Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages

Definitions

• the present invention relates to a silicon compound containing a hexafluoroisopropanol group, a method for producing the same, and a polymer compound obtained by polymerization thereof.
• the polymer compound of the present invention can be used in coating materials or sealants that require high heat resistance, particularly resist materials that require alkali solubility in the semiconductor field.
• a polymer compound containing a siloxane bond (hereinafter sometimes referred to as a polysiloxane polymer compound) is used in the semiconductor field as a coating material and a sealing material, taking advantage of its high heat resistance and transparency.
• an alkali developer an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass is usually used in photolithography.
• Patent Document 1 discloses an alkali-soluble polysiloxane resin characterized by containing an alkali-soluble group-containing siloxane unit and an alkali-insoluble group-containing siloxane unit having no acid-dissociable group.
• This polysiloxane resin is useful for a process using a light source of a shorter wavelength than KrF excimer laser (248 nm), for example, F 2 excimer laser (157 nm) or EUV (vacuum ultraviolet ray 13 nm), and has a high resolution and a sectional shape. It is a positive resist composition capable of forming a good resist pattern.
• an acidic group can be introduced into the polysiloxane polymer compound.
• examples of such an acidic group include a phenol group, a carboxyl group, and a fluorocarbinol group.
• a polysiloxane polymer compound containing a phenol group or a carboxyl group is inferior in heat resistance such as deterioration of transparency and coloring when used at a high temperature.
• an acidic group such as a fluorocarbinol group, for example, a hexafluoroisopropanol group ⁇ 2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [—C (CF 3 ) 2 OH], hereinafter referred to as HFIP group ⁇ , is disclosed in Patent Document 2 and Patent Document 3.
• a fluorocarbinol group for example, a hexafluoroisopropanol group ⁇ 2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [—C (CF 3 ) 2 OH], hereinafter referred to as HFIP group ⁇
• Patent Document 3 a fluorocarbinol group is bonded to a main chain composed only of siloxane via a linear, branched, cyclic or bridged divalent hydrocarbon group having 1 to 20 carbon atoms.
• Polymeric compounds are disclosed.
• the organosilicon compound described in Patent Document 2 includes an ethylene bond (—CH 2 —CH 2 —) between the HFIP group and the silicon atom Si, and the polymer compound described in Patent Document 3 includes an HFIP group and a siloxane main group. Since an aliphatic hydrocarbon group is interposed between the silicon atoms of the chain, there is a problem that heat resistance is impaired.
• Non-Patent Document 1 describes a method of directly reacting an aromatic halogen compound and metal silicon and a method using a Grignard reaction as means for obtaining an aromatic silicon compound by directly bonding a silyl group to an aromatic ring. .
• a Grignard reaction as means for obtaining an aromatic silicon compound by directly bonding a silyl group to an aromatic ring.
• Non-Patent Documents 1 and 2 and Patent Document 4 a compound containing an aromatic halogen compound and a hydrosilyl (Si—H) group (hereinafter sometimes referred to as a hydrosilyl compound) is used as a raw material compound, and a transition metal catalyst is used to produce an aromatic compound.
• a method for synthesizing a group III silicon compound is disclosed.
• Non-Patent Document 2 discloses the synthesis of an aromatic silicon compound containing a hydroxy (OH) group.
• Patent Document 4 discloses a method of performing this production method using an inexpensive aromatic chlorine compound as a raw material.
• Patent Document 5 methods for synthesizing HFIP group-containing aromatic halogen compounds are disclosed in Patent Document 5 and Non-Patent Documents 3 and 4.
• An object of the present invention is to provide a polysiloxane polymer compound that is soluble in an alkali developer and has excellent heat resistance, and a silicon compound as a precursor thereof.
• the present inventors have reacted a HFIP group-containing aromatic compound having a halogen group with a silicon compound having a hydrosilyl group and an alkoxysilyl group in the presence of a transition metal catalyst, whereby an HFIP group and an alkoxysilyl group are reacted. It was found that an HFIP group-containing silicon compound directly bonded to an aromatic ring can be synthesized.
• the HFIP group-containing polysiloxane polymer compound obtained by polymerizing this HFIP group-containing silicon compound was found to exhibit high heat resistance and alkali solubility, and the present invention was achieved.
• the present invention includes the following inventions 1 to 8.
• R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms.
• the silicon compound of the invention 1 represented by these.
• the HFIP group-containing polysiloxane polymer compound of the present invention is soluble in an alkali developer and has excellent heat resistance, and the precursor compound HFIP group-containing silicon compound is the HFIP group-containing polysiloxane polymer compound. It is useful for the production of
• the HFIP group-containing silicon compound of the present invention and the production method thereof, and then the HFIP group-containing polysiloxane polymer compound obtained by the polymerization reaction of the HFIP group-containing silicon compound of the present invention will be described in order.
• HFIP group-containing silicon compound [HFIP group-containing silicon compound represented by the general formula (1)]
• the HFIP group-containing silicon compound (1) represented by the general formula (1) of the present invention will be described.
• n is preferably 3. It is preferable that a is 1 or 2, and aa is 1.
• the number of HFIP group-containing aryl groups contained in the HFIP group-containing silicon compound (1) is preferably one, specifically, the HFIP group represented by the general formula (2) It is preferable that it is a containing silicon compound (2).
• R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms.
• [HFIP group-containing silicon compound represented by general formula (3)] Of the HFIP group-containing silicon compound (1), the HFIP group-containing silicon compound (3) represented by the following general formula (3) is more preferable.
• R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a is an integer of 1 to 5)
• the HFIP group-containing silicon compound of the present invention the HFIP group-containing compound (3-1) represented by the following formula (3-1) and the HFIP group-containing compound represented by the formula (3-2):
• the compound (3-2) and the HFIP group-containing compound (3-3) represented by the formula (3-3) can be shown.
• Et is an ethyl group (—CH 2 CH 3 ), and the same applies hereinafter.
• the present invention relates to a method for producing a HFIP group-containing silicon compound.
• X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (p—C 6 H 4 CH 3 ) group or —OSO 2 CF 3 group, and a is an integer of 1 to 5)
• HFIP group-containing aromatic compound (4) represented by the general formula (5) wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluor
• the HFIP group-containing silicon compound (1) is represented by the HFIP group-containing aromatic compound (4) represented by the general formula (4) and the general formula (5).
• the resulting hydrosilyl group-containing silicon compound (5) is obtained by heating and reacting in an organic solvent under a transition metal catalyst.
• R 1 is a hydrogen atom, having 1 to 10 carbon atoms
• R 2 are each Independently, it is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is 1 to 3.
• HFIP group-containing aromatic compound (4) and a hydrosilyl group-containing silicon compound (5), a transition metal catalyst, an organic solvent, a base, and an additive are collected in a reaction vessel, mixed, heated, and reacted.
• HFIP group-containing silicon compound (1) can be obtained by distillation purification of the reaction product.
• reaction and raw material compound The reaction and raw material compound, reaction product, catalyst, organic solvent, reaction conditions, etc. will be described below.
• HFIP group-containing aromatic compound Specific examples of the HFIP group-containing aromatic compound (4) include an HFIP group-containing aromatic compound (4-1) represented by the following general formula (4-1) and a general formula (4-2). Examples thereof include HFIP group-containing aromatic compound (4-2) and HFIP group-containing aromatic compound (4-3) represented by formula (4-3).
• Patent Document 5 describes a method for synthesizing an HFIP group-containing aromatic compound (4-1).
• Non-Patent Document 3 describes an HFIP group-containing aromatic compound (4-2),
• Non-Patent Document 4 Describes a method for synthesizing an HFIP group-containing aromatic compound (4-3).
• X in the HFIP group-containing aromatic compound (4) is preferably a bromine atom.
• the HFIP group-containing silicon compound (1) is obtained from the HFIP group-containing aromatic compound (4) and the hydrosilyl group-containing silicon compound (5).
• the combination of the HFIP group-containing aromatic compound (4) and the hydrosilyl group-containing silicon compound (5) is not particularly limited. Below, the case where triethoxysilane is used as a hydrosilyl group containing silicon compound (5) is illustrated.
• the HFIP group-containing aromatic compounds (4-1) to (4-3) are used as the HFIP group-containing aromatic compound (4), they are represented by the following formulas (3-1) to (3-3). HFIP group-containing silicon compounds (3-1) to (3-3) can be obtained.
• hydrosilyl group-containing silicon compound (5) can be selected from monoalkoxysilane, dialkoxysilane, or trialkoxysilane.
• Examples of the monoalkoxysilane include methoxysilane, ethoxysilane, isopropoxysilane, ethoxydimethylsilane, methoxydimethylsilane, ethoxymethylsilane, and methoxymethylsilane.
• Examples of dialkoxysilane include diethoxysilane, dimethoxysilane, diethoxymethylsilane, dimethoxymethylsilane, diethoxyphenylsilane, and dimethoxyphenylsilane.
• Examples of trialkoxysilanes include triethoxysilane, trimethoxysilane, and triisopropoxysilane.
• triethoxysilane, trimethoxysilane, diethoxymethylsilane or dimethoxymethylsilane is preferable.
• HFIP group-containing polysiloxane polymer compounds having relatively high molecular weight can be obtained by polymerization reaction in HFIP group-containing silicon compounds using these compounds as raw materials. .
• transition metal catalyst used in this reaction is a group 8-10 element, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, and an organometallic complex, metal salt or metal thereof.
• An oxide can be illustrated.
• the HFIP group-containing silicon compound (1) of the present invention can be obtained in a high yield, specifically, chloro (1,5-cyclooctadiene) rhodium (I) dimer, bis (acetonitrile) (1,5 -Cyclooctadiene) rhodium (I) tetrafluoroborate, bis (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate, bis (triphenylphosphine) rhodium (I) carbonyl chloride, palladium (II) Dichloride, tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct, bis (tri-tert-butylphosphine) palladium (0), palladium (II) acetate or oxidation Platinum (IV) is a preferred example
• Organic solvent used for this reaction should just be a solvent in which a raw material compound melt
• N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, 1,4-dioxane, diethyl ether or diisopropyl ether can be exemplified.
• a base for capturing the by-product acid coexists in the reaction system.
• Specific examples include triethylamine, diethylamine, diisopropylethylamine, pyridine, potassium carbonate, potassium acetate, potassium phosphate, potassium hydroxide, sodium hydroxide, or lithium hydroxide.
• the amount of the base is not particularly limited as long as the by-product acid can be supplemented. It is preferable that they are 0.1 mol or more and 10 mol or less with respect to 1 mol of HFIP group containing aromatic compounds (4).
• the additive may be exemplified by tetrabutylammonium iodide, tetrapropylammonium iodide, tetraethylammonium iodide, tetramethylammonium iodide, tetrahexylammonium iodide, potassium iodide or sodium iodide. it can.
• reaction temperature The reaction temperature in this reaction is preferably in the range of room temperature (about 20 ° C. in the present invention) to 120 ° C.
• HFIP group-containing polysiloxane polymer compound [HFIP group-containing polysiloxane polymer compound containing a repeating unit represented by formula (6)]
• the HFIP group-containing polysiloxane polymer compound (6) of the present invention containing the repeating unit represented by the general formula (6) will be described.
• R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms,
• a branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, and each R 2 independently represents 1 to 4 is a linear or branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m
• the HFIP group-containing polysiloxane polymer compound of the present invention includes any one of the following formulas (6-1) to (6-3).
• Formula (6-1) represents a case where n is 1 in Formula (6), Formula (6-2) is n, and Formula (6-3) is n.
• formula (6-1), formula (6-2) and formula (6-3) may be mixed with each other in the polysiloxane chain, that is, may coexist.
• R 1a is a monovalent organic group represented by the following formula (6-4)
• R 1b and R 1c are represented by the following formula ( A monovalent organic group represented by 6-4) or an organic group represented by R 1 .
• a line segment intersecting with the wavy line represents a coupling position.
• the molecular weight of the HFIP group-containing polysiloxane polymer compound of the present invention is preferably 1,000 or more and 200,000 or less, expressed as a weight average molecular weight in terms of polystyrene.
• the content of the HFIP group of the HFIP group-containing polysiloxane polymer compound (6) of the present invention is not particularly limited as long as alkali solubility can be imparted.
• the content of HFIP groups is one silicon atom.
• HFIP Group-Containing Polysiloxane Polymer Containing Repeating Unit Represented by General Formula (7) In the HFIP group-containing polysiloxane polymer compound (6), it is preferable that the number of HFIP group-containing aryl groups contained is one from the viewpoint of ease of production, and the HFIP group includes a repeating unit represented by the general formula (7). It is preferable that it is a containing silicon compound (7).
• HFIP Group-Containing Polysiloxane Polymer Containing Repeating Unit Represented by General Formula (7-1), General Formula (7-2), or General Formula (7-3) Specifically, an HFIP group-containing polysiloxane polymer compound (7-1) containing a repeating unit represented by the following general formula (7-1), and a repeating represented by the following general formula (7-2) HFIP group-containing polysiloxane polymer compound (7-2) containing a unit or HFIP group-containing polysiloxane polymer compound (7-3) containing a repeating unit represented by the following general formula (7-3) can do.
• Method for Producing HFIP Group-Containing Polysiloxane Polymer Compound HFIP group-containing polysiloxane polymer compound (6), (7), (7-1), (7-2) or (7-3) of the present invention is
• the HFIP group-containing silicon compounds (1) to (3) are obtained by hydrolysis and polycondensation reaction. This hydrolysis and polycondensation reaction can be performed by a general method in the hydrolysis and condensation reaction of alkoxysilane.
• the reaction vessel When the reaction is carried out with heating, in order to prevent unreacted raw materials, water, acid catalyst or reaction solvent in the reaction system from distilling out of the reaction system, the reaction vessel is closed or a condenser is used.
• the reaction system is preferably refluxed.
• the time required for the condensation reaction is usually from 3 hours to 24 hours depending on the type of acid catalyst, and the reaction temperature is from room temperature to 180 ° C.
• the removal of the water, alcohol, and acid catalyst may be performed by an extraction operation, or a solvent that does not adversely influence the reaction, such as toluene, may be added to the reaction system and removed azeotropically with a Dean-Stark tube.
• a solvent that does not adversely influence the reaction such as toluene
• the water used is expressed in a molar ratio with respect to the total number of moles of alkoxy groups of the raw material HFIP group-containing aromatic silicon compound. 0.5 mol or more and 5.0 mol or less. If the amount is less than 0.5 mol, hydrolysis does not proceed efficiently, and if it exceeds 5.0 mol, gelation tends to be difficult.
• acid catalyst used in the polycondensation reaction include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid.
• organic acids include acetic acid, Examples include fluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, formic acid, oxalic acid, maleic acid, camphorsulfonic acid, benzenesulfonic acid or tosylic acid.
• the reaction solvent used in the polycondensation reaction is preferably an alcohol solvent.
• the organic solvent used as an extraction solvent for the HFIP group-containing polysiloxane polymer compound (6) which is a condensate in the system after the polycondensation reaction, can dissolve and extract the HFIP group-containing polysiloxane polymer compound (6). If it is a thing, it will not specifically limit. Specifically, diethyl ether, diisopropyl ether, dibutyl ether, chloroform, dichloromethane, ethyl acetate, toluene and the like can be exemplified.
• Solid desiccant After the reaction system is extracted and washed with an organic solvent, a trace amount of water dissolved in the extract may be removed using a solid desiccant, if necessary.
• the solid desiccant used is not particularly limited. Specifically, magnesium sulfate, sodium sulfate, calcium sulfate, or synthetic zeolite can be exemplified.
• an HFIP group represented by the general formula (1) which is an alkoxysilane for the purpose of adjusting physical properties such as solubility in an alkali developer and heat resistance.
• other dialkoxysilanes, trialkoxysilanes or tetraalkoxysilanes may be copolymerized.
• dialkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiphenoxysilane, Dipropyldimethoxysilane, dipropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane or methyl (3,3,3-trifluoro) A propyl) dimethoxysilane can be illustrated.
• trialkoxysilane examples include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and propyltriethoxy.
• Silane isopropyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltripropoxysilane, isopropyltripropoxysilane, phenyltripropoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, propyl Triisopropoxysilane, isopropyltriisopropoxysilane, phenyltriisopropoxysilane, trifluoromethyl Trimethoxysilane, pentafluoroethyl trimethoxysilane may be exemplified 3,3,3-trifluoropropyl trimethoxy silane or 3,3,3-trifluoropropyl triethoxysilane.
• tetraalkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
• dialkoxysilane, trialkoxysilane or tetraalkoxysilane may be used alone or in combination of two or more.
• At least one compound selected from the dialkoxysilane, trialkoxysilane, and tetraalkoxysilane is referred to as “other alkoxysilane”.
• the total amount is not particularly limited, but is preferably 0.1 to 10 moles per mole of the HFIP group-containing aromatic compound, 0.2 to More preferably, it is 5 moles. If it exceeds 10 mol, alkali solubility may not be imparted.
• Film containing HFIP group-containing polysiloxane polymer compound The HFIP group-containing polysiloxane polymer compound of the present invention can be dissolved in an organic solvent and applied as a coating solution to form a film. At that time, additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer can be added as necessary.
• the HFIP group-containing polysiloxane polymer compound of the present invention is dissolved in an organic solvent to form a coating solution, which is then applied to a substrate such as a glass substrate, a silicon substrate or a metal substrate, and then dried to form a film.
• organic solvent examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. be able to.
• the concentration of the HFIP group-containing polysiloxane polymer compound when the HFIP group-containing polysiloxane of the present invention is dissolved in the organic solvent is not particularly limited.
• the range is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less.
• the method for applying the coating solution is not particularly limited, and a known method such as spin coating, bar coater or dip coating can be used.
• a coating film can be obtained by the above method without using an organic solvent.
• HFIP group-containing polysiloxane polymer compound of the present invention and the film obtained therefrom are soluble in an alkaline developer is an effect due to having HFIP groups in the chemical structure. Furthermore, since the silicon atom and the aromatic ring are directly bonded in the chemical structure, the HFIP group-containing polysiloxane polymer compound of the present invention and the film obtained therefrom are excellent in heat resistance.
• the coated film can be made into a cured film having better mechanical strength and solvent resistance by heating, addition of an acid or base, or condensation using a photopolymerization initiator.
• the curing conditions are not particularly limited.
• the temperature is preferably 100 ° C. or higher and 350 ° C. or lower, and the curing time is preferably 1 hour or longer and 24 hours or shorter.
• the HFIP group-containing polysiloxane polymer compound of the present invention is solid or liquid at room temperature, and in the case of liquid, a bulk cured product can be obtained by performing potting molding and the above-described curing method.
• the HFIP group-containing polysiloxane polymer compound of the present invention and a film obtained therefrom are soluble in an alkaline developer and excellent in heat resistance, and thus are used for a protective film for a semiconductor, a protective film for a display, and a resist material. be able to.
• the bulk cured product can be used for optical transparent encapsulants including those for LEDs, heat-resistant encapsulants for semiconductors, and the like.
• Nuclear Magnetic Resonance Measurement Using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model AL400) with a resonance frequency of 400 MHz, 1 H-NMR, 19 F-NMR, 13 C-NMR Alternatively, HFIP group-containing silicon compounds and HFIP group-containing polysiloxane polymer compounds were identified by measuring 29 Si-NMR.
• GPC Gel Permeation Chromatography
• thermogravimetric measurement (TGA, manufactured by Rigaku Corporation, type TG8120) was carried out to thermally decompose the temperature at which the weight loss was 5% of the initial weight. The temperature (T d5 ) was used.
• Example 1 Synthesis of HFIP group-containing silicon compound (3-1)
• the following reaction for synthesizing the HFIP group-containing silicon compound (3-1) was performed.
• Et is an ethyl group (—CH 2 CH 3 ), and the same applies hereinafter.
• reaction product was distilled and purified using a Kugelrohr distillation apparatus under the conditions of a temperature of 130 ° C. to 140 ° C. and a pressure of 180 Pa to obtain 1.82 g of HFIP group-containing silicon compound (3-1) as a colorless liquid. Obtained at 32%.
• HFIP group-containing aromatic compound (4-2), 6.46 g (20.0 mmol), tetrabutylammonium iodide, 7.38 g (40.0 mmol) and bis (acetonitrile) (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate, 0.2280 g (0.60 mmol) were collected at room temperature.
• the resulting precipitate was contacted with celite and filtered, and the filtrate was washed 3 times with 100 mL of water, dried by adding Na 2 SO 4 , further filtered, and then the solvent was distilled off.
• the residue as a reaction product was purified by distillation using a Kugelrohr apparatus under conditions of a temperature of 140 ° C. to 190 ° C. and a pressure of 200 Pa to obtain 4.56 g of a HFIP group-containing silicon compound (3-2) as a colorless liquid. Obtained at 56%.
• Example 3 Synthesis of HFIP group-containing silicon compound (3-3)
• the following reaction for synthesizing the HFIP group-containing silicon compound (3-3) was performed.
• the reaction was carried out in the same manner as in Example 2 except that the HFIP group-containing aromatic compound (4-3) was used instead of the HFIP group-containing aromatic compound (4-2). After completion of the reaction, the reaction mixture was post-treated in the same manner as in Example 2 and purified by distillation using a Kugelrohr apparatus to obtain 2.84 g of a HFIP group-containing silicon compound (3-3) as a colorless liquid in a yield of 35%. It was.
• Example 4 [Synthesis of HFIP group-containing polysiloxane polymer compound using HFIP group-containing silicon compound (3-1) as a raw material compound] HFIP group-containing silicon compound (3-1), 11.45 g (20.0 mmol) was dissolved in methanol to a total amount of 57 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (8) containing a repeating unit represented by the following formula (8) as a colorless transparent highly viscous liquid.
• Example 5 [Synthesis of HFIP group-containing polysiloxane polymer compound (9) using HFIP group-containing silicon compound (3-2) as a raw material] HFIP group-containing silicon compound (3-2), 8.13 g (20.0 mmol) was dissolved in methanol to a total amount of 41 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (9) containing a repeating unit represented by the following formula (9) as a colorless transparent highly viscous liquid.
• Example 6 [Synthesis of HFIP group-containing polysiloxane polymer compound (10) using HFIP group-containing silicon compound (3-3) as a raw material] HFIP group-containing silicon compound (3-3), 1.63 g (4.0 mmol), dissolved in methanol to a total amount of 8.2 g, 0.216 mL (12.0 mmol) of water, 0.1 mol of 4 mol / L hydrochloric acid, 05 mL was added and stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (10) containing a repeating unit represented by the following formula (10) as a colorless transparent highly viscous liquid.
• Example 7 [Synthesis of HFIP group-containing polysiloxane polymer compound (11) containing HFIP group-containing silicon compound (3-1)] To a 50 mL flask, HFIP group-containing silicon compound (3-1), 4.58 g (8 mmol), phenyltrimethoxysilane, 6.35 g (32 mmol), water, 2.16 g (120 mmol), acetic acid, 0.12 g ( 2 mmol) was added and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.) to distill off water, generated ethanol, methanol and acetic acid. Finally, toluene is distilled off to obtain the following formula (11). An HFIP group-containing polysiloxane polymer compound (11) containing the represented repeating unit was obtained as a white solid.
• Example 8 [Synthesis of HFIP group-containing polysiloxane polymer compound (12) containing HFIP group-containing silicon compound (3-2)]
• HFIP group-containing silicon compound (3-2) 5.59 g (13.75 mmol), phenyltrimethoxysilane, 2.23 g (11.25 mmol), water, 1.35 g (75 mmol), acetic acid, 0.075 g (1.25 mmol) was added, and the mixture was stirred at 100 ° C. for 12 hours.
• Table 1 shows the mass ratio of the raw material compounds in Examples 4 to 8.
• Comparative Example 1 Comparative polysiloxane polymer compound 1 was synthesized as a polysiloxane polymer compound not within the scope of the present invention. Dissolve 4.80 g (20.0 mmol) of phenyltriethoxysilane in methanol to make a total amount of 27 g, mix 1.08 mL of water and 0.25 mL of 4 mol / L hydrochloric acid, and perform the same procedure as in Example 4 for comparison. Polysiloxane polymer compound 1 was obtained. Mw obtained from GPC measurement of the obtained comparative polysiloxane polymer compound 1 was 2000, and the solubility in an alkali developer was confirmed to be “insoluble”.
• Comparative Example 3 HFIP group-containing silicon compound (13) represented by the following formula (13), 4.34 g (10.0 mmol) was dissolved in methanol to make the total amount 21.74 g. This, 0.54 g of water, and 0.125 mL of 4 mol / L hydrochloric acid were mixed, and a comparative polysiloxane polymer compound 3 was obtained in the same procedure as in Example 4.
• the HFIP group-containing silicon compound (13) and the comparative polysiloxane polymer compound 3 obtained therefrom have an ethylene bond (—CH 2 —CH 2 —) between the silicon atom and the aromatic ring. Therefore, it differs from the HFIP group-containing silicon compound and HFIP group-containing polysiloxane polymer compound of the present invention in which a silicon atom and an aromatic ring are directly bonded.
• Mw of the obtained comparative polysiloxane polymer compound 3 was 3400.
• the solubility in an alkaline developer was confirmed, it was “dissolved”.
• the 5% mass reduction temperature (T d5 ) was 320 ° C. This result was lower than the 5% mass reduction temperature (T d5 ) of the HFIP group-containing polysiloxane polymer compounds (8) to (12) of the present invention obtained in Examples 4 to 8.
• Table 1 shows the raw material compounds in Comparative Examples 1 to 3 above.
• Table 2 shows Mw obtained from GPC measurement in the above comparative polysiloxane polymer compounds 1 to 3, solubility in alkali developer, and 5% mass reduction temperature (T d5 ).

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• 2014
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