass of the resin (Al,) to the resin (Al,). .

There is no particular restriction on the temperature at which the rosin (ΑΙ ') is washed, but it increases the solubility of impurities. Therefore, the temperature is preferably 20 ° C or higher, more preferably 30 ° C or higher. In addition, in order to prevent the deterioration of the resin (ΑΙ ′), the temperature is preferably 100 ° C or lower, more preferably 80 ° C or lower. The amount of the organic solvent (S1 ′) used is not particularly limited. From the standpoint of its excellent effect, it is preferably 1.5 times by mass or more and more preferably 2.0 times by mass or more with respect to the mass (solid content) of the resin (ΑΙ '). The upper limit value is preferably 20 times by mass or less, more preferably 15 times by mass or less in consideration of processing efficiency, cost, and the like.

[0155] The resin (A1 ') after the above step (i) contains the organic solvent (S1') used in the purification.

The strong resin (ΑΙ ') can be used in the process of refining the resin for lithography, without removing the organic solvent (S1') by drying under reduced pressure.

[0156] · Process (ii):

In the purification method (P1), after the step (i), the resin (A1 ′) washed in the step (i) is dissolved in the organic resin without dissolving the resin (A1 ′). You may perform the step (ii) of washing with an organic solvent (S2 ') that is miscible with the solvent (S1')! /.

The organic solvent (S2,) used in step (ii) does not dissolve the resin (A1 ′) and is miscible with the organic solvent (S1 ′).

Here, “miscible with organic solvent (S 1 ′)” means that a uniform solution is obtained when 2 times the amount of organic solvent (S 1 ′) is added at 80 ° C. To do.

In addition, since the organic solvent (S2 ′) is used for washing the resin (ΑΙ ′), it does not dissolve the resin (A1,) and needs to be a solvent.

[0157] As the organic solvent (S2,), specifically, propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate (PGMEA), lactic acid ethyl, methyl ethyl ketone, propylene glycol monomethyl ether, cyclohexane Xanone and the like.

When the organic solvent (S1 ') is the above-mentioned γ-petit mouth outside, the organic solvent (S2') has good compatibility with PGMEA is preferred, especially propylene glycol monoalkyl ether acetate! [0158] In X @ (ii), washing can be performed, for example, by adding organic solvent (S2 ') in an amount equal to or greater than the mass of rosin (ΑΙ') to rosin (ΑΙ '). .

There is no particular limitation on the temperature at which the rosin (ΑΙ ') is washed, but in order to increase the solubility of impurities, it is preferably 20 ° C or higher, more preferably 40 ° C or higher. . Further, in order to sufficiently prevent the deterioration of the resin (ΑΙ ′), 100 ° C. or lower is preferable, and 80 ° C. or lower is more preferable.

The amount of the organic solvent (S2 ′) used is not particularly limited, but is preferably 1.5 times by mass or more with respect to the mass (solid content) of the resin (榭 ′) because of the excellent effect of the present invention. More than mass times are more preferable. The upper limit value is preferably 20 times by mass or less, more preferably 15 times by mass or less in consideration of processing efficiency, cost, and the like.

[0159] Washing may be performed once or two or more times. In the present invention, the washing with the organic solvent (S 2 ′) is preferably performed until the organic solvent (S1 ′) can be completely removed from the resin (A1 ′).

Whether the organic solvent (S1 ') has been completely removed from the resin (S'), for example, analyze the organic solvent (S2,) after cleaning the resin (A1,) by gas chromatography (GC), etc. It can be confirmed by measuring the concentration of the organic solvent (S1 ′) in the organic solvent (S2 ′). If the organic solvent (S 2 ′) contains the organic solvent (S 1 ′), the washing process is repeated until the organic solvent (S 1 ′) cannot be detected.

[0160] The resin (A1,) after the above step (ii) contains the organic solvent (S2 ') used in the purification.

Powerful rosin (ΑΙ ') can be used in the refining process of lithographic resin as it is without removing the organic solvent (S2') by drying under reduced pressure.

[0161] · Process (iii):

In the purification method (PI), after the step (i) or (ii), the organic solvent (S1 ′) or (S2 ′) The step (iii) may be performed by replacing with an organic solvent (S3,) having a boiling point lower than that of the solvent (S1 ') or (S2,)!

[0162] When the organic solvent (S1,) or (S2,) is the propylene glycol monoalkyl ether acetate described above, the organic solvent (S3,) may be propylene glycol monoalkyl. Tetrahydrofuran (THF; boiling point 66 ° C) is preferred because of its good miscibility with ruether acetate and availability.

[0163] The amount of the organic solvent (S3 ') used is not particularly limited as long as it can completely remove the organic solvent (S2') from the resin (榭 '). Usually, it is preferable to be in the range of 1.5 to 20 times by mass, more preferably in the range of 2 to 15 times by mass with respect to the mass of rosin (ΑΙ ′). When it is at least the lower limit value, the effect of removing the organic solvent (S2 ′) is excellent, and when it is at most the upper limit value, the solvent can be replaced in a short time.

[0164] After the solvent replacement, the organic solvent (S3 ') may be removed, or may be used as it is in a process for refining a resin for lithography.

The removal of the organic solvent (S3 ′) from the resin (ΑΙ ′) can be carried out, for example, by heating at a temperature below the boiling point of the organic solvent (S3 ′).

[0165] More specifically, the purification method (P1) can be performed, for example, by the following procedure.

First, add the organic solvent (Sl,) to the solid resin (Al,) and stir at 0.5 ~: LO time, 20 ~ 80 ° C, and add the organic solvent (S 1 ') Absorb (swell).

Next, the organic solvent (S2 ′) is optionally added to and removed from the resin (A1 ′). It is preferable to add or remove the organic solvent (S2 ′) until the organic solvent (S1 ′) in the resin (A1 ′) is completely removed.

Next, optionally, an organic solvent (S3 ′) is added to the resin (ΑΙ ′), and the mixture is stirred for 0.5 to 10 hours at 20 to 80 ° C. After removing the organic solvent (S3 ′), Further, drying under reduced pressure is performed.

In this way, purified rosin (A1,) is obtained.

[0166] <Contact method>

The method of bringing the resin solution (R1) in which the resin (A1) is dissolved in the organic solvent (S1) into contact with the resin (A1,) is not particularly limited. For example, a method of filling a liquid-permeable container such as a column with the resin (ΑΙ ′) and passing the liquid-permeable container through the resin solution (R1); Examples thereof include a method of adding and stirring a fat (Α 1 ′) into the fat solution (R1).

[0167] In the present invention, since the separation of the resin solution (R1) and the resin (A1 ') is easy, etc. Fill the container and fill the container A method of passing through (Rl) is preferable.

As a method for allowing the resin solution (R1) to pass through the container through which liquid can pass, for example, after putting the resin solution (R1) into a cylindrical container filled with resin (A 1 '), For example, a method of dropping (eluting) by the method of the above, a method of continuously passing the resin solution (R1) through the cylindrical container filled with the resin (A1 ′), and the like.

As shown in FIG. 1, the cylindrical container can prevent the granular resin (A1,) 2 filled in the casing from flowing out at both ends of the cylindrical casing 1, and can also prevent the resin solution ( For example, a commercially available column can be used as a container that can be installed with filters 3 and 4 through which R1) can pass.

Instead of the filters 3 and 4, the one with the same function, for example, cotton or other fibers may be packed at both ends of the cylindrical container.

For example, as shown in FIG. 1, a filter 4 is arranged at one end, for example, below, of a cylindrical casing 1 to form a granular resin (ΑΙ ′) 2 After pouring the liquid in which the powder is dispersed into the casing 1 to fill the resin (A1 ′) 2, the filter 3 is placed thereon. A method in which the resin solution (R1) is poured from the upper part of the filter 3 and dripped (eluted) by gravity. In the cylindrical container filled with the resin (A1 ′), the resin solution (R 1) is continuously added. By allowing the liquid to pass therethrough, the resin solution (R1) can be brought into contact with the resin (resin).

Among these, the method of dropping (eluting) is preferable because the effect of the present invention is high because the removal effect of the rataton rich polymer is high.

The elution rate for dropping is not particularly limited. It is preferably in the range of 0.1 to 5 mlZ seconds. Force S is preferred, 0.1 to 4 mlZ seconds is more preferred 0.2 to 3.5 mlZ seconds is more preferred. . Within the above range, the bridge mode differential reduction effect is excellent. Further, if it is at least the lower limit value, the production efficiency is good, and if it is less than the upper limit value, the total number of the diffs can be reduced.

(Other processes)

In the present invention, the organic solvent (S4) is added to the resin solution (R1) before bringing the resin solution (R1) into contact with the resin (R ′), and Process to reduce concentration (dilution It is preferable to perform the step). As a result, by-products contained in the resin (A1) (for example, oligomers by-produced in the polymerization reaction, low molecular weight polymers, or polymers having a higher molecular weight than the target mass average molecular weight, especially the inclusion of specific structural units) The amount of the polymer, oligomer, etc. having a high ratio and uneven composition can be reduced, and the effect of the present invention is further improved.

[0169] Examples of the organic solvent (S4) are the same as those exemplified as the organic solvent (S1).

The addition amount of the organic solvent (S4) is preferably 2 to 5 times, more preferably 4 to 5 times the mass of the resin solution (R1).

At this time, the concentration of the resin (A1) in the resist composition in which the resin (A1) is used is defined as, and the concentration of the resin (A1) in the diluted resin solution (R1) is defined as C2. In this case, it is preferable to add the organic solvent (S4) so that C2 is smaller than C1, since the effects of the present invention are excellent.

Here, generally, the wavelength of the exposure light source is 248 nm or less (for example, KrF, ArF, or F

2 The base resin concentration C1 in the resist composition corresponding to the wavelength of excimer laser light, Extreme UV (extreme ultraviolet light), EB (electron beam) or X-ray) is not particularly limited. Since an appropriate film thickness for the light source can be provided, it is preferably adjusted to 2 to 20% by mass, more preferably 5 to 15% by mass.

The value of C2 is not limited as long as it is prepared so as to be smaller than C1 as described above. Therefore, C2 may be less than the numerical value of C1.

[0170] In the dilution step, for example, an organic solvent (S4) is added to the resin solution (R1), preferably 10 to 40. Preferably 20 to 30 for C. C can be carried out by stirring, shaking, etc. for 10 to 60 minutes, preferably 25 to 35 minutes.

[0171] In the present invention, before contacting the cocoon solution, rosin solution (R1) and rosin (Al,), the rosin solution (R1) is mixed with an organic solvent (S1) such as water. A washing step (water washing step) may be performed using an aqueous solvent (S5) that can be separated into two layers. As a result, oligomers and low molecular weight polymers in rosin (A1), particularly oligomers having relatively high polarity and low molecular weight polymers (such as rataton rich polymers) can be dissolved in the aqueous layer and removed.

As the aqueous solvent (S5), water is preferably used. [0172] As a specific operation, for example, first, the aqueous solvent (S5) is added to the resin solution (R1). At this time, the use ratio (mass ratio) of the organic solvent (S1) and the aqueous solvent (S5) in the resin solution (R1) is not particularly limited as long as it can be separated into two layers. (S1): Aqueous solvent 5) = 1: 1 to 4: 1 (mass ratio) is preferable, and 2: 1 to 3: 1 is preferable. Use ratio power of aqueous solvent (S5): When it is 1 or more, a sufficient cleaning effect can be obtained, and when it is 1: 1 or less, it is well separated from organic solvent (S1), and the resin (A1) is aqueous The resin (A1) can be recovered with a good yield that is difficult to move to the solvent (S5) phase, which is effective in improving productivity and reducing costs.

Next, after adding the aqueous solvent (S5) to the rosin solution (R1), it is stirred at 10 to 40 ° C, preferably at 20 to 30 ° C, for 10 to 60 minutes, preferably for 25 to 35 minutes. Wash by shaking. Next, when the stirring is completed and the liquid is allowed to stand, the organic solvent (S1) phase is the upper layer and the aqueous solvent (S5) phase is the lower layer. The lower aqueous solvent (S5) phase is removed from the liquid separated into two layers, and the organic solvent (S1) phase in which the resin (A1) is dissolved is recovered.

The water washing step may be performed once or two or more times.

[0173] Furthermore, in the present invention, the step of allowing the resin solution (R1) to pass through the filter having a filtration membrane before and after contact with the resin solution (R1) and the resin (ΑΙ '). It is preferable to perform (filtration step).

As the filter, any filter that has been used so far for filtration of a resin solution or the like is not particularly limited.

Examples of filter membranes include fluorine resins such as PTFE (polytetrafluoroethylene); polyolefin resins such as polypropylene and polyethylene; polyamide resins such as nylon 6 and nylon 66, and the like.

In the present invention, in particular, a filter having at least one selected from three types of filter membranes made of nylon such as nylon 66 and nylon 6, a filter membrane made of polyethylene, and a filter membrane made of polypropylene is used. In particular, it is preferable to use a filter having a nylon filtration membrane. By using a filter equipped with these filtration membranes, it is possible to effectively remove oligomers and low molecular weight polymers by-produced by the polymerization reaction, or polymers having a higher molecular weight than the target weight average molecular weight. As a result, the effect of the present invention The fruit is further improved.

The pore size of the finoleta is 0.02 to 0.1 111 m, more preferably 0.02 to 0.05 m force. Also, if the filter pore size is 0.02 m or more, the filtration rate can be increased and good productivity can be maintained. Moreover, when it is 0.1 μm or less, an oligomer or a low molecular weight polymer by-produced by the polymerization reaction, or a polymer having a higher molecular weight than the target mass average molecular weight can be effectively removed.

[0174] Filtration may be performed in one step or in two or more steps. Moreover, the kind of filtration membrane and filter to be used may be one kind or a combination of two or more kinds.

[0175] The resin solution (R1) thus obtained can be adjusted to a concentration suitable for semiconductor lithography using the resin (A1) by removing (concentrating) a certain amount of organic solvent. Good. Such a resin solution can be used as it is as a resin solution for preparing a resist composition, for example, an acid generator component and other optional components can be prepared in the resin solution to efficiently produce a resist composition. ,preferable.

The resin solution (R1) can also be used for semiconductor lithography applications such as the production of resist compositions as a solid resin by completely removing the organic solvent.

[0176] <Resist composition>

The resin (A1) produced by the production method of the present invention is used for semiconductor lithography, and is particularly suitably used as a resin component of a resist composition. Among them, as described above, the base component (A) (component (A)) whose alkali solubility changes due to the action of acid, and the acid generator component (B) ((B) that generates acid upon irradiation with radiation. In the chemically amplified resist composition containing the component)), it can be suitably used as the base component (A).

The resist composition may be positive or negative as long as it contains the resin (A1) as the component (A). A positive type is preferred.

In the case of the negative type, a crosslinking agent is blended in the resist composition together with the alkali-soluble resin and the component (B). When an acid is generated from the component (B) by exposure at the time of forming a resist pattern, a strong acid acts to cause cross-linking between the alkali-soluble resin and the cross-linking agent, thereby changing to alkali-insoluble.

As a crosslinking agent, for example, usually a methylol group or an alkoxymethyl group, especially It is preferable to use an amino crosslinking agent such as glycoluril having a butoxymethyl group, a melamine crosslinking agent, a urea crosslinking agent, or an ethyleneurea crosslinking agent because a good resist pattern can be formed. The amount of the crosslinking agent is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

[0178] In the case of the positive type, the component (A) is an alkali-insoluble one having a so-called acid dissociable, dissolution inhibiting group, and when an acid is generated from the component (B) by exposure, a strong acid is converted into the acid. By dissociating the dissociable, dissolution inhibiting group, the component (A) becomes alkali-soluble. Therefore, in the formation of the resist pattern, when the resist composition applied on the substrate is selectively exposed, the alkali solubility in the exposed portion is increased and alkali development can be performed.

[0179] [(A) component]

In the present invention, the component (A) is rosin (A1) produced by the production method of the present invention.

In the present invention, in addition to the resin (A1), other resin components that can be used in the resist composition, such as known polyhydroxystyrene resin and (meth) acrylic resin, may be appropriately blended. However, for the effect of the present invention, it is preferable that the ratio of the resin (A1) in the component (A) contained in the resist composition is 80% by mass or more, more preferably 90% by mass or more. Most preferred is 100% by mass.

The proportion of the component (A) in the resist composition can be appropriately adjusted depending on the intended resist film thickness.

[0180] [(B) component]

The component (B) can be used without particular limitation from known acid generators used in conventional chemically amplified resist compositions.

Examples of such acid generators include onium salt acid generators such as ododonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfol-diazomethanes, There are various known diazomethane acid generators such as (bissulfol) diazomethanes, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, and disulfone acid generators.

[0181] As a specific example of an acid salt-based acid generator, trifluorometa Sulphonate or nonafluorobutane sulphonate, bis (4-tert-butylphenol) trifluoromethane sulphonate or nonafluorobutane sulphonate, trifluorosulphonyl trifluorosulphonate, its heptafluoroprote Pansulfonate or its nonafluorobutanesulfonate, tri (4 methylphenol) snorephonium trifunoleolomethane sulphonate, its heptafluororeopropane sulphonate or its nonafluorobutane sulfonate, dimethyl (4-hydroxy Naphthyl trifonoreomethane sulphonate of snorephonium, its heptafluororeopropane sulphonate or its nonafluorobutane sulphonate, monophenyl dimethylsulphonium trif Fluoromethane sulfonate, its heptafluoropropane sulfonate, or its nonafluorobutane sulfonate, trifluoromethane sulfonate of diphenyl monomethyl sulfone, its heptafluoropropane sulfonate, or its nonafluorobutane sulfonate , Trifluoromethane sulfonate of (4 methyl phenol) diphenyl sulfone, methane sulfonate thereof, heptafluoropropane sulfonate or nonafluorobutane sulfonate thereof, trifluoromethane sulfonate of (4-methoxyphenol) diphenyl sulfone, Heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4-tert-butyl) phenol sulfone trifluoromethane sulfonate, its heptafluoropropane sulfonate Such sulfonate or nona Full O Rob Tan sulfonates and the like.

Specific examples of the oxime sulfonate-based acid generator include α- (ρ-toluenesulfo-sulfoximino) -benzyl cyanide, α- (ρ-chlorobenzenesulfo-luoximino) -benzyl cyanide, α- (4 -Nitrobenzenesulfo-loxyimino) -benzyl cyanide, _α- (4-nitro-2-trifluoromethylbenzenesulfonyloxymino) -benzyl cyanide, α- (benzenesulfo-loxyimino) -4-chloro Oral benzil cyanide, α- (Benzenesulfo-ruximino)-2,4-Dichlorobenzil cyanide, α- (Benzenesulfuroxyximino)-2,6-Dichlorobenzil cyanide, α- (Benzenesulfo) -Luoxyimino) -4-methoxybenzyl cyanide, α- (2-chlorobenzenesulfo-Luoxyimino) -4-methoxybenzyl cyanide, a-(Benzenesulfol) Kishiimino) - Cheng - 2 Iruaseto nitriles, (X - (4-dodecylbenzenesulfonate - Ruokishiimino) - Benjirushia - de, alpha - [( p-toluenesulfo-ruximino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfo-ruximino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-cerciad , A-(Methylsulfo-Luoxyimino)-1 -Cyclopentylacetonitrile, OC-(Methylsulfo-Luoxyimino)-1 -Cyclohexyl-Luaceto-Tolyl, α-(Methylsulfo-Luoxyimino)-1 -Cycloheptulaceto Nitriles, α- (Methylsulfo-ruximino) -1-cyclooctaturacetonitrile, at- (Trifluoromethylsulfo-ruximino) -1-cyclopenteru-nitronitrile, α- (Trifluoromethylsulfo-ruximino) -cyclohexylhexonitrile, α-(Ethylsulfo-Loximino)- Ruacetonitrile, OC- (propylsulfo-oxyximino) -propylacetonitrile, OC- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfo-ruximino) -cyclohexylhexonitrile, α- (Cyclohexylsulfo-luoxyimino)-1 -Cyclopentyl-acetonitrile, _α- (Ethylsulfo-Luoxyimino)-1 -Cyclopente-rucetonitrile, _α- (Isopropylsulfol-luoxyimino)-1 -Cyclopentyl-rucetonitrile, α-( η-butylsulfo-oxyximino)-1 -cyclopenteruacetonitrile, (X-(ethylsulfo-ruximino)-1 -cyclohexa-nitronitrile, at-(isopropylsulfo-ruximino)-1 -cyclohexenylacetonitrile, _α- ( _η -Butylsulfonyloxyimino) -1-cyclohexylacetonitrile, OC- (methylsulfo-ruximino) -phenolacetonitrile, a- (methylsulfo-oxyximino) -p-methoxyphenylacetonitrile, α- (Trifluoromethylsulfo-ruximino) Phenylacetonitrile, _α — (Trifluoromethylsulfo-ruximino) —ρ-methoxyphenylacetonitrile, α- (Ethylsulfo-ruxitimino) —ρ-methoxyphenyl-rucetonitrile, α- (Propylsulfo-ruximino) ) -Ρ-methylphenolacetonitrile, (X- (methylsulfo-luoxyimino) -ρ bromophenolacetonitrile, and the like. Of these, _α- (methylsulfoxy-ximino) -ρ-methoxyphenylacetonitrile is preferred.

Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis (ρ toluenesulfol) diazomethane, bis (1,1-dimethyl). Ethylsulfol) diazomethane, bi S (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane and the like.

Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used. Examples of poly (bissulfol) diazomethanes include 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1, 4 disclosed in JP-A-11 322707. Bis (phenylsulfodiazomethylsulfol) butane, 1,6-bis (phenolsulfodiazomethylsulfol) hexane, 1,10-bis (phenolsulfoldiol) Zomethylsulfo) decane, 1,2-bis (cyclohexylsulfodiazomethylsulfo) ethane, 1,3 bis (cyclohexylsulfodiazomethylsulfo) propane, 1,6 bis (cyclohexylsulfo-) (Luazomethylsulfol) hexane, 1,10-bis (cyclohexylsulfoldiazomethylsulfol) decane, and the like.

[0184] As the component (B), one type of these acid generators may be used alone, or two or more types may be used in combination. As the component (B), an onium salt having a fluorinated alkyl sulfonate ion as an anion is particularly preferable.

The content of the component (B) in the resist composition is 0.5 to 30 parts by mass, preferably 1 to L0 parts by mass with respect to 100 parts by mass of the component (A). By making it within the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

[0185] [Optional ingredients]

The resist composition further includes, as an optional component, in order to improve the resist pattern shape, post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer, and the like. Nitrogen organic compound (D) (hereinafter referred to as component (D)) can be blended.

Since a wide variety of components (D) have already been proposed, any known one can be used, but cyclic amines, aliphatic amines, especially secondary aliphatic amines are tertiary fats. Aliphatic amines are preferred. Here, the aliphatic amine is an amine having one or more aliphatic groups. And the aliphatic group preferably has 112 carbon atoms.

Aliphatic amines contain at least one hydrogen atom of ammonia NH and have 12 or more carbon atoms.

Three

Examples include amines substituted with the lower alkyl group or hydroxyalkyl group (alkylamines or alkylalcoholamines). Specific examples thereof include monoalkylamines such as n-hexylamine, n-ptylamine, n-octylamine, n-noramine, n-decylamine; Dialkylamines such as dicyclohexylamine; trimethylamine, triethylamine, tri- _n -propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-ptyluamine, tri-n-octylamine, tri - n- Bruno - Ruamin, tri - n- de force - Ruamin, tri - tri Arukiruamin such n- Dodeshiruamin; diethanol § Min, triethanolamine § Min, diisopropanolamine § Min, triisopropanolamine § Min, di _n - O Kutanamamine, tree n -Alkyl alcoholamines such as octanolamine.

Of these, alkyl alcoholamines are preferred, with alkyl alcoholamines and trialkylamines being preferred. Of the alkyl alcoholamines, triethanolamine and triisopropanolamine are most preferred.

Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic ammine) or polycyclic (aliphatic polycyclic ammine).

Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. Aliphatic polycyclic amines having 6 to 10 carbon atoms are preferred, specifically 1, 5

—Diazabicyclo [4. 3. 0] — 5—Nonene, 1, 8—Diazabicyclo [5. 4. 0] — 7—Undecene, Hexamethylenetetramine, 1,4-Diazabicyclo [2. 2. 2] Octane Etc.

These can be used alone or in combination of two or more.

Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).

Resist compositions have a sensitivity reduction, resist pattern shape, For the purpose of improving qualitative properties and the like, an organic carboxylic acid or phosphorus oxoacid or its derivative (E) (hereinafter referred to as component (E)) can be contained as an optional component.

As the organic carboxylic acid, for example, acetic acid, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.

Phosphoric acid or its derivatives include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenol ester and other phosphoric acid or derivatives such as those esters, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acid such as n-butyl ester, phenol phosphonic acid, diphosphoric phosphonic acid ester, dibenzyl phosphonic acid ester and derivatives thereof, phosphinic acid such as phosphinic acid, phenol phosphinic acid and the like Derivatives such as esters are mentioned.

Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).

[0187] The resist composition may further contain, if desired, miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving coatability, and a dissolution inhibitor. In addition, plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be appropriately added and contained.

[0188] The resist composition can be produced by dissolving the material in an organic solvent (S) (hereinafter also referred to as component (S)).

As the component (S), it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Two or more kinds can be appropriately selected and used.

For example, latones such as γ-butyrolatatane; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-η-amyl ketone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene Polyhydric alcohols such as glycol and derivatives thereof; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the polyhydric alcohols or Monomethyl ether, monoethyl etherate, monopropino resin, monobutyne resin, etc. Derivatives of polyhydric alcohols such as compounds having an ether bond such as benzene or monophenyl ether; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, pyruvin Esters such as methyl acid, ethyl pyruvate, methyl methoxypropionate, ethoxypropionate, etc .; Asol, ethinolevenolineatere, crezinoremethinoreatenore, dipheninoreethenore, dibenzinoreethenore, feneto Examples thereof include aromatic organic solvents such as mononole, butinolevenoleethenole, ethenolebenzene, jetinobenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene.

These organic solvents can be used alone or as a mixed solvent of two or more. Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and EL are preferable.

In addition, as the component (S), a mixed solvent of at least one selected from among PGMEA and EL and γ-petit-mouth rataton is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.

The amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate, etc., and can be appropriately set according to the coating film thickness. It is used so as to be in the range of 20% by mass, preferably 5 to 15% by mass.

The material can be dissolved in the component (S) by, for example, mixing and stirring each of the above components in the usual manner, and if necessary, a disperser such as a dissolver, a homogenizer, or a three-roll mill can be used. You may use and disperse and mix. Further, after mixing, the mixture may be filtered using a cocoon mesh or a membrane filter. [0190] <Resist pattern formation method>

The resist pattern forming method using the resist composition can be performed, for example, as follows.

First, the positive resist composition is applied onto a substrate such as a silicon wafer with a spinner and the like, and a pre-beta (post-apply beta (PAB)) is applied for 40 to 120 seconds at a temperature of 80 to 150 ° C. Preferably, it is applied for 60 to 90 seconds, and this is selectively exposed to ArF excimer laser light through a desired mask pattern using, for example, an ArF exposure apparatus, and then subjected to PEB under a temperature condition of 80 to 150 ° C. (Post-exposure heating) is applied for 40 to 120 seconds, preferably 60 to 90 seconds. This is then developed using an alkaline developer such as an aqueous solution of 0.1 to: LO mass% tetramethylammonium hydroxide. In this way, a resist pattern faithful to the mask pattern can be obtained.

An organic or inorganic antireflection film can be provided between the substrate and the coating layer of the resist composition.

The wavelength used for exposure can be set appropriately according to the type of rosin (A1), for example, ArF excimer laser, KrF excimer laser, F excimer laser, EUV (extreme purple)

2

External radiation), VUV (vacuum ultraviolet light), EB (electron beam), X-rays, soft X-rays, etc. can be selected and used.

Example

Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

The measurement methods used in the following synthesis examples and examples are shown below.

The polymerization conversion rate of the resin (polymer) was determined by determining the amount of unreacted monomer present in the polymerization reaction solution for each monomer and calculating the consumption rate for each monomer in reverse.

[0192] In the case of a polymer produced by the suspension polymerization method, the amount of monomer remaining in the polymer was determined by the following method. First, 0.1 lg of a polymer that has been subjected to post-treatment such as washing and drying is collected, the acetonitrile is added, and the total volume is made 50 mL using a volumetric flask, followed by sonication. The polymer was dispersed. This dispersion was filtered through a 0.2 m membrane filter, and the amount of each unreacted monomer was determined using a high performance liquid chromatograph HPLC-8020 (product name) manufactured by Tosoh.

[0193] In this measurement, one separation column, Inertsil ODS-2 (trade name) manufactured by GL Sciences, was used, the mobile phase was water Z-acetonitrile gradient system, the flow rate was 0.8 mLZmin, and the detector was manufactured by Tosoh UV. Visible absorption photometer UV-8020 (trade name), detection wavelength 220nm, measurement temperature 40 ° C, injection amount 4 and using polystyrene as standard polymer. Inertsil ODS-2 (trade name), which is a separation column, had a silica gel particle size of 5 μm, a column inner diameter of 4.6 mm, and a column length of 450 mm. The gradient conditions of the mobile phase were as follows, with liquid A being water and liquid B being acetonitrile.

Measurement time 0 to 3 minutes: A liquid ZB liquid = 90 vol% Z10 vol%

Measurement time 3 to 40 minutes: A solution ZB solution = 90 volume ⁰ / OZlO vol% → 50 vol% Z50 volume ^_0/0 Measurement time 40-62 minutes: A solution ZB solution = 50 vol% Z50 vol% → 0 vol% Z100 volume%

Measurement time 62-70 minutes: A liquid ZB liquid = 0 vol% Z100 vol%

[0194] <Specific surface area (Nitrogen adsorption method)>

It was measured using a Nikkiso Co., Ltd. specific surface area measuring device Beta Soap Model 4200 (trade name). About 4g of the crosslinked polymer is put into a dedicated cell, set in a measuring device, degassed at 150 ° C for 60 minutes, then adsorbed with nitrogen gas at liquid nitrogen temperature, and the specific surface area is measured. did

[0195] <Content of each structural unit>

The content of each structural unit of the resin for semiconductor lithography was determined by NMR measurement. ^ H—NMR measurement was performed using a GSX-400 FT-NMR (trade name) manufactured by JEOL Ltd., and a solution of about 5% by mass of a polymer sample for semiconductor lithography (deuterated dimethyls The sulfoxide solution was placed in a test tube with a diameter of 5 mm and was accumulated 64 times in a single pulse mode at an observation frequency of 400 MHz. The measurement temperature was 60 ° C.

[0196] <Mass average molecular weight (Mw)>

Dissolve about 20 mg of resin lithography resin in 5 mL of THF and add 0.5 m membrane. A sample solution was prepared by filtration through a membrane filter, and this sample solution was measured using Tosoh gel permeation 'chromatography (GPC). For this measurement, three separation columns, Shodex GPC K-805L (trade name), in series were used as the separation column, the solvent was THF, the flow rate was 1. OmL / min, and the detector was a differential refractometer. The measurement was performed using polystyrene as a standard polymer at a temperature of 40 ° C. and an injection volume of 0.1 mL.

[0197] <Pyrolysis temperature (Td)>

About 10 mg of resin fat for semiconductor lithography was weighed in a special aluminum pan and measured using a TGZDTA6200 thermal analyzer (trade name) manufactured by Seiko Instruments. The temperature elevation condition was 10 ° CZmin.

[0198] Glass transition temperature (Tg)>

About 10 mg of a resin for semiconductor lithography was weighed in a dedicated aluminum pan and measured using a DSC6200 thermal analyzer (trade name) manufactured by Seiko Instruments. The temperature rise condition is

It was measured at 10 ° CZmin.

[0199] Synthesis Example 1

In a polymerization apparatus that can be heated and cooled, 200 parts by mass of deionized water and polyvinyl alcohol (80% degree of polymerization, degree of polymerization 1700) are mixed and 0.6 parts by mass are stirred, After complete dissolution, the agitation is once stopped, and α-metatalylloy oxy-γ-butyral rataton represented by the following formula (ml) (hereinafter referred to as GBLMA. SP value is 18.5 (j / crn) ^1/2 ₀ ) 95.0 parts by mass (composition ratio: 97.4 mol%) and trimethylolpropane trimetatalylate (hereinafter referred to as TMPTMA) represented by the following formula (m2). SP value is 17.2 Q / cm ³ ) ^1/2 ₀ ) 5.0 parts by mass (prepared composition ratio: 2.6 mol%) was added, and stirring was started again, adding 0.5 parts by mass of lauroyl peroxide to 75 ° After the temperature was raised to C, the reaction was carried out for 3 hours while maintaining a temperature of 75 to 80 ° C. Thereafter, the temperature of the reaction solution was further raised to 95 ° C., and this state was maintained for 1 hour to complete the reaction.

[0200] [Chemical 34]

[0201] After completion of the reaction, the reaction solution was cooled to 50 ° C, 0.3 parts by mass of sodium carbonate was added, and the mixture was stirred for 0.5 hour. Thereafter, the obtained aqueous suspension is filtered through a nylon filter cloth having an opening of 45 μm, washed, and the obtained filtrate is dried at 40 ° C. for about 16 hours. — A granular rosin (Α′-1) represented by 1) was obtained.

The polymerization conversion of rosin (Α'-1) was 99.6%. The specific surface area of rosin (Α'-1) measured by the nitrogen adsorption method was 0.07m ² Zg.

The SP value of rosin (A,-1) is 18.5 Q / cm ³ ) ^1/2 for GBLMA, and 17.2 (j / cm ³ ) ^1/2 for TMPTMA. since, SP value of GBLMA / TMPTMA = 9 7.4 moles ⁰ /OZ2.6 mole ^_0/0 of the polymer, 18.5X0.974 + 17.2X0.026 = 18.5 (j / cm 3) was ^1/2 .

[0202]

[mVn '= 97.4 / 2.6 (molar ratio)]

[0203] Next, 200 g of the resin (A, — l) obtained in Synthesis Example 1 and 400 g of γ-petit-mouth rataton (GBL; SP value 18.4 CiZcm ³ ) ^1/2 ) were put into a container. The mixture was stirred at 60 ° C for 3 hours. After stirring, The fat (Α′-1) was swollen by absorbing all the γ-petit mouth ratatones.

Next, 600g of PGMEA was placed in the same container, stirred (refluxed) with rosin (Α'-1) for 2 hours at 80 ° C, and then the solvent was removed (cleaning treatment). It was.

At this time, a small amount of the solvent was collected and analyzed by gas chromatography (GC) to measure the GBL concentration in the solvent. When the above washing process (PGMEA addition and solvent removal) was repeated four more times, no GBL was detected in the solvent power. The GBL concentration in the solvent after 5 washing treatments is 5.8% after 1 washing treatment, 0.8% after 2 washing treatments, 0.1% after 3 washing treatments, respectively. After 4 washing treatments: 0.04% After 5 washing treatments: ND (below detection limit).

[0204] Next, an operation of adding 400 g of tetrahydrofuran (THF) to rosin (-, -1) and stirring (refluxing) at 60 ° C for 1 hour to remove the solvent was repeated twice. (Α'-1) was dried under reduced pressure for 24 hours to obtain purified rosin (Α'-1).

In the following, refined resin (A '-l) is converted to resin (A "-1) and coffee.

As a result of conducting the same measurement as above for rosin (A "-1), the specific surface area of rosin (A" -1) was 0.07 m ² Zg. The SP value of rosin (A, -1) is the same as the SP value of rosin (A, 1-1).

[Example 1]

A column (inner diameter: 7 cm, length: 38 cm) was packed with 100 g of resin (A "-l) using PGMEA.

Next, 1400 parts by weight of PGMEA 2400 parts by weight is added to 1600 parts by weight of a solution containing the resin (A-1) represented by the following formula (A-1) (PGMEA solution with a solid content of 25% by mass). The solid concentration is 10 mass. / (^ PGMEA oil solution.

[0206] [Chemical 36]

[nZmZlZk = 35Z35Zl5Zl5 (molar ratio), Mw = 10000, Mw / Mn = l. 8, M w / Mn = l. 8]

[0207] Next, 1000 parts by mass of this PGMEA resin solution was poured into a column packed with resin (A "-1), and the PGMEA resin solution in the column was fed at a flow rate of 3.3 (mlZs). The resulting eluate was filtered using a nylon filter (product name: Ultipor N66, manufactured by Pall Co., Ltd.) with a pore size of 0.04 m. Then, it was concentrated so that the solid content concentration of the rosin solution was about 20% by mass.

[0208] [Example 2]

A resin solution was prepared in the same manner as in Example 1 except that the flow rate (elution rate) at which the PGMEA resin solution was dropped was set to 0.38 (ml, s). This was designated as rosin solution 2.

[0209] [Example 3]

A resist resin solution was prepared in the same manner as in Example 1 except that the flow rate (elution rate) at which the PGMEA resin solution was dropped was 0.24 (ml / s). This was designated as rosin solution 3.

[0210] [Comparative Example 1]

A resist resin solution was prepared in the same manner as in Example 1, except that the PGMEA resin solution was not passed through the column. This was designated as rosin solution 4.

[0211] The following evaluations were performed using the obtained rosin solutions 1 to 4.

[Different evaluation]

With respect to each of the resin solutions 1 to 4 obtained in Examples 1 to 3 and Comparative Example 1, 2.0 parts by mass of triphenylsulfo-munonafluorobutane sulfonate and 0.2% of triethanolamine were added. Mass parts, 900 parts by mass of PGMEA, 25 parts by mass of γ-petit-mouth rataton, 0.1 parts by mass of surfactant (product name: R-08, manufactured by Dainippon Ink & Chemicals, Inc.) The solution was filtered with a nylon filter (product name: Urpotia 名 66, manufactured by Pole Corporation) with a pore size of 0.04 m, and a polypropylene filter (product name: Two-pore 'Polyfix, kit with a pore size of 0.02 / zm. And a positive resist composition solution 1 to 4 was prepared.

[0212] Next, an organic antireflection film material (product name: ARC-29A, manufactured by Brew Science Co., Ltd.) was applied on an 8-inch silicon wafer and baked at 205 ° C for 60 seconds. Film thickness 77nm An antireflection film was formed as a substrate.

The positive resist composition solution obtained above is uniformly coated on the substrate using a spinner, pre-betaned at 120 ° C for 90 seconds on a hot plate, and dried to give a film thickness of 250 nm. The resist layer was formed.

Next, an ArF excimer laser (193 nm) was passed through the mask pattern using an ArF exposure system (wavelength 193 nm) NSR-S306 (product name, manufactured by Nikon, NA (number of apertures) = 0.78, 2Z3 annular illumination). Selectively exposed.

Then, PEB treatment was performed at 120 ° C for 90 seconds, followed by development at 23 ° C for 60 seconds with a developer (2.38 mass% tetramethylammonium hydroxide aqueous solution), and then using pure water for 15 seconds. Then rinsed with water and dried by shaking. Thereafter, the film was dried by heating at 100 ° C. for 90 seconds to form a line-and-space resist pattern (LZS pattern) having a line width of 120 nm and a pitch of 240 nm.

Next, the surface defect observation device KLA2351 (product name) manufactured by KLA Tencor was used to observe the surface of the L ZS pattern, and the total number of all diffetats in the wafer and the number of bridge mode defetats were determined. The results are shown in Table 1.

[table 1]

[Contact Impact Assessment]

The resin solutions 1 to 4 and the PGMEA resin solution before passing through the column were analyzed by GPC and NMR.

As a result, it was confirmed that GPC had almost the same peak, and almost no influence on the molecular weight distribution by passing through the column. The NMR results are also the same. The difference was a lot of power.

Further, as a result of measuring the thermal decomposition temperature Td and the glass transition temperature Tg of these resin solutions, V and the deviation had the same Td and Tg.

[0215] [Lithography characterization]

An LZS pattern with a line width of 100 nm and a pitch of 200 nm was formed in the same manner as in the above-described diffraction evaluation.

When the obtained LZS pattern was observed with a scanning electron microscope (SEM), the pattern was formed in a good shape in any of the examples.

In addition, the optimum exposure dose Eop (mjZcm ² ) at which the LZS pattern is formed and the depth of focus (in the above Eop, the focus is appropriately shifted up and down, and the LZS pattern is in the range of the dimensional change rate of 100 nm ± 10%. When the depth of focus (DOF) width (m)) obtained in the above was obtained, all were almost equal.

[0216] As shown in the above results, the resin solution passed through a column packed with resin (A "-1) 1 to

The resist pattern formed by using the positive resist composition 1 to 3 obtained using 3 The number of diffetats on the surface is reduced in both the total diffet number and the bridge mode diffet number. Was significantly reduced. The lithography properties were also good.

In addition, when comparing the positive resist compositions 1 to 3, the total number of diffetats tends to decrease as the dissolution rate of the PGMEA resin solution increases. The bridge mode diffet number greatly increases regardless of the dissolution rate. It was reduced to.

Further, these positive resist compositions also had various lithography properties such as resolution, resist pattern shape, sensitivity, and DOF.

On the other hand, in Comparative Example 1 using the positive resist composition 4 obtained by passing through the column and using the resin solution 4, both the total number of differentials and the number of bridge mode differentials were very large.

From these results, it is clear that the resin (A ″ -1) produced by the production method of the present invention is suitable for semiconductor lithography.

Industrial applicability ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the resin for semiconductor lithography which can suppress generation | occurrence | production of a differential, especially bridge | bridging mode differential is provided.

Claims

Claims [1] A resin for semiconductor lithography containing the structural unit (a2) having a latathone-containing cyclic group

A resin solution (R1) in which (A1) is dissolved in an organic solvent (S1) has a solubility parameter in the range of 17-20 Ci Zcm ³ ) ^1/2 and a specific surface area of 0.005 to lm ² Zg. A method for producing a resin for semiconductor lithography, comprising contacting the resin (A1 ′) in the range.

2. The method for producing a resin for semiconductor lithography according to claim 1, wherein the resin (A1,) contains a structural unit (a2 ′) having a latathone-containing cyclic group.

3. The method for producing a resin for semiconductor lithography according to claim 1, wherein the resin for semiconductor lithography (A1) contains a structural unit (al) containing an acid dissociable, dissolution inhibiting group.